Updates to In-Line Calculation of Photolysis Rates

EPA Science Inventory

How photolysis rates are calculated affects ozone and aerosol concentrations predicted by the CMAQ model and the model?s run-time. The standard configuration of CMAQ uses the inline option that calculates photolysis rates by solving the radiative transfer equation for the needed ...

Photolysis of aromatic pollutants in clean and dirty ice

NASA Astrophysics Data System (ADS)

Kahan, T.; Malley, P.; Stathis, A.

2015-12-01

Anthropogenic aromatic pollutants such as polycyclic aromatic hydrocarbons (PAHs) and substituted benzenes often become more toxic following atmospheric oxidation. Photolysis of these pollutants in ice can be much faster than that in aqueous solution, which might lead to higher carcinogenic loadings in snow-covered regions. In this work we investigate two things. First, we investigate whether toluene, which has been detected at very elevated concentrations near hydraulic fracturing operations, can undergo photolysis at ice surfaces. Toluene in aqueous solution does not absorb sunlight, so photolysis has not been considered a potential atmospheric fate. However, benzene was recently demonstrated to undergo a significant red shift in its absorbance at ice surfaces, leading to photolysis under environmentally-relevant conditions. Here we show that toluene also undergoes photolysis at ice surfaces. In a second set of experiments, we have investigated the effects of organic matter on the photolysis kinetics ofPAHs in ice and at ice surfaces. We found that very small loadings of hydrophobic organics such as octanol can significantly suppress PAH photolysis kinetics in ice, but that the primary effect of the more soluble fulvic acid is competitive photon absorption. Our results show that photochemistry of anthropogenic pollutants can follow very different mechanisms and kinetics in ice than in aqueous solution, and that the photochemical fate of these pollutants depends strongly on the composition of the snow. These results have implications for pollutant fate and human health in a wide range of snow-covered environments including remote areas, cities, and regions near gas and oil extraction operations.

Fulvic Acid Mediated Photolysis of Ibuprofen in Water.

EPA Science Inventory

Photolysis of the nonsteroidal anti-inflammatory drug ibuprofen was studied in solutions of fulvic acid (FA) isolated from Pony Lake, Antarctica; Suwannee River, GA, USA; and Old Woman Creek, OH, USA. At an initial concentration of 10 µM ibuprofen degrades by direct photolysis...

Precision of NO2 photolysis rate measurements

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.

1980-01-01

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-08-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

DOE PAGES

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; ...

2015-08-20

This paper presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C 12 and C 16 n-alkane reactions with OH at low and high NO x. Simulations are conducted formore » typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NO x) to ~45 % (high NO x) for α-pinene, ~15 % for toluene, ~25 % for C 12 n-alkane, and ~10 % for C 16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C 16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA

EMERGING TECHNOLOGY REPORT: BENCH-SCALE TESTING OF PHOTOLYSIS, CHEMICAL OXIDATION AND BIODEGRADATION OF PCB CONTAMINATED SOILS AND PHOTOLYSIS OF TCDD CONTAMINATED SOILS

EPA Science Inventory

This report presents the results of bench-scale testing on degradation of 2,3,7,8-TCDD using W photolysis, and PCB degradation using UV photolysis, chemical oxidation and biological treatment. Bench-scale tests were conducted to investigate the feasibility of a two-phase detoxifi...

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

PubMed

Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

2017-10-01

Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

The aqueous photolysis of ethylene glycol adsorbed on geothite

USGS Publications Warehouse

Cunningham, Kirkwood M.; Goldberg, Marvin C.; Weiner, E.R.

1985-01-01

Suspensions of goethite (α-FeOOH) were photolyzed in aerated ethylene glycol-water solutions at pH 6.5, with ultraviolet light in the wavelength range300–400 nm. Under these conditions, formaldehyde and glycolaldehyde were detected as photoproducts. Quantum yields of formaldehyde production ranged from 1.9 7times; 10-5 to 2.9 × 10-4 over the ethylene glycol concentration range of 0.002-2.0 mol/ℓ, and gave evidence that the reaction occurred at the goethite surface. Quantum yields of glycolaldehyde were 20% less than those of formaldehyde, and displayed a concentration-dependent relationship with ethylene glycol similar to that of formaldehyde. Immediately after photolysis, Fe2+ was measured to be 4.6 × 10-7 mol/ℓ in an aerated suspension containing 1.3 mol/ℓ ethylene glycol, and 8.5 × 10-6 mol/ℓ in the corresponding deoxygenated suspension. Glycolaldehyde was not generated in the deoxygenated suspensions. These results are consistent with a mechanism involving the transfer of an electron from an adsorbed ethylene glycol molecule to an excited state of Fe3+ (Iron[III]) in the goethite lattice, to produce Fe2+ and an organic cation. In a series of reactions involving O2, FeOOH, and Fe2+, the organic cation decomposes to form formaldehyde and the intermediate radicals “OH and” CH2OH. OH reacts further with ethylene glycol in the presence of O2to yield glycolaldehyde. Aqueous photolysis of ethylene glycol sorbed onto goethite is typical of reactions that can occur in the aquatic environment.

How UV photolysis accelerates the biodegradation and mineralization of sulfadiazine (SD).

PubMed

Pan, Shihui; Yan, Ning; Liu, Xinyue; Wang, Wenbing; Zhang, Yongming; Liu, Rui; Rittmann, Bruce E

2014-11-01

Sulfadiazine (SD), one of broad-spectrum antibiotics, exhibits limited biodegradation in wastewater treatment due to its chemical structure, which requires initial mono-oxygenation reactions to initiate its biodegradation. Intimately coupling UV photolysis with biodegradation, realized with the internal loop photobiodegradation reactor, accelerated SD biodegradation and mineralization by 35 and 71 %, respectively. The main organic products from photolysis were 2-aminopyrimidine (2-AP), p-aminobenzenesulfonic acid (ABS), and aniline (An), and an SD-photolysis pathway could be identified using C, N, and S balances. Adding An or ABS (but not 2-AP) into the SD solution during biodegradation experiments (no UV photolysis) gave SD removal and mineralization rates similar to intimately coupled photolysis and biodegradation. An SD biodegradation pathway, based on a diverse set of the experimental results, explains how the mineralization of ABS and An (but not 2-AP) provided internal electron carriers that accelerated the initial mono-oxygenation reactions of SD biodegradation. Thus, multiple lines of evidence support that the mechanism by which intimately coupled photolysis and biodegradation accelerated SD removal and mineralization was through producing co-substrates whose oxidation produced electron equivalents that stimulated the initial mono-oxygenation reactions for SD biodegradation.

Primary processes in photolysis of octopus rhodopsin.

PubMed

Ohtani, H; Kobayashi, T; Tsuda, M; Ebrey, T G

1988-01-01

The photolysis of octopus rhodopsin was studied by picosecond time-resolved spectroscopy at physiological temperature (8 degrees C) and by steady-state spectroscopy at very low temperature (10 K). Both hypsorhodopsin and bathorhodopsin were formed from a bathorhodopsin-like red-shifted intermediate "primerhodopsin," which was the primary photoproduct with our time resolution (36 ps). Though it was proposed that hypsorhodopsin is formed solely by a multiphoton process, the present results obtained by using blue light pulses (461 nm) of low intensity showed that hypsorhodopsin is formed by a single photon mechanism via thermal decay from primerhodopsin. When the excitation intensity is increased, a channel for the photochemical formation of hypsorhodopsin from primerhodopsin is opened. There are two thermal pathways leading from primerhodopsin. One process is the formation of hypsorhodopsin, which is later thermally converted to bathorhodopsin, and the other is the direct formation of bathorhodopsin from primerhodopsin. The formation efficiencies at room temperature of hypsorhodopsin and bathorhodopsin at very low excitation intensity were estimated to be larger than 0.6 and smaller than 0.4, respectively. The formation of hypsorhodopsin was also found in the early stages of the irradiation of octopus rhodopsin with weak continuous light at 10 K. However bathorhodopsin is formed three times more efficiently than hypsorhodopsin at 10 K.At physiological temperatures the formation of hypsorhodopsin in D(2)O takes place more slowly than in H(2)O. This indicates that the lifetime of primerhodopsin is decreased by H(2)O/D(2)O exchange. The rate constant for the primerhodopsin --> bathorhodopsin conversion is more sensitive than that for the primerhodopsin --> hypsorhodopsin conversion. The transformation of hypsorhodopsin to bathorhodopsin shows no deuterium effect at low temperature.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-03-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

Aqueous photolysis of the organic ultraviolet filter chemical octyl methoxycinnamate.

PubMed

MacManus-Spencer, Laura A; Tse, Monica L; Klein, Jacob L; Kracunas, Alison E

2011-05-01

Organic UV filter chemicals are the active ingredients in personal care products designed to protect the skin from UV radiation, and hundreds of tons are estimated to be produced annually. Despite their entrance into the aquatic environment by both direct and indirect routes and their detection in surface waters and fish, little is known about their environmental fate. UV filter chemicals are designed to be photostable, but some undergo transformation upon exposure to UV light. Octyl methoxycinnamate (OMC), a commonly used UV filter chemical, degrades rapidly by direct photolysis; previous studies have focused on its photoisomerization, and a few investigators have reported the formation of cyclodimers. Here, we present the kinetics and quantum efficiency of the direct photolysis of OMC and confirm that dimerization occurs as a result of direct photolysis in aqueous solution. Likely identities of the dimers are offered based on comparison to reported results for other cinnamate derivatives. We have identified additional products of direct photolysis that have not been previously reported and investigated their photostability, as well as the mechanism of product formation. There is also some evidence of indirect photolysis in the presence of dissolved natural organic matter.

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

NASA Technical Reports Server (NTRS)

Nickolaisen, Scott L.; Sander, Stanley P.; Friedl, Randall R.

1996-01-01

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Classification of Rhinoentomophthoromycosis into Atypical, Early, Intermediate, and Late Disease: A Proposal

PubMed Central

Blumentrath, Christian G.; Grobusch, Martin P.; Matsiégui, Pierre-Blaise; Pahlke, Friedrich; Zoleko-Manego, Rella; Nzenze-Aféne, Solange; Mabicka, Barthélemy; Sanguinetti, Maurizio; Kremsner, Peter G.; Schaumburg, Frieder

2015-01-01

Background Rhinoentomophthoromycosis, or rhino-facial conidiobolomycosis, is a rare, grossly disfiguring disease due to an infection with entomophthoralean fungi. We report a case of rhinoentomophthoromycosis from Gabon and suggest a staging system, which provides information on the prognosis and duration of antifungal therapy. Methods We present a case of rhinoentomophthoromycosis including the histopathology, mycology, and course of disease. For the suggested staging system, all cases on confirmed rhinoentomophthoromycosis published in the literature without language restriction were eligible. Exclusion criteria were missing data on (i) duration of disease before correct diagnosis, (ii) outcome, and (iii) confirmation of entomophthoralean fungus infection by histopathology and/or mycology. We classified cases into atypical (orbital cellulitis, severe pain, fever, dissemination), early, intermediate, and late disease based on the duration of symptoms before diagnosis. The outcome was evaluated for each stage of disease. Findings The literature search of the Medpilot database was conducted on January 13, 2014, (updated on January 18, 2015). The search yielded 8,333 results including 198 cases from 117 papers; of these, 145 met our inclusion criteria and were included in the final analysis. Median duration of treatment was 4, 3, 4, and 5 months in atypical, early, intermediate, and late disease, respectively. Cure rates were clearly associated with stage of disease and were 57%, 100%, 82%, and 43% in atypical, early, intermediate, and late disease, respectively. Conclusion We suggest a clinical staging system that underlines the benefit of early case detection and may guide the duration of antifungal treatment. The scientific value of this classification is its capacity to structure and harmonize the clinical and research approach towards rhinoentomophthoromycosis. PMID:26426120

Infrared measurements on ultraviolet photolysis products at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Dong, Weibing; He, Ping; Wang, Jessie; Zhou, Zhaohui; Wang, Hongxin

2013-01-01

Combination of ultraviolet (UV) photolysis with infrared (IR) spectroscopy (or UV/IR for abbreviation) is a powerful tool to study various chemical photoreactions, while cryostat and sample-cell windows define the working ranges for both UV and IR beams. Although diamond window has a very wide transmission range from UV to IR, the extreme cost, the absorptions at 1800-2600 cm-1 and other problems prevent it from being the solution for all cases. In this paper, a gas-exchange cryostat was modified to realize a UV/mid-IR experiment at cryogenic temperatures. Several windows (including diamond) were discussed as options. A di-nitrogen iron complex trans-[Fe(DMeOPrPE)2(N2)H][BPh4] [DMeOPrPE = 1,2-bis(dimethoxypropylphosphino)ethane] was studied as a real photolysis example. Alternatively, a cold-finger cryostat was modified for UV/far-IR compatible experiments. Non-photolysis samples K5[Mo4O11(R,S-Hhomocit)2]Cl·5H2O (H4homocit = homocitric acid) and [(n-Bu)4N]2[Fe4S4(PPh)4] were studied at cryogenic temperatures. Sample cell windows can also be used as a natural way for choosing photolysis wavelength (in addition to the use of optical filters).

Visual Function Metrics in Early and Intermediate Dry Age-related Macular Degeneration for Use as Clinical Trial Endpoints.

PubMed

Cocce, Kimberly J; Stinnett, Sandra S; Luhmann, Ulrich F O; Vajzovic, Lejla; Horne, Anupama; Schuman, Stefanie G; Toth, Cynthia A; Cousins, Scott W; Lad, Eleonora M

2018-05-01

To evaluate and quantify visual function metrics to be used as endpoints of age-related macular degeneration (AMD) stages and visual acuity (VA) loss in patients with early and intermediate AMD. Cross-sectional analysis of baseline data from a prospective study. One hundred and one patients were enrolled at Duke Eye Center: 80 patients with early AMD (Age-Related Eye Disease Study [AREDS] stage 2 [n = 33] and intermediate stage 3 [n = 47]) and 21 age-matched, normal controls. A dilated retinal examination, macular pigment optical density measurements, and several functional assessments (best-corrected visual acuity, macular integrity assessment mesopic microperimety, dark adaptometry, low-luminance visual acuity [LLVA] [standard using a log 2.0 neutral density filter and computerized method], and cone contrast test [CCT]) were performed. Low-luminance deficit (LLD) was defined as the difference in numbers of letters read at standard vs low luminance. Group comparisons were performed to evaluate differences between the control and the early and intermediate AMD groups using 2-sided significance tests. Functional measures that significantly distinguished between normal and intermediate AMD were standard and computerized (0.5 cd/m 2 ) LLVA, percent reduced threshold and average threshold on microperimetry, CCTs, and rod intercept on dark adaptation (P < .05). The intermediate group demonstrated deficits in microperimetry reduced threshhold, computerized LLD2, and dark adaptation (P < .05) relative to early AMD. Our study suggests that LLVA, microperimetry, CCT, and dark adaptation may serve as functional measures differentiating early-to-intermediate stages of dry AMD. Copyright © 2018 Elsevier Inc. All rights reserved.

Photolysis of three antiviral drugs acyclovir, zidovudine and lamivudine in surface freshwater and seawater.

PubMed

Zhou, Chengzhi; Chen, Jingwen; Xie, Qing; Wei, Xiaoxuan; Zhang, Ya-nan; Fu, Zhiqiang

2015-11-01

Photodegradation is an important elimination process for many pharmaceuticals in surface waters. In this study, photodegradation of three antiviral drugs, acyclovir, zidovudine, and lamivudine, was investigated in pure water, freshwater, and seawater under the irradiation of simulated sunlight. Results showed that zidovudine was easily transformed via direct photolysis, while acyclovir and lamivudine were mainly transformed via indirect photolysis. We found that in freshwater, nitrate enhanced the photodegradation of the three antiviral drugs, bicarbonate promoted the photodegradation of acyclovir, and dissolved organic matter (DOM) accelerated the photolysis of acyclovir and lamivudine. In seawater, the photolysis of acyclovir was not susceptible to Cl(-), Br(-) and ionic strength; however, the photolysis of zidovudine was inhibited by Cl(-) and Br(-), and the photolysis of lamivudine was enhanced by Cl(-), Br(-) and ionic strength. Second-order reaction rate constants for the three antiviral drugs with (1)O2 (k1O2) and OH (kOH) were also measured. These results are important for fate and ecological risk assessment of the antiviral drugs in natural waters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

NASA Astrophysics Data System (ADS)

Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

2015-07-01

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eyring, E.M.

1992-01-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eyring, E.M.

1992-10-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

Mass spectrometry of the photolysis of sulfonylurea herbicides in Prairie waters.

PubMed

Headley, John V; Du, Jing-Long; Peru, Kerry M; McMartin, Dena W

2010-01-01

This review of mass spectrometry of sulfonylurea herbicides includes a focus on studies relevant to Canadian Prairie waters. Emphasis is given to data gaps in the literature for the rates of photolysis of selected sulfonylurea herbicides in different water matrices. Specifically, results are evaluated for positive ion electrospray tandem mass spectrometry with liquid chromatography separation for the study of the photolysis of chlorsulfuron, tribenuron-methyl, thifensulfuron-methyl, metsulfuron-methyl, and ethametsulfuron-methyl. LC-MS/MS is shown to be the method of choice for the quantification of sulfonylurea herbicides with instrumental detection limits ranging from 1.3 to 7.2 pg (on-column). Tandem mass spectrometry coupled with the use of authentic standards likewise has proven to be well suited for the identification of transformation products. To date, however, the power of time-of-flight MS and ultrahigh resolution MS has not been exploited fully for the identification of unknown photolysis products. Dissipation of the herbicides under natural sunlight fit pseudo-first-order kinetics with half-life values ranging from 4.4 to 99 days. For simulated sunlight, radiation wavelengths shorter than 400 nm are required to induce significant photolytic reactions. The correlation between field dissipation studies and laboratory photolysis experiments suggests that photolysis is a major pathway for the dissipation of some sulfonylurea herbicides in natural Prairie waters. 2009 Wiley Periodicals, Inc.

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

NASA Technical Reports Server (NTRS)

Mazely, Troy L.; Friedl, Randall R.; Sander, Stanley P.

1965-01-01

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

Flash photolysis of rhodopsin in the cat retina

PubMed Central

1981-01-01

The bleaching of rhodopsin by short-duration flashes of a xenon discharge lamp was studied in vivo in the cat retina with the aid of a rapid, spectral-scan fundus reflectometer. Difference spectra recorded over a broad range of intensities showed that the bleaching efficacy of high-intensity flashes was less than that of longer duration, steady lights delivering the same amount of energy. Both the empirical results and those derived from a theoretical analysis of flash photolysis indicate that, under the conditions of these experiments, the upper limit of the flash bleaching of rhodopsin in cat is approximately 90%. Although the fact that a full bleach could not be attained is attributable to photoreversal, i.e., the photic regeneration of rhodopsin from its light-sensitive intermediates, the 90% limit is considerably higher than the 50% (or lower) value obtained under other experimental circumstances. Thus, it appears that the duration (approximately 1 ms) and spectral composition of the flash, coupled with the kinetic parameters of the thermal and photic reactions in the cat retina, reduce the light-induced regeneration of rhodopsin to approximately 10%. PMID:7252476

Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases

NASA Astrophysics Data System (ADS)

Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.

2016-03-01

Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

Photolysis of RDX and nitroglycerin in the context of military training ranges.

PubMed

Bordeleau, Geneviève; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

2013-09-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and nitroglycerin (NG) are two energetic materials commonly found in the environment on military training ranges. They are deposited on the ground in the form of solid particles, which can then dissolve in infiltration water or in surface water bodies. The objective of this study was to evaluate whether photolysis by sunlight can significantly contribute to the natural attenuation of RDX and NG (as solid particles or dissolved in surface water) at mid-northern latitudes, where training ranges of Canada and many European countries are located. Experiments conducted at 46.9°N show that both compounds are degraded by sunlight when dissolved in water, with half-lives between 1 and 120d, depending on the compound and time of year. Numerical models may be useful in predicting such photolysis rates, but the models should take into account current ozone levels, as older radiation datasets, collected before the ozone depletion observed since the late 1970s, underestimate the RDX/NG photolysis rate. For solid RDX or NG-bearing particles, photolysis is slower (half-lives of 2-4months), but the degradation rate is still rapid enough to make this process significant in a natural attenuation context. However, photolysis of NG embedded within solid propellant particles cannot proceed to completion, due to the stable nitrocellulose matrix of the propellant. Nonetheless, photolysis clearly constitutes an important attenuation mechanism that should be considered in conceptual models and included in numerical modeling efforts. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photochemical transformation of phenylurea herbicides in surface waters: a model assessment of persistence, and implications for the possible generation of hazardous intermediates.

PubMed

Fabbri, Debora; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-01-01

This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Predicting transformation products from the direct photolysis of organic compounds in aquatic systems

EPA Science Inventory

Direct photolysis is an important degradation pathway for organic compounds bearing sunlight-absorbing chromophores in aquatic systems. An ever-growing body of process science underlying direct photolysis transformation pathways provides the basis for the development of predictiv...

UV photolysis for enhanced phenol biodegradation in the presence of 2,4,6-trichlorophenol (TCP).

PubMed

Song, Jiaxiu; Wang, Wenbing; Li, Rongjie; Zhu, Jun; Zhang, Yongming; Liu, Rui; Rittmann, Bruce E

2016-02-01

A bacterial strain isolated from activated sludge and identified as Bacillus amyloliquefaciens could biodegrade phenol, but 2,4,6-trichlorophenol (TCP) inhibited phenol biodegradation and biomass growth. UV photolysis converted TCP into dichlorocatechol, monochlorophenol, and dichlorophenol, and this relieved inhibition by TCP. Phenol-removal and biomass-growth rates were significantly accelerated after UV photolysis: the monod maximum specific growth rate (μ(max)) increased by 9% after TCP photolysis, and the half-maximum-rate concentration (K(S)) decreased by 36%. Thus, the major benefit of UV photolysis in this case was to transform TCP into a set of much-less-inhibitory products.

Associations of personal and family preeclampsia history with the risk of early-, intermediate- and late-onset preeclampsia.

PubMed

Boyd, Heather A; Tahir, Hassaan; Wohlfahrt, Jan; Melbye, Mads

2013-12-01

Preeclampsia encompasses multiple conditions of varying severity. We examined the recurrence and familial aggregation of preeclampsia by timing of onset, which is a marker for severity. We ascertained personal and family histories of preeclampsia for women who delivered live singletons in Denmark in 1978-2008 (almost 1.4 million pregnancies). Using log-linear binomial regression, we estimated risk ratios for the associations between personal and family histories of preeclampsia and the risk of early-onset (before 34 weeks of gestation, which is typically the most severe), intermediate-onset (at 34-36 weeks of gestation), and late-onset (after 36 weeks of gestation) preeclampsia. Previous early-, intermediate-, or late-onset preeclampsia increased the risk of recurrent preeclampsia with the same timing of onset 25.2 times (95% confidence interval (CI): 21.8, 29.1), 19.7 times (95% CI: 17.0, 22.8), and 10.3 times (95% CI: 9.85, 10.9), respectively, compared with having no such history. Preeclampsia in a woman's family was associated with a 24%-163% increase in preeclampsia risk, with the strongest associations for early- and intermediate-onset preeclampsia in female relatives. Preeclampsia in the man's family did not affect a woman's risk of early-onset preeclampsia and was only weakly associated with her risks of intermediate- and late-onset preeclampsia. Early-onset preeclampsia appears to have the largest genetic component, whereas environmental factors likely contribute most to late-onset preeclampsia. The role of paternal genes in the etiology of preeclampsia appears to be limited.

Photolysis of rhodamine-WT dye

USGS Publications Warehouse

Tai, D.Y.; Rathbun, R.E.

1988-01-01

Photolysis of rhodamine-WT dye under natural sunlight conditions was determined by measuring the loss of fluorescence as a function of time. Rate coefficients at 30?? north latitude ranged from 4.77 x 10-2 day-1 for summer to 3.16 x 10-2 day-1 for winter. Experimental coefficients were in good agreement with values calculated using a laboratory-determined value of the quantum yield.

Effective absorption cross sections and photolysis rates of anthropogenic and biogenic secondary organic aerosols

NASA Astrophysics Data System (ADS)

Romonosky, Dian E.; Ali, Nujhat N.; Saiduddin, Mariyah N.; Wu, Michael; Lee, Hyun Ji (Julie); Aiona, Paige K.; Nizkorodov, Sergey A.

2016-04-01

Mass absorption coefficient (MAC) values were measured for secondary organic aerosol (SOA) samples produced by flow tube ozonolysis and smog chamber photooxidation of a wide range of volatile organic compounds (VOC), specifically: α-pinene, β-pinene, β-myrcene, d-limonene, farnesene, guaiacol, imidazole, isoprene, linalool, ocimene, p-xylene, 1-methylpyrrole, and 2-methylpyrrole. Both low-NOx and high-NOx conditions were employed during the chamber photooxidation experiments. MAC values were converted into effective molecular absorption cross sections assuming an average molecular weight of 300 g/mol for SOA compounds. The upper limits for the effective photolysis rates of SOA compounds were calculated by assuming unity photolysis quantum yields and convoluting the absorption cross sections with a time-dependent solar spectral flux. A more realistic estimate for the photolysis rates relying on the quantum yield of acetone was also obtained. The results show that condensed-phase photolysis of SOA compounds can potentially occur with effective lifetimes ranging from minutes to days, suggesting that photolysis is an efficient and largely overlooked mechanism of SOA aging.

Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources.

PubMed

Sanches, S; Leitão, C; Penetra, A; Cardoso, V V; Ferreira, E; Benoliel, M J; Crespo, M T Barreto; Pereira, V J

2011-09-15

The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm(2), anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested. Copyright © 2011 Elsevier B.V. All rights reserved.

Photolysis of low concentration H2S under UV/VUV irradiation emitted from high frequency discharge electrodeless lamps.

PubMed

Xu, Jianhui; Li, Chaolin; Liu, Peng; He, Di; Wang, Jianfeng; Zhang, Qian

2014-08-01

The photolysis of low concentration of H2S malodorous gas was studied under UV irradiation emitted by self-made high frequency discharge electrodeless lamp with atomic mercury lines at 185/253.7nm. Experiments results showed that the removal efficiency (ηH2S) of H2S was decreased with increasing initial H2S concentration and increased slightly with gas residence time. ηH2S was increased dramatically with relative humidity from<5% to 43% while the concentration of oxygen in gas environments affected the removal of H2S. The mechanisms for direct and indirect photolysis (generation of ozone) were illustrated by the experimental results on photolysis of H2S under argon environments and ozonation of H2S under air environments, respectively. The overall ηH2S by photolysis is higher than the combination of ηH2S by direct photolysis and ozonation, suggesting that hydroxyl radical-mediated indirect photolysis played an important role during photolysis processes. The main photolysis product was confirmed to be SO4(2-) with ion chromatograph. Copyright © 2014 Elsevier Ltd. All rights reserved.

Early and intermediate age-related macular degeneration: update and clinical review.

PubMed

García-Layana, Alfredo; Cabrera-López, Francisco; García-Arumí, José; Arias-Barquet, Lluís; Ruiz-Moreno, José M

2017-01-01

Age-related macular degeneration (AMD) is the leading cause of irreversible central vision loss in developed countries. With the aging of population, AMD will become globally an increasingly important and prevalent disease worldwide. It is a complex disease whose etiology is associated with both genetic and environmental risk factors. An extensive decline in the quality of life and progressive need of daily living assistance resulting from AMD among those most severely affected highlights the essential role of preventive strategies, particularly advising patients to quit smoking. In addition, maintaining a healthy diet, controlling other risk factors (such as hypertension, obesity, and atherosclerosis), and the use of nutritional supplements (antioxidants) are recommendable. Genetic testing may be especially important in patients with a family history of AMD. Recently, unifying criteria for the clinical classification of AMD, defining no apparent aging changes; normal aging changes; and early, intermediate, and late AMD stages, are of value in predicting AMD risk of progression and in establishing recommendations for the diagnosis, therapeutic approach, and follow-up of patients. The present review is focused on early and intermediate AMD and presents a description of the clinical characteristics and ophthalmological findings for these stages, together with algorithms for the diagnosis and management of patients, which are easily applicable in daily clinical practice.

Early and intermediate age-related macular degeneration: update and clinical review

PubMed Central

García-Layana, Alfredo; Cabrera-López, Francisco; García-Arumí, José; Arias-Barquet, Lluís; Ruiz-Moreno, José M

2017-01-01

Age-related macular degeneration (AMD) is the leading cause of irreversible central vision loss in developed countries. With the aging of population, AMD will become globally an increasingly important and prevalent disease worldwide. It is a complex disease whose etiology is associated with both genetic and environmental risk factors. An extensive decline in the quality of life and progressive need of daily living assistance resulting from AMD among those most severely affected highlights the essential role of preventive strategies, particularly advising patients to quit smoking. In addition, maintaining a healthy diet, controlling other risk factors (such as hypertension, obesity, and atherosclerosis), and the use of nutritional supplements (antioxidants) are recommendable. Genetic testing may be especially important in patients with a family history of AMD. Recently, unifying criteria for the clinical classification of AMD, defining no apparent aging changes; normal aging changes; and early, intermediate, and late AMD stages, are of value in predicting AMD risk of progression and in establishing recommendations for the diagnosis, therapeutic approach, and follow-up of patients. The present review is focused on early and intermediate AMD and presents a description of the clinical characteristics and ophthalmological findings for these stages, together with algorithms for the diagnosis and management of patients, which are easily applicable in daily clinical practice. PMID:29042759

CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis.

PubMed

Galí, Martí; Kieber, David J; Romera-Castillo, Cristina; Kinsey, Joanna D; Devred, Emmanuel; Pérez, Gonzalo L; Westby, George R; Marrasé, Cèlia; Babin, Marcel; Levasseur, Maurice; Duarte, Carlos M; Agustí, Susana; Simó, Rafel

2016-12-20

Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m 3 (mol quanta) -1 ). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m 3 (mol quanta) -1 . The largest AQY(330), up to 34 m 3 (mol quanta) -1 ), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d -1 ), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

Comparision of photocatalysis and photolysis processes for arsenic oxidation in water.

PubMed

Fontana, Klaiani B; Lenzi, Giane G; Seára, Eriton C R; Chaves, Eduardo S

2018-04-30

The oxidation of As(III) to As(V) in aqueous solution was evaluated using heterogeneous photocatalysis and photolysis. The influence of TiO 2 as catalyst in different crystalline (rutile, anatase) and commercial forms was evaluated in a batch reactor and an insignificant difference was observed between them. The process by photocatalysis reached up to 97% As(III) oxidation and no significant difference was observed comparing to results obtained by photolysis. The photolysis experiments (UV radiation only), also carried out in a batch system, showed a high oxidation rate of As(III) (90% in 20min). The influence of different matrices (well water, river water and public water supply) were evaluated. Additionally, the effect of As(V) concentration, generated during the oxidation process, was studied. Continuous photolysis experiments using only UV radiation were performed, resulting in a high As(III) oxidation rate. Using a flow rate of 5mLmin -1 and an initial concentration of As(III) 200µgL -1 , gave an oxidation percentage of As(III) of up to 72%, showing a simple and economical alternative to the oxidation step of As(III) to As(V) in the treatment of water contaminated with arsenic. Copyright © 2018 Elsevier Inc. All rights reserved.

Laboratory simulations of PH3 photolysis in the atmospheres of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Khwaja, H.

1985-01-01

The effects of pressure, temperature, light wavelength and intensity, and components of the atmosphere of the Jovian planets on the photolysis of PH3 were experimentally studied. The products of the photolysis, P2H4 and red phosphorus, exhibited little variation when the irradiation experiments were performed under conditions prevalent in Jupiter's atmosphere. No quenching of PH2 radicals by the levels of hydrocarbons present in the Jovian atmosphere was noted. The high partial pressure of hydrogen present on Jupiter should have no effect on the course of the photolysis. The low temperatures on Jupiter and Saturn may result in some condensation of P2H4, but P2H4 had sufficient vapor pressure in the experimental studies at 157 K to be slowly converted to red phosphorus. The products of PH3 photolysis were the same whether a 147, 184.9, or 206.2 nm monochromatic light source or a xenon lamp with a broad spectral output was used.

The photolysis of CO2 at 1849 and 2139A

NASA Technical Reports Server (NTRS)

Krezenski, D.; Simonaitis, R.; Heicklen, J.

1971-01-01

The quantum yield for CO2 photodissociation at 25 C was found to be 1.08 + or - 0.12 for direct photolysis at 1849 A and between 200 and 800 torr; 0.48 + or - 0.02 for the Hg 6(1 P 1) sensitized decomposition between 130 and 730 torr; and 0.16 + or - 0.05 for the direct photolysis at 2139 A and between 300 and 600 torr. At these wavelengths, there was insufficient energy found to produce O(1 D). The primary process used is CO2 + hv yields CO + O(3 P).

Solar actinic flux spectroradiometry: a technique for measuring photolysis frequencies in the atmosphere.

PubMed

Hofzumahaus, A; Kraus, A; Müller, M

1999-07-20

A spectroradiometer has been developed for direct measurement of the solar actinic UV flux (scalar intensity) and determination of photolysis frequencies in the atmosphere. The instrument is based on a scanning double monochromator with an entrance optic that exhibits an isotropic angular response over a solid angle of 2pi sr. Actinic flux spectra are measured at a resolution of 1 nm across a range of 280-420 nm, which is relevant for most tropospheric photolysis processes. The photolysis frequencies are derived from the measured radiation spectra by use of published absorption cross sections and quantum yields. The advantage of this technique compared with the traditional chemical actinometry is its versatility. It is possible to determine the photolysis frequency for any photochemical reaction of interest provided that the respective molecular photodissociation parameters are known and the absorption cross section falls within a wavelength range that is accessible by the spectroradiometer. The instrument and the calibration procedures are described in detail, and problems specific to measurement of the actinic radiation are discussed. An error analysis is presented together with a discussion of the spectral requirements of the instrument for accurate measurements of important tropospheric photolysis frequencies (J(O(1))(D), J(NO(2)), J(HCHO)). An example of measurements from previous atmospheric chemistry field campaigns are presented and discussed.

Continuous Monitoring of Photolysis Products by Thz Spectroscopy

NASA Astrophysics Data System (ADS)

Omar, Abdelaziz; Cuisset, Arnaud; Mouret, Gaël; Hindle, Francis; Eliet, Sophie; Bocquet, Robin

2015-06-01

We demonstrate the potential of THz spectroscopy to monitor the real time evolution of the gas phase concentration of photolysis products and determine the kinetic reaction rate constant. In the primary work, we have chosen to examine the photolysis of formaldehyde (H_2CO). Exposure of H_2CO to a UVB light (250 to 360 nm) in a single pass of 135 cm length cell leads to decomposition via two mechanisms: the radical channel with production of HCO and the molecular channel with production of CO. A commercial THz source (frequency multiplication chain) operating in the range 600-900 GHz was used to detect and quantify the various chemical species as a function of time. Monitoring the concentrations of CO and H_2CO via rotational transitions, allowed the kinetic rate of H_2CO consummation to be obtained, and an estimation of the rate constants for both the molecular and radical photolysis mechanisms. We have modified our experimental setup to increase the sensitivity of the spectrometer and changed sample preparation protocol specifically to quantify the HCO concentration. Acetaldehyde was used as the precursor for photolysis by UVC resulting in the decompositon mechanism can be described by: CH_3CHO+hν→ CH_3 + HCO → CH_4 + CO Frequency modulation of the source and Zeeman modulation is used to achieve the high sensitivity required. Particular attention has been paid to the mercury photosensitization effect that allowed us to increase the HCO production enabling quantification of the monitored radical. We quantify the HCO radical and start a spectroscopic study of the line positions. H. M. Pickett and T. L. Boyd, Chem. Phys. Lett, Vol 58, 446-449, (1978) S. Eliet, A. Cuisset, M Guinet, F. Hindle, G. Mouret, R. Bocquet, and J. Demaison, Journal of Molecular Spectroscopy, Vol 279, 12-15 (2012). G. Mouret, M. Guinet, A. Cuisset, L. Croizé, S. Eliet, R. Bocquet and F. Hindle, Sensors Journal. IEEE, Vol 13, 133 - 138, (2013)

Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

NASA Technical Reports Server (NTRS)

Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Hand, K. P.; Johnson, R. E.; Loeffler, M. J.; Baragiola, R. A.

2010-01-01

The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carboncontajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

Effect of Nicotinamide on the Photolysis of Riboflavin in Aqueous Solution

PubMed Central

Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Anwar, Zubair; Qadeer, Kiran; Noor, Adnan; Evstigneev, Maxim P.

2016-01-01

The photolysis of riboflavin (RF) in aqueous solution in the presence of nicotinamide (NA) by visible light has been studied in the pH range 1.0–12.0 and the various photoproducts have been identified as known compounds. RF has been determined in degraded solutions by a specific multicomponent spectrometric method in the presence of its photoproducts and NA. The second-order rate constants (k2) for the bimolecular interaction of RF and NA range from 0.54 (pH 1.0) to 9.66 M–1 min–1 (pH 12.0). The log k2–pH profile for the photolysis reaction follows a sigmoid curve showing a gradual increase in the rate of pH due to a change in the ionization behavior of the molecule. The lower rate in the acid region is probably due to protonation of the molecule since the cationic form of RF is less susceptible to photolysis than the neutral form. Similarly, a slowing of the rate in the alkaline region is due to anion formation of the molecule. NA is involved as an electron acceptor during the sequence of reactions and thus enhances the rate of photolysis of RF. Absorption and fluorescence measurements did not provide evidence for the complex formation between the two compounds under the present conditions. PMID:27222605

Aquatic photolysis of β2-agonist salbutamol: kinetics and mechanism studies.

PubMed

Zhou, Lei; Wang, Qi; Zhang, Ya; Ji, Yuefei; Yang, Xi

2017-02-01

Salbutamol (SAL) has been widely used as medicine both in treating asthma and in animal primary production; an increasing number of reports have detected SAL in natural waters. The photolysis kinetic and pathway of SAL in aquatic system were studied, as well as the effect of several natural water constituents, such as nitrate, dissolved oxygen (DO) and ferric ions. According to our research, the direct photolysis of SAL followed pseudo-first-order reaction kinetics. Alkaline condition could promote the degradation of SAL; the increase of solution pH would simultaneously increase the fraction of the deprotonated forms of SAL (including the deprotonated and zwitterionic species), which were easier to be excited, and result in the bathochromic shift of the UV-Vis spectrum and, finally, accelerate the degradation rate of SAL. The presence of nitrate could enhance the removal rate of SAL via generation hydroxyl radical (·OH) under irradiation. In addition, the absence of oxygen in the reaction solution could decrease the photolysis. Moreover, Fe(III) was able to chelate with SAL to form an octahedral complex, which was photochemically reactive. The octahedral complex could generate ·OH to oxidize SAL itself in turn. The pathways of SAL photolysis were also investigated by means of the solid phase extraction (SPE)-LC-MS method. The major pathways of SAL photodegradation included oxidation and side-chain cleavage.

In Situ Investigation the Photolysis of the PAHs Adsorbed on Mangrove Leaf Surfaces by Synchronous Solid Surface Fluorimetry

PubMed Central

Wang, Ping; Wu, Tun-Hua; Zhang, Yong

2014-01-01

An established synchronous solid surface fluorimetry (S-SSF) was utilized for in situ study the photolysis processes of anthracene (An) and pyrene (Py) adsorbed on the leaf surfaces of Kandelia obovata seedlings (Ko) and Aegiceras corniculata (L.) Blanco seedlings (Ac). Experimental results demonstrated that the photolysis of An and Py adsorbed on the leaf surfaces of two mangrove species under the laboratory conditions, followed first-order kinetics with their photolysis rates in the order of Ac>Ko. In addition, with the same amount of substances, the photolysis rate of An adsorbed on the same mangrove leaf surfaces was much faster than the adsorbed Py. In order to investigate further, the photolysis processes of An and Py in water were also studied for comparison. And the photolysis of An and Py in water also followed first-order kinetics. Moreover, for the same initial amount, the photolysis rate of the PAH in water was faster than that adsorbed on the leaf surfaces of two mangrove species. Therefore, photochemical behaviors of PAHs were dependent not only on their molecular structures but also the physical-chemical properties of the substrates on which they are adsorbed. PMID:24404158

Why is gas phase 2-nitrophenol photolysis a potentially important source of OH radicals in the polluted atmosphere?

NASA Astrophysics Data System (ADS)

Zhu, L.

2017-12-01

2-Nitrophenol is an important component of "brown carbon" in the atmosphere. The concentration of 2-nitrophenol is higher in polluted urban areas where there are increased emissions of aromatic hydrocarbons. To assess the air quality impacts of pollutant emissions, it is important to understand the oxidant formation potential of the emitted species. Photolysis is the dominant atmospheric removal process for 2-nitrophenol. Although photodissociation dynamics studies of 2-nitrophenol have reported OH formation at photolysis wavelengths of 266 nm, 355 nm, and over the 361-390 nm range, and HONO has been observed as a product from 2-nitrophenol photolysis in an environmental chamber, the lack of quantitative absorption cross section and product quantum yield information has prevented quantitative assessment of the extent of oxidant formation from the photolysis of 2-nitrophenol in the atmosphere. My group determined the gas phase absorption cross sections of 2-nitrophenol in the 295-400 nm region by using cavity ring-down spectroscopy. The OH, HONO, and NO2 formation channels following the gas phase photolysis of 2-nitrophenol at 308 and 351 nm were investigated. Direct NO2 formation was not observed. OH and HONO were direct products from the 2-nitrophenol photolysis, and their quantum yields were obtained. The sum of the OH and the HONO quantum yields was about unity at both photolysis wavelengths. The estimated photolysis rate constant of 2-nitrophenol was about twice that of NO2. I will discuss the importance of 2-nitrophenol gas phase photolysis as a potential source of OH and HONO in regions of high anthropogenic emissions.

Novel approach to real-time flash photolysis and confocal [Ca2+] imaging

PubMed Central

Sobie, Eric A.; Kao, Joseph P.Y.; Lederer, W. J.

2008-01-01

Flash photolysis of “caged” compounds using ultraviolet light is a powerful experimental technique for producing rapid changes in concentrations of bioactive signaling molecules. Studies that employ this technique have used diverse strategies for controlling the spatial and temporal application of light to the specimen. Here we describe a new system for flash photolysis that delivers light from a pulsed, adjustable intensity laser through an optical fiber coupled into the epifluorescence port of a commercial confocal microscope. Photolysis is achieved with extremely brief (5 ns) pulses of ultraviolet light (355 nm) that can be synchronized with respect to confocal laser scanning. The system described also localizes the UV intensity spatially so that uncaging only occurs in defined sub-cellular regions; moreover, since the microscope optics are used in localization, the photolysis volume can be easily adjusted. Experiments performed on rat ventricular myocytes loaded with the Ca2+ indicator fluo-3 and the Ca2+ cage NP-EGTA demonstrate the system's capabilities. Localized intracellular increases in [Ca2+] can trigger sarcoplasmic reticular Ca2+ release events such as Ca2+ sparks and, under certain conditions, regenerative Ca2+ waves. This relatively simple and inexpensive system is therefore a useful tool for examining local signaling in heart and other tissues. PMID:17323075

Very early reaction intermediates detected by microsecond time scale kinetics of cytochrome cd1-catalyzed reduction of nitrite.

PubMed

Sam, Katharine A; Strampraad, Marc J F; de Vries, Simon; Ferguson, Stuart J

2008-10-10

Paracoccus pantotrophus cytochrome cd(1) is a nitrite reductase found in the periplasm of many denitrifying bacteria. It catalyzes the reduction of nitrite to nitric oxide during the denitrification part of the biological nitrogen cycle. Previous studies of early millisecond intermediates in the nitrite reduction reaction have shown, by comparison with pH 7.0, that at the optimum pH, approximately pH 6, the earliest intermediates were lost in the dead time of the instrument. Access to early time points (approximately 100 micros) through use of an ultra-rapid mixing device has identified a spectroscopically novel intermediate, assigned as the Michaelis complex, formed from reaction of fully reduced enzyme with nitrite. Spectroscopic observation of the subsequent transformation of this species has provided data that demand reappraisal of the general belief that the two subunits of the enzyme function independently.

Effect of nitrate, carbonate/bicarbonate, humic acid, and H2O2 on the kinetics and degradation mechanism of Bisphenol-A during UV photolysis.

PubMed

Kang, Young-Min; Kim, Moon-Kyung; Zoh, Kyung-Duk

2018-08-01

In this study, the effects of natural water components (nitrate, carbonate/bicarbonate, and humic acid) on the kinetics and degradation mechanisms of bisphenol A (BPA) during UV-C photolysis and UV/H 2 O 2 reaction were examined. The presence of NO 3 - (0.04-0.4 mM) and CO 3 2- /HCO 3 - (0.4-4 mM) ions increased BPA degradation during UV photolysis. Humic acid less than 3 mg/L promoted BPA degradation, but greater than 3 mg/L of humic acid inhibited BPA degradation. During the UV/H 2 O 2 reaction, all water matrix components acted as radical scavengers in the order of humic acid > CO 3 2- /HCO 3 -  > NO 3 - . All of the degradation reactions agreed with the pseudo-first-order kinetics. While eight byproducts (m/z = 122, 136, 139, 164, 181, 244, 273, 289) were identified in UV-C/NO 3 - photolysis reaction, four (m/z = 122, 136, 164, 244) and three byproducts (m/z = 122, 136, 164) were observed during UV-C/NO 3 - /CO 3 2- /HCO 3 - and UV-C/CO 3 2- /HCO 3 - reactions. Nitrogenated and hydrogenated byproducts were first observed during the UV-C/NO 3 - photolysis, but only hydrogenated byproducts as adducts were detected during the UV-C/NO 3 - /CO 3 2- /HCO 3 - photolysis. Nitrogenated and hydrogenated byproducts were formed in the early stage of degradation by OH or NO 2 radicals, and these byproducts were subsequently degraded into smaller compounds with further reaction during UV-C/NO 3 - and UV-C/NO 3 - /CO 3 2- /HCO 3 - reactions. In contrast, BPA was directly degraded into smaller compounds by β-scission of the isopropyl group by CO 3 - /HCO 3 radicals during UV-C/CO 3 2- /HCO 3 - reaction. Our results imply that the water components can change the degradation mechanism of BPA during UV photolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Natural solar photolysis of total organic chlorine, bromine and iodine in water.

PubMed

Abusallout, Ibrahim; Hua, Guanghui

2016-04-01

Municipal wastewater has been increasingly used to augment drinking water supplies due to the growing water scarcity. Wastewater-derived disinfection byproducts (DBPs) may negatively affect the aquatic ecosystems and human health of downstream communities during water reuse. The objective of this research was to determine the degradation kinetics of total organic chlorine (TOCl), bromine (TOBr) and iodine (TOI) in water by natural sunlight irradiation. Outdoor solar photolysis experiments were performed to investigate photolytic degradation of the total organic halogen (TOX) formed by fulvic acid and real water and wastewater samples. The results showed that TOX degradation by sunlight irradiation followed the first-order kinetics with half-lives in the range of 2.6-10.7 h for different TOX compounds produced by fulvic acid. The TOX degradation rates were generally in the order of TOI > TOBr ≅ TOCl(NH2Cl) > TOCl(Cl2). High molecular weight TOX was more susceptible to solar photolysis than corresponding low molecular weight halogenated compounds. The nitrate and sulfite induced indirect TOX photolysis rates were less than 50% of the direct photolysis rates under the conditions of this study. Fulvic acid and turbidity in water reduced TOX photodegradation. These results contribute to a better understanding of the fate of chlorinated, brominated and iodinated DBPs in surface waters. Published by Elsevier Ltd.

Photolysis of O3 at 3130A

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Braslavsky, S.; Heicklen, J.; Nicolet, M.

1972-01-01

The photolysis of O3 at 3130 A and 25 C has been studied in the presence of a large excess of N2O to react with any O(1D) atoms produced. From the N2 produced, the quantum efficiency for O(1D) production was found to be 0.50 + or - 0.03.

Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

NASA Astrophysics Data System (ADS)

MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

2014-12-01

Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

Hydride Conformers of the Nitrogenase FeMo-cofactor Two-Electron Reduced State E2(2H), Assigned Using Cryogenic Intra Electron Paramagnetic Resonance Cavity Photolysis.

PubMed

Lukoyanov, Dmitriy A; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2018-03-24

Early studies in which nitrogenase was freeze-trapped during enzymatic turnover revealed the presence of high-spin ( S = 3 / 2 ) electron paramagnetic resonance (EPR) signals from the active-site FeMo-cofactor (FeMo-co) in electron-reduced intermediates of the MoFe protein. Historically denoted as 1b and 1c, each of the signals is describable as a fictitious spin system, S' = 1 / 2 , with anisotropic g' tensor, 1b with g' = [4.21, 3.76, ?] and 1c with g' = [4.69, ∼3.20, ?]. A clear discrepancy between the magnetic properties of 1b and 1c and the kinetic analysis of their appearance during pre-steady-state turnover left their identities in doubt, however. We subsequently associated 1b with the state having accumulated 2[e - /H + ], denoted as E 2 (2H), and suggested that the reducing equivalents are stored on the catalytic FeMo-co cluster as an iron hydride, likely an [Fe-H-Fe] hydride bridge. Intra-EPR cavity photolysis (450 nm; temperature-independent from 4 to 12 K) of the E 2 (2H)/1b state now corroborates the identification of this state as storing two reducing equivalents as a hydride. Photolysis converts E 2 (2H)/1b to a state with the same EPR spectrum, and thus the same cofactor structure as pre-steady-state turnover 1c, but with a different active-site environment. Upon annealing of the photogenerated state at temperature T = 145 K, it relaxes back to E 2 (2H)/1b. This implies that the 1c signal comes from an E 2 (2H) hydride isomer of E 2 (2H)/1b that stores its two reducing equivalents either as a hydride bridge between a different pair of iron atoms or an Fe-H terminal hydride.

Photolysis of natural B-triketonic herbicides in water

USDA-ARS?s Scientific Manuscript database

The fate of four natural triketones (leptospermone, isoleptospermone, grandiflorone and flavesone, pKa=4.0 to 4.5) in aqueous solution, in the dark and upon simulated solar light irradiation was investigated. In anionic form, triketones undergo oxidation in the dark, however, photolysis is much fast...

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

NASA Astrophysics Data System (ADS)

Bouzidi, H.; Laversin, H.; Tomas, A.; Coddeville, P.; Fittschen, C.; El Dib, G.; Roth, E.; Chakir, A.

2014-12-01

Hydroxycarbonyl compounds are important secondary reaction products in the oxidation of Volatile Organic Compounds (VOCs) in the atmosphere. The atmospheric fate of these oxygenated VOCs is however poorly understood, especially the relevance of the photolytic pathway. In this work, a combined investigation of the photolysis and temperature-dependent OH radical reaction of 3-hydroxy-3-methyl-2-butanone (3H3M2B) is presented. A photolysis lifetime of about 4-5 days was estimated with a global quantum yield of 0.10. The OH reaction rate coefficient follows the Arrhenius trend (298-356 K) and could be modelled through the following expression: k3H3M2B(T) = (5.12 ± 0.07) × 10-12 exp(-563 ± 119/T) in cm3 molecule-1 s-1. A 3H3M2B atmospheric lifetime of 15 days towards the OH radical was evaluated. Our results showed that the photolysis pathway is the major degradation channel for 3H3M2B. Photolysis products were identified and quantified in the present work with a carbon balance of around 80% enabling a reaction mechanism to be proposed. The present work underlines the need for further studies on the atmospheric chemistry of oxygenated VOCs.

Photocatalytic degradation of 4-amino-6-chlorobenzene-1,3-disulfonamide stable hydrolysis product of hydrochlorothiazide: Detection of intermediates and their toxicity.

PubMed

Armaković, Sanja J; Armaković, Stevan; Četojević-Simin, Dragana D; Šibul, Filip; Abramović, Biljana F

2018-02-01

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO 2 Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO 2 suspension under SSI, while the nitrogen was predominantly present as NH 4 + . Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth. Copyright © 2017 Elsevier Ltd. All rights reserved.

Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meusinger, Carl; Johnson, Matthew S.; Berhanu, Tesfaye A.

2014-06-28

Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently amore » result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.« less

Identification of early fumonisin biosynthetic intermediates by inactivation of the FUM6 gene in Fusarium verticillioides

USDA-ARS?s Scientific Manuscript database

Fumonisins are polyketide mycotoxins produced by the maize pathogen Fusarium verticillioides and are associated with multiple human and animal diseases. A fumonisin biosynthetic pathway has been proposed, but structures of early pathway intermediates have not been demonstrated. The F. verticillioide...

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1977-01-01

Hydrogen is produced by the solar photolysis of water in a first photooxidation vessel with a transparent wall in the presence of a water soluble photooxidizable reagent and an insoluble hydrogen recombination catalyst. Simultaneously oxygen is produced in a second photoreduction reactor with a transparent wall in the presence of an insoluble photoreduction reagent catalyst. When spent, the solution from the first reactor is fed into the second reactor. A reaction occurs in the dark in which the redox reagents are regenerated, and the regenerated photooxidation reagent solution is recycled to the first reactor. The photoreduction-catalyst is a bifunctional reagent catalyst including a transition metal salt together with a hydroxyl or chlorohydroxyl decomposition catalyst of high area.

Theoretical study on the photolysis mechanism of 2,3-diazabicyclo[2.2.2]oct-2-ene.

PubMed

Chen, Hui; Li, Shuhua

2005-09-28

A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state.

Photolysis of oxyfluorfen in aqueous methanol.

PubMed

Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

2013-01-01

Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.

Degradation of thiamethoxam and metoprolol by UV, O3 and UV/O3 hybrid processes: Kinetics, degradation intermediates and toxicity

NASA Astrophysics Data System (ADS)

Šojić, D.; Despotović, V.; Orčić, D.; Szabó, E.; Arany, E.; Armaković, S.; Illés, E.; Gajda-Schrantz, K.; Dombi, A.; Alapi, T.; Sajben-Nagy, E.; Palágyi, A.; Vágvölgyi, Cs.; Manczinger, L.; Bjelica, L.; Abramović, B.

2012-11-01

SummaryA comprehensive study of the degradation of thiamethoxam (THIA) and metoprolol (MET) was conducted by using UV-induced photolysis (λ = 254 nm), ozonation, and a combination of these methods. In order to investigate how molecular structure of the substrate influences the rate of its degradation, we compared these three processes for the insecticide THIA and the drug MET (a β1-blocker). Of the three treatments applied, the UV photolysis and the combination of UV/O3 were found to be most effective in the degradation of THIA, while the UV/O3 process appeared to be the most efficient in terms of MET decay. The degradation kinetics was monitored by LC-DAD, and spectrophotometry, while the mineralization of the substrates was studied by TOC analysis. Reaction intermediates were studied in detail and a number of them were identified using LC-MS (ESI+/ESI-). Both parent compounds showed slight toxic effects towards algae Pseudokirchneriella subcapitata and bacteria Vibrio fischeri. However, the toxicity of the solutions containing also the degradation intermediates appeared to be much higher for all the test organisms. The inhibition/mortality rates were reduced most efficiently by the UV/O3 procedure. Ames test and Comet assay were used to follow the genotoxicity during the degradation of the studied compounds. Genotoxic intermediates were frequently detected in the case of MET in the UV treatment alone or in the presence of ozone. Treatments of THIA samples resulted less frequently in genotoxic intermediates. To our best knowledge, this work is the first genotoxicological investigation dealing with the photolytic degradation process of the studied compounds.

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues.

PubMed

Bernstein, Max P; Dworkin, Jason P; Sandford, Scott A; Cooper, George W; Allamandola, Louis J

2002-03-28

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George W.; Allamandola, Louis J.

2002-01-01

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

Laser photolysis of caged compounds at 405 nm: photochemical advantages, localisation, phototoxicity and methods for calibration.

PubMed

Trigo, Federico F; Corrie, John E T; Ogden, David

2009-05-30

Rapid, localised photolytic release of neurotransmitters from caged precursors at synaptic regions in the extracellular space is greatly hampered at irradiation wavelengths in the near-UV, close to the wavelength of maximum absorption of the caged precursor, because of inner-filtering by strong absorption of light in the cage solution between the objective and cell. For this reason two-photon excitation is commonly used for photolysis, particularly at multiple points distributed over large fields; or, with near-UV, if combined with local perfusion of the cage. These methods each have problems: the small cross-sections of common cages with two-photon excitation require high cage concentrations and light intensities near the phototoxic limit, while local perfusion gives non-uniform cage concentrations over the field of view. Single-photon photolysis at 405 nm, although less efficient than at 330-350 nm, with present cages is more efficient than two-photon photolysis. The reduced light absorption in the bulk cage solution permits efficient wide-field uncaging at non-toxic intensities with uniform cage concentration. Full photolysis of MNI-glutamate with 100 micros pulses required intensities of 2 mW microm(-2) at the preparation, shown to be non-toxic with repeated exposures. Light scattering at 405 nm was estimated as 50% at 18 microm depth in 21-day rat cerebellum. Methods are described for: (1) varying the laser spot size; (2) photolysis calibration in the microscope with the caged fluorophore NPE-HPTS over the wavelength range 347-405 nm; and (3) determining the point-spread function of excitation. Furthermore, DM-Nitrophen photolysis at 405 nm was efficient for intracellular investigations of Ca2+-dependent processes.

Impacts of cloud water droplets on the OH production rate from peroxide photolysis.

PubMed

Martins-Costa, M T C; Anglada, J M; Francisco, J S; Ruiz-López, Manuel F

2017-12-06

Understanding the difference between observed and modeled concentrations of HO x radicals in the troposphere is a current major issue in atmospheric chemistry. It is widely believed that existing atmospheric models miss a source of such radicals and several potential new sources have been proposed. In recent years, interest has increased on the role played by cloud droplets and organic aerosols. Computer modeling of ozone photolysis, for instance, has shown that atmospheric aqueous interfaces accelerate the associated OH production rate by as much as 3-4 orders of magnitude. Since methylhydroperoxide is a main source and sink of HO x radicals, especially at low NO x concentrations, it is fundamental to assess what is the influence of clouds on its chemistry and photochemistry. In this study, computer simulations for the photolysis of methylhydroperoxide at the air-water interface have been carried out showing that the OH production rate is severely enhanced, reaching a comparable level to ozone photolysis.

Photolysis of α-KETO Acids in Model Atmospheric Water

NASA Astrophysics Data System (ADS)

Eugene, A. J.; Guzman, M. I.

2017-12-01

Recent work has reported the potential of aqueous-phase photochemistry to promote secondary organic aerosol (SOA) formation. New aqueous photochemical SOA sources may contribute to bridging the gap between field measurements of SOA and models of SOA formation. The ubiquitous α-ketocarboxylic acids pyruvic and glyoxylic acid are known products of the atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) as well as of biogenic volatile organic compounds (VOCs). The combination of a carbonyl chromophore (absorbing at wavelengths λ ≥ 300 nm) and hydrophilic functional groups makes these acids likely candidates for forming aqueous SOA by direct sunlight photolysis. We use a variety of analytical techniques including: 2,4-dinitrophenylhydrazine (DNPH) derivatization; ultra-high performance liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry;1H and 13C NMR; and 13C gCOSY NMR to probe the kinetics and mechanisms of the direct photolysis of model solutions of pyruvic acid and glyoxylic acid. The results indicate that despite the structural similarity between the two acids, they each react via very different primary photochemical pathways. Pyruvic acid undergoes a proton-coupled electron transfer (PCET) mechanism with radical recombination, resulting in CO2 and 6-8 carbon organic acids. In contrast, glyoxylic acid primarily undergoes α-cleavage to generate CO, CO2, and glyoxal which is a key species in SOA formation. This work demonstrates that aqueous photolysis is a very competitive atmospheric sink for both pyruvic and glyoxylic acid, indicating that these photoreactions are capable of contributing substantially to SOA formation.

Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

PubMed

Kao, Joseph P Y; Muralidharan, Sukumaran

2013-01-01

Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter.

Reversible Photoinduced Reductive Elimination of H2 from the Nitrogenase Dihydride State, the E(4)(4H) Janus Intermediate.

PubMed

Lukoyanov, Dmitriy; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2016-02-03

We recently demonstrated that N2 reduction by nitrogenase involves the obligatory release of one H2 per N2 reduced. These studies focus on the E4(4H) "Janus intermediate", which has accumulated four reducing equivalents as two [Fe-H-Fe] bridging hydrides. E4(4H) is poised to bind and reduce N2 through reductive elimination (re) of the two hydrides as H2, coupled to the binding/reduction of N2. To obtain atomic-level details of the re activation process, we carried out in situ 450 nm photolysis of E4(4H) in an EPR cavity at temperatures below 20 K. ENDOR and EPR measurements show that photolysis generates a new FeMo-co state, denoted E4(2H)*, through the photoinduced re of the two bridging hydrides of E4(4H) as H2. During cryoannealing at temperatures above 175 K, E4(2H)* reverts to E4(4H) through the oxidative addition (oa) of the H2. The photolysis quantum yield is temperature invariant at liquid helium temperatures and shows a rather large kinetic isotope effect, KIE = 10. These observations imply that photoinduced release of H2 involves a barrier to the combination of the two nascent H atoms, in contrast to a barrierless process for monometallic inorganic complexes, and further suggest that H2 formation involves nuclear tunneling through that barrier. The oa recombination of E4(2H)* with the liberated H2 offers compelling evidence for the Janus intermediate as the point at which H2 is necessarily lost during N2 reduction; this mechanistically coupled loss must be gated by N2 addition that drives the re/oa equilibrium toward reductive elimination of H2 with N2 binding/reduction.

Gene–Environment Interactions and Intermediate Phenotypes: Early Trauma and Depression

PubMed Central

Hornung, Orla P.; Heim, Christine M.

2013-01-01

This review focuses on current research developments in the study of gene by early life stress (ELS) interactions and depression. ELS refers to aversive experiences during childhood and adolescence such as sexual, physical or emotional abuse, emotional or physical neglect as well as parental loss. Previous research has focused on investigating and characterizing the specific role of ELS within the pathogenesis of depression and linking these findings to neurobiological changes of the brain, especially the stress response system. The latest findings highlight the role of genetic factors that increase vulnerability or, likewise, promote resilience to depression after childhood trauma. Considering intermediate phenotypes has further increased our understanding of the complex relationship between early trauma and depression. Recent findings with regard to epigenetic changes resulting from adverse environmental events during childhood promote current endeavors to identify specific target areas for prevention and treatment schemes regarding the long-term impact of ELS. Taken together, the latest research findings have underscored the essential role of genotypes and epigenetic processes within the development of depression after childhood trauma, thereby building the basis for future research and clinical interventions. PMID:24596569

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

The photolysis of NH3 in the presence of substituted acetylenes - A possible source of oligomers and HCN on Jupiter

NASA Technical Reports Server (NTRS)

Ferris, James P.; Jacobson, Richard R.; Guillemin, Jean C.

1992-01-01

An NMR spectral study is presently conducted of NH3 photolysis in the presence of substituted acetylenes with NMR spectra and gas chromatography. Quantum yields and percentage conversions to products are reported. It is shown that acetylenic hydrocarbons generated during methane photolysis in Jupiter's stratosphere can react with radicals formed by NH3 photolysis to yield nonvolatile, yellow-brown polymers, alkylnitriles, and in due course, HCN, as observed on Jupiter.

EFFECTS OF SUSPENDED SEDIMENTS ON PHOTOLYSIS RATES OF DISSOLVED POLLUTANTS

EPA Science Inventory

Data are presented concerning the effects of suspended sediments upon photolysis rates of dissolved ultraviolet (u.v.) absorbing pollutants. The malachite green leucocyanide actinometer was found to be a convenient and sensitive device for measurement of solar u.v. radiation (abo...

Intermediate-term forecasting of aftershocks from an early aftershock sequence: Bayesian and ensemble forecasting approaches

NASA Astrophysics Data System (ADS)

Omi, Takahiro; Ogata, Yosihiko; Hirata, Yoshito; Aihara, Kazuyuki

2015-04-01

Because aftershock occurrences can cause significant seismic risks for a considerable time after the main shock, prospective forecasting of the intermediate-term aftershock activity as soon as possible is important. The epidemic-type aftershock sequence (ETAS) model with the maximum likelihood estimate effectively reproduces general aftershock activity including secondary or higher-order aftershocks and can be employed for the forecasting. However, because we cannot always expect the accurate parameter estimation from incomplete early aftershock data where many events are missing, such forecasting using only a single estimated parameter set (plug-in forecasting) can frequently perform poorly. Therefore, we here propose Bayesian forecasting that combines the forecasts by the ETAS model with various probable parameter sets given the data. By conducting forecasting tests of 1 month period aftershocks based on the first 1 day data after the main shock as an example of the early intermediate-term forecasting, we show that the Bayesian forecasting performs better than the plug-in forecasting on average in terms of the log-likelihood score. Furthermore, to improve forecasting of large aftershocks, we apply a nonparametric (NP) model using magnitude data during the learning period and compare its forecasting performance with that of the Gutenberg-Richter (G-R) formula. We show that the NP forecast performs better than the G-R formula in some cases but worse in other cases. Therefore, robust forecasting can be obtained by employing an ensemble forecast that combines the two complementary forecasts. Our proposed method is useful for a stable unbiased intermediate-term assessment of aftershock probabilities.

Evidence for close side-chain packing in an early protein folding intermediate previously assumed to be a molten globule

PubMed Central

Rosen, Laura E.; Connell, Katelyn B.; Marqusee, Susan

2014-01-01

The molten globule, a conformational ensemble with significant secondary structure but only loosely packed tertiary structure, has been suggested to be a ubiquitous intermediate in protein folding. However, it is difficult to assess the tertiary packing of transiently populated species to evaluate this hypothesis. Escherichia coli RNase H is known to populate an intermediate before the rate-limiting barrier to folding that has long been thought to be a molten globule. We investigated this hypothesis by making mimics of the intermediate that are the ground-state conformation at equilibrium, using two approaches: a truncation to generate a fragment mimic of the intermediate, and selective destabilization of the native state using point mutations. Spectroscopic characterization and the response of the mimics to further mutation are consistent with studies on the transient kinetic intermediate, indicating that they model the early intermediate. Both mimics fold cooperatively and exhibit NMR spectra indicative of a closely packed conformation, in contrast to the hypothesis of molten tertiary packing. This result is important for understanding the nature of the subsequent rate-limiting barrier to folding and has implications for the assumption that many other proteins populate molten globule folding intermediates. PMID:25258414

Evidence for close side-chain packing in an early protein folding intermediate previously assumed to be a molten globule.

PubMed

Rosen, Laura E; Connell, Katelyn B; Marqusee, Susan

2014-10-14

The molten globule, a conformational ensemble with significant secondary structure but only loosely packed tertiary structure, has been suggested to be a ubiquitous intermediate in protein folding. However, it is difficult to assess the tertiary packing of transiently populated species to evaluate this hypothesis. Escherichia coli RNase H is known to populate an intermediate before the rate-limiting barrier to folding that has long been thought to be a molten globule. We investigated this hypothesis by making mimics of the intermediate that are the ground-state conformation at equilibrium, using two approaches: a truncation to generate a fragment mimic of the intermediate, and selective destabilization of the native state using point mutations. Spectroscopic characterization and the response of the mimics to further mutation are consistent with studies on the transient kinetic intermediate, indicating that they model the early intermediate. Both mimics fold cooperatively and exhibit NMR spectra indicative of a closely packed conformation, in contrast to the hypothesis of molten tertiary packing. This result is important for understanding the nature of the subsequent rate-limiting barrier to folding and has implications for the assumption that many other proteins populate molten globule folding intermediates.

New Measurements of Methyl Ethyl Ketone (MEK) Photolysis Rates and Their Relevance to Global Oxidative Capacity

NASA Astrophysics Data System (ADS)

Brewer, J.; Ravishankara, A. R.; Mellouki, A.; Fischer, E. V.; Kukui, A.; Véronique, D.; Ait-helal, W.; Leglise, J.; Ren, Y.

2017-12-01

Methyl ethyl ketone (MEK) is one of the most abundant ketones in the atmosphere. MEK can be emitted directly into the atmosphere from both anthropogenic and natural sources, and it is also formed during the gas-phase oxidation of volatile organic compounds (VOCs). MEK is lost via reaction with OH, photolysis and deposition to the surface. Similar to the other atmospheric ketones, the photolysis of MEK may represent a source of HOx (OH + HO2) radicals in the upper troposphere. The degradation of MEK also leads to the atmospheric formation of acetaldehyde and formaldehyde. This work presents a new analysis of the temperature dependence of MEK photolysis cross-sections and a quantification of MEK photolysis rates under surface pressures using the CNRS HELIOS outdoor atmospheric chamber (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans; http://www.era-orleans.org/ERA-TOOLS/helios-project.html). Additionally, we use the GEOS-Chem 3-D CTM (version 10-01, www.geos-chem.org) to investigate the impact of these newly measured rates and cross-sections on the global distribution and seasonality of MEK, as well as its importance to the tropospheric oxidative capacity.

Time-kill kinetic analysis of antimicrobial chemotherapy based on hydrogen peroxide photolysis against Streptococcus mutans biofilm.

PubMed

Shirato, Midori; Nakamura, Keisuke; Kanno, Taro; Lingström, Peter; Niwano, Yoshimi; Örtengren, Ulf

2017-08-01

A recently developed antimicrobial technique utilizing hydroxyl radicals generated by hydrogen peroxide (H 2 O 2 ) photolysis represents a promising new therapy for preventing and treating dental caries. The present study compared the antimicrobial time-kill kinetics of H 2 O 2 photolysis, conventional antiseptics, and antimicrobial photodynamic therapy (aPDT) against biofilm-forming Streptococcus mutans (cariogenic bacteria) grown on hydroxyapatite disks. H 2 O 2 photolysis was performed by irradiating the biofilm immersed in 3% H 2 O 2 with 365-nm light-emitting diode (LED) light at an irradiance of 1000mW/cm 2 for up to 1.5min. Antiseptic treatments consisted of 0.2% chlorhexidine gluconate, 0.5% povidone-iodine, and 3% H 2 O 2 . The biofilm was immersed in each antiseptic for up to 4min. aPDT was performed by irradiating the biofilm immersed in 100μM methylene blue or toluidine blue O with 655-nm laser light at 1000mW/cm 2 for up to 4min. Based on the time-kill assay, the decimal reduction value (D-value) of each treatment was determined. With a D-value of 0.06min, H 2 O 2 photolysis exhibited the highest bactericidal effect against biofilm-forming S. mutans. In contrast, antiseptics and aPDT exerted a slower bactericidal effect, with D-values of 0.9-2.7min. In conclusion, the antimicrobial technique based on H 2 O 2 photolysis using 365-nm LED represents a strong adjunctive chemotherapy for dental caries treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

The aqueous photolysis of α-pinene in solution with humic acid

USGS Publications Warehouse

Goldberg, Marvin C.; Cunningham, Kirkwood M.; Aiken, George R.; Weiner, Eugene R.; ,

1992-01-01

Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.

Sulfur mass-independent fractionation during photolysis and photoexcitation of SO2 and CS2 and implications to the source reactions for Archean sulfur isotope anomaly

NASA Astrophysics Data System (ADS)

Ono, S.; Whitehill, A. R.; Oduro, H. D.

2012-12-01

Signatures of sulfur mass-independent fractionations (S-MIF) in Archean sedimentary rocks provide critical constraints on the atmospheric oxygen level of an early atmosphere and documents fundamental difference in early sulfur biogeochemical cycle from that of today. Archcean sulfide and sulfate minerals often yield correlated relationships among δ34S, Δ33S and Δ36S values. Our goal is to use this S-MIF pattern to pinpoint the S-MIF source reaction(s), and to constrain early atmospheric conditions beyond the oxygen level. Such an effort may lead to a new hypothesis about the cause of the Great Oxidation Event at 2.4 Billion years ago. We will present new results of laboratory photochemical experiments that are designed to calibrate the pattern of S-MIF during the photochemistry of SO2 and CS2 as a function of UV spectrum regions, partial pressure of SO2 and CS2 (0.1 mbar and above) and total N2 pressure (0.25 to 1.0 bar). Both SO2 and CS2 exhibit high energy absorption band (190 to 220 nm) that leads to direct photolysis (SO2 → SO + O or CS2 → CS + S), and low energy band (>240 nm for SO2 and 280 nm for CS2) that excites molecules to low lying electronic states under dissociation thresholds. Broadband UV light sources (Xenon or Deuterium arc lamps) are used in combination with a series of bandpass (200±35 nm), longpass (250 or 280 nm) filters to isolate specific electronic transitions. Excited state SO2 is trapped by acetylene and excited state CS2 polymerizes in the reactor, and are collected for sulfur isotope ratio analysis. Although SO2 photolysis under 190 to 220 nm is thought to be the main Archean S-MIF source reaction, its S-MIF is characterized by high δ34S values (up to 140 ‰) and relatively low Δ36S/Δ33S values (-3.3 to -5.9) compared to Archean data (-0.9 to -1.5). Strong pSO2 dependence suggests S-MIF is primarily due to isotopologue self-shielding at least under our experimental conditions. In contrast, SO2 photoexciation under >250 nm

Brominated 7-hydroxycoumarin-4-ylmethyls: Photolabile protecting groups with biologically useful cross-sections for two photon photolysis

PubMed Central

Furuta, Toshiaki; Wang, Samuel S.-H.; Dantzker, Jami L.; Dore, Timothy M.; Bybee, Wendy J.; Callaway, Edward M.; Denk, Winfried; Tsien, Roger Y.

1999-01-01

Photochemical release (uncaging) of bioactive messengers with three-dimensional spatial resolution in light-scattering media would be greatly facilitated if the photolysis could be powered by pairs of IR photons rather than the customary single UV photons. The quadratic dependence on light intensity would confine the photolysis to the focus point of the laser, and the longer wavelengths would be much less affected by scattering. However, previous caged messengers have had very small cross sections for two-photon excitation in the IR region. We now show that brominated 7-hydroxycoumarin-4-ylmethyl esters and carbamates efficiently release carboxylates and amines on photolysis, with one- and two-photon cross sections up to one or two orders of magnitude better than previously available. These advantages are demonstrated on neurons in brain slices from rat cortex and hippocampus excited by glutamate uncaged from N-(6-bromo-7-hydroxycoumarin-4-ylmethoxycarbonyl)-l-glutamate (Bhc-glu). Conventional UV photolysis of Bhc-glu requires less than one-fifth the intensities needed by one of the best previous caged glutamates, γ-(α-carboxy-2-nitrobenzyl)-l-glutamate (CNB-glu). Two-photon photolysis with raster-scanned femtosecond IR pulses gives the first three-dimensionally resolved maps of the glutamate sensitivity of neurons in intact slices. Bhc-glu and analogs should allow more efficient and three-dimensionally localized uncaging and photocleavage, not only in cell biology and neurobiology but also in many technological applications. PMID:9990000

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

NASA Technical Reports Server (NTRS)

Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

1975-01-01

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Early versus delayed invasive strategy for intermediate- and high-risk acute coronary syndromes managed without P2Y12 receptor inhibitor pretreatment: Design and rationale of the EARLY randomized trial.

PubMed

Lemesle, Gilles; Laine, Marc; Pankert, Mathieu; Puymirat, Etienne; Cuisset, Thomas; Boueri, Ziad; Maillard, Luc; Armero, Sébastien; Cayla, Guillaume; Bali, Laurent; Motreff, Pascal; Peyre, Jean-Pascal; Paganelli, Franck; Kerbaul, François; Roch, Antoine; Michelet, Pierre; Baumstarck, Karine; Bonello, Laurent

2018-01-01

According to recent literature, pretreatment with a P2Y 12 ADP receptor antagonist before coronary angiography appears no longer suitable in non-ST-segment elevation acute coronary syndrome (NSTE-ACS) due to an unfavorable risk-benefit ratio. Optimal delay of the invasive strategy in this specific context is unknown. We hypothesize that without P2Y 12 ADP receptor antagonist pretreatment, a very early invasive strategy may be beneficial. The EARLY trial (Early or Delayed Revascularization for Intermediate- and High-Risk Non-ST-Segment Elevation Acute Coronary Syndromes?) is a prospective, multicenter, randomized, controlled, open-label, 2-parallel-group study that plans to enroll 740 patients. Patients are eligible if the diagnosis of intermediate- or high-risk NSTE-ACS is made and an invasive strategy intended. Patients are randomized in a 1:1 ratio. In the control group, a delayed strategy is adopted, with the coronary angiography taking place between 12 and 72 hours after randomization. In the experimental group, a very early invasive strategy is performed within 2 hours. A loading dose of a P2Y 12 ADP receptor antagonist is given at the time of intervention in both groups. Recruitment began in September 2016 (n = 558 patients as of October 2017). The primary endpoint is the composite of cardiovascular death and recurrent ischemic events at 1 month. The EARLY trial aims to demonstrate the superiority of a very early invasive strategy compared with a delayed strategy in intermediate- and high-risk NSTE-ACS patients managed without P2Y 12 ADP receptor antagonist pretreatment. © 2018 Wiley Periodicals, Inc.

Calcium released by photolysis of DM-nitrophen stimulates transmitter release at squid giant synapse.

PubMed

Delaney, K R; Zucker, R S

1990-07-01

1. Transmitter release at the squid giant synapse was stimulated by photolytic release of Ca2+ from the 'caged' Ca2+ compound DM-nitrophen (Kaplan & Ellis-Davies, 1988) inserted into presynaptic terminals. 2. Competing binding reactions cause the amount of Ca2+ released by DM-nitrophen photolysis to depend on the concentrations of DM-nitrophen, total Ca2+, Mg+, ATP and native cytoplasmic Ca2+ buffer. Measurements of presynaptic [Ca2+] changes by co-injection of the fluorescent indicator dye Fura-2 show that DM-nitrophen photolysis causes a transient rise in Ca2+ followed by decay within about 150 ms to an increased steady-state level. 3. Rapid photolysis of Ca2(+)-loaded nitrophen within the presynaptic terminal was followed in less than a millisecond by depolarization of the postsynaptic membrane. As with action potential-evoked excitatory postsynaptic potentials (EPSPs), the light-evoked response was partially and reversibly blocked by 1-3 mM-kainic acid which desensitizes postsynaptic glutamate receptors. 4. Release was similar in magnitude and rate to normal action potential-mediated EPSPs. 5. The release of transmitter by photolysis of Ca2(+)-loaded DM-nitrophen was not affected by removal of Ca2+ from the saline or addition of tetrodotoxin. Photolysis of DM-nitrophen injected into presynaptic terminals without added Ca2+ did not stimulate release of transmitter nor did it interfere with normal action potential-mediated release. 6. Stimulation of presynaptic action potentials in Ca2(+)-free saline during the light-evoked response did not elicit increased release of transmitter if the ganglion was bathed in Ca2(+)-free saline, i.e. in the absence of Ca2+ influx. Increasing the intensity of the light or stimulating presynaptic action potentials in Ca2(+)-containing saline increased the release of transmitter. Therefore the failure of presynaptic voltage change to increase transmitter release resulting from release of caged Ca2+ was not due to saturation or

Quantifying soil surface photolysis under conditions simulating water movement in the field: a new laboratory test design.

PubMed

Hand, Laurence H; Nichols, Carol; Kuet, Sui F; Oliver, Robin G; Harbourt, Christopher M; El-Naggar, Essam M

2015-10-01

Soil surface photolysis can be a significant dissipation pathway for agrochemicals under field conditions, although it is assumed that such degradation ceases once the agrochemical is transported away from the surface following rainfall or irrigation and subsequent drainage of soil porewater. However, as both downward and upward water movements occur under field conditions, relatively mobile compounds may return to the surface, prolonging exposure to ultraviolet light and increasing the potential for degradation by photolysis. To test this hypothesis, a novel experimental system was used to quantify the contribution of photolysis to the overall dissipation of a new herbicide, bicyclopyrone, under conditions that mimicked field studies more closely than the standard laboratory test guidance. Soil cores were taken from 3 US field study sites, and the surfaces were treated with [(14) C]-bicyclopyrone. The radioactivity was redistributed throughout the cores using a simulated rainfall event, following which the cores were incubated under a xenon-arc lamp with continuous provision of moisture from below and a wind simulator to induce evaporation. After only 2 d, most of the test compound had returned to the soil surface. Significantly more degradation was observed in the irradiated samples than in a parallel dark control sample. Degradation rates were very similar to those observed in both the thin layer photolysis study and the field dissipation studies and significantly faster than in the soil metabolism studies conducted in the dark. Thus, for highly soluble, mobile agrochemicals, such as bicyclopyrone, photolysis is not terminated permanently by rainfall or irrigation but can resume following transport to the surface in evaporating water. © 2015 SETAC.

Degradation of naproxen by UV, VUV photolysis and their combination.

PubMed

Arany, Eszter; Szabó, Rita Katalin; Apáti, László; Alapi, Tünde; Ilisz, István; Mazellier, Patrick; Dombi, András; Gajda-Schrantz, Krisztina

2013-11-15

Naproxen is a widely used nonsteroidal anti-inflammatory drug. Recently, this medicine was detected both in natural waters (up to 1.5 μg L(-1)) and in sewage treatment plant effluents (up to 5.2 μg L(-1)). Moreover, naproxen is only partly eliminated by classical processes used in sewage treatment plants. Therefore, its degradation is of utmost interest. Advanced oxidation processes proved to be the most suitable methods for the elimination of persistent organic contaminants. In this work ultraviolet (UV, 254 nm), vacuum ultraviolet photolysis (VUV, 172 nm) and their combination (UV/VUV, 254/185 nm) were investigated. The efficiency of the methods increased in the following order: UV < VUV < UV/VUV photolysis. However, VUV irradiation was found to mineralize the contaminant molecule most effectively. The chemical structures of three out of four aromatic by-products and of some aliphatic carboxylic acids were presumed. The effects of dissolved O2 and the initial concentration of naproxen on the degradation were also investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

INFLUENCE OF HUMIC SUBSTANCES ON PHOTOLYSIS OF NITROAROMATIC COMPOUNDS IN AQUEOUS SYSTEMS

EPA Science Inventory

Results are reported for kinetic studies of the photolysis of 19 nitroaromatic compounds in water. The results indicate that dissolved humic substances in natural waters enhance the sunlight-induced photodegradation rates of nitrobenzenes, nitrotoluenes, and nitroxylenes compared...

Photolysis of Caged Ca2+ But Not Receptor-Mediated Ca2+ Signaling Triggers Astrocytic Glutamate Release

PubMed Central

Smith, Nathan A.; Xu, Qiwu; Goldman, Siri; Peng, Weiguo; Huang, Jason H.; Takano, Takahiro; Nedergaard, Maiken

2013-01-01

Astrocytes in hippocampal slices can dynamically regulate synaptic transmission in a process mediated by increases in intracellular Ca2+. However, it is debated whether astrocytic Ca2+ signals result in release of glutamate. We here compared astrocytic Ca2+ signaling triggered by agonist exposure versus photolysis side by side. Using transgenic mice in which astrocytes selectively express the MrgA1 receptor, we found that receptor-mediated astrocytic Ca2+ signaling consistently triggered neuronal hyperpolarization and decreased the frequency of miniature excitatory postsynaptic currents (EPSCs). In contrast, photolysis of caged Ca2+ (o-nitrophenyl–EGTA) in astrocytes led to neuronal depolarization and increased the frequency of mEPSCs through a metabotropic glutamate receptor-mediated pathway. Analysis of transgenic mice in which astrocytic vesicular release is suppressed (dominant-negative SNARE mice) and pharmacological manipulations suggested that glutamate is primarily released by opening of anion channels rather than exocytosis. Combined, these studies show that photolysis but not by agonists induced astrocytic Ca2+ signaling triggers glutamate release. PMID:24174673

Enhanced Heterogeneous Nitrates Photolysis on Ice and Potential Impacts on NOx Emissions

NASA Astrophysics Data System (ADS)

Ayotte, P.; Marcotte, G.; Pronovost, S.; Marchand, P.; Laffon, C.; Parent, P.

2015-12-01

Nitrates photolysis plays a key role in the chemistry of the polar boundary layer and of the lower troposphere over snow-covered areas (1). Using a combination of vibrational (2) and photo-absorption spectroscopies (3), we show that nitric acid is mostly dissociated upon its adsorption onto, and its dissolution within ice at temperatures as low 20K. Using amorphous solid water as a model substrate for the disordered surface layer at the interstitial air-ice interface, UV irradiation in the environmentally relevant n-π* transition uncovers the fact that the photolysis rates are significantly higher for surface-bound nitrates compared to those dissolved within the bulk. The complex coupled interfacial transport and reaction kinetics result in the formation of a thin photochemically active layer at the surface of ice which may magnify the impact of surface-enhanced nitrates photolysis rates on ice thereby providing a significant contribution to the intense photochemical NOxfluxes observed to emanate from the sunlit snowpack upon polar sunrise.(4) (1) F. Dominé, P.B. Shepson, Science, 297, 1506-1510 (2002).(2) P. Marchand, G. Marcotte, and P. Ayotte, Spectroscopic Study of HNO3 Dissociation on Ice, J. Phys. Chem. A 116, 12112-12122 (2012).(3) G. Marcotte, P. Ayotte, A. Bendounan, F. Sirotti, C. Laffon and P. Parent, J. Phys. Chem. Lett. 4, 2643-2648 (2013).(4) G. Marcotte, P. Marchand, S. Pronovost, P. Ayotte, C. Laffon and P. Parent, J. Phys. Chem. A 119, 1996-2005 (2015).

Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

PubMed

Orge, C A; Faria, J L; Pereira, M F R

2015-01-01

Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

Dynein-ADP as a force-generating intermediate revealed by a rapid reactivation of flagellar axoneme.

PubMed Central

Tani, T; Kamimura, S

1999-01-01

Fragmented flagellar axonemes of sand dollar spermatozoa were reactivated by rapid photolysis of caged ATP. After a time lag of 10 ms, axonemes treated with protease started sliding disintegration. Axonemes without protease digestion started nanometer-scale high-frequency oscillation after a similar time lag. Force development in the sliding disintegration was measured with a flexible glass needle and its time course was corresponded well to that of the dynein-ADP intermediate production estimated using kinetic rates previously reported. However, with a high concentration ( approximately 80 microM) of vanadate, which binds to the dynein-ADP intermediate and forms a stable complex of dynein-ADP-vanadate, the time course of force development in sliding disintegration was not affected at all. In the case of high frequency oscillation, the time lag to start the oscillation, the initial amplitude, and the initial frequency were not affected by vanadate, though the oscillation once started was damped more quickly at higher concentrations of vanadate. These results suggest that during the initial turnover of ATP hydrolysis, force generation of dynein is not blocked by vanadate. A vanadate-insensitive dynein-ADP is postulated as a force-generating intermediate. PMID:10465762

Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.; Schmatz, K.

1982-08-01

Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9more » figures, 3 tables.« less

Multi-photon UV photolysis of gaseous polycyclic aromatic hydrocarbons: Extinction spectra and dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walsh, A. J.; Gash, E. W.; Mansfield, M. W. D.

The extinction spectra of static naphthalene and static biphenylene vapor, each buffered with a noble gas at room temperature, were measured as a function of time in the region between 390 and 850 nm after UV multi-photon laser photolysis at 308 nm. Employing incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), the spectra were found to be unstructured with a general lack of isolated features suggesting that the extinction was not solely based on absorption but was in fact dominated by scattering from particles formed in the photolysis of the respective polycyclic aromatic hydrocarbon. Following UV multi-photon photolysis, the extinction dynamicsmore » of the static (unstirred) closed gas-phase system exhibits extraordinary quasi-periodic and complex oscillations with periods ranging from seconds to many minutes, persisting for up to several hours. Depending on buffer gas type and pressure, several types of dynamical responses could be generated (classified as types I, II, and III). They were studied as a function of temperature and chamber volume for different experimental conditions and possible explanations for the oscillations are discussed. A conclusive model for the observed phenomena has not been established. However, a number of key hypotheses have made based on the measurements in this publication: (a) Following the multi-photon UV photolysis of naphthalene (or biphenylene), particles are formed on a timescale not observable using IBBCEAS. (b) The observed temporal behavior cannot be described on basis of a chemical reaction scheme alone. (c) The pressure dependence of the system's responses is due to transport phenomena of particles in the chamber. (d) The size distribution and the refractive indices of particles are time dependent and evolve on a timescale of minutes to hours. The rate of particle coagulation, involving coalescent growth and particle agglomeration, affects the observed oscillations. (e) The walls of the chamber act

Multi-photon UV photolysis of gaseous polycyclic aromatic hydrocarbons: Extinction spectra and dynamics

NASA Astrophysics Data System (ADS)

Walsh, A. J.; Ruth, A. A.; Gash, E. W.; Mansfield, M. W. D.

2013-08-01

The extinction spectra of static naphthalene and static biphenylene vapor, each buffered with a noble gas at room temperature, were measured as a function of time in the region between 390 and 850 nm after UV multi-photon laser photolysis at 308 nm. Employing incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), the spectra were found to be unstructured with a general lack of isolated features suggesting that the extinction was not solely based on absorption but was in fact dominated by scattering from particles formed in the photolysis of the respective polycyclic aromatic hydrocarbon. Following UV multi-photon photolysis, the extinction dynamics of the static (unstirred) closed gas-phase system exhibits extraordinary quasi-periodic and complex oscillations with periods ranging from seconds to many minutes, persisting for up to several hours. Depending on buffer gas type and pressure, several types of dynamical responses could be generated (classified as types I, II, and III). They were studied as a function of temperature and chamber volume for different experimental conditions and possible explanations for the oscillations are discussed. A conclusive model for the observed phenomena has not been established. However, a number of key hypotheses have made based on the measurements in this publication: (a) Following the multi-photon UV photolysis of naphthalene (or biphenylene), particles are formed on a timescale not observable using IBBCEAS. (b) The observed temporal behavior cannot be described on basis of a chemical reaction scheme alone. (c) The pressure dependence of the system's responses is due to transport phenomena of particles in the chamber. (d) The size distribution and the refractive indices of particles are time dependent and evolve on a timescale of minutes to hours. The rate of particle coagulation, involving coalescent growth and particle agglomeration, affects the observed oscillations. (e) The walls of the chamber act as a sink

Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg2+ Effects by Quantum Chemical Calculations.

PubMed

Wang, Se; Wang, Zhuang

2017-11-11

The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg 2+ effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR 2+ < NOR⁰ < NOR⁺) and showed different photolysis reactivity. Analysis of transition states (TS) and reaction activation energies ( E a ) indicated NOR⁺ generally underwent loss of the piperazine ring (C10-N13 bond cleavage) and damage to piperazine ring (N13-C14 bond cleavage). For NOR 2+ , the main direct photolysis pathways were de-ethylation (N7-C8 bond cleavage) and decarboxylation (C2-C5 bond cleavage). Furthermore, the presence of Mg 2+ changed the order of the wavelength at maximum electronic absorbance (NOR⁺-Mg 2+ < NOR⁰-Mg 2+ < NOR 2+ -Mg 2+ ) and increased the intensities of absorbance peaks of all three dissociation species of NOR, implying that Mg 2+ played an important role in the direct photolysis of NOR⁰, NOR⁺, and NOR 2+ . The calculated TS results indicated that the presence of Mg 2+ increased E a for most direct photolysis pathways of NOR, while it decreased E a for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR⁰ and the defluorination of NOR⁺.

Lifetimes and reactivities of some 1,2-didehydroazepines commonly used in photoaffinity labeling experiments in aqueous solutions.

PubMed

Rizk, Mary S; Shi, Xiaofeng; Platz, Matthew S

2006-01-17

The reactive 1,2-didehydroazepine (cyclic ketenimine) intermediates produced upon photolysis of phenyl azide, 3-hydroxyphenyl azide, 3-methoxyphenyl azide, and 3-nitrophenyl azide in water and in HEPES buffer were studied by laser flash photolysis techniques with UV-vis detection of the transient intermediates. The lifetimes of the 1,2-didehydroazepines were obtained along with the absolute rate constants of their reactions with typical amino acids, nucleosides, and other simple reagents present in a biochemical milieu. The nitro substituent greatly accelerates the bimolecular reactions of the cyclic ketenimines, and the 3-methoxy group greatly decelerates the absolute reactivity of 1,2-didehydroazepines. The intermediate produced by photolysis of 3-hydroxyphenyl azide is much more reactive than the intermediate produced by photolysis of 3-methoxyphenyl azide. We propose that the hydroxyl-substituted 1,2-didehydoazepines rapidly (<10 micros) tautomerize in water to form azepinones and much more rapidly than the corresponding 3-methoxy-substituted cyclic ketenimines undergo hydrolysis. Azepinones react more rapidly with nucleophiles than do methoxy-substituted 1,2-didehydroazepines and are the active species present upon the photolysis of 3-hydroxyphenyl azide in aqueous solution.

Study of the simulated sunlight photolysis mechanism of ketoprofen: the role of superoxide anion radicals, transformation byproducts, and ecotoxicity assessment.

PubMed

Wang, Yingfei; Deng, Wen; Wang, Fengliang; Su, Yuehan; Feng, Yiping; Chen, Ping; Ma, Jingshuai; Su, Haiying; Yao, Kun; Liu, Yang; Lv, Wenying; Liu, Guoguang

2017-09-20

The aim of this study was to investigate the photolysis mechanism of ketoprofen (KET) under simulated sunlight. The results demonstrated that the photolysis of KET aligned well with pseudo first-order kinetics. Radical scavenging experiments and dissolved oxygen experiments revealed that the superoxide anion radical (O 2 ˙ - ) played a primary role in the photolytic process in pure water. Bicarbonate slightly increased the photodegradation of KET through generating carbonate radicals, while DOM inhibited the photolysis via both attenuating light and competing radicals. Moreover, Zhujiang river water inhibited KET phototransformation. Potential KET degradation pathways were proposed based on the identification of products using LC/MS/MS and GC/MS techniques. The theoretical prediction of reaction sites was derived from Frontier Electron Densities (FEDs), which primarily involved the KET decarboxylation reaction. The ecotoxicity of the treated solutions was evaluated by employing Daphnia magna and V. fischeri as biological indicators. Ecotoxicity was also hypothetically predicted through the "ecological structure-activity relationship" (ECOSAR) program, which revealed that toxic products might be generated during the photolysis process.

Direct observation of ClO from chlorine nitrate photolysis. [as mechanism of polar ozone depletion

NASA Technical Reports Server (NTRS)

Minton, Timothy K.; Nelson, Christine M.; Moore, Teresa A.; Okumura, Mitchio

1992-01-01

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Degradation of herbicide 2,4-dichlorophenoxybutanoic acid in the photolysis of [FeOH]2+ and [Fe(Ox)3]3- complexes: A mechanistic study.

PubMed

Pozdnyakov, Ivan; Sherin, Peter; Grivin, Vjacheslav; Plyusnin, Victor

2016-03-01

In the present work the Fe(III)-assisted photodegradation of the herbicide 2,4-dichlorophenoxybutanoic acid (2,4-DB) has been studied by means of stationary (308 nm) and laser flash (355 nm) photolysis. The initial quantum yield of 2,4-DB photodegradation in [FeOH](2+) and [Fe(Ox)3](3-) systems was evaluated to be 0.11 and 0.17 upon 308 nm exposure, respectively. The prolonged photolysis of [FeOH](2+) and [Fe(Ox)3](3-) systems results in the complete degradation of 2,4-DB with almost complete mineralization of herbicide and its aromatic products in the case of [FeOH](2+) photolysis and the accumulation of some persistent aromatic products in the case of [Fe(Ox)3](3-) photolysis. For both systems the main primary products of 2,4-DB photolysis determined by liquid chromatography - mass spectrometry are products of the hydroxylation, the substitution of chlorine atom to OH group, the loss of aliphatic tail and the opening of benzene ring. The obtained results indicate ROS species (mainly OH radical) to be responsible for the herbicide photodegradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photodegradation of Mefenamic Acid in Aqueous Media: Kinetics, Toxicity and Photolysis Products.

PubMed

Chen, Ping; Wang, Feng Liang; Yao, Kun; Ma, Jing Shuai; Li, Fu Hua; Lv, Wen Ying; Liu, Guo Guang

2016-02-01

The present study investigated the photolytic behavior and photodegradation products of mefenamic acid (MEF) under ultraviolet-C irradiation. The results demonstrated that the photodegradation of MEF followed pseudo-first-order kinetics and the direct photolysis quantum yield of mefenamic acid was observed to be 2.63 ± 0.28 × 10⁻³. Photodegradation of MEF included degradation by direct photolysis and by self-sensitization that the contribution rates of self-sensitized photodegradation were 5.70, 11.25 and 18.96 % for ·OH, ¹O₂ and O·₂⁻ , respectively. Primary transformation products of MEF were identified using ultra performance liquid chromatography and quadrupole time-of-flight mass spectrometer (UPLC-Q-TOF-MS). The identified transformation products suggested three possible pathways of MEF photodegradation: dehydrogenation, hydroxylation, and ketonized reactions. Toxicity of phototransformation products were evaluated using the Microtox test, which revealed that photodegradation likely provides a critical pathway for MEF toxicity reduction in drinking water and wastewater treatment facilities.

Role of distal arginine in early sensing intermediates in the heme domain of the oxygen sensor FixL.

PubMed

Jasaitis, Audrius; Hola, Klara; Bouzhir-Sima, Latifa; Lambry, Jean-Christophe; Balland, Veronique; Vos, Marten H; Liebl, Ursula

2006-05-16

FixL is a bacterial heme-based oxygen sensor, in which release of oxygen from the sensing PAS domain leads to activation of an associated kinase domain. Static structural studies have suggested an important role of the conserved residue arginine 220 in signal transmission at the level of the heme domain. To assess the role of this residue in the dynamics and properties of the initial intermediates in ligand release, we have investigated the effects of R220X (X = I, Q, E, H, or A) mutations in the FixLH heme domain on the dynamics and spectral properties of the heme upon photolysis of O(2), NO, and CO using femtosecond transient absorption spectroscopy. Comparison of transient spectra for CO and NO dissociation with steady-state spectra indicated less strain on the heme in the ligand dissociation species for all mutants compared to the wild type (WT). For CO and NO, the kinetics were similar to those of the wild type, with the exception of (1) a relatively low yield of picosecond NO rebinding to R220A, presumably related to the increase in the free volume of the heme pocket, and (2) substantial pH-dependent picosecond to nanosecond rebinding of CO to R220H, related to formation of a hydrogen bond between CO and histidine 220. Upon excitation of the complex bound with the physiological sensor ligand O(2), a 5-8 ps decay phase and a nondecaying (>4 ns) phase were observed for WT and all mutants. The strong distortion of the spectrum associated with the decay phase in WT is substantially diminished in all mutant proteins, indicating an R220-induced role of the heme in the primary intermediate in signal transmission. Furthermore, the yield of dissociated oxygen after this phase ( approximately 10% in WT) is increased in all mutants, up to almost unity in R220A, indicating a key role of R220 in caging the oxygen near the heme through hydrogen bonding. Molecular dynamics simulations corroborate these findings and suggest motions of O(2) and arginine 220 away from the heme

Photolysis Rate Coefficient Calculations in Support of SOLVE II

NASA Technical Reports Server (NTRS)

Swartz, William H.

2005-01-01

A quantitative understanding of photolysis rate coefficients (or "j-values") is essential to determining the photochemical reaction rates that define ozone loss and other crucial processes in the atmosphere. j-Values can be calculated with radiative transfer models, derived from actinic flux observations, or inferred from trace gas measurements. The primary objective of the present effort was the accurate calculation of j-values in the Arctic twilight along NASA DC-8 flight tracks during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II), based in Kiruna, Sweden (68 degrees N, 20 degrees E) during January-February 2003. The JHU/APL radiative transfer model was utilized to produce a large suite of j-values for photolysis processes (over 70 reactions) relevant to the upper troposphere and lower stratosphere. The calculations take into account the actual changes in ozone abundance and apparent albedo of clouds and the Earth surface along the aircraft flight tracks as observed by in situ and remote sensing platforms (e.g., EP-TOMS). A secondary objective was to analyze solar irradiance data from NCAR s Direct beam Irradiance Atmospheric Spectrometer (DIAS) on-board the NASA DC-8 and to start the development of a flexible, multi-species spectral fitting technique for the independent retrieval of O3,O2.02, and aerosol optical properties.

Photolysis of Low-Brominated Diphenyl Ethers and Their Reactive Oxygen Species-Related Reaction Mechanisms in an Aqueous System

PubMed Central

Wang, Mei; Wang, Huili; Zhang, Rongbo; Ma, Meiping; Mei, Kun; Fang, Fang; Wang, Xuedong

2015-01-01

To date, no report was concerned with participation of reactive oxygen species in waters during photolysis of low-brominated diphenyl ethers (LBDEs). Herein, we found that electron spin resonance (ESR) signals rapidly increased with increasing irradiation time in the solution of LBDEs and 4-oxo-TMP solutions. But this phenomenon did not occur in the presence of NaN3 (1O2 quencher) demonstrating generation of 1O2 in process of LBDEs photolysis. The indirect photolytic contribution rate for BDE-47 and BDE-28 was 18.8% and 17.3% via 1O2, and 4.9% and 6.6% via ·OH, respectively. Both D2O and NaN3 experiments proved that the indirect photolysis of LBDEs was primarily attributable to 1O2. The bimolecular reaction rate constants of 1O2 with BDE-47 and BDE-28 were 3.12 and 3.64 × 106 M-1 s-1, respectively. The rate constants for BDE-47 and BDE-28 (9.01 and 17.52 × 10−3 min-1), added to isopropyl alcohol, were very close to those (9.65 and 18.42 × 10−3 min-1) in water, proving the less indirect photolytic contribution of ·OH in water. This is the first comprehensive investigation examining the indirect photolysis of LBDEs in aqueous solution. PMID:26274605

Degradation mechanisms of Microcystin-LR during UV-B photolysis and UV/H2O2 processes: Byproducts and pathways.

PubMed

Moon, Bo-Ram; Kim, Tae-Kyoung; Kim, Moon-Kyung; Choi, Jaewon; Zoh, Kyung-Duk

2017-10-01

The removal and degradation pathways of microcystin-LR (MC-LR, [M+H] +  = 995.6) in UV-B photolysis and UV-B/H 2 O 2 processes were examined using liquid chromatography-tandem mass spectrometry. The UV/H 2 O 2 process was more efficient than UV-B photolysis for MC-LR removal. Eight by-products were newly identified in the UV-B photolysis ([M+H] +  = 414.3, 417.3, 709.6, 428.9, 608.6, 847.5, 807.4, and 823.6), and eleven by-products were identified in the UV-B/H 2 O 2 process ([M+H] +  = 707.4, 414.7, 429.3, 445.3, 608.6, 1052.0, 313.4, 823.6, 357.3, 245.2, and 805.7). Most of the MC-LR by-products had lower [M+H] + values than the MC-LR itself during both processes, except for the [M+H] + value of 1052.0 during UV-B photolysis. Based on identified by-products and peak area patterns, we proposed potential degradation pathways during the two processes. Bond cleavage and intramolecular electron rearrangement by electron pair in the nitrogen atom were the major reactions during UV-B photolysis and UV-B/H 2 O 2 processes, and hydroxylation by OH radical and the adduct formation reaction between the produced by-products were identified as additional pathways during the UV-B/H 2 O 2 process. Meanwhile, the degradation by-products identified from MC-LR during UV-B/H 2 O 2 process can be further degraded by increasing H 2 O 2 dose. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter.

PubMed

Luning Prak, Dianne J; Breuer, James E T; Rios, Evelyn A; Jedlicka, Erin E; O'Sullivan, Daniel W

2017-01-30

The influence of salinity, pH, temperature, and dissolved organic matter on the photolysis rate of 2,4,6-trinitrotoluene (TNT) in marine, estuary, and laboratory-prepared waters was studied using a Suntest CPS+® solar simulator equipped with optical filters. TNT degradation rates were determined using HPLC analysis, and products were identified using LC/MS. Minimal or no TNT photolysis occurred under a 395-nm long pass filter, but under a 295-nm filter, first-order TNT degradation rate constants and apparent quantum yields increased with increasing salinity in both natural and artificial seawater. TNT rate constants increased slightly with increasing temperature (10 to 32°C) but did not change significantly with pH (6.4 to 8.1). The addition of dissolved organic matter (up to 5mg/L) to ultrapure water, artificial seawater, and natural seawater increased the TNT photolysis rate constant. Products formed by TNT photolysis in natural seawater were determined to be 2,4,6-trinitrobenzaldehyde, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzoic acid, and 2-amino-4,6-dinitrobenzoic acid. Published by Elsevier Ltd.

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

USGS Publications Warehouse

Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

1993-01-01

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

The effect of clouds on photolysis rates and ozone formation in the unpolluted troposphere

NASA Technical Reports Server (NTRS)

Thompson, A. M.

1984-01-01

The photochemistry of the lower atmosphere is sensitive to short- and long-term meteorological effects; accurate modeling therefore requires photolysis rates for trace gases which reflect this variability. As an example, the influence of clouds on the production of tropospheric ozone has been investigated, using a modification of Luther's two-stream radiation scheme to calculate cloud-perturbed photolysis rates in a one-dimensional photochemical transport model. In the unpolluted troposphere, where stratospheric inputs of odd nitrogen appear to represent the photochemical source of O3, strong cloud reflectance increases the concentration of NO in the upper troposphere, leading to greatly enhanced rates of ozone formation. Although the rate of these processes is too slow to verify by observation, the calculation is useful in distinguishing some features of the chemistry of regions of differing mean cloudiness.

Aqueous photolysis of niclosamide

USGS Publications Warehouse

Graebing, P.W.; Chib, J.S.; Hubert, T.D.; Gingerich, W.H.

2004-01-01

The photodegradation of [14C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 A? 1.0 A?C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising 40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

Kinetics of the Reactions between the Criegee Intermediate CH2OO and Alcohols.

PubMed

Tadayon, Sara V; Foreman, Elizabeth S; Murray, Craig

2018-01-11

Reactions of the simplest Criegee intermediate (CH 2 OO) with a series of alcohols have been studied in a flash photolysis flow reactor. Laser photolysis of diiodomethane at 355 nm in the presence of molecular oxygen was used to produce CH 2 OO, and the absolute number densities were determined as a function of delay time from analysis of broadband transient absorption spectra obtained using a pulsed LED. The kinetics for the reactions of CH 2 OO with methanol, ethanol, and 2-propanol were measured under pseudo-first-order conditions at 295 K, yielding rate constants of (1.4 ± 0.4) × 10 -13 cm 3 s -1 , (2.3 ± 0.6) × 10 -13 cm 3 s -1 , and (1.9 ± 0.5) × 10 -13 cm 3 s -1 , respectively. Complementary ab initio calculations were performed at the CCSD(T)/aug-cc-pVTZ//CCSD/cc-pVDZ level of theory to characterize stationary points on the reaction enthalpy and free energy surfaces and to elucidate the thermochemistry and mechanisms. The reactions proceed over free energy barriers of ∼8 kcal mol -1 to form geminal alkoxymethyl hydroperoxides: methoxymethyl hydroperoxide (MMHP), ethoxymethyl hydroperoxide (EMHP), and isopropoxymethyl hydroperoxide (PMHP). The experimental and theoretical results are compared to reactions of CH 2 OO with other hydroxylic compounds, such as water and carboxylic acids, and trends in reactivity are discussed.

Flash photolysis resonance fluorescence investigation of the reaction of O /P-3/ atoms with ClONO2

NASA Technical Reports Server (NTRS)

Kurylo, M. J.

1977-01-01

The rate constant for the reaction of O (P-3) atoms with ClONO2 at 10 torr total pressure is assessed over the temperature range 225-273 K by the flash photolysis resonance fluorescence technique. The data, taken together with results given by Molina et al. (1977), have been used to formulate an Arrhenius expression suitable for stratospheric modeling applications. Comparison of the rate of ClONO2 destruction via the oxygen atom reaction with the solar photolysis rate shows that chemical reaction accounts for less than 15% of the CLONO2 removal at altitudes between 20 and 30 km.

Role of Lactobacillus Species in the Intermediate Vaginal Flora in Early Pregnancy: A Retrospective Cohort Study.

PubMed

Farr, Alex; Kiss, Herbert; Hagmann, Michael; Machal, Susanne; Holzer, Iris; Kueronya, Verena; Husslein, Peter Wolf; Petricevic, Ljubomir

2015-01-01

Poor obstetrical outcomes are associated with imbalances in the vaginal flora. The present study evaluated the role of vaginal Lactobacillus species in women with intermediate vaginal flora with regard to obstetrical outcomes. We retrospectively analysed data from all women with singleton pregnancies who had undergone routine screening for asymptomatic vaginal infections at our tertiary referral centre between 2005 and 2014. Vaginal smears were Gram-stained and classified according to the Nugent scoring system as normal flora (score 0-3), intermediate vaginal flora (4-6), or bacterial vaginosis (7-10). Only women with intermediate vaginal flora were investigated. Women with a Nugent score of 4 were categorised into those with and without Lactobacilli. Follow-up smears were obtained 4-6 weeks after the initial smears. Descriptive data analysis, the Welch's t-test, the Fisher's exact test, and multiple regression analysis with adjustment for confounders were performed. Gestational age at delivery and birth weight were the outcome measures. At antenatal screening, 529/8421 women presented with intermediate vaginal flora. Amongst these, 349/529 (66%) had a Nugent score of 4, 94/529 (17.8%) a Nugent score of 5, and 86/529 (16.2%) a Nugent score of 6. Amongst those with a Nugent score of 4, 232/349 (66.5%) women were in the Lactobacilli group and 117/349 (33.5%) in the Non-Lactobacilli group. The preterm delivery rate was significantly lower in the Lactobacilli than in the Non-Lactobacilli group (OR 0.34, CI 0.21-0.55; p<0.001). Mean birth weight was 2979 ± 842 g and 2388 ± 1155 g in the study groups, respectively (MD 564.12, CI 346.23-781.92; p<0.001). On follow-up smears, bacterial vaginosis rates were 9% in the Lactobacilli and 7.8% in the Non-Lactobacilli group. The absence of vaginal Lactobacillus species and any bacterial colonisation increases the risks of preterm delivery and low birth weight in women with intermediate vaginal flora in early pregnancy.

Impacts of aerosol direct effects on tropospheric ozone through changes in atmospheric dynamics and photolysis rates

NASA Astrophysics Data System (ADS)

Xing, Jia; Wang, Jiandong; Mathur, Rohit; Wang, Shuxiao; Sarwar, Golam; Pleim, Jonathan; Hogrefe, Christian; Zhang, Yuqiang; Jiang, Jingkun; Wong, David C.; Hao, Jiming

2017-08-01

Aerosol direct effects (ADEs), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease ozone (O3) formation in polluted areas. One the other hand, evidence also suggests that ADE-associated cooling suppresses atmospheric ventilation, thereby enhancing surface-level O3. Assessment of ADE impacts is thus important for understanding emission reduction strategies that seek co-benefits associated with reductions in both particulate matter and O3 levels. This study quantifies the impacts of ADEs on tropospheric ozone by using a two-way online coupled meteorology and atmospheric chemistry model, WRF-CMAQ, using a process analysis methodology. Two manifestations of ADE impacts on O3 including changes in atmospheric dynamics (ΔDynamics) and changes in photolysis rates (ΔPhotolysis) were assessed separately through multiple scenario simulations for January and July of 2013 over China. Results suggest that ADEs reduced surface daily maxima 1 h O3 (DM1O3) in China by up to 39 µg m-3 through the combination of ΔDynamics and ΔPhotolysis in January but enhanced surface DM1O3 by up to 4 µg m-3 in July. Increased O3 in July is largely attributed to ΔDynamics, which causes a weaker O3 sink of dry deposition and a stronger O3 source of photochemistry due to the stabilization of the atmosphere. Meanwhile, surface OH is also enhanced at noon in July, though its daytime average values are reduced in January. An increased OH chain length and a shift towards more volatile organic compound (VOC)-limited conditions are found due to ADEs in both January and July. This study suggests that reducing ADEs may have the potential risk of increasing O3 in winter, but it will benefit the reduction in maxima O3 in summer.

Study of the chemistry of ortho- and para-biphenylnitrenes by laser flash photolysis and time-resolved IR experiments and by B3LYP and CASPT2 calculations.

PubMed

Tsao, Meng-Lin; Gritsan, Nina; James, Tammi R; Platz, Matthew S; Hrovat, David A; Borden, Weston Thatcher

2003-08-06

The photochemistry of ortho-biphenyl azide (1a) has been studied by laser flash photolysis (LFP), with UV-vis and IR detection of the transient intermediates formed. LFP (266 nm) of 1a in glassy 3-methylpentane at 77 K releases singlet ortho-biphenylnitrene (1b) (lambda(max) = 410 nm, tau = 59 +/- 6 ns), which under these conditions decays cleanly to the lower energy triplet state. In fluid solution at 298 K, 1b rapidly (tau < 10 ns) partitions between formation of isocarbazole (4) (lambda(max) = 430 nm, tau = 70 ns) and benzazirine (1e) (lambda(max) = 305 nm, tau = 12 ns). Isocarbazole 4 undergoes a 1,5-hydrogen shift, with k(H)/k(D) = 3.4 at 298 K to form carbazole 9 and smaller amounts of two other isocarbazoles (7 and 8). Benzazirine 1e ring-opens reversibly to azacycloheptatetraene (1f), which serves as a reservoir for singlet nitrene 1b. Azacycloheptatetraene 1f ultimately forms carbazole 9 on the millisecond time scale by the pathway 1f --> 1e --> 1b --> 4 --> 9. The energies of the transient intermediates and of the transition structures connecting them were successfully predicted by CASPT2/6-31G calculations. The electronic and vibrational spectra of the intermediates, computed by density functional theory, support the assignment of the transient spectra, observed in the formation of 9 from 1a.

Isotope Fractionation in the Stratospheric Nitrous Oxide Sinks: Photolysis and "Photooxidation"

NASA Astrophysics Data System (ADS)

Chen, N.; Bianchi, T. S.; McKee, B. A.; Bland, J. M.; Kaiser, J.; Rockmann, T.; Bruhl, C.; Brenninkmeijer, C. A.

2002-05-01

N2O is an important greenhouse gas and a key factor in the ozone cycle, being the major source of stratospheric NOx. It is produced mainly at Earth's surface by microbial N conversion processes. Despite the atmospheric significance of N2O, its global budget is relatively ill-constrained: Recent estimates of the total nitrogen source flux span a range from 6.7-36.6 Tg/a as opposed to the better-quantified stratospheric losses of 9-16 Tg/a and the observed increase in the global atmospheric N2O load by 3.9 Tg/a [IPCC, 2001]. Isotope measurements have been used tentatively to improve these estimates, but without immediate success. However, spawned by the development of new spectrometric techniques which can distinguish between the isotope ratios of the terminal and central nitrogen sites in N2O, it is hoped that the global budget can now be constrained better. Detailed knowledge about the factors determining the stratospheric N2O isotope ratios is required to incorporate them into chemistry and transport models. To this end, we will present measurements of fractionation constants for N2O photolysis at different wavelengths and temperatures as well as a complete kinetic characterization of the second N2O loss reaction, N2O+O(1D), at all stratospherically relevant conditions. The intramolecular distribution of 15N is always accounted for. The laboratory measurements are interpreted in the context of stratospheric air samples which revealed strong altitude-dependent enrichments of heavy N2O isotopomers (15N14NO, 14N15NO, N218O) in the lower and middle stratosphere. Taken as a whole, these observations can be interpreted by a Rayleigh fractionation pattern in the decrease of N2O mixing ratios due to photolysis (90 % of total sink) and oxidation by O(1D) (10 % of total sink). The apparent fractionation constants are depleted in the lower stratosphere (<200 nmol/mol N2O), caused by chemistry or transport. However, even the ratio of 14N15NO and 15N14NO decreases towards the

Comparison of photocatalysis and photolysis of malathion, isomalathion, malaoxon, and commercial malathion--products and toxicity studies.

PubMed

Bavcon Kralj, M; Cernigoj, U; Franko, M; Trebse, P

2007-11-01

Malathion, one of the most widely applied insecticides, is still used in agriculture. There are many studies regarding its degradation under different experimental conditions, but few deal with its transformation products, i.e. malaoxon and isomalathion. Thus, malathion, malaoxon, isomalathion, and Radotion (one of its over 6000 commercial forms) were studied in terms of their degradation kinetics, identification of their transformation products, their toxicity, and their degree of mineralization, during UV photolysis (lambda = 254 nm) and TiO(2) photocatalysis (lambda = 355 nm). The degradation kinetics was similar for all four starting materials. More than 75% of theoretically expected sulfur in PS and P-S groups was oxidized after 240 min of photolysis and photocatalysis. On the other hand, less than 30% of stoichiometrically predicted amounts of phosphate was detected in the photolytic experiments, but more than 80% of expected phosphate was detected after photocatalytic treatment of all four organophosphorous materials. Several transformation products were identified by mass spectra of representative gas chromatographic peaks. Oxidation and isomerization were found as the main reactions of butenedioc acid diethyl esters and their analogs. The formation of malaoxon, isomalathion or trimethyl phosphate esters correlated well with the induced toxicity (inhibition of acetylcholinesterase), which was observed in photocatalysis of malathion and Radotion, and in photolysis of malaoxon and Radotion.

Hydrolysis and photolysis of diacylhydrazines-type insect growth regulator JS-118 in aqueous solutions under abiotic conditions.

PubMed

Hu, J-Y; Liu, C; Zhang, Y-C; Zheng, Z-X

2009-05-01

JS-118 is a diacylhydrazines-type insect growth regulator which is now used extensively in China. The hydrolysis and photolysis of the pesticide JS-118 in aqueous solutions have been assessed under natural and controlled conditions in this project. Hydrolysis experimental results show that JS-118 is quite stable in aqueous solutions in dark, with no significant variations be observed in degradation under various conditions. Abiotic hydrolysis is relatively unimportant compared to photolysis. The rate of photodecomposition of JS-118 in aqueous solutions follows first-order kinetics both in UV radiation and natural sunlight. The degradation rates are faster under UV light than sunlight, with the half-lives (t (1/2) = ln2/k) of 6.00-10.85 min and 6.63-10.16 day, respectively. Under UV light, two major photoproducts are detected, and tentatively identified according to HPLC-MS spectral information as N-t-butyl-N-(3,5-dimethylbenzoyl) and 3,7-dimethyl-benzoatedihydrofuran. The corresponding photolysis pathways of JS-118 are also proposed. The results obtained indicate that direct photoreaction is an important dissipation pathway of JS-118 in natural water systems.

Photolysis of Pure Solid O3 and O2 Films at 193nm

NASA Technical Reports Server (NTRS)

Raut, U.; Loeffler, M. J.; Fama, M.; Baragiola, R. A.

2011-01-01

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

PubMed

Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

NASA Astrophysics Data System (ADS)

Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

2014-06-01

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of 15ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well

In vitro and in vivo anti-Staphylococcus aureus activities of a new disinfection system utilizing photolysis of hydrogen peroxide.

PubMed

Hayashi, Eisei; Mokudai, Takayuki; Yamada, Yasutomo; Nakamura, Keisuke; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2012-08-01

The present study aimed to evaluate in vitro and in vivo antibacterial activity of hydroxyl radical generation system by photolysis of H(2)O(2), which is a new disinfection system for the treatment of oral infection diseases such as periodontitis developed in our laboratory. Firstly, generation of the hydroxyl radical by the photolysis of H(2)O(2) in which 1 mol l(-1) H(2)O(2) was irradiated with a dual wavelength-light emitting diode (LED) at wavelengths of 400 and 465 nm was confirmed by applying an electron spin resonance-spin trapping technique. Secondly, the bactericidal effect of the system was examined under a similar condition in which Staphylococcus aureus suspended in 1 mol l(-1) H(2)O(2) was irradiated with LED light, resulting in substantial reduction of the colony forming unit (CFU) of the bacteria within a short time as 2 min. Finally, in vivo antibacterial effect of the photolysis of H(2)O(2) on a rat model of S. aureus infection was evaluated by a culture study. Since a significant reduction of recovered CFU of S. aureus was obtained, it is expected that in vitro antibacterial effect attributable to hydroxyl radicals generated by photolysis of H(2)O(2) could be well reflected in in vivo superficial bacterial infection. Copyright © 2012 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Antimicrobial activity of hydroxyl radicals generated by hydrogen peroxide photolysis against Streptococcus mutans biofilm.

PubMed

Nakamura, Keisuke; Shirato, Midori; Kanno, Taro; Örtengren, Ulf; Lingström, Peter; Niwano, Yoshimi

2016-10-01

Prevention of dental caries with maximum conservation of intact tooth substance remains a challenge in dentistry. The present study aimed to evaluate the antimicrobial effect of H2O2 photolysis on Streptococcus mutans biofilm, which may be a novel antimicrobial chemotherapy for treating caries. S. mutans biofilm was grown on disk-shaped hydroxyapatite specimens. After 1-24 h of incubation, growth was assessed by confocal laser scanning microscopy and viable bacterial counting. Resistance to antibiotics (amoxicillin and erythromycin) was evaluated by comparing bactericidal effects on the biofilm with those on planktonic bacteria. To evaluate the effect of the antimicrobial technique, the biofilm was immersed in 3% H2O2 and was irradiated with an LED at 365 nm for 1 min. Viable bacterial counts in the biofilm were determined by colony counting. The thickness and surface coverage of S. mutans biofilm increased with time, whereas viable bacterial counts plateaued after 6 h. When 12- and 24-h-old biofilms were treated with the minimum concentration of antibiotics that killed viable planktonic bacteria with 3 log reduction, their viable counts were not significantly decreased, suggesting the biofilm acquired antibiotic resistance by increasing its thickness. By contrast, hydroxyl radicals generated by photolysis of 3% H2O2 effectively killed S. mutans in 24-h-old biofilm, with greater than 5 log reduction. The technique based on H2O2 photolysis is a potentially powerful adjunctive antimicrobial chemotherapy for caries treatment. Copyright © 2016 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

Dependence of upper atmosphere photochemistry on the shape of the diurnal cycle of the photolysis rates

NASA Astrophysics Data System (ADS)

Montecinos, S.; Barrientos, P.

2006-03-01

A photochemical model of the atmosphere constitutes a non-linear, non-autonomous dynamical system, enforced by the Earth's rotation. Some studies have shown that the region of the mesopause tends towards non-linear responses such as period-doubling cascades and chaos. In these studies, simple go approximations for the diurnal variations of the photolysis rates are assumed. The goal of this article is to investigate what happens if the more realistic, calculated photolysis rates are introduced. It is found that, if the usual approximations-sinusoidal and step functions-are assumed, the responses of the system are similar: it converges to a 2-day periodic solution. If the more realistic, calculated diurnal cycle is introduced, a new 4-day subharmonic appear.

Solar photolysis versus TiO2-mediated solar photocatalysis: a kinetic study of the degradation of naproxen and diclofenac in various water matrices.

PubMed

Kanakaraju, Devagi; Motti, Cherie A; Glass, Beverley D; Oelgemöller, Michael

2016-09-01

Given that drugs and their degradation products are likely to occur as concoctions in wastewater, the degradation of a mixture of two nonsteroidal anti-inflammatory drugs (NSAIDs), diclofenac (DCF) and naproxen (NPX), was investigated by solar photolysis and titanium dioxide (TiO2)-mediated solar photocatalysis using an immersion-well photoreactor. An equimolar ratio (1:1) of both NSAIDs in distilled water, drinking water, and river water was subjected to solar degradation. Solar photolysis of the DCF and NPX mixture was competitive particularly in drinking water and river water, as both drugs have the ability to undergo photolysis. However, the addition of TiO2 in the mixture significantly enhanced the degradation rate of both APIs compared to solar photolysis alone. Mineralization, as measured by chemical oxygen demand (COD), was incomplete under all conditions investigated. TiO2-mediated solar photocatalytic degradation of DCF and NPX mixtures produced 15 identifiable degradants corresponding to degradation of the individual NSAIDs, while two degradation products with much higher molecular weight than the parent NSAIDs were identified by liquid chromatography mass spectrometry (LC-MS) and Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS). This study showed that the solar light intensity and the water matrix appear to be the main factors influencing the overall performance of the solar photolysis and TiO2-mediated solar photocatalysis for degradation of DCF and NPX mixtures.

Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater.

PubMed

Xing, Rui; Zheng, Zhongyuan; Wen, Donghui

2015-03-01

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%-35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD5/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%-47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH4+-N), 17% more nitrite nitrogen (NO2--N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO3--N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent. Copyright © 2015. Published by Elsevier B.V.

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

PubMed

Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

2012-11-20

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

New photolysis system for NO2 measurements in the lower stratosphere

NASA Technical Reports Server (NTRS)

Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Ciciora, S. J.; Proffitt, M. H.; Thompson, T. L.; Mclaughlin, R. J.; Fahey, D. W.

1994-01-01

A new system for NO2 detection has been developed for use on the NASA ER-2 aircraft. The system converts NO2 to NO using UV photolysis with the NO product subsequently detected with an on-board chemiluminescence detector. The new system is compact, light weight, has high time resolution (approximately 1 s), and is significantly more efficient then some previous designs. Details of the system design and airborne performance are discussed.

Photolysis frequency and cloud dynamics during DC3 and SEAC4RS

NASA Astrophysics Data System (ADS)

Hall, S. R.; Ullmann, K.; Madronich, S.; Hair, J. W.; Butler, C. F.; Fenn, M. A.

2013-12-01

Cloud shading plays a critical role in extending the lifetime of short-lived chemical species. During convection, photochemistry is reduced such that short-lived species may be transported from the boundary layer to the upper troposphere/ lower stratosphere. In the anvil outflow, shading continues within and below the cloud. However, near the highly scattering cloud top, the chemistry is greatly accelerated. In this rapidly evolving environment, accurate photolysis frequencies are required to study photochemical evolution of the complex composition. During the Deep Convective Clouds and Chemistry (DC3, 2012) and the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, 2013) campaigns, photolysis frequencies were determined by measurement of spectrally resolved actinic flux by the Charge-coupled device Actinic Flux Spectroradiometer (CAFS) on the NASA DC-8 and the HIAPER Airborne Radiation Package (HARP) on the NCAR G-V aircraft. Vertical flight profiles allowed in situ characterization of the radiation environment. Input of geometrical cloud characteristics into the Tropospheric Ultraviolet and Visible (TUV) Radiation was used to constrain cloud optical depths for more spatially and temporally stable conditions.

Optimal Timing for Elective Early Primary Repair of Tetralogy of Fallot: Analysis of Intermediate Term Outcomes.

PubMed

Cunningham, Michael E A; Donofrio, Mary T; Peer, Syed Murfad; Zurakowski, David; Jonas, Richard A; Sinha, Pranava

2017-03-01

We have previously demonstrated that early primary repair of tetralogy of Fallot with pulmonary stenosis (TOF) can be safely performed without increase in hospital resource utilization or compromise to surgical technical performance scores (TPS). We sought to identify the optimal timing for elective early primary repair of TOF with respect to intermediate-term reintervention. Retrospective review of all patients with TOF undergoing elective primary repair between September 2004 and December 2013 was performed. Patients were stratified into reintervention group or no reintervention group. Multivariable Cox regression analysis identified independent predictors of reintervention. Youden's J-index in receiver operating characteristic analysis identified optimal age cutoff predictive of reintervention. Kaplan-Meier analysis with the log-rank test compared reintervention rates stratified by age and TPS. A total of 129 patients with median (interquartile range) age and weight of 78 days (56 to 111) and 5 kg (4.1 to 5.7), respectively, underwent primary repair. After a median (interquartile range) follow-up of 2.3 years (0.1 to 4.6), 18 patients (14%) required a total of 22 reinterventions. Youden's J-index revealed significantly lower risk of intermediate-term reintervention when repaired after 55 days of age (8% for >55 days old versus 31% for ≤55 days of age). Multivariable Cox regression identified age 55 days and younger (hazard ratio [HR] 4.5, 95% confidence interval [CI] 1.6 to 12.8, p = 0.004), valve sparing repair (HR 15.3, 95% CI 1.8 to 128.5, p < 0.001), residual right ventricular outflow tract (RVOT) gradient (HR 1.11, 95% CI 1.1 to 1.2, p < 0.001), and inadequate TPS (HR 21.5, 95% CI 7.4 to 63, p < 0.001) as independent predictors of overall intermediate-term reintervention. Elective repair in patients greater than 55 days of age, irrespective of size of the patient, can be safely performed without any increase in reintervention rates. Both residual peak

Role of Lactobacillus Species in the Intermediate Vaginal Flora in Early Pregnancy: A Retrospective Cohort Study

PubMed Central

Farr, Alex; Kiss, Herbert; Hagmann, Michael; Machal, Susanne; Holzer, Iris; Kueronya, Verena; Husslein, Peter Wolf; Petricevic, Ljubomir

2015-01-01

intermediate vaginal flora in early pregnancy. PMID:26658473

The photolysis of CH3ONO

NASA Technical Reports Server (NTRS)

Wiebe, H. A.; Heicklen, J.

1972-01-01

The photolysis of CH3ONO, alone and in the presence of NO, NO-N2 mixtures, and NO-CO mixtures was studied between 25 and 150 C. The major products are CH2O, N2O, and H2O. The quantum yields of N2O were measured. The N2O yield is large at low pressures but approaches a high-pressure limiting value of 0.055 at all temperatures as the excited CH3O produced in the primary step is stabilized by collision. In the presence of excess CO, and N2O yield drops, and CO2 is produced (though not in sufficient amounts to account for the drop in N2O). When pure CH2ONO is photolyzed, CO is produced and NO accumulates in the system. Both products are formed in related processes and result from CH3O attack on CH2O.

Cross-bridge kinetics in the presence of MgADP investigated by photolysis of caged ATP in rabbit psoas muscle fibres.

PubMed Central

Dantzig, J A; Hibberd, M G; Trentham, D R; Goldman, Y E

1991-01-01

1. The interaction between MgADP and rigor cross-bridges in glycerol-extracted single fibres from rabbit psoas muscle has been investigated using laser pulse photolysis of caged ATP (P3-1(2-nitrophenyl)ethyladenosine 5'-triphosphate) in the presence of MgADP and following small length changes applied to the rigor fibre. 2. Addition of 465 microM-MgADP to a rigor fibre caused rigor tension to decrease by 15.3 +/- 0.7% (S.E.M., n = 24 trials in thirteen fibres). The half-saturation value for this tension reduction was 18 +/- 4 microM (n = 23, thirteen fibres). 3. Relaxation from rigor by photolysis of caged ATP in the absence of Ca2+ was markedly slowed by inclusion of 20 microM-2 mM-MgADP in the photolysis medium. 4. Four phases of tension relaxation occurred with MgADP in the medium: at, a quick partial relaxation (in pre-stretch fibres); bt, a slowing of relaxation or a rise in tension for 50-100 ms; ct, a sudden acceleration of relaxation; and dt, a final, nearly exponential relaxation. 5. Experiments at varied MgATP and MgADP concentrations suggested that phase at is due to MgATP binding to nucleotide-free cross-bridges. 6. Phase bt was abbreviated by including 1-20 mM-orthophosphate (Pi) in the photolysis medium, or by applying quick stretches before photolysis or during phase bt. These results suggest that phases bt and ct are complex processes involving ADP dissociation, cross-bridge reattachment and co-operative detachment involving filament sliding and the Ca(2+)-regulatory system. 7. Stretching relaxed muscle fibres to 3.2-3.4 microns striation spacing followed by ATP removal and release of the rigor fibre until tension fell below the relaxed level allowed investigation of the strain dependence of relaxation in the regions of negative cross-bridge strain. In the presence of 50 microM-2 mM-MgADP and either 10 mM-Pi or 20 mM-2,3-butanedione monoxime, relaxation following photolysis of caged ATP was 6- to 8-fold faster for negatively strained cross

Structure of GroEL in Complex with an Early Folding Intermediate of Alanine Glyoxylate Aminotransferase*

PubMed Central

Albert, Armando; Yunta, Cristina; Arranz, Rocío; Peña, Álvaro; Salido, Eduardo; Valpuesta, José María; Martín-Benito, Jaime

2010-01-01

Primary hyperoxaluria type 1 is a rare autosomal recessive disease caused by mutations in the alanine glyoxylate aminotransferase gene (AGXT). We have previously shown that P11L and I340M polymorphisms together with I244T mutation (AGXT-LTM) represent a conformational disease that could be amenable to pharmacological intervention. Thus, the study of the folding mechanism of AGXT is crucial to understand the molecular basis of the disease. Here, we provide biochemical and structural data showing that AGXT-LTM is able to form non-native folding intermediates. The three-dimensional structure of a complex between the bacterial chaperonin GroEL and a folding intermediate of AGXT-LTM mutant has been solved by cryoelectron microscopy. The electron density map shows the protein substrate in a non-native extended conformation that crosses the GroEL central cavity. Addition of ATP to the complex induces conformational changes on the chaperonin and the internalization of the protein substrate into the folding cavity. The structure provides a three-dimensional picture of an in vivo early ATP-dependent step of the folding reaction cycle of the chaperonin and supports a GroEL functional model in which the chaperonin promotes folding of the AGXT-LTM mutant protein through forced unfolding mechanism. PMID:20056599

Structure of GroEL in complex with an early folding intermediate of alanine glyoxylate aminotransferase.

PubMed

Albert, Armando; Yunta, Cristina; Arranz, Rocío; Peña, Alvaro; Salido, Eduardo; Valpuesta, José María; Martín-Benito, Jaime

2010-02-26

Primary hyperoxaluria type 1 is a rare autosomal recessive disease caused by mutations in the alanine glyoxylate aminotransferase gene (AGXT). We have previously shown that P11L and I340M polymorphisms together with I244T mutation (AGXT-LTM) represent a conformational disease that could be amenable to pharmacological intervention. Thus, the study of the folding mechanism of AGXT is crucial to understand the molecular basis of the disease. Here, we provide biochemical and structural data showing that AGXT-LTM is able to form non-native folding intermediates. The three-dimensional structure of a complex between the bacterial chaperonin GroEL and a folding intermediate of AGXT-LTM mutant has been solved by cryoelectron microscopy. The electron density map shows the protein substrate in a non-native extended conformation that crosses the GroEL central cavity. Addition of ATP to the complex induces conformational changes on the chaperonin and the internalization of the protein substrate into the folding cavity. The structure provides a three-dimensional picture of an in vivo early ATP-dependent step of the folding reaction cycle of the chaperonin and supports a GroEL functional model in which the chaperonin promotes folding of the AGXT-LTM mutant protein through forced unfolding mechanism.

The Production of NO subscript 2 from the Photolysis of Peroxyacetyl Nitrate

NASA Technical Reports Server (NTRS)

Mazely, T.; Friedl, R.; Sander, S.

1994-01-01

PAN vapor was photolyzed at 248 nm and the NO subscript 2 photoproduct was detected by laser induced fluorescence (LIF). By comparison to the NO subscript 2 production from the photolysis of HNO subscript 3 under identical experimental conditions, we have obtained a relative quantum yield for the production of NO subscript 2. The implications of these results for atmospheric PAN chemistry will be discussed.

Direct photolysis rates and transformation pathways of the lampricides TFM and niclosamide in simulated sunlight

USGS Publications Warehouse

McConville, Megan B.; Hubert, Terrance D.; Remucal, Christina K.

2016-01-01

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2–5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Direct Photolysis Rates and Transformation Pathways of the Lampricides TFM and Niclosamide in Simulated Sunlight.

PubMed

McConville, Megan B; Hubert, Terrance D; Remucal, Christina K

2016-09-20

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2',5-dichloro-4'-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2-5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Pulsed laser photolysis kinetics study of the O(3P) + ClO reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Wine, P. H.; Ravishankara, A. R.

1988-01-01

A pulsed laser photolysis technique was used to investigate the kinetics of the important stratospheric reaction O + ClO yields Cl + O2 in buffer gas over the temperature and pressure ranges of 231-367 K and 25-500 torr. The results indicate a lack of pressure dependence at 298 K over the 25-500 torr range.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results frommore » studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by

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

PubMed

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).

Galactic rings revisited. II. Dark gaps and the locations of resonances in early-to-intermediate-type disc galaxies

NASA Astrophysics Data System (ADS)

Buta, Ronald J.

2017-10-01

Dark gaps are commonly seen in early-to-intermediate-type barred galaxies having inner and outer rings or related features. In this paper, the morphologies of 54 barred and oval ringed galaxies have been examined with the goal of determining what the dark gaps are telling us about the structure and evolution of barred galaxies. The analysis is based mainly on galaxies selected from the Galaxy Zoo 2 data base and the Catalogue of Southern Ringed Galaxies. The dark gaps between inner and outer rings are of interest because of their likely association with the L4 and L5 Lagrangian points that would be present in the gravitational potential of a bar or oval. Since the points are theoretically expected to lie very close to the corotation resonance (CR) of the bar pattern, the gaps provide the possibility of locating corotation in some galaxies simply by measuring the radius rgp of the gap region and setting rCR=rgp. With the additional assumption of generally flat rotation curves, the locations of other resonances can be predicted and compared with observed morphological features. It is shown that this `gap method' provides remarkably consistent interpretations of the morphology of early-to-intermediate-type barred galaxies. The paper also brings attention to cases where the dark gaps lie inside an inner ring, rather than between inner and outer rings. These may have a different origin compared to the inner/outer ring gaps.

Laser photolysis studies of ω-bond dissociation in aromatic carbonyls with a C-C triple bond stimulated by triplet sensitization.

PubMed

Yamaji, Minoru; Horimoto, Ami; Marciniak, Bronislaw

2017-07-14

We have prepared three types of carbonyl compounds, benzoylethynylmethyl phenyl sulfide (2@SPh), (p-benzoyl)phenylethynylmethyl phenyl sulfide (3@SPh) and p-(benzoylethynyl)benzyl phenyl sulfide (4@SPh) with benzoyl and phenylthiylmethyl groups, which are interconnected with a C-C triple bond and a phenyl ring. Laser flash photolysis of 3@SPh and 4@SPh in acetonitrile provided the transient absorption spectra of the corresponding triplet states where no chemical reactions were recognized. Upon laser flash photolysis of 2@SPh, the absorption band due to the phenylthiyl radical (PTR) was obtained, indicating that the C-S bond cleaved in the excited state. Triplet sensitization of these carbonyl compounds using acetone and xanthone was conducted using laser photolysis techniques. The formation of triplet 3@SPh was seen in the transient absorption, whereas the PTR formation was observed for 2@SPh and 4@SPh, indicating that the triplet states were reactive for the C-S bond dissociation. The C-S bond dissociation mechanism for 4@SPh upon triplet sensitization is discussed in comparison with those for 2@SPh and 3@SPh.

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

NASA Astrophysics Data System (ADS)

Carraher, Jack McCaslin

-olefins selectively. This process is made catalytic by the introduction of O2. Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu +. Longer-chain acids also yield alpha olefins as exclusive products. In the absence of continued purging with O2 to aid removal of olefin, Cu+(olefin) complexes accumulate and catalytic activity slows dramatically due to depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids. Free Oxygen Atom in Solution from 4-Benzoylpyridine N-Oxide Excited Singlet. Photolysis of 4-benzoylpyridine N-oxide (BPyO) in the presence of quenchers of the triplet excited state produces up to 41% O(3P) (as determined by generation of ethylene upon scavenging with cyclopentene). In the absence of 3BPyO* quenchers a maximum of 13% O(3P) relative to consumed BPyO is obtained. The remaining products are hydroxylated-4-benzoylpyridine and 4-benzoylpyridine. Additionally, the rate of BPyO consumption (as determined by UV-vis) decreases in the presence of 3BPyO* quenching agents. Second order rate constants for 3BPyO* quenching were determined. A mechanism for photochemical deoxygenation of BPyO is proposed on the basis of kinetic data and product distribution under various conditions. Additionally, comparisons are made between the observed intermediates and similar triplet excited states and radical anions.

Pediatric Early Warning Systems aid in triage to intermediate versus intensive care for pediatric oncology patients in resource-limited hospitals.

PubMed

Agulnik, Asya; Nadkarni, Anisha; Mora Robles, Lupe Nataly; Soberanis Vasquez, Dora Judith; Mack, Ricardo; Antillon-Klussmann, Federico; Rodriguez-Galindo, Carlos

2018-04-10

Pediatric oncology patients hospitalized in resource-limited settings are at high risk for clinical deterioration resulting in mortality. Intermediate care units (IMCUs) provide a cost-effective alternative to pediatric intensive care units (PICUs). Inappropriate IMCU triage, however, can lead to poor outcomes and suboptimal resource utilization. In this study, we sought to characterize patients with clinical deterioration requiring unplanned transfer to the IMCU in a resource-limited pediatric oncology hospital. Patients requiring subsequent early PICU transfer had longer PICU length of stay. PEWS results prior to IMCU transfer were higher in patients requiring early PICU transfer, suggesting PEWS can aid in triage between IMCU and PICU care. © 2018 Wiley Periodicals, Inc.

Photolysis study of octyl p-methoxycinnamate loaded microemulsion by molecular fluorescence and chemometric approach

NASA Astrophysics Data System (ADS)

Nascimento, Danielle Silva; Insausti, Matías; Band, Beatriz Susana Fernández; Grünhut, Marcos

2018-02-01

Octyl p-methoxycinnamate (OMC) is one of the most widely used sunscreen agents. However, the efficiency of OMC as UV filter over time is affected due to the formation of the cis-isomer which presents a markedly lower extinction coefficient (εcis = 12,600 L mol- 1 cm- 1 at 291 nm) than the original trans-isomer (εtrans = 24,000 L mol- 1 cm- 1 at 310 nm). In this work, a novel carrier for OMC based on an oil-in-water microemulsion is proposed in order to improve the photostability of this sunscreen. The formulation was composed of 29.2% (w/w) of a 3:1 mixture of ethanol (co-surfactant) and decaethylene glycol mono-dodecyl ether (surfactant), 1.5% (w/w) of oleic acid (oil phase) and 69.2% (w/w) of water. This microemulsion was prepared in a simple way, under moderate stirring at 25 °C and using acceptable, biocompatible and accessible materials for topical use. OMC was incorporated in the vehicle at a final concentration of 5.0% (w/w), taking into account the maximum permitted levels established by international norms. Then, a photolysis study of the loaded formulation was performed using a continuous flow system. The direct photolysis was monitored over time by molecular fluorescence. The recorded spectra data between 370 y 490 nm were analyzed by multivariate curve resolution-alternating least squares algorithm. The kinetic rate constants corresponding to the photolysis of the trans-OMC were calculated from the concentration profiles, resulting in 0.0049 s- 1 for the trans-OMC loaded microemulsion and 0.0131 s- 1 for the trans-OMC in aqueous media. These results demonstrate a higher photostability of the trans-OMC when loaded in the proposed vehicle with respect to the free trans-OMC in aqueous media.

Photolysis study of octyl p-methoxycinnamate loaded microemulsion by molecular fluorescence and chemometric approach.

PubMed

Nascimento, Danielle Silva; Insausti, Matías; Band, Beatriz Susana Fernández; Grünhut, Marcos

2018-02-15

Octyl p-methoxycinnamate (OMC) is one of the most widely used sunscreen agents. However, the efficiency of OMC as UV filter over time is affected due to the formation of the cis-isomer which presents a markedly lower extinction coefficient (ε cis =12,600L mol -1 cm -1 at 291nm) than the original trans-isomer (ε trans =24,000L mol -1 cm -1 at 310nm). In this work, a novel carrier for OMC based on an oil-in-water microemulsion is proposed in order to improve the photostability of this sunscreen. The formulation was composed of 29.2% (w/w) of a 3:1 mixture of ethanol (co-surfactant) and decaethylene glycol mono-dodecyl ether (surfactant), 1.5% (w/w) of oleic acid (oil phase) and 69.2% (w/w) of water. This microemulsion was prepared in a simple way, under moderate stirring at 25°C and using acceptable, biocompatible and accessible materials for topical use. OMC was incorporated in the vehicle at a final concentration of 5.0% (w/w), taking into account the maximum permitted levels established by international norms. Then, a photolysis study of the loaded formulation was performed using a continuous flow system. The direct photolysis was monitored over time by molecular fluorescence. The recorded spectra data between 370 y 490nm were analyzed by multivariate curve resolution-alternating least squares algorithm. The kinetic rate constants corresponding to the photolysis of the trans-OMC were calculated from the concentration profiles, resulting in 0.0049s -1 for the trans-OMC loaded microemulsion and 0.0131s -1 for the trans-OMC in aqueous media. These results demonstrate a higher photostability of the trans-OMC when loaded in the proposed vehicle with respect to the free trans-OMC in aqueous media. Copyright © 2017 Elsevier B.V. All rights reserved.

Photoinduced Reductive Elimination of H2 from the Nitrogenase Dihydride (Janus) State Involves a FeMo-cofactor-H2 Intermediate.

PubMed

Lukoyanov, Dmitriy; Khadka, Nimesh; Dean, Dennis R; Raugei, Simone; Seefeldt, Lance C; Hoffman, Brian M

2017-02-20

N 2 reduction by nitrogenase involves the accumulation of four reducing equivalents at the active site FeMo-cofactor to form a state with two [Fe-H-Fe] bridging hydrides (denoted E 4 (4H), the Janus intermediate), and we recently demonstrated that the enzyme is activated to cleave the N≡N triple bond by the reductive elimination (re) of H 2 from this state. We are exploring a photochemical approach to obtaining atomic-level details of the re activation process. We have shown that, when E 4 (4H) at cryogenic temperatures is subjected to 450 nm irradiation in an EPR cavity, it cleanly undergoes photoinduced re of H 2 to give a reactive doubly reduced intermediate, denoted E 4 (2H)*, which corresponds to the intermediate that would form if thermal dissociative re loss of H 2 preceded N 2 binding. Experiments reported here establish that photoinduced re primarily occurs in two steps. Photolysis of E 4 (4H) generates an intermediate state that undergoes subsequent photoinduced conversion to [E 4 (2H)* + H 2 ]. The experiments, supported by DFT calculations, indicate that the trapped intermediate is an H 2 complex on the ground adiabatic potential energy suface that connects E 4 (4H) with [E 4 (2H)* + H 2 ]. We suggest that this complex, denoted E 4 (H 2 ; 2H), is a thermally populated intermediate in the catalytically central re of H 2 by E 4 (4H) and that N 2 reacts with this complex to complete the activated conversion of [E 4 (4H) + N 2 ] into [E 4 (2N2H) + H 2 ].

Photoinduced Reductive Elimination of H 2 from the Nitrogenase Dihydride (Janus) State Involves a FeMo-cofactor-H 2 Intermediate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lukoyanov, Dmitriy; Khadka, Nimesh; Dean, Dennis R.

N2 reduction by nitrogenase involves the accumulation of four reducing equivalents at the active site FeMo-cofactor to form a state with two [Fe-H-Fe] bridging hydrides (denoted E4(4H), the Janus intermediate), and we recently demonstrated that the enzyme is activated to cleave the N≡N triple bond by the reductive elimination (re) of H2 from this state. We are exploring a photochemical approach to obtaining atomic-level details of the re activation process. We have shown that when E4(4H) at cryogenic temperatures is subjected to 450 nm irradiation in an EPR cavity, it cleanly undergoes photoinduced re of H2 to give a reactivemore » doubly-reduced intermediate, denoted E4(2H)*, which corresponds to the intermediate that would form if thermal dissociative re loss of H2 preceded N2 binding. Experiments reported here establish that photoinduced re occurs in two steps. Photolysis of E4(4H) generates an intermediate state that undergoes subsequent photoinduced conversion to [E4(2H)* + H2]. The experiments, supported by DFT calculation, indicate that the trapped intermediate is an H2 complex on the ground adiabatic potential energy suface that connects E4(4H) with [E4(2H)* + H2]. We suggest this complex, denoted E4(H2; 2H), is a thermally populated intermediate in the catalytically central re of H2 by E4(4H), and that N2 reacts with this complex to complete the activated conversion of [E4(4H) + N2] into [E4(2N2H) + H2].« less

Impacts of aerosol direct effects on tropospheric ozone through changes in atmospheric dynamics and photolysis rates

EPA Science Inventory

Aerosol direct effects (ADE), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease O3 formation in polluted areas. One the other hand, evidence also suggests that ADE associated coo...

Solar photolysis of ozone to singlet D oxygen atoms

NASA Technical Reports Server (NTRS)

Blackburn, Thomas E.; Bairai, Solomon T.; Stedman, Donald H.

1992-01-01

The ground-level photolysis frequency of ozone J(O3) to produce metastable singlet D oxygen atoms (O (D-1)) is measured using a novel instrumental technique involving electrical conductivity. The O(D-1) atoms produced react with nitrous oxide (N2O) carrier gas to form higher oxides of nitrogen (NO(x)). These oxides were detected by mixing with methanol and determining the increase in electrical conductivity with a continuous-flow dual conductivity cell. Over 70 days of data were collected under varying sky conditions. The effect of temperature on J(O3) was measured. The results agree with model predictions. The effects of atmospheric aerosols, changes in overhead ozone column, and local cloudiness are discussed.

Photolysis of retinol in liposomes and its protection with tocopherol and oxybenzone.

PubMed

Young, A M; Gregoriadis, G

1996-03-01

In this work the stabilities of retinol in methanolic solutions and liposomal suspensions exposed to UV light were compared using absorbance spectroscopy and the ability of alpha-tocopherol and the sunscreen additive, oxybenzone, to reduce the rate of retinol decomposition assessed. Retinol in methanol decolorized almost completely within a few minutes of exposure to a 6 W 350 nm wavelength lamp. From the concentration dependence of the reaction rates it appears that retinol activated by light can decomposed either directly or after collision with a second retinol molecule. Several reaction products are formed. alpha-Tocopherol solutions were unaffected by 350 nm light but they did darken when irradiated with 250 nm wavelength light. Addition of alpha-tocopherol or removal of oxygen from the retinol in methanol solutions reduced only slightly the rates of retinol photolysis. When dispersed in water within liposomes made of equimolar egg phosphatidylcholine (PC) and cholesterol, up to six-fold increases in the decomposition rate of the retinol were observed. The reaction rate could be reduced but only slightly by increasing the ratio of PC to retinol. A mechanism that explains the concentration dependence of the retinol photolysis is that the reduction in reaction rate on diluting the retinol concentration within a given liposome was due to the prevention of the reaction between one light-activated retinol molecule with another within the same liposome. Incorporation of oxybenzone into the liposomes reduced the reaction rates. The results suggested that most of the protection in this case arises through the oxybenzone closet to the light source absorbing the light, thereby preventing it reaching retinol much further into the sample. Incorporation of alpha-tocopherol into the liposomes could also reduce substantially the photolysis rate of co-entrapped retinol. The mechanism of protection in this case appears to be via the tocopherol quenching activated retinol

Comparison of UV photolysis, nanofiltration, and their combination to remove hormones from a drinking water source and reduce endocrine disrupting activity.

PubMed

Sanches, Sandra; Rodrigues, Alexandre; Cardoso, Vitor V; Benoliel, Maria J; Crespo, João G; Pereira, Vanessa J

2016-06-01

A sequential water treatment combining low pressure ultraviolet direct photolysis with nanofiltration was evaluated to remove hormones from water, reduce endocrine disrupting activity, and overcome the drawbacks associated with the individual processes (production of a nanofiltration-concentrated retentate and formation of toxic by-products). 17β-Estradiol, 17α-ethinylestradiol, estrone, estriol, and progesterone were spiked into a real water sample collected after the sedimentation process of a drinking water treatment plant. Even though the nanofiltration process alone showed similar results to the combined treatment in terms of the water quality produced, the combined treatment offered advantage in terms of the load of the retentate and decrease in the endocrine-disrupting activity of the samples. Moreover, the photolysis by-products produced, with higher endocrine disrupting activity than the parent compounds, were effectively retained by the membrane. The combination of direct LP/UV photolysis with nanofiltration is promising for a drinking water utility that needs to cope with sudden punctual discharges or deterioration of the water quality and wants to decrease the levels of chemicals in the nanofiltration retentate.

Investigation of early molybdopterin biosynthetic intermediates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wuebbens, M.M.; Rajagopalan, K.V.

1991-03-11

Little information is available regarding the early steps in the biosynthetic pathway of molybdopterin (MPT). In order to explore these early reactions, and in particular to investigate the origin of the ring and side chain carbons of MPT, a metabolic approach employing the incorporation of {sup 14}C label was chosen. This method was facilitated by the recent purification and characterization of desulfomolybdopterin 2{prime},4{prime}-cyclic phosphate, the precursor which is converted directly to active molybdopterin in Escherichia coli by the addition of vicinal sulfurs to the side chain. This labile precursor readily oxidizes to Compound Z, a stable 6-alkyl pterin which retainsmore » all of the carbon atoms present in molybdopterin. Compound Z, rather than molybdopterin itself was chosen as the end product for labeling due to its overproduction in some MPT-deficient strains, as well as its stability and ease of purification. The authors report here the isolation of {sup 14}C-labelled Compound Z from E.coli chlN cells cultured in minimal media supplemented with U-{sup 14}C guanosine. Successive cleavage of the side chain carbons by permanganate treatment and UV light produced a decrease in the specific radioactivity of the resulting pterins. These data indicate that the early portion of the molybdopterin biosynthetic pathway may be similar to that of the bioactive pterins folate and biopterin, both of which are derived from guanosine triphosphate.« less

Photolysis of pure solid O{sub 3} and O{sub 2} films at 193 nm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raut, U.; Loeffler, M. J.; Fama, M.

2011-05-21

We studied quantitatively the photochemistry of solid O{sub 3} and O{sub 2} films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O{sub 3}, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O{sub 2} produced O{sub 3} in an amount that increased with photon fluence to a stationary level. For both O{sub 2} and O{sub 3} films, the O{sub 3}:O{sub 2} ratio at large fluences is {approx}0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed tomore » the increased photodissociation of O{sub 2} due to photoabsorption by O{sub 2} dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, {Phi}(O{sub 3}) = 0.24 {+-} 0.06, and quantum yields for destruction of O{sub 3} and O{sub 2} in their parent solids, {Phi}(-O{sub 3}) = 1.0 {+-} 0.2 and {Phi}(-O{sub 2}) = 0.36 {+-} 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 {+-} 0.1 for O{sub 3} fragments and 0.88 {+-} 0.03 for oxygen atoms from O{sub 2} dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O{sub 2} vs. O{sub 3} to be 0.1-0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.« less

Laser flash-photolysis and gas discharge in N2O-containing mixture: kinetic mechanism

NASA Astrophysics Data System (ADS)

Kosarev, Ilya; Popov, Nikolay; Starikovskaia, Svetlana; Starikovskiy, Andrey; mipt Team

2011-10-01

The paper is devoted to further experimental and theoretical analysis of ignition by ArF laser flash-photolysis and nanosecond discharge in N2O-containing mixture has been done. Additional experiments have been made to assure that laser emission is distributed uniformly throughout the cross-section. The series of experiments was proposed and carried out to check validity of O(1D) determination in experiments on plasma assisted ignition initiated by flash-photolysis. In these experiments, ozone density in the given mixture (mixture composition and kinetics has been preliminary analyzed) was measured using UV light absorption in Hartley band. Good coincidence between experimental data and results of calculations have been obtained Temporal behavior of energy input, electric field and electric current has been measured and analyzed. These data are considered as initial conditions for numerical modeling of the discharge in O2:N2O:H2:Ar = 0.3:1:3:5 mixture. Ion-molecular reactions and reactions of active species production in Ar:H2:O2:N2O mixture were analyzed. The set of reactions to describe chemical transformation in the system due to the discharge action has been selected.

The early faint sun paradox: organic shielding of ultraviolet-labile greenhouse gases

NASA Technical Reports Server (NTRS)

Sagan, C.; Chyba, C.

1997-01-01

Atmospheric mixing ratios of approximately 10(-5 +/- 1) for ammonia on the early Earth would have been sufficient, through the resulting greenhouse warming, to counteract the temperature effects of the faint early sun. One argument against such model atmospheres has been the short time scale for ammonia photodissociation by solar ultraviolet light. Here it is shown that ultraviolet absorption by steady-state amounts of high-altitude organic solids produced from methane photolysis may have shielded ammonia sufficiently that ammonia resupply rates were able to maintain surface temperatures above freezing.

Unexpected photoproduct generated via the acetone-sensitized photolysis of 5-bromo-2'-deoxyuridine in a water/isopropanol solution: experimental and computational studies.

PubMed

Polska, Katarzyna; Zielonka, Justyna; Chomicz, Lidia; Czerwicka, Małgorzata; Stepnowski, Piotr; Guzow, Katarzyna; Wiczk, Wiesław; Smużyńska, Maria; Kasprzykowski, Franciszek; Żylicz-Stachula, Agnieszka; Skowron, Piotr; Rak, Janusz

2010-12-23

The acetone-sensitized photolysis of 5-bromo-2'-deoxyuridine (5-BrdU) in a water/isopropanol solution with 300 nm photons leads to the formation of 2'-deoxyuridine (dU) and a comparable amount of another photoproduct that has not been reported in the literature so far. The negative and positive mass spectra recorded for this species indicate that they originate from the molecular mass of 286 Da, which corresponds to an adduct of 2'-deoxyuridine and 2-propanol. Quantum chemical calculations carried out at the DFT and TDDFT levels reveal both the structure and the UV spectrum of that adduct. The latter computational characteristic matches well the experimental UV spectrum of the new photoproduct. Our findings indicate that the acetone-sensitized photolysis of 5-BrdU is more complicated than has hitherto been assumed. Nevertheless, since electron transfer is one of the pathways responsible for 5-BrdU decay, acetone-sensitized photolysis of the halogen derivatives of nucleobases could be a convenient tool for studying their radiosensitivity in aqueous solutions.

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.; Chameides, W. L.; Crutzen, P. J.; Fishman, J.

1979-01-01

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Effect of Wildfire Aerosols on NO2 Photolysis and Ozone Production at the Mt. Bachelor Observatory

NASA Astrophysics Data System (ADS)

Baylon, P.; Jaffe, D. A.; Hall, S. R.; Ullmann, K.; Lefer, B. L.

2015-12-01

In this study, we have two goals: to quantify the effect of biomass burning aerosols on jNO2 photolysis and to look at O3 formation in biomass burning plumes as it relates to jNO2 photolysis. Wildfire plumes were observed during the summer of 2015 at the Mt. Bachelor Observatory, a high-elevation (2.8 km a.s.l.) mountaintop site located in central Oregon. These plumes were identified using the following criteria: (1) 5-minute ambient aerosol scattering σsp ≥ 20 Mm-1 for at least two hours, (2) 5-minute CO ≥ 150 ppbv for at least two hours, (3) strong correlation (r2 ≥ 0.70) between σsp and CO, and (4) consistent air mass back trajectories indicating transport over known fire locations. We measure nitrogen oxides using a chemiluminescence detector and jNO2 photolysis using a diode array actinic flux spectroradiometer. We also measure O3 using two techniques: (a) UV method with a cavity ring-down spectrometer and (b) chemiluminescence method with a custom-made instrument. We compare fire event observations between these two procedures to prove consistency. Based on these measurements, we quantify a lower bound for the HO2 and RO2 radical concentrations in wildfire plumes. We then look at plume and non-plume data and examine deviations from the photostationary state. Finally, we use the TUV model v5.2 to simulate clear-sky conditions and therefore quantify the reduction/enhancement in jNO2 values and O3 production due to wildfire aerosols. This gives us insight into the photochemical environment in biomass burning plumes, which until now, remains poorly understood.

Nitrate photolysis in salty snow

NASA Astrophysics Data System (ADS)

Donaldson, D. J.; Morenz, K.; Shi, Q.; Murphy, J. G.

2016-12-01

Nitrate photolysis from snow can have a significant impact on the oxidative capacity of the local atmosphere, but the factors affecting the release of gas phase products are not well understood. Here, we report the first systematic study of the amounts of NO, NO2, and total nitrogen oxides (NOy) emitted from illuminated snow samples as a function of both nitrate and total salt (NaCl and Instant Ocean) concentration. We show that the release of nitrogen oxides to the gas phase is directly related to the expected nitrate concentration in the brine at the surface of the snow crystals, increasing to a plateau value with increasing nitrate, and generally decreasing with increasing NaCl or Instant Ocean (I.O.). In frozen mixed nitrate (25 mM) - salt (0-500 mM) solutions, there is an increase in gas phase NO2 seen at low added salt amounts: NO2 production is enhanced by 35% at low prefreezing [NaCl] and by 70% at similar prefreezing [I.O.]. Raman microscopy of frozen nitrate-salt solutions shows evidence of stronger nitrate exclusion to the air interface in the presence of I.O. than with added NaCl. The enhancement in nitrogen oxides emission in the presence of salts may prove to be important to the atmospheric oxidative capacity in polar regions.

Early spatiotemporal-specific changes in intermediate signals are predictive of cytotoxic sensitivity to TNFα and co-treatments

NASA Astrophysics Data System (ADS)

Loo, Lit-Hsin; Bougen-Zhukov, Nicola Michelle; Tan, Wei-Ling Cecilia

2017-03-01

Signaling pathways can generate different cellular responses to the same cytotoxic agents. Current quantitative models for predicting these differential responses are usually based on large numbers of intracellular gene products or signals at different levels of signaling cascades. Here, we report a study to predict cellular sensitivity to tumor necrosis factor alpha (TNFα) using high-throughput cellular imaging and machine-learning methods. We measured and compared 1170 protein phosphorylation events in a panel of human lung cancer cell lines based on different signals, subcellular regions, and time points within one hour of TNFα treatment. We found that two spatiotemporal-specific changes in an intermediate signaling protein, p90 ribosomal S6 kinase (RSK), are sufficient to predict the TNFα sensitivity of these cell lines. Our models could also predict the combined effects of TNFα and other kinase inhibitors, many of which are not known to target RSK directly. Therefore, early spatiotemporal-specific changes in intermediate signals are sufficient to represent the complex cellular responses to these perturbations. Our study provides a general framework for the development of rapid, signaling-based cytotoxicity screens that may be used to predict cellular sensitivity to a cytotoxic agent, or identify co-treatments that may sensitize or desensitize cells to the agent.

Early spatiotemporal-specific changes in intermediate signals are predictive of cytotoxic sensitivity to TNFα and co-treatments

PubMed Central

Loo, Lit-Hsin; Bougen-Zhukov, Nicola Michelle; Tan, Wei-Ling Cecilia

2017-01-01

Signaling pathways can generate different cellular responses to the same cytotoxic agents. Current quantitative models for predicting these differential responses are usually based on large numbers of intracellular gene products or signals at different levels of signaling cascades. Here, we report a study to predict cellular sensitivity to tumor necrosis factor alpha (TNFα) using high-throughput cellular imaging and machine-learning methods. We measured and compared 1170 protein phosphorylation events in a panel of human lung cancer cell lines based on different signals, subcellular regions, and time points within one hour of TNFα treatment. We found that two spatiotemporal-specific changes in an intermediate signaling protein, p90 ribosomal S6 kinase (RSK), are sufficient to predict the TNFα sensitivity of these cell lines. Our models could also predict the combined effects of TNFα and other kinase inhibitors, many of which are not known to target RSK directly. Therefore, early spatiotemporal-specific changes in intermediate signals are sufficient to represent the complex cellular responses to these perturbations. Our study provides a general framework for the development of rapid, signaling-based cytotoxicity screens that may be used to predict cellular sensitivity to a cytotoxic agent, or identify co-treatments that may sensitize or desensitize cells to the agent. PMID:28272488

Photolysis of the organic UV filter, avobenzone, combined with octyl methoxycinnamate by nano-TiO2 composites.

PubMed

Kim, E J; Kim, M J; Im, N R; Park, S N

2015-08-01

A protection of the skin from harmful UV rays is important in preventing the skin damage and skin aging when exposed to sunlight. Titanium dioxide composites are used as a UV filter in sunscreen products combined with organic compounds such as butyl methoxydibenzoyl methane (avobenzone) and octyl methoxycinnamate (OMC) to improve the function of the sunscreen. In this study, the photolysis of avobenzone and OMC caused by the photocatalytic TiO2 nano composites (NCs) is investigated. Three different types of oil/water (O/W) sunscreen formulations containing avobenzone and OMC were prepared. Each formulation contained one of three different types of surface modified TiO2 NCs, which were WP-S (small sized hydrophilic TiO2NCs, ~10nm), OP-S (small sized hydrophobic TiO2NCs, ~15nm), and OP-L (large sized hydrophobic TiO2NCs, ~200nm). The physicochemical properties of the NCs were analyzed using biophysical tools. Addition of a different size of TiO2NCs into O/W sunscreen formulations significantly increased the photolysis of OMC. Effect of quercetin on degradation of avobenzone and OMC by the NCs was also studied for all three formulations. Although the OP-S NCs showed the lowest photocatalytic ability and the highest UV blocking capability, the NCs promoted the photolysis of OMC to the greatest extent. These results can be utilized to design more effective sunscreens, which could potentially ensure optimal photo-protection. Copyright © 2015 Elsevier B.V. All rights reserved.

Stabilizing effect of citrate buffer on the photolysis of riboflavin in aqueous solution

PubMed Central

Ahmad, Iqbal; Sheraz, Muhammad Ali; Ahmed, Sofia; Kazi, Sadia Hafeez; Mirza, Tania; Aminuddin, Mohammad

2011-01-01

In the present investigation the photolysis of riboflavin (RF) in the presence of citrate species at pH 4.0–7.0 has been studied. A specific multicomponent spectrophotometric method has been used to assay RF in the presence of photoproducts during the reactions. The overall first-order rate constants (kobs) for the photolysis of RF range from 0.42 to 1.08×10–2 min−1 in the region. The values of kobs have been found to decrease with an increase in citrate concentration indicating an inhibitory effect of these species on the rate of reaction. The second-order rate constants for the interaction of RF with total citrate species causing inhibition range from 1.79 to 5.65×10–3 M−1 min−1 at pH 4.0–7.0. The log k–pH profiles for the reactions at 0.2–1.0 M citrate concentration show a gradual decrease in kobs and the value at 1.0 M is more than half compared to that of k0, i.e., in the absence of buffer, at pH 5.0. Divalent citrate ions cause a decrease in RF fluorescence due to the quenching of the excited singlet state resulting in a decrease in the rate of reaction and consequently leading to the stabilization of RF solutions. The greater quenching of fluorescence at pH 4.0 compared to that of 7.0 is in accordance with the greater concentration of divalent citrate ions (99.6%) at that pH. The trivalent citrate ions exert a greater inhibitory effect on the rate of RF photolysis compared to that of the divalent citrate ions probably as a result of excited triplet state quenching. The values of second-order rate constants for the interaction of divalent and trivalent citrate ions are 0.44×10–2 and 1.06×10–3 M–1 min–1, respectively, indicating that the trivalent ions exert a greater stabilizing effect, compared to the divalent ions, on RF solutions. PMID:25755977

Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains

NASA Technical Reports Server (NTRS)

Ferris, J. P.

1986-01-01

With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species

UV absorption cross sections between 290 and 380 nm of a series of furanaldehydes: Estimation of their photolysis lifetimes

NASA Astrophysics Data System (ADS)

Colmenar, Inmaculada; González, Sergio; Jiménez, Elena; Martín, Pilar; Salgado, Sagrario; Cabañas, Beatriz; Albaladejo, José

2015-02-01

Furanaldehydes, such as 2-furanaldehyde (also known as furfural), 3-furanaldehyde and 5-methyl-2-furanaldehyde, are aromatic aldehydes which can be present in the atmosphere as primary and secondary pollutants. The atmospheric removal initiated by sunlight for these species is not well-known in the solar actinic region (at λ > 290 nm), mainly due to the absence of data concerning the UV absorption cross sections (σλ) and photolysis frequencies (Ji(z,θ)). In this work σλ for the mentioned furanaldehydes have been determined between 290 and 380 nm at room temperature for the first time. Experiments were performed in an absorption jacketed Pyrex cell, employing a deuterium lamp as irradiation source and a CCD detector. The obtained absorption spectra exhibit absorption maxima around 320 nm with absolute absorption cross sections of 1.13, 0.75 and 1.14 × 10-19 cm2 molecule-1 for 2-furanaldehyde, 3-furanaldehyde and 5-methyl-2-furanaldehyde, respectively. The reported UV absorption cross sections were used to provide estimates of Ji(z,θ) and, therefore, estimates of the lifetime (τhν) due to this atmospheric removal process, under different solar radiation situations. Estimated τhν have been compared with the lifetimes due to the homogeneous reaction with the main diurnal tropospheric oxidants. The results obtained suggest that photolysis in the actinic region can be the main degradation pathway for these furanaldehydes when assuming a quantum yield (Φλ) of unity and the maximum solar actinic flux, while photolysis can compete with the reaction of OH radicals when assuming Φλ = 0.1. On the contrary, the removal of all three furanaldehydes by the reactions with OH radicals becomes more important than the UV photolysis under low solar actinic flux conditions independently of Φλ. If the emission source of these furanaldehydes also occurs during the nighttime NO3 radicals will dominate the elimination process of these species.

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.

PubMed

DeWitt, H Langley; Hasenkopf, Christa A; Trainer, Melissa G; Farmer, Delphine K; Jimenez, Jose L; McKay, Christopher P; Toon, Owen B; Tolbert, Margaret A

2010-10-01

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

Hospital at home for chronic obstructive pulmonary disease: an integrated hospital and community based generic intermediate care service for prevention and early discharge.

PubMed

Davison, A G; Monaghan, M; Brown, D; Eraut, C D; O'Brien, A; Paul, K; Townsend, J; Elston, C; Ward, L; Steeples, S; Cubitt, L

2006-01-01

Recent randomized controlled studies have reported success for hospital at home for prevention and early discharge of chronic obstructive pulmonary disease (COPD) patients using hospital based respiratory nurse specialists. This observational study reports results using an integrated hospital and community based generic intermediate care service. The length of care, readmission within 60 days and death within 60 days in the early discharge (9.37 days, 21.1%, 7%) and the prevention of admission (five to six days, 34.1%, 3.8%) are similar to previous studies. We suggest that this generic community model of service may allow hospital at home services for COPD to be introduced in more areas.

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang Chunfan; Su Hongmei; Sun Xuezhong

2012-05-28

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing themore » photodissociation and depopulating the excited S{sub 2} or S{sub 3} state molecules to the lowest T{sub 1} state with a rate of {approx}2.5 ps after a delayed onset of {approx}3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T{sub 1} excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T{sub 1} excited state. The measured ultrafast formation of T{sub 1} excited state supports the existence of the surface intersections of S{sub 2}/S{sub 1}, S{sub 2}/T{sub 2}, and S{sub 1}/T{sub 1}/T{sub 2}, and the large T{sub 1} quantum yield of {approx}0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.« less

Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways.

PubMed

Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldan, Gloria; Rodriguez, Elena

2013-02-01

The photolysis of five frequent emerging contaminants (Benzotriazole, Chlorophene, N,N-diethyl-m-toluamide or DEET, Methylindole, and Nortriptyline HCl) was investigated in ultrapure water under monochromatic ultraviolet radiation at 254 nm and by a combination of UV and hydrogen peroxide. The results revealed that the photolysis rates followed first-order kinetics, with rate constant values depending on the nature of the specific compound, the pH, and the presence or absence of the scavenger tert-butanol. Quantum yields were also determined and values in the range of 53.8 × 10⁻³ - 9.4 × 10⁻³ mol E⁻¹ for Benzotriazole, 525 × 10⁻³ - 469 × 10⁻³ mol E⁻¹ for Chlorophene, 2.8 × 10⁻³ - 0.9 × 10⁻³ mol E⁻¹ for DEET, 108 × 10⁻³ - 165 × 10⁻³ mol E⁻¹ for Methylindole, and 13.8 × 10⁻³ - 15.0 × 10⁻³ mol E⁻¹ for Nortriptyline were obtained. The study also found that the UV/H₂O₂ process enhanced the oxidation rate in comparison to direct photolysis. High-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS) technique was applied to the concentrations evaluation and further identification of the parent compounds and their by-products, which allowed the proposal of the degradation pathways for each compound. Finally, in order to assess the aquatic toxicity in the photodegradation of these compounds, the Vibrio fischeri acute toxicity test was used, and the results indicated an initial increase of this parameter in all cases, followed by a decrease in the specific case of Benzotriazole, DEET, Methylindole, and Chlorophene. Copyright © 2012 Elsevier Ltd. All rights reserved.

Constraints on the photolysis and the equilibrium constant of ClO-dimer from airborne and balloon-borne measurements of chlorine compounds

NASA Astrophysics Data System (ADS)

Kleinboehl, A.; Canty, T. P.; Salawitch, R. J.; Khosravi, M.; Urban, J.; Toon, G. C.; Kuellmann, H.; Notholt, J.

2011-12-01

Significant differences exist between different laboratory measurements of the photolysis cross-sections of ClO-dimer, and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. This leads to uncertainties in the calculations of stratospheric ozone loss in the winter polar regions. One way to constrain the plausibility of these parameters is the measurement of ClO across the terminator in the activated polar vortex. Here we analyze measurements of ClO taken by the airborne submillimeter radiometer ASUR in the Arctic winter of 1999/2000. We use measured ClO at low solar zenith angles (SZA) to estimate the total active chlorine (ClOx). We estimate total available inorganic chlorine (Cly) using ASUR measurements of N2O in January 2000 and a N2O-Cly correlation established by a balloon measurement of the MarkIV interferometer in December 1999. We compare the ClOx estimates based on different photolysis rates of ClO-Dimer. Our results show that cross-sections leading to fast photolysis rates like the ones by Burkholder et al. [1990] or Papanastasiou et al. [2009] give ClOx mixing ratios that overlap with our estimated range of available Cly. Slower photolysis rates like the ones by von Hobe et al. [2009] and Pope et al. [2007] lead to ClOx values that are significantly higher than the available Cly. We use the calculated ClOx from low SZA to estimate the ClO in darkness with different equilibrium constants, and compare it with ASUR ClO measurements before sunrise (SZA > 95). We find that calculations with equilibrium constants published in the JPL evaluation of the last few years all give good agreement with observed ClO mixing ratios. The equilibrium constant estimated by von Hobe et al. [2005] yields ClO values that are higher than the ones observed.

Intermediates and the folding of proteins L and G

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Scott; Head-Gordon, Teresa

We use a minimalist protein model, in combination with a sequence design strategy, to determine differences in primary structure for proteins L and G that are responsible for the two proteins folding through distinctly different folding mechanisms. We find that the folding of proteins L and G are consistent with a nucleation-condensation mechanism, each of which is described as helix-assisted {beta}-1 and {beta}-2 hairpin formation, respectively. We determine that the model for protein G exhibits an early intermediate that precedes the rate-limiting barrier of folding and which draws together misaligned secondary structure elements that are stabilized by hydrophobic core contactsmore » involving the third {beta}-strand, and presages the later transition state in which the correct strand alignment of these same secondary structure elements is restored. Finally the validity of the targeted intermediate ensemble for protein G was analyzed by fitting the kinetic data to a two-step first order reversible reaction, proving that protein G folding involves an on-pathway early intermediate, and should be populated and therefore observable by experiment.« less

Intermediates and the folding of proteins L and G

PubMed Central

Brown, Scott; Head-Gordon, Teresa

2004-01-01

We use a minimalist protein model, in combination with a sequence design strategy, to determine differences in primary structure for proteins L and G, which are responsible for the two proteins folding through distinctly different folding mechanisms. We find that the folding of proteins L and G are consistent with a nucleation-condensation mechanism, each of which is described as helix-assisted β-1 and β-2 hairpin formation, respectively. We determine that the model for protein G exhibits an early intermediate that precedes the rate-limiting barrier of folding, and which draws together misaligned secondary structure elements that are stabilized by hydrophobic core contacts involving the third β-strand, and presages the later transition state in which the correct strand alignment of these same secondary structure elements is restored. Finally, the validity of the targeted intermediate ensemble for protein G was analyzed by fitting the kinetic data to a two-step first-order reversible reaction, proving that protein G folding involves an on-pathway early intermediate, and should be populated and therefore observable by experiment. PMID:15044729

Efficacy of UV-C photolysis of bisphenol A on transcriptome alterations of genes in zebrafish embryos.

PubMed

Saeed, Asma; Hashmi, Imran; Zare, Ava; Mehrabani-Zeinabad, Mitra; Achari, Gopal; Habibi, Hamid R

2016-09-18

The purpose of this study was to investigate the efficacy of UV-C direct photolysis of bisphenol A (BPA) as a remediation method of BPA contamination. We used zebrafish embryos as a model organism to test the toxicity and residual biological activity by measuring cytochrome P4501A1 (CYP1A), aromatase B (Aro B) and heat shock proteins (HSP-70) transcript levels. The mRNA levels of CYP1A gene increased about two fold while exposure of zebrafish embryos at 72 hpf resulted in significant induction (P = 0.048) of Aro B at 100 µg/L of BPA. Exposure of zebrafish embryos at 72 hpf to increasing concentrations of BPA resulted in significant induction (P = 0.0031) of HSP-70 transcript level. UV treatment of BPA resulted in a significant reduction in toxicity by reducing mortality of zebrafish embryos. The results suggest that UV-C direct photolysis may be an effective method for remediation of BPA contamination. Further studies will be necessary for better understanding of the identity and relative activity of the UV degradation by-products.

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction-Diffusion Approach.

PubMed

Dóka, Éva; Lente, Gábor

2017-04-13

This work presents a rigorous mathematical study of the effect of unavoidable inhomogeneities in laser flash photolysis experiments. There are two different kinds of inhomegenities: the first arises from diffusion, whereas the second one has geometric origins (the shapes of the excitation and detection light beams). Both of these are taken into account in our reported model, which gives rise to a set of reaction-diffusion type partial differential equations. These equations are solved by a specially developed finite volume method. As an example, the aqueous reaction between the sulfate ion radical and iodide ion is used, for which sufficiently detailed experimental data are available from an earlier publication. The results showed that diffusion itself is in general too slow to influence the kinetic curves on the usual time scales of laser flash photolysis experiments. However, the use of the absorbances measured (e.g., to calculate the molar absorption coefficients of transient species) requires very detailed mathematical consideration and full knowledge of the geometrical shapes of the excitation laser beam and the separate detection light beam. It is also noted that the usual pseudo-first-order approach to evaluating the kinetic traces can be used successfully even if the usual large excess condition is not rigorously met in the reaction cell locally.

Quantitative assessment on the contribution of direct photolysis and radical oxidation in photochemical degradation of 4-chlorophenol and oxytetracycline.

PubMed

Liu, Yiqing; He, Xuexiang; Fu, Yongsheng; Dionysiou, Dionysios D

2016-07-01

In UV-254 nm/H2O2 advanced oxidation process (AOP), the potential degradation pathways for organic pollutants include (1) hydrolysis, (2) direct H2O2 oxidation, (3) UV direct photolysis, and (4) hydroxyl radical (HO(•)) reaction. In this study, the contribution of these pathways was quantitatively assessed in the photochemical destruction of 4-chlorophenol (4-CP), demonstrating pathways (3) and (4) to be predominantly responsible for the removal of 4-CP by UV/H2O2 in 50 mM phosphate buffer solution. Increasing reaction pH could significantly enhance the contribution of direct photolysis in UV/H2O2 process. The contribution of HO(•) oxidation was improved with increasing initial H2O2 concentration probably due to the increased formation of HO(•). Presence of sodium carbonate (Na2CO3) as in UV/H2O2/Na2CO3 system promoted the degradation of 4-CP, with carbonate radical (CO3 (•-)) reaction and direct photolysis identified to be the main contributing pathways. The trends in the contribution of each factor were further evaluated and validated on the degradation of the antibiotic compound oxytetracycline (OTC). This study provides valuable information on the relative importance of different reaction pathways on the photochemical degradation of organic contaminants such as 4-CP and OTC in the presence and absence of a CO3 (•-) precursor.

Direct UV photolysis of selected pharmaceuticals, personal care products and endocrine disruptors in aqueous solution.

PubMed

Carlson, Jules C; Stefan, Mihaela I; Parnis, J Mark; Metcalfe, Chris D

2015-11-01

Pharmaceuticals and personal care products (PPCPs), and endocrine disrupting compounds (EDCs) are micropollutants of emerging concern that have been detected in the aquatic environment and in some cases, in drinking water at nanogram per liter levels. The goal of this study was to evaluate the removal of 15 model PPCPs and EDCs from water by direct UV photolysis, using either low (LP)-or medium (MP) -pressure mercury vapor arc lamps. Some of the model compounds are either weak bases or weak acids, and therefore, the pKa values were determined or confirmed for those compounds using spectrophotometric titrations. The molar absorption coefficients of ionized and non-ionized forms were also determined. The quantum yields at 253.7 nm in phosphate buffer solutions of pH 7.2 were determined to be 0.033 ± 0.004 for sulfamethoxazole, 0.0035 ± 0.0008 for sulfachloropyridazine, 0.006 ± 0.002 for acetaminophen, 0.34 ± 0.07 for triclosan, 0.35 ± 0.14 for estrone, 0.08 ± 0.05 for 17α-ethinylestradiol, 0.086 ± 0.012 for ibuprofen. The quantum yield for 4-n-nonylphenol photolysis at 253.7 nm varied with the initial concentration from 0.32 ± 0.08 at 23 μg/L to 0.092 ± 0.006 at 230 μg/L. The pseudo-first order rate constants determined for direct photolysis at 253.7 nm of the studied micropollutants followed the order: triclosan ≈ sulfamethoxazole > 4-n-nonylphenol ≈ sulfachloropyridazine ≈ estrone > acetaminophen ≈ 17α-ethinylestradiol ≈ ibuprofen. In contrast to the results observed for the monochromatic radiation (LP lamp), all 15 model compounds photolyzed under exposure to the broadband radiation emitted by the MP lamp. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of Direct and Indirect Photolysis in Imazosulfuron Photodegradation.

PubMed

Rering, Caitlin; Williams, Katryn; Hengel, Matt; Tjeerdema, Ronald

2017-04-19

Imazosulfuron, a sulfonylurea herbicide used in rice cultivation, has been shown to undergo photodegradation in water, but neither the photochemical mechanism nor the role of indirect photolysis is known. The purpose of this study was to investigate the underlying processes that operate on imazosulfuron during aqueous photodegradation. Our data indicate that in the presence of oxygen, most photochemical degradation proceeds through a direct singlet-excited state pathway, whereas triplet-excited state imazosulfuron enhanced decay rates under low dissolved oxygen conditions. Oxidation by hydroxyl radical and singlet oxygen were not significant. At dissolved organic matter (DOM) concentrations representative of rice field conditions, fulvic acid solutions exhibited faster degradation than rice field water containing both humic and fulvic acid fractions. Both enhancement, via reaction with triplet-state DOM, and inhibition, via competition for photons, of degradation was observed in DOM solutions.

The examination of berberine excited state by laser flash photolysis

NASA Astrophysics Data System (ADS)

Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

2009-07-01

The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

The role of direct photolysis and indirect photochemistry in the environmental fate of ethylhexyl methoxy cinnamate (EHMC) in surface waters.

PubMed

Vione, D; Calza, P; Galli, F; Fabbri, D; Santoro, V; Medana, C

2015-12-15

The aquatic environmental fate of ethylhexyl methoxy cinnamate (EHMC), one of the most used UVB filters worldwide, was studied by assessing its environmental persistence and photoinduced transformations. The role of direct and indirect photolysis was evaluated. Direct photolysis was shown to play a key role, and this process is expected to be the main attenuation route of EHMC in sunlit surface waters. In contrast, the reaction with OH radicals would be negligible and that with (3)CDOM* would at most be a secondary process. The measurement of the quantum yield of direct photolysis and of the rate constants of reaction with photogenerated transient species (or, sometimes, the use of reasonable values for the latter) allowed the prediction of the EHMC half-life time in surface waters, by means of a validated photochemical model. The predicted EHMC lifetime is of the order of hours to a few days in fair-weather summertime, and the main factors controlling the EHMC phototransformation in sunlit surface waters would be the water depth and the dissolved organic carbon (DOC) content. The formation of transformation products (TPs) was followed as well via HPLC/HRMS. Three TPs were detected in the samples exposed to UVA radiation, while one additional TP was detected in the samples exposed to UVB radiation. The detected TPs comprised 4-methoxybenzaldehyde, a hydroxylated derivative and dimeric species. Through the use of heterogeneous photocatalysis with TiO2, seven additional TPs were identified, most of them resulting from the further degradation of primary TPs formed through direct photolysis and that might be detected in aquatic systems as well. The photodegradation of EHMC in the presence of TiO2 yielded more toxic TPs than the parent compound (as determined with the Vibrio fischeri Microtox assay). The increased toxicity is partially accounted for by the formation of 4-methoxybenzaldehyde. Copyright © 2015 Elsevier B.V. All rights reserved.

High-O2, low-CO2 atmosphere on early Mars inferred from manganese oxide deposits

NASA Astrophysics Data System (ADS)

Sekine, Y.; Imanura, S.; Noda, N.; Takahashi, Y.; Uesugi, S.; Kurisu, M.; Hartmann, J.

2017-12-01

The atmospheric composition and its redox state are central to understanding of geochemical cycles, aqueous environment, and habitability on early Mars. Findings of manganese (Mn) oxide deposits together with some trace metals (e.g., Zn and Ni) by the Curiosity and Opportunity rovers suggest a more oxidizing surface environments on early Mars, possibly with higher amount of O2, than in the present day [Lanza et al., 2016; Arvidson et al., 2016; Hurowitz et al., 2017]. However, the abundance and formation mechanism of O2 have been poorly constrained. In the present study, we report results of laboratory experiments to constrain the redox state of the aqueous environment and atmospheric composition responsible for formation of the Mn oxides on early Mars. Our results of scavenging pattern of trace metals show that the Mn oxides found by the rovers are MnO2, which requires highly oxidizing water (Eh > 0.4 V at pH 7-8) and high atmospheric O2 (> a few mbar) for deposition. We suggest that a low-CO2 condition are also required to prevent formation of Mn carbonate in the aqueous environments. We suggest a low CO2/O2 atmosphere, e.g., CO2/O2 < 1, on early Mars at the time of deposition. This in turn implies that O2 would not have been derived mainly from CO2 photolysis and may require more effective paths (e.g., H2O photolysis and effective atmospheric escape) for producing O2 in the very early stage of Mars' history.

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

PubMed

Copeland, G; Lee, E P F; Williams, R G; Archibald, A T; Shallcross, D E; Dyke, J M

2014-01-01

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

Velocity measurement in rocket exhaust and general aerodynamic flows by photolysis of H2O and laser induced fluorescence of OH

NASA Technical Reports Server (NTRS)

Boedeker, Laurence R.

1992-01-01

A 'tagging' approach in which the photolysis of H2O by an excimer laser creates a zone of enhanced OH concentration, while a second, pulsed-UV laser detects tagged-zone convection via time-delayed excitation of OH fluorescence, depends on the photodissociation process and the kinetics of OH decay (relative to velocity). For application to the fuel-rich, high supersonic Mach number exhaust flow of the SSME, the detection of OH is being accomplished with either a pulsed narrowband UV dye laser or a tunable XeCl excimer laser for excitation of an OH 0-0 band transition, while the two-photon photolysis of H2O is conducted by focusing an injection-locked KrF excimer laser into the flow.

Predicting Reactive Intermediate Quantum Yields from Dissolved Organic Matter Photolysis Using Optical Properties and Antioxidant Capacity.

PubMed

Mckay, Garrett; Huang, Wenxi; Romera-Castillo, Cristina; Crouch, Jenna E; Rosario-Ortiz, Fernando L; Jaffé, Rudolf

2017-05-16

The antioxidant capacity and formation of photochemically produced reactive intermediates (RI) was studied for water samples collected from the Florida Everglades with different spatial (marsh versus estuarine) and temporal (wet versus dry season) characteristics. Measured RI included triplet excited states of dissolved organic matter ( 3 DOM*), singlet oxygen ( 1 O 2 ), and the hydroxyl radical ( • OH). Single and multiple linear regression modeling were performed using a broad range of extrinsic (to predict RI formation rates, R RI ) and intrinsic (to predict RI quantum yields, Φ RI ) parameters. Multiple linear regression models consistently led to better predictions of R RI and Φ RI for our data set but poor prediction of Φ RI for a previously published data set,1 probably because the predictors are intercorrelated (Pearson's r > 0.5). Single linear regression models were built with data compiled from previously published studies (n ≈ 120) in which E2:E3, S, and Φ RI values were measured, which revealed a high degree of similarity between RI-optical property relationships across DOM samples of diverse sources. This study reveals that • OH formation is, in general, decoupled from 3 DOM* and 1 O 2 formation, providing supporting evidence that 3 DOM* is not a • OH precursor. Finally, Φ RI for 1 O 2 and 3 DOM* correlated negatively with antioxidant activity (a surrogate for electron donating capacity) for the collected samples, which is consistent with intramolecular oxidation of DOM moieties by 3 DOM*.

Electron microscopic analysis of rotavirus assembly-replication intermediates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boudreaux, Crystal E.; Kelly, Deborah F.; McDonald, Sarah M., E-mail: mcdonaldsa@vtc.vt.edu

2015-03-15

Rotaviruses (RVs) replicate their segmented, double-stranded RNA genomes in tandem with early virion assembly. In this study, we sought to gain insight into the ultrastructure of RV assembly-replication intermediates (RIs) using transmission electron microscopy (EM). Specifically, we examined a replicase-competent, subcellular fraction that contains all known RV RIs. Three never-before-seen complexes were visualized in this fraction. Using in vitro reconstitution, we showed that ~15-nm doughnut-shaped proteins in strings were nonstructural protein 2 (NSP2) bound to viral RNA transcripts. Moreover, using immunoaffinity-capture EM, we revealed that ~20-nm pebble-shaped complexes contain the viral RNA polymerase (VP1) and RNA capping enzyme (VP3). Finally,more » using a gel purification method, we demonstrated that ~30–70-nm electron-dense, particle-shaped complexes represent replicase-competent core RIs, containing VP1, VP3, and NSP2 as well as capsid proteins VP2 and VP6. The results of this study raise new questions about the interactions among viral proteins and RNA during the concerted assembly–replicase process. - Highlights: • Rotaviruses replicate their genomes in tandem with early virion assembly. • Little is known about rotavirus assembly-replication intermediates. • Assembly-replication intermediates were imaged using electron microscopy.« less

Chemically Patterned Inverse Opal Created by a Selective Photolysis Modification Process.

PubMed

Tian, Tian; Gao, Ning; Gu, Chen; Li, Jian; Wang, Hui; Lan, Yue; Yin, Xianpeng; Li, Guangtao

2015-09-02

Anisotropic photonic crystal materials have long been pursued for their broad applications. A novel method for creating chemically patterned inverse opals is proposed here. The patterning technique is based on selective photolysis of a photolabile polymer together with postmodification on released amine groups. The patterning method allows regioselective modification within an inverse opal structure, taking advantage of selective chemical reaction. Moreover, combined with the unique signal self-reporting feature of the photonic crystal, the fabricated structure is capable of various applications, including gradient photonic bandgap and dynamic chemical patterns. The proposed method provides the ability to extend the structural and chemical complexity of the photonic crystal, as well as its potential applications.

Photolysis and cellular toxicities of the organic ultraviolet filter chemical octyl methoxycinnamate and its photoproducts.

PubMed

Stein, Hannah V; Berg, Courtney J; Maung, Jessica N; O'Connor, Lauren E; Pagano, Alexandra E; MacManus-Spencer, Laura A; Paulick, Margot G

2017-06-21

Organic ultraviolet filter chemicals (UVFCs) are the active ingredients used in many sunscreens to protect the skin from UV light; these chemicals have been detected in numerous aquatic environments leading to concerns about how they might affect aquatic organisms and humans. One commonly used organic UVFC is octyl methoxycinnamate (OMC), better known by its commercial name, octinoxate. Upon exposure to UV light, OMC degrades rapidly, forming numerous photoproducts, some of which have been previously identified. In this study, we isolated and completely characterized the major products of OMC photolysis, including the two major stable OMC cyclodimers. One of these cyclodimers is a δ-truxinate, resulting from a head-to-head dimerization of two OMC molecules, and the other cyclodimer is an α-truxillate, resulting from a head-to-tail dimerization of two OMC molecules. Additionally, the cellular toxicities of the individual photoproducts were determined; it was found that the parent UVFC, OMC, 4-methoxybenzaldehyde, and two cyclodimers are significantly toxic to cells. The photoproduct 2-ethylhexanol is not cytotoxic, demonstrating that different components of OMC photolysate contribute differently to its cellular toxicity. This study thus provides an enhanced understanding of OMC photolysis and gives toxicity data that can be used to better evaluate OMC as a sunscreen agent.

Bactericidal Effect of Photolysis of H2O2 in Combination with Sonolysis of Water via Hydroxyl Radical Generation.

PubMed

Sheng, Hong; Nakamura, Keisuke; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2015-01-01

The bactericidal effect of hydroxyl radical (·OH) generated by combination of photolysis of hydrogen peroxide (H2O2) and sonolysis of water was examined under the condition in which the yield of ·OH increased additively when H2O2 aqueous solution was concomitantly irradiated with laser and ultrasound. The suspension of Staphylococcus aureus mixed with the different concentrations of H2O2 was irradiated simultaneously with a laser light (wavelength: 405 nm, irradiance: 46 and 91 mW/cm2) and ultrasound (power: 30 w, frequency: 1.65 MHz) at 20 ± 1°C of the water bulk temperature for 2 min. The combination of laser and ultrasound irradiation significantly reduced the viable bacterial count in comparison with the laser irradiation of H2O2 alone. By contrast, the ultrasound irradiation alone exerted almost no bactericidal effect. These results suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity was synergistic. A multi-way analysis of variance also revealed that the interaction of H2O2 concentration, laser power and ultrasound irradiation significantly affected the bactericidal activity. Since the result of oxidative DNA damage evaluation demonstrated that the combination of laser and ultrasound irradiation significantly induced oxidative damage of bacterial DNA in comparison with the laser irradiation of H2O2 alone, it was suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity would be exerted via oxidative damage of cellular components such as DNA.

Photolysis of Mono- and Dichloramines in UV/Hydrogen Peroxide: Effects on 1,4-Dioxane Removal and Relevance in Water Reuse.

PubMed

Patton, Samuel; Romano, Mariano; Naddeo, Vincenzo; Ishida, Kenneth P; Liu, Haizhou

2018-06-05

Growing demands and increasing scarcity of fresh water resources necessitate potable water reuse, which has been implemented with the aid of UV-based advanced oxidation processes (UV/AOPs) that remove potentially hazardous trace organic contaminants from reclaimed water. During the potable reuse treatment process, chloramines are added to prevent membrane fouling that are carried over to the UV/AOP, where hydrogen peroxide (H 2 O 2 ) is commonly added. However, the impact of chloramines on the photolysis of H 2 O 2 and the overall performance of the UV/AOP remains unknown. This study investigated the impacts of the photochemistry of monochloramine (NH 2 Cl) and dichloramine (NHCl 2 ) associated with the photolysis of H 2 O 2 on the degradation of 1,4-dioxane (1,4-D), a trace organic contaminant ubiquitous in recycled water. Results indicated that NH 2 Cl and NHCl 2 alone functioned as oxidants upon UV photolysis, which produced HO • and Cl 2 •- as the two primary oxidative radicals. The speciation of chloramines did not have a significant impact on the degradation kinetics. The inclusion of monochloramine in UV/H 2 O 2 greatly decreased 1,4-D removal efficiency. HO • was the major radical in the mixed H 2 O 2 /chloramine system. Results from this study suggest that recognizing the existence of chloramines in UV/H 2 O 2 systems is important for predicting UV/AOP performance in the treatment train of potable reuse.

Topical treatment of oral cavity and wounded skin with a new disinfection system utilizing photolysis of hydrogen peroxide in rats.

PubMed

Yamada, Yasutomo; Mokudai, Takayuki; Nakamura, Keisuke; Hayashi, Eisei; Kawana, Yoshiko; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2012-01-01

The present study aimed to evaluate the acute locally injurious property of hydroxyl radical generation system by photolysis of H(2)O(2), which is a new disinfection system for the treatment of periodontitis developed in our laboratory. Firstly, generation of the hydroxyl radical by a test device utilizing the photolysis of H(2)O(2) was confirmed by applying an electron spin resonance (ESR)-spin trapping technique. Secondly, the bactericidal effect of the device was examined under a simulant condition in which Staphylococcus aureus suspended in 1 M H(2)O(2) was irradiated with laser light emitted from the test device, resulting in substantial reduction of the colony forming unit of the bacteria within a short time as 2 min. Finally, acute topical effect of the disinfection system on rat oral mucosa and wounded skin was evaluated by histological examination. No abnormal findings were observed in the buccal mucosal region treated three times with 1 M H(2)O(2) and irradiation. Similarly, no abnormal findings were observed during the healing of skin treated with 1 M H(2)O(2) and irradiation immediately after wounding. Since topical treatment with the novel disinfection technique utilizing the photolysis of H(2)O(2) had no detrimental effect on the oral mucosa and the healing of full thickness skin wounds in rats, it is expected that the acute locally injurious property of the disinfection technique is low.

The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

NASA Technical Reports Server (NTRS)

DeWitt, H. Langley; Hasenkopf, Christa A.; Trainer, Melissa G.; Farmer, Delphine K.; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

2010-01-01

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

Modelling the photochemical attenuation pathways of the fibrate drug gemfibrozil in surface waters.

PubMed

Fabbri, Debora; Maurino, Valter; Minella, Marco; Minero, Claudio; Vione, Davide

2017-03-01

Gemfibrozil (GFZ) is a relatively persistent pollutant in surface-water environments and it is rather recalcitrant to biological degradation. The GFZ photochemical lifetimes are relatively short in shallow waters with low levels of dissolved organic carbon (DOC), but they can reach the month-year range in deep and high-DOC waters. The main reason is that GFZ undergoes negligible reaction with singlet oxygen or degradation sensitised by the triplet states of chromophoric dissolved organic matter, which are the usually prevalent photochemical pathways in deep and high-DOC sunlit waters. Nitrate and nitrite scarcely affect the overall GFZ lifetimes, but they can shift photodegradation from direct photolysis to the OH process. These two pathways are the main GFZ phototransformation routes, with the direct photolysis prevailing in shallow environments during summer. Under these conditions the GFZ photochemical lifetimes are also shorter and the environmental significance of photodegradation correspondingly higher. The direct photolysis of GFZ under UVB irradiation yielded several transformation intermediates deriving from oxidation or cleavage of the aliphatic lateral chain. A quinone derivative (2,5-dimethyl-1,4-benzoquinone), a likely oxidation product of the transformation intermediate 2,5-dimethylphenol, is expected to be the most acutely and chronically toxic compound arising from GFZ direct photolysis. Interestingly, literature evidence suggests that the same toxic intermediate would be formed upon OH reaction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Assessing cloud radiative effects on tropospheric photolysis rates and key oxidants during aircraft campaigns using satellite cloud observations and a global chemical transport model

NASA Astrophysics Data System (ADS)

Zhang, B.; Liu, H.; Crawford, J. H.; Chen, G.; Voulgarakis, A.; Fairlie, T. D.; Duncan, B. N.; Ham, S. H.; Kato, S.; Payer Sulprizio, M.; Yantosca, R.

2017-12-01

Clouds affect tropospheric photochemistry through modifying solar radiation that determines photolysis rates. Observational and modeling studies have indicated that photolysis rates are enhanced above and in the upper portion of cloud layers and are reduced below optically thick clouds due to their dominant backscattering effect. However, large uncertainties exist in the representation of cloud spatiotemporal (especially vertical) distributions in global models, which makes understanding of cloud radiative effects on tropospheric chemistry challenging. Our previous study using a global 3-D chemical transport model (GEOS-Chem) driven by various meteorological data sets showed that the radiative effects of clouds on photochemistry are more sensitive to the differences in the vertical distribution of clouds than to those in the magnitude of column cloud optical depths. In this work, we evaluate monthly mean cloud optical properties and distributions in the MERRA-2 reanalysis with those in C3M, a 3-D cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We conduct tropospheric chemistry simulations for the periods of several aircraft campaigns, including ARCTAS (April, June-July, 2008), DC3 (May-June, 2012), and SEAC4RS (August-September, 2013) with GEOS-Chem driven by MERRA-2. We compare model simulations with and without constraints of cloud optical properties and distributions from C3M, and evaluate model photolysis rates (J[O1D] and J[NO2]) and key oxidants (e.g., OH and ozone) with aircraft profile measurements. We will assess whether the constraints provided by C3M improve model simulations of photolysis rates and oxidants as well as their variabilities.

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

NASA Technical Reports Server (NTRS)

Tyson, Daniel S.; Ilhan, Faysal; Meador, Mary Ann B.; Smith, Dee Dee; Scheiman, Daniel A.; Meador, Michael A.

2004-01-01

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

d-Amino acids in molecular evolution in space - Absolute asymmetric photolysis and synthesis of amino acids by circularly polarized light.

PubMed

Sugahara, Haruna; Meinert, Cornelia; Nahon, Laurent; Jones, Nykola C; Hoffmann, Søren V; Hamase, Kenji; Takano, Yoshinori; Meierhenrich, Uwe J

2018-07-01

Living organisms on the Earth almost exclusively use l-amino acids for the molecular architecture of proteins. The biological occurrence of d-amino acids is rare, although their functions in various organisms are being gradually understood. A possible explanation for the origin of biomolecular homochirality is the delivery of enantioenriched molecules via extraterrestrial bodies, such as asteroids and comets on early Earth. For the asymmetric formation of amino acids and their precursor molecules in interstellar environments, the interaction with circularly polarized photons is considered to have played a potential role in causing chiral asymmetry. In this review, we summarize recent progress in the investigation of chirality transfer from chiral photons to amino acids involving the two major processes of asymmetric photolysis and asymmetric synthesis. We will discuss analytical data on cometary and meteoritic amino acids and their potential impact delivery to the early Earth. The ongoing and future ambitious space missions, Hayabusa2, OSIRIS-REx, ExoMars 2020, and MMX, are scheduled to provide new insights into the chirality of extraterrestrial organic molecules and their potential relation to the terrestrial homochirality. This article is part of a Special Issue entitled: d-Amino acids: biology in the mirror, edited by Dr. Loredano Pollegioni, Dr. Jean-Pierre Mothet and Dr. Molla Gianluca. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed Central

2014-01-01

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

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

PubMed

Dobaradaran, Sina; Lutze, Holger; Mahvi, Amir Hossein; Schmidt, Torsten C

2014-01-08

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

{Mo96La8} eggshell ring and self-assembly to {Mo132} Keplerate through Mo-blue intermediate, involved in UV-photolysis of [Mo7O24](6-)/carboxylic acid system at pH 4.

PubMed

Yamase, Toshihiro; Kumagai, Shun; Prokop, Petra V; Ishikawa, Eri; Tomsa, Adrian-Raul

2010-10-18

The prolonged UV-photolysis of aqueous solutions containing [Mo(7)O(24)](6-) and C(2)H(5)CO(2)H (as electron donor) at pH 3.9-4.1 generates the carboxylate-coordinated {Mo(132)} Keplerate (1a) isolated as a formamidinium/ammonium-mixed salt, [HC(NH(2))(2)](26)(NH(4))(28)[Mo(V)(60)Mo(VI)(72)O(372)(H(2)O)(48)(C(2)H(5)CO(2))(36)((i)C(3)H(7)CO(2))(6)]·16H(2)O (1), through the Mo-blue intermediate (2). The coordination of 2 to La(3+) gives rise to the formation of the chain structure of the C(2)-symmetric {Mo(96)La(8)} eggshell rings, formulated by H(22)[Mo(V)(20)Mo(VI)(76)O(301)(H(2)O)(29){La(H(2)O)(6)}(2)]{La(H(2)O)(5)}(6)]·54.5H(2)O (3). The eggshell-ring geometry results from the insertion of [Mo(VI)(2)O(7)(H(2)O)](2-) (spacer) into the equator outer ring of the wheel-shaped Mo-blue, and 10 {(Mo(VI))(Mo(VI)(5))} pentagonal subunits alternately above and below the equator outer ring are connected by eight La(3+) and two {Mo(VI)(2)} linkers within two inner rings. The neighboring eggshell rings are linked through two Mo-O-Mo bonds formed by dehydrative condensation between the {Mo(VI)(2)} linkers to result in the chain structure. Together with the results of the elemental analysis and IR, electronic absorption, (13)C NMR, and ESI-MS spectra for 2, the ring profile analysis of 3 let us identify 2 with a carbolylate-coordinated Mo-blue ring of high nuclearity. The Mo(VI)→Mo(V) photoreductive change of 2 to the 60-electron reduced Keplerate in the presence of C(2)H(5)CO(2)H involves both degradation of the outer ring and splitting of the binuclear linkers, which leads to the formation of [(Mo(VI))Mo(VI)(5)O(21)(H(2)O)(4)(carboxylate)](7-) pentagonal subunits and [Mo(V)(2)O(4)(carboxylate)](+)/[Mo(V)O(2)(carboxylate)(1/2)](0.5+)-mixed linkers for 1.

Chloroplast precursor proteins compete to form early import intermediates in isolated pea chloroplasts.

PubMed

Row, P E; Gray, J C

2001-01-01

In order to ascertain whether there is one site for the import of precursor proteins into chloroplasts or whether different precursor proteins are imported via different import machineries, chloroplasts were incubated with large quantities of the precursor of the 33 kDa subunit of the oxygen-evolving complex (pOE33) or the precursor of the light-harvesting chlorophyll a/b-binding protein (pLHCP) and tested for their ability to import a wide range of other chloroplast precursor proteins. Both pOE33 and pLHCP competed for import into chloroplasts with precursors of the stromally-targeted small subunit of Rubisco (pSSu), ferredoxin NADP(+) reductase (pFNR) and porphobilinogen deaminase; the thylakoid membrane proteins LHCP and the Rieske iron-sulphur protein (pRieske protein); ferrochelatase and the gamma subunit of the ATP synthase (which are both associated with the thylakoid membrane); the thylakoid lumenal protein plastocyanin and the phosphate translocator, an integral membrane protein of the inner envelope. The concentrations of pOE33 or pLHCP required to cause half-maximal inhibition of import ranged between 0.2 and 4.9 microM. These results indicate that all of these proteins are imported into the chloroplast by a common import machinery. Incubation of chloroplasts with pOE33 inhibited the formation of early import intermediates of pSSu, pFNR and pRieske protein.

Nitrogen-Containing, Light-Absorbing Oligomers Produced in Aerosol Particles Exposed to Methylglyoxal, Photolysis, and Cloud Cycling.

PubMed

De Haan, David O; Tapavicza, Enrico; Riva, Matthieu; Cui, Tianqu; Surratt, Jason D; Smith, Adam C; Jordan, Mary-Caitlin; Nilakantan, Shiva; Almodovar, Marisol; Stewart, Tiffany N; de Loera, Alexia; De Haan, Audrey C; Cazaunau, Mathieu; Gratien, Aline; Pangui, Edouard; Doussin, Jean-François

2018-04-03

Aqueous methylglyoxal chemistry has often been implicated as an important source of oligomers in atmospheric aerosol. Here we report on chemical analysis of brown carbon aerosol particles collected from cloud cycling/photolysis chamber experiments, where gaseous methylglyoxal and methylamine interacted with glycine, ammonium, or methylammonium sulfate seed particles. Eighteen N-containing oligomers were identified in the particulate phase by liquid chromatography/diode array detection/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. Chemical formulas were determined and, for 6 major oligomer products, MS 2 fragmentation spectra were used to propose tentative structures and mechanisms. Electronic absorption spectra were calculated for six tentative product structures by an ab initio second order algebraic-diagrammatic-construction/density functional theory approach. For five structures, matching calculated and measured absorption spectra suggest that they are dominant light-absorbing species at their chromatographic retention times. Detected oligomers incorporated methylglyoxal and amines, as expected, but also pyruvic acid, hydroxyacetone, and significant quantities of acetaldehyde. The finding that ∼80% (by mass) of detected oligomers contained acetaldehyde, a methylglyoxal photolysis product, suggests that daytime methylglyoxal oligomer formation is dominated by radical addition mechanisms involving CH 3 CO*. These mechanisms are evidently responsible for enhanced browning observed during photolytic cloud events.

Tunable UV Laser Photolysis of NF2: Quantum Yield for NF(a1 delta) Production.

DTIC Science & Technology

1988-05-25

UV Laser Photolysis of NF2: Quantum Yield for NF(a A) Production ’v0 LR. F. HEIDNER, H . HELVAJIAN , 4and J. B. KOFFEND Aerophysics Laboratory...experiments, the chemistry of NF2 with various hydrocarbons has been studied. It has also been shown that the addition-elimination reaction between H and NF2...COMPLI R LEN SP, 3 ,HAND L BE AM~ H O [ I , , i 1 CAIHOC IAM COOLED GaAs CAPACITANCE PHOTOTUIBE MANOMETER _ LENS /’~ ~L + . ANMEE _.... BANDPASS FILTER

Combustion Processes Indoors: a Source of High OH Radical Concentrations Through the Photolysis of Hono

NASA Astrophysics Data System (ADS)

Bartolomei, V.; Gomez Alvarez, E.; Glor, M.; Gligorovski, S.; Temime-Roussel, B.; Quivet, E.; Strekowski, R.; Zetzsch, C.; Held, A. B.; Wortham, H.

2013-12-01

Hydroxyl radical (OH) is one of the most important oxidant species in the atmosphere controlling its self-oxidizing capacity. The main sources of OH radicals are photolysis of ozone and photolysis of nitrous acid (HONO), among the others. In the indoor air, the ozonolysis of alkenes has been suggested as the main OH formation pathway. The possibility for OH formation through photolytic pathways in the indoor environment has been, up to now, ignored (Gómez Alvarez et al., 2012). Models and indirect measurements to the present time predicted concentrations of OH radicals in the order of 104 -105 cm-3. Recently, by direct measurements we have detected high OH radical concentrations of 1.8 106 cm-3 in a classroom in Marseille and we demonstrated that its main source is the photolysis of HONO (Gómez Alvarez et al., 2013). The concentrations of HONO are quite high indoors, reaching levels in the order of a few tens of ppbV (Gómez Alvarez et al., 2013). This is mainly due to 1) direct combustion sources and 2) heterogeneous reactions of NO2 on the numerous surfaces present in the indoor environment. HONO levels of 30 ppb were measured in a previous campaign carried out in Bayreuth in July 2012 as direct emissions from the combustion of a candle. The combination between so high concentrations of HONO and higher than expected light transmissions indoors (or indoor artificial lighting) could have a significant impact on the OH concentrations indoors which could feasibly become considerably higher than we measured in our school campaign (Gomez Alvarez et al., 2013). In order to evaluate these upper limits under combustion conditions in the indoor environment, we have carried out a campaign in the LOTASC chamber (Bayreuth, Germany). For this aim, the exhaust fumes from the burning of a commonly used domestic candle have been introduced in the chamber. The chamber was irradiated under well research indoor lighting conditions. A thorough characterization of light intensities

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

PubMed

Shushakov, Anton A; Pozdnyakov, Ivan P; Grivin, Vjacheslav P; Plyusnin, Victor F; Vasilchenko, Danila B; Zadesenets, Andrei V; Melnikov, Alexei A; Chekalin, Sergey V; Glebov, Evgeni M

2017-07-25

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] and trans,trans,trans-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.

The Formation of Racemic Amino Acids by UV Photolysis of Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Small biologically relevant organic molecules including the amino acids glycine, alanine, and marine were formed in the laboratory by the UV (Ultraviolet) photolysis of realistic interstellar ice analogs, composed primarily of H2O, and including CH3OH, NH3, and HCN, under interstellar conditions. N-formyl glycine, cycloserine (4-amino-3-isoxazolidinone), and glycerol were detected before hydrolysis, and glycine, racemic alanine, racemic marine, glycerol, ethanolamine, and glyceric acid were found after hydrolysis. This suggests that some meteoritic amino acids (and other molecules) may be the direct result of interstellar ice photochemistry, expanding the current paradigm that they formed by reactions in liquid water on meteorite parent bodies.

[The advance in synthetic biology: towards a microbe-derived paclitaxel intermediates].

PubMed

Wang, Wei; Yang, Yan; Zheng, Xiao-Dong; Huang, Shu-Qiong; Guo, Lei; Kong, Jian-Qiang; Cheng, Ke-Di

2013-02-01

The synthetic biology matures to promote the heterologous biosynthesis of the well-known drug paclitaxel that is one of the most important and active chemotherapeutic agents for the first-line clinical treatment of cancer. This review focuses on the construction and regulation of the biosynthetic pathway of paclitaxel intermediates in both Escherichia coli and Saccharomyces cerevisiae. In particular, the review also features the early efforts to design and overproduce taxadiene and the bottleneck of scale fermentation for producing the intermediates.

Ablation of lens epithelial cells with a laser photolysis system: Histopathology, ultrastructure, and immunochemistry

PubMed Central

Mamalis, Nick; Grossniklaus, Hans E.; Waring, George O.; Werner, Liliana; Brubaker, Jacob; Davis, Don; Espandar, Ladan; Walker, Rudolf; Thyzel, Reinhardt

2010-01-01

PURPOSE To evaluate efficacy of a neodymium:YAG (Nd:YAG) laser photolysis system in removing lens epithelial cells (LECs) and characterize the effect of the laser on laminin and fibronectin involved in LEC adhesion and migration. METHODS Cadaver eyes were evaluated using the Miyake technique. The lenses were removed with phacoemulsification. The modified Nd:YAG laser was used to clean the LECs from the capsule. Only the fornix was cleaned in some eyes and the anterior subcapsular area in other eyes. Some areas were not treated and acted as controls. Standard irrigation/aspiration (I/A) removal of LECs was performed in additional eyes. The eyes were analyzed using light microscopy and immunohistochemical staining. RESULTS Histopathologic evaluation showed that the laser removed the LECs from the anterior lens capsule and from the fornix. Immunohistochemical staining showed fibronectin and laminin staining in the untreated areas that was absent in the treated areas. Standard I/A removal of the LECs showed absence of cells but persistent laminin and fibronectin. Electron microscopy showed epithelial cells in untreated areas with an absence of the LECs and debris in treated areas. CONCLUSIONS The laser photolysis system removed LECs from the anterior lens capsule and capsule fornix. Along with the cells, laminin, fibronectin, and cell debris remained in the untreated areas but were removed by the treatment. This treatment may be useful in preventing posterior capsule opacification. Financial Disclosure No author has a financial or proprietary interest in any material or method mentioned. Additional disclosures are found in the footnotes. PMID:20494774

Acquisition of a Nanosecond Laser Flash Photolysis Spectrometer to Enhance Understanding of Photochemistry and Reaction Kinetics in Undergraduate Research/Curriculum

DTIC Science & Technology

2016-03-31

photolysis # Compound # Compound 1 1,4-Dinitrobenzene 9 Azulene 2 1,2-Dinitrobenzene 10 4-Cyanophenol 3 Ferrocene 11 2-Nitrotoluene 4 4-Phenylphenol 12...Anthracene 4-Hydroxy-3-methoxybenzoic acid Cyclohexane Dithieno[3,2-b:2’,3’-d] thiophene Ferrocene Dimthylaniline Benzene 1,4- Diazabicyclo[2.2.2

FlashPhotol: Using a Flash Photolysis Apparatus Simulator to Introduce Students to the Kinetics of Transient Species and Fast Reactions

ERIC Educational Resources Information Center

Bigger, Stephen W.

2016-01-01

FlashPhotol is an educational software package that introduces students to the kinetics of transient species and fast reactions. This is achieved by means of a computer-simulated flash photolysis apparatus that comprises all major functional elements and that students can use to perform various experiments. The experimental interface presents a…

Carbon Stable Isotope Fractionation of Sulfamethoxazole during Biodegradation by Microbacterium sp. Strain BR1 and upon Direct Photolysis.

PubMed

Birkigt, Jan; Gilevska, Tetyana; Ricken, Benjamin; Richnow, Hans-Hermann; Vione, Davide; Corvini, Philippe F-X; Nijenhuis, Ivonne; Cichocka, Danuta

2015-05-19

Carbon isotope fractionation of sulfamethoxazole (SMX) during biodegradation by Microbacterium sp. strain BR1 (ipso-hydroxylation) and upon direct photolysis was investigated. Carbon isotope signatures (δ(13)C) of SMX were measured by LC-IRMS (liquid chromatography coupled to isotope ratio mass spectrometry). A new LC-IRMS method for the SMX metabolite, 3-amino-5-methylisoxazole (3A5MI), was established. Carbon isotope enrichment factors for SMX (ε(C)) were -0.6 ± 0.1‰ for biodegradation and -2.0 ± 0.1‰ and -3.0 ± 0.2‰ for direct photolysis, at pH 7.4 and pH 5, respectively. The corresponding apparent kinetic isotope effects (AKIE) for ipso-hydroxylation were 1.006 ± 0.001; these fall in the same range as AKIE in previously studied hydroxylation reactions. The differences in SMX and 3A5MI fractionation upon biotic and abiotic degradation suggest that compound specific stable isotope analysis (CSIA) is a suitable method to distinguish SMX reaction pathways. In addition, the study revealed that the extent of isotope fractionation during SMX photolytic cleavage is pH-dependent.

DEUTERIUM FRACTIONATION DURING AMINO ACID FORMATION BY PHOTOLYSIS OF INTERSTELLAR ICE ANALOGS CONTAINING DEUTERATED METHANOL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira

2016-08-10

Deuterium (D) atoms in interstellar deuterated methanol might be distributed into complex organic molecules through molecular evolution by photochemical reactions in interstellar grains. In this study, we use a state-of-the-art high-resolution mass spectrometer coupled with a high-performance liquid chromatography system to quantitatively analyze amino acids and their deuterated isotopologues formed by the photolysis of interstellar ice analogs containing singly deuterated methanol CH{sub 2}DOH at 10 K. Five amino acids (glycine, α -alanine, β -alanine, sarcosine, and serine) and their deuterated isotopologues whose D atoms are bound to carbon atoms are detected in organic residues formed by photolysis followed by warmingmore » up to room temperature. The abundances of singly deuterated amino acids are in the range of 0.3–1.1 relative to each nondeuterated counterpart, and the relative abundances of doubly and triply deuterated species decrease with an increasing number of D atoms in a molecule. The abundances of amino acids increase by a factor of more than five upon the hydrolysis of the organic residues, leading to decreases in the relative abundances of deuterated species for α -alanine and β -alanine. On the other hand, the relative abundances of the deuterated isotopologues of the other three amino acids did not decrease upon hydrolysis, indicating different formation mechanisms of these two groups upon hydrolysis. The present study facilitates both qualitative and quantitative evaluations of D fractionation during molecular evolution in the interstellar medium.« less

Theoretical Study of the Photolysis Mechanisms of Methylpentaphenyldimetallanes (Ph₃MM'Ph₂Me; M, M' = Si and Ge).

PubMed

Su, Shih-Hao; Su, Ming-Der

2018-06-04

The mechanisms of the photolysis reactions are studied theoretically at the M06-2X/6-311G(d) level of theory, using the four types of group 14 molecules that have the general structure, Ph₃M⁻M'Ph₂Me (M and M' = Si and Ge), as model systems. This study provides the first theoretical evidence for the mechanisms of these photorearrangements of compounds that contain a M⁻M' single bond. The model investigations indicate that the preferred reaction route for the photolysis reactions is, as follows: reactant → Franck-Condon (FC) region → minimum (triplet) → transition state (triplet) → triplet/singlet intersystem crossing → photoproducts (both di-radicals and singlets). The theoretical findings demonstrate that the formation of radicals results from reactions of the triplet states of these reactants. This could be because both the atomic radius and the chemical properties of silicon and germanium are quite similar to each other and compared to other group 14 elements, their photolytic mechanisms are nearly the same. The results for the photolytic mechanisms that are studied in this work are consistent with the available experimental observations and allow for a number of predictions for other group 14 dimetallane analogues to be made.

Photolysis of low concentration H2S under UV/VUV irradiation emitted from microwave discharge electrodeless lamps.

PubMed

Xia, Lan-Yan; Gu, Ding-Hong; Tan, Jing; Dong, Wen-Bo; Hou, Hui-Qi

2008-04-01

The photolysis of simulating low concentration of hydrogen sulfide malodorous gas was studied under UV irradiation emitted by self-made microwave discharge electrodeless lamps (i.e. microwave UV electrodeless mercury lamp (185/253.7 nm) and iodine lamp (178.3/180.1/183/184.4/187.6/206.2 nm)). Experiments results showed that the removal efficiency (eta H2S) of hydrogen sulfide was decreased with increasing initial H2S concentration and increased slightly with gas residence time; H2S removal efficiency was decreased dramatically with enlarged pipe diameter. Under the experimental conditions with pipe diameter of 36 mm, gas flow rate of 0.42 standard l s(-1), eta H2S was 52% with initial H2S concentration of 19.5 mg m(-3) by microwave mercury lamp, the absolute removal amount (ARA) was 4.30 microg s(-1), and energy yield (EY) was 77.3 mg kW h(-1); eta H2S was 56% with initial H2S concentration of 18.9 mg m(-3) by microwave iodine lamp, the ARA was 4.48 microg s(-1), and the EY was 80.5mg kW h(-1). The main photolysis product was confirmed to be SO4(2-) with IC.

Photophysical and photochemical effects of UV and VUV photo-oxidation and photolysis on PET and PEN

NASA Astrophysics Data System (ADS)

Morgan, Andrew

Polyethylene Terephthalate (PET) is a widely used polymer in the bottling, packaging, and clothing industry. In recent years an increasing global demand for PET has taken place due to the Solar Disinfection (SODIS) process. SODIS is a method of sterilizing fresh water into drinkable water. The PET bottles are used in the process to contain the water during solar irradiation due to its highly transparent optical property. Alongside PET, polyethylene 2,6-napthalate (PEN) is used in bottling and flexible electronic applications. The surface of PEN would need to be modified to control the hydrophilicity and the interaction it exudes as a substrate. The UV light absorption properties of PET and PEN are of great importance for many applications, and thus needs to be studied along with its photochemical resistance. The optical and chemical nature of PET was studied as it was treated by UV photo-oxidation, photo-ozonation, and photolysis under atmospheric pressure. Another investigation was also used to study PEN and PET as they are treated by vacuum UV (VUV) photo-oxidation, VUV photolysis, and remote oxygen reactions. The extent of the photoreactions' effect into the depth of the polymers is examined as treatment conditions are changed. The different experimental methods established the rate of several competing photoreactions on PET and PEN during irradiance, and their effect on the optical quality of the polymers.

Deglacial Ocean Circulation Scheme at Intermediate Depths in the Tropical North Atlantic

NASA Astrophysics Data System (ADS)

Xie, R. C.; Marcantonio, F.; Schmidt, M. W.

2014-12-01

In the modern Atlantic Ocean, intermediate water circulation is largely governed by the southward flowing upper North Atlantic Deep Water (NADW) and the northward return flow Antarctic Intermediate Water (AAIW). During the last deglaciation, it is commonly accepted that the southward flow Glacial North Atlantic Intermediate Water, the glacial analogue of NADW, contributed significantly to past variations in intermediate water circulation. However, to date, there is no common consensus of the role AAIW played during the last deglaciation, especially across abrupt climate events such as the Heinrich 1 and the Younger Dryas. This study aims to reconstruct intermediate northern- and southern-sourced water circulation in the tropical North Atlantic during the past 22 kyr and attempts to confine the boundary between AAIW and northern-sourced intermediate waters in the past. High-resolution Nd isotopic compositions (ɛNd thereafter) of fish debris and bulk sediment acid-reductive leachate from the Southern Caribbean (VM12-107; 1079 m) are inconsistent, again casting concerns, as already raised by recent studies, on the reliability of the leachate method in extracting seawater ɛNd signature. This urges the need to carefully verify the seawater ɛNd integrity in sediment acid-reductive leachate in various oceanic settings. Fish debris Nd isotope record in our study displays a two-step decreasing trend from the early deglaciation to early Holocene. We interpret this as recording a two-step deglacial recovery of the upper NADW, given the assumption on a more radiogenic glacial northern-sourced water is valid. Comparing with authigenic ɛNd records in the Florida Straits [1] and the Demarara Rise [2], our new fish debris ɛNd results suggest that, in the tropical western North Atlantic, glacial and deglacial AAIW never penetrated beyond the lower depth limit of modern AAIW. [1] Xie et al., GCA (140) 2014; [2] Huang et al., EPSL (389) 2014

Trepanation in South-Central Peru during the early late intermediate period (ca. AD 1000-1250).

PubMed

Kurin, Danielle S

2013-12-01

This study evaluates trepanations from five well-contextualized prehistoric sites in the south-central highlands of Andahuaylas, Peru. The emergence of trepanation in this region coincides with the collapse of the Wari Empire, ca. ad 1000. Thirty-two individuals from Andahuaylas, AMS radiocarbon dated to the early Late Intermediate Period (ca. ad 1000-1250), were found to have 45 total trepanations. Various surgical techniques were being employed concurrently throughout the region. Scraping trepanations evinced the highest survival rate; circular grooving, drilling and boring, and linear cutting were far less successful. Evidence of perioperative procedures like hair shaving, poultice application, and possible cranioplasty use aimed to ensure the survival of a trepanation recipient. Postmortem trepanations, also present in Andahuaylas, were likely executed on corpses as a means of better understanding cranial anatomy and improving techniques. Similarities in trepanation patterns throughout the region attest to common motivations to engage in surgery. Although moderate physical head trauma seems to be the impetus for intervention in many cases of trepanation, other motivations included physiological and possibly psychosomatic factors. Nevertheless, treatment was not for everyone. In Andahuaylas, trepanations were withheld from subadults, females, and those individuals who practiced cranial modification. Copyright © 2013 Wiley Periodicals, Inc.

Verification of RDX Photolysis Mechanism

DTIC Science & Technology

1999-11-01

which re-addition of HN02 was proposed to yield a hydroxydiazo intermediate that then decomposed to an alcohol . This sequence is shown for...various organic products such as alcohols , or undergo carbon- nitrogen (C-N) bond cleavage (Noller 1965). This reaction is sufficiently quanti...carbon-centered functional group such as the alcohol shown below, or C-N bond cleavage. 42 CERL TR 99/93 N02 N02 No2 ^Nv. N ’ ( ^| H2

Kinetic studies of the reaction between pesticides and hydroxyl radical generated by laser flash photolysis.

PubMed

Gozzi, Fábio; Oliveira, Silvio C; Dantas, Renato F; Silva, Volnir O; Quina, Frank H; Machulek, Amilcar

2016-03-30

Due to contamination of the environment by pesticides and their mishandling, there is the need for treatment of contaminated sites and correct disposal of materials containing them. Thus, studies with advanced oxidation processes are expanding and can determine the rate constant of the hydroxyl radical with organic compounds of great importance in environmental contamination. In this context, the use of laser flash photolysis has been shown to be viable for the determination of these constants. The reaction rate constants of different pesticides with HO(•) in degassed acetonitrile have been determined. They were 1.6 × 10(9)  M(-1)  s(-1), 0.6 × 10(9)  M(-1)  s(-1), 1.2 × 10(9)  M(-1)  s(-1), 2.4 × 10(9)  M(-1)  s(-1) and 2.2 × 10(9)  M(-1)  s(-1) for the pesticides carbaryl, propoxur, fenoxycarb, ethoxysulfuron and chlorimuron-ethyl, respectively. These values are about an order of magnitude smaller than the diffusion controlled rate and correlate with the relative rates of disappearance of the pesticides in the photo-Fenton reaction in water. The correlation of the relative rate constants determined by laser flash photolysis with the relative rates of photo-Fenton degradation of the pesticides is compelling evidence for the participation of the hydroxyl radical in the degradation of these pesticides in the latter system. © 2015 Society of Chemical Industry.

Association of 70-Gene Signature Assay Findings With Physicians' Treatment Guidance for Patients With Early Breast Cancer Classified as Intermediate Risk by the 21-Gene Assay.

PubMed

Tsai, Michaela; Lo, Shelly; Audeh, William; Qamar, Rubina; Budway, Raye; Levine, Ellis; Whitworth, Pat; Mavromatis, Blanche; Zon, Robin; Oldham, Dwight; Untch, Sarah; Treece, Tina; Blumencranz, Lisa; Soliman, Hatem

2018-01-11

Among patients who undergo the 21-gene assay (21-GA), 39% to 67% receive an intermediate risk result and may receive ambiguous treatment guidance. The 70-gene signature assay (70-GS) may be associated with physicians' treatment decisions in this population with early breast cancer. To determine whether 70-GS findings are associated with physicians' decisions about adjuvant treatment and confidence in their recommendations and to evaluate the dichotomous (high- vs low-risk) and continuous distribution of 70-GS indices among this group of patients with intermediate risk. The Prospective Study of MammaPrint in Breast Cancer Patients With an Intermediate Recurrence Score (PROMIS trial) was an impact study conducted from May 20, 2012, through December 31, 2015, that enrolled 840 patients with early-stage breast cancer and a 21-gene assay recurrence score of 18 to 30. Patients were treated in 58 US institutions. The 70-GS result was given to physicians before adjuvant treatment. Change in physician treatment decision before vs after receiving the 70-GS result. With a treatment change of greater than 20%, the odds ratio (OR) was applied. Among the 840 patients who underwent 70-GS classification (mean age, 59 years; range, 27-93 years), 374 (44.5%) had a low-risk and 466 (55.5%) had a high-risk result. The distribution of 70-GS indices did not correlate with recurrence score within the 21-GA intermediate range, with 70-GS low- and high-risk patients observed at every recurrence score. A significant change in adjuvant treatment was associated with receiving the 70-GS classifications with an OR of 0.64 (95% CI, 0.50-0.82; McNemar test, P < .001) for all patients. Among the low-risk patients, 108 of 374 (28.9%) had chemotherapy removed from their treatment recommendation; among the high-risk patients, 171 of 466 (36.7%) had chemotherapy added. Results of the 70-GS were associated with the physician's adjuvant treatment recommendation; 409 high-risk patients (87.8%) were

UV Photolysis of Chloramine and Persulfate for 1,4-Dioxane Removal in Reverse-Osmosis Permeate for Potable Water Reuse.

PubMed

Li, Wei; Patton, Samuel; Gleason, Jamie M; Mezyk, Stephen P; Ishida, Kenneth P; Liu, Haizhou

2018-06-05

A sequential combination of membrane treatment and UV-based advanced oxidation processes (UV/AOP) has become the industry standard for potable water reuse. Chloramines are used as membrane antifouling agents and therefore carried over into the UV/AOP. In addition, persulfate (S 2 O 8 2- ) is an emerging oxidant that can be added into a UV/AOP, thus creating radicals generated from both chloramines and persulfate for water treatment. This study investigated the simultaneous photolysis of S 2 O 8 2- and monochloramine (NH 2 Cl) on the removal of 1,4-dioxane (1,4-D) for potable-water reuse. The dual oxidant effects of NH 2 Cl and S 2 O 8 2- on 1,4-D degradation were examined at various levels of oxidant dosage, chloride, and solution pH. Results showed that a NH 2 Cl-to-S 2 O 8 2- molar ratio of 0.1 was optimal, beyond which the scavenging by NH 2 Cl of HO • , SO 4 •- , and Cl 2 •- radicals decreased the 1,4-D degradation rate. At the optimal ratio, the degradation rate of 1,4-D increased linearly with the total oxidant dose up to 6 mM. The combined photolysis of NH 2 Cl and S 2 O 8 2- was sensitive to the solution pH due to a disproportionation of NH 2 Cl at pH lower than 6 into less-photoreactive dichloramine (NHCl 2 ) and radical scavenging by NH 4 + . The presence of chloride transformed HO • and SO 4 •- to Cl 2 •- that is less-reactive with 1,4-D, while the presence of dissolved O 2 promoted gaseous nitrogen production. Results from this study suggest that the presence of chloramines can be beneficial to persulfate photolysis in the removal of 1,4-D; however, the treatment efficiency depends on a careful control of an optimal NH 2 Cl dosage and a minimal chloride residue.

Capturing the radical ion-pair intermediate in DNA guanine oxidation

PubMed Central

Jie, Jialong; Liu, Kunhui; Wu, Lidan; Zhao, Hongmei; Song, Di; Su, Hongmei

2017-01-01

Although the radical ion pair has been frequently invoked as a key intermediate in DNA oxidative damage reactions and photoinduced electron transfer processes, the unambiguous detection and characterization of this species remain formidable and unresolved due to its extremely unstable nature and low concentration. We use the strategy that, at cryogenic temperatures, the transient species could be sufficiently stabilized to be detectable spectroscopically. By coupling the two techniques (the cryogenic stabilization and the time-resolved laser flash photolysis spectroscopy) together, we are able to capture the ion-pair transient G+•⋯Cl− in the chlorine radical–initiated DNA guanine (G) oxidation reaction, and provide direct evidence to ascertain the intricate type of addition/charge separation mechanism underlying guanine oxidation. The unique spectral signature of the radical ion-pair G+•⋯Cl− is identified, revealing a markedly intense absorption feature peaking at 570 nm that is distinctive from G+• alone. Moreover, the ion-pair spectrum is found to be highly sensitive to the protonation equilibria within guanine-cytosine base pair (G:C), which splits into two resolved bands at 480 and 610 nm as the acidic proton transfers along the central hydrogen bond from G+• to C. We thus use this exquisite sensitivity to track the intrabase-pair proton transfer dynamics in the double-stranded DNA oligonucleotides, which is of critical importance for the description of the proton-coupled charge transfer mechanisms in DNA. PMID:28630924

Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign

NASA Technical Reports Server (NTRS)

Lloyd, Steven A.; Swartz, William H.

2001-01-01

The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the MSX/UVISI satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.

Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign

NASA Technical Reports Server (NTRS)

Lloyd, Steven A.; Swartz, William H.

2001-01-01

The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the Midcourse Space Experiment(MSX)/Ultraviolet and Visible Imagers and Spectrographic Imagers (UVISI) satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.

Laser photolysis of DPNI-GABA, a tool for investigating the properties and distribution of GABA receptors and for silencing neurons in situ.

PubMed

Trigo, Federico F; Papageorgiou, George; Corrie, John E T; Ogden, David

2009-07-30

Laser photolysis to release GABA at precisely defined times and locations permits investigation of the distribution of functional GABA(A) receptors in neuronal compartments, the activation kinetics and pharmacology of GABA(A) receptors in situ, and the role of individual neurons in neural circuits by selective silencing with low GABA concentrations. We describe the experimental evaluation and applications of a new nitroindoline-caged GABA, DPNI-GABA, modified to minimize the pharmacological interference commonly found with caged GABA reagents, but retaining the advantages of nitroindoline cages. Unlike the 5-methoxycarbonylmethyl-7-nitroindolinyl-GABA tested previously, DPNI-GABA inhibited GABA(A) receptors with much lower affinity, reducing peak GABA-evoked responses with an IC(50) of approximately 0.5 mM. Most importantly, the kinetics of receptor activation, determined as 10-90% rise-times, were comparable to synaptic events and were little affected by DPNI-GABA present at 1mM concentration, permitting photolysis of DPNI-GABA to mimic synaptic activation of GABA(A) receptors. With a laser spot of 1 microm applied to cerebellar molecular layer interneurons, the spatial resolution of uncaging DPNI-GABA in dendrites was estimated as 2 microm laterally and 7.5 microm focally. Finally, at low DPNI-GABA concentration, photorelease restricted to the area of the soma suppressed spiking in single Purkinje neurons or molecular layer interneurons for periods controlled by the flash intensity and duration. DPNI-GABA has properties better adapted for fast kinetic studies with laser photolysis at GABA(A) receptors than previously reported caged GABA reagents, and can be used in experiments where spatial resolution is determined by the dimensions of the laser light spot.

Intermediate treatments

Treesearch

John R. Jones; Wayne D. Shepperd

1985-01-01

Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

Laser photolysis study of the exciplex between triplet benzil and triethylamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Encinas, M.V.; Scaiano, J.C.

1979-12-19

Nanosecond laser flash photolysis techniques have been used to examine the triplet decay and radical-ion formation in the triethylamine (TEA) - benzil system in wet acetonitrile. Under conditions of high TEA concentrations yielding short triplet lifetime, the formation of the benzil radical anion was found to be considerably slower than the decay of the triplet state. This effect is attributed to the intermediacy of a relatively stable exciplex whose properties are reported here. Results of a study of optical density of the system with time following laser excitation led to the assignment of a lifetime of 55ns to the exciplexmore » formed between the triplet benzil and TEA. A structure is suggested for the exciplex. Results of experiments with the non-polar medium n-heptane indicated a shorter lifetime exciplex or one with very different properties from the species identified in the polar medium, wet acetonitrile. (BLM)« less

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

2002-01-01

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Degradation of 4-chloro 2-aminophenol using a novel combined process based on hydrodynamic cavitation, UV photolysis and ozone.

PubMed

Barik, Arati J; Gogate, Parag R

2016-05-01

The degradation of 4-chloro 2-aminophenol (4C2AP), an acute toxic organic compound, has been studied using different approaches based on the hydrodynamic cavitation (HC) with orifice plate as cavitating device, photolysis (UV) and ozonation (O3). The dependency of extent of degradation on operating parameters like operating pressure (2-5 bar), initial pH (3-8) and temperature (30-38 °C) have been established initially to maximize the efficacy of hydrodynamic cavitation. Subsequently the degradation has been studied using combined treatment strategies as HC+UV, HC+O3, UV+O3 and HC+UV+O3 at the established optimum parameters of operating temperature as 30 °C, initial pH of 6 and inlet pressure of 4 bar. The maximum extent of degradation as 96.85% and 73.6% reduction in TOC has been obtained using hydrodynamic cavitation in combination with UV photolysis and ozonation under the optimized operating conditions. The degradation products of 4C2AP have been identified using GC-MS. The present work has clearly established the efficacy of combined treatment approach (HC+UV+O3) for the removal of organic pollutant for the first time. Copyright © 2015 Elsevier B.V. All rights reserved.

Organic haze on Titan and the early Earth

PubMed Central

Trainer, Melissa G.; Pavlov, Alexander A.; DeWitt, H. Langley; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

2006-01-01

Recent exploration by the Cassini/Huygens mission has stimulated a great deal of interest in Saturn's moon, Titan. One of Titan's most captivating features is the thick organic haze layer surrounding the moon, believed to be formed from photochemistry high in the CH4/N2 atmosphere. It has been suggested that a similar haze layer may have formed on the early Earth. Here we report laboratory experiments that demonstrate the properties of haze likely to form through photochemistry on Titan and early Earth. We have used a deuterium lamp to initiate particle production in these simulated atmospheres from UV photolysis. Using a unique analysis technique, the aerosol mass spectrometer, we have studied the chemical composition, size, and shape of the particles produced as a function of initial trace gas composition. Our results show that the aerosols produced in the laboratory can serve as analogs for the observed haze in Titan's atmosphere. Experiments performed under possible conditions for early Earth suggest a significant optical depth of haze may have dominated the early Earth's atmosphere. Aerosol size measurements are presented, and implications for the haze layer properties are discussed. We estimate that aerosol production on the early Earth may have been on the order of 1014 g·year−1 and thus could have served as a primary source of organic material to the surface. PMID:17101962

Characterization of reaction intermediate aggregates in aniline oxidative polymerization at low proton concentration.

PubMed

Ding, Zhongfen; Sanchez, Timothy; Labouriau, Andrea; Iyer, Srinivas; Larson, Toti; Currier, Robert; Zhao, Yusheng; Yang, Dali

2010-08-19

Aggregates of reaction intermediates form during the early stages of aniline oxidative polymerization whenever the initial mole ratio of proton concentration to aniline monomer concentration is low ([H(+)](0)/[An](0) intermediate aggregates show a UV-Vis absorption peak at around 410 nm when dispersed in aqueous solution, whereas the peak is centered on 370 nm when dissolved in an organic solvent such as N-methylpyrrolidone. The electronic band gap decreases when the intermediates aggregate to form a solid, and thus, the absorption peak is red-shifted. Gel permeation chromatography (GPC) shows the aggregates contain a major low molecular weight peak with a long tail. The oligoanilines with low molecular weights consistently show a UV-Vis absorption peak at around 370 nm. Mass spectrometry confirms that the intermediate aggregates contain mainly a component with mass number 363 (M + H(+)), likely a tetramer. UV-Vis, GPC, mass spectrometry, NMR, FTIR, and XRD characterization results are presented and chemical structures for the tetramer are proposed. The major components of the intermediate aggregates are likely highly symmetric phenazine- and dihydrophenazine-containing structures. These particular organic compounds have not been identified before as intermediates. The aggregation and precipitation of the tetramers apparently stabilizes these intermediates. The aggregates are highly crystalline, as evidenced by powder X-ray diffraction. A new reaction mechanism for the formation of these intermediates is proposed.

Was early Mars warmed by ammonia?

NASA Technical Reports Server (NTRS)

Kasting, J. F.; Brown, L. L.; Acord, J. M.; Pollack, J. B.

1992-01-01

Runoff channels and valley networks present on ancient, heavily cratered Martian terrain suggests that the climate of Mars was originally warm and wet. One explanation for the formation of these channels is that the surface was warmed by the greenhouse effect of a dense, CO2 atmosphere. However, recent work shows that this theory is not consistent for the early period of the solar system. One way to increase the surface temperature predicted is to assume that other greenhouse gases were present in Mars' atmosphere in addition to CO2 and H2O. This possible gas is ammonia, NH3. If ammonia was present in sufficient quantities, it could have raised the surface temperature to 273 K. An adequate source would have been volcanic outgassing if the NH3 produced was shielded from photolysis by an ultraviolet light absorber.

Photo-fenton degradation of diclofenac: identification of main intermediates and degradation pathway.

PubMed

Pérez-Estrada, Leónidas A; Malato, Sixto; Gernjak, Wolfgang; Agüera, Ana; Thurman, E Michael; Ferrer, Imma; Fernández-Alba, Amadeo R

2005-11-01

In recent years, the presence of pharmaceuticals in the aquatic environment has been of growing interest. These new contaminants are important because many of them are not degraded under the typical biological treatments applied in the wastewater treatment plants and represent a continuous input into the environment. Thus, compounds such as diclofenac are present in surface waters in all Europe and a crucial need for more enhanced technologies that can reduce its presence in the environment has become evident. In this sense, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous nonbiodegradable pollutants. This work deals with the solar photodegradation of diclofenac, an antiinflammatory drug, in aqueous solutions by photo-Fenton reaction. A pilot-scale facility using a compound parabolic collector (CPC) reactor was used for this study. Results obtained show rapid and complete oxidation of diclofenac after 60 min, and total mineralization (disappearance of dissolved organic carbon, DOC) after 100 min of exposure to sunlight. Although diclofenac precipitates during the process at low pH, its degradation takes place in the homogeneous phase governed by a precipitation-redissolution-degradation process. Establishment of the reaction pathway was made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Gas chromatography-mass spectrometry (GC/ MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) were used to identify 18 intermediates, in two tentative degradation routes. The main one was based on the initial hydroxylation of the phenylacetic acid moiety in the C-4 position and subsequent formation of a quinone imine derivative that was the starting point for further multistep degradation involving hydroxylation, decarboxylation, and oxidation reactions. An alternative route was based on the transient preservation of the biphenyl amino moiety

Intermediate-mass Black Holes and Dark Matter at the Galactic Center

NASA Astrophysics Data System (ADS)

Lacroix, Thomas; Silk, Joseph

2018-01-01

Could there be a large population of intermediate-mass black holes (IMBHs) formed in the early universe? Whether primordial or formed in Population III, these are likely to be very subdominant compared to the dark matter density, but could seed early dwarf galaxy/globular cluster and supermassive black hole formation. Via survival of dark matter density spikes, we show here that a centrally concentrated relic population of IMBHs, along with ambient dark matter, could account for the Fermi gamma-ray “excess” in the Galactic center because of dark matter particle annihilations.

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

NASA Technical Reports Server (NTRS)

Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

2002-01-01

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

Photodegradation of gallic acid under UV irradiation: insights regarding the pH effect on direct photolysis and the ROS oxidation-sensitized process of DOM.

PubMed

Du, Yingxun; Chen, Hui; Zhang, Yuanyuan; Chang, Yuguang

2014-03-01

In this study, the degradation of gallic acid (GA), a model compound for dissolved organic matter (DOM) in controlled UV/N2, UV/air, UV/Fe(3+)/N2, and UV/Fe(3+)/air systems was investigated to elucidate the contribution of direct photolysis and reactive oxygen species (ROS) oxidation to GA degradation at various pH values. In general, the order of the degradation rate of GA in these four systems was as follows: UV/Fe(3+)/air>UV/air>UV/Fe(3+)/N2≈UV/N2. In the UV/N2 system, GA underwent slow direct photolysis, the rate of which decreased with decreasing pH. In the UV/Fe(3+)/air system, the most rapid GA degradation was achieved at pH 5. ROS are mainly derived from two sources. The first source is attributed to the role of DO and the other is attributed to the interaction of Fe(3+) and DO. The contribution of ROS to GA oxidation is much greater (>71%) than that of direct photolysis (<29%) at each pH value and is most obvious at pH 5. H2O2 formation was detected during GA degradation in the UV/air and UV/Fe(3+)/air systems. Using ROS scavengers, it was found that oxidation by OH was the main mechanism of GA degradation in the UV/Fe(3+)/air system. Based on the experimental results, a mechanism for GA degradation and ROS formation involving the effect of pH was proposed. This study furthers our understanding of changes in DOM degradation mechanisms due to global acidification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Force, Michael; Briggs, Robert G.; Ferris, James P.; Persans, Peter; Chera, John J.

2008-01-01

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the C tbnd N frequency at 2210 cm -1 in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3

DOE PAGES

Prather, M. J.

2015-05-27

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observed statistics for the vertical correlation of cloud layers, Cloud-J 7.3 provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations represented by four quadrature atmospheres produces mean J values in an atmospheric column with root-mean-square errors of 4% or less compared with 10–20% errors using simpler approximations.more » Cloud-J is practical for chemistry-climate models, requiring only an average of 2.8 Fast-J calls per atmosphere, vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections is also incorporated into Cloud-J.« less

Synthesis and Photolysis of Model Compounds for Mechanistic Studies of 1,3,5-Trinitro-1,3,5-Triazacyclohexane (RDX) Decomposition.

DTIC Science & Technology

1978-06-01

However, once irradiation was stopped the radical disappeared within a half hour . When the temperature was Increased to 40 °C the radical existed...and Russat proposed that the mechanism is bimolecular with the products OK - . ‘ being the nitrone and hydroxy l amine. Experimenta l support for this...process was provided by K. U. Ingold 15 . Kaminsky and Lamchen 16 and ethers have shown that the photolysis of cyclic nitrones gives oxi- ziridines

Magnetic Field Effect: An Efficient Tool To Investigate The Mechanism Of Reactions Using Laser Flash Photolysis Technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basu, Samita; Bose, Adity; Dey, Debarati

2008-04-24

Magnetic field effect combined with laser flash photolysis technique have been used to study the mechanism of interactions between two drug-like quinone molecules, Menadione (1,4-naphthoquinone, MQ) and 9, 10 Anthraquinone (AQ) with one of the DNA bases, Adenine in homogeneous acetonitrile/water and heterogeneous micellar media. A switchover in reaction mode from electron transfer to hydrogen abstraction is observed with MQ on changing the solvent from acetonitrile/water to micelle; whereas, AQ retains its mode of interaction towards Adenine as electron transfer in both the media due to its bulky structure compared to MQ.

Magnetic Field Effect: An Efficient Tool To Investigate The Mechanism Of Reactions Using Laser Flash Photolysis Technique

NASA Astrophysics Data System (ADS)

Basu, Samita; Bose, Adity; Dey, Debarati

2008-04-01

Magnetic field effect combined with laser flash photolysis technique have been used to study the mechanism of interactions between two drug-like quinone molecules, Menadione (1,4-naphthoquinone, MQ) and 9, 10 Anthraquinone (AQ) with one of the DNA bases, Adenine in homogeneous acetonitrile/water and heterogeneous micellar media. A switchover in reaction mode from electron transfer to hydrogen abstraction is observed with MQ on changing the solvent from acetonitrile/water to micelle; whereas, AQ retains its mode of interaction towards Adenine as electron transfer in both the media due to its bulky structure compared to MQ.

A rare case of os odontoideum from an Early Intermediate period tomb at the Huacas de Moche, Peru.

PubMed

Titelbaum, A R; Castillo, S Uceda

2015-12-01

Os odontoideum is an uncommon vertebral anomaly where there is a smoothly corticated ossicle independent from a shortened odontoid peg. An example of os odontoideum was observed in an Early Intermediate period skeleton excavated from the Huacas de Moche (Moche IV, AD 400-700), Peru. The affected individual is a middle adult male who presents additional minor developmental anomalies of the axial skeleton. This individual was interred with a middle adult female who also has developmental anomalies of the axial skeleton, including block cervical vertebra (Klippel-Feil). Os odontoideum is infrequently reported in the medical literature and there continues to be debate about whether it is acquired or congenital. Unlike clinical cases, archaeological cases present an opportunity to examine the entirety of the skeleton. In the present case, there does not appear to be macroscopic or radiographic evidence for a healed fracture, and since the individual has multiple minor axial developmental anomalies, a congenital etiology is plausible. This case is the first to be described from the archaeological context of South America and one of few paleopathological examples worldwide. Copyright © 2015 Elsevier Inc. All rights reserved.

Generalized thickness and configuration of the top of the intermediate aquifer, west-central Florida

USGS Publications Warehouse

Corral, Miguel A.; Wolansky, Richard M.

1984-01-01

Generalized map show the thickness and top of the intermediate aquifer in west-central Florida within the boundaries of the Southwest Florida Water Management District. The intermediate aquifer consists of a series of water-bearing units and confining beds between the surficial aquifer (water table) and the Floridan aquifer. This aquifer contains from one to several water-bearing units in west-central Florida. The aquifer and confining beds consist of the Tamiami and Hawthorn Formations of late and middle Miocene age and parts of the Tampa Limestone of early Miocene age. The top of the intermediate aquifer is about 100 feet above sea level in the north and slopes to about 100 feet below sea level in the south. The thickness ranges from zero in the north to more than 600 feet in the south. Despite the high mineral content of the water in some areas, the intermediate aquifer offers the best source of ground water to the coastal and southern areas of west-central Florida. (USGS)

Extended main sequence turnoffs in intermediate-age star clusters: a correlation between turnoff width and early escape velocity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goudfrooij, Paul; Kozhurina-Platais, Vera; Kalirai, Jason S.

2014-12-10

We present a color-magnitude diagram analysis of deep Hubble Space Telescope imaging of a mass-limited sample of 18 intermediate-age (1-2 Gyr old) star clusters in the Magellanic Clouds, including eight clusters for which new data were obtained. We find that all star clusters in our sample feature extended main-sequence turnoff (eMSTO) regions that are wider than can be accounted for by a simple stellar population (including unresolved binary stars). FWHM widths of the MSTOs indicate age spreads of 200-550 Myr. We evaluate the dynamical evolution of clusters with and without initial mass segregation. Our main results are (1) the fractionmore » of red clump (RC) stars in secondary RCs in eMSTO clusters scales with the fraction of MSTO stars having pseudo-ages of ≲1.35 Gyr; (2) the width of the pseudo-age distributions of eMSTO clusters is correlated with their central escape velocity v {sub esc}, both currently and at an age of 10 Myr. We find that these two results are unlikely to be reproduced by the effects of interactive binary stars or a range of stellar rotation velocities. We therefore argue that the eMSTO phenomenon is mainly caused by extended star formation within the clusters; and (3) we find that v {sub esc} ≥ 15 km s{sup –1} out to ages of at least 100 Myr for all clusters featuring eMSTOs, and v {sub esc} ≤ 12 km s{sup –1} at all ages for two lower-mass clusters in the same age range that do not show eMSTOs. We argue that eMSTOs only occur for clusters whose early escape velocities are higher than the wind velocities of stars that provide material from which second-generation stars can form. The threshold of 12-15 km s{sup –1} is consistent with wind velocities of intermediate-mass asymptotic giant branch stars and massive binary stars in the literature.« less

Formation of tryptophan radicals in irradiated aqueous solutions of hexachloroplatinate(IV): a flash photolysis study.

PubMed

Zang, L; Rodgers, M A

1999-10-01

The oxidation of tryptophan photosensitized by PtCl6(2-) has been investigated in aqueous solutions at different pH using nanosecond laser flash photolysis. Cationic and neutral radicals of tryptophan were detected at pH 2.8 and 8.5, respectively. The generation of the radical was attributed to oxidation by Cl2- that was formed from the homolytic bond cleavage in the excited state of PtCl6(2-). The bimolecular rate constant derived from the kinetics analysis, 2.8 +/- 0.2 x 10(9) M-1 s-1, is in good agreement with the value obtained in earlier pulse radiolysis studies. Both the cationic and neutral radicals decayed by second-order kinetics, consistent with the dimerization process.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K.; Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309

2012-10-28

Oxalyl chloride, (ClCO){sub 2}, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO){sub 2} and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11more » discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, {Phi}({lambda}), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO){sub 2} has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl){sub 2}+ hv{yields} ClCO*+ Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO*{yields} Cl + CO (3a), {yields} ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M {yields} Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO){sub 2}. {Phi}(193 nm) was found to be 2.07 {+-} 0.37 independent of bath gas pressure (25.8-105.7 Torr, N{sub 2}), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO){sub 2} is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 {+-} 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 {+-} 0.26 independent of bath gas pressure (15-70 Torr, N{sub 2}). {Phi}(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N{sub 2}). The

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Burkholder, James B

2012-10-28

Oxalyl chloride, (ClCO)(2), has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)(2) and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV∕vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)(2) has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)(2) + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO* → Cl + CO (3a), → ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M → Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO)(2). Φ(193 nm) was found to be 2.07 ± 0.37 independent of bath gas pressure (25.8-105.7 Torr, N(2)), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO)(2) is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 ± 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 ± 0.26 independent of bath gas pressure (15-70 Torr, N(2)). Φ(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N(2)). The low-pressure limit of the total Cl atom quantum yield, Φ(0)(351 nm), was 2

A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene.

PubMed

Gritsan, N P; Gudmundsdóttir, A D; Tigelaar, D; Zhu, Z; Karney, W L; Hadad, C M; Platz, M S

2001-03-07

Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet nitrenes were detected by transient absorption spectroscopy, and their spectra are characterized by sharp absorption bands with maxima in the range of 300-365 nm. The kinetics of their decay were analyzed as a function of temperature to yield observed decay rate constants, k(OBS). The observed rate constant in inert solvents is the sum of k(R) + k(ISC) where k(R) is the absolute rate constant of rearrangement of singlet nitrene to an azirine and k(ISC) is the absolute rate constant of nitrene intersystem crossing (ISC). Values of k(R) and k(ISC) were deduced after assuming that k(ISC) is independent of temperature. Barriers to cyclization of 4-fluoro-, 3,5-difluoro-, 2-fluoro-, 2,6-difluoro-, and 2,3,4,5,6-pentafluorophenylnitrene in inert solvents are 5.3 +/- 0.3, 5.5 +/- 0.3, 6.7 +/- 0.3, 8.0 +/- 1.5, and 8.8 +/- 0.4 kcal/mol, respectively. The barrier to cyclization of parent singlet phenylnitrene is 5.6 +/- 0.3 kcal/mol. All of these values are in good quantitative agreement with CASPT2 calculations of the relative barrier heights for the conversion of fluoro-substituted singlet aryl nitrenes to benzazirines (Karney, W. L. and Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347). A single ortho-fluorine substituent exerts a small but significant bystander effect on remote cyclization that is not steric in origin. The influence of two ortho-fluorine substituents on the cyclization is pronounced. In the case of the singlet 2-fluorophenylnitrene system, evidence is presented that the benzazirine is an intermediate and that the corresponding singlet nitrene and benzazirine interconvert. Ab initio calculations at different levels of theory on a series of benzazirines, their isomeric ketenimines, and the transition

Prognostic Value of Transthoracic Doppler Echocardiography Coronary Flow Velocity Reserve in Patients with Nonculprit Stenosis of Intermediate Severity Early after Primary Percutaneous Coronary Intervention.

PubMed

Tesic, Milorad; Djordjevic-Dikic, Ana; Giga, Vojislav; Stepanovic, Jelena; Dobric, Milan; Jovanovic, Ivana; Petrovic, Marija; Mehmedbegovic, Zlatko; Milasinovic, Dejan; Dedovic, Vladimir; Zivkovic, Milorad; Juricic, Stefan; Orlic, Dejan; Stojkovic, Sinisa; Vukcevic, Vladan; Stankovic, Goran; Nedeljkovic, Milan; Ostojic, Miodrag; Beleslin, Branko

2018-04-03

Treatment of nonculprit coronary stenosis during primary percutaneous coronary intervention in patients with ST-segment elevation myocardial infarction may be beneficial, but the mode and timing of the intervention are still controversial. The aim of this study was to examine the significance and prognostic value of preserved coronary flow velocity reserve (CFVR) in patients with nonculprit intermediate stenosis early after primary percutaneous coronary intervention. Two hundred thirty patients with remaining intermediate (50%-70%) stenosis of non-infarct-related arteries, in whom CFVR was performed within 7 days after primary percutaneous coronary intervention, were prospectively enrolled. Twenty patients with reduced CFVR and positive results on stress echocardiography or impaired fractional flow reserve underwent revascularization and were not included in further analysis. The final study population of 210 patients (mean age, 58 ± 10 years; 162 men) was divided into two groups on the basis of CFVR: group 1, CFVR > 2 (n = 174), and group 2, CFVR ≤ 2 (n = 36). Cardiac death, nonfatal myocardial infarction, and revascularization of the evaluated vessel were considered adverse events. Mean follow-up duration was 47 ± 16 months. Mean CFVR for the whole group was 2.36 ± 0.40. There were six adverse events (3.4%) related to the nonculprit coronary artery in group 1, including one cardiac death, one ST-segment elevation myocardial infarction, and four revascularizations. In group 2, there were 30 adverse events (83.3%, P < .001 vs group 1), including two cardiac deaths, two ST-segment elevation myocardial infarctions, and 26 revascularizations. In patients with CFVR > 2 of the intermediate nonculprit coronary lesion, deferral of revascularization is safe and associated with excellent long-term clinical outcomes. Copyright © 2018 American Society of Echocardiography. Published by Elsevier Inc. All rights reserved.

Effects of blue or violet light on the inactivation of Staphylococcus aureus by riboflavin-5'-phosphate photolysis.

PubMed

Wong, Tak-Wah; Cheng, Chien-Wei; Hsieh, Zong-Jhe; Liang, Ji-Yuan

2017-08-01

The light sensitive compound riboflavin-5'-phosphate (or flavin mononucleotide, FMN) generates reactive oxygen species (ROS) upon photo-irradiation. FMN is required by all flavoproteins because it is a cofactor of biological blue-light receptors. The photochemical effects of FMN after irradiation by blue or violet light on the inactivation of Staphylococcus aureus strains, including a methicillin-resistant strain (MRSA), were investigated in this study. Upon blue- or violet-light photo-treatment, FMN was shown to inactivate S. aureus due to the generated ROS. Effective bacterial inactivation can be achieved by FMN photolysis without an exogenous electron provider. Inactivation rates of 94.9 and 95.2% in S. aureus and MRSA, respectively, can be reached by blue light irradiation (2.0mW/cm 2 ) with 120μM FMN for 120min. A lower FMN concentration and a shorter time are required to reach similar effects by violet light irradiation. Inactivation rates of 96.3 and 97.0% in S. aureus and MRSA, respectively, can be reached by violet light irradiation (1.0mW/cm 2 ) with 30μM FMN for 30min. The sensitivity of the inherent photosensitizers is lower under blue-light irradiation. A long exposure photolytic treatment of FMN by blue light is required to inactivate S. aureus. Violet light was found to be more efficient in S. aureus inactivation at the same radiant intensity. FMN photolysis with blue or violet light irradiation enhanced the inactivation rates of S. aureus and MRSA. FMN photochemical treatment could be a supplemental technique in hygienic decontamination processes. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of the spectra of silica colloidal crystals with assembled silver obtained from a photolysis method

NASA Astrophysics Data System (ADS)

Li, Wenjiang; He, Jinglong; He, Sailing

2005-02-01

The colorful artificial 3D silica colloidal crystals (opal) were prepared through self-assembly of silica spheres in the visible frequency range. We directly synthesized nano silver particles in the void of the silica artificial opal film using the photolysis of silver nitrate under UV light, nano silver particles were self-deposited around the surface of silica sphere. The shifts of the stop band of the artificial crystals after exposing different time under UV light were studied. Synthetic silica opal with three-dimensional (3D) structure is potentially useful for the development of diffractive optical devices, micro mechanical systems, and sensory elements because photonic band gaps obtained from self-assembled closely packed periodic structures.

Characterization of the transient species generated by the photoionization of Berberine: A laser flash photolysis study

NASA Astrophysics Data System (ADS)

Cheng, Ling-Li; Wang, Mei; Zhu, Hui; Li, Kun; Zhu, Rong-Rong; Sun, Xiao-Yu; Yao, Si-De; Wu, Qing-Sheng; Wang, Shi-Long

2009-09-01

Using 266 nm laser flash photolysis it has been demonstrated that Berberine (BBR) in aqueous solution is ionized via a mono-photonic process giving a hydrated electron, anion radical that formed by hydrated electron react with steady state of BBR, and neutral radical that formed from rapid deprotonation of the radical cation of BBR. The quantum yield of photoionization is determined to be 0.03 at room temperature with KI solution used as a reference. Furthermore utilizing pH changing method and the SO 4rad - radical oxidation method, the assignment of radical cation of BBR was further confirmed, the p Ka value of it was calculated, and the related set up rate constant was also determined.

Infrared absorption spectrum of the simplest deuterated Criegee intermediate CD{sub 2}OO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Yu-Hsuan; Nishimura, Yoshifumi; Witek, Henryk A., E-mail: hwitek@mail.nctu.edu.tw, E-mail: yplee@mail.nctu.edu.tw

We report a transient infrared (IR) absorption spectrum of the simplest deuterated Criegee intermediate CD{sub 2}OO recorded using a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. CD{sub 2}OO was produced from photolysis of flowing mixtures of CD{sub 2}I{sub 2}, N{sub 2}, and O{sub 2} (13 or 87 Torr) with laser light at 308 nm. The recorded spectrum shows close structural similarity with the spectrum of CH{sub 2}OO reported previously [Y.-T. Su et al., Science 340, 174 (2013)]. The four bands observed at 852, 1017, 1054, and 1318 cm{sup −1} are assigned to the OO stretching mode, two distinctmore » in-plane OCD bending modes, and the CO stretching mode of CD{sub 2}OO, respectively, according to vibrational wavenumbers, IR intensities, rotational contours, and deuterium-isotopic shifts predicted with extensive quantum-chemical calculations. The CO-stretching mode of CD{sub 2}OO at 1318 cm{sup −1} is blue shifted from the corresponding band of CH{sub 2}OO at 1286 cm{sup −1}; this can be explained by a mechanism based on mode mixing and isotope substitution. A band near 936 cm{sup −1}, observed only at higher pressure (87 Torr), is tentatively assigned to the CD{sub 2} wagging mode of CD{sub 2}IOO.« less

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3c

DOE PAGES

Prather, M. J.

2015-08-14

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and is implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observations of the vertical correlation of cloud layers, Cloud-J 7.3c provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations by four quadrature atmospheres produces mean J values in an atmospheric column with root mean square (rms) errors of 4 % or less compared with 10–20 %more » errors using simpler approximations. Cloud-J is practical for chemistry–climate models, requiring only an average of 2.8 Fast-J calls per atmosphere vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections, is also incorporated into Cloud-J.« less

Reconstruction of intermediate water circulation in the tropical North Atlantic during the past 22,000 years

NASA Astrophysics Data System (ADS)

Xie, Ruifang C.; Marcantonio, Franco; Schmidt, Matthew W.

2014-09-01

Decades of paleoceanographic studies have reconstructed a well-resolved water mass structure for the deep Atlantic Ocean during the Last Glacial Maximum (LGM). However, the variability of intermediate water circulation in the tropics over the LGM and deglacial abrupt climate events is still largely debated. This study aims to reconstruct intermediate northern- and southern-sourced water circulation in the tropical North Atlantic during the past 22 kyr and attempts to confine the boundary between Antarctic Intermediate Water (AAIW) and northern-sourced intermediate water (i.e., upper North Atlantic Deep Water (NADW) or Glacial North Atlantic Intermediate Water) in the past. High-resolution Nd isotopic compositions of fish debris and acid-reductive leachate of bulk sediment in core VM12-107 (1079 m depth) from the Southern Caribbean are not in agreement. We suggest that the leachate method does not reliably extract the Nd isotopic compositions of seawater at this location, and that it needs to be tested in more detail in various oceanic settings. The fish debris εNd values display a general decrease from the early deglaciation to the end of the Younger Dryas, followed by a greater drop toward less radiogenic values into the early Holocene. We propose a potentially more radiogenic glacial northern endmember water mass and interpret this pattern as recording a recovery of the upper NADW during the last deglaciation. Comparing our new fish debris Nd isotope data to authigenic Nd isotope studies in the Florida Straits (546 and 751 m depth), we propose that both glacial and deglacial AAIW do not penetrate beyond the lower depth limit of modern AAIW in the tropical Atlantic.

IR-Monitored Photolysis of CO-Inhibited Nitrogenase: A Major EPR-Silent Species with Coupled Terminal CO Ligands

PubMed Central

Yan, Lifen; Dapper, Christie H.; Scott, Aubrey D.; Newton, William E.

2015-01-01

We have used Fourier transform infrared spectroscopy (FT-IR) to observe the photolysis and recombination of a novel EPR-silent CO-inhibited form of α-H195Q nitrogenase from Azotobacter vinelandii. Photolysis at 4 K yields a strong negative IR difference band at 1938 cm−1, along with a weaker negative feature at 1911 cm−1. These bands and the associated chemical species have both been assigned the label ‘Hi-3’. A positive band at 1921 cm−1 is assigned to the ‘Lo-3’ photoproduct. By using an isotopic mixture of 12C16O and 13C18O, we show that the Hi-3 bands arise from coupling of two similar CO oscillators with one uncoupled frequency at ~1917 cm−1. Although in previous studies Lo-3 was not observed to recombine, by extending the observation range to 200–240 K we found that recombination to Hi-3 does indeed occur, with an activation energy of ~6.5 kJ mol−1. The frequencies of the Hi-3 bands suggest terminal CO ligation. We tested this hypothesis with DFT calculations on models with terminal CO ligands on Fe2 and Fe6 of the FeMo-cofactor. An S = 0 model with both CO ligands in exo positions predicts symmetric and asymmetric stretches at 1938 and 1909 cm−1 respectively, with relative band intensities of ~3.5:1, in good agreement with experiment. From the observed IR intensities, we find that Hi-3 is present at a concentration about equal to that of the EPR-active Hi-1 species. The relevance of Hi-3 to the nitrogenase catalytic mechanism and its recently discovered Fischer-Tropsch chemistry is discussed. PMID:23136072

Formation kinetics of a novel product from photolysis of cytosine in phosphate-buffered solutions

NASA Astrophysics Data System (ADS)

Wenqing, Wang; Feng, Lin; Jilan, Wu

1999-01-01

For studying the role of phosphate in the origin of life and the effect of far-ultraviolet light induced photochemical damage to RNA, DNA and its components, it was found that the photolysis of nucleobases, nucleosides and nucleotides was strongly enhanced by phosphate under the irradiation of medium pressure mercury lamp (MPML). Ultraviolet irradiation (190-220 nm) of cytosine in 0.05 mol dm -3 phosphate buffered solution at pH 8-9 leads to the production of a novel compound C 4H 6N 3O 5P in the presence of oxygen. The main photoproduct has been isolated, purified and characterized by use of 1H- and 31P-NMR spectroscopy, elemental analysis, ultraviolet and infrared spectroscopy and electron impact mass spectrometry. Phosphate effect can be inhibited by amino acids. The formation mechanism of the photoproduct and the kinetics was studied.

Removal of organic matter from a variety of water matrices by UV photolysis and UV/H2O2 method.

PubMed

Vilhunen, Sari; Vilve, Miia; Vepsäläinen, Mikko; Sillanpää, Mika

2010-07-15

A re-circulated flow-through photoreactor was used to evaluate the ultraviolet (UV) photolysis and UV/H(2)O(2) oxidation process in the purification of three different water matrices. Chemically coagulated and electrocoagulated surface water, groundwater contaminated with creosote wood preservative and 1,2-dichloroethane (DCE) containing washing water from the plant manufacturing tailor-made ion-exchange resins were used as sample waters. The organic constituents of creosote consist mainly of harmful polycyclic aromatic hydrocarbons (PAH) whereas 1,2-DCE is a toxic volatile organic compound (VOC). Besides analyzing the specific target compounds, total organic carbon (TOC) analysis and measurement of change in UV absorbance at 254 nm (UV(254)) were performed. Initial TOC, UV(254) and pH varied significantly among treated waters. Initial H(2)O(2) concentrations 0-200 mg/l were used. The UV/H(2)O(2) treatment was efficient in removing the hazardous target pollutants (PAHs and 1,2-DCE) and natural organic matter (NOM). In addition, high removal efficiency for TOC was achieved for coagulated waters and groundwater. Also, the efficiency of direct photolysis in UV(254) removal was significant except in the treatment of 1,2-DCE containing washing water. Overall, UV(254) and TOC removal rates were high, except in case of washing water, and the target pollutants were efficiently decomposed with the UV/H(2)O(2) method. 2010 Elsevier B.V. All rights reserved.

Laser Flash Photolysis Studies of Radical-Radical Reaction Kinetics: The O((sup 3)P(sub J)) + BrO Reaction

NASA Technical Reports Server (NTRS)

Thorn, R. P.; Cronkhite, J. M.; Nicovich, J. M.; Wine, P. H.

1997-01-01

A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction 0((sup 3)P(sub j)) + Br yields(k1) BrO((sup 2)P(sub J)) + O2 as a function of temperature (231-328 K) and pressure (25-150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T) = 1.91 x 10(exp -11)(230/J) cu cm/ molecule.s; the absolute accuracy of measured values for k1 is estimated to vary from +/- 20 percent at at T approximately 230 K to +/- 30 percent at T approximately 330 K. Our results demonstrate that the O((sup 3)P(sub j)) + BrO rate coefficient is significantly faster than previously 'guesstimated,' and suggest that the catalytic cycle with the O((sup 3)P(sub j)) + BrO reaction as its rate-limiting step is the dominant stratospheric BrO(x), odd-oxygen destruction cycle at altitudes above 24 km.

Timing of Biochemical Failure and Distant Metastasis for Low, Intermediate, and High Risk Prostate Cancer after Radiotherapy

PubMed Central

Morgan, Peter B.; Hanlon, Alexandra L.; Horwitz, Eric M.; Buyyounouski, Mark K.; Uzzo, Robert G.; Pollack, Alan

2007-01-01

Condensed Abstract The timing of biochemical failure and distant metastasis after radiotherapy for low, intermediate and high-risk prostate cancer was determined. The patterns of failure suggest that the majority of early failures were due to subclinical micrometastases present at diagnosis, whereas a late wave of metastasis at 10–12 years in every risk group was consistent with tumor spread from local persistence of disease. Background The relationship of prostate cancer risk group stratification and the timing of biochemical failure (BF) and distant metastasis (DM) is not well defined. We sought to differentiate early failures due to subclinical micrometastasis at presentation from late failures due to local persistence. Methods A total of 1833 men with clinically localized prostate cancer treated with 3D-conformal radiotherapy with or without short-term androgen deprivation were retrospectively analyzed. The interval hazard rates of DM and BF, using ASTRO and Phoenix (Nadir+2) definitions, were determined for men with low, intermediate, and high risk disease. Results Median follow-up was 67 months. Multivariate analysis showed that increasing risk group was independently associated with higher ASTRO BF (P<.0001) and Nadir+2 BF (P<.0001). The preponderance (87%) of ASTRO BF occurred ≤4 years after RT, while Nadir+2 BF was more evenly spread over years 1–12, with 43% at >4 years. The hazard of Nadir+2 BF persisted in years 8–12 in all risk groups. The interval hazard function for DM appeared to be biphasic (early and late peaks) for intermediate and high risk patients, but no distinct early wave was evident for low risk patients. Conclusions ASTRO BF underestimates late BF due to backdating. Local persistence of disease is suggested by delayed Nadir+2 BF and subsequent late DM in every risk group. The paucity of early DM among those with low risk tumors supports the hypothesis that occult micrometastases contributed to the early wave. PMID:17520705

Tropospheric HONO Distribution and Chemistry in the Southeastern U.S.

NASA Astrophysics Data System (ADS)

Zhou, X.; Ye, C.; Pu, D.; Stutz, J.; Festa, J.; Spolaor, M.; Weinheimer, A. J.; Campos, T. L.; Haggerty, J. A.; Cantrell, C. A.; Mauldin, L.; Guenther, A. B.; Hornbrook, R. S.; Apel, E. C.; Jensen, J. B.

2014-12-01

During the NOMADSS field campaign, nitrous acid (HONO) and particulate nitrate (pNO3) was measured on NCAR C-130 research aircraft during five research flights over the Southeast U.S. Aerosol samples were also collected on Teflon filters for the determination of pNO3 photolysis rate constants in the laboratory. Daytime HONO concentrations range from low ppt in free troposphere to 10-20 ppt in the boundary layer in the background air masses, to up to 40 ppt in the industrial and urban plumes. While daytime HONO sink is well defined, dominated by its photolysis, daytime sources vary in different types of air masses: pNO3 photolysis appears to be the major HONO source in the background terrestrial air masses in both the boundary layer and the free troposphere. With an average pNO3 photolysis rate constant of (2.8±1.7)×10-4 s-1, p-NO3 photolysis becomes to be an effective pathway to recycle HNO3 to NOx in the troposphere, with HONO as a dominant intermediate product. Within the high-NOx industrial plumes encountered, HONO is predominantly produced by secondary formation processes involving NOx as the precursor. Away from ground surface, no significant nighttime HONO accumulation exists in the background terrestrial air mass.

Supervising Remote Humanoids Across Intermediate Time Delay

NASA Technical Reports Server (NTRS)

Hambuchen, Kimberly; Bluethmann, William; Goza, Michael; Ambrose, Robert; Rabe, Kenneth; Allan, Mark

2006-01-01

The President's Vision for Space Exploration, laid out in 2004, relies heavily upon robotic exploration of the lunar surface in early phases of the program. Prior to the arrival of astronauts on the lunar surface, these robots will be required to be controlled across space and time, posing a considerable challenge for traditional telepresence techniques. Because time delays will be measured in seconds, not minutes as is the case for Mars Exploration, uploading the plan for a day seems excessive. An approach for controlling humanoids under intermediate time delay is presented. This approach uses software running within a ground control cockpit to predict an immersed robot supervisor's motions which the remote humanoid autonomously executes. Initial results are presented.

Forest Canopy Water Cycling Responses to an Intermediate Disturbance Revealed Through Stable Water Vapor Isotopes

NASA Astrophysics Data System (ADS)

Fiorella, R.; Poulsen, C. J.; Matheny, A. M.; Rey Sanchez, C.; Fotis, A. T.; Morin, T. H.; Vogel, C. S.; Gough, C. M.; Aron, P.; Bohrer, G.

2016-12-01

Forest structure, age, and species composition modulate fluxes of carbon and water between the land surface and the atmosphere. The response of forests to intermediate disturbances such as ecological succession, species-specific insect invasion, or selective logging that disrupt the canopy but do not promote complete stand replacement, shape how these fluxes evolve through time. We investigate the impact of an intermediate disturbance to water cycling processes by comparing vertical profiles of stable water isotopes in two closely located forest canopies in the northern lower peninsula of Michigan using cavity ring-down spectroscopy. In one of the canopies, an intermediate disturbance was prescribed in 2008 by inducing mortality in all canopy-dominant early successional species. Isotopic compositions of atmospheric water vapor are measured at six heights during two time periods (summer and early fall) at two flux towers and compared with local meteorology and calculated atmospheric back-trajectories. Disturbance has little impact on low-frequency changes in isotopic composition (e.g., >1 day); at these timescales, isotopic composition is strongly related to large-scale moisture transport. In contrast, disturbance has substantial impacts on the vertical distribution of water isotopes throughout the canopy when transpiration rates are high during the summer, but impact is muted during early fall. Sub-diurnal differences in canopy water vapor cycling are likely related to differences in species composition and response to disturbance and changes in canopy structure. Predictions of transpiration fluxes by land-surface models that do not account species-specific relationships and canopy structure are unlikely to capture these relationships, but addition of stable isotopes to land surface models may provide a useful parameter to improve these predictions.

Direct detection of the triphenylpyrylium-derived short-lived intermediates in the photocatalyzed degradation of acetaminophen, acetamiprid, caffeine and carbamazepine.

PubMed

Martinez-Haya, R; Gomis, J; Arques, A; Amat, A M; Miranda, M A; Marin, M L

2017-09-09

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP + ) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP + . Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP + reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct detection of the triphenylpyrylium-derived short-lived intermediates in the photocatalyzed degradation of acetaminophen, acetamiprid, caffeine and carbamazepine.

PubMed

Martinez-Haya, R; Gomis, J; Arques, A; Amat, A M; Miranda, M A; Marin, M L

2018-08-15

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP + ) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP + . Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP + reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process. Copyright © 2018. Published by Elsevier B.V.

Pulsed laser photolysis study of the reaction between O(3P) and HO2

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.; Nicovich, J. M.

1983-01-01

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Photochemical reactions in interstellar grains photolysis of CO, NH3, and H2O

NASA Technical Reports Server (NTRS)

Agarwal, V. K.; Ferris, J. P.; Schutte, W.; Greenberg, J. M.; Briggs, R.

1985-01-01

The interstellar grains are currently considered to be the basic building blocks of comets and, possibly, meteorites. To test this theory, a simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH3:H2O gas mixture on an Al block at 10 K, with concomitant irradiation with vacuum UV. The results of the HPLC and IR analyses of the nonvolatile residue formed by photolysis at 10 K are compared with those observed at 77 K and 298 K. Some of the compounds that may be present on the surfaces of interstellar dust particles have been identified, and some specific predictions concerning the types of molecular species present in comets could be drawn. The results also suggest that photochemical reactions may have been important for the formation of meteorite components. The implication of the findings to the questions of the source of organic matter on earth and the origin of life are discussed.

Hygroscopicity of Early Earth and Titan Laboratory Aerosol Analogs

NASA Astrophysics Data System (ADS)

Hasenkopf, C. A.; Beaver, M. R.; Freedman, M. A.; Toon, O. B.; Tolbert, M. A.

2009-12-01

We have explored the ability of organic hazes, known to exist in the atmosphere of Titan and postulated to have existed in the Archean Earth atmosphere, to act as cloud condensation nuclei (CCN). These laboratory aerosol analogs are generated via UV-photolysis of early Earth and Titan analog gas mixtures and are designed to mimic the present day atmospheric conditions on Titan and the early Earth atmosphere before the rise of oxygen. Water uptake is observed to occur on the early Earth and Titan aerosol analogs at relative humidities of 80% - 90% via optical growth measurements using cavity ring-down aerosol extinction spectroscopy. We find the optical growth of these aerosols is similar to known slightly-soluble organic acids, such as phthalic and pyromellitic acids. On average, the optical growth of the early Earth analog is slightly larger than the Titan analog. In order to translate our measurements obtained in a subsaturated regime into the CCN ability of these particles, we rely on the hygroscopicity parameter κ, developed by Petters & Kreidenweis (2007). We retrieve κ = 0.17±0.03 and 0.06±0.01 for the early Earth and Titan analogs, respectively. This early Earth analog hygroscopicity value indicates that the aerosol could activate at reasonable water vapor supersaturations. We use previous aerosol mass spectrometry results to correlate the chemical structure of the two types of analog with their hygroscopicity. The hygroscopicity of the early Earth aerosol analog, coupled with the apparent lack of other good CCN during the Archean, helps explain the role of the organic haze in the indirect effect of clouds on the early Earth and indicates that it may have had a significant impact on the hydrological cycle.

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

1993-01-01

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

Characterization of two distinct beta2-microglobulin unfolding intermediates that may lead to amyloid fibrils of different morphology.

PubMed

Armen, Roger S; Daggett, Valerie

2005-12-13

The self-assembly of beta(2)-microglobulin into fibrils leads to dialysis-related amyloidosis. pH-mediated partial unfolding is required for the formation of the amyloidogenic intermediate that then self-assembles into amyloid fibrils. Two partially folded intermediates of beta(2)-microglobulin have been identified experimentally and linked to the formation of fibrils of distinct morphology, yet it remains difficult to characterize these partially unfolded states at high resolution using experimental approaches. Consequently, we have performed molecular dynamics simulations at neutral and low pH to determine the structures of these partially unfolded amyloidogenic intermediates. In the low-pH simulations, we observed the formation of alpha-sheet structure, which was first proposed by Pauling and Corey. Multiple simulations were performed, and two distinct intermediate state ensembles were identified that may account for the different fibril morphologies. The predominant early unfolding intermediate was nativelike in structure, in agreement with previous NMR studies. The late unfolding intermediate was significantly disordered, but it maintained an extended elongated structure, with hydrophobic clusters and residual alpha-extended chain strands in specific regions of the sequence that map to amyloidogenic peptides. We propose that the formation of alpha-sheet facilitates self-assembly into partially unfolded prefibrillar amyloidogenic intermediates.

Kinetic evidence for folding and unfolding intermediates in staphylococcal nuclease.

PubMed

Walkenhorst, W F; Green, S M; Roder, H

1997-05-13

The complex kinetic behavior commonly observed in protein folding studies suggests that a heterogeneous population of molecules exists in solution and that a number of discrete steps are involved in the conversion of unfolded molecules to the fully native form. A central issue in protein folding is whether any of these kinetic events represent conformational steps important for efficient folding rather than side reactions caused by slow steps such as proline isomerization or misfolding of the polypeptide chain. In order to address this question, we used stopped-flow fluorescence techniques to characterize the kinetic mechanism of folding and unfolding for a Pro- variant of SNase in which all six proline residues were replaced by glycines or alanines. Compared to the wild-type protein, which exhibits a series of proline-dependent slow folding phases, the folding kinetics of Pro- SNase were much simpler, which made quantitative kinetic analysis possible. Despite the absence of prolines or other complicating factors, the folding kinetics still contain several phases and exhibit a complex denaturant dependence. The GuHCl dependence of the major observable folding phase and a distinct lag in the appearance of the native state provide clear evidence for an early folding intermediate. The fluorescence of Trp140 in the alpha-helical domain is insensitive to the formation of this early intermediate, which is consistent with a partially folded state with a stable beta-domain and a largely disordered alpha-helical region. A second intermediate is required to model the kinetics of unfolding for the Pro- variant, which shows evidence for a denaturant-induced change in the rate-limiting unfolding step. With the inclusion of these two intermediates, we are able to completely model the major phase(s) in both folding and unfolding across a wide range of denaturant concentrations using a sequential four-state folding mechanism. In order to model the minor slow phase observed for the

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

NASA Technical Reports Server (NTRS)

Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

1981-01-01

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

Physics of intermediate shocks: A review

NASA Technical Reports Server (NTRS)

Karimabadi, H.

1995-01-01

Intermediate shocks (ISs) lead to a transition from super-Alfvenic to sub-Alfvenic flow and are different from slow and fast shocks in that an IS rotates the component of the magnetic field tangent to the shock plane by 180 deg. Another peculiarity of ISs is that for the same upstream conditions an IS can have two different downstream states. There also exist a second class of ISs which rotate the magnetic field by an angle other than 180 deg. Due to their noncoplanar nature they cannot be time-stationary and are referred to as time-dependent intermediate shocks (TDIS). The existence of ISs has been the subject of much controversy over the years. Early studies questioned the physical reality of ISs. However, the studies of ISs found a new impetus when C.C. Wu showed that ISs do exist and are stable within the resistive MHD framework. In this paper, after a brief historical overview of the subject, we will review the latest developments in the study of ISs. In particular, we will address the questions of stability and structure of ISs and the relationship between ISs and other discontinuities. One of the recent developments has been the finding that ISs can be unsteady, reforming in time. Details of this process will be discussed. Finally, we examine the effect of anisotropy on the resolutions and discuss the relevance of ISs to the observed field rotations at the Earth's magnetopause.

Involving older people in intermediate care.

PubMed

Andrews, JoyAnn; Manthorpe, Jill; Watson, Roger

2004-05-01

Intermediate care has become a crucial part of the United Kingdom government's programme for improving services for older people. Older people comprise a substantial part of the user base for these services, and it is increasingly recognized that there is a need for greater user involvement in service development for intermediate care. National initiatives undertaken in intermediate care have sought to widen and deepen the remit of such services, and in this way promote greater independence and improved quality of care for older people. In particular, the government has set out clear plans for reshaping services for older people in the National Health Service Plan and the rationale for greater involvement of older people in service development. This article considers ways in which these national and local objectives may be achieved and considers some of the implications for nursing. This paper aims to explore the concept of intermediate care and to identify trends and existing evidence of user involvement in care. In this way it charts a possible way forward for the development of a more 'user sensitive' approach. The following databases were searched: Medline, Cochrane Library, the Social Science Citation Index and CINAHL. Key words were 'intermediate care', 'older people', 'formal care', 'primary care', 'social services' and 'geriatrics', used in combination. The findings from this study indicate that there is considerable scope for increased user involvement in service development for intermediate care. Such challenges may be more effectively met through greater clarity of the concept of intermediate care, and a bridging of user involvement at the practice and policy levels. Nurses are key providers of intermediate care in the community. The involvement of older people in intermediate care service development must be premised on a shared comprehension of the purpose and function of intermediate care. Nurses must be involved in shifting intermediate care from

Potential climatic impact of organic haze on early Earth.

PubMed

Hasenkopf, Christa A; Freedman, Miriam A; Beaver, Melinda R; Toon, Owen B; Tolbert, Margaret A

2011-03-01

We have explored the direct and indirect radiative effects on climate of organic particles likely to have been present on early Earth by measuring their hygroscopicity and cloud nucleating ability. The early Earth analog aerosol particles were generated via ultraviolet photolysis of an early Earth analog gas mixture, which was designed to mimic possible atmospheric conditions before the rise of oxygen. An analog aerosol for the present-day atmosphere of Saturn's moon Titan was tested for comparison. We exposed the early Earth aerosol to a range of relative humidities (RHs). Water uptake onto the aerosol was observed to occur over the entire RH range tested (RH=80-87%). To translate our measurements of hygroscopicity over a specific range of RHs into their water uptake ability at any RH < 100% and into their ability to act as cloud condensation nuclei (CCN) at RH > 100%, we relied on the hygroscopicity parameter κ, developed by Petters and Kreidenweis. We retrieved κ=0.22 ±0.12 for the early Earth aerosol, which indicates that the humidified aerosol (RH < 100 %) could have contributed to a larger antigreenhouse effect on the early Earth atmosphere than previously modeled with dry aerosol. Such effects would have been of significance in regions where the humidity was larger than 50%, because such high humidities are needed for significant amounts of water to be on the aerosol. Additionally, Earth organic aerosol particles could have activated into CCN at reasonable-and even low-water-vapor supersaturations (RH > 100%). In regions where the haze was dominant, it is expected that low particle concentrations, once activated into cloud droplets, would have created short-lived, optically thin clouds. Such clouds, if predominant on early Earth, would have had a lower albedo than clouds today, thereby warming the planet relative to current-day clouds. © Mary Ann Liebert, Inc.

Time-resolved resonance Raman spectroscopy of intermediates of bacteriorhodopsin: The bK(590) intermediate.

PubMed

Terner, J; Hsieh, C L; Burns, A R; El-Sayed, M A

1979-07-01

We have combined microbeam and flow techniques with computer subtraction methods to obtain the resonance Raman spectrum of the short lived batho-intermediate (bK(590)) of bacteriorhodopsin. Comparison of the spectra obtained in (1)H(2)O and (2)H(2)O, as well as the fact that the bK(590) intermediate shows large optical red shifts, suggests that the Schiff base linkage of this intermediate is protonated. The fingerprint region of the spectrum of bK(590), sensitive to the isomeric configuration of the retinal chromophore, does not resemble the corresponding region of the parent bR(570) form. The resonance Raman spectrum of bK(590) as well as the spectra of all of the other main intermediates in the photoreaction cycle of bacteriorhodopsin are discussed and compared with resonance Raman spectra of published model compounds.

Role of Intermediate Filaments in Vesicular Traffic.

PubMed

Margiotta, Azzurra; Bucci, Cecilia

2016-04-25

Intermediate filaments are an important component of the cellular cytoskeleton. The first established role attributed to intermediate filaments was the mechanical support to cells. However, it is now clear that intermediate filaments have many different roles affecting a variety of other biological functions, such as the organization of microtubules and microfilaments, the regulation of nuclear structure and activity, the control of cell cycle and the regulation of signal transduction pathways. Furthermore, a number of intermediate filament proteins have been involved in the acquisition of tumorigenic properties. Over the last years, a strong involvement of intermediate filament proteins in the regulation of several aspects of intracellular trafficking has strongly emerged. Here, we review the functions of intermediate filaments proteins focusing mainly on the recent knowledge gained from the discovery that intermediate filaments associate with key proteins of the vesicular membrane transport machinery. In particular, we analyze the current understanding of the contribution of intermediate filaments to the endocytic pathway.

Intermediality: Bridge to Critical Media Literacy.

ERIC Educational Resources Information Center

Pailliotet, Ann Watts; Semali, Ladislaus; Rodenberg, Rita K.; Giles, Jackie K.; Macaul, Sherry L.

2000-01-01

Defines "intermediality" as the ability to critically read and write with and across varied symbol systems. Relates it to critical media literacy. Offers rationales for teaching critical media literacy in general, and intermedial instruction in particular. Identifies seven guiding intermedial elements: theory, texts, processes, contexts,…

The effects of MgADP on cross-bridge kinetics: a laser flash photolysis study of guinea-pig smooth muscle.

PubMed Central

Nishiye, E; Somlyo, A V; Török, K; Somlyo, A P

1993-01-01

1. The effects of MgADP on cross-bridge kinetics were investigated using laser flash photolysis of caged ATP (P3-1(2-nitrophenyl) ethyladenosine 5'-triphosphate), in guinea-pig portal vein smooth muscle permeabilized with Staphylococcus aureus alpha-toxin. Isometric tension and in-phase stiffness transitions from rigor state were monitored upon photolysis of caged ATP. The estimated concentration of ATP released from caged ATP by high-pressure liquid chromatography (HPLC) was 1.3 mM. 2. The time course of relaxation initiated by photolysis of caged ATP in the absence of Ca2+ was well fitted during the initial 200 ms by two exponential functions with time constants of, respectively, tau 1 = 34 ms and tau 2 = 1.2 s and relative amplitudes of 0.14 and 0.86. Multiple exponential functions were needed to fit longer intervals; the half-time of the overall relaxation was 0.8 s. The second order rate constant for cross-bridge detachment by ATP, estimated from the rate of initial relaxation, was 0.4-2.3 x 10(4) M-1 s-1. 3. MgADP dose dependently reduced both the relative amplitude of the first component and the rate constant of the second component of relaxation. Conversely, treatment of muscles with apyrase, to deplete endogenous ADP, increased the relative amplitude of the first component. In the presence of MgADP, in-phase stiffness decreased during force maintenance, suggesting that the force per cross-bridge increased. The apparent dissociation constant (Kd) of MgADP for the cross-bridge binding site, estimated from its concentration-dependent effect on the relative amplitude of the first component, was 1.3 microM. This affinity is much higher than the previously reported values (50-300 microM for smooth muscle; 18-400 microM for skeletal muscle; 7-10 microM for cardiac muscle). It is possible that the high affinity reflects the properties of a state generated during the co-operative reattachment cycle, rather than that of the rigor bridge. 4. The rate constant of Mg

Defining the Nature of Thermal Intermediate in 3 State Folding Proteins: Apoflavodoxin, a Study Case

PubMed Central

García-Fandiño, Rebeca; Bernadó, Pau; Ayuso-Tejedor, Sara; Sancho, Javier; Orozco, Modesto

2012-01-01

The early stages of the thermal unfolding of apoflavodoxin have been determined by using atomistic multi microsecond-scale molecular dynamics (MD) simulations complemented with a variety of experimental techniques. Results strongly suggest that the intermediate is reached very early in the thermal unfolding process and that it has the properties of an “activated” form of the native state, where thermal fluctuations in the loops break loop-loop contacts. The unrestrained loops gain then kinetic energy corrupting short secondary structure elements without corrupting the core of the protein. The MD-derived ensembles agree with experimental observables and draw a picture of the intermediate state inconsistent with a well-defined structure and characteristic of a typical partially disordered protein. Our results allow us to speculate that proteins with a well packed core connected by long loops might behave as partially disordered proteins under native conditions, or alternatively behave as three state folders. Small details in the sequence, easily tunable by evolution, can yield to one or the other type of proteins. PMID:22927805

Photo-degradation of clofibric acid by ultraviolet light irradiation at 185 nm.

PubMed

Li, Wenzhen; Lu, Shuguang; Chen, Nuo; Gu, Xiaogang; Qiu, Zhaofu; Fan, Ji; Lin, Kuangfei

2009-01-01

As a metabolite of lipid regulators, clofibric acid (CA) was investigated in this study for its ultraviolet (UV) degradation at monochromatic wavelength of 185 nm using Milli-Q water and sewage treatment plant (STP) effluent. The effects of CA initial concentration, solution pH, humic acid (HA), nitrate and bicarbonate anions on CA degradation performances were evaluated. All CA degradation patterns well fitted the pseudo-first-order kinetic model. The results showed that OH generated from water photolysis by UV185 irradiation was involved, resulting in indirect CA photolysis but contributed less to the whole CA removal when compared to the main direct photolysis process. Acid condition favored slightly to CA degradation and other constituents in solution, such as HA (5.0-100.0 mg L(-1)), nitrate and bicarbonate anions (1.0x10(-3) mol L(-1) and 0.1 mol L(-1)), had negative effects on CA degradation. When using real STP effluent CA degradation could reach 97.4% (without filtration) and 99.3% (with filtration) after 1 hr irradiation, showing its potential mean in pharmaceuticals removal in UV disinfection unit. Mineralization tests showed that rapid chloride ion release happened, resulting in no chlorinated intermediates accumulation, and those non-chlorinated intermediate products could further be nearly completely degraded to CO2 and H2O after 6 hrs.

Early Exposure to Intermediate-Frequency Magnetic Fields Alters Brain Biomarkers without Histopathological Changes in Adult Mice

PubMed Central

Win-Shwe, Tin-Tin; Ohtani, Shin; Ushiyama, Akira; Kunugita, Naoki

2015-01-01

Recently we have reported that intermediate-frequency magnetic field (IF-MF) exposure transiently altered the mRNA expression levels of memory function-related genes in the hippocampi of adult male mice. However, the effects of IF-MF exposure during brain development on neurological biomarkers have not yet been clarified. In the present study, we investigated the effect of IF-MF exposure during development on neurological and immunological markers in the mouse hippocampus in 3- and 7-week-old male mice. Pregnant C57BL/6J mice were exposed to IF-MF (21 kHz, 3.8 mT) for one hour per day from organogenesis period day 7 to 17. At adolescence, some IF-MF-exposed mice were further divided into exposure, recovery, and sham-exposure groups. The adolescent-exposure groups were exposed again to IF-MF from postnatal day 27 to 48. The expression of mRNA in the hippocampi was examined using a real-time RT-PCR method, and microglia activation was examined by immunohistochemical analysis. The expression levels of NR1 and NR2B as well as transcription factors (CaMKIV, CREB1), inflammatory mediators (COX2, IL-1 β,TNF-α), and the oxidative stress marker heme-oxygenase (HO)-1 were significantly increased in the IF-MF-exposed mice, compared with the control group, in the 7-week-old mice, but not in the 3-week-old mice. Microglia activation was not different between the control and other groups. This study provides the first evidence that early exposure to IF-MF reversibly affects the NMDA receptor, its related signaling pathways, and inflammatory mediators in the hippocampus of young adult mice; these changes are transient and recover after termination of exposure without histopathological changes. PMID:25913185

Direct observation of intermediate states in model membrane fusion

PubMed Central

Keidel, Andrea; Bartsch, Tobias F.; Florin, Ernst-Ludwig

2016-01-01

We introduce a novel assay for membrane fusion of solid supported membranes on silica beads and on coverslips. Fusion of the lipid bilayers is induced by bringing an optically trapped bead in contact with the coverslip surface while observing the bead’s thermal motion with microsecond temporal and nanometer spatial resolution using a three-dimensional position detector. The probability of fusion is controlled by the membrane tension on the particle. We show that the progression of fusion can be monitored by changes in the three-dimensional position histograms of the bead and in its rate of diffusion. We were able to observe all fusion intermediates including transient fusion, formation of a stalk, hemifusion and the completion of a fusion pore. Fusion intermediates are characterized by axial but not lateral confinement of the motion of the bead and independently by the change of its rate of diffusion due to the additional drag from the stalk-like connection between the two membranes. The detailed information provided by this assay makes it ideally suited for studies of early events in pure lipid bilayer fusion or fusion assisted by fusogenic molecules. PMID:27029285

Direct observation of intermediate states in model membrane fusion.

PubMed

Keidel, Andrea; Bartsch, Tobias F; Florin, Ernst-Ludwig

2016-03-31

We introduce a novel assay for membrane fusion of solid supported membranes on silica beads and on coverslips. Fusion of the lipid bilayers is induced by bringing an optically trapped bead in contact with the coverslip surface while observing the bead's thermal motion with microsecond temporal and nanometer spatial resolution using a three-dimensional position detector. The probability of fusion is controlled by the membrane tension on the particle. We show that the progression of fusion can be monitored by changes in the three-dimensional position histograms of the bead and in its rate of diffusion. We were able to observe all fusion intermediates including transient fusion, formation of a stalk, hemifusion and the completion of a fusion pore. Fusion intermediates are characterized by axial but not lateral confinement of the motion of the bead and independently by the change of its rate of diffusion due to the additional drag from the stalk-like connection between the two membranes. The detailed information provided by this assay makes it ideally suited for studies of early events in pure lipid bilayer fusion or fusion assisted by fusogenic molecules.

Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis

PubMed Central

Nkosi, Steven S; Mwakikunga, Bonex W; Sideras-Haddad, Elias; Forbes, Andrew

2012-01-01

Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III) acetylacetonate and Pt(II) acetylacetonate. Fe(II) and Pt(I) acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001) diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence. PMID:24198494

Enhanced Photolysis of Nucleic Acid Monomers by Pyrophosphate in the Simulated Primitive Soup

NASA Astrophysics Data System (ADS)

Kongjiang, Wang; Zhifang, Chai; Xianming, Pan

1999-05-01

In our simulation of the photochemistry of the primitive soup, it was found that yield of chromophore loss of some nucleic acid bases, nucleosides and nucleotides [NA] undergoing ultraviolet radiation by medium pressure mercury lamp [MPML] was enhanced by pyrophosphate and triphosphate whether O2 is present or not. The yield of chromophore loss of guanosine, uracil, 5' CMP, and the derivatives of adenine and thymine was observed to rise with the increase of molar concentration of pyrophosphate in N2-saturated systems. In air-saturated samples, increase in yield of chromophore loss was observed when the concentration of pyrophosphate reaches 5×10-4 M, relative yield of chromophore loss (CLrel) coming to maximum in the range from 0.01 to 0.1 M, followed by a slight decline with the further increase of pyrophosphate concentration. The enhancement of photolysis of NA by pyrophosphate was due to the interaction between NA and pyrophosphate radicals photoionized by UV quanta of wavelength less than about 210 nm in the emission spectrum of a MPML. The relevance of this phenomenon to the origin of life has been discussed as well.

Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

PubMed

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

2015-04-07

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

Laser photolysis studies of the phenolic H-atom transfer mechanism for a triplet π,π ∗ ketone in solution revisited

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Aoyama, Yutaka; Furukawa, Takashi; Itoh, Takao; Tobita, Seiji

2006-03-01

The mechanism of the H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-naphthacenequinone (5,12-NQ) has been examined by means of laser flash photolysis at 295 K. Based on the Hammett plots and the Rehm-Weller equation for the quenching rate constants, the phenolic H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-NQ is shown to proceed via the electron transfer followed by proton transfer. The previously proposed mechanism for H-atom transfer of π,π ∗ triplets, that proton transfer is followed by electron transfer, was not verified in the present systems.

[Therapy of intermediate uveitis].

PubMed

Doycheva, D; Deuter, C; Zierhut, M

2014-12-01

Intermediate uveitis is a form of intraocular inflammation in which the vitreous body is the major site of inflammation. Intermediate uveitis is primarily treated medicinally and systemic corticosteroids are the mainstay of therapy. When recurrence of uveitis or side effects occur during corticosteroid therapy an immunosuppressive treatment is required. Cyclosporine A is the only immunosuppressive agent that is approved for therapy of uveitis in Germany; however, other immunosuppressive drugs have also been shown to be effective and well-tolerated in patients with intermediate uveitis. In severe therapy-refractory cases when conventional immunosuppressive therapy has failed, biologics can be used. In patients with unilateral uveitis or when the systemic therapy is contraindicated because of side effects, an intravitreal steroid treatment can be carried out. In certain cases a vitrectomy may be used.

Dementia and art: neuronal intermediate filament inclusion disease and dissolution of artistic creativity.

PubMed

Budrys, Valmantas; Skullerud, Kari; Petroska, Donatas; Lengveniene, Jurate; Kaubrys, Gintaras

2007-01-01

The paper presents a new case of neuronal intermediate filament inclusion disease (NIFID), a recently described new variant of early-onset frontotemporal dementia. Documented with repetitive brain images, morphologically proven cases additionally endorse evolving the clinical and pathological phenotype of NIFID. For the first time the paper describes the probable influence of NIFID on the artistic creativity of an accomplished artist showing rapid dissolution of artistic talent. Copyright (c) 2007 S. Karger AG, Basel.

Photocatalytic degradation of cylindrospermopsin under UV-A, solar and visible light using TiO2. Mineralization and intermediate products.

PubMed

Fotiou, Theodora; Triantis, Theodoros; Kaloudis, Triantafyllos; Hiskia, Anastasia

2015-01-01

Cyanobacteria (blue-green algae) are considered an important water quality problem, since several genera can produce toxins, called cyanotoxins that are harmful to human health. Cylindrospermopsin (CYN) is an alkaloid-like potent cyanotoxin that has been reported in water reservoirs and lakes worldwide. In this paper the removal of CYN from water by UV-A, solar and visible light photocatalysis was investigated. Two different commercially available TiO2 photocatalysts were used, i.e., Degussa P25 and Kronos-vlp7000. Complete degradation of CYN was achieved with both photocatalysts in 15 and 40 min under UV-A and 40 and 120 min under solar light irradiation, for Degussa P25 and Kronos vlp-7000 respectively. Experiments in the absence of photocatalysts showed that direct photolysis was negligible. Under visible light irradiation only the Kronos vlp-7000 which is a visible light activated catalyst was able to degrade CYN. A number of intermediates were identified and a complete degradation pathway is proposed, leading to the conclusion that hydroxyl radical attack is the main mechanism followed. TOC and inorganic ions (NO2-, NO3-, SO4(2-) and NH4+) determinations suggested that complete mineralization of CYN was achieved under UV-A in the presence of Degussa P25. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

NASA Technical Reports Server (NTRS)

Zahnle, K. J.

1986-01-01

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Effect of Intermediate Hosts on Emerging Zoonoses.

PubMed

Cui, Jing-An; Chen, Fangyuan; Fan, Shengjie

2017-08-01

Most emerging zoonotic pathogens originate from animals. They can directly infect humans through natural reservoirs or indirectly through intermediate hosts. As a bridge, an intermediate host plays different roles in the transmission of zoonotic pathogens. In this study, we present three types of pathogen transmission to evaluate the effect of intermediate hosts on emerging zoonotic diseases in human epidemics. These types are identified as follows: TYPE 1, pathogen transmission without an intermediate host for comparison; TYPE 2, pathogen transmission with an intermediate host as an amplifier; and TYPE 3, pathogen transmission with an intermediate host as a vessel for genetic variation. In addition, we established three mathematical models to elucidate the mechanisms underlying zoonotic disease transmission according to these three types. Stability analysis indicated that the existence of intermediate hosts increased the difficulty of controlling zoonotic diseases because of more difficult conditions to satisfy for the disease to die out. The human epidemic would die out under the following conditions: TYPE 1: [Formula: see text] and [Formula: see text]; TYPE 2: [Formula: see text], [Formula: see text], and [Formula: see text]; and TYPE 3: [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] Simulation with similar parameters demonstrated that intermediate hosts could change the peak time and number of infected humans during a human epidemic; intermediate hosts also exerted different effects on controlling the prevalence of a human epidemic with natural reservoirs in different periods, which is important in addressing problems in public health. Monitoring and controlling the number of natural reservoirs and intermediate hosts at the right time would successfully manage and prevent the prevalence of emerging zoonoses in humans.

A Walk through TRIDEC's intermediate Tsunami Early Warning System

NASA Astrophysics Data System (ADS)

Hammitzsch, M.; Reißland, S.; Lendholt, M.

2012-04-01

The management of natural crises is an important application field of the technology developed in the project Collaborative, Complex, and Critical Decision-Support in Evolving Crises (TRIDEC), co-funded by the European Commission in its Seventh Framework Programme. TRIDEC is based on the development of the German Indonesian Tsunami Early Warning System (GITEWS) and the Distant Early Warning System (DEWS) providing a service platform for both sensor integration and warning dissemination. In TRIDEC new developments in Information and Communication Technology (ICT) are used to extend the existing platform realising a component-based technology framework for building distributed tsunami warning systems for deployment, e.g. in the North-eastern Atlantic, the Mediterranean and Connected Seas (NEAM) region. The TRIDEC system will be implemented in three phases, each with a demonstrator. Successively, the demonstrators are addressing challenges, such as the design and implementation of a robust and scalable service infrastructure supporting the integration and utilisation of existing resources with accelerated generation of large volumes of data. These include sensor systems, geo-information repositories, simulation tools and data fusion tools. In addition to conventional sensors also unconventional sensors and sensor networks play an important role in TRIDEC. The system version presented is based on service-oriented architecture (SOA) concepts and on relevant standards of the Open Geospatial Consortium (OGC), the World Wide Web Consortium (W3C) and the Organization for the Advancement of Structured Information Standards (OASIS). In this way the system continuously gathers, processes and displays events and data coming from open sensor platforms to enable operators to quickly decide whether an early warning is necessary and to send personalized warning messages to the authorities and the population at large through a wide range of communication channels. The system

The production of trace gases by photochemistry and lightning in the early atmosphere

NASA Technical Reports Server (NTRS)

Levine, J. S.; Tennille, G. M.; Towe, K. M.; Khanna, R. K.

1986-01-01

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Effects of Using Instructional Video Games on Teaching English Vocabulary to Iranian Pre-Intermediate EFL Learners

ERIC Educational Resources Information Center

Salehi, Hadi

2017-01-01

This study aims to investigate whether there is any benefit in using IVGs among the Iranian pre-intermediate EFL learners or not. Therefore, 60 EFL learners from Padideh Derakhshan Institute in Sahinshahr, Isfahan, Iran were chosen as the sample. First, a test of novelty was administered at the early stage to ensure the novelty of to-be-instructed…

Using Early Silent Film to Teach French: The Language of "Cinema Muet."

ERIC Educational Resources Information Center

Bloom, Michelle E.

1995-01-01

Discusses the use of early silent films in second-language classrooms, focusing on the experiences of one instructor in using early French silents in elementary and intermediate French courses. Sample lesson plans and information on the availability of French silents are also provided. (Contains 17 references.) (MDM)

Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm

NASA Technical Reports Server (NTRS)

Brock, J. C.; Watson, R. T.

1980-01-01

The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.

Photodissociation of CF2ICF2I in solid para-hydrogen: infrared spectra of anti- and gauche-˙C2F4I radicals.

PubMed

Haupa, Karolina Anna; Lim, Manho; Lee, Yuan-Pern

2018-05-09

The photolysis of 1,2-diiodotetrafluoroethane (CF2ICF2I) has served as a prototypical system in ultrafast reaction dynamics. Even though the intermediates, anti- and gauche-iodotetrafluoroethyl (˙C2F4I) radicals, have been characterized with electron diffraction and X-ray diffraction, their infrared spectra are unreported. We report the formation and infrared identification of these radical intermediates upon ultraviolet photodissociation of CF2ICF2I in solid para-hydrogen (p-H2) at 3.3 K. Lines at 1364.9/1358.5, 1283.2, 1177.1, 1162.2, 1126.8, 837.3, 658.0, 574.2, and 555.2 cm-1 are assigned to anti-˙C2F4I, and lines at 1325.9, 1259.7, 1143.4, 1063.4, 921.0, and 765.3 cm-1 to gauche-˙C2F4I. A secondary photodissociation leading to C2F4 was also observed. The assignments were derived according to behavior on secondary photolysis, comparison of the vibrational wavenumbers and the IR intensities of the observed lines with values predicted with the B3PW91/aug-cc-pVTZ-pp method. This spectral identification provides valuable information for future direct spectral probes of these important intermediates.

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry.

PubMed

Wentrup, Curt

2018-05-29

There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years due to the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered. Numerous rearrangements and fragmentations have been documented. This minireview aims to give an overview of some of these developments but will not generally cover laser flash photolysis and chemical reactions in liquid solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Masonry. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Thompson, Moses

Several intermediate performance objectives and corresponding criterion measures are listed for each of 13 terminal objectives for an intermediate masonry course. These materials, developed for a two-semester (3 hours daily) course, are designed to provide the student with the skills and knowledge necessary for entry level employment in the field…

Hydroxo radicals, C-H activation, and Pt-C bond formation from 77 K photolysis of a platinum(IV) hydroxo complex.

PubMed

Wickramasinghe, Lasantha A; Sharp, Paul R

2014-11-17

Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

Protein vivisection reveals elusive intermediates in folding

PubMed Central

Zheng, Zhongzhou; Sosnick, Tobin R.

2010-01-01

Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu→Glu−) to destabilize and unfold a specific region of the protein. We apply this strategy to Ubiquitin, reversibly trapping a folding intermediate in which the β5 strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high energy states. PMID:20144618

Welding. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Vincent, Kenneth

Several intermediate performance objectives and corresponding criterion measures are listed for each of nine terminal objectives for an intermediate welding course. The materials were developed for a 36-week (3 hours daily) course designed to prepare the student for employment in the field of welding. Electric welding and specialized (TIG & MIG)…

Intermediate filament protein nestin is expressed in developing meninges.

PubMed

Yay, A; Ozdamar, S; Canoz, O; Baran, M; Tucer, B; Sonmez, M F

2014-01-01

Nestin is a type VI intermediate filament protein known as a marker for progenitor cells that can be mostly found in tissues during the embryonic and fetal periods. In our study, we aimed to determine the expression of nestin in meninges covering the brain tissue at different developmental stages and in the new born. In this study 10 human fetuses in different development stages between developmental weeks 9-34 and a newborn brain tissue were used. Fetuses in paraffin section were stained with H+E and nestin immunohistochemical staining protocol was performed. In this study, in the human meninges intense nestin expression was detected as early as in the 9th week of development. Intensity of this expression gradually decreased in later stages of development and nestin expression still persisted in a small population of newborn meningeal cells. In the present study, nestin positive cells gradually diminished in the developing and maturing meninges during the fetal period. This probably depends on initiation of a decrease in nestin expression and replacement with other tissue-specific intermediate filaments while the differentiation process continues. These differences can make significant contributions to the investigation and diagnosis of various pathological disorders (Tab. 1, Fig. 3, Ref. 36).

Endoplasmic Reticulum-Golgi Intermediate Compartment Membranes and Vimentin Filaments Participate in Vaccinia Virus Assembly

PubMed Central

Risco, Cristina; Rodríguez, Juan R.; López-Iglesias, Carmen; Carrascosa, José L.; Esteban, Mariano; Rodríguez, Dolores

2002-01-01

Vaccinia virus (VV) has a complex morphogenetic pathway whose first steps are poorly characterized. We have studied the early phase of VV assembly, when viral factories and spherical immature viruses (IVs) form in the cytoplasm of the infected cell. After freeze-substitution numerous cellular elements are detected around assembling viruses: membranes, ribosomes, microtubules, filaments, and unidentified structures. A double membrane is clearly resolved in the VV envelope for the first time, and freeze fracture reveals groups of tubules interacting laterally on the surface of the viroplasm foci. These data strongly support the hypothesis of a cellular tubulovesicular compartment, related to the endoplasmic reticulum-Golgi intermediate compartment (ERGIC), as the origin of the first VV envelope. Moreover, the cytoskeletal vimentin intermediate filaments are found around viral factories and inside the viroplasm foci, where vimentin and the VV core protein p39 colocalize in the areas where crescents protrude. Confocal microscopy showed that ERGIC elements and vimentin filaments concentrate in the viral factories. We propose that modified cellular ERGIC membranes and vimentin intermediate filaments act coordinately in the construction of viral factories and the first VV form through a unique mechanism of viral morphogenesis from cellular elements. PMID:11799179

29 CFR 452.123 - Elections of intermediate body officers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 2 2011-07-01 2011-07-01 false Elections of intermediate body officers. 452.123 Section... intermediate body officers. Section 401(d) states that officers of intermediate bodies shall be elected either... intermediate bodies. Such delegates may therefore participate in the election of officers of intermediate...

29 CFR 452.123 - Elections of intermediate body officers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 2 2010-07-01 2010-07-01 false Elections of intermediate body officers. 452.123 Section... intermediate body officers. Section 401(d) states that officers of intermediate bodies shall be elected either... intermediate bodies. Such delegates may therefore participate in the election of officers of intermediate...

Validation of intermediate end points in cancer research.

PubMed

Schatzkin, A; Freedman, L S; Schiffman, M H; Dawsey, S M

1990-11-21

Investigations using intermediate end points as cancer surrogates are quicker, smaller, and less expensive than studies that use malignancy as the end point. We present a strategy for determining whether a given biomarker is a valid intermediate end point between an exposure and incidence of cancer. Candidate intermediate end points may be selected from case series, ecologic studies, and animal experiments. Prospective cohort and sometimes case-control studies may be used to quantify the intermediate end point-cancer association. The most appropriate measure of this association is the attributable proportion. The intermediate end point is a valid cancer surrogate if the attributable proportion is close to 1.0, but not if it is close to 0. Usually, the attributable proportion is close to neither 1.0 nor 0; in this case, valid surrogacy requires that the intermediate end point mediate an established exposure-cancer relation. This would in turn imply that the exposure effect would vanish if adjusted for the intermediate end point. We discuss the relative advantages of intervention and observational studies for the validation of intermediate end points. This validation strategy also may be applied to intermediate end points for adverse reproductive outcomes and chronic diseases other than cancer.

A high-resolution, confocal laser-scanning microscope and flash photolysis system for physiological studies.

PubMed

Parker, I; Callamaras, N; Wier, W G

1997-06-01

We describe the construction of a high-resolution confocal laser-scanning microscope, and illustrate its use for studying elementary Ca2+ signalling events in cells. An avalanche photodiode module and simple optical path provide a high efficiency system for detection of fluorescence signals, allowing use of a small confocal aperture giving near diffraction-limited spatial resolution (< 300 nm lateral and < 400 nm axial). When operated in line-scan mode, the maximum temporal resolution is 1 ms, and the associated computer software allows complete flexibility to record line-scans continuously for long (minutes) periods or to obtain any desired pixel resolution in x-y scans. An independent UV irradiation system permits simultaneous photolysis of caged compounds over either a uniform, wide field (arc lamp source) or at a tightly focussed spot (frequency-tripled Nd:YAG laser). The microscope thus provides a versatile tool for optical studies of dynamic cellular processes, as well as excellent resolution for morphological studies. The confocal scanner can be added to virtually any inverted microscope for a component cost that is only a small fraction of that of comparable commercial instruments, yet offers better performance and greater versatility.

Curriculum for the Special Education Early Childhood Center.

ERIC Educational Resources Information Center

Taulbee, Dianne R.; And Others

This document presents Jackson County (Michigan) Intermediate School District's Special Education Early Childhood Center's 1988 curriculum. Sections focus on: (1) the center's program; (2) play observation; (3) eligibility; (4) classroom structure and function; (5) the importance of play; (6) developmental milestones; (7) planning and teaching…

The intermediate endpoint effect in logistic and probit regression

PubMed Central

MacKinnon, DP; Lockwood, CM; Brown, CH; Wang, W; Hoffman, JM

2010-01-01

Background An intermediate endpoint is hypothesized to be in the middle of the causal sequence relating an independent variable to a dependent variable. The intermediate variable is also called a surrogate or mediating variable and the corresponding effect is called the mediated, surrogate endpoint, or intermediate endpoint effect. Clinical studies are often designed to change an intermediate or surrogate endpoint and through this intermediate change influence the ultimate endpoint. In many intermediate endpoint clinical studies the dependent variable is binary, and logistic or probit regression is used. Purpose The purpose of this study is to describe a limitation of a widely used approach to assessing intermediate endpoint effects and to propose an alternative method, based on products of coefficients, that yields more accurate results. Methods The intermediate endpoint model for a binary outcome is described for a true binary outcome and for a dichotomization of a latent continuous outcome. Plots of true values and a simulation study are used to evaluate the different methods. Results Distorted estimates of the intermediate endpoint effect and incorrect conclusions can result from the application of widely used methods to assess the intermediate endpoint effect. The same problem occurs for the proportion of an effect explained by an intermediate endpoint, which has been suggested as a useful measure for identifying intermediate endpoints. A solution to this problem is given based on the relationship between latent variable modeling and logistic or probit regression. Limitations More complicated intermediate variable models are not addressed in the study, although the methods described in the article can be extended to these more complicated models. Conclusions Researchers are encouraged to use an intermediate endpoint method based on the product of regression coefficients. A common method based on difference in coefficient methods can lead to distorted

Hg-sensitized photolysis of diethylamine in the absence and presence of O/sub 2/ or N/sub 2/O

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeStefano, G.; Heicklen, J.

1986-09-11

The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O/sub 2/ or N/sub 2/O at room temperature. In the absence of foreign gases, the products were H/sub 2/, CH/sub 3/CH=NC/sub 2/H/sub 5/ and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and similarly ordered 0.02. Thus CH/sub 3/CHNHC/sub 2/H/sub 5/ radicals are produced exclusively and they are removed by self reaction: 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. DEA + CH/sub 3/CH=NC/sub 2/H/sub 5/ (4a) and 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. diamine III (4b), with k/sub 4a//k/sub 4b/ = 47.0 +/- 5.6. In the presence ofmore » O/sub 2/ the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH/sub 3/CH=NC/sub 2/H/sub 5/ as the exclusive product: (CH/sub 3/CHNHC/sub 2/H/sub 5/ + O/sub 2/ ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + HO/sub 2/ (5). The Hg-sensitized photolysis of N/sub 2/O gives O(/sup 3/P) atoms, which in the presence of DEA react to give the imine and (C/sub 2/H/sub 5/)/sub 2/NOH (DEHA) as products in concerted parallel steps: O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + H/sub 2/O (9a) and O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. (C/sub 2/H/sub 5/)/sub 2/NOH (9b), with k/sub 9a//k/sub 9b/ similarly ordered 9.5 +/- 1.7.« less

The effect of Cu(2+) chelation on the direct photolysis of oxytetracycline: A study assisted by spectroscopy analysis and DFT calculation.

PubMed

Jin, Xin; Qiu, Shanshan; Wu, Ke; Jia, Mingyun; Wang, Fang; Gu, Chenggang; Zhang, Aiqian; Jiang, Xin

2016-07-01

The extensive usage of OTC and Cu(2+) in livestock and poultry industry caused high residues in natural environment. Co-contamination of OTC and Cu(2+) was a considerable environmental problem in surface waters. In this study, Cu(2+) mediated direct photolysis of OTC was studied. Cu(2+) chelating with OTC was found to greatly inhibit OTC photodegradation. To reveal the chelation mechanism of OTC-Cu complexes, multiple methods including UV-Vis absorption spectra, Infrared (IR) spectra, mass spectroscopy, and density functional theoretical (DFT) modeling were performed. Four OTC-Cu complexes were proposed. Cu(2+) preferably bond to O11O12 site with the binding constants logK = 8.19 and 7.86 for CuHL+ and CuL±, respectively. The second chelating site was suggested to be O2O3 with the binding constants of logK = 4.41 and 4.62 for Cu2HL3+ and Cu2L2+, respectively. The suppressed quantum yield of OTC by Cu2+ chelation was accused for their intra-/inter-molecular electron transfer, by which the energy in activated states was distributed. The occurrence of electron transfer between BCD ring and A ring also from BCD ring to Cu was evidenced by the TD-DFT result only for the OTC-Cu complexes. Besides, the cyclic voltammetry measurement also suggested one OTC-Cu(II)/OTC-Cu(I) redox couple. These results suggested that the persistence of OTC in environmental surface waters will probably be underestimated for neglecting the chelating effect of Cu2+. The photolysis quantum yield of OTC-Cu complexes, as well as the specific molar absorption constants, the equilibrium binding constants of Cu2+ with OTC could contribute to more accurate kinetic models of OTC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Laser flash photolysis and CIDNP studies of steric effects on coupling rate constants of imidazolidine nitroxide with carbon-centered radicals, methyl isobutyrate-2-yl and tert-butyl propionate-2-yl.

PubMed

Zubenko, Dmitry; Tsentalovich, Yuri; Lebedeva, Nataly; Kirilyuk, Igor; Roshchupkina, Galina; Zhurko, Irina; Reznikov, Vladimir; Marque, Sylvain R A; Bagryanskaya, Elena

2006-08-04

Time-resolved chemically induced dynamic nuclear polarization (TR-CIDNP) and laser flash photolysis (LFP) techniques have been used to measure rate constants for coupling between acrylate-type radicals and a series of newly synthesized stable imidazolidine N-oxyl radicals. The carbon-centered radicals under investigation were generated by photolysis of their corresponding ketone precursors RC(O)R (R = C(CH3)2-C(O)OCH3 and CH(CH3)-C(O)-OtBu) in the presence of stable nitroxides. The coupling rate constants kc for modeling studies of nitroxide-mediated polymerization (NMP) experiments were determined, and the influence of steric and electronic factors on kc values was addressed by using a Hammett linear free energy relationship. The systematic changes in kc due to the varied steric (Es,n) and electronic (sigmaL,n) characters of the substituents are well-described by the biparameter equation log(kc/M- 1s(-1)) = 3.52sigmaL,n + 0.47Es,n + 10.62. Hence, kc decreases with the increasing steric demand and increases with the increasing electron-withdrawing character of the substituents on the nitroxide.

Holographic Photolysis for Multiple Cell Stimulation in Mouse Hippocampal Slices

PubMed Central

Papagiakoumou, Eirini; Ventalon, Cathie; Angulo, María Cecilia; Emiliani, Valentina

2010-01-01

Background Advanced light microscopy offers sensitive and non-invasive means to image neural activity and to control signaling with photolysable molecules and, recently, light-gated channels. These approaches require precise and yet flexible light excitation patterns. For synchronous stimulation of subsets of cells, they also require large excitation areas with millisecond and micrometric resolution. We have recently developed a new method for such optical control using a phase holographic modulation of optical wave-fronts, which minimizes power loss, enables rapid switching between excitation patterns, and allows a true 3D sculpting of the excitation volumes. In previous studies we have used holographic photololysis to control glutamate uncaging on single neuronal cells. Here, we extend the use of holographic photolysis for the excitation of multiple neurons and of glial cells. Methods/Principal Findings The system combines a liquid crystal device for holographic patterned photostimulation, high-resolution optical imaging, the HiLo microscopy, to define the stimulated regions and a conventional Ca2+ imaging system to detect neural activity. By means of electrophysiological recordings and calcium imaging in acute hippocampal slices, we show that the use of excitation patterns precisely tailored to the shape of multiple neuronal somata represents a very efficient way for the simultaneous excitation of a group of neurons. In addition, we demonstrate that fast shaped illumination patterns also induce reliable responses in single glial cells. Conclusions/Significance We show that the main advantage of holographic illumination is that it allows for an efficient excitation of multiple cells with a spatiotemporal resolution unachievable with other existing approaches. Although this paper focuses on the photoactivation of caged molecules, our approach will surely prove very efficient for other probes, such as light-gated channels, genetically encoded photoactivatable

Crystal structure of a photolysis product of vitamin B6: A pyridodihydrofuran-condensed skeleton compound of pyridoxal 5‧-phosphate

NASA Astrophysics Data System (ADS)

Aoki, Katsuyuki; Nakamura, Hideyuki; Hattori, Toshiaki; Hu, Ning-Hai; Onishi, Masayoshi

2017-11-01

An aqueous solution dissolving pyridoxal 5‧-phosphate (PLP) was exposed to sun-light at room temperature to yield a photolysis product, 4b,9b-dihydro-4b,9b-dihydroxy-1,6-dimethyl-4,9-bis(phosphonooxymethyl){pyrido[3‧,4‧:2,3]furo[4,5-b]}pyrido[4,3-d]furan (1), whose structure was crystallographically determined. The product 1 was found to be a novel C(sp3)-C(sp3) side-sharing pyridodihydrofuran-condensed skeleton compound with the two pyridodihydrofuran planes taking a 'V-shape'-like molecular configuration. Hydrogen bonding patterns of molecules of 1 in the crystal lattice are analyzed by the graph set approach. The most probable mechanism for the formation of 1 is described.

(CH3)3COOH (tert-butyl hydroperoxide): OH reaction rate coefficients between 206 and 375 K and the OH photolysis quantum yield at 248 nm.

PubMed

Baasandorj, Munkhbayar; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Hasson, Alam S; Burkholder, James B

2010-10-14

Rate coefficients, k, for the gas-phase reaction of the OH radical with (CH(3))(3)COOH (tert-butyl hydroperoxide) were measured as a function of temperature (206-375 K) and pressure (25-200 Torr (He, N(2))). Rate coefficients were measured under pseudo-first-order conditions using pulsed laser photolysis to produce OH and laser induced fluorescence (PLP-LIF) to measure the OH temporal profile. Two independent methods were used to determine the gas-phase infrared cross sections of (CH(3))(3)COOH, absolute pressure and chemical titration, that were used to determine the (CH(3))(3)COOH concentration in the LIF reactor. The temperature dependence of the rate coefficients is described, within the measurement precision, by the Arrhenius expression k(1)(T) = (7.0 ± 1.0) × 10(-13) exp[(485 ± 20)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (3.58 ± 0.54) × 10(-12) cm(3) molecule(-1) s(-1). The uncertainties are 2σ (95% confidence level) and include estimated systematic errors. UV absorption cross sections of (CH(3))(3)COOH were determined at 185, 214, 228, and 254 nm and over the wavelength range 210-300 nm. The OH quantum yield following the 248 nm pulsed laser photolysis of (CH(3))(3)COOH was measured relative to the OH quantum yields of H(2)O(2) and HNO(3) using PLP-LIF and found to be near unity.

Providing effective and preferred care closer to home: a realist review of intermediate care.

PubMed

Pearson, Mark; Hunt, Harriet; Cooper, Chris; Shepperd, Sasha; Pawson, Ray; Anderson, Rob

2015-11-01

Intermediate care is one of the number of service delivery models intended to integrate care and provide enhanced health and social care services closer to home, especially to reduce reliance on acute care hospital beds. In order for health and social care practitioners, service managers and commissioners to make informed decisions, it is vital to understand how to implement the admission avoidance and early supported discharge components of intermediate care within the context of local care systems. This paper reports the findings of a theory-driven (realist) review conducted in 2011-2012. A broad range of evidence contained in 193 sources was used to construct a conceptual framework for intermediate care. This framework forms the basis for exploring factors at service user, professional and organisational levels that should be considered when designing and delivering intermediate care services within a particular local context. Our synthesis found that involving service users and their carers in collaborative decision-making about the objectives of care and the place of care is central to achieving the aims of intermediate care. This pivotal involvement of the service user relies on practitioners, service managers and commissioners being aware of the impact that organisational structures at the local level can have on enabling or inhibiting collaborative decision-making and care co-ordination. Through all interactions with service users and their care networks, health and social care professionals should establish the meaning which alternative care environments have for different service users. Doing so means decisions about the best place of care will be better informed and gives service users choice. This in turn is likely to support psychological and social stability, and the attainment of functional goals. At an organisational level, integrated working can facilitate the delivery of intermediate care, but there is not a straightforward relationship between

The intermediate filament network protein, vimentin, is required for parvoviral infection.

PubMed

Fay, Nikta; Panté, Nelly

2013-09-01

Intermediate filaments (IFs) have recently been shown to serve novel roles during infection by many viruses. Here we have begun to study the role of IFs during the early steps of infection by the parvovirus minute virus of mice (MVM). We found that during early infection with MVM, after endosomal escape, the vimentin IF network was considerably altered, yielding collapsed immunofluorescence staining near the nuclear periphery. Furthermore, we found that vimentin plays an important role in the life cycle of MVM. The number of cells, which successfully replicated MVM, was reduced in infected cells in which the vimentin network was genetically or pharmacologically modified; viral endocytosis, however, remained unaltered. Perinuclear accumulation of MVM-containing vesicles was reduced in cells lacking vimentin. Our data suggests that vimentin is required for the MVM life cycle, presenting possibly a dual role: (1) following MVM escape from endosomes and (2) during endosomal trafficking of MVM. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

Generation mechanism of hydroxyl radical species and its lifetime prediction during the plasma-initiated ultraviolet (UV) photolysis

PubMed Central

Attri, Pankaj; Kim, Yong Hee; Park, Dae Hoon; Park, Ji Hoon; Hong, Young J.; Uhm, Han Sup; Kim, Kyoung-Nam; Fridman, Alexander; Choi, Eun Ha

2015-01-01

Through this work, we have elucidated the mechanism of hydroxyl radicals (OH•) generation and its life time measurements in biosolution. We observed that plasma-initiated ultraviolet (UV) photolysis were responsible for the continues generation of OH• species, that resulted in OH• to be major reactive species (RS) in the solution. The density and lifetime of OH• species acted inversely proportional to each other with increasing depth inside the solution. The cause of increased lifetime of OH• inside the solution is predicted using theoretical and semiempirical calculations. Further, to predict the mechanism of conversion of hydroxide ion (OH−) to OH• or H2O2 (hydrogen peroxide) and electron, we determined the current inside the solution of different pH. Additionally, we have investigated the critical criterion for OH• interaction on cancer cell inducing apoptosis under effective OH• exposure time. These studies are innovative in the field of plasma chemistry and medicine. PMID:25790968

Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride

NASA Astrophysics Data System (ADS)

Thomson, Robert K.; Cantat, Thibault; Scott, Brian L.; Morris, David E.; Batista, Enrique R.; Kiplinger, Jaqueline L.

2010-09-01

Uranium nitride [U≡N]x is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U≡N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U≡N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C6F5)3. These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.

Study of the photochemical transformation of 2-ethylhexyl 4-(dimethylamino)benzoate (OD-PABA) under conditions relevant to surface waters.

PubMed

Calza, P; Vione, D; Galli, F; Fabbri, D; Dal Bello, F; Medana, C

2016-01-01

We studied the aquatic environmental fate of 2-ethylhexyl 4-(dimethylamino)benzoate (OD-PABA), a widespread sunscreen, to assess its environmental persistence and photoinduced transformation. Direct photolysis is shown to play a key role in phototransformation, and this fast process is expected to be the main attenuation route of OD-PABA in sunlit surface waters. The generation of transformation products (TPs) was followed via HPLC/HRMS. Five (or four) TPs were detected in the samples exposed to UVB (or UVA) radiation, respectively. The main detected TPs of OD-PABA, at least as far as HPLC-HRMS peak areas are concerned, would involve a dealkylation or hydroxylation/oxidation process in both direct photolysis and indirect phototransformation. The latter was simulated by using TiO2-based heterogeneous photocatalysis, involving the formation of nine additional TPs. Most of them resulted from the further degradation of the primary TPs that can also be formed by direct photolysis. Therefore, these secondary TPs might also occur as later transformation intermediates in natural aquatic systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-).

PubMed

Yempally, Veeranna; Moncho, Salvador; Hasanayn, Faraj; Fan, Wai Yip; Brothers, Edward N; Bengali, Ashfaq A

2017-09-18

The photochemistry of two Mn(bpy)(CO) 3 X complexes (X = PhCC - , Br - ) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO) 2 ] affords the ionic complex [1-(MeCN) 2 ]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br - . Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth.

PubMed

Catling, D C; Zahnle, K J; McKay, C

2001-08-03

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.

Appliance Services. Intermediate Course. Career Education.

ERIC Educational Resources Information Center

Killough, Joseph

Several intermediate performance objectives and corresponding criterion measures are listed for each of 16 terminal objectives for an intermediate appliance repair course. The materials were developed for a 36-week course (3 hours daily) covering the areas of refrigeration, maintenance, repair, and troubleshooting of refrigerators and air…

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 19 2013-07-01 2013-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 19 2012-07-01 2012-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 18 2011-07-01 2011-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

Biospheric-atmospheric coupling on the early Earth

NASA Technical Reports Server (NTRS)

Levine, J. S.

1991-01-01

Theoretical calculations performed with a one-dimensional photochemical model have been performed to assess the biospheric-atmospheric transfer of gases. Ozone reached levels to shield the Earth from biologically lethal solar ultraviolet radiation (220-300 nm) when atmospheric oxygen reached about 1/10 of its present atmospheric level. In the present atmosphere, about 90 percent of atmospheric nitrous oxide is destroyed via solar photolysis in the stratosphere with about 10 percent destroyed via reaction with excited oxygen atoms. The reaction between nitrous oxide and excited oxygen atoms leads to the production of nitric oxide in the stratosphere, which is responsible for about 70 percent of the global destruction of oxygen in the stratosphere. In the oxygen/ozone deficient atmosphere, solar photolysis destroyed about 100 percent of the atmospheric nitrous oxide, relegating the production of nitric oxide via reaction with excited oxygen to zero. Our laboratory and field measurements indicate that atmospheric oxygen promotes the biogenic production of N2O and NO via denitrification and the biogenic production of methane by methanogenesis.

Air Conditioning. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Long, William

Several intermediate performance objectives and corresponding criterion measures are listed for each of seven terminal objectives for an intermediate air conditioning course. The titles of the seven terminal objectives are Refrigeration Cycle, Job Requirement Skills, Air Conditioning, Trouble Shooting, Performance Test, Shop Management, and S.I.E.…

42 CFR 54.12 - Treatment of intermediate organizations.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 1 2010-10-01 2010-10-01 false Treatment of intermediate organizations. 54.12... intermediate organizations. If a nongovernmental organization (referred to here as an “intermediate organization”), acting under a contract or other agreement with the Federal Government or a State or local...

The dichotomy between strong and ultra-weak magnetic fields among intermediate-mass stars

NASA Astrophysics Data System (ADS)

Lignières, François; Petit, Pascal; Aurière, Michel; Wade, Gregg A.; Böhm, Torsten

2014-08-01

Until recently, the detection of magnetic fields at the surface of intermediate-mass main-sequence stars has been limited to Ap/Bp stars, a class of chemically peculiar stars. This class represents no more than 5-10% of the stars in this mass range. This small fraction is not explained by the fossil field paradigm that describes the Ap/Bp type magnetism as a remnant of an early phase of the star-life. Also, the limitation of the field measurements to a small and special group of stars is obviously a problem to study the effect of the magnetic fields on the stellar evolution of a typical intermediate-mass star. Thanks to the improved sensitivity of a new generation of spectropolarimeters, a lower bound to the magnetic fields of Ap/Bp stars, a two orders of magnitude desert in the longitudinal magnetic field and a new type of sub-gauss magnetism first discovered on Vega have been identified. These advances provide new clues to understand the origin of intermediate-mass magnetism as well as its influence on stellar evolution. In particular, a scenario has been proposed whereby the magnetic dichotomy between Ap/Bp and Vega-like magnetism originate from the bifurcation between stable and unstable large scale magnetic configurations in differentially rotating stars. In this paper, we review these recent observational findings and discuss this scenario.

14 CFR 398.8 - Number of intermediate stops.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Number of intermediate stops. 398.8 Section 398.8 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION... Number of intermediate stops. (a) Except in Alaska, no more than one intermediate stop is permitted in...

14 CFR 398.8 - Number of intermediate stops.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false Number of intermediate stops. 398.8 Section 398.8 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION... Number of intermediate stops. (a) Except in Alaska, no more than one intermediate stop is permitted in...

Diesel Mechanics. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Tidwell, Joseph

Several intermediate performance objectives and corresponding criterion measures are listed for each of six terminal objectives for an intermediate diesel mechanics course (two semesters, 3 hours daily) designed for high school students who upon completion would be ready for an on-the-job training experience in diesel service and repair. Through…

Sensitized and heavy atom induced production of acenaphthylene triplet: A laser flash photolysis study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samanta, A.; Fessenden, R.W.

1989-07-27

The triplet state of acenaphthylene has been examined by nanosecond laser flash photolysis using sensitization and heavy atom perturbation techniques. Although acenaphthylene does not form any observable triplet upon direct flash excitation, a transient with microsecond lifetime ({lambda}{sub max} = 315 nm) is observable when a solution of the sample is excited by sensitizers (benzophenone, thioxanthone, benzil). This transient is ascribed to the triplet of acenaphthylene on the basis of its quenching behavior toward oxygen, ferrocene, azulene, and {beta}-carotene. Quantitative data concerning the triplet-triplet absorption and quenching constants are presented. The triplet energy is estimated to lie between 46 andmore » 47 kcal/mol. The triplet can also be produced by direct excitation in solvents containing heavy atoms (ethyl bromide, ethyl iodide). The triplet yield is found to increase with an increase of the amount of the heavy atom containing solvent. No saturation limit is obtained. These facts together with the effect of heavy atoms on the T{sub 1} {yields} S{sub 0} process allow the differing behavior of ethyl bromide and ethyl iodide on the photodimerization process of acenaphthylene to be explained. Triplet-state parameters (extinction coefficient and triplet yield) have been estimated in these solvents by the energy-transfer technique and actinometry.« less

Hydroxyacetone production from C 3 Criegee intermediates

DOE PAGES

Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon; ...

2016-12-21

Hydroxyacetone (CH 3C(O)CH 2OH) is observed as a stable end product from reactions of the (CH 3) 2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerizationmore » via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.« less

Radio and Television Servicing. Intermediate Course.

ERIC Educational Resources Information Center

Campbell, Guy; And Others

Several intermediate performance objectives and corresponding criterion measures are listed for each of 32 terminal objectives for an intermediate (second year) radio/TV servicing course. This 1-year course (3 hours daily) was designed to provide the student with the basic skills and knowledges necessary for entry level employment in the Radio/TV…

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth

NASA Technical Reports Server (NTRS)

Cooper, G.; Kimmich, N.; Belisle, W.; Sarinana, J.; Brabham, K.; Garrel, L.

2001-01-01

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 19 Customs Duties 1 2011-04-01 2011-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 19 Customs Duties 1 2010-04-01 2010-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 19 Customs Duties 1 2012-04-01 2012-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 19 Customs Duties 1 2014-04-01 2014-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 19 Customs Duties 1 2013-04-01 2013-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

Nucleation via an unstable intermediate phase.

PubMed

Sear, Richard P

2009-08-21

The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

Inability to determine tissue health is main indication of allograft use in intermediate extent burns.

PubMed

Fletcher, John L; Cancio, Leopoldo C; Sinha, Indranil; Leung, Kai P; Renz, Evan M; Chan, Rodney K

2015-12-01

Cutaneous allograft is commonly used in the early coverage of excised burns when autograft is unavailable. However, allograft is also applied in intermediate-extent burns (25-50%), during cases in which it is possible to autograft. In this population, there is a paucity of data on the indications for allograft use. This study explores the indications for allograft usage in moderate size burns. Under an IRB-approved protocol, patients admitted to our burn unit between March 2003 and December 2010 were identified through a review of the burn registry. Data on allograft use, total burn surface area, operation performed, operative intent, number of operations, intensive care unit length of stay, and overall length of stay were collected and analyzed. Data are presented as means±standard deviations, except where noted. In the study period, 146 patients received allograft during their acute hospitalization. Twenty-five percent of allograft recipients sustained intermediate-extent burns. Patients with intermediate-extent burns received allograft later in their hospitalization than those with large-extent (50-75% TBSA) burns (6.8 days vs. 3.4 days, p=0.01). Allografted patients with intermediate-extent burns underwent more operations (10.8 vs. 6.1, p=0.002) and had longer hospitalizations (78.3 days vs. 40.9 days, p<0.001) than non-allografted patients, when controlled for TBSA. Clinical rationale for placement of allograft in this population included autograft failure, uncertain depth of excision, lack of autograft donor site, and wound complexity. When uncertain depth of excision was the indication, allograft was universally applied onto the face. In half of allografted intermediate-extent burn patients the inability to identify a viable recipient bed was the ultimate reason for allograft use. Unlike large body surface area burns, allograft skin use in intermediate-extent injury occurs later in the hospitalization and is driven by the inability to determine wound bed

Contingency Table Browser - prediction of early stage protein structure.

PubMed

Kalinowska, Barbara; Krzykalski, Artur; Roterman, Irena

2015-01-01

The Early Stage (ES) intermediate represents the starting structure in protein folding simulations based on the Fuzzy Oil Drop (FOD) model. The accuracy of FOD predictions is greatly dependent on the accuracy of the chosen intermediate. A suitable intermediate can be constructed using the sequence-structure relationship information contained in the so-called contingency table - this table expresses the likelihood of encountering various structural motifs for each tetrapeptide fragment in the amino acid sequence. The limited accuracy with which such structures could previously be predicted provided the motivation for a more indepth study of the contingency table itself. The Contingency Table Browser is a tool which can visualize, search and analyze the table. Our work presents possible applications of Contingency Table Browser, among them - analysis of specific protein sequences from the point of view of their structural ambiguity.

Accelerating Quinoline Biodegradation and Oxidation with Endogenous Electron Donors.

PubMed

Bai, Qi; Yang, Lihui; Li, Rongjie; Chen, Bin; Zhang, Lili; Zhang, Yongming; Rittmann, Bruce E

2015-10-06

Quinoline, a recalcitrant heterocyclic compound, is biodegraded by a series of reactions that begin with mono-oxygenations, which require an intracellular electron donor. Photolysis of quinoline can generate readily biodegradable products, such as oxalate, whose bio-oxidation can generate endogenous electron donors that ought to accelerate quinoline biodegradation and, ultimately, mineralization. To test this hypothesis, we compared three protocols for the biodegradation of quinoline: direct biodegradation (B), biodegradation after photolysis of 1 h (P1h+B) or 2 h (P2h+B), and biodegradation by adding oxalate commensurate to the amount generated from photolysis of 1 h (O1+B) or 2 h (O2+B). The experimental results show that P1h+B and P2h+B accelerated quinoline biodegradation by 19% and 50%, respectively, compared to B. Protocols O1+B and O2+B also gave 19% and 50% increases, respectively. During quinoline biodegradation, its first intermediate, 2-hydroxyquinoline, accumulated gradually in parallel to quinoline loss but declined once quinoline was depleted. Mono-oxygenation of 2-hydroxyquinoline competed with mono-oxygenation of quinoline, but the inhibition was relieved when extra electrons donors were added from oxalate, whether formed by UV photolysis or added exogenously. Rapid oxalate oxidation stimulated both mono-oxygenations, which accelerated the overall quinoline oxidation that provided the bulk of the electron donor.

An intermediate level of BMP signaling directly specifies cranial neural crest progenitor cells in zebrafish.

PubMed

Schumacher, Jennifer A; Hashiguchi, Megumi; Nguyen, Vu H; Mullins, Mary C

2011-01-01

The specification of the neural crest progenitor cell (NCPC) population in the early vertebrate embryo requires an elaborate network of signaling pathways, one of which is the Bone Morphogenetic Protein (BMP) pathway. Based on alterations in neural crest gene expression in zebrafish BMP pathway component mutants, we previously proposed a model in which the gastrula BMP morphogen gradient establishes an intermediate level of BMP activity establishing the future NCPC domain. Here, we tested this model and show that an intermediate level of BMP signaling acts directly to specify the NCPC. We quantified the effects of reducing BMP signaling on the number of neural crest cells and show that neural crest cells are significantly increased when BMP signaling is reduced and that this increase is not due to an increase in cell proliferation. In contrast, when BMP signaling is eliminated, NCPC fail to be specified. We modulated BMP signaling levels in BMP pathway mutants with expanded or no NCPCs to demonstrate that an intermediate level of BMP signaling specifies the NCPC. We further investigated the ability of Smad5 to act in a graded fashion by injecting smad5 antisense morpholinos and show that increasing doses first expand the NCPCs and then cause a loss of NCPCs, consistent with Smad5 acting directly in neural crest progenitor specification. Using Western blot analysis, we show that P-Smad5 levels are dose-dependently reduced in smad5 morphants, consistent with an intermediate level of BMP signaling acting through Smad5 to specify the neural crest progenitors. Finally, we performed chimeric analysis to demonstrate for the first time that BMP signal reception is required directly by NCPCs for their specification. Together these results add substantial evidence to a model in which graded BMP signaling acts as a morphogen to pattern the ectoderm, with an intermediate level acting in neural crest specification.

Smc5/6-Mms21 Prevents and Eliminates Inappropriate Recombination Intermediates in Meiosis

PubMed Central

Xaver, Martin; Huang, Lingzhi; Chen, Doris; Klein, Franz

2013-01-01

Repairing broken chromosomes via joint molecule (JM) intermediates is hazardous and therefore strictly controlled in most organisms. Also in budding yeast meiosis, where production of enough crossovers via JMs is imperative, only a subset of DNA breaks are repaired via JMs, closely regulated by the ZMM pathway. The other breaks are repaired to non-crossovers, avoiding JM formation, through pathways that require the BLM/Sgs1 helicase. “Rogue” JMs that escape the ZMM pathway and BLM/Sgs1 are eliminated before metaphase by resolvases like Mus81-Mms4 to prevent chromosome nondisjunction. Here, we report the requirement of Smc5/6-Mms21 for antagonizing rogue JMs via two mechanisms; destabilizing early intermediates and resolving JMs. Elimination of the Mms21 SUMO E3-ligase domain leads to transient JM accumulation, depending on Mus81-Mms4 for resolution. Absence of Smc6 leads to persistent rogue JMs accumulation, preventing chromatin separation. We propose that the Smc5/6-Mms21 complex antagonizes toxic JMs by coordinating helicases and resolvases at D-Loops and HJs, respectively. PMID:24385936

Cytoplasmic peptidoglycan intermediate levels in Staphylococcus aureus.

PubMed

Vemula, Harika; Ayon, Navid J; Gutheil, William G

2016-02-01

Intracellular cytoplasmic peptidoglycan (PG) intermediate levels were determined in Staphylococcus aureus during log-phase growth in enriched media. Levels of UDP-linked intermediates were quantitatively determined using ion pairing LC-MS/MS in negative mode, and amine intermediates were quantitatively determined stereospecifically as their Marfey's reagent derivatives in positive mode. Levels of UDP-linked intermediates in S. aureus varied from 1.4 μM for UDP-GlcNAc-Enolpyruvyate to 1200 μM for UDP-MurNAc. Levels of amine intermediates (L-Ala, D-Ala, D-Ala-D-Ala, L-Glu, D-Glu, and L-Lys) varied over a range of from 860 μM for D-Ala-D-Ala to 30-260 mM for the others. Total PG was determined from the D-Glu content of isolated PG, and used to estimate the rate of PG synthesis (in terms of cytoplasmic metabolite flux) as 690 μM/min. The total UDP-linked intermediates pool (2490 μM) is therefore sufficient to sustain growth for 3.6 min. Comparison of UDP-linked metabolite levels with published pathway enzyme characteristics demonstrates that enzymes on the UDP-branch range from >80% saturation for MurA, Z, and C, to <5% saturation for MurB. Metabolite levels were compared with literature values for Escherichia coli, with the major difference in UDP-intermediates being the level of UDP-MurNAc, which was high in S. aureus (1200 μM) and low in E. coli (45 μM). Copyright © 2015 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Femtosecond Photolysis of CO-Ligated Protoheme and Hemoproteins: Appearance of Deoxy Species with a 350-Fsec Time Constant

NASA Astrophysics Data System (ADS)

Martin, J. L.; Migus, A.; Poyart, C.; Lecarpentier, Y.; Astier, R.; Antonetti, A.

1983-01-01

Photolysis of HbCO, MbCO, and CO-protoheme has been investigated by measuring transient differential spectra and kinetics of induced absorption after excitation with a 250-fsec laser pulse at 307 nm. Probing was performed by a part of a continuum pulse between 395 and 445 nm. Photodissociation of the three liganded species occurred within the pulse duration. By contrast, the formation of deoxy species appeared with a mean (± SD) response time of 350± 50 fsec. This time constant was identical for the three species and independent of the presence or absence of the protein structure. Our results suggest the formation of a transient high-spin in plane iron (II) species which relaxes in 350 fsec to a high-spin stable state with concerted kinetics of CO departure and iron displacement. The spin transition is suspected to occur via liganded excited states which relax in part to nonreactive states with a 3,2-psec time constant.

Exploring the negative social evaluation of patients by specialist physiotherapists working in residential intermediate care.

PubMed

Thomson, Di; Love, Helen

2013-03-01

Residential intermediate care represents an innovative model of care that facilitates early hospital discharge and avoids unnecessary hospital admission. It also represents an environment where patients may demonstrate emotional vulnerability following a period of acute illness or injury, and this may impact on the quality of the patient/physiotherapist relationship. To gain an understanding of the negative social evaluation of patients by specialist physiotherapists, and to explore possible coping strategies in order to engage patients in appropriately designed rehabilitation programmes. Using a grounded theory approach, physiotherapists working in an intermediate care facility in a senior role were invited to participate in a focus group. Following the focus group analysis, a further four physiotherapists, with similar levels of experience to those in the focus group, were recruited to participate in semi-structured interviews to explore the emerging categories in greater depth. The findings revealed some categories that the therapists believed resided with the patients (alcohol dependency, failing to adapt/accept their condition and patients whose families hindered the process of rehabilitation) and some that appeared to reside within the context of intermediate rehabilitation (labelling, the 6-week model of intermediate care and the process of transition into the service). Coping strategies cited were workforce planning, goal setting and reflective practice. While supportive strategies have been developed locally to assist staff in managing their anxiety related to therapeutic interactions with 'difficult patients', it is also recognised that they have the potential for demotivation and are a possible precursor for stress. Copyright © 2011 Chartered Society of Physiotherapy. Published by Elsevier Ltd. All rights reserved.

Accounting for dissociation and photolysis: a review of the algal toxicity of triclosan.

PubMed

Roberts, Jayne; Price, Oliver R; Bettles, Nicola; Rendal, Cecilie; van Egmond, Roger

2014-11-01

Triclosan, an antimicrobial agent commonly used in down-the-drain consumer products, is toxic to freshwater microalgae. However, the rapid photolysis and pH-dependent dissociation of this compound may give rise to uncertainty in growth inhibition tests with freshwater microalgae, if these are not well characterized. Methods are presented to minimize these uncertainties by stabilizing pH with an organic buffering agent (Bis-Tris) and by the application of ultraviolet (UV) covers to remove UV wavelengths. Toxicity tests with these methods were in compliance with the validity criteria of the Organisation for Economic Co-operation and Development test 201, and no negative effects were seen in controls relative to the unmodified method. The methods were used for toxicity tests with triclosan at pH levels of 7.0, 8.0, and 8.5, yielding effective concentration, 10% values of 0.5 µg/L, 0.6 µg/L, and 12.1 µg/L, respectively. The observed change in toxicity with pH was proportional to the change in bioconcentration factor (BCF) as calculated using the cell model (a dynamic flux model based on the Fick-Nernst-Planck equations, in this case parameterized for an algal cell). Effect concentrations produced with the methods presented in the present study offer robust data on which to base risk assessment, and it is suggested that similar approaches be used to minimize uncertainty when other compounds that dissociate and photolyse are tested. © 2014 SETAC.

Isoporphyrin Intermediate in Heme Oxygenase Catalysis

PubMed Central

Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

2008-01-01

Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

Remission of Intermediate Uveitis: Incidence and Predictive Factors.

PubMed

Kempen, John H; Gewaily, Dina Y; Newcomb, Craig W; Liesegang, Teresa L; Kaçmaz, R Oktay; Levy-Clarke, Grace A; Nussenblatt, Robert B; Rosenbaum, James T; Sen, H Nida; Suhler, Eric B; Thorne, Jennifer E; Foster, C Stephen; Jabs, Douglas A; Payal, Abhishek; Fitzgerald, Tonetta D

2016-04-01

To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Retrospective cohort study. Involved eyes of patients with primary noninfectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval [CI], 7.4-10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (hazard ratio [HR] [vs no PPV] = 2.39; 95% CI, 1.42-4.00), diagnosis of intermediate uveitis within the last year (HR [vs diagnosis >5 years ago] =3.82; 95% CI, 1.91-7.63), age ≥45 years (HR [vs age <45 years] = 1.79; 95% CI, 1.03-3.11), female sex (HR = 1.61; 95% CI, 1.04-2.49), and Hispanic race/ethnicity (HR [vs white race] = 2.81; 95% CI, 1.23-6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed patients and older, female, and Hispanic patients were more likely to remit. With regard to management, pars plana vitrectomy was associated with increased probability of remission. Copyright © 2016 Elsevier Inc. All rights reserved.

Remission of Intermediate Uveitis: Incidence and Predictive Factors

PubMed Central

Kempen, John H.; Gewaily, Dina Y.; Newcomb, Craig W.; Liesegang, Teresa L.; Kaçmaz, R. Oktay; Levy-Clarke, Grace A.; Nussenblatt, Robert B.; Rosenbaum, James T.; Sen, H. Nida; Suhler, Eric B.; Thorne, Jennifer E.; Foster, C. Stephen; Jabs, Douglas A.; Payal, Abhishek; Fitzgerald, Tonetta D.

2016-01-01

Purpose To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Design Retrospective cohort study. Methods Involved eyes of patients with primary non-infectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Results Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1,934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval (CI), 7.4–10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (HR (vs. no PPV)=2.39; 95% CI, 1.42–4.00), diagnosis of intermediate uveitis within the last year (vs. diagnosis >5 years ago)=3.82; 95% CI, 1.91–7.63), age ≥45 years (HR (vs. age <45 years)=1.79; 95% CI, 1.03–3.11), female sex (HR=1.61; 95% CI, 1.04–2.49), and Hispanic race/ethnicity (HR (vs. white race)=2.81; 95% CI, 1.23–6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Conclusions Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed cases, and older, female and Hispanic cases were more likely to remit. With regards to management, pars plana vitrectomy was associated with increased probability of remission. PMID:26772874

Marine Engine Mechanics. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Jones, Marion

Several intermediate performance objectives and corresponding criterion measures are presented for each of ten terminal objectives for a two-semester course (3 hours daily). This 540-hour intermediate course includes advanced troubleshooting techniques on outboard marine engines, inboard-outboard marine engines, inboard marine engines, boat…

APPL endosomes are not obligatory endocytic intermediates but act as stable cargo-sorting compartments

PubMed Central

Kalaidzidis, Inna; Miaczynska, Marta; Brewińska-Olchowik, Marta; Hupalowska, Anna; Ferguson, Charles; Parton, Robert G.; Kalaidzidis, Yannis

2015-01-01

Endocytosis allows cargo to enter a series of specialized endosomal compartments, beginning with early endosomes harboring Rab5 and its effector EEA1. There are, however, additional structures labeled by the Rab5 effector APPL1 whose role in endocytic transport remains unclear. It has been proposed that APPL1 vesicles are transport intermediates that convert into EEA1 endosomes. Here, we tested this model by analyzing the ultrastructural morphology, kinetics of cargo transport, and stability of the APPL1 compartment over time. We found that APPL1 resides on a tubulo-vesicular compartment that is capable of sorting cargo for recycling or degradation and that displays long lifetimes, all features typical of early endosomes. Fitting mathematical models to experimental data rules out maturation of APPL1 vesicles into EEA1 endosomes as a primary mechanism for cargo transport. Our data suggest instead that APPL1 endosomes represent a distinct population of Rab5-positive sorting endosomes, thus providing important insights into the compartmental organization of the early endocytic pathway. PMID:26459602

Phototransformation of the sunlight filter benzophenone-3 (2-hydroxy-4-methoxybenzophenone) under conditions relevant to surface waters.

PubMed

Vione, Davide; Caringella, Rosalinda; De Laurentiis, Elisa; Pazzi, Marco; Minero, Claudio

2013-10-01

The UV filter benzophenone-3 (BP3) has UV photolysis quantum yield ΦBP3=(3.1±0.3)·10(-5) and the following second-order reaction rate constants: with (•)OH, k(BP3,(•)OH)=(2.0±0.4)·10(10) M(-1) s(-1); with the triplet states of chromophoric dissolved organic matter ((3)CDOM*), K(BP3,(3)CDOM*)=(1.1±0.1)·10(9) M(-1) s(-1); with (1)O2, k(BP3,(1)O2)=(2.0±0.1)·10(5) M(-1) s(-1), and with CO3(-•), k(BP3,CO3(-•))<5·10(7) M(-1) s(-1). These data allow the modelling of BP3 photochemical transformation, which helps filling the knowledge gap about the environmental persistence of this compound. Under typical surface-water conditions, direct photolysis and reactions with (•)OH and (3)CDOM* would be the main processes of BP3 phototransformation. Reaction with (•)OH would prevail at low DOC, direct photolysis at intermediate DOC (around 5 mg C L(-1)), and reaction with (3)CDOM* at high DOC. If the reaction rate constant with CO3(-•) is near the upper limit of experimental measures (5·10(7) M(-1) s(-1)), the CO3(-•) degradation process could be somewhat important for DOC<1 mg C L(-1). The predicted half-life time of BP3 in surface waters under summertime conditions would be of some weeks, and it would increase with increasing depth and DOC. BP3 transformation intermediates were detected upon reaction with (•)OH. Two methylated derivatives were tentatively identified, and they were probably produced by reaction between BP3 and fragments arising from photodegradation. The other intermediates were benzoic acid (maximum concentration ~10% of initial BP3) and benzaldehyde (1%). Copyright © 2013 Elsevier B.V. All rights reserved.

Transformation products of amoxicillin and ampicillin after photolysis in aqueous matrices: Identification and kinetics.

PubMed

Arsand, Juliana Bazzan; Hoff, Rodrigo Barcellos; Jank, Louise; Meirelles, Lucas N; Silvia Díaz-Cruz, M; Pizzolato, Tânia Mara; Barceló, Damià

2018-06-18

Antibiotics are widely used in human medicine and veterinary production. Residues of these compounds reach the water sources through waste or direct application (e.g. aquaculture). The constant input of the parent drugs and their transformation products into the environment leads these pharmaceuticals to be considered as emerging pollutants. For some molecules, the pathway of degradation and formation in products is less known. To assess the impact of these substances in the environment and in the human health, it is necessary to elucidate the transformation products and their kinetic of degradation to evaluate the possible risks. In the present report, the characterization and the degradation kinetic of two widely used β-lactams antibiotics - amoxicillin and ampicillin - was evaluated. Surface water samples containing these antibiotics were submitted to photolysis and analyzed by liquid chromatography coupled to mass spectrometry with Orbitrap detection in order to establish the profile of degradation and the formation of transformation products. Results showed that the degradation of amoxicillin and ampicillin is almost complete and reach their maximum at 48 h in river water. Moreover, a database containing >65 transformation products of amoxicillin and ampicillin was build and real samples of industrial wastewater were analyzed to investigate the occurrence of amoxicillin, ampicillin and their transformation products. Copyright © 2018. Published by Elsevier B.V.

The second national audit of intermediate care.

PubMed

Young, John; Gladman, John R F; Forsyth, Duncan R; Holditch, Claire

2015-03-01

Intermediate care services have developed internationally to expedite discharge from hospital and to provide an alternative to an emergency hospital admission. Inconsistencies in the evidence base and under-developed governance structures led to concerns about the care quality, outcomes and provision of intermediate care in the NHS. The National Audit of Intermediate Care was therefore established by an interdisciplinary group. The second national audit reported in 2013 and included crisis response teams, home-based and bed-based services in approximately a half of the NHS. The main findings were evidence of weak local strategic planning, considerable under-provision, delays in accessing the services and lack of mental health involvement in care. There was a very high level of positive patient experience reported across all types of intermediate care, though reported involvement with care decisions was less satisfactory. © The Author 2014. Published by Oxford University Press on behalf of the British Geriatrics Society. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Characteristics of the larval Echinococcus vogeli Rausch and Bernstein, 1972 in the natural intermediate host, the paca, Cuniculus paca L. (Rodentia: Dasyproctidae).

PubMed

Rausch, R L; D'Alessandro, A; Rausch, V R

1981-09-01

In Colombia, the natural intermediate host of Echinococcus vogeli Rausch and Bernstein, 1972 is the paca, Cuniculus paca L. (Rodentia: Dasyproctidae). The larval cestode develops in the liver of the host, where it usually is situated superficially, partly exposed beneath Glisson's capsule. The infective larva consists of a subspherical to asymmetrical, fluid-filled vesicle, up to 30 mm in diameter, enclosed by a thick laminated membrane. It typically contains numerous chambers, often interconnected, produced by endogenous proliferation of germinal and laminated tissue, within which brood capsules arise in an irregular pattern from the germinal layer. Invasive growth by means of exogenous proliferation, typical of infections in man, was not observed in the natural intermediate host. The development of the larval cestode is described on the basis of material from pacas, supplemented by observations on early-stage lesions in experimentally infected nutrias, Myocastor coypus (Molina) (Rodentia: Capromyidae). The tissue response is characterized for early-stage, mature (infective), and degenerating larvae in the comparatively long-lived intermediate host. In addition to previously reported differences in size and form of rostellar hooks, other morphologic characteristics are defined by which the larval stage of E. vogeli is distinguished from that of E. oligarthrus (Diesing, 1863). Pathogenesis by the larval E. vogeli in man, like that by the larval E. multilocularis Leuckart, 1863, is the consequence of atypical proliferation of vesicles attributable to parasite-host incompatibility.

Automotive Body Repair. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Lang, Thomas

Several intermediate performance objectives and corresponding criterion measures are listed for each of 10 terminal objectives for an intermediate automotive body repair and refinishing course. The materials were developed for a two-semester (3 hours daily) course for specialized classrooms, shop, and practical experiences designed to enable the…

Cyclohexane isomerization. Unimolecular dynamics of the twist-boat intermediate.

PubMed

Kakhiani, Khatuna; Lourderaj, Upakarasamy; Hu, Wenfang; Birney, David; Hase, William L

2009-04-23

Direct dynamics simulations were performed at the HF/6-31G level of theory to investigate the intramolecular and unimolecuar dynamics of the twist-boat (TB) intermediate on the cyclohexane potential energy surface (PES). Additional calculations were performed at the MP2/aug-cc-pVDZ level of theory to further characterize the PES's stationary points. The trajectories were initiated at the C(1) and C(2) half-chair transition states (TSs) connecting a chair conformer with a TB intermediate, via an intrinsic reaction coordinate (IRC). Energy was added in accord with a microcanonical ensemble at the average energy for experiments at 263 K. Important nontransition state theory (TST), non-IRC, and non-RRKM dynamics were observed in the simulations. Trajectories initially directed toward the chair conformer had a high probability of recrossing the TS, with approximately 30% forming a TB intermediate instead of accessing the potential energy well for the conformer. The TB intermediate initially formed was not necessarily the one connected to the TS via the IRC. Of the trajectories initiated at the C(2) half-chair TS and initially directed toward the chair conformer, 35% formed a TB intermediate instead of the chair conformer. Also, of the trajectories forming a TB intermediate, only 16% formed the TB intermediate connected with the C(2) TS via the IRC. Up to eight consecutive TB --> TB isomerizations were followed, and non-RRKM behavior was observed in their dynamics. A TB can isomerize to two different TBs, one by a clockwise rotation of C-C-C-C dihedral angles and the other by a counterclockwise rotation. In contrast to RRKM theory, which predicts equivalent probabilities for these rotations, the trajectory dynamics show they are not equivalent and depend on whether the C(1) or C(2) half-chair TS is initially excited. Non-RRKM dynamics is also observed in the isomerization of the TB intermediates to the chair conformers. RRKM theory assumes equivalent probabilities for

Social predisposition dependent neuronal activity in the intermediate medial mesopallium of domestic chicks (Gallus gallus domesticus).

PubMed

Mayer, Uwe; Rosa-Salva, Orsola; Lorenzi, Elena; Vallortigara, Giorgio

2016-09-01

Species from phylogenetically distant animal groups, such as birds and primates including humans, share early experience-independent social predispositions that cause offspring, soon after birth, to attend to and learn about conspecifics. One example of this phenomenon is provided by the behaviour of newly-hatched visually-naïve domestic chicks that preferentially approach a stimulus resembling a conspecific (a stuffed fowl) rather than a less naturalistic object (a scrambled version of the stuffed fowl). However, the neuronal mechanisms underlying this behaviour are mostly unknown. Here we analysed chicks' brain activity with immunohistochemical detection of the transcription factor c-Fos. In a spontaneous choice test we confirmed a significant preference for approaching the stuffed fowl over a texture fowl (a fowl that was cut in small pieces attached to the sides of a box in scrambled order). Comparison of brain activation of a subgroup of chicks that approached either one or the other stimulus revealed differential activation in an area relevant for imprinting (IMM, intermediate medial mesopallium), suggesting that a different level of plasticity is associated with approach to naturalistic and artificial stimuli. c-Fos immunoreactive neurons were present also in the intermediate layers of the optic tectum (a plausible candidate for processing early social predispositions) showing a trend similar to the results for the IMM. Copyright © 2016 Elsevier B.V. All rights reserved.

Intermediate-energy nuclear chemistry workshop

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butler, G.W.; Giesler, G.C.; Liu, L.C.

1981-05-01

This report contains the proceedings of the LAMPF Intermediate-Energy Nuclear Chemistry Workshop held in Los Alamos, New Mexico, June 23-27, 1980. The first two days of the Workshop were devoted to invited review talks highlighting current experimental and theoretical research activities in intermediate-energy nuclear chemistry and physics. Working panels representing major topic areas carried out indepth appraisals of present research and formulated recommendations for future research directions. The major topic areas were Pion-Nucleus Reactions, Nucleon-Nucleus Reactions and Nuclei Far from Stability, Mesonic Atoms, Exotic Interactions, New Theoretical Approaches, and New Experimental Techniques and New Nuclear Chemistry Facilities.

Membrane Fission: Model for Intermediate Structures

PubMed Central

Kozlovsky, Yonathan; Kozlov, Michael M.

2003-01-01

Membrane budding-fission is a fundamental process generating intracellular carriers of proteins. Earlier works were focused only on formation of coated buds connected to the initial membrane by narrow membrane necks. We present the theoretical analysis of the whole pathway of budding-fission, including the crucial stage where the membrane neck undergoes fission and the carrier separates from the donor membrane. We consider two successive intermediates of the reaction: 1), a constricted membrane neck coming out of aperture of the assembling protein coat, and 2), hemifission intermediate resulting from self-fusion of the inner monolayer of the neck, while its outer monolayer remains continuous. Transformation of the constricted neck into the hemifission intermediate is driven by the membrane stress produced in the neck by the protein coat. Although apparently similar to hemifusion, the fission is predicted to have an opposite dependence on the monolayer spontaneous curvature. Analysis of the further stages of the process demonstrates that in all practically important cases the hemifission intermediate decays spontaneously into two separate membranes, thereby completing the fission process. We formulate the “job description” for fission proteins by calculating the energy they have to deliver and the radii of the protein coat aperture which have to be reached to drive the fission process. PMID:12829467

Ultrasonographic detection of regional lymph node metastases in patients with intermediate or thick malignant melanoma.

PubMed

Brountzos, Elias N; Panagiotou, Irene E; Bafaloukos, Dimitrios I; Kelekis, Dimitrios A

2003-01-01

Careful monitoring of regional lymph nodes and early detection of metastases in malignant melanoma patients has an impact on their survival, since it may permit beneficial surgical therapy. Palpation is routinely used in clinical practice. The value of ultrasonography for routine follow-up of melanoma patients, still, is not generally accepted. The aim of our study was to assess the sensitivity and specificity of ultrasound and clinical examination respectively, in the detection of melanoma regional node metastases. Additionally, we evaluated whether early detection of metastases improved overall survival. One hundred and forty-eight melanoma patients with an intermediate or thick primary lesion were followed between January 1997 and May 2001. Clinical examination and concomitant regional lymph node ultrasonography were performed, every 3-4 months. If suspicious findings were identified, regional lymph node dissection was undertaken. Forty-four from the initial 148 patients relapsed with regional lymph nodal metastases. In 11 patients (25%) palpation failed to reveal the disease and metastases were depicted only by ultrasonography. In only 1 patient ultrasonography was false-negative. The sensitivity and specificity of palpation were 72.7 and 97% respectively, while those of ultrasonography were 97.7 (p<0.001) and 98% respectively. Ultrasonography was more sensitive in detecting lymph node metastases in the axilla (100%) and the groin (93.3%). When overall survival of patients presenting with local-regional recurrence was calculated--depending on the number of involved lymph nodes--a survival benefit (p<0.05) was found for patients with only one lymph node metastasis. In conclusion, ultrasonography is superior to clinical examination in the early detection of regional lymph node metastases from an intermediate or thick malignant melanoma and should be a part of those patients' surveillance.

The ARES High-level Intermediate Representation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moss, Nicholas David

The LLVM intermediate representation (IR) lacks semantic constructs for depicting common high-performance operations such as parallel and concurrent execution, communication and synchronization. Currently, representing such semantics in LLVM requires either extending the intermediate form (a signi cant undertaking) or the use of ad hoc indirect means such as encoding them as intrinsics and/or the use of metadata constructs. In this paper we discuss a work in progress to explore the design and implementation of a new compilation stage and associated high-level intermediate form that is placed between the abstract syntax tree and when it is lowered to LLVM's IR. Thismore » highlevel representation is a superset of LLVM IR and supports the direct representation of these common parallel computing constructs along with the infrastructure for supporting analysis and transformation passes on this representation.« less

Glutamate Induced Thermal Equilibrium Intermediate and Counteracting Effect on Chemical Denaturation of Proteins.

PubMed

Anumalla, Bramhini; Prabhu, N Prakash

2018-01-25

When organisms are subjected to stress conditions, one of their adaptive responses is accumulation of small organic molecules called osmolytes. These osmolytes affect the structure and stability of the biological macromolecules including proteins. The present study examines the effect of a negatively charged amino acid osmolyte, glutamate (Glu), on two model proteins, ribonuclease A (RNase A) and α-lactalbumin (α-LA), which have positive and negative surface charges at pH 7, respectively. These proteins follow two-state unfolding transitions during both heat and chemical induced denaturation processes. The addition of Glu stabilizes the proteins against temperature and induces an early equilibrium intermediate during unfolding. The stability is found to be enthalpy-driven, and the free energy of stabilization is more for α-LA compared to RNase A. The decrease in the partial molar volume and compressibility of both of the proteins in the presence of Glu suggests that the proteins attain a more compact state through surface hydration which could provide a more stable conformation. This is also supported by molecule dynamic simulation studies which demonstrate that the water density around the proteins is increased upon the addition of Glu. Further, the intermediates could be completely destabilized by lower concentrations (∼0.5 M) of guanidinium chloride and salt. However, urea subverts the Glu-induced intermediate formed by α-LA, whereas it only slightly destabilizes in the case of RNase A which has a positive surface charge and could possess charge-charge interactions with Glu. This suggests that, apart from hydration, columbic interactions might also contribute to the stability of the intermediate. Gdm-induced denaturation of RNase A and α-LA in the absence and the presence of Glu at different temperatures was carried out. These results also show the Glu-induced stabilization of both of the proteins; however, all of the unfolding transitions followed two

Business Machine Maintenance. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

McMinn, Robert

Several intermediate performance objectives and corresponding criterion measures are listed for each of 28 terminal objectives presented in this guide for an intermediate business machine maintenance course at the secondary level. (For the basic course guide see CE 010 949.) Titles of the 28 terminal objective sections are Career Opportunities,…

Gasoline Engine Mechanics. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Jones, Marion

Several intermediate performance objectives and corresponding criterion measures are listed for each of six terminal objectives presented in this curriculum guide for an intermediate gasoline engine mechanics course at the secondary level. (For the beginning course guide see CE 010 947.) The materials were developed for a two-semester (2 hour…

Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

PubMed

Mercado, D Fabio; Bracco, Larisa L B; Arques, Antonio; Gonzalez, Mónica C; Caregnato, Paula

2018-01-01

Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 10 9 s -1 M -1 for the reaction of the fungicide with HO and 4.6 × 10 8  s -1  M -1 for the same reaction with SO 4 - radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S 2 O 8 2- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. Copyright © 2017. Published by Elsevier Ltd.

The physical chemistry of Criegee intermediates in the gas phase

DOE PAGES

Osborn, David L.; Taatjes, Craig A.

2015-07-24

Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular andmore » bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.« less

Screening the modern girl: intermediality in the adaptation of "Flaming Youth".

PubMed

Ross, Sara

2010-01-01

In the early 1920s, the film industry seized on the furor over the modern girls' demands for sexual liberty and fulfillment inside and outside of marriage to introduce not only new subject matter, but new modes of addressing its diverse audience. Social upheaval in this period coincided with the media industries' movement toward unprecedented speed of adaptation and cooperation, making possible a powerful new intermediality. The film industry used this to generate layered meanings beyond the confines of the film text, encouraging bold viewers to see through the camouflage with which it sought to appease more traditionalist audience members. With Flaming Youth, through a smokescreen of melodramatic conventions and moral lessons, it delivered a strikingly modern conception of sexuality and marriage to the big screen.

Safety and efficiency of ultrasound-guided intermediate cervical plexus block for carotid surgery.

PubMed

Leblanc, Isabelle; Chterev, Vladimir; Rekik, Mohamed; Boura, Benoit; Costanzo, Alessandro; Bourel, Patrick; Combes, Myriam; Philip, Ivan

2016-04-01

Since stroke and myocardial ischaemia are major causes of perioperative morbidity and mortality associated with carotid endarterectomy, monitoring the brain and ensuring the best haemodynamic stability are important goals of the management. As regional anaesthesia was reported to improve haemodynamic stability during carotid endarterectomy (CEA), we conducted a prospective observational study on the efficacy and safety of ultrasound-guided intermediate cervical plexus blocks (CPB), with early (immediate postoperative) and mid-term (day 30) outcomes in awake patients undergoing CEA. After the ethics committee approval, 50 patients undergoing a carotid endarterectomy with CPB from April 2011 to May 2013 were included. Anaesthesia and surgical dissection parameters, early complications and haemodynamic stability were recorded, as well as neurologic and cardiac outcomes initially and one month later. Cervical space was easy to locate by ultrasound in 90% of the patients. The quality of anaesthesia and surgical dissection was good in 86 and 88% of patients, respectively. No conversion to GA was required, secondary to a lack of analgesia. Two patients (4%) had severe hypotension (<100mmHg). Three patients required a shunt after carotid clamping for loss of consciousness with a favourable neurological outcome. We observed one elevation of cTnI (0.95ng·ml(-1)) without ECG change and 1 death occurred after a postoperative haemorrhagic stroke. The present work reports our first 50 cases of intermediate CPB using ultrasound guidance. The results underline that this technique is easy to perform, safe and reliable, provided good surgical conditions with continuous intraoperative neurologic monitoring and stable haemodynamics are respected. Copyright © 2016. Published by Elsevier Masson SAS.

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers.

PubMed

Kanrar, Bappaditya; Bhattacharyya, Anjan

2009-11-01

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (lambda max > or = 250 nm) and sunlight in presence or absence of sensitizers (TiO(2) and KNO(3)). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M(1)-M(5)) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO(2) as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M(1) (Phenol), M(2) [2, 6-Dihydroxy benzoic acid], M(3) [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M(4) [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M(5) as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M(6)-M(11)) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M(6) [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M(7) [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M(8) [4, 6-Dimethoxy-pyrimidin-2-ol], M(9) [6-Methoxy-pyrimidine-2, 4-diol], M(10) [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M(11) [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.

Medical Advice for Sick-reported Students (MASS) in intermediate vocational education schools: design of a controlled before-and-after study.

PubMed

Van der Vlis, Madelon K; Lugtenberg, Marjolein; Vanneste, Yvonne T M; Berends, Wenda; Mulder, Wico; Bannink, Rienke; Van Grieken, Amy; Raat, Hein; de Kroon, Marlou L A

2017-06-29

School absenteeism, including medical absenteeism, is associated with early school dropout and may result in physical, mental, social and work-related problems in later life. Especially at intermediate vocational education schools, high rates of medical absenteeism are found. In 2012 the Dutch intervention 'Medical Advice for Sick-reported Students' (MASS), previously developed for pre-vocational secondary education, was adjusted for intermediate vocational education schools. The aim of the study outlined in this paper is to evaluate the effectiveness of the MASS intervention at intermediate vocational education schools in terms of reducing students' medical absenteeism and early dropping out of school. Additionally, the extent to which biopsychosocial and other factors moderate the effectiveness of the intervention will be assessed. A controlled before-and-after study will be conducted within Intermediate Vocational Education schools. Schools are allocated to be an intervention or control school based on whether the schools have implemented the MASS intervention (intervention schools) or not (control schools). Intervention schools apply the MASS intervention consisting of active support for students with medical absenteeism provided by the school including a consultation with the Youth Health Care (YHC) professional if needed. Control schools provide care as usual. Data will be collected by questionnaires among students in both groups meeting the criteria for extensive medical absenteeism (i.e. 'reported sick four times in 12 school weeks or for more than six consecutive school days' at baseline and at 6 months follow-up). Additionally, in the intervention group a questionnaire is completed after each consultation with a YHC professional, by both the student and the YHC professional. Primary outcome measures are duration and cumulative incidence of absenteeism and academic performances. Secondary outcome measures are biopsychosocial outcomes of the students. It

Early wide spacing in red alder (Alnus rubra Bong.): effects on stem form and stem growth.

Treesearch

Bernard T. Bormann

1985-01-01

A thinning trial was established in 1962 in a 7-year-old red alder stand in northwestern Washington. Spacings were 8 x 8 ft (dense), 12 x 12 it (intermediate), and 16 x 16 ft (open). The effect of early thinning on growth and stem form was measured in 1982, 20 years after spacing treatment. There was negligible tree lean and sweep in open and intermediate stands except...

Intermediate tax sanctions: an overview.

PubMed

Peregrine, M W

1997-07-01

New federal tax law applies intermediate tax sanctions when tax-exempt organizations enter into so-called excess benefit transactions with corporate insiders. The sanctions take the form of a two-tiered penalty excise tax, which is assessed not on the tax-exempt organization itself but on the insider who receives the excess benefit and the organizational managers and board members who knowingly participate in an improper transaction. The intermediate tax sanctions, therefore, present tax-planning challenges for tax-exempt hospitals and integrated delivery systems as well as for 501(c)(4) HMOs. Forthcoming treasury regulations are expected to add clarity to the new law.

Intermediate connector for stacked organic light emitting devices

DOEpatents

D& #x27; Andrade, Brian

2013-02-12

A device is provided, having an anode, a cathode, and an intermediate connector disposed between the anode and the cathode. A first organic layer including an emissive sublayer is disposed between the anode and the intermediate connector, and a second including an emissive sublayer is disposed between the intermediate connector and the cathode. The intermediate connector includes a first metal having a work function lower than 4.0 eV and a second metal having a work function lower than 5.0 eV. The work function of the first metal is at least 0.5 eV less than the work function of the second metal. The first metal is in contact with a sublayer of the second organic layer that includes a material well adapted to receive holes from a low work function metal.

Holocene Relative Sea-Level Changes from Near-, Intermediate-, and Far-Field Locations

NASA Astrophysics Data System (ADS)

Walker, J. S.; Khan, N.; Shaw, T.; Ashe, E.; Vacchi, M.; Peltier, W. R.; Kopp, R. E.; Horton, B.

2015-12-01

Holocene relative sea-level (RSL) records exhibit spatial and temporal variability that arises mainly from the interaction of eustatic (land ice volume and thermal expansion) and isostatic (glacio- and hydro-) factors. We fit RSL histories from near-, intermediate-, and far-field locations with noisy-input Gaussian process models to assess rates of RSL change from selected study areas. Records from near-field regions (e.g., Antarctica, Greenland, Canada, Sweden, and Scotland) reveal a complex pattern of RSL fall from a maximum marine limit due to the net effect of eustatic sea-level rise and glacial-isostatic uplift with rates of RSL fall as great as -69 ± 9 m/ka. Intermediate-field regions (e.g., mid-Atlantic and Pacific coasts of the United States, Netherlands, Southern France, St. Croix) display variable rates of RSL rise from the cumulative effect of isostatic and eustatic factors. Fast rates of RSL rise (up to 10 ± 1 m/ka) are found in the early Holocene in regions near the center of forebulge collapse. Far-field RSL records exhibit a mid-Holocene highstand, the timing (between 8 and 4 ka) and magnitude (between <1 and 6 m) of which varies across South America, Africa, Asia and Australia regions.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less

Chromosome nondisjunction during bipolar mitoses of binucleated intermediates promote aneuploidy formation along with multipolar mitoses rather than chromosome loss in micronuclei induced by asbestos

PubMed Central

Zhang, Tianwei; Lv, Lei; Huang, Yun; Ren, Xiaohui; Shi, Qinghua

2017-01-01

Asbestos is a well-known occupational carcinogen that can cause aneuploidy during the early stages of neoplastic development. To explore the origins of asbestos-induced aneuploidy, we performed long-term live-cell imaging followed by fluorescence in situ hybridization of chromosomes 8 and 12 in human bronchial epithelial (HBEC) and mesothelial (MeT5A) cells. We demonstrate that asbestos induces aneuploidy via binucleated intermediates resulting from cytokinesis failure. On the one hand, asbestos increases chromosome nondisjunction during bipolar divisions of binucleated intermediates and produces near-tetraploidy. On the other hand, asbestos increases multipolar divisions of binucleated intermediates to produce aneuploidy. Surprisingly, chromosomes in asbestos-induced micronucleated cells are not truly lost by the cells, and do not contribute to aneuploid cell formation in either cell type. These results clarify the cellular source of asbestos-induced aneuploidy. In particular, they show the asbestos-induced disruption of bipolar chromosomal segregation in tetraploid cells, thereby demonstrating the causality between binucleated intermediates and aneuploidy evolution, rather than chromosome loss in micronuclei. PMID:28038458

Chromosome nondisjunction during bipolar mitoses of binucleated intermediates promote aneuploidy formation along with multipolar mitoses rather than chromosome loss in micronuclei induced by asbestos.

PubMed

Zhang, Tianwei; Lv, Lei; Huang, Yun; Ren, Xiaohui; Shi, Qinghua

2017-02-14

Asbestos is a well-known occupational carcinogen that can cause aneuploidy during the early stages of neoplastic development. To explore the origins of asbestos-induced aneuploidy, we performed long-term live-cell imaging followed by fluorescence in situ hybridization of chromosomes 8 and 12 in human bronchial epithelial (HBEC) and mesothelial (MeT5A) cells. We demonstrate that asbestos induces aneuploidy via binucleated intermediates resulting from cytokinesis failure. On the one hand, asbestos increases chromosome nondisjunction during bipolar divisions of binucleated intermediates and produces near-tetraploidy. On the other hand, asbestos increases multipolar divisions of binucleated intermediates to produce aneuploidy. Surprisingly, chromosomes in asbestos-induced micronucleated cells are not truly lost by the cells, and do not contribute to aneuploid cell formation in either cell type. These results clarify the cellular source of asbestos-induced aneuploidy. In particular, they show the asbestos-induced disruption of bipolar chromosomal segregation in tetraploid cells, thereby demonstrating the causality between binucleated intermediates and aneuploidy evolution, rather than chromosome loss in micronuclei.

Photolysis of CH{sub 3}CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH{sub 3} and HCO radicals and H atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morajkar, Pranay; Schoemaecker, Coralie; Fittschen, Christa, E-mail: christa.fittschen@univ-lille1.fr

2014-06-07

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH{sub 3}CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO{sub 2} radicals by reaction with O{sub 2}. The CH{sub 3} radical yield has been determined using the same technique following their conversion into CH{sub 3}O{sub 2}. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO{sub 2} profiles, obtained under various O{sub 2} concentrations, to a complex model, while the CH{submore » 3} yield has been determined relative to the CH{sub 3} yield from 248 nm photolysis of CH{sub 3}I. Time resolved HO{sub 2} profiles under very low O{sub 2} concentrations suggest that another unknown HO{sub 2} forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O{sub 2}. HO{sub 2} profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH{sub 3}CHO + hν{sub 248nm} → CH{sub 3}CHO{sup *}, CH{sub 3}CHO{sup *} → CH{sub 3} + HCO ϕ{sub 1a} = 0.125 ± 0.03, CH{sub 3}CHO{sup *} → CH{sub 3} + H + CO ϕ{sub 1e} = 0.205 ± 0.04, CH{sub 3}CHO{sup *}→{sup o{sub 2}}CH{sub 3}CO + HO{sub 2} ϕ{sub 1f} = 0.07 ± 0.01. The CH{sub 3}O{sub 2} quantum yield has been determined in separate experiments as ϕ{sub CH{sub 3}} = 0.33 ± 0.03 and is in excellent agreement with the CH{sub 3} yields derived from the HO{sub 2} measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH{sub 3}CHO. From arithmetic considerations taking into account the HO{sub 2} and CH{sub 3} measurements we deduce a remaining quantum yield for the molecular pathway: CH{sub 3}CHO{sup *} → CH{sub 4} + CO ϕ{sub 1b} = 0.6. All experiments

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James H.; Considine, David B.; Platnick, Steven; Norris, Peter M.; Duncan, Bryan N.; Pierce, Robert B.; Chen, Gao; Yantosca, Robert M.

2009-01-01

Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest

Insights into intermediate phases of human intestinal fluids visualized by atomic force microscopy and cryo-transmission electron microscopy ex vivo.

PubMed

Müllertz, Anette; Fatouros, Dimitrios G; Smith, James R; Vertzoni, Maria; Reppas, Christos

2012-02-06

The current work aims to study at the ultrastructural level the morphological development of colloidal intermediate phases of human intestinal fluids (HIFs) produced during lipid digestion. HIFs were aspirated near the ligament of Treitz early (30 min), Aspirate(early), and 1 h, Aspirate(1h)(ave,comp), after the administration of a heterogeneous liquid meal into the antrum. The composition of the sample aspirated 1 h after meal administration was similar to the average lumenal composition 1 h after meal administration (Aspirate(1h)(ave,comp)). The colloidal structures of individual aspirates and supernatants of aspirates after ultracentrifugation (micellar phase) were characterized by means of atomic force microscopy (AFM) and cryogenic transmission electron microscopy (Cryo-TEM). AFM revealed domain-like structures in Aspirate(early) and both vesicles and large aggregates Aspirate(1h)(ave,comp). Rough surfaces and domains varying in size were frequently present in the micellar phase of both Aspirate(early) and Aspirate(1h)(ave,comp). Cryo-TEM revealed an abundance of spherical micelles and occasionally presented worm-like micelles coexisting with faceted and less defined vesicles in Aspirate(early) and Aspirate(1h)(ave,comp). In Aspirate(1h)(ave,comp) oil droplets were visualized with bilayers closely located to their surface suggesting lipolytic product phases accumulated on the surface of the oil droplet. In the micellar phase of Aspirate(early), Cryo-TEM revealed the presence of spherical micelles, small vesicles, membrane fragments, oil droplets and plate-like structures. In the micellar phase of Aspirate(1h)(ave,comp) the only difference was the absence of oil droplets. Visualization studies previously performed with biorelevant media revealed structural features with many similarities as presented in the current investigation. The impression of the complexity and diversion of these phases has been reinforced with the excessive variation of structural

Production of photocurrent due to intermediate-to-conduction-band transitions: a demonstration of a key operating principle of the intermediate-band solar cell.

PubMed

Martí, A; Antolín, E; Stanley, C R; Farmer, C D; López, N; Díaz, P; Cánovas, E; Linares, P G; Luque, A

2006-12-15

We present intermediate-band solar cells manufactured using quantum dot technology that show for the first time the production of photocurrent when two sub-band-gap energy photons are absorbed simultaneously. One photon produces an optical transition from the intermediate-band to the conduction band while the second pumps an electron from the valence band to the intermediate-band. The detection of this two-photon absorption process is essential to verify the principles of operation of the intermediate-band solar cell. The phenomenon is the cornerstone physical principle that ultimately allows the production of photocurrent in a solar cell by below band gap photon absorption, without degradation of its output voltage.

Ecotoxicological effect of ketamine: Evidence of acute, chronic and photolysis toxicity to Daphnia magna.

PubMed

Li, Shih-Wei; Wang, Yu-Hsiang; Lin, Angela Yu-Chen

2017-09-01

Ketamine has been increasingly used in medicine and has the potential for abuse or illicit use around the world. Ketamine cannot be removed by conventional wastewater treatment plants. Although ketamine and its metabolite norketamine have been detected to a significant degree in effluents and aquatic environments, their ecotoxicity effects in aquatic organisms remain undefined. In this study, we investigated the acute toxicity of ketamine and its metabolite, along with the chronic reproductive toxicity of ketamine (5-100μg/L) to Daphnia magna. Multiple environmental scenarios were also evaluated, including drug mixtures and sunlight irradiation toxicity. Ketamine and norketamine caused acute toxicity to D. magna, with half lethal concentration (LC 50 ) values of 30.93 and 25.35mg/L, respectively, after 48h of exposure. Irradiated solutions of ketamine (20mg/L) significantly increased the mortality of D. magna; pre-irradiation durations up to 2h rapidly increased the death rate to 100%. A new photolysis byproduct (M.W. 241) of norketamine that accumulates during irradiation was identified for the first time. The relevant environmental concentration of ketamine produced significant reproductive toxicity effects in D. magna, as revealed by the reduction of the number of total live offspring by 33.6-49.8% (p < 0.05). The toxicity results indicate that the environmental hazardous risks of the relevant ketamine concentration cannot be ignored and warrant further examination. Copyright © 2017 Elsevier Inc. All rights reserved.

GFP's Mechanical Intermediate States

PubMed Central

Saeger, John; Hytönen, Vesa P.; Klotzsch, Enrico; Vogel, Viola

2012-01-01

Green fluorescent protein (GFP) mutants have become the most widely used fluorescence markers in the life sciences, and although they are becoming increasingly popular as mechanical force or strain probes, there is little direct information on how their fluorescence changes when mechanically stretched. Here we derive high-resolution structural models of the mechanical intermediate states of stretched GFP using steered molecular dynamics (SMD) simulations. These structures were used to produce mutants of EGFP and EYFP that mimic GFP's different mechanical intermediates. A spectroscopic analysis revealed that a population of EGFP molecules with a missing N-terminal α-helix was significantly dimmed, while the fluorescence lifetime characteristic of the anionic chromophore state remained unaffected. This suggests a mechanism how N-terminal deletions can switch the protonation state of the chromophore, and how the fluorescence of GFP molecules in response to mechanical disturbance might be turned off. PMID:23118864

Early stages of soldering reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lord, R.A.; Umantsev, A.

2005-09-15

An experiment on the early stages of intermetallic compound layer growth during soldering and its theoretical analysis were conducted with the intent to study the controlling factors of the process. An experimental technique based on fast dipping and pulling of a copper coupon in liquid solder followed by optical microscopy allowed the authors to study the temporal behavior of the sample on a single micrograph. The technique should be of value for different areas of metallurgy because many experiments on crystallization may be described as the growth of a layer of intermediate phase. Comparison of the experimental results with themore » theoretical calculations allowed one to identify the kinetics of dissolution as the rate-controlling mechanism on the early stages and measure the kinetic coefficient of dissolution. A popular model of intermetallic compound layer structure coarsening is discussed.« less

Pathways and intermediates in forced unfolding of spectrin repeats.

PubMed

Altmann, Stephan M; Grünberg, Raik G; Lenne, Pierre-François; Ylänne, Jari; Raae, Arnt; Herbert, Kristina; Saraste, Matti; Nilges, Michael; Hörber, J K Heinrich

2002-08-01

Spectrin repeats are triple-helical coiled-coil domains found in many proteins that are regularly subjected to mechanical stress. We used atomic force microscopy technique and steered molecular dynamics simulations to study the behavior of a wild-type spectrin repeat and two mutants. The experiments indicate that spectrin repeats can form stable unfolding intermediates when subjected to external forces. In the simulations the unfolding proceeded via a variety of pathways. Stable intermediates were associated to kinking of the central helix close to a proline residue. A mutant stabilizing the central helix showed no intermediates in experiments, in agreement with simulation. Spectrin repeats may thus function as elastic elements, extendable to intermediate states at various lengths.

Mercury-arc photolysis: a method for examining second messenger regulation of endothelial cell monolayer integrity.

PubMed

Patton, W F; Alexander, J S; Dodge, A B; Patton, R J; Hechtman, H B; Shepro, D

1991-07-01

Cell-cell apposition in bovine pulmonary endothelial cell monolayers was modulated by inducing transient increases in intracellular adenosine 3':5'-cyclic monophosphate (cAMP) and 1,4,5-inositol triphosphate (IP3). This was accomplished by mercury-arc flash photolysis of o-nitrobenzyl derivatives of the second messengers (caged compounds). Second messenger release by the mercury-arc lamp was determined by radioimmunoassay of cAMP to have a t1/2 of approximately 8 min. Each second messenger induced the phosphorylation of a distinct subset of cytoskeletal proteins; however, both IP3 and cAMP increased vimentin phosphorylation. Actin isoform patterns were not altered by the second messengers. Intracellular pulses of IP3 in pulmonary endothelial cells caused disruption of endothelial monolayer integrity as determined by phase-contrast microscopy and by visualization of actin stress fibers with rhodamine-phalloidin. Intracellular pulses of cAMP increased cell-cell contact, cell surface area, and apposition. IP3 appeared to have its greatest effect on the actin peripheral band. In silicone rubber contractility assays this agent caused contraction of pulmonary microvascular endothelial cells as visualized by an increase in wrinkles beneath the cells. On the other hand, cAMP appeared to effect both the peripheral band and centralized actin domains. Caged cAMP caused relaxation of endothelial cells as visualized by a disappearance of wrinkles beneath the cells.

Laser studies of the photodissociation dynamics of cometary radicals

NASA Technical Reports Server (NTRS)

Jackson, William M.

1991-01-01

In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.

A primitive protostegid from Australia and early sea turtle evolution

PubMed Central

Kear, Benjamin P; Lee, Michael S.Y

2005-01-01

Sea turtles (Chelonioidea) are a prominent group of modern marine reptiles whose early history is poorly understood. Analysis of exceptionally well preserved fossils of Bouliachelys suteri gen. et sp. nov., a large-bodied basal protostegid (primitive chelonioid) from the Early Cretaceous (Albian) of Australia, indicates that early sea turtles were both larger and more diverse than previously thought. The analysis implies at least five distinct sea turtle lineages existed around 100 million years ago. Currently, the postcranially primitive Ctenochelys and Toxochelys are interpreted as crown-group sea turtles closely related to living cheloniids (e.g. Chelonia); in contrast, the new phylogeny suggests that they are transitional (intermediate stem-taxa) between continental testudines and derived, pelagic chelonioids. PMID:17148342

9 CFR 3.86 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., and Transportation of Nonhuman Primates 2 Transportation Standards § 3.86 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a nonhuman primate for transport... consigning a nonhuman primate to extend this time by up to 2 hours. (b) Carriers and intermediate handlers...

9 CFR 3.86 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2011 CFR

2011-01-01

..., and Transportation of Nonhuman Primates 2 Transportation Standards § 3.86 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a nonhuman primate for transport... consigning a nonhuman primate to extend this time by up to 2 hours. (b) Carriers and intermediate handlers...

Which visual functions depend on intermediate visual regions? Insights from a case of developmental visual form agnosia.

PubMed

Gilaie-Dotan, Sharon

2016-03-01

A key question in visual neuroscience is the causal link between specific brain areas and perceptual functions; which regions are necessary for which visual functions? While the contribution of primary visual cortex and high-level visual regions to visual perception has been extensively investigated, the contribution of intermediate visual areas (e.g. V2/V3) to visual processes remains unclear. Here I review more than 20 visual functions (early, mid, and high-level) of LG, a developmental visual agnosic and prosopagnosic young adult, whose intermediate visual regions function in a significantly abnormal fashion as revealed through extensive fMRI and ERP investigations. While expectedly, some of LG's visual functions are significantly impaired, some of his visual functions are surprisingly normal (e.g. stereopsis, color, reading, biological motion). During the period of eight-year testing described here, LG trained on a perceptual learning paradigm that was successful in improving some but not all of his visual functions. Following LG's visual performance and taking into account additional findings in the field, I propose a framework for how different visual areas contribute to different visual functions, with an emphasis on intermediate visual regions. Thus, although rewiring and plasticity in the brain can occur during development to overcome and compensate for hindering developmental factors, LG's case seems to indicate that some visual functions are much less dependent on strict hierarchical flow than others, and can develop normally in spite of abnormal mid-level visual areas, thereby probably less dependent on intermediate visual regions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Intermediate load-center photovoltaic application experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burgess, E. L.

1980-01-01

A total of nine intermediate load-center photovoltaic systems were carried into the construction phase this year. These nine systems range in size from 20 to 225 kW/sub p/ electrical output and total almost 1 MW/sub p/. They are being installed in a diverse set of applications and locations and represent the bulk of the photovoltaic initial system evaluation experiments (ISEE) for the intermediate load-center sector. Each of these experiments are briefly described and the status of the construction phase is given for each project.

A structural intermediate between triisodontids and mesonychians (Mammalia, Acreodi) from the earliest Eocene of Portugal.

PubMed

Tabuce, Rodolphe; Clavel, Julien; Antunes, Miguel Telles

2011-02-01

A new mammal, Mondegodon eutrigonus gen. et sp. nov., is described from the earliest Eocene locality of Silveirinha, Portugal. This species shows dental adaptations indicative of a carnivorous diet. M. eutrigonus is referred to the order Acreodi and considered, along with the early Paleocene North American species Oxyclaenus cuspidatus, as a morphological intermediate between two groups of ungulate-like mammals, namely, the triisodontids and mesonychians. Considering that triisodontids are early to early-late Paleocene North American taxa, Mondegodon probably belongs to a group that migrated from North America towards Europe during the first part of the Paleocene. Mondegodon could represent thus a relict genus, belonging to the ante-Eocene European mammalian fauna. The occurrence of such a taxon in Southern Europe may reflect a period of isolation of this continental area during the Paleocene/Eocene transition. In this context, the non-occurrence of closely allied forms of Mondegodon in the Eocene North European mammalian faunas is significant. This strengthens the hypothesis that the mammalian fauna from Southern Europe is characterized by a certain degree of endemism during the earliest Eocene. Mondegodon also presents some striking similarities with an unnamed genus from the early Eocene of India which could represent the first Asian known transitional form between the triisodontids and mesonychians.

Searching for intermediate-mass black holes in extremely-metal poor galaxies

NASA Astrophysics Data System (ADS)

Mezcua, Mar

2016-09-01

Extremely metal-poor dwarf galaxies (XMPs) are star-forming, low-mass galaxies with metallicites highly sub-solar. Their regions of star formation could be triggered by the accretion of pristine gas from the cosmic web and harbour Population III stars. XMPs are thus ideal laboratories for searching for the seed black holes or intermediate-mass black holes (IMBHs) that populated the early Universe. The combination of X-ray, radio and optical observations offer the best tool for detecting such IMBHs in the local Universe. We propose Chandra observations of a sample of XMPs whose optical spectra indicate the possible presence of an active black hole of 1e4 - 1e6 Msun. The Chandra data could confirm this and yield the first detection of an IMBH in these type of galaxies.

Molecular Gels as Intermediates in the Synthesis of Porous Materials and Fluorescent Films: Concepts and Applications.

PubMed

Miao, Rong; Peng, Junxia; Fang, Yu

2017-10-10

Low-molecular-mass organic gelator (LMOG)-based molecular gels are known as one of the most attractive soft materials and have received great attention since the early 1990s. In the last few decades, many LMOGs have been synthesized, and a series of theories have been proposed to better understand molecular gels. However, only limited applications of LMOGs have been realized for a variety of reasons, such as their lack of stability compared to chemical gels. Therefore, efforts to explore the applications of these materials are especially meaningful. As an example, this feature article mainly introduces studies on the application of LMOGs as intermediates in porous materials and fluorescent sensing films. Particular attention will be paid to gelator design, LMOG emulsion preparation, solid surface modification, and the practical application of the obtained materials. Concepts that are related to these studies, such as organic gel-water interface equilibria and molecular gel strategies, will be comprehensively illustrated. Finally, we will conclude with a study of LMOG-based intermediates. Some challenges and future perspectives related to these research areas will also be presented. It is anticipated that this feature article will not only contribute to the further understanding of LMOG-based intermediates but also will help to promote the practical application of molecular gels and facilitate development in related research areas.

Commercial and Advertising Art. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Atkinson, Floyd

Several intermediate performance objectives and corresponding criterion measures are listed for each of eight terminal objectives for an intermediate commercial and advertising art course for high school vocational students. The materials were developed for a two-semester (3 hours daily) course involving specialized classroom, shop, and practical…

Two-Step Amyloid Aggregation: Sequential Lag Phase Intermediates

NASA Astrophysics Data System (ADS)

Castello, Fabio; Paredes, Jose M.; Ruedas-Rama, Maria J.; Martin, Miguel; Roldan, Mar; Casares, Salvador; Orte, Angel

2017-01-01

The self-assembly of proteins into fibrillar structures called amyloid fibrils underlies the onset and symptoms of neurodegenerative diseases, such as Alzheimer’s and Parkinson’s. However, the molecular basis and mechanism of amyloid aggregation are not completely understood. For many amyloidogenic proteins, certain oligomeric intermediates that form in the early aggregation phase appear to be the principal cause of cellular toxicity. Recent computational studies have suggested the importance of nonspecific interactions for the initiation of the oligomerization process prior to the structural conversion steps and template seeding, particularly at low protein concentrations. Here, using advanced single-molecule fluorescence spectroscopy and imaging of a model SH3 domain, we obtained direct evidence that nonspecific aggregates are required in a two-step nucleation mechanism of amyloid aggregation. We identified three different oligomeric types according to their sizes and compactness and performed a full mechanistic study that revealed a mandatory rate-limiting conformational conversion step. We also identified the most cytotoxic species, which may be possible targets for inhibiting and preventing amyloid aggregation.

Electron microscopic analysis of rotavirus assembly-replication intermediates

PubMed Central

Boudreaux, Crystal E.; Kelly, Deborah F.; McDonald, Sarah M.

2015-01-01

Rotaviruses (RVs) replicate their segmented, double-stranded RNA genomes in tandem with early virion assembly. In this study, we sought to gain insight into the ultrastructure of RV assembly-replication intermediates (RIs) using transmission electron microscopy (EM). Specifically, we examined a replicase-competent, subcellular fraction that contains all known RV RIs. Three never-before-seen complexes were visualized in this fraction. Using in vitro reconstitution, we showed that ~15-nm doughnut-shaped proteins in strings were nonstructural protein 2 (NSP2) bound to viral RNA transcripts. Moreover, using immunoaffinity-capture EM, we revealed that ~20-nm pebble-shaped complexes contain the viral RNA polymerase (VP1) and RNA capping enzyme (VP3). Finally, using a gel purification method, we demonstrated that ~30–70-nm electron-dense, particle-shaped complexes represent replicase-competent core RIs, containing VP1, VP3, and NSP2 as well as capsid proteins VP2 and VP6. The results of this study raise new questions about the interactions among viral proteins and RNA during the concerted assembly-replicase process. PMID:25635339

Exploring the early steps of amyloid peptide aggregation by computers.

PubMed

Mousseau, Normand; Derreumaux, Philippe

2005-11-01

The assembly of normally soluble proteins into amyloid fibrils is a hallmark of neurodegenerative diseases. Because protein aggregation is very complex, involving a variety of oligomeric metastable intermediates, the detailed aggregation paths and structural characterization of the intermediates remain to be determined. Yet, there is strong evidence that these oligomers, which form early in the process of fibrillogenesis, are cytotoxic. In this paper, we review our current understanding of the underlying factors that promote the aggregation of peptides into amyloid fibrils. We focus here on the structural and dynamic aspects of the aggregation as observed in state-of-the-art computer simulations of amyloid-forming peptides with an emphasis on the activation-relaxation technique.

9 CFR 3.13 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2013 CFR

2013-01-01

..., and Transportation of Dogs and Cats 1 Transportation Standards § 3.13 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a dog or cat for transport in... a dog or cat to extend this time by up to 2 hours. (b) Carriers and intermediate handlers must not...

9 CFR 3.13 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2012 CFR

2012-01-01

..., and Transportation of Dogs and Cats 1 Transportation Standards § 3.13 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a dog or cat for transport in... a dog or cat to extend this time by up to 2 hours. (b) Carriers and intermediate handlers must not...

9 CFR 3.13 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2014 CFR

2014-01-01

..., and Transportation of Dogs and Cats 1 Transportation Standards § 3.13 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a dog or cat for transport in... a dog or cat to extend this time by up to 2 hours. (b) Carriers and intermediate handlers must not...

9 CFR 3.13 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2011 CFR

2011-01-01

..., and Transportation of Dogs and Cats 1 Transportation Standards § 3.13 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a dog or cat for transport in... a dog or cat to extend this time by up to 2 hours. (b) Carriers and intermediate handlers must not...

42 CFR 440.150 - Intermediate care facility (ICF/MR) services.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 4 2010-10-01 2010-10-01 false Intermediate care facility (ICF/MR) services. 440....150 Intermediate care facility (ICF/MR) services. (a) “ICF/MR services” means those items and services furnished in an intermediate care facility for the mentally retarded if the following conditions are met: (1...

9 CFR 3.13 - Consignments to carriers and intermediate handlers.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., and Transportation of Dogs and Cats 1 Transportation Standards § 3.13 Consignments to carriers and intermediate handlers. (a) Carriers and intermediate handlers must not accept a dog or cat for transport in... a dog or cat to extend this time by up to 2 hours. (b) Carriers and intermediate handlers must not...

The Intermediate Neutrino Program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, C.; Alonso, J. R.; Ankowski, A. M.

2017-04-03

The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topicsmore » on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summarizes discussion and conclusions from the workshop.« less

Intermediate-Mass Black Holes

NASA Astrophysics Data System (ADS)

Miller, M. Coleman; Colbert, E. J. M.

2004-01-01

The mathematical simplicity of black holes, combined with their links to some of the most energetic events in the universe, means that black holes are key objects for fundamental physics and astrophysics. Until recently, it was generally believed that black holes in nature appear in two broad mass ranges: stellar-mass (M~3 20 M⊙), which are produced by the core collapse of massive stars, and supermassive (M~106 1010 M⊙), which are found in the centers of galaxies and are produced by a still uncertain combination of processes. In the last few years, however, evidence has accumulated for an intermediate-mass class of black holes, with M~102 104 M⊙. If such objects exist they have important implications for the dynamics of stellar clusters, the formation of supermassive black holes, and the production and detection of gravitational waves. We review the evidence for intermediate-mass black holes and discuss future observational and theoretical work that will help clarify numerous outstanding questions about these objects.

Intermediate-Mass Black Holes

NASA Astrophysics Data System (ADS)

Coleman Miller, M.; Colbert, E. J. M.

The mathematical simplicity of black holes, combined with their links to some of the most energetic events in the universe, means that black holes are key objects for fundamental physics and astrophysics. Until recently, it was generally believed that black holes in nature appear in two broad mass ranges: stellar-mass (M~3-20 M⊙), which are produced by the core collapse of massive stars, and supermassive (M~106-1010 M⊙), which are found in the centers of galaxies and are produced by a still uncertain combination of processes. In the last few years, however, evidence has accumulated for an intermediate-mass class of black holes, with M~102-104 M⊙. If such objects exist they have important implications for the dynamics of stellar clusters, the formation of supermassive black holes, and the production and detection of gravitational waves. We review the evidence for intermediate-mass black holes and discuss future observational and theoretical work that will help clarify numerous outstanding questions about these objects.

A 2D Microphysical Analysis of Aerosol Nucleation in the Polar Winter Stratosphere: Implications for H2SO4 Photolysis and Nucleation Mechanisms

NASA Technical Reports Server (NTRS)

Mills, Michael J.; Toon, Owen B.; Mills, Michael J.; Solomon, Susan

1997-01-01

Each spring a layer of small particles forms between 20 and 30 km in the polar regions. Results are presented from a 2D microphysical model of sulfate aerosol, which provide the first self-consistent explanation of the observed "CN layer." Photochemical conversion of sulfuric acid to SO2 in the upper stratosphere and mesosphere is necessary for this layer to form. Recent laboratory measurements of H2SO4 and SO3 photolysis rates are consistent with such conversion, though an additional source of SO2 may be required. Nucleation throughout the polar winter extends the top of the aerosol layer to higher altitudes, despite strong downward transport of ambient air. This finding may be important to heterogeneous chemistry at the top of the aerosol layer in polar winter and spring.

Criegee intermediates in the indoor environment. New insights

DOE PAGES

Shallcross, D. E.; Taatjes, C. A.; Percival, C. J.

2014-03-25

Criegee intermediates are formed in the ozonolysis of alkenes and play an important role in indoor chemistry, notably as a source of OH radicals. Recent studies have shown that these Criegee intermediates react very quickly with NO 2, SO 2, and carbonyls, and in this study, steady-state calculations are used to inspect the potential impact of these data on indoor chemistry. It is shown that these reactions could accelerate NO 3 formation and SO 2 removal in the indoor environment significantly. In addition, reaction between Criegee intermediates and halogenated carbonyls could provide a significant loss process indoors, where currently onemore » does not exist.« less

Projecting non-diffracting waves with intermediate-plane holography.

PubMed

Mondal, Argha; Yevick, Aaron; Blackburn, Lauren C; Kanellakopoulos, Nikitas; Grier, David G

2018-02-19

We introduce intermediate-plane holography, which substantially improves the ability of holographic trapping systems to project propagation-invariant modes of light using phase-only diffractive optical elements. Translating the mode-forming hologram to an intermediate plane in the optical train can reduce the need to encode amplitude variations in the field, and therefore complements well-established techniques for encoding complex-valued transfer functions into phase-only holograms. Compared to standard holographic trapping implementations, intermediate-plane holograms greatly improve diffraction efficiency and mode purity of propagation-invariant modes, and so increase their useful non-diffracting range. We demonstrate this technique through experimental realizations of accelerating modes and long-range tractor beams.

Early evolution without a tree of life.

PubMed

Martin, William F

2011-06-30

Life is a chemical reaction. Three major transitions in early evolution are considered without recourse to a tree of life. The origin of prokaryotes required a steady supply of energy and electrons, probably in the form of molecular hydrogen stemming from serpentinization. Microbial genome evolution is not a treelike process because of lateral gene transfer and the endosymbiotic origins of organelles. The lack of true intermediates in the prokaryote-to-eukaryote transition has a bioenergetic cause.

27 CFR 17.126 - Formulas for intermediate products.

Code of Federal Regulations, 2010 CFR

2010-04-01

... which that ingredient is used, or unless the formula for the ingredient is contained in one of the... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Formulas for intermediate... NONBEVERAGE PRODUCTS Formulas and Samples § 17.126 Formulas for intermediate products. (a) The manufacturer...

27 CFR 17.126 - Formulas for intermediate products.

Code of Federal Regulations, 2012 CFR

2012-04-01

... which that ingredient is used, or unless the formula for the ingredient is contained in one of the... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Formulas for intermediate... NONBEVERAGE PRODUCTS Formulas and Samples § 17.126 Formulas for intermediate products. (a) The manufacturer...

27 CFR 17.126 - Formulas for intermediate products.

Code of Federal Regulations, 2014 CFR

2014-04-01

... which that ingredient is used, or unless the formula for the ingredient is contained in one of the... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Formulas for intermediate... NONBEVERAGE PRODUCTS Formulas and Samples § 17.126 Formulas for intermediate products. (a) The manufacturer...

27 CFR 17.126 - Formulas for intermediate products.

Code of Federal Regulations, 2011 CFR

2011-04-01

... which that ingredient is used, or unless the formula for the ingredient is contained in one of the... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Formulas for intermediate... NONBEVERAGE PRODUCTS Formulas and Samples § 17.126 Formulas for intermediate products. (a) The manufacturer...

27 CFR 17.126 - Formulas for intermediate products.

Code of Federal Regulations, 2013 CFR

2013-04-01

... which that ingredient is used, or unless the formula for the ingredient is contained in one of the... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Formulas for intermediate... NONBEVERAGE PRODUCTS Formulas and Samples § 17.126 Formulas for intermediate products. (a) The manufacturer...

49 CFR 37.201 - Intermediate and rest stops.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 1 2010-10-01 2010-10-01 false Intermediate and rest stops. 37.201 Section 37.201 Transportation Office of the Secretary of Transportation TRANSPORTATION SERVICES FOR INDIVIDUALS WITH DISABILITIES (ADA) Over-the-Road Buses (OTRBs) § 37.201 Intermediate and rest stops. (a) Whenever an OTRB makes...

A new intermediate in the Prins reaction

PubMed Central

Fukuda, Takeshi; Yamazaki, Shoko

2013-01-01

Summary Two Prins reactions were investigated by the use of DFT calculations. A model composed of R–CH=CH2 + H3O+(H2O)13 + (H2C=O)2, R = Me and Ph, was adopted to trace reaction paths. For both alkenes, the concerted path forming 1,3-diols was obtained as the rate determining step (TS1). TS stands for a transition state. From the 1,3-diol, a bimolecular elimination (TS2) leads to the allylic alcohol as the first channel. In the second channel, the 1,3-diol was converted via TS3 into an unprecedented hemiacetal intermediate, HO–CH2–O–CH(R)–CH2–CH2–OH. This intermediate undergoes ring closure (TS4), affording the 1,3-dioxane product. The intermediate is of almost the same stability as the product, and two species were suggested to be in a state of equilibrium. While the geometry of TS1 appears to be forwarded to that of a carbocation intermediate, the cation disappeared through the enlargement of the water cluster. Dynamical calculations of a classical trajectory using the atom-centered density matrix propagation molecular dynamics model on the four TSs were carried out, and results of IRC calculations were confirmed by them. PMID:23532354

Arctic intermediate water in the Norwegian sea

NASA Astrophysics Data System (ADS)

Blindheim, Johan

1990-09-01

At least two types of intermediate water propagate into the Norwegian Sea from the Iceland and Greenland seas. North Icelandic Winter Water flows along the slope of the Faroe-Iceland Ridge towards the Faroes. The distribution of this intermediate water is limited to the southern Norwegian Sea. The second type intrudes between the bottom water and the Atlantic Water, and can be traced as a slight salinity minimum of the entire area of the Norwegian Sea. There seems to be along-isopycnal advection of this water type along the Arctic Front from both the Iceland and Greenland Seas. Although the salinity minimum is less distinct along the slope of the continental shelf than in the western Norwegian Sea, this intermediate water separates the deep water and the Atlantic Water, and prohibits direct mixing of these two water masses.

Photon ratchet intermediate band solar cells

NASA Astrophysics Data System (ADS)

Yoshida, M.; Ekins-Daukes, N. J.; Farrell, D. J.; Phillips, C. C.

2012-06-01

In this paper, we propose an innovative concept for solar power conversion—the "photon ratchet" intermediate band solar cell (IBSC)—which may increase the photovoltaic energy conversion efficiency of IBSCs by increasing the lifetime of charge carriers in the intermediate state. The limiting efficiency calculation for this concept shows that the efficiency can be increased by introducing a fast thermal transition of carriers into a non-emissive state. At 1 sun, the introduction of a "ratchet band" results in an increase of efficiency from 46.8% to 48.5%, due to suppression of entropy generation.

Early detection: the impact of genomics.

PubMed

van Lanschot, M C J; Bosch, L J W; de Wit, M; Carvalho, B; Meijer, G A

2017-08-01

The field of genomics has shifted our view on disease development by providing insights in the molecular and functional processes encoded in the genome. In the case of cancer, many alterations in the DNA accumulate that enable tumor growth or even metastatic dissemination. Identification of molecular signatures that define different stages of progression towards cancer can enable early tumor detection. In this review, the impact of genomics will be addressed using early detection of colorectal cancer (CRC) as an example. Increased understanding of the adenoma-to-carcinoma progression has led to the discovery of several diagnostic biomarkers. This combined with technical advancements, has facilitated the development of molecular tests for non-invasive early CRC detection in stool and blood samples. Even though several tests have already made it to clinical practice, sensitivity and specificity for the detection of precancerous lesions still need improvement. Besides the diagnostic qualities, also the accuracy of the intermediate endpoint is an important issue on how the effectiveness of a novel test is perceived. Here, progression biomarkers may provide a more precise measure than the currently used morphologically based features. Similar developments in biomarker use for early detection have taken place in other cancer types.

SPACE: Intermediate Level Modules.

ERIC Educational Resources Information Center

Indiana State Dept. of Education, Indianapolis. Center for School Improvement and Performance.

These modules were developed to assist teachers at the intermediate level to move away from extensive skill practice and toward more meaningful interdisciplinary learning. This packet, to be used by teachers in the summer Extended Learning Program, provides detailed thematic lesson plans matched to the Indiana Curriculum Proficiency Guide. The…

Direct measurements of unimolecular and bimolecular reaction kinetics of the Criegee intermediate (CH 3) 2COO

DOE PAGES

Chhantyal-Pun, Rabi; Welz, Oliver; Savee, John D.; ...

2016-10-18

Here, the Criegee intermediate acetone oxide, (CH 3) 2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O 2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO 2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10 –11 cm 3 s –1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10 –10 cm 3 s –1 at 298 K and 10 Torr (He buffer). These values are similar tomore » directly measured rate coefficients of anti-CH 3CHOO with SO 2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N 2 from cavity ring-down decay of the ultraviolet absorption of (CH 3) 2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10 –10 to (2.29 ± 0.08) × 10 –10 cm 3 s –1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO 2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10 –12 cm 3 s –1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH 3CHOO with NO 2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH 3) 2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s –1, is similar to determinations from ozonolysis. The present measurements confirm the large

Deglacial Evolution of Atlantic Mid-Depth and Intermediate-Depth Water Variability

NASA Astrophysics Data System (ADS)

Oppo, D.; Gebbie, G.; Huang, K. F.; Guo, W.; Schmittner, A.; Liu, Z.; Curry, W. B.

2014-12-01

Deglacial variations in the Atlantic Meridional Overturning Circulation (AMOC) feature prominently in hypotheses of deglacial climate variability and atmospheric CO2rise. However, there is lingering uncertainty in the glacial deepwater mass configuration (e.g. Gebbie, 2014) and deglacial AMOC variability is even more poorly understood. For example, the deglacial evolution of the contribution of northern and southern source waters to the middle and intermediate depths of the Atlantic is still vigorously debated. Here, we evaluate the evolution of subsurface Atlantic ventilation, emphasizing middle and intermediate depths, by comparing new and published records of water mass variability to output from transient model simulations designed to provide insight into the climatic and oceanographic effects of a dramatic reduction in the AMOC, such as apparently occurred during Heinrich Stadial 1 (Liu et al., 2009; Schmittner and Lund, 2014). Gebbie, G. (2014), How much did Glacial North Atlantic Water shoal? Paleoceanography, 29, 190-209, doi: 10.1002/2013PA002557. Liu, Z., B. Otto-Bliesner, F. He, E. Brady, R. Thomas, P. U. Clark, A. E. Carlson, J. Lynch-Stieglitz, W. Curry, E. Brook, D. Erickson, R. Jacob, J. Kutzbach, J., and J. Chen (2009), Transient climate simulation of last deglaciation with a new mechanism for Bølling-Allerød warming, Science, 325, 310-314. Schmittner, A., and Lund, D. C. (submitted), Carbon Isotopes Support Atlantic Meridional Overturning Circulation Decline as a Trigger for Early Deglacial CO2 rise Climate of the Past Discussions.

Early work on the stratospheric ozone depletion-CFC issue

NASA Astrophysics Data System (ADS)

Molina, M.

2012-12-01

I became involved with the atmospheric chemistry of chlorofluorocarbons (CFCs) shortly after joining Sherry Rowland's research group at the University of California, Irvine, in 1973. CFCs had been detected in the troposphere by James Lovelock in 1971, and the question we set out to answer was the fate of these compounds of industrial origin in the environment, as well as possibly identifying any consequences of their accumulation in the atmosphere. After examining many potential sinks for these compounds we realized that because of their unusual stability the most likely destruction process was photolysis in the stratosphere. I carried out measurements of the absorption spectra of these compounds in the near ultraviolet; previous work involved only spectra in the far ultraviolet, not relevant for atmospheric chemistry. The results indicated that photolysis would take place in the upper stratosphere. I subsequently carried out calculations using one-dimensional atmospheric models to estimate their atmospheric residence times, which turned out to be many decades. We realized that the chlorine atoms generated by photolysis of the CFCs would participate in a catalytic chain reaction that would efficiently destroy ozone. Furthermore, we estimated that the amount of CFCs produced industrially was comparable to the amount of nitric oxide produced naturally in the stratosphere by the decomposition of nitrous oxide; work by Paul Crutzen and Harold Johnston had indicated that the abundance of ozone in the stratosphere was controlled by nitric oxide. We then formulated the hypothesis that the continued release of CFCs to the environment posed a threat to the stability of the ozone layer, and published our results in the journal Nature in 1974. The publication was noticed almost exclusively by the community of experts in stratospheric chemistry, and hence Sherry Rowland and I decided at that time that it was our responsibility to communicate this finding to society at large

INTERMEDIATE READINGS IN TAGALOG.

ERIC Educational Resources Information Center

BOWEN, J. DONALD, ED.

THE SECOND IN A SERIES OF TEXTS DESIGNED TO HELP THE STUDENT ACHIEVE AN UNDERSTANDING OF FILIPINO CULTURE AND ACQUIRE ENOUGH PROFICIENCY IN TAGALOG TO COMMUNICATE EASILY AND MEANINGFULLY, THESE INTERMEDIATE READINGS ARE COORDINATED WITH THE EDITOR'S "BEGINNING TAGALOG" (ED 014 696). INCLUDED IN PART I ARE READINGS WRITTEN ESPECIALLY FOR THIS TEXT…

AIDS Elementary/Intermediate Curriculum.

ERIC Educational Resources Information Center

Kellogg, Nancy Rader

This Acquired Immune Deficiency Syndrome (AIDS) Curriculum was developed for intermediate elementary (5th, 6th, and 7th grade) students. It is an integrated unit that encompasses health, science, social studies, math, and language arts. The curriculum is comprised of nine class activities designed to meet the following objectives: (1) to determine…

UV and solar photo-degradation of naproxen: TiO₂ catalyst effect, reaction kinetics, products identification and toxicity assessment.

PubMed

Jallouli, Nabil; Elghniji, Kais; Hentati, Olfa; Ribeiro, Ana R; Silva, Adrián M T; Ksibi, Mohamed

2016-03-05

Direct photolysis and TiO2-photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pHinitial 6.5) was 83% after 3h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO2-UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant (kapp) for NPX degradation by photolysis ranged from 0.0050 min(-1) at pH 3.5 to 0.0095 min(-1) at pH 6.5, while it was estimated to be 0.0063 min(-1) under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Photodegradation of naproxen and its photoproducts in aqueous solution at 254 nm: a kinetic investigation.

PubMed

Marotta, Raffaele; Spasiano, Danilo; Di Somma, Ilaria; Andreozzi, Roberto

2013-01-01

The kinetics of photodegradation of the non steroidal anti-inflammatory drug naproxen (+)-S-2-(6-methoxynaphthalen-2-yl)propanoic acid, an emerging organic pollutant, was studied in aqueous solutions under deaerated and aerated conditions. The photolysis experiments were carried out under monochromatic irradiation (λ = 254 nm) at pH = 7.0 and T = 25 °C. Simplified reaction schemes of photodegradation of naproxen are proposed in absence and in presence of oxygen respectively. The schemes take into account the photolysis of naproxen and its photoproducts and the reactions of the measured species with oxygen dissolved in the liquid bulk. According to these schemes, two kinetic models were developed which correlate the experimental data, for runs performed in absence and in presence of oxygen, with a fair accuracy and allowed to estimate the best values for the unknown kinetic parameters. The calculated quantum yield of direct photolysis of naproxen under deaerated media is in good agreement with the one previously reported. Under aerated conditions, the generation of singlet oxygen has also been taken into account. The obtained results, under the adopted conditions, indicated a marked influence of dissolved oxygen on the photodegradation rates of naproxen and the relative distribution of the major reaction intermediates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Degradation of parathion and the reduction of acute toxicity in TiO2 photocatalysis.

PubMed

Zoh, K D; Kim, T S; Kim, J G; Choi, K H

2005-01-01

Photocatalytic degradation of methyl parathion was done using a circulating TiO2/UV and TiO2/solar reactor. Indoor experimental results showed that, under the photocatalysis conditions, parathion was more effectively degraded than under the photolysis and TiO2 only conditions. Parathion (38 microM) was completely degraded under photocatalysis within 90 min, and more than 80% TOC decrease after 150 minutes. The main ionic byproducts during the photocatalysis were measured, and almost complete nitrogen recovery was achieved as mainly NO3- NO2-, and NH4+, and 80% of sulfur as recovered as SO4(2)-. Organic intermediates such as nitrophenol and methyl paraoxon were also identified during the photocatalysis of parathion, and these were further degraded after 90 minutes. Microtox bioassay using Vibrio fischeri was used in evaluating the toxicity of solutions treated by photocatalysis and photolysis of parathion. The results showed that the acute toxicity expressed as EC50 almost reduced after 90 min under the photocatalysis condition whereas only 40% reduction of toxicity as EC50 was achieved in photolysis condition. The outdoor results using a TiO2/solar system were similar to the TiO2 indoor system, indicating the possibility of applying TiO2/solar system for the treatment of parathion-contaminated water.

The intermediate filament network protein, vimentin, is required for parvoviral infection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fay, Nikta; Panté, Nelly, E-mail: pante@zoology.ubc.ca

Intermediate filaments (IFs) have recently been shown to serve novel roles during infection by many viruses. Here we have begun to study the role of IFs during the early steps of infection by the parvovirus minute virus of mice (MVM). We found that during early infection with MVM, after endosomal escape, the vimentin IF network was considerably altered, yielding collapsed immunofluorescence staining near the nuclear periphery. Furthermore, we found that vimentin plays an important role in the life cycle of MVM. The number of cells, which successfully replicated MVM, was reduced in infected cells in which the vimentin network wasmore » genetically or pharmacologically modified; viral endocytosis, however, remained unaltered. Perinuclear accumulation of MVM-containing vesicles was reduced in cells lacking vimentin. Our data suggests that vimentin is required for the MVM life cycle, presenting possibly a dual role: (1) following MVM escape from endosomes and (2) during endosomal trafficking of MVM. - Highlights: • MVM infection changes the distribution of the vimentin network to perinuclear regions. • Disrupting the vimentin network with acrylamide decreases MVM replication. • MVM replication is significantly reduced in vimentin-null cells. • Distribution of MVM-containing vesicles is affected in MVM infected vimentin-null cells.« less

Capturing a flavivirus pre-fusion intermediate.

PubMed

Kaufmann, Bärbel; Chipman, Paul R; Holdaway, Heather A; Johnson, Syd; Fremont, Daved H; Kuhn, Richard J; Diamond, Michael S; Rossmann, Michael G

2009-11-01

During cell entry of flaviviruses, low endosomal pH triggers the rearrangement of the viral surface glycoproteins to a fusion-active state that allows the release of the infectious RNA into the cytoplasm. In this work, West Nile virus was complexed with Fab fragments of the neutralizing mAb E16 and was subsequently exposed to low pH, trapping the virions in a pre-fusion intermediate state. The structure of the complex was studied by cryo-electron microscopy and provides the first structural glimpse of a flavivirus fusion intermediate near physiological conditions. A radial expansion of the outer protein layer of the virion was observed compared to the structure at pH 8. The resulting approximately 60 A-wide shell of low density between lipid bilayer and outer protein layer is likely traversed by the stem region of the E glycoprotein. By using antibody fragments, we have captured a structural intermediate of a virus that likely occurs during cell entry. The trapping of structural transition states by antibody fragments will be applicable for other processes in the flavivirus life cycle and delineating other cellular events that involve conformational rearrangements.

A five-year model to assess the early cost-effectiveness of new diagnostic tests in the early diagnosis of rheumatoid arthritis.

PubMed

Buisman, Leander R; Luime, Jolanda J; Oppe, Mark; Hazes, Johanna M W; Rutten-van Mölken, Maureen P M H

2016-06-10

There is a lack of information about the sensitivity, specificity and costs new diagnostic tests should have to improve early diagnosis of rheumatoid arthritis (RA). Our objective was to explore the early cost-effectiveness of various new diagnostic test strategies in the workup of patients with inflammatory arthritis (IA) at risk of having RA. A decision tree followed by a patient-level state transition model, using data from published literature, cohorts and trials, was used to evaluate diagnostic test strategies. Alternative tests were assessed as add-on to or replacement of the ACR/EULAR 2010 RA classification criteria for all patients and for intermediate-risk patients. Tests included B-cell gene expression (sensitivity 0.60, specificity 0.90, costs €150), MRI (sensitivity 0.90, specificity 0.60, costs €756), IL-6 serum level (sensitivity 0.70, specificity 0.53, costs €50) and genetic assay (sensitivity 0.40, specificity 0.85, costs €750). Patients with IA at risk of RA were followed for 5 years using a societal perspective. Guideline treatment was assumed using tight controlled treatment based on DAS28; if patients had a DAS28 >3.2 at 12 months or later patients could be eligible for starting biological drugs. The outcome was expressed in incremental cost-effectiveness ratios (€2014 per quality-adjusted life year (QALY) gained) and headroom. The B-cell test was the least expensive strategy when used as an add-on and as replacement in intermediate-risk patients, making it the dominant strategy, as it has better health outcomes and lower costs. As add-on for all patients, the B-cell test was also the most cost-effective test strategy. When using a willingness-to-pay threshold of €20,000 per QALY gained, the IL-6 and MRI strategies were not cost-effective, except as replacement. A genetic assay was not cost-effective in any strategy. Probabilistic sensitivity analysis revealed that the B-cell test was consistently superior in all strategies. When

Cost-effectiveness of an autoantibody test (EarlyCDT-Lung) as an aid to early diagnosis of lung cancer in patients with incidentally detected pulmonary nodules.

PubMed

Edelsberg, John; Weycker, Derek; Atwood, Mark; Hamilton-Fairley, Geoffrey; Jett, James R

2018-01-01

Patients who have incidentally detected pulmonary nodules and an estimated intermediate risk (5-60%) of lung cancer frequently are followed via computed tomography (CT) surveillance to detect nodule growth, despite guidelines for a more aggressive diagnostic strategy. We examined the cost-effectiveness of an autoantibody test (AABT)-Early Cancer Detection Test-Lung (EarlyCDT-LungTM)-as an aid to early diagnosis of lung cancer among such patients. We developed a decision-analytic model to evaluate use of the AABT versus CT surveillance alone. In the model, patients with a positive AABT-because they are at substantially enhanced risk of lung cancer-are assumed to go directly to biopsy, resulting in diagnosis of lung cancer in earlier stages than under current guidelines (a beneficial stage shift). Patients with a negative AABT, and those scheduled for CT surveillance alone, are assumed to have periodic CT screenings to detect rapid growth and thus to have their lung cancers diagnosed-on average-at more advanced stages. Among 1,000 patients who have incidentally detected nodules 8-30 mm, have an intermediate-risk of lung cancer, and are evaluated by CT surveillance alone, 95 (9.5%) are assumed to have lung cancer (local, 73.6%; regional, 22.0%; distant, 4.4%). With use of the AABT set at a sensitivity/specificity of 41%/93% (stage shift = 10.8%), although expected costs would be higher by $949,442 ($949 per person), life years would be higher by 53 (0.05 per person), resulting in a cost per life-year gained of $18,029 and a cost per quality-adjusted life year (QALY) gained of $24,330. With use of the AABT set at a sensitivity/specificity of 28%/98% (stage shift = 7.4%), corresponding cost-effectiveness ratios would be $18,454 and $24,833. Under our base-case assumptions, and reasonable variations thereof, using AABT as an aid in the early diagnosis of lung cancer in patients with incidentally detected pulmonary nodules who are estimated to be at intermediate risk of

Potentiometric surfaces of the intermediate aquifer system, west-central Florida, September 2000

USGS Publications Warehouse

Duerr, A.D.

2001-01-01

The intermediate aquifer system underlies a 5,000-square-mile area within the Southwest Florida Water Management District including De Soto, Sarasota, Hardee, Manatee, and parts of Charlotte, Hillsborough, Highlands, Polk, and Lee Counties.  The intermediate aquifer system is overlain by the surficial aquifer system and is underlain by the Floridan aquifer system.  The intermediate aquifer system consists of layers of sand, shell, clay, calcareous clay, limestone, and dolomite of the Tamiami Formation and Hawthorn Group of Oligocene to Pleistocene age (Wingard and others, 1995).  The intermediate aquifer system contains one or more water-bearing units separated by discontinuous confining units.  The intermediate aquifer system is the principal source of potable water in the southwestern part of the study area and is widely used as a source of water where wells are open to the intermediate aquifer system or to both the intermediate and Floridan aquifer systems.  Yields of individual wells open to the intermediate aquifer system vary from a few gallons to several hundred gallons per minute.  The volume of water withdrawn from the intermediate aquifer system is considerably less than that withdrawn from the Floridan aquifer system in the study area (Duerr and others, 1988).

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

PubMed

Li, Kun; Wang, Mei; Wang, Jin; Zhu, Rongrong; Sun, Dongmei; Sun, Xiaoyu; Wang, Shi-Long

2013-01-01

Photoexcitation to generate triplet state has been proved to be the main photoreaction in homogeneous system for many benzoquinone derivatives, including oxidized coenzyme Q (CoQ) and its analogs. In the present study, microemulsion of CoQ, a heterogeneous system, is employed to mimic the distribution of CoQ in biomembrane. The photochemistry of CoQ(10) in microemulsion and cyclohexane is investigated and compared using laser flash photolysis and results show that CoQ(10) undergoes photoionization via a monophotonic process to generate radical cation of CoQ(10) in microemulsion and photoexcitation to generate excited triplet state in cyclohexane. Meanwhile, photoreactions of duroquinone (DQ) and CoQ(0) in microemulsion are also investigated to analyze the influence of molecular structure on the photochemistry of benzoquinone derivatives in microemulsion. Results suggest that photoexcitation, which is followed by excited state-involved hydrogen-abstraction reaction, is the main photoreaction for DQ and CoQ(0) in microemulsion. However, photoexcited CoQ(0) also leads to the formation of hydrated electrons. The isoprenoid side chain-involved high resonance stabilization is proposed to explain the difference in photoreactions of CoQ(0) and CoQ(10) in microemulsion. Considering that microemulsion is close to biomembrane system, its photoionization in microemulsion may be helpful to understand the real photochemistry of biological quinones in biomembrane system. © 2012 Tongji University. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Detection of Early Loss of Color Vision in Age-Related Macular Degeneration - With Emphasis on Drusen and Reticular Pseudodrusen.

PubMed

Vemala, Roopa; Sivaprasad, Sobha; Barbur, John L

2017-05-01

To evaluate chromatic sensitivity in patients with age-related macular degeneration (AMD) characterized by drusen and reticular pseudodrusen. To investigate whether the severity of color vision loss can distinguish between various stages of AMD and hence be used as an index of progression toward advanced AMD. Chromatic sensitivity was measured by using the Color Assessment and Diagnosis (CAD) test in asymptomatic individuals with early and intermediate AMD and compared to normative data. All study participants had logMAR visual acuity of 0.3 or better. The CAD thresholds measured in eyes with and without reticular pseudodrusen were also compared and related to central macular thickness (CMT). Student's t-test P values < 0.05 were considered significant. All early- and intermediate-AMD eyes (n = 90) had chromatic sensitivity loss in either RG (red/green) or YB (yellow/blue), or both (P < 0.0001) as compared to age-matched normal subjects. The eyes exhibited a range of CAD thresholds affecting both color mechanisms, but YB color thresholds were in general higher than RG thresholds (P < 0.001). Intermediate-AMD patients exhibited large intersubject variability. In general, eyes with reticular pseudodrusen and eyes with CMT < 200 μm had significantly higher CAD thresholds. The anatomic integrity of cone photoreceptors remains relatively unaffected in early and intermediate stages of AMD. The processing of cone signals in the retina can, however, be heavily disrupted with subsequent loss of both YB and RG chromatic sensitivity. The greatest losses were observed in eyes with reticular pseudodrusen.

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

NASA Technical Reports Server (NTRS)

Vander Wood, T. B.; Thiemens, M. H.

1980-01-01

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

29 CFR 452.122 - Delegates from intermediate bodies; method of election.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 2 2011-07-01 2011-07-01 false Delegates from intermediate bodies; method of election. 452... Delegates from intermediate bodies; method of election. A delegate from an intermediate body who... secret ballot vote of the individual members of the constituent units of that body. He may not...

42 CFR 440.150 - Intermediate care facility (ICF/IIDICF/IID) services.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 42 Public Health 4 2012-10-01 2012-10-01 false Intermediate care facility (ICF/IIDICF/IID... Definitions § 440.150 Intermediate care facility (ICF/IIDICF/IID) services. (a) “ICF/IIDICF/IID services” means those items and services furnished in an intermediate care facility for Individuals with...

42 CFR 440.150 - Intermediate care facility (ICF/IIDICF/IID) services.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 42 Public Health 4 2013-10-01 2013-10-01 false Intermediate care facility (ICF/IIDICF/IID... Definitions § 440.150 Intermediate care facility (ICF/IIDICF/IID) services. (a) “ICF/IIDICF/IID services” means those items and services furnished in an intermediate care facility for Individuals with...

29 CFR 452.122 - Delegates from intermediate bodies; method of election.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 2 2010-07-01 2010-07-01 false Delegates from intermediate bodies; method of election. 452... Delegates from intermediate bodies; method of election. A delegate from an intermediate body who... secret ballot vote of the individual members of the constituent units of that body. He may not...

Ultra-Widefield Fluorescein Angiography in Intermediate Uveitis.

PubMed

Laovirojjanakul, Wipada; Acharya, Nisha; Gonzales, John A

2017-10-17

To examine associations between pattern of vascular leakage on ultrawide-field fluorescein angiography (UWFFA) and visual acuity, cystoid macular edema (CME), and inflammatory activity in intermediate uveitis. Single center cross-sectional, retrospective review of medical records, spectral domain optical coherence tomography (SD-OCT) and angiographic images of intermediate uveitis patients who underwent UWFFA over a 12-month period. Forty-one eyes from 24 patients were included. Twelve eyes (29%) exhibited peripheral leakage, 26 eyes (64%) had diffuse leakage and three eyes (7%) had no leakage. Diffuse leakage was associated with 0.2 logMAR worse visual acuity than peripheral leakage (p = 0.02). There was no statistically significant difference in the odds of having CME when diffuse leakage was compared to peripheral leakage. UWFFA identifies retinal vascular pathology in intermediate uveitis not present on clinical examination. Diffuse retinal vascular leakage was associated with worse visual acuity when compared to peripheral and no leakage patterns.

Intermediate band solar cell with extreme broadband spectrum quantum efficiency.

PubMed

Datas, A; López, E; Ramiro, I; Antolín, E; Martí, A; Luque, A; Tamaki, R; Shoji, Y; Sogabe, T; Okada, Y

2015-04-17

We report, for the first time, about an intermediate band solar cell implemented with InAs/AlGaAs quantum dots whose photoresponse expands from 250 to ∼6000  nm. To our knowledge, this is the broadest quantum efficiency reported to date for a solar cell and demonstrates that the intermediate band solar cell is capable of producing photocurrent when illuminated with photons whose energy equals the energy of the lowest band gap. We show experimental evidence indicating that this result is in agreement with the theory of the intermediate band solar cell, according to which the generation recombination between the intermediate band and the valence band makes this photocurrent detectable.

DNA intermediates and telomere addition during genome reorganization in Euplotes crassus.

PubMed

Roth, M; Prescott, D M

1985-06-01

Three gene-sized molecules cloned intact from macronuclear DNA served as hybridization probes to study excision of these molecules from chromosomes and their processing during macronuclear development in the hypotrich Euplotes crassus. These molecules occur in integrated forms within polytene chromosomal DNA during macronuclear developmental. After transection of the polytene chromosomes, the three molecules occur in intermediate forms. One of the three molecules first appeared in a large intermediate that was subsequently replaced by a second intermediate, approximately 140 bp larger than the final molecule. The other two macronuclear molecules were detected only in intermediates approximately 140 bp larger than the mature form. These penultimate intermediates are larger by virtue of oversized telomeres, which are pared to yield the mature gene-sized molecules.

Heterophobia: Subverting Heterosexual Hegemony through Intermedial Applied Performance for Young People

ERIC Educational Resources Information Center

Phillips, Hannah

2016-01-01

This article responds to intermediality through a case study of an intermedial applied performance for young people. "Heterophobia," a hybrid fusion of live performance, digital technology, social media and urban street art, aimed to challenge homophobia in schools and online. Intermediality was used as a tool to enhance young people's…

Comparison of classical fenton, nitrilotriacetic acid (NTA)-Fenton, UV-Fenton, UV photolysis of Fe-NTA, UV-NTA-Fenton, and UV-H2O2 for the degradation of cyclohexanoic acid.

PubMed

Zhang, Ying; Klamerth, Nikolaus; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

2017-05-01

The treatment of a naphthenic acid model compound, cyclohexanoic acid, with classical Fenton, UV-H 2 O 2 , UV-Fenton, nitrilotriacetic acid (NTA)-Fenton, UV-NTA-Fenton, and UV photolysis of Fe-NTA processes at pHs 3 and 8 was investigated. At 1.47 mM H 2 O 2 , 0.089 mM Fe, and 0.18 mM NTA, the UV-NTA-Fenton process at pH 3 exhibited the highest H 2 O 2 decomposition (100% in 25 min), CHA removal (100% in 12 min) with a rate constant of 0.27 ± 0.025 min -1 , and NTA degradation (100% in 6 min). Due to the formation of H 2 O 2 -Fe(III)NTA adduct, the total Fe concentration in the UV-NTA-Fenton system (0.063 mM at the end of the reaction) at pH 8 was much higher than that in the UV photolysis of Fe(III)NTA process (0.024 mM). The co-complexing effect of borate buffer helped to keep iron soluble; however, it imposed a negative influence on the CHA degradation in the UV-NTA-Fenton process (68% CHA removal in 60 min in the borate buffer compared to 92% in MilliQ water). The results demonstrated that the most efficient process for the CHA degradation under the experimental conditions was the UV-NTA-Fenton process at pH 3. Copyright © 2017 Elsevier Ltd. All rights reserved.

Borderline Personality Disorder in an Intermediate Psychological Therapies Service

ERIC Educational Resources Information Center

Ryan, Seamus; Danquah, Adam N.; Berry, Katherine; Hopper, Mary

2017-01-01

The intermediate psychological therapies service is provided for individuals referred with common mental health problems within the primary care psychological therapies service, but whose difficulties are longstanding and/or complex. The prevalence of borderline personality disorder (BPD) in intermediate psychological therapy services has not been…

42 CFR 54a.12 - Treatment of intermediate organizations.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 1 2010-10-01 2010-10-01 false Treatment of intermediate organizations. 54a.12... CHARITABLE CHOICE REGULATIONS APPLICABLE TO STATES, LOCAL GOVERNMENTS AND RELIGIOUS ORGANIZATIONS RECEIVING... ABUSE PREVENTION AND TREATMENT SERVICES § 54a.12 Treatment of intermediate organizations. If a...

Intermediate inflation from a non-canonical scalar field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rezazadeh, K.; Karami, K.; Karimi, P., E-mail: rezazadeh86@gmail.com, E-mail: KKarami@uok.ac.ir, E-mail: parvin.karimi67@yahoo.com

2015-09-01

We study the intermediate inflation in a non-canonical scalar field framework with a power-like Lagrangian. We show that in contrast with the standard canonical intermediate inflation, our non-canonical model is compatible with the observational results of Planck 2015. Also, we estimate the equilateral non-Gaussianity parameter which is in well agreement with the prediction of Planck 2015. Then, we obtain an approximation for the energy scale at the initial time of inflation and show that it can be of order of the Planck energy scale, i.e. M{sub P} ∼ 10{sup 18}GeV. We will see that after a short period of time, inflation entersmore » in the slow-roll regime that its energy scale is of order M{sub P}/100 ∼ 10{sup 16}GeV and the horizon exit takes place in this energy scale. We also examine an idea in our non-canonical model to overcome the central drawback of intermediate inflation which is the fact that inflation never ends. We solve this problem without disturbing significantly the nature of the intermediate inflation until the time of horizon exit.« less

Intermediate outcomes in randomized clinical trials: an introduction

PubMed Central

2013-01-01

Background Intermediate outcomes are common and typically on the causal pathway to the final outcome. Some examples include noncompliance, missing data, and truncation by death like pregnancy (e.g. when the trial intervention is given to non-pregnant women and the final outcome is preeclampsia, defined only on pregnant women). The intention-to-treat approach does not account properly for them, and more appropriate alternative approaches like principal stratification are not yet widely known. The purposes of this study are to inform researchers that the intention-to-treat approach unfortunately does not fit all problems we face in experimental research, to introduce the principal stratification approach for dealing with intermediate outcomes, and to illustrate its application to a trial of long term calcium supplementation in women at high risk of preeclampsia. Methods Principal stratification and related concepts are introduced. Two ways for estimating causal effects are discussed and their application is illustrated using the calcium trial, where noncompliance and pregnancy are considered as intermediate outcomes, and preeclampsia is the main final outcome. Results The limitations of traditional approaches and methods for dealing with intermediate outcomes are demonstrated. The steps, assumptions and required calculations involved in the application of the principal stratification approach are discussed in detail in the case of our calcium trial. Conclusions The intention-to-treat approach is a very sound one but unfortunately it does not fit all problems we find in randomized clinical trials; this is particularly the case for intermediate outcomes, where alternative approaches like principal stratification should be considered. PMID:23510143

Mechanisms of deterioration of intermediate moisture food systems

NASA Technical Reports Server (NTRS)

Labuza, T. P.

1972-01-01

A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

Intermediate-consumer identity and resources alter a food web with omnivory.

PubMed

Kneitel, Jamie M

2007-07-01

1. Omnivory is an important interaction that has been the centre of numerous theoretical and empirical studies in recent years. Most of these studies examine the conditions necessary for coexistence between an omnivore and an intermediate consumer. Trait variation in ecological interactions (competition and predator tolerance) among intermediate consumers has not been considered in previous empirical studies despite the evidence that variation in species-specific traits can have important community-level effects. 2. I conducted a multifactorial microcosm experiment using species from the Sarracenia purpurea phytotelmata community, organisms that inhabit the water collected within its modified leaves. The basal trophic level consisted of bacterial decomposers, the second trophic level (intermediate consumers) consisted of protozoa and rotifers, and the third trophic level (omnivore) were larvae of the pitcher plant mosquito Wyeomyia smithii. Trophic level number (1, 2 and 3), resources (low and high), omnivore density (low and high) and intermediate consumer (monoculture of five protozoa and rotifers) identity were manipulated. Abundance of the basal trophic level, intermediate consumers, and growth of the omnivore were measured, as well as time to extinction (intermediate consumers) and time to pupation (mosquito larvae). 3. The presence of different intermediate consumers affected both bacteria abundance and omnivore growth. At high resource levels, Poteriochromonas, Colpidium and Habrotrocha rosa reduced bacteria densities greater than omnivore reduction of bacteria. Mosquito larvae did not pupate at low resource levels except when Poteriochromonas and Colopoda were present as intermediate consumers. Communities with H. rosa were the only ones consistent with the prediction that omnivores should exclude intermediate consumers at high resources. 4. These results had mixed support for predictions from omnivory food web theory. Intermediate consumers responded and

9 CFR 2.77 - Records: Carriers and intermediate handlers.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 9 Animals and Animal Products 1 2010-01-01 2010-01-01 false Records: Carriers and intermediate handlers. 2.77 Section 2.77 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE ANIMAL WELFARE REGULATIONS Records § 2.77 Records: Carriers and intermediate...

Linking Incoming Plate Faulting and Intermediate Depth Seismicity

NASA Astrophysics Data System (ADS)

Kwong, K. B.; van Zelst, I.; Tong, X.; Eimer, M. O.; Naif, S.; Hu, Y.; Zhan, Z.; Boneh, Y.; Schottenfels, E.; Miller, M. S.; Moresi, L. N.; Warren, J. M.; Wiens, D. A.

2017-12-01

Intermediate depth earthquakes, occurring between 70-350 km depth, are often attributed to dehydration reactions within the subducting plate. It is proposed that incoming plate normal faulting associated with plate bending at the trench may control the amount of hydration in the plate by producing large damage zones that create pathways for the infiltration of seawater deep into the subducting mantle. However, a relationship between incoming plate seismicity, faulting, and intermediate depth seismicity has not been established. We compiled a global dataset consisting of incoming plate earthquake moment tensor (CMT) solutions, focal depths, bend fault spacing and offset measurements, along with plate age and convergence rates. In addition, a global intermediate depth seismicity dataset was compiled with parameters such as the maximum seismic moment and seismicity rate, as well as thicknesses of double seismic zones. The maximum fault offset in the bending region has a strong correlation with the intermediate depth seismicity rate, but a more modest correlation with other parameters such as convergence velocity and plate age. We estimated the expected rate of seismic moment release for the incoming plate faults using mapped fault scarps from bathymetry. We compare this with the cumulative moment from normal faulting earthquakes in the incoming plate from the global CMT catalog to determine whether outer rise fault movement has an aseismic component. Preliminary results from Tonga and the Middle America Trench suggest there may be an aseismic component to incoming plate bending faulting. The cumulative seismic moment calculated for the outer rise faults will also be compared to the cumulative moment from intermediate depth earthquakes to assess whether these parameters are related. To support the observational part of this study, we developed a geodynamic numerical modeling study to systematically explore the influence of parameters such as plate age and convergence

AmeriFlux US-Wi1 Intermediate hardwood (IHW)

DOE Data Explorer

Chen, Jiquan [Michigan State University

2016-01-01

This is the AmeriFlux version of the carbon flux data for the site US-Wi1 Intermediate hardwood (IHW). Site Description - The Wisconsin Intermediate Hardwoods site is located in the Washburn Ranger District of the Chequamegon National Forest. A member of the northern coniferous-deciduous biome, surveys from the mid-19th century indicate the region consisted of a mixed stand of red, white, and jack pines. After extensive timber harvesting, wildfires, and farming activity, the region turned into a fragmented mosaic of stands of various ages and composition. The intermediate hardwoods site is one of ten sites that collectively represent the successional stages of development in the predominant stand types of a physically homogeneous landscape. In 2001, northern hardwood stands of all ages occupied 45% of the region.

Abundant aftershock sequence of the 2015 Mw7.5 Hindu Kush intermediate-depth earthquake

NASA Astrophysics Data System (ADS)

Li, Chenyu; Peng, Zhigang; Yao, Dongdong; Guo, Hao; Zhan, Zhongwen; Zhang, Haijiang

2018-05-01

The 2015 Mw7.5 Hindu Kush earthquake occurred at a depth of 213 km beneath the Hindu Kush region of Afghanistan. While many early aftershocks were missing from the global earthquake catalogues, this sequence was recorded continuously by eight broad-band stations within 500 km. Here we use a waveform matching technique to systematically detect earthquakes around the main shock. More than 3000 events are detected within 35 d after the main shock, as compared with 42 listed in the Advanced National Seismic System catalogue (or 196 in the International Seismological Centre catalogue). The aftershock sequence generally follows the Omori's law with a decay constant p = 0.92. We also apply the recently developed double-pair double-difference technique to relocate all detected aftershocks. Most of them are located to the west of the hypocentre of the main shock, consistent with the westward propagation of the main-shock rupture. The aftershocks outline a nearly vertical southward dipping plane, which matches well with one of the nodal planes of the main shock. We conclude that the aftershock sequence of this intermediate-depth earthquake shares many similarities with those for shallow earthquakes and infer that there are some common mechanisms responsible for shallow and intermediate-depth earthquakes.

29 CFR 452.81 - Rights in intermediate body elections.

Code of Federal Regulations, 2010 CFR

2010-07-01

... LABOR-MANAGEMENT STANDARDS GENERAL STATEMENT CONCERNING THE ELECTION PROVISIONS OF THE LABOR-MANAGEMENT REPORTING AND DISCLOSURE ACT OF 1959 Campaign Safeguards § 452.81 Rights in intermediate body elections... 29 Labor 2 2010-07-01 2010-07-01 false Rights in intermediate body elections. 452.81 Section 452...

A new intermediate for the production of flexible stable polymers

NASA Technical Reports Server (NTRS)

Webster, J. A.

1973-01-01

Method of incorporating ether linkages into perfluoroalkylene segment of a dianydride intermediate yields intermediate that may be used in synthesis of flexible, stable polyimides for use as high-temperature, solvent-resistant sealants.

Exploring Granular Flows at Intermediate Velocities

NASA Astrophysics Data System (ADS)

Brodsky, E. E.; van der Elst, N.

2012-12-01

Geophysical and geomorphological flows often encompass a wide range of strain rates. Landslides accelerate from nearly static conditions to velocities in the range of meters/seconds. The rheology of granular flows for the end-members is moderately well-understood, but the constitutive low at intermediate velocities is largely unexplored. Here we present evidence that granular flows transition through a regime in which internally generated acoustic waves play a critical role in controlling rheology. In laboratory experiments on natural sand under shear in a commercial rheometer, we observe that the steady-state flows at intermediate velocities are compacted relative to the end members. In a confined volume, this compaction results in a decrease in stress on the boundaries. We establish the key role of the acoustic waves by measuring the noise generated by the shear flows with an accelerometer and then exciting the flow with similar amplitude noise under lower shear rate conditions. The observed compaction for a given amplitude noise is the same in both cases, regardless of whether the noise is generated internally by the grains colliding or artificially applied externally. The boundaries of this acoustically controlled regime can be successfully predicted through non-dimensional analysis balancing the overburden, acoustic pressure and granular inertial terms. In our laboratory experiments, this regime corresponds to 0.1 to 10 cm/s. The controlling role of acoustic waves in intermediate velocities is significant because: (1) Geological systems must pass through this regime on their route to instability. (2) Acoustic waves are much more efficiently generated by angular particles, likely to be found in natural samples, than by perfectly spherical particles, which are more tractable for laboratory and theoretical studies. Therefore, this regime is likely to be missed in many analog and computational approaches. (3) Different mineralogies and shapes result in different

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

PubMed

Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

2017-01-03

The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

PubMed

Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

2011-07-01

Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

Transcatheter vs Surgical Aortic Valve Replacement for Aortic Stenosis in Low-Intermediate Risk Patients: A Meta-analysis.

PubMed

Tam, Derrick Y; Vo, Thin Xuan; Wijeysundera, Harindra C; Ko, Dennis T; Rocha, Rodolfo Vigil; Friedrich, Jan; Fremes, Stephen E

2017-09-01

Transcatheter aortic valve replacement (TAVR) has emerged as the treatment of choice for patients with severe aortic stenosis at high surgical risk; the role of TAVR compared with surgical aortic valve replacement (SAVR) in the low-intermediate surgical risk population remains uncertain. Our primary objective was to determine differences in 30-day and late mortality in patients treated with TAVR compared with SAVR at low-intermediate risk (Society of Thoracic Surgeons Predicted Risk of Mortality < 10%). Medline and Embase were searched from 2010 to March 2017 for studies that compared TAVR with SAVR in the low-intermediate surgical risk population, restricted to randomized clinical trials and matched observational studies. Two investigators independently abstracted the data and a random effects meta-analysis was performed. Four randomized clinical trials (n = 4042) and 9 propensity score-matched observational studies (n = 4192) were included in the meta-analysis (n = 8234). There was no difference in 30-day mortality between TAVR and SAVR (3.2% vs 3.1%, pooled risk ratio: 1.02; 95% confidence interval, 0.80-1.30; P = 0.89; I 2  = 0%) or mortality at a median of 1.5-year follow-up (incident rate ratio: 1.01; 95% confidence interval, 0.90-1.15; P = 0.83; I 2  = 0%). There was a higher risk of pacemaker implantation and greater than trace aortic insufficiency in the TAVR group whereas the risk of early stroke, atrial fibrillation, acute kidney injury, cardiogenic shock, and major bleeding was higher in the SAVR group. Although there was no difference in 30-day and late mortality, the rate of complications differed between TAVR and SAVR in the low-intermediate surgical risk population. Copyright © 2017 Canadian Cardiovascular Society. Published by Elsevier Inc. All rights reserved.

29 CFR 452.81 - Rights in intermediate body elections.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 2 2011-07-01 2011-07-01 false Rights in intermediate body elections. 452.81 Section 452... REPORTING AND DISCLOSURE ACT OF 1959 Campaign Safeguards § 452.81 Rights in intermediate body elections. While the literal language in section 401(c) relating to distribution of campaign literature and to...

29 CFR 452.81 - Rights in intermediate body elections.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 29 Labor 2 2012-07-01 2012-07-01 false Rights in intermediate body elections. 452.81 Section 452... REPORTING AND DISCLOSURE ACT OF 1959 Campaign Safeguards § 452.81 Rights in intermediate body elections. While the literal language in section 401(c) relating to distribution of campaign literature and to...

29 CFR 452.81 - Rights in intermediate body elections.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 29 Labor 2 2014-07-01 2014-07-01 false Rights in intermediate body elections. 452.81 Section 452... REPORTING AND DISCLOSURE ACT OF 1959 Campaign Safeguards § 452.81 Rights in intermediate body elections. While the literal language in section 401(c) relating to distribution of campaign literature and to...

29 CFR 452.81 - Rights in intermediate body elections.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 29 Labor 2 2013-07-01 2013-07-01 false Rights in intermediate body elections. 452.81 Section 452... REPORTING AND DISCLOSURE ACT OF 1959 Campaign Safeguards § 452.81 Rights in intermediate body elections. While the literal language in section 401(c) relating to distribution of campaign literature and to...