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.

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

Development of novel two-photon absorbing chromophores

NASA Astrophysics Data System (ADS)

Rogers, Joy E.; Slagle, Jonathan E.; McLean, Daniel G.; Sutherland, Richard L.; Krein, Douglas M.; Cooper, Thomas M.; Brant, Mark; Heinrichs, James; Kannan, Ramamurthi; Tan, Loon-Seng; Urbas, Augustine M.; Fleitz, Paul A.

2006-08-01

There has been much interest in the development of two-photon absorbing materials and many efforts to understand the nonlinear absorption properties of these dyes but this area is still not well understood. A computational model has been developed in our lab to understand the nanosecond nonlinear absorption properties that incorporate all of the measured one-photon photophysical parameters of a class of materials called AFX. We have investigated the nonlinear and photophysical properties of the AFX chromophores including the two-photon absorption cross-section, the excited state cross-section, the intersystem crossing quantum yield, and the singlet and triplet excited state lifetimes using a variety of experimental techniques that include UV-visible, fluorescence and phosphorescence spectroscopy, time correlated single photon counting, ultrafast transient absorption, and nanosecond laser flash photolysis. The model accurately predicts the nanosecond nonlinear transmittance data using experimentally measured parameters. Much of the strong nonlinear absorption has been shown to be due to excited state absorption from both the singlet and triplet excited states. Based on this understanding of the nonlinear absorption and the importance of singlet and triplet excited states we have begun to develop new two-photon absorbing molecules within the AFX class as well as linked to other classes of nonlinear absorbing molecules. This opens up the possibilities of new materials with unique and interesting properties. Specifically we have been working on a new class of two-photon absorbing molecules linked to platinum poly-ynes. In the platinum poly-yne chromophores the photophysics are more complicated and we have just started to understand what drives both the linear and non-linear photophysical properties.

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

Transient spectra study on photo-dynamics of curcumin

NASA Astrophysics Data System (ADS)

Qian, Tingting; Wang, Mei; Wang, Jiao; Zhu, Rongrong; He, Xiaolie; Sun, Xiaoyu; Sun, Dongmei; Wang, Qingxiu; Wang, ShiLong

2016-09-01

A novel mechanism of DNA damage induced by photosensitized curcumin (Cur) was explored using laser flash photolysis, pulse radiolysis and gel electrophoresis. Cur neutral radical (Currad) was confirmed as an identical product in photo-sensitization of Cur by laser flash photolysis and pulse radiolysis. A series of reaction rate constants between Currad and nucleic acid bases/nucleotides were determined by pulse radiolysis. Gel electrophoresis was carried out to investigate damage induced by photosensitized Cur to biologically active DNA. The results indicate that the damage to DNA may be caused by Currad produced from the photosensitization of Cur.

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.

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

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

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.

Shedding light into the detailed excited-state relaxation pathways and reaction mechanisms of thionaphthol isomers.

PubMed

Riyad, Yasser M; Naumov, Sergej; Hermann, Ralf; Abel, Bernd

2011-02-10

Nanosecond laser flash photolysis employing transient detection of emission and absorption in combination with pulse radiolysis and quantum theory has been employed to shed light into the kinetics, quantum yields, and mechanisms of the deactivation of the first excited singlet state of 1- and 2-thionaphthols (NpSH(S(1))). In contrast to thiophenols (ArSH(S(1))), the results revealed that the decay of the first excited singlet state of 1- and 2-thionaphthols (NpSH(S(1))) is governed by radiationless internal conversion (Φ(IC) = 0.29-0.46; 0.016-0.190) and intersystem crossing (Φ(ISC) = 0.14-0.15; 0.4-0.6), respectively, with pronounced S-H photodissociation (Φ(D) = 0.40-0.55; 0.35-0.40). Fluorescence as a deactivation channel plays a minor role (Φ(F) = 0.001-0.010; 0.010-0.034). Quantum chemical calculations helped in understanding the formation of naphthylthiyl radicals and rationalizing the differences in the efficiency of intersystem crossing of the 1- and 2-thionaphthol systems.

Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

NASA Technical Reports Server (NTRS)

Watson, R. T.; Sander, S. P.; Yung, Y. L.

1979-01-01

The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

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.

An Experimental and Master Equation Study of the Kinetics of OH/OD + SO2: The Limiting High-Pressure Rate Coefficients.

PubMed

Blitz, Mark A; Salter, Robert J; Heard, Dwayne E; Seakins, Paul W

2017-05-04

The kinetics of the reaction OH/OD + SO 2 were studied using a laser flash photolysis/laser-induced fluorescence technique. Evidence for two-photon photolysis of SO 2 at 248 nm is presented and quantified, and which appears to have been evident to some extent in most previous photolysis studies, potentially leading to values for the rate coefficient k 1 that are too large. The kinetics of the reaction OH(v = 0) + SO 2 (T = 295 K, p = 25-300 torr) were measured under conditions where SO 2 photolysis was taken into account. These results, together with literature data, were modeled using a master equation analysis. This analysis highlighted problems with the literature data: the rate coefficients derived from flash photolysis data were generally too high and from the flow tube data too low. Our best estimate of the high-pressure limiting rate coefficient k 1 ∞ was obtained from selected data and gives a value of (7.8 ± 2.2) × 10 -13 cm 3 molecule -1 s -1 , which is lower than that recommended in the literature. A parametrized form of k 1 ([N 2 ],T) is provided. The OD(v = 0) + SO 2 (T = 295 K, p = 25-300 torr) data are reported for the first time, and master equation analysis reinforces our assignment of k 1 ∞ .

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.

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 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.

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.

Measured pulse width of sonoluminescence flashes in the form of resonance radiation

NASA Astrophysics Data System (ADS)

Giri, Asis; Arakeri, Vijay H.

1998-09-01

Recent studies have shown that the measured flash widths from single and multibubble sonoluminescence are in subnanosecond or even picosecond regime. Here, we provide conclusive evidence for the existence of nanosecond multibubble sonoluminescence. This has become possible by our ability to find a medium from which exclusive sodium D line resonance radiation as a form of sonoluminescence is possible. The measured flash width of this emission is found to be in the range of tens of nanoseconds and is sensitively dependent on experimental parameters. Our finding is important since all the earlier pulse width measurements have been limited to emission with the physical source or species responsible for observed optical radiation not being clearly identified. We propose that the presently observed resonance radiation is from ``soft'' bubble collapse as analyzed by V. Kamath et al. [J. Acoust. Soc. Am. 94, 248 (1993)].

Time-resolved spectroscopic studies of photosynthetic reaction centers and tetrapyrrole chromophores for biomedical and solar-energy applications

NASA Astrophysics Data System (ADS)

Kee, Hooi Ling

2008-10-01

The photophysical properties of diverse tetrapyrrole chromophores as well as energy and electron transfer processes in tetrapyrrole dyads are investigated using static and time-resolved (femtoseconds to seconds) absorption and fluorescence spectroscopy. The goal of these studies is to elucidate the molecular design principals necessary to construct chromophores with the specific and tunable properties that will enhance applications in optical molecular imaging, photodynamic therapy, and solar-energy conversion. The kinetic properties of the transient intermediate P+H B- involving the bacteriopheophytin molecule HB on the normally inactive (B) cofactor branch of the bacterial photosynthetic reaction center are examined in Rhodobacter capsulatus mutants. Using nanosecond flash photolysis and F(L181)Y/Y(M208)F/L(M212)H mutant, the decay pathways and yields of P+HB- were measured, giving an overall yield of 13% for B-side charge separation P* → P+HB- → P+ QB- in this mutant. The goal of these studies is to understand the fundamental differences in the rates, yields, and mechanisms of charge separation and charge recombination along the two parallel electron-transport chains in the bacterial reaction center.

Photoinduced reduction of the medial FeS center in the hydrogenase small subunit HupS from Nostoc punctiforme.

PubMed

Raleiras, Patrícia; Hammarström, Leif; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

2015-07-01

The small subunit from the NiFe uptake hydrogenase, HupSL, in the cyanobacterium Nostoc punctiforme ATCC 29133, has been isolated in the absence of the large subunit (P. Raleiras, P. Kellers, P. Lindblad, S. Styring, A. Magnuson, J. Biol. Chem. 288 (2013) 18,345-18,352). Here, we have used flash photolysis to reduce the iron-sulfur clusters in the isolated small subunit, HupS. We used ascorbate as electron donor to the photogenerated excited state of Ru(II)-trisbipyridine (Ru(bpy)3), to generate Ru(I)(bpy)3 as reducing agent. Our results show that the isolated small subunit can be reduced by the Ru(I)(bpy)3 generated through flash photolysis. Copyright © 2015 Elsevier Inc. All rights reserved.

A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

NASA Technical Reports Server (NTRS)

Bosco, S. R.

1982-01-01

The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

Photodissociation dynamics of nitromethane at 226 and 271 nm at both nanosecond and femtosecond time scales.

PubMed

Guo, Y Q; Bhattacharya, A; Bernstein, E R

2009-01-08

Photodissociation of nitromethane has been investigated for decades both theoretically and experimentally; however, as a whole picture, the dissociation dynamics for nitromethane are still not clear, although many different mechanisms have been proposed. To make a complete interpretation of these different mechanisms, photolysis of nitromethane at 226 and 271 nm under both collisional and collisionless conditions is investigated at nanosecond and femtosecond time scales. These two laser wavelengths correspond to the pi* <-- pi and pi* <-- n excitations of nitromethane, respectively. In nanosecond 226 nm (pi* <-- pi) photolysis experiments, CH(3) and NO radicals are observed as major products employing resonance enhanced multiphoton ionization techniques and time-of-flight mass spectrometry. Additionally, OH and CH(3)O radicals are weakly observed as dissociation products employing laser induced fluorescence spectroscopy; the CH(3)O product is only observed under collisional conditions. In femtosecond 226 nm experiments, CH(3), NO(2), and NO products are observed. These results confirm that rupture of C-N bond should be the main primary process for the photolysis of nitromethane after the pi* <-- pi excitation at 226 nm, and the NO(2) molecule should be the precursor of the observed NO product. Formation of the CH(3)O radical after the recombination of CH(3) and NO(2) species under collisional conditions rules out a nitro-nitrite isomerization mechanism for the generation of CH(3)O and NO from pi pi* CH(3)NO(2). The OH radical formation for pi pi* CH(3)NO(2) should be a minor dissociation channel because of the weak OH signal in both nanosecond and femtosecond (nonobservable) experiments. Single color femtosecond pump-probe experiments at 226 nm are also employed to monitor the dynamics of the dissociation of nitromethane after the pi* <-- pi excitation. Because of the ultrafast dynamics of product formation at 226 nm, the pump-probe transients for the three dissociation products are measured as an autocorrelation of the laser pulse, indicating the dissociation of nitromethane in the pi pi* excited state is faster than the laser pulse duration (180 fs). In nanosecond 271 nm (pi* <-- n) photolysis experiments, pump-probe experiments are performed to detect potential dissociation products, such as CH(3), NO(2), CH(3)O, and OH; however, none of them is observed. In femtosecond 271 nm laser experiments, the nitromethane parent ion is observed with major intensity, together with CH(3), NO(2), and NO fragment ions with only minor intensities. Pump-probe transients for both nitromethane parent and fragment ions at 271 nm excitation and 406.5 nm ionization display a fast exponential decay with a constant time of 36 fs, which we suggest to be the lifetime of the excited n pi* state of nitromethane. Combined with the 271 nm nanosecond pump-probe experiments, in which none of the CH(3), NO(2), CH(3)O, or OH fragment is observed, we suggest that all the fragment ions generated in 271 nm femtosecond laser experiments are derived from the parent ion, and dissociation of nitromethane from the n pi* excited electronic state does not occur in a supersonic molecular beam under collisionless conditions.

Molecular Basis of the Bohr Effect in Arthropod Hemocyanin

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

Hirota, S.; Kawahara, T; Beltramini, M

2008-01-01

Flash photolysis and K-edge x-ray absorption spectroscopy (XAS) were used to investigate the functional and structural effects of pH on the oxygen affinity of three homologous arthropod hemocyanins (Hcs). Flash photolysis measurements showed that the well-characterized pH dependence of oxygen affinity (Bohr effect) is attributable to changes in the oxygen binding rate constant, kon, rather than changes in koff. In parallel, coordination geometry of copper in Hc was evaluated as a function of pH by XAS. It was found that the geometry of copper in the oxygenated protein is unchanged at all pH values investigated, while significant changes were observedmore » for the deoxygenated protein as a function of pH. The interpretation of these changes was based on previously described correlations between spectral lineshape and coordination geometry obtained for model compounds of known structure A pH-dependent change in the geometry of cuprous copper in the active site of deoxyHc, from pseudotetrahedral toward trigonal was assigned from the observed intensity dependence of the 1s ? 4pz transition in x-ray absorption near edge structure (XANES) spectra. The structural alteration correlated well with increase in oxygen affinity at alkaline pH determined in flash photolysis experiments. These results suggest that the oxygen binding rate in deoxyHc depends on the coordination geometry of Cu(I) and suggest a structural origin for the Bohr effect in arthropod Hcs.« less

Statistical Evolution of the Lightning Flash

NASA Astrophysics Data System (ADS)

Zoghzoghy, F. G.; Cohen, M.; Said, R.; Inan, U. S.

2012-12-01

Natural lightning is one of the most fascinating and powerful electrical processes on Earth. To date, the physics behind this natural phenomenon are not fully understood, due primarily to the difficulty of obtaining measurements inside thunderstorms and to the wide range of timescales involved (from nanoseconds to seconds). Our aim is to use accurate lightning geo-location data from the National Lightning Detection Network (NLDN) to study statistical patterns in lightning, taking advantage of the fact that millions of lightning flashes occur around the globe every day. We present two sets of results, one involving the patterns of flashes in a storm, and a second involving the patterns of strokes in a flash. These patterns can provide a surrogate measure of the timescales and the spatial extents of the underlying physical processes. First, we study the timescales of charge buildup inside thunderstorms. We find that, following a lightning flash, the probability of another neighboring flash decreases and takes tens of seconds to recover. We find that this suppression effect is a function of flash type, stroke peak current, cloud-to-ground (CG) stroke multiplicity, and other lightning and geographical parameters. We find that the probabilities of subsequent flashes are more suppressed following oceanic lightning, or following flashes with higher peak currents and/or higher multiplicities (for CG flashes). Second, we use NLDN data to study the evolution of the strokes within a CG flash. A CG flash typically includes multiple return strokes, which can occur in the same channel or in multiple channels within a few kilometers. We cluster NLDN stroke data into flashes and produce the probability density function of subsequent strokes as a function of distance and time-delays relative to the previous stroke. Using this technique, we investigate processes which occur during the CG lightning flash with nanosecond to millisecond timescales. For instance, our results suggest that subsequent strokes that occur in a newly formed channel follow a pattern that propagates at a speed of ~200 km/s. We present our statistical techniques and discuss more thoroughly our work and results.

Pressure Studies of Protein Dynamics

DTIC Science & Technology

1989-02-26

infrared flash photolysis system with the monitoring light produced by a Spectra-Physics/ Laser Analytics tunable- diode laser and detected by a liquid...refrigerator. Time range extends from about 100 ms to 100 s. The diode laser current is modulated at 10 kHz and the signal is amplified with a PAR 5101...Photolysis is obtained with a Phase-R D 121OOC dye laser using rhodamine 6G (pulse 4 width 500 ns, 0.3 J). Kinetic spectra are obtained from about 10

Contraction of small mesenteric arteries induced by micromolar concentrations of ATP released from caged ATP.

PubMed

Sjöblom-Widfeldt, N; Arner, A; Nilsson, H

1993-01-01

The concentration dependence of ATP-induced contractions in isolated resistance arteries was estimated using photolysis of caged ATP. Rat mesenteric vessels were isolated and mounted for force registration in a small chamber allowing illumination from a xenon-flash lamp. Photolysis of 100 microM caged ATP, which released about 20 microM ATP within a few milliseconds in the vessel, induced a transient contraction with an amplitude approximately 40-50% of the response induced by 10 microM noradrenaline. The responses could neither be induced by the light flash as such nor by caged ATP alone nor by photolysis of caged phosphate. The amplitude of the contractions was dependent on the concentration of caged ATP, and the effective concentration for ATP was estimated to be in the range of 1-10 microM. In contrast, when ATP was introduced by diffusion, about a 100-fold higher concentration was required. Thus photolytic release of ATP minimizes metabolism before its action on receptors and reveals action of ATP in a concentration range consistent with a role of ATP as a transmitter in nervous regulation of the tone of resistance vessels.

Photochemistry of bromoacetylene - Formation of HBr and quenching of excited Br/4 2P 0 1/2/

NASA Technical Reports Server (NTRS)

Laufer, A. H.

1979-01-01

The photolysis of bromacetylene is examined by means of vacuum ultraviolet flash photolysis-kinetic spectroscopy, with attention given to the production of Br atoms in the 2P 0 3/2 and 2P 0 1/2 states, the production of HBr, and UV absorption attributable to the ethynyl radical. Although Br(2P 0 1/2) and Br(2P 0 3/2) were both directly observed at the shortest delay time after the flash, strongly indicating the presence of the ethynyl radical, transient absorption by C2H was not detected in the range 125 to 180 nm. Quenching rate constants for the decay of the 2P 0 1/2 state of Br, which is observed to form concurrently with the ground state, are derived for quenching by He, CH2Br, CF4, and D2 from the pseudo-first-order decay rates. HBr was observed as a secondary photolysis product, and a model of its formation by the exothermic reaction of ground-state atoms with C2HBR, coupled with the secondary production of Br atoms, is found to agree well with the experiment.

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.

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.

High-resolution discrete absorption spectrum of α-methallyl free radical in the vapor phase

NASA Astrophysics Data System (ADS)

Bayrakçeken, Fuat; Telatar, Ziya; Arı, Fikret; Tunçyürek, Lale; Karaaslan, İpek; Yaman, Ali

2006-09-01

The α-methallyl free radical is formed in the flash photolysis of 3-methylbut-1-ene, and cis-pent-2-ene in the vapor phase, and then subsequent reactions have been investigated by kinetic spectroscopy and gas-liquid chromatography. The photolysis flash was of short duration and it was possible to follow the kinetics of the radicals' decay, which occurred predominantly by bimolecular recombination. The measured rate constant for the α-methallyl recombination was (3.5 ± 0.3) × 10 10 mol -1 l s -1 at 295 ± 2 K. The absolute extinction coefficients of the α-methallyl radical are calculated from the optical densities of the absorption bands. Detailed analysis of related absorption bands and lifetime measurements in the original α-methallyl high-resolution discrete absorption spectrum image were also carried out by image processing techniques.

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3. [in troposphere

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Anderson, P. C.; Klais, O.

1979-01-01

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations.

PubMed

Gould, Ian R; Wosinska, Zofia M; Farid, Samir

2006-01-01

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

Unraveling Charge Carriers Generation, Diffusion, and Recombination in Formamidinium Lead Triiodide Perovskite Polycrystalline Thin Film.

PubMed

Piatkowski, Piotr; Cohen, Boiko; Ponseca, Carlito S; Salado, Manuel; Kazim, Samrana; Ahmad, Shahzada; Sundström, Villy; Douhal, Abderrazzak

2016-01-07

We report on studies of the formamidinium lead triiodide (FAPbI3) perovskite film using time-resolved terahertz (THz) spectroscopy (TRTS) and flash photolysis to explore charge carriers generation, migration, and recombination. The TRTS results show that upon femtosecond excitation above the absorption edge, the initial high photoconductivity (∼75 cm(2) V(-1) s(-1)) remains constant at least up to 8 ns, which corresponds to a diffusion length of 25 μm. Pumping below the absorption edge results in a mobility of 40 cm(2) V(-1) s(-1) suggesting lower mobility of charge carriers located at the bottom of the conduction band or shallow sub-bandgap states. Furthermore, analysis of the THz kinetics reveals rising components of <1 and 20 ps, reflecting dissociation of excitons having different binding energies. Flash photolysis experiments indicate that trapped charge carriers persist for milliseconds.

Nicotinic acetylcholine receptor probed with a photoactivatable agonist: improved labeling specificity by addition of CeIV/glutathione. Extension to laser flash photolabeling.

PubMed

Grutter, T; Goeldner, M; Kotzyba-Hibert, F

1999-06-08

The molecular structure of Torpedo marmorata acetylcholine binding sites has been investigated previously by photoaffinity labeling. However, besides the nicotine molecule [Middleton et al. (1991) Biochemistry 30, 6987-6997], all other photosensitive probes used for this purpose interacted only with closed receptor states. In the perspective of mapping the functional activated state, we synthesized and developed a new photoactivatable agonist of nAChR capable of alkylation of the acetylcholine (ACh) binding sites, as reported previously [Kotzyba-Hibert et al. (1997) Bioconjugate Chem. 8, 472-480]. Here, we describe the setup of experimental conditions that were made in order to optimize the photolabeling reaction and in particular its specificity. We found that subsequent addition of the oxidant ceric ion (CeIV) and reduced glutathione before the photolabeling step lowered considerably nonspecific labeling (over 90% protection with d-tubocurarine) without affecting the binding properties of the ACh binding sites. As a consequence, irradiation at 360 nm for 20 min in these new conditions gave satisfactory coupling yields (7.5%). A general mechanism was proposed to explain the successive reactions occurring and their drastic effect on the specificity of the labeling reaction. Last, these incubation conditions can be extended to nanosecond pulsed laser photolysis leading to the same specific photoincorporation as for usual irradiations (8.5% coupling yield of ACh binding sites, 77% protection with carbamylcholine). Laser flash photocoupling of a diazocyclohexadienoyl probe on nAChR was achieved for the first time. Taken together, these data indicate that future investigation of the molecular dynamics of allosteric transitions occurring at the activated ACh binding sites should be possible.

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

Inbar, S.; Linschitz, H.; Cohen, S.G.

Nanosecond flash photolysis, steady irradiation, and deuterium substitution studies have been carried out on solutions of benzophenone with added reductants. Quantum yields (phi/sub ketyl/) for reduction in benzene of benzophenone triplet to ketyl radical, based on phi = 2 for benzhydrol (I), were approx. 1 for cyclohexane (II), tert-butylamine (III), 2-aminobutane (IV), cyclohexylamine (V), di-n-propylamine (VI), and triethylamine (VII), approx. 0.7 for 1,4-diazabicyclo(2.2.2)octane (VIII), and approx. 0 for tert-butyl alcohol (IX). Thus, quenching, without radical formation by H abstraction from N and/or ..cap alpha..-C, does not occur with common aliphatic amines but does with Dabco (VIII). The latter quenching ismore » markedly increased by small additions of acetonitrile; the flash spectrum from this compound indicates formation of a triplet amine CT complex or radical ion pair. Triplet-reductant interaction rate constants, k/sur ir/, are high for the amines (approx. 10/sup 8/-10/sup 9/ M/sup -1/ s/sup -1/) but also show significant deuterium kinetic isotope effects: 1.9 with III-N-d/sub 2/; 1.4 with IV-N-d/sub 2/; 1.2-1.3 with IV-..cap alpha..-C-d. It is proposed that k/sub ir/ measures H atom abstraction, favored in the transition state by an initial charge-transfer interaction. Overall steady irradiation quantum yields of reduction by amines, phi/sub Red/, are much lower than phi/sub ketyl/. This is attributed to disproportionationreactions of ketyl and alkylaminyl radicals for primary and secondary amines, and, possibly, aminoalkyl radicals for tertiary amines. In the case of tert-butylamine, the rate constant for disproportionation is obtained from the decay kinetics of ketyl radical and leads to phi/sub Red/ in agreement with that directly measured.« less

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.

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.

Fast repetition rate (FRR) flasher

DOEpatents

Kolber, Zbigniew; Falkowski, Paul

1997-02-11

A fast repetition rate (FRR) flasher suitable for high flash photolysis including kinetic chemical and biological analysis. The flasher includes a power supply, a discharge capacitor operably connected to be charged by the power supply, and a flash lamp for producing a series of flashes in response to discharge of the discharge capacitor. A triggering circuit operably connected to the flash lamp initially ionizes the flash lamp. A current switch is operably connected between the flash lamp and the discharge capacitor. The current switch has at least one insulated gate bipolar transistor for switching current that is operable to initiate a controllable discharge of the discharge capacitor through the flash lamp. Control means connected to the current switch for controlling the rate of discharge of the discharge capacitor thereby to effectively keep the flash lamp in an ionized state between Successive discharges of the discharge capacitor. Advantageously, the control means is operable to discharge the discharge capacitor at a rate greater than 10,000 Hz and even up to a rate greater than about 250,000 Hz.

Synthesis and characterization of near-infrared absorbing water soluble squaraines and study of their photodynamic effects in DLA live cells.

PubMed

Shafeekh, Kulathinte M; Soumya, Mohanannair S; Rahim, Moochikkadavath A; Abraham, Annie; Das, Suresh

2014-01-01

Here, we report the synthesis, photophysical properties and photodynamic effects in DLA live cells of three water soluble squaraine dyes, viz. bisbenzothiazolium squaraine dyes SQMI and SQDI with iodine in one and both benzothiazolium units, respectively, and an unsymmetrical squaraine dye ASQI containing iodinated benzothiazolium and aniline substituents. The diiodinated SQDI showed an anomalous trend in both fluorescence and triplet quantum yields over the monoiodinated SQMI, with SQDI showing higher fluorescence and lower triplet quantum yields compared to SQMI. Nanosecond laser flash photolysis of SQDI and SQMI indicated the formation of triplet excited states with quantum yield of 0.19 and 0.26, respectively. On photoirradiation, both the SQDI and SQMI generate singlet oxygen and it was observed that both dyes undergoing oxidation reactions with the singlet oxygen generated. ASQI which exhibited a lower triplet quantum yield of 0.06 was, however, stable and did not react with the singlet oxygen generated. In vitro cytotoxicity studies of these dyes in DLA live cells were performed using Trypan blue dye exclusion method and it reflect an order of cytotoxicity of SQDI>SQMI>ASQI. Intracellular generation of the ROS was confirmed by dichlorofluorescein assay after the in vitro PDT. © 2014 The American Society of Photobiology.

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

Molecular oxygen migration through the xenon docking sites of human hemoglobin in the R-state.

PubMed

Lepeshkevich, Sergei V; Gilevich, Syargey N; Parkhats, Marina V; Dzhagarov, Boris M

2016-09-01

A nanosecond laser flash-photolysis technique was used to study bimolecular and geminate molecular oxygen (O2) rebinding to tetrameric human hemoglobin and its isolated α and β chains in buffer solutions equilibrated with 1atm of air and up to 25atm of xenon. Xenon binding to the isolated α chains and to the α subunits within tetrameric hemoglobin was found to cause a decrease in the efficiency of O2 escape by a factor of ~1.30 and 3.3, respectively. A kinetic model for O2 dissociation, rebinding, and migration through two alternative pathways in the hemoglobin subunits was introduced and discussed. It was shown that, in the isolated α chains and α subunits within tetrameric hemoglobin, nearly one- and two-third escaping molecules of O2 leave the protein via xenon docking sites, respectively. The present experimental data support the idea that O2 molecule escapes from the β subunits mainly through the His(E7) gate, and show unambiguously that, in the α subunits, in addition to the direct E7 channel, there is at least one alternative escape route leading to the exterior via the xenon docking sites. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy

PubMed Central

Zhou, Shengqiang; Liu, Fang; Prucnal, S.; Gao, Kun; Khalid, M.; Baehtz, C.; Posselt, M.; Skorupa, W.; Helm, M.

2015-01-01

Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability. PMID:25660096

4-Pyridylnitrene and 2-pyrazinylcarbene

PubMed Central

Reisinger, Ales; Kvaskoff, David

2013-01-01

Summary Both flash vacuum thermolysis (FVT) and matrix photolysis generate 2-diazomethylpyrazine (22) from 1,2,3-triazolo[1,5-a]pyrazine (24). FVT of 4-azidopyridine (18) as well as of 24 or 2-(5-tetrazolyl)pyrazine (23) affords the products expected from the nitrene, i.e., 4,4’-azopyridine and 2- and 3-cyanopyrroles. Matrix photolyses of both 18 and 24 result in ring expansion of 4-pyridylnitrene/2-pyrazinylcarbene to 1,5-diazacyclohepta-1,2,4,6-tetraene (20). Further photolysis causes ring opening to the ketenimine 27. PMID:23766787

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.

Self-initiation of UV photopolymerization reactions using tetrahalogenated bisphenol A (meth)acrylates.

PubMed

Pelras, Théophile; Knolle, Wolfgang; Naumov, Sergej; Heymann, Katja; Daikos, Olesya; Scherzer, Tom

2017-05-17

The potential of tetrachlorinated and tetrabrominated bisphenol A diacrylates and dimethacrylates for self-initiation of a radical photopolymerization was investigated. The kinetics of the photopolymerization of an acrylic model varnish containing halogenated monomers was studied by real-time FTIR spectroscopy, whereas the formation of reactive species and secondary products was elucidated by laser flash photolysis and product analysis by GC-MS after steady-state photolysis. The interpretation of the experimental data and the analysis of possible reaction pathways were assisted by quantum chemical calculations. It was shown that all halogenated monomers lead to a significant acceleration of the photopolymerization kinetics at a minimum concentration of 5 wt%. Steady-state and laser flash photolysis measurements as well as quantum chemical calculations showed that brominated and chlorinated samples do not follow the same pathway to generate radical species. Whereas chlorinated (meth)acrylates may cleave only at the C-O bonds of the carboxyl groups resulting in acrolein and oxyl radicals for initiation, brominated monomers may cleave either at the C-O bonds or at the C-Br bonds delivering aryl and bromine radicals. The quantum yields for the photolysis of the halogenated monomers were found to be in the order of 0.1 for acrylates and 0.2 for methacrylates (with an estimated error of 25%), independently of the attached Br and Cl halogens. Finally, the trihalogenated bisphenol A di(meth)acrylate radicals and the acrolein radicals were found to show the highest efficiencies for the reaction with another acrylic double bond leading to the formation of a polymer network.

Magnetic field effect corroborated with docking study to explore photoinduced electron transfer in drug-protein interaction.

PubMed

Chakraborty, Brotati; Roy, Atanu Singha; Dasgupta, Swagata; Basu, Samita

2010-12-30

Conventional spectroscopic tools such as absorption, fluorescence, and circular dichroism spectroscopy used in the study of photoinduced drug-protein interactions can yield useful information about ground-state and excited-state phenomena. However, photoinduced electron transfer (PET) may be a possible phenomenon in the drug-protein interaction, which may go unnoticed if only conventional spectroscopic observations are taken into account. Laser flash photolysis coupled with an external magnetic field can be utilized to confirm the occurrence of PET and authenticate the spin states of the radicals/radical ions formed. In the study of interaction of the model protein human serum albumin (HSA) with acridine derivatives, acridine yellow (AY) and proflavin (PF(+)), conventional spectroscopic tools along with docking study have been used to decipher the binding mechanism, and laser flash photolysis technique with an associated magnetic field (MF) has been used to explore PET. The results of fluorescence study indicate that fluorescence resonance energy transfer takes place from the protein to the acridine-based drugs. Docking study unveils the crucial role of Ser 232 residue of HSA in explaining the differential behavior of the two drugs towards the model protein. Laser flash photolysis experiments help to identify the radicals/radical ions formed in the due course of PET (PF(•), AY(•-), TrpH(•+), Trp(•)), and the application of an external MF has been used to characterize their initial spin-state. Owing to its distance dependence, MF effect gives an idea about the proximity of the radicals/radical ions during interaction in the system and also helps to elucidate the reaction mechanisms. A prominent MF effect is observed in homogeneous buffer medium owing to the pseudoconfinement of the radicals/radical ions provided by the complex structure of the protein.

Fast repetition rate (FRR) flasher

DOEpatents

Kolber, Z.; Falkowski, P.

1997-02-11

A fast repetition rate (FRR) flasher is described suitable for high flash photolysis including kinetic chemical and biological analysis. The flasher includes a power supply, a discharge capacitor operably connected to be charged by the power supply, and a flash lamp for producing a series of flashes in response to discharge of the discharge capacitor. A triggering circuit operably connected to the flash lamp initially ionizes the flash lamp. A current switch is operably connected between the flash lamp and the discharge capacitor. The current switch has at least one insulated gate bipolar transistor for switching current that is operable to initiate a controllable discharge of the discharge capacitor through the flash lamp. Control means connected to the current switch for controlling the rate of discharge of the discharge capacitor thereby to effectively keep the flash lamp in an ionized state between successive discharges of the discharge capacitor. Advantageously, the control means is operable to discharge the discharge capacitor at a rate greater than 10,000 Hz and even up to a rate greater than about 250,000 Hz. 14 figs.

Radiation Chemistry in Organized Assemblies.

ERIC Educational Resources Information Center

Thomas, J. K.; Chen, T. S.

1981-01-01

Expands the basic concepts regarding the radiation chemistry of simple aqueous systems to more complex, but well defined, organized assemblies. Discusses the differences in behavior in comparison to simple systems. Reviews these techniques: pulse radiolysis, laser flash, photolysis, and steady state irradiation by gamma rays or light. (CS)

Laser flash photolysis and magnetic-field-effect studies on interaction of thymine and thymidine with menadione: role of sugar in controlling reaction pattern

NASA Astrophysics Data System (ADS)

Bose, Adity; Dey, Debarati; Basu, Samita

2008-04-01

The magnetic field effect (MFE) in conjunction with laser flash photolysis has been used for the study of the interaction of one of the small drug like quinone molecules, 2-methyl, 1,4-naphthoquinone, commonly known as menadione (MQ), with one of the DNA bases, thymine (THN), and its corresponding nucleoside, thymidine (THDN), in acetonitrile (ACN) and sodium dodecylsulfate (SDS) micelles. It has been observed that THN undergoes electron transfer (ET) and hydrogen (H) abstraction with MQ, while THDN undergoes only H abstraction in both the media. However, our earlier studies showed that a purine base, adenine (ADN), and its nucleoside, 2'-deoxyadenosine (ADS), undergo ET in ACN and H abstraction in SDS. Here we have attempted to explain the differences in the reactions of these DNA bases with MQ. We also reveal the crucial role of a sugar unit in altering the behavior of purine and pyrimidine bases with respect to ET and H abstraction.

Synthesis and characterization of TiO₂ and TiO₂/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

PubMed

Ramos, Dayana Doffinger; Bezerra, Paula C S; Quina, Frank H; Dantas, Renato F; Casagrande, Gleison A; Oliveira, Silvio C; Oliveira, Márcio R S; Oliveira, Lincoln C S; Ferreira, Valdir S; Oliveira, Samuel L; Machulek, Amilcar

2015-01-01

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

Thermal ring closure in Mo(CO){sub 5}L (L = bpy, dmbpy, dpbpy) transients generated by pulsed laser flash photolysis. Mechanistic information from high-pressure effects

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

Reddy, K.B.; Hoffmann, R.; Konya, G.

1992-06-01

The kinetics of the ring-closure reactions of Mo(CO){sub 5}L, produced during the laser flash photolysis of Mo(CO){sub 6} and L where L = 2,2{prime}-bipyridine (bpy), 4,4{prime}-dimethyl-2,2{prime}-bipyridine (dpbpy) and 4,4{prime}-dephenyl-2,2{prime}-bipyridine (dpbpy) were studied as a function of temperature and pressure. The values of the activation parameters and pressure. The values of the activation parameters {Delta}S and {Delta}V are small and negative for L = bpy and dmbpy supporting an associative interchange mechanism (I{sub a}) for CO extrusion. For L = dpbpy, {Delta}V is small and positive in line with a dissociative interchange mechanism (I{sub d}). The results demonstrate a changeover inmore » mechanism from I{sub a} to I{sub d} with increasing steric hindrance on the bidentate ligand L. 36 refs., 1 fig., 2 tabs.« less

LOFAR Lightning Imaging: Mapping Lightning With Nanosecond Precision

NASA Astrophysics Data System (ADS)

Hare, B. M.; Scholten, O.; Bonardi, A.; Buitink, S.; Corstanje, A.; Ebert, U.; Falcke, H.; Hörandel, J. R.; Leijnse, H.; Mitra, P.; Mulrey, K.; Nelles, A.; Rachen, J. P.; Rossetto, L.; Rutjes, C.; Schellart, P.; Thoudam, S.; Trinh, T. N. G.; ter Veen, S.; Winchen, T.

2018-03-01

Lightning mapping technology has proven instrumental in understanding lightning. In this work we present a pipeline that can use lightning observed by the LOw-Frequency ARray (LOFAR) radio telescope to construct a 3-D map of the flash. We show that LOFAR has unparalleled precision, on the order of meters, even for lightning flashes that are over 20 km outside the area enclosed by LOFAR antennas (˜3,200 km2), and can potentially locate over 10,000 sources per lightning flash. We also show that LOFAR is the first lightning mapping system that is sensitive to the spatial structure of the electrical current during individual lightning leader steps.

Flash Photolysis and Its Applications: Meeting in Honour of Sir George Porter, P.R.S. held in London, England on 14-16 July 1986,

DTIC Science & Technology

1986-07-16

present the design and results from the current flash spectroscopic system at the R.I. A hybrid mode-locked, cavity dumped dye laser is used to seed a...date require a HE sum of at least three exponentials to achieve an acceptable fit. Lettuce chloroplasts exhibit decay times of 100 psec., 500-600 psec...other lettuce preparations. A PS1 preparation from the cyanobacterium Chlorogloea Fritschii, which has been thoroughly characterised previously [2

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.

Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

PubMed

Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

2014-03-11

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

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.

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.

Research Studies on Radiative Collision Lasers

DTIC Science & Technology

1980-06-01

34Branching Ratios for TlBr Photodissocia- tion with 2660 X Radiation." Abstract: Selective molecular photodi:ssociation as a pumping mechanism to invert...following the flash photolysis of CF I. In the present work we examine the selective 3 photodissociation of TlBr into the Tl(6p 2 P3 / 2 ) metastable state

Kinetics of activation of a Ca2+-dependent K+ current induced by flash photolysis of caged carbachol in isolated guinea-pig outer hair cells.

PubMed

Chan, E; Evans, M G

1998-09-18

It has been shown that the application of acetylcholine activates a Ca2+-dependent K+ current in outer hair cells, and the resulting hyperpolarization is thought to be an important part of the inhibition mediated by cholinergic efferent nerve fibres to the cochlea. In order to study the kinetics of the current, flash photolysis has been used to apply a cholinergic agonist, carbachol, rapidly to isolated outer hair cells. A delay in the onset of the outward potassium current following photorelease of carbachol was consistently observed, and the activation phase of the response could be described by a sigmoidal-like function with a mean delay of 59 ms and time constant of 71 ms. The sum of these values lies within the time scale reported for the onset of the inhibition following electrical stimulation of the efferent nerves. Although a distinct current attributable to an acetylcholine receptor was not visible in these experiments, indirect evidence for a carbachol-induced influx of Ca2+ was obtained.

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.

Rate constant for the fraction of atomic chlorine with formaldehyde from 200 to 500K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.

1978-01-01

A flash photolysis - resonance fluorescence technique was used to measure rate constant. The results were independent of substantial variations in H2CO, total pressure (Ar), and flash intensity (i.e., initial Cl). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being K = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

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.

Evidence for the load-dependent mechanical efficiency of individual myosin heads in skeletal muscle fibers activated by laser flash photolysis of caged calcium in the presence of a limited amount of ATP.

PubMed

Sugi, H; Iwamoto, H; Akimoto, T; Ushitani, H

1998-03-03

Although a contracting muscle regulates its energy output depending on the load imposed on it ("Fenn effect"), the mechanism underlying the load-dependent energy output remains obscure. To explore the possibility that the mechanical efficiency, with which chemical energy derived from ATP hydrolysis is converted into mechanical work, of individual myosin heads changes in a load-dependent manner, we examined the auxotonic shortening of glycerinated rabbit psoas muscle fibers, containing ATP molecules almost equal in number to the myosin heads, after laser-flash photolysis of caged calcium. Immediately before laser-flash activation, almost all of the myosin heads in the fiber are in the state M.ADP.Pi, and can undergo only one ATP hydrolysis cycle after activation. When the fibers were activated to shorten under various auxotonic loads, the length, force, and power output changes were found to be scaled according to the auxotonic load. Both the power and energy outputs were maximal under a moderate auxotonic load. The amount of M.ADP.Pi utilized at a time after activation was estimated from the amount of isometric force developed after interruption of fiber shortening. This amount was minimal in the isometric condition and increased nearly in proportion to the distance of fiber shortening. These results are taken as evidence that the efficiency of chemomechanical energy conversion in individual myosin heads changes in a load-dependent manner.

Load-dependent mechanical efficiency of individual myosin heads in skeletal muscle fibers activated by laser flash photolysis of caged calcium in the presence of a limited amount of ATP.

PubMed

Sugi, H; Iwamoto, H; Akimoto, T; Ushitani, H

1998-01-01

Although a contracting muscle regulates its energy output depending on the load imposed on it ("Fenn effect"), the mechanism underlying the load-dependent energy output remains obscure. To explore the possibility that the mechanical efficiency, with which chemical energy derived from ATP hydrolysis is converted into mechanical work, of individual myosin heads changes in a load-dependent manner, we examined the auxotonic shortening of glycerinated rabbit psoas muscle fibers, containing ATP molecules almost equal in number to the myosin heads, following laser flash photolysis of caged calcium. Immediately before laser flash activation, almost all of the myosin heads in the fiber are in the state, M.ADP.Pi, and can undergo only one ATP hydrolysis cycle after activation. When the fibers were activated to shorten under various auxotonic loads, the length, force and power output changes were found to be scaled according to the auxotonic load. Both the power and energy outputs were maximal under a moderate auxotonic load. The amount of M.ADP.Pi utilized at a time after activation was estimated from the amount of isometric force developed after interruption of fiber shortening. This amount was minimal in the isometric condition, and increased nearly in proportion to the distance of fiber shortening. These results are taken as evidence that the efficiency of chemo-mechanical energy conversion in individual myosin heads changes in a load-dependent manner.

Absolute rate of the reaction of C l(2P) with methane from 200-500 K

NASA Technical Reports Server (NTRS)

Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

1976-01-01

Rate constants for the reaction of atomic chlorine with methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

Transient-Absorption Spectroscopy of Cis-Trans Isomerization of N,N-dimethyl-4,4'-Azodianiline with 3D-Printed Temperature-Controlled Sample Holder

ERIC Educational Resources Information Center

Kosenkov, Dmytro; Shaw, James; Zuczek, Jennifer; Kholod, Yana

2016-01-01

The laboratory unit demonstrates a project based approach to teaching physical chemistry laboratory where upper-division undergraduates carry out a transient-absorption experiment investigating the kinetics of cis-trans isomerization of N,N-dimethyl-4,4'-azodianiline. Students participate in modification of a standard flash-photolysis spectrometer…

Is [Co4(H2O)2(α-PW9O34)2](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments.

PubMed

Natali, Mirco; Berardi, Serena; Sartorel, Andrea; Bonchio, Marcella; Campagna, Sebastiano; Scandola, Franco

2012-09-11

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.

Solving Kinetic Equations for the Laser Flash Photolysis Experiment on Nitric Oxide Synthases: Effect of Conformational Dynamics on the Interdomain Electron Transfer.

PubMed

Astashkin, Andrei V; Feng, Changjian

2015-11-12

The production of nitric oxide by the nitric oxide synthase (NOS) enzyme depends on the interdomain electron transfer (IET) between the flavin mononucleotide (FMN) and heme domains. Although the rate of this IET has been measured by laser flash photolysis (LFP) for various NOS proteins, no rigorous analysis of the relevant kinetic equations was performed so far. In this work, we provide an analytical solution of the kinetic equations underlying the LFP approach. The derived expressions reveal that the bulk IET rate is significantly affected by the conformational dynamics that determines the formation and dissociation rates of the docking complex between the FMN and heme domains. We show that in order to informatively study the electron transfer across the NOS enzyme, LFP should be used in combination with other spectroscopic methods that could directly probe the docking equilibrium and the conformational change rate constants. The implications of the obtained analytical expressions for the interpretation of the LFP results from various native and modified NOS proteins are discussed. The mathematical formulas derived in this work should also be applicable for interpreting the IET kinetics in other modular redox enzymes.

Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

DOE PAGES

Ford, Peter C.

2001-01-01

Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO. his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls. hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

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-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

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 and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Flash Kα radiography of laser-driven solid sphere compression for fast ignition

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

Sawada, H.; Lee, S.; Shiroto, T.

2016-06-20

Time-resolved compression of a laser-driven solid deuterated plastic sphere with a cone was measured with flash Kα x-ray radiography. A spherically converging shockwave launched by nanosecond GEKKO XII beams was used for compression while a flash of 4.51 keV Ti Kα x-ray backlighter was produced by a high-intensity, picosecond laser LFEX (Laser for Fast ignition EXperiment) near peak compression for radiography. Areal densities of the compressed core were inferred from two-dimensional backlit x-ray images recorded with a narrow-band spherical crystal imager. The maximum areal density in the experiment was estimated to be 87 ± 26 mg/cm 2. Lastly, the temporalmore » evolution of the experimental and simulated areal densities with a 2-D radiation-hydrodynamics code is in good agreement.« less

Flash Kα radiography of laser-driven solid sphere compression for fast ignition

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

Sawada, H.; Lee, S.; Nagatomo, H.

2016-06-20

Time-resolved compression of a laser-driven solid deuterated plastic sphere with a cone was measured with flash Kα x-ray radiography. A spherically converging shockwave launched by nanosecond GEKKO XII beams was used for compression while a flash of 4.51 keV Ti Kα x-ray backlighter was produced by a high-intensity, picosecond laser LFEX (Laser for Fast ignition EXperiment) near peak compression for radiography. Areal densities of the compressed core were inferred from two-dimensional backlit x-ray images recorded with a narrow-band spherical crystal imager. The maximum areal density in the experiment was estimated to be 87 ± 26 mg/cm{sup 2}. The temporal evolution of the experimental andmore » simulated areal densities with a 2-D radiation-hydrodynamics code is in good agreement.« less

Experimental observation of the luminescence flash at the collapse phase of a bubble produced by pulsed discharge in water

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

Huang, Yifan; Zhang, Liancheng; Zhu, Xinlei

2015-11-02

This letter presents an experimental observation of luminescence flash at the collapse phase of an oscillating bubble produced by a pulsed discharge in water. According to the high speed records, the flash lasts around tens of microseconds, which is much longer than the lifetime of laser and ultrasound induced luminescence flashes in nanoseconds and picoseconds, respectively. The pulse width of temperature waveform and minimum radius calculated at the collapse phase also show that the thermodynamic and dynamic signatures of the bubbles in this work are much larger than those of ultrasound and laser induced bubbles both in time and spacemore » scales. However, the peak temperature at the point of collapse is close to the results of ultrasound and laser induced bubbles. This result provides another possibility for accurate emission spectrum measurement other than amplification of the emitted light, such as increasing laser energy or sound energy or substituting water with sulphuric acid.« less

Photodegradation routes of the herbicide bromoxynil in solution and sorbed on silica nanoparticles.

PubMed

Escalada, Juan P; Arce, Valeria B; Carlos, Luciano; Porcal, Gabriela V; Biasutti, M Alicia; Criado, Susana; García, Norman A; Mártire, Daniel O

2014-04-01

Some organic contaminants dissolved in natural waters tend to adsorb on suspended particles and sediments. In order to mimic the photodegradation routes in natural waters of bromoxynil (BXN) adsorbed on silica, we here prepare and characterize silica nanoparticles modified with BXN (NP-BXN). We measure the direct photolysis quantum yield of aqueous BXN at 307 nm (0.064 ± 0.001) and detect the formation of bromide ions as a reaction product. Under similar conditions the photolysis quantum yield of BXN bonded to NP-BXN is much lower (0.0021 ± 0.0004) and does not lead to formation of bromide ions. The rate constant of the reaction of NP-BXN with the excited triplet states of riboflavin, a molecule employed as a proxy of chromophore dissolved organic matter (DOM) was measured in laser flash-photolysis experiments. The rate constants for the overall (kt) and chemical interaction (kr) of singlet oxygen with NP-BXN were also measured. Kinetic computer simulations show that the relevance of the direct and indirect (through reactions with reactive species generated in photoinduced processes) photodegradation routes of BXN is very much affected by sorption on silica. Immobilization of the herbicide on the particles, on one hand, affects the photolysis mechanism and lowers its photolysis quantum yield. On the other hand, the results obtained in aqueous suspensions indicate that immobilization also lowers the rate of collisional encounter, which affects the quenching rate constants of excited triplet states and singlet oxygen with the herbicide.

A kinetics investigation of several reactions involving chlorine containing compounds

NASA Technical Reports Server (NTRS)

Davis, D. D.

1978-01-01

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Flash Photolysis Experiment of o-Methyl Red as a Function of pH: A Low-Cost Experiment for the Undergraduate Physical Chemistry Lab

ERIC Educational Resources Information Center

Larsen, Molly C.; Perkins, Russell J.

2016-01-01

A low-cost, time-resolved spectroscopy experiment appropriate for third year physical chemistry students is presented. Students excite o-methyl red in basic solutions with a laser pointer and use a modular spectrometer with a CCD array detector to monitor the transient spectra as the higher-energy cis conformer of the molecule converts back to the…

Laser induced photoluminescence spectroscopy of cometary radicals

NASA Technical Reports Server (NTRS)

Jackson, W. M.; Cody, R. J.; Sabety-Dzvonik, M.

1976-01-01

Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

Temperature dependence of the NO3 absorption spectrum

NASA Technical Reports Server (NTRS)

Sander, Stanley P.

1986-01-01

The absorption spectrum of the gas-phase NO3 radical has been studied between 220 and 700 nm by using both flash photolysis and discharge flow reactors for the production of NO3. In the flash photolysis method, cross sections at the peak of the (0,0) band at 661.9 nm were measured relative to the cross section of ClONO2 at several different wavelengths. From the best current measurements of the ClONO2 spectrum, the NO3 cross section at 661.9 nm was determined to be (2.28 + or 0.34) x 10 to the -17th sq cm/molecule at 298 K. Measurements at 230 K indicated that the cross section increases by a factor of 1.18 at the peak of the (0,0) band. The discharge flow method was used both to obtain absolute cross sections at 661.9 nm and to obtain relative absorption spectra between 300 and 700 nm at 298 and 230 K. A value of (1.83 + or - 0.27) x 10 to the -17th sq cm/molecule was obtained for sigma NO3 at 661.9 nm at 298 K. Upper limits to the NO3 cross sections were also measured between 220 and 260 nm with the discharge flow method.

Photophysical properties of C60 colloids suspended in water with Triton X-100 surfactant: excited-state properties with femtosecond resolution.

PubMed

Clements, Andrew F; Haley, Joy E; Urbas, Augustine M; Kost, Alan; Rauh, R David; Bertone, Jane F; Wang, Fei; Wiers, Brian M; Gao, De; Stefanik, Todd S; Mott, Andrew G; Mackie, David M

2009-06-11

We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.

Photoinduced Electron Transfer from Various Aniline Derivatives to Graphene Quantum Dots.

PubMed

Ghosh, Tufan; Chatterjee, Swarupa; Prasad, Edamana

2015-12-10

The present study utilizes the luminescence nature of the graphene quantum dots (GQDs) to analyze the mechanistic aspects of the photoinduced electron transfer (PET) processes between GQDs and aniline derivatives. A systematic investigation of PET from various aniline derivatives to GQDs has been presented. Solution-processable GQDs have been synthesized from graphene oxide (GO) at 200 °C. The as-synthesized GQDs exhibit a strong green luminescence at 510 nm, upon photoexcitation at 440 nm. Various aniline derivatives (aniline, N-methylaniline, N,N'-dimethylaniline, N-ethylaniline, N,N'-diethylaniline, and N,N'-diphenylaniline) have been utilized as electron donors to probe the PET process. Results from UV-visible absorption and steady-state and time-resolve luminescence spectroscopy suggest that the GQDs interact with the aniline derivatives in the excited state, which results in a significant luminescence quenching of the GQDs. The bimolecular rate constants of the dynamic quenching have been deduced for various donor-acceptor systems, and the values are in the range of (1.06-2.68) × 10(9) M(-1) s(-1). The negative values of the free energy change of the electron transfer process suggest that PET from aniline derivatives to GQDs is feasible and could be responsible for the luminescence quenching. The PET has been confirmed by detecting radical cations for certain aniline derivatives, using a nanosecond laser flash photolysis setup. The present study shows that among the various types of graphene systems, GQDs are better candidates for understanding the mechanism of PET in graphene-based donor-acceptor systems.

Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors

NASA Astrophysics Data System (ADS)

Sivakumar, V.; Ponnamma, Deepalekshmi; Hussein, Yasser H. A.

2017-02-01

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQT) but not the triplets AQT or AQST. However in aqueous medium, AN quenches AQST and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQT or AQST while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications.

Electron transfer reactions of excited dyes with metal complexes. Progress report, May 1, 1976--January 31, 1977. [Fe(III)--thionine reaction

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

Lichtin, N.N.

1977-02-01

A study was initiated of the factors which determine quantum efficiency of transfer of reducing equivalents between excited dye molecules and metal complexes in their ground state and composition and dynamics of formation and decay of related photostationary states. A ruby laser capable of delivering a 3.6 J, 19 nsec flash was acquired and assembly of an apparatus for laser flash photolysis begun. At the same time, conventional flash photolysis was used to pursue investigation of the dependence upon solvent, anions, pH, and ionic strength of the kinetics of the spontaneous dark reaction of Fe(H/sub 2/O)/sup 3 +//sub 6/ withmore » leucothionine and with semithionine, reactions which contribute to the composition and dynamics of formation and decay of the photostationary state of the iron-thionine photoredox reaction. Results are consistent with formation of an intermediate complex between leucothionine and Fe(III), K/sub A/ = 380 M/sup -1/ and k(elec. transfer) = 0.88 s/sup -1/ at approximately 22/sup 0/ in water solution at pH2, with sulfate as anion and ..mu.. = .05 - .1 M. Under similar conditions in 50 v/v percent aqueous CH/sub 3/CN, K/sub A/ = 780 M/sup -1/, k(elec. transfer) = 0.55 s/sup -1/. In both solvents, sulfate produces a large positive salt effect. Intermediacy of a complex was not established for the faster reaction of Fe(III) with semithionine under similar conditions: K/sub A/ . k(elec. transfer) approximately 3.5 x 10/sup 5/ M/sup -1/s/sup -1/ in H/sub 2/O, approximately 1.0 x 10/sup 4/ in 50 v/v percent aqueous CH/sub 3/CN.« less

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.

Mechanistic study of fulvic acid assisted propranolol photodegradation in aqueous solution.

PubMed

Makunina, Maria P; Pozdnyakov, Ivan P; Chen, Yong; Grivin, Vyacheslav P; Bazhin, Nikolay M; Plyusnin, Victor F

2015-01-01

Laser flash (355 nm) and stationary (365 nm) photolysis were used to study the mechanisms of propranolol photolysis in the presence of fulvic acid in aqueous solutions. The FA-assisted photodegradation of propranolol was observed using UV-A irradiation (where propranolol is stable). Direct evidence indicated that the photodegradation resulted from the static quenching of the FA triplet state by propranolol via the electron transfer mechanism. The triplet state yield (ϕT≈0.6%) and the T-T absorption coefficient (ɛT(620 nm)≈5×10(4) M(-1) cm(-1)) were estimated for the first time by modeling the yields of the FA triplet state in the presence of propranolol. Thus, fulvic acid is a promising agent for accelerating propranolol photodegradation in aqueous solutions under UV-A light irradiation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

NASA Technical Reports Server (NTRS)

Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

1976-01-01

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

Pressure Studies of Protein Dynamics.

DTIC Science & Technology

1987-02-20

applicable ) Office of Naval Research ONR N00014-86-K-0270 kc. ADDRESS (City, State,and ZIP Code) 10. SOURCE OF FUNDING NUMBERS - PROGRAM PROJECT I TASK IWORK...Pressure Studies of Protein Dynamics 12. PERSONAL AUTHOR(S) Hans Frauenfelder and Robert D. Young 13a. TYPE OF REPORT |13b. TIME COVERED 114 DATE OF...relatioihbetween dynamic structure and function of protein protein dyna -bsey observing the phenomena induced by flash photolysis using near ultravfilet

Quantitative imaging of single-shot liquid distributions in sprays using broadband flash x-ray radiography

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

Halls, B. R.; Roy, S.; Gord, J. R.

Flash x-ray radiography is used to capture quantitative, two-dimensional line-of-sight averaged, single-shot liquid distribution measurements in impinging jet sprays. The accuracy of utilizing broadband x-ray radiation from compact flash tube sources is investigated for a range of conditions by comparing the data with radiographic high-speed measurements from a narrowband, high-intensity synchrotron x-ray facility at the Advanced Photon Source (APS) of Argonne National Laboratory. The path length of the liquid jets is varied to evaluate the effects of energy dependent x-ray attenuation, also known as spectral beam hardening. The spatial liquid distributions from flash x-ray and synchrotron-based radiography are compared, alongmore » with spectral characteristics using Taylor’s hypothesis. The results indicate that quantitative, single-shot imaging of liquid distributions can be achieved using broadband x-ray sources with nanosecond temporal resolution. Practical considerations for optimizing the imaging system performance are discussed, including the coupled effects of x-ray bandwidth, contrast, sensitivity, spatial resolution, temporal resolution, and spectral beam hardening.« less

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 they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.

Laboratory studies of stratospheric bromine chemistry: Kinetics of the reactions of bromine monoxide with nitrogen dioxide and atomic oxygen

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton

A laser flash photolysis - long path absorption - technique has been employed to study the kinetics of the reaction BrO+NO2+M(k(sub 16)) yields products as a function of temperature (248-346 K), pressure (16-800 Torr), and buffer gas identity (N2, CF4). 351 nm photolysis of NO2/Br2/N2 mixtures generated BrO. The BrO decay in the presence of excess NO2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k(sub 16)(P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k(sub 16)(P,T) for use in modeling stratospheric BrO(x) chemistry. The kinetics of the important stratospheric reaction BrO+O(P-3)(k(sub 14)) yields Br+O2 in N2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25-150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of Br2/O3/N2 mixtures produces O atoms in excess over Br2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolysis a small fraction of the O3 to generate O(P-3). The decay of O(P-3) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resoved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k(sub 14)(T) is k(sub 14)(T) = 1.64 x 10(exp -11) exp(263/T) cm(exp 3) molecule(exp-1)s(exp -1). The absolute accuracy of k(sub 14)(T) at any temperature within the range studied is estimated to be +/- 25%. Possible kinetic interferences from production of vibrationally or electronically excited O2 are discussed. The effect of the faster reaction rate coefficients that are reported for the BrO + NO2 + M and BrO + O(P-3) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

Observation of nanosecond laser induced fluorescence of in vitro seawater phytoplankton

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

Bensky, Thomas J.; Clemo, Lisa; Gilbert, Chris

2008-08-01

Seawater has been irradiated using a train of 70 ns flashes from a 440 nm laser source. This wavelength is on resonance with the blue absorption peak of Chlorophyll pigment associated with the photosystem of in vitro phytoplankton. The resulting fluorescence at 685 nm is instantaneously recorded during each laser pulse using a streak camera. Delayed fluorescence is observed, yielding clues about initiation of the photosynthetic process on a nanosecond time scale. Further data processing allows for determination of the functional absorption cross section, found to be 0.0095 ?{sup 2}, which is the first reporting of this number for inmore » vitro phytoplankton. Unlike other flash-pump studies of Chlorophyll, using a LED or flashlamp-based sources, the short laser pulse used here does not reveal any pulse-to-pulse hysteresis (i.e., variable fluorescence), indicating that the laser pulses used here are not able to drive the photosynthetic process to completion. This is attributed to competition from a back reaction between the photoexcited photosystem II and the intermediate electron acceptor. The significance of this work as a new type of deployable ocean fluorimeter is discussed, and it is believed the apparatus will have applications in thin-layer phytoplankton research.« less

Hydrogen chemistry - Perspective on experiment and theory. [atmospheric chemistry

NASA Technical Reports Server (NTRS)

Kaufman, F.

1975-01-01

A review is presented of the advantages and limitations of various experimental methods for the investigation of the kinetics of hydrogen chemistry, including classic thermal and photochemical methods and the crossed molecular beam method. Special attention is given to the flash photolysis-resonance fluorescence apparatus developed by Braun et al, in which repetitive vacuum UV flashes result in the photolytic generation of the desired species, and to the discharge-flow technique. The use of various theoretical methods for the selection or elimination of kinetic data is considered in a brief discussion of the rate theory of two-body encounters and recombination-dissociation processes in neutral reactions. Recent kinetic studies of a series of OH reactions and of a major loss process for odd H in the stratosphere are summarized.

Following radical pair reactions in solution: a step change in sensitivity using cavity ring-down detection.

PubMed

Maeda, Kiminori; Neil, Simon R T; Henbest, Kevin B; Weber, Stefan; Schleicher, Erik; Hore, P J; Mackenzie, Stuart R; Timmel, Christiane R

2011-11-09

The study of radical pair intermediates in biological systems has been hampered by the low sensitivity of the optical techniques usually employed to investigate these highly reactive species. Understanding the physical principles governing the spin-selective and magneto-sensitive yields and kinetics of their reactions is essential in identifying the mechanism governing bird migration, and might have significance in the discussion of potential health hazards of electromagnetic radiation. Here, we demonstrate the powerful capabilities of optical cavity-enhanced techniques, such as cavity ring-down spectroscopy (CRDS) in monitoring radical recombination reactions and associated magnetic field effects (MFEs). These include submicrosecond time-resolution, high sensitivity (baseline noise on the order of 10(-6) absorbance units) and small (μL) sample volumes. Combined, we show that these represent significant advantages over the single-pass flash-photolysis techniques conventionally applied. The studies described here focus on photoinduced radical pair reactions involving the protein lysozyme and one of two possible photosensitizers: anthraquinone-2,6-disulphonate and flavin mononucleotide. CRDS-measured MFEs are observed in pump-probe experiments and discussed in terms of the sensitivity gains and sample-volume minimization afforded by CRDS when compared with flash photolysis methods. Finally, CRDS is applied to an in vitro MFE study of intramolecular electron transfer in the DNA-repair enzyme, Escherichia coli photolyase, a protein closely related to cryptochrome which has been proposed to mediate animal magnetoreception.

H2/O2 three-body rates at high temperatures

NASA Technical Reports Server (NTRS)

Marinelli, William J.; Kessler, William J.; Piper, Lawrence G.; Rawlins, W. Terry

1990-01-01

The extraction of thrust from air breathing hypersonic propulsion systems is critically dependent on the degree to which chemical equilibrium is reached in the combustion process. In the combustion of H2/Air mixtures, slow three-body chemical reactions involving H-atoms, O-atoms, and the OH radical play an important role in energy extraction. A first-generation high temperature and pressure flash-photolysis/laser-induced fluorescence reactor was designed and constructed to measure these important three-body rates. The system employs a high power excimer laser to produce these radicals via the photolysis of stable precursors. A novel two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical thickness or O2 absorption problems. To demonstrate the feasibility of the technique the apparatus in the program is designed to perform preliminary measurements on the H + O2 + M reaction at temperatures from 300 to 835 K.

A flash photolysis-resonance fluorescence study of the formation of O(D-1) in the photolysis of water and reaction of O(D-1) with H2, Ar and He

NASA Technical Reports Server (NTRS)

Stief, L. J.; Payne, W. A.; Klemm, R. B.

1974-01-01

The relative importance of two primary processes in the photolyis of water: (1) H2O + h (nu) yields H + OH, and (2) H2O + h (nu) yields H2 + OD-1 were determined in a direct manner by time resolved detection (via resonance fluorescence) of H and O formed in processes 1 and 2 respectively. The initially formed OD-1 was deactivated to ground state OP-3 prior to detection via resonance fluorescence. The relative quantum yields for processes 1 and 2 are 0.89 and 0.11 for the wavelength interval 105 to 145nm and = to or greater than 0.99, and = to or less than 0.01 for the wavelength interval 145 to 185nm. Rate constants at 300 K for the reactions OD-1 + H2, + Ar, and + He are presented.

Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

PubMed

Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

2004-12-27

Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief discussion of the dehalogenation chemistry, along with relevant environmental perspectives, is included.

Analog pixel array detectors.

PubMed

Ercan, A; Tate, M W; Gruner, S M

2006-03-01

X-ray pixel array detectors (PADs) are generally thought of as either digital photon counters (DPADs) or X-ray analog-integrating pixel array detectors (APADs). Experiences with APADs, which are especially well suited for X-ray imaging experiments where transient or high instantaneous flux events must be recorded, are reported. The design, characterization and experimental applications of several APAD designs developed at Cornell University are discussed. The simplest design is a ;flash' architecture, wherein successive integrated X-ray images, as short as several hundred nanoseconds in duration, are stored in the detector chips for later off-chip digitization. Radiography experiments using a prototype flash APAD are summarized. Another design has been implemented that combines flash capability with the ability to continuously stream X-ray images at slower (e.g. milliseconds) rates. Progress is described towards radiation-hardened APADs that can be tiled to cover a large area. A mixed-mode PAD, design by combining many of the attractive features of both APADs and DPADs, is also described.

Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors.

PubMed

Sivakumar, V; Ponnamma, Deepalekshmi; Hussein, Yasser H A

2017-02-15

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQ T ) but not the triplets AQ T or AQS T . However in aqueous medium, AN quenches AQS T and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQ T or AQS T while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Photoreactions of biacetyl, benzophenone, and benzil with electron-rich alkenes

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

Gersdorf, J.; Mattay, J.; Goerner, H.

1987-02-18

The rate constants (k/sub q/) for fluorescence and phosphorescence quenching of biacetyl by electron-rich alkenes were measured in acetonitrile solution at room temperature. A weak dependence of log k/sub q/ on the free enthalpy change (..delta..G/sub 2/) for electron transfer in the triplet state in the range 0 < ..delta..G/sub 2/ < 1.0 eV indicates formation of a polar exciplex. The strong enhancement of k/sub q/ for 0 > ..delta..G/sub 2/ > -0.70 eV points to electron-transfer processes in singlet and triplet states. Quenching of the phosphorescence and the T-T absorption of benzophenone reveals larger (smaller) k/sub q/ values inmore » the endergonic (exergonic) region, as compared to the Rehm-Weller correlation. The slope of the plot of log k/sub q/ vs. ..delta..G/sub 2/ is similar to that of biacetyl in the endergonic region. The latter indicates that electron transfer in this instance is not the primary step. For benzil the plot of log k/sub q/ vs ..delta..G/sub 2/ resembles more closely that of biacetyl, pointing to a similar mechanism. In the exergonic region electron transfer is observed for benzil (major process) and benzophenone (minor process) by detection of the radical anion with use of nanosecond laser flash photolysis. The yield and half-life of the radical anion depend on the nature of the electron donor and the ketone, the solvent polarity, and the additives (e.g., LiClO/sub 4/, special salt effect). The solvent effect on the photoproducts (oxetanes) is correlated with the free enthalpies of radical ion pair formation.« less

Rate constant for reaction of atomic hydrogen with germane

NASA Technical Reports Server (NTRS)

Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

1990-01-01

Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

Conference on Singlet Molecular Oxygen (COSMO 84) Held at Clearwater, Beach, Florida on 4-7 January 1984. Program and Abstracts.

DTIC Science & Technology

1984-09-24

BREAKS will be announced by the SESSION CHAIRMAN. 6. LOCAL INFORMATION may be obtained at the HILTON REGISTRATION DESK or the LOBBY REGISTRATION DESK...carotene and laser flash photolysis experiments to determine the rates of quenching of 3 BChl a by oxygen, $-carotene#,3 tetracene and pentacene . References...with the tumor localizing and photosensitizing constituent of HPD strongly suggests that the in situ "’ * tumor sensitizer in photoradiation therapy is

Photochemistry and photooxidation of tetraphenyl-p-dioxin

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

George, M.V.; Kumar, C.V.; Scaiano, J.C.

1979-09-20

Laser flash photolysis studies of tetraphenyl-p-dioxin have led to the characterization of its triplet state. The T-T absorption spectra shows maxima at 350 and 545 nm; the triplet has a lifetime of 535 ns in methanol and can be quenched by di-tert-butyl nitroxide, paraquat dications, oxygen, and di-tert-butyl selenoketone. The interaction of the triplet with oxygen leads to the formation of singlet oxygen which in turn reacts with the title compound to yield benzil.

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

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

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

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.

Laboratory-scale photoredox catalysis using hydrated electrons sustainably generated with a single green laser.

PubMed

Naumann, Robert; Kerzig, Christoph; Goez, Martin

2017-11-01

The ruthenium-tris-bipyridyl dication as catalyst combined with the ascorbate dianion as bioavailable sacrificial donor provides the first regenerative source of hydrated electrons for chemical syntheses on millimolar scales. This electron generator is operated simply by illumination with a frequency-doubled Nd:YAG laser (532 nm) running at its normal repetition rate. Much more detailed information than by product studies alone was obtained by photokinetical characterization from submicroseconds (time-resolved laser flash photolysis) up to one hour (preparative photolysis). The experiments on short timescales established a reaction mechanism more complex than previously thought, and proved the catalytic action by unchanged concentration traces of the key transients over a number of flashes so large that the accumulated electron total surpassed the catalyst concentration many times. Preparative photolyses revealed that the sacrificial donor greatly enhances the catalyst stability through quenching the initial metal-to-ligand charge-transfer state before destructive dd states can be populated from it, such that the efficiency of this electron generator is no longer limited by catalyst decomposition but by electron scavenging by the accumulating oxidation products of the ascorbate. Applications covered dechlorinations of selected aliphatic and aromatic chlorides and the reduction of a model ketone. All these substrates are impervious to photoredox catalysts exhibiting lower reducing power than the hydrated electron, but the combination of an extremely negative standard potential and a long unquenched life allowed turnover numbers up to 1400 with our method.

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.

Studies on photoinduced H-atom and electron transfer reactions of o-naphthoquinones by laser flash photolysis.

PubMed

Pan, Yang; Fu, Yao; Liu, Shaoxiong; Yu, Haizhu; Gao, Yuhe; Guo, Qingxiang; Yu, Shuqin

2006-06-15

The quenching of the triplets of 1,2-naphthoquinone (NQ) and 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) by various electron and H-atom donors was investigated by laser flash photolysis measurement in acetonitrile and benzene. The results showed that the reactivities and configurations of 3NQ* (3NQS*) are governed by solvent polarity. All the quenching rate constants (kq) measured in benzene are larger than those in acetonitrile. The SO3Na substituent at the C-4 position of NQS makes 3NQS* more reactive than 3NQ* in electron/H-atom transfer reactions. Large differences of kq values were discovered in H-atom transfer reactions for alcohols and phenols, which can be explained by different H-abstraction mechanisms. Detection of radical cations of amines/anilines in time-resolved transient absorption spectra confirms an electron transfer mechanism. Triplets are identified as precursors of formed radical anions of NQ and NQS in photoinduced reactions. The dependence of electron transfer rate constants on the free energy changes (DeltaG) was treated by using the Rehm-Weller equation. For the four anilines with different substituents on the para or meta position of amidocyanogen, good correlation between log kq values with Hammett sigma constants testifies the correctness of empirical Hammett equation. Charge density distributions, adiabatic ionization/affinity potentials and redox potentials of NQ (NQS) and some quenchers were studied by quantum chemistry calculation.

Medium-dependent interactions of quinones with cytosine and cytidine: a laser flash photolysis study with magnetic field effect.

PubMed

Bose, Adity; Basu, Samita

2009-03-01

Laser flash photolysis and an external magnetic field have been used for the study of the interaction of two quinone molecules, namely, 9,10-anthraquinone (AQ) and 2-methyl 1,4-naphthoquinone (or menadione, MQ) with a DNA base, cytosine (C) and its nucleoside cytidine (dC) in two media, a homogeneous one composed of acetonitrile/water (ACN/H(2)O, 9:1, v/v) and a SDS micellar heterogeneous one. We have applied an external magnetic field for the proper identification of the transients formed during the interactions in micellar media. Cytosine exhibits electron transfer (ET) followed by hydrogen abstraction (HA) while dC reveals a reduced ET compared to C, with both quinones in organic homogeneous medium (ACN/H(2)O). Due to a higher electron affinity, AQ supports more faciler ET than MQ with dC in ACN/H(2)O but observations in SDS have been just the reverse. In SDS, ET from dC is completely quenched and a dominant HA is all that could be discerned. This work reveals two main findings: first, a drop in ET on addition of a ribose unit to C, which has been attributed to a role of keto-enol tautomerism in inducing ET from electron-rich nucleus and second, the effect of medium in controlling reaction mechanism by favoring HA with AQ although it is intrinsically more prone towards ET.

Pump-probe imaging of nanosecond laser-induced bubbles in agar gel.

PubMed

Evans, R; Camacho-López, S; Pérez-Gutiérrez, F G; Aguilar, G

2008-05-12

In this paper we show results of Nd:YAG laser-induced bubbles formed in a one millimeter thick agar gel slab. The nine nanosecond duration pulse with a wave length of 532 nm was tightly focused inside the bulk of the gel sample. We present for the first time a pump-probe laser-flash shadowgraphy system that uses two electronically delayed Nd:YAG lasers to image the the bubble formation and shock wave fronts with nanosecond temporal resolution and up to nine seconds of temporal range. The shock waves generated by the laser are shown to begin at an earlier times within the laser pulse as the pulse energy increases. The shock wave velocity is used to infer a shocked to unshocked material pressure difference of up to 500 MPa. The bubble created settles to a quasi-stable size that has a linear relation to the maximum bubble size. The energy stored in the bubble is shown to increase nonlinearly with applied laser energy, and corresponds in form to the energy transmission in the agar gel. We show that the interaction is highly nonlinear, and most likely is plasma-mediated.

Flash x-ray radiography of argon jets in ambient air

NASA Astrophysics Data System (ADS)

Geiswiller, J.; Robert, E.; Huré, L.; Cachoncinlle, C.; Viladrosa, R.; Pouvesle, J. M.

1998-09-01

This paper describes the development and application of a soft x-ray flash radiography technique. A very compact soft x-ray flash source has been specially designed for these studies. The table-top x-ray source developed in this work emits strong doses, up to one roentgen at the output window, of x-ray photons, with most of them in the characteristic lines of the anode material (photon energy in the energy range 5-10 keV), in pulse of 20 ns FWHM with an x-ray emission zone smaller than 0957-0233/9/9/024/img1. All these characteristics make this source attractive for the x-ray radiography of high-speed phenomena, down to ten nanoseconds duration and/or for the media presenting weak absorption for the harder x-ray photons emitted by more conventional flash x-ray systems. Argon streams in ambient air were chosen as a typical case to enlighten the potentialities of this method. Single-shot radiographs of such an argon jet through rectangular nozzles were obtained. No attempt of quantitative measurement of local density in the argon stream has yet been performed, only the qualitative structure of the jet has been investigated. Nevertheless, these preliminary results enable us to state that the diagnostics of gaseous or plasma media, even at rather low pressures, can proceed using soft x-ray flash radiography.

Kinetics of the reactions of alkyl radicals with HBr and DBr

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Van Dijk, C. A.; Kreutter, K. D.; Wine, P. H.

1991-01-01

The kinetics of the reactions CH3 + HBr, CD3 + HBr, CH3 + DBr, C2H5 + HBr, C2H5 + DBr, t-C4H9 + HBr, and t-C4H9 + DBr is studied as a function of temperature (257-430 K) and pressure (10-300 Torr of N2). Time-resolved resonance fluorescence detection of Br atom appearance following laser flash photolysis of RI was used in the experiments. Results show that the rates of all reactions increased as the temperature decreased.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

NASA Technical Reports Server (NTRS)

Zhao, Z.; Stickel, R. E.; Wine, P. H.

1995-01-01

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Study of photodissociation parameters of carboxyhemoglobin

NASA Astrophysics Data System (ADS)

Kuz'min, V. V.; Salmin, V. V.; Salmina, A. B.; Provorov, A. S.

2008-07-01

The general properties of photodissociation of carboxyhemoglobin (HbCO) in buffer solutions of whole human blood are studied by the flash photolysis method on a setup with intersecting beams. It is shown that the efficiency of photoinduced dissociation of the HbCO complex virtually linearly depends on the photolytic irradiation intensity for the average power density not exceeding 45 mW cm-2. The general dissociation of the HbCO complex in native conditions occurs in a narrower range of values of the saturation degree than in model experiments with the hemoglobin solution. The dependence of the pulse photolysis efficiency of HbCO on the photolytic radiation wavelength in the range from 550 to 585 nm has a broad bell shape. The efficiency maximum corresponds to the electronic Q transition (porphyrin π—π* absorption) in HbCO at a wavelength of 570 nm. No dissociation of the complex was observed under given experimental conditions upon irradiation of solutions by photolytic radiation at wavelengths above 585 nm.

Nanosecond Absorption Spectroscopy of Hemoglobin: Elementary Processes in Kinetic Cooperativity

NASA Astrophysics Data System (ADS)

Hofrichter, James; Sommer, Joseph H.; Henry, Eric R.; Eaton, William A.

1983-04-01

A nanosecond absorption spectrometer has been used to measure the optical spectra of hemoglobin between 3 ns and 100 ms after photolysis of the CO complex. The data from a single experiment comprise a surface, defined by the time-ordered set of 50-100 spectra. Singular value decomposition is used to represent the observed spectra in terms of a minimal set of basis spectra and the time course of their amplitudes. Both CO rebinding and conformational changes are found to be multiphasic. Prior to the quaternary structural change, two relaxations are observed that are assigned to geminate recombination followed by a tertiary structural change. These relaxations are interpreted in terms of a kinetic model that points out their potential role in kinetic cooperativity. The rapid escape of CO from the heme pocket compared with the rate of rebinding observed for both R and T quaternary states shows that the quaternary structure controls the overall dissociation rate by changing the rate at which the Fe--CO bond is broken. A comparable description of the control of the overall association rates must await a more complete experimental description of the kinetics of the quaternary T state.

Development of cable fed flash X-ray (FXR) system

NASA Astrophysics Data System (ADS)

Menon, Rakhee; Mitra, S.; Patel, A. S.; Kumar, R.; Singh, G.; Senthil, K.; Kumar, Ranjeet; Kolge, T. S.; Roy, Amitava; Acharya, S.; Biswas, D.; Sharma, Archana

2017-08-01

Flash X-ray sources driven by pulsed power find applications in industrial radiography, and a portable X-ray source is ideal where the radiography needs to be taken at the test site. A compact and portable flash X-ray (FXR) system based on a Marx generator has been developed with the high voltage fed to the FXR tube via a cable feed-through arrangement. Hard bremsstrahlung X-rays of few tens of nanosecond duration are generated by impinging intense electron beams on an anode target of high Z material. An industrial X-ray source is developed with source size as low as 1 mm. The system can be operated from 150 kV to 450 kV peak voltages and a dose of 10 mR has been measured at 1 m distance from the source window. The modeling of the FXR source has been carried out using particle-in-cell and Monte Carlo simulations for the electron beam dynamics and X-ray generation, respectively. The angular dose profile of X-ray has been measured and compared with the simulation.

Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton, Jr.

A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic interferences from production of vibrationally or electronically excited O_2 are discussed. The effect of the faster reaction rate coefficients that are reported for the rm BrO + NO_2 + M and BrO + O(^3P) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

Biophysical Characterisation of Neuroglobin of the Icefish, a Natural Knockout for Hemoglobin and Myoglobin. Comparison with Human Neuroglobin

PubMed Central

Giordano, Daniela; Boron, Ignacio; Abbruzzetti, Stefania; Van Leuven, Wendy; Nicoletti, Francesco P.; Forti, Flavio; Bruno, Stefano; Cheng, C-H. Christina; Moens, Luc; di Prisco, Guido; Nadra, Alejandro D.; Estrin, Darío; Smulevich, Giulietta; Dewilde, Sylvia; Viappiani, Cristiano; Verde, Cinzia

2012-01-01

The Antarctic icefish Chaenocephalus aceratus lacks the globins common to most vertebrates, hemoglobin and myoglobin, but has retained neuroglobin in the brain. This conserved globin has been cloned, over-expressed and purified. To highlight similarities and differences, the structural features of the neuroglobin of this colourless-blooded fish were compared with those of the well characterised human neuroglobin as well as with the neuroglobin from the retina of the red blooded, hemoglobin and myoglobin-containing, closely related Antarctic notothenioid Dissostichus mawsoni. A detailed structural and functional analysis of the two Antarctic fish neuroglobins was carried out by UV-visible and Resonance Raman spectroscopies, molecular dynamics simulations and laser-flash photolysis. Similar to the human protein, Antarctic fish neuroglobins can reversibly bind oxygen and CO in the Fe2+ form, and show six-coordination by distal His in the absence of exogenous ligands. A very large and structured internal cavity, with discrete docking sites, was identified in the modelled three-dimensional structures of the Antarctic neuroglobins. Estimate of the free-energy barriers from laser-flash photolysis and Implicit Ligand Sampling showed that the cavities are accessible from the solvent in both proteins. Comparison of structural and functional properties suggests that the two Antarctic fish neuroglobins most likely preserved and possibly improved the function recently proposed for human neuroglobin in ligand multichemistry. Despite subtle differences, the adaptation of Antarctic fish neuroglobins does not seem to parallel the dramatic adaptation of the oxygen carrying globins, hemoglobin and myoglobin, in the same organisms. PMID:23226490

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.

Laboratory Investigations of Stratospheric Halogen Chemistry

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

1997-01-01

A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

Enhancement of photoisomerization of polymethine dyes in complexes with biomacromolecules

NASA Astrophysics Data System (ADS)

Tatikolov, Alexander S.; Akimkin, Timofei M.; Pronkin, Pavel G.; Yarmoluk, Sergiy M.

2013-01-01

Photochemical processes (photoisomerization and generation of the triplet state) of the thiacarbocyanine dyes 3,3',9-trimethylthiacarbocyanine iodide (Cyan 2), 3,3'-diethyl-9-methylthiacarbocyanine iodide (DMTC), and 3,3',9-triethylthiacarbocyanine iodide (TETC) in complexes with biomacromolecules—DNA and chondroitin-4-sulfate—were studied by flash photolysis. It has been shown that, along with generation of the triplet state, enhancement of the photoisomer formation is observed for Cyan 2 and DMTC complexed with the biomolecules. This effect can be explained by the influence of the biopolymer matrix on the potential energy curves of the photoisomerization process.

Is Photolytic Production a Viable Source of HCN and HNC in Astrophysical Environments? A Laboratory-based Feasibility Study of Methyl Cyanoformate

NASA Astrophysics Data System (ADS)

Wilhelm, Michael J.; Martínez-Núñez, Emilio; González-Vázquez, Jesús; Vázquez, Saulo A.; Smith, Jonathan M.; Dai, Hai-Lung

2017-11-01

Motivated by the possibility that cyano-containing hydrocarbons may act as photolytic sources for HCN and HNC in astrophysical environments, we conducted a combined experimental and theoretical investigation of the 193 nm photolysis of the cyano-ester, methyl cyanoformate (MCF). Experimentally, nanosecond time-resolved infrared emission spectroscopy was used to detect the emission from nascent products generated in the photolysis reaction. The time-resolved spectra were analyzed using a recently developed spectral reconstruction analysis, which revealed spectral bands assignable to HCN and HNC. Fitting of the emission band shape and intensity allowed determination of the photolysis quantum yields of HCN, HNC, and {CN}({A}2{{{\\Pi }}}1) and an HNC/HCN ratio of ˜0.076 ± 0.059. Additionally, multiconfiguration self-consistent field calculations were used to characterize photoexcitation-induced reactions in the ground and four lowest singlet excited states of MCF. At 193 nm excitation, dissociation is predicted to occur predominantly on the repulsive S 2 state, with minor pathways via internal conversion from S 2 to highly excited ground state. An automated transition-state search algorithm was employed to identify the corresponding ground-state dissociation channels, and Rice-Ramsperger-Kassel-Marcus and Kinetic Monte Carlo simulations were used to calculate the associated branching ratios. The proposed mechanisms were validated using the experimentally measured and quasi-classical trajectory-deduced nascent internal energy distributions of HCN and HNC. This work, along with previous studies, illustrates the propensity for cyano-containing hydrocarbons to act as photolytic sources for astrophysical HCN and HNC and may help explain the observed overabundance of HNC in astrophysical environments.

Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor.

PubMed

Zhang, Min; E, Wenbo; Ohkubo, Kei; Sanchez-Garcia, David; Yoon, Dae-Wi; Sessler, Jonathan L; Fukuzumi, Shunichi; Kadish, Karl M

2008-02-21

Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.

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 MgADP release from cross-bridges, estimated from its concentration-dependent effect on the rate constant of the second (tau 2) component, was 0.35-7.7 s-1. To the extent that reattachment of cross-bridges could slow relaxation even during the initial 200 ms, this rate constant may be an underestimate. 5. Inorganic phosphate (Pi, 30 mM) did not affect the rate of relaxation during the initial approximately 50 ms, but accelerated the slower phase of relaxation, consistent with a cyclic cross-bridge model in which Pi increases the proportion of cross-bridges in detached ('weakly bound') states.(ABSTRACT TRUNCATED AT 400 WORDS) Images Fig. 1 PMID:8487195

Excited triplet state of N-(9-methylpurin-6-yl)pyridinium cation as an efficient photosensitizer in the oxidation of sulfur-containing amino acids. Laser flash and steady-state photolysis studies

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

Marciniak, B.; Hug, G.L.; Bobrowski, K.

1995-01-11

In this paper, we present and discuss the results of a detailed mechanistic study of the photosensitized oxidation of sulfur-containing amino acids by N-(9-methylpurin-6-yl)pyridinium cations in aqueous solution. The results provide data on the photoreactivity of the pyridinium salts (derived from the purine bases) in the presence of the electron donors such as sulfur-containing organic compounds and give new experimental evidence for the general mechanism of the sensitized photooxidation of thioethers proposed previously. 39 refs., 6 figs., 2 tabs.

Photoinduced triplet-triplet energy transfer via the 2-ureido-4[1H]-pyrimidinone self-complementary quadruple hydrogen-bonded module.

PubMed

Wang, Su-Min; Yu, Mao-Lin; Ding, Jie; Tung, Chen-Ho; Wu, Li-Zhu

2008-05-01

Phosphorescence quenching and flash photolysis experiments demonstrate that photoinduced intra-assembly triplet-triplet energy transfer can take place via a 2-ureido-4[1H]-pyrimidinone-bridged benzophenone-naphthalene assembly I with a rate constant of 3.0 x 106 s-1 and an efficiency of 95% in CH2Cl2. This new finding suggests that with high binding strength and directionality, the 2-ureido-4[1H]-pyrimidinone hydrogen-bonded module may serve as a new model to illustrate the fundamental principles governing the triplet-triplet energy-transfer process through hydrogen bonds.

The protective effect of salicylic acid on lysozyme against riboflavin-mediated photooxidation

NASA Astrophysics Data System (ADS)

Li, Kun; Wang, Hongbao; Cheng, Lingli; Zhu, Hui; Wang, Mei; Wang, Shi-Long

2011-06-01

As a metabolite of aspirin in vivo, salicylic acid was proved to protect lysozyme from riboflavin-mediated photooxidation in this study. The antioxidative properties of salicylic acid were further studied by using time-resolved laser flash photolysis of 355 nm. It can quench the triplet state of riboflavin via electron transfer from salicylic acid to the triplet state of riboflavin with a reaction constant of 2.25 × 10 9 M -1 s -1. Mechanism of antioxidant activities of salicylic acid on lysozyme oxidation was discussed. Salicylic acid can serve as a potential antioxidant to quench the triplet state of riboflavin and reduce oxidative pressure.

Laser flash photolysis experiments on the effects of freezing and salt addition on intramolecular electron transfer within one-electron reduced ascorbate oxidase.

PubMed

Hazzard, J T; Maritano, S; Tollin, G; Marchesini, A

1997-03-01

Laser flash photolysis has been used to investigate the effects of freezing protein solutions and of adding various salts on the kinetics of one-electron photoreduction by 5-deazariboflavin semiquinone (5-DRFH.) of oxidized ascorbate oxidase (AO) from zucchini in 100 mM phosphate buffer (pH 7.0). The initial reaction between oxidized AO and 5-DRFH. is quite rapid (k approximately 10(8) M-1 s-1) and occurs at the blue Type I Cu center. Subsequent to this, a slower, protein concentration-independent intramolecular reoxidation of the Type I Cu is observed, with kET approximately 150 s-1, resulting in 40-50% reoxidation of the blue Cu center and the establishment of an electron transfer (ET) equilibrium between the various Cu centers in AO. When such a sample of AO was frozen overnight at -30 degrees C, flash photolysis of the thawed sample showed no effect on the kinetics of reduction of the Type I Cu by 5-DRFH. However, the rate constant for intramolecular ET decreased to a value of 2.7 s-1, with only 20% reoxidation of the Type I center. Reduction of the enzyme with ascorbic acid, followed by O2 oxidation, resulted in restoration of rapid intramolecular reoxidation (kET = 130 s-1), with 33% of the Type I Cu reduced by 5-DRFH. being reoxidized. These results are consistent with previous work which showed that samples of AO with initially low activity can be reactivated by ascorbic acid turnover in the presence of O2. When AO was frozen in the presence of ascorbic acid, similar inhibition of intramolecular ET was obtained, whereas upon turnover of this sample by further addition of ascorbic acid and exposure to O2, activity was not restored. The effects of addition of (NH4)2SO4, Na2SO4, NH4Cl, NaCl, KCl, and KF on the kinetics of Type I Cu reduction by 5-deazariboflavin semiquinone and on the subsequent intramolecular ET were also examined. A twofold increase in the bimolecular rate constant for reduction of the Type I Cu was observed for the two sodium salts at high concentrations (500 mM). Intramolecular ET was also significantly affected upon addition of all three chloride salts. Although the intramolecular ET rate constant was not altered, the fraction of reduced Type I Cu reoxidized by the trinuclear cluster decreased with increasing Cl- concentration, regardless of the cation. Total inhibition of intramolecular ET was observed at a significantly lower concentration of KF than observed with the Cl- salts. Sulfate ion had no effect on either parameter. These changes are thus ion specific, suggesting that they are related to ion binding by the protein, possibly at one of the coppers of the trinuclear cluster.

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

1980-01-01

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

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.

Double-pulse dichromatic photolysis of fac-CIRe(CO){sub 3}L{sub 2} (L=4-phenylpyridine or 4-cyanopyridine): Photohomolysis of Re-L bonds insuced by irradiation of photochemically unreactive charge transfer states

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

Feliz, M.; Ferraudi, G.

1992-04-02

Photochemical reactions of fac-ClRe(CO){sub 3}L{sub 2} (L=4-phenylpyridine or 4-cyanopyridine), were investigated by sequential biphotonic excitations: one laser flash was used for the preparation of the compounds in the lowest lying MLCT (Re{r_arrow}) state and another flash for the irradiation of the compounds in such excited states. These photolyses led to photodecompostions into CIRe(CO){sub 3}L{sup +} and L{sup .} in a charge transfer state placed 40 Kk above ground state. Quantum yields determined or various excitation energies show that not all the excited state populated in monophotonic excitations can be reached under the sequential biphotonic regime. Therefore, photogeneration of the biradicalmore » intermediate, ClRe(CO){sub 3}L{sup +} and L{sup .}, from ligand-centered states has not been detected in these experiments. Results from monophotonic and biphotonic excitations have been used for a semiquantitative mapping of the excited-state potential surfaces. 41 refs., 6 figs.« less

Interaction of proflavin with aromatic amines in homogeneous and micellar media: Photoinduced electron transfer probed by magnetic field effect

NASA Astrophysics Data System (ADS)

Chakraborty, Brotati; Basu, Samita

2010-02-01

Photoinduced electron transfer (PET) between proflavin (PF +) and two aromatic amines viz., dimethylaniline (DMA) and 4,4'-bis(dimethylamino)diphenylmethane (DMDPM) is studied in homogeneous and heterogeneous media using steady-state as well as time-resolved fluorescence spectroscopy and laser flash photolysis with an associated magnetic field. Ionic micelles have been used to study the effect of charge of proflavin on PET with amines. Magnetic field effect on PET reactions reveals that the parent spin-state of precursors of PET for DMA-PF + system is singlet while for DMDPM-PF + system is triplet, implying that the dynamics of PET is influenced by the structure of the donor.

Amino acid residues in Anabaena ferredoxin crucial to interaction with ferredoxin-NADP+ reductase: site-directed mutagenesis and laser flash photolysis.

PubMed

Hurley, J K; Salamon, Z; Meyer, T E; Fitch, J C; Cusanovich, M A; Markley, J L; Cheng, H; Xia, B; Chae, Y K; Medina, M

1993-09-14

Ferredoxin (Fd) functions in photosynthesis to transfer electrons from photosystem I to ferredoxin-NADP+ reductase (FNR). We have made several site-directed mutants of Anabaena 7120 Fd and have used laser flash photolysis to investigate the effects of these mutations on the kinetics of reduction of oxidized Fd by deazariboflavin semiquinone (dRfH.) and the reduction of oxidized Anabaena FNR by reduced Fd. None of the mutations influenced the second-order rate constant for dRfH. reduction by more than a factor of 2, suggesting that the ability of the [2Fe-2S] cluster to participate in electron transfer was not seriously affected. In contrast, a surface charge reversal mutation, E94K, resulted in a 20,000-fold decrease in the second-order rate constant for electron transfer from Fd to FNR, whereas a similar mutation at an adjacent site, E95K, produced little or no change in reaction rate constant compared to wild-type Fd. Such a dramatic difference between contiguous surface mutations suggests a very precise surface complementarity at the protein-protein interface. Mutations introduced at F65 (F65I and F65A) also decreased the rate constant for the Fd/FNR electron transfer reaction by more than 3 orders of magnitude. Spectroscopic and thermodynamic measurements with both the E94 and F65 mutants indicated that the kinetic differences cannot be ascribed to changes in gross conformation, redox potential, or FNR binding constant but rather reflect the protein-protein interactions that control electron transfer. Several mutations at other sites in the vicinity of E94 and F65 (R42, T48, D68, and D69) resulted in little or no perturbation of the Fd/FNR interaction.(ABSTRACT TRUNCATED AT 250 WORDS)

Simultaneous measurement and modulation of multiple physiological parameters in the isolated heart using optical techniques

PubMed Central

Lee, Peter; Yan, Ping; Ewart, Paul; Kohl, Peter

2012-01-01

Whole-heart multi-parametric optical mapping has provided valuable insight into the interplay of electro-physiological parameters, and this technology will continue to thrive as dyes are improved and technical solutions for imaging become simpler and cheaper. Here, we show the advantage of using improved 2nd-generation voltage dyes, provide a simple solution to panoramic multi-parametric mapping, and illustrate the application of flash photolysis of caged compounds for studies in the whole heart. For proof of principle, we used the isolated rat whole-heart model. After characterising the blue and green isosbestic points of di-4-ANBDQBS and di-4-ANBDQPQ, respectively, two voltage and calcium mapping systems are described. With two newly custom-made multi-band optical filters, (1) di-4-ANBDQBS and fluo-4 and (2) di-4-ANBDQPQ and rhod-2 mapping are demonstrated. Furthermore, we demonstrate three-parameter mapping using di-4-ANBDQPQ, rhod-2 and NADH. Using off-the-shelf optics and the di-4-ANBDQPQ and rhod-2 combination, we demonstrate panoramic multi-parametric mapping, affording a 360° spatiotemporal record of activity. Finally, local optical perturbation of calcium dynamics in the whole heart is demonstrated using the caged compound, o-nitrophenyl ethylene glycol tetraacetic acid (NP-EGTA), with an ultraviolet light-emitting diode (LED). Calcium maps (heart loaded with di-4-ANBDQPQ and rhod-2) demonstrate successful NP-EGTA loading and local flash photolysis. All imaging systems were built using only a single camera. In conclusion, using novel 2nd-generation voltage dyes, we developed scalable techniques for multi-parametric optical mapping of the whole heart from one point of view and panoramically. In addition to these parameter imaging approaches, we show that it is possible to use caged compounds and ultraviolet LEDs to locally perturb electrophysiological parameters in the whole heart. PMID:22886365

High repetition rate compact source of nanosecond pulses of 5-100 keV x-ray photons

NASA Astrophysics Data System (ADS)

Khacef, A.; Viladrosa, R.; Cachoncinlle, C.; Robert, E.; Pouvesle, J. M.

1997-06-01

A powerful, compact, and repetitive flash x-ray system based on a cable transformer technology powered by ceramic capacitors in a Blumlein-like configuration has been developed. Open circuit voltages in excess of 100 kV can be achieved while commutation occurs at low voltage (<20 kV). The x-ray emission from a low impedance x-ray diode with a hollow cathode configuration was observed under a wide range of experimental conditions. The critical parameters limiting the flash x-ray performances are mainly the pressure in the x-ray diode and the anode-cathode space. This true table top device is able to produce doses up to 1 R per shot, measured at the output window, of x-rays between 5 and 100 keV. The pulse widths were about 20 ns and the maximum repetition rate was about 60 Hz. Operation is possible in air or in other gases (He, Ne, Ar, Kr, Xe, H2, N2) at pressures varying from 10-3 mbar for xenon to about 1 mbar for helium.

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.

1977-01-01

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

NASA Technical Reports Server (NTRS)

Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

1984-01-01

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Single shot damage mechanism of Mo/Si multilayer optics under intense pulsed XUV-exposure.

PubMed

Khorsand, A R; Sobierajski, R; Louis, E; Bruijn, S; van Hattum, E D; van de Kruijs, R W E; Jurek, M; Klinger, D; Pelka, J B; Juha, L; Burian, T; Chalupsky, J; Cihelka, J; Hajkova, V; Vysin, L; Jastrow, U; Stojanovic, N; Toleikis, S; Wabnitz, H; Tiedtke, K; Sokolowski-Tinten, K; Shymanovich, U; Krzywinski, J; Hau-Riege, S; London, R; Gleeson, A; Gullikson, E M; Bijkerk, F

2010-01-18

We investigated single shot damage of Mo/Si multilayer coatings exposed to the intense fs XUV radiation at the Free-electron LASer facility in Hamburg - FLASH. The interaction process was studied in situ by XUV reflectometry, time resolved optical microscopy, and "post-mortem" by interference-polarizing optical microscopy (with Nomarski contrast), atomic force microscopy, and scanning transmission electron microcopy. An ultrafast molybdenum silicide formation due to enhanced atomic diffusion in melted silicon has been determined to be the key process in the damage mechanism. The influence of the energy diffusion on the damage process was estimated. The results are of significance for the design of multilayer optics for a new generation of pulsed (from atto- to nanosecond) XUV sources.

Kinetics of the BrO + NO2 Association Reaction. Temperature and Pressure Dependence in the Falloff Regime

NASA Technical Reports Server (NTRS)

Thron, R. P.; Daykin, E. P.; Wine, P.H.

1997-01-01

A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reaction BrO + NO2 + M yields (k1) products as a function of temperature (248-346 K), pressure (16-800 torr), and buffer gas identity (N2,CF4) The reaction is found to be in the falloff regime between third and second-order over the entire range of conditions investigated This is the first study where temperature-dependent measurements of k1(P,T) have been reported at pressures greater than 12 torr; hence, our results help constrain choices of k1(P,T) for use in models of lower stratospheric BrO(x) chemistry. Approximate falloff parameters in a convenient form for atmospheric modeling are derived.

Constrained Photophysics of 5,7-dimethoxy-2,3,4,9-tetrahydro-1H-carbazol-1-one in the Bioenvironment of Serum Albumins: A Spectroscopic Endeavour Supported by Molecular Docking Analysis.

PubMed

Mitra, Amrit Krishna; Sau, Abhishek; Pal, Uttam; Saha, Chandan; Basu, Samita

2017-07-01

This paper vividly indicates that steady state as well as time-resolved fluorescence techniques can serve as highly sensitive monitors to explore the interactions of 5,7-dimethoxy-2,3,4,9-tetrahydro-1H-carbazol-1-one with model transport proteins, bovine serum albumin (BSA) and human serum albumin (HSA). Besides these, we have used fluorescence anisotropy study to assess the degree of restrictions imparted by the micro-environments of serum albumins. Again, to speculate the triplet excited state interaction between such fluorophore and albumin proteins (BSA& HSA), laser flash-photolysis experiments have been carried out. Molecular docking experiments have also been performed to support the conclusions obtained from steady state experiments.

Energy transfer mechanisms in photobiological reactions. Final report, 1 April 1960--31 March 1979. [Photodynamic processes in selected biomolecules

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

Spikes, J.D.

1979-03-31

This project was concerned primarily with studies of the mechanisms of the sensitized photooxidation of selected biomolecules using a variety of phtosensitizers. Such reactions are often termed photodynamic processes. In particular we have carried out steady-state kinetic studies, flash photolysis and spectral studies, and product formation studies of the sensitized photooxidation of the five susceptible amino acids (cycteine, histidine, methonine, tryptophan, and tyrosine) and their derivatives, as well as purines and pyrimidines. A number of studies were also carried out on the mechanisms of the photodynamic inactivation of enzymes (trypsin, ribonuclease, lysozyme). Mechanism of photosensitization were studied using a varietymore » of sensitizers including flavins, porphyrins, and a number of synthetic dyes (substituted fluoresceins, acridines, thyazines).« less

Benzophenone as a photoprobe of polymer films

NASA Astrophysics Data System (ADS)

Levin, Peter P.; Efremkin, Alexei F.; Khudyakov, Igor V.

2017-09-01

The review article is devoted to kinetics of fast reactions following photoexcitation of benzophenone in polymer films. We observed three processes by ns laser flash photolysis in elastomers: (i) decay of a triple state of benzophenone with hydrogen abstraction from polymer matrix, (ii) formation and decay of geminate radical pairs, (iii) cross-termination of the formed radicals in the polymer bulk. Application of external magnetic field (MF) of B = 0.2 T essentially affects recombination of geminate (G-) and a bimolecular recombination of free radicals, which escaped polymer cage (F-pairs). Theoretical calculation of MF effects on G- and F-pairs is in agreement with corresponding experimental data. Elongation of elastomer leads to an unexpected observation: recombination in the bulk becomes slower. An explanation of this phenomenon based on elastomer free volume Vf approach was suggested.

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

Devadoss, C.; Fessenden, R.W.

The transient that is produced in the quenching of triplet benzophenone by 1,4-diazabicyclo(2.2.2)octane (DABCO) has been examined by use of nano- and picosecond laser photolysis. The initial step in all solvents, both polar and nonpolar, is electron transfer to form a triplet contact ion pair. In nonpolar solvents, the ion pair remains in this form until it decays. For polar solvents, the spectra change somewhat over the first 100 ps showing that the solvation changes and the ion pair becomes solvent separated. The lifetime of the ion pair varies greatly with the solvent. In saturated hydrocarbons it is about 80more » ps. Nonpolar solvents with either {pi} electrons or a lone pair of electrons stabilize the ion pair on the nanosecond to microsecond time scale. A small amount of alcohol in benzene also stabilizes the ion pair by hydrogen bonding. A shift in the peak position with time toward the blue accompanies the formation of hydrogen bonds in this case.« less

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.

Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment

NASA Astrophysics Data System (ADS)

Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Lei, Yu; Wang, Jizhong; Chen, Tianhu

2017-05-01

Nitrous acid (HONO) is an important tropospheric pollutant and a major source of hydroxyl radical in the atmospheric gas phase. However, studies on the role of HONO in atmospheric aqueous phase chemistry processes are relatively few. The present work investigated the photochemical reaction of HONO with triclosan (TCS), which is an emerging contaminant, using a combination of laser flash photolysis spectrometry and gas chromatography mass spectrometry. With these techniques, the reaction pathway of HONO with TCS was proposed by directly monitoring the transient species and detecting the stable products. ·OH was generated from the photodissociation of the HONO aqueous solution and attacked TCS molecules on different sites to produce the TCS-OH adducts with a second-order rate constant of 1.11 × 109 L mol-1 s-1. The ·OH added a C atom adjacent to the ether bond in the aromatic ring of TCS and self-decayed when the ether bond broke. The intermediates generated from the addition of ·OH to the benzene ring of the TCS molecular structure were immediately nitrated by HONO, which played a key role in the formation process of nitrocompounds. An atmospheric model suggests that the aqueous oxidation of TCS by ·OH is a major reaction at high liquid water concentrations, and the photolysis of TCS dominates under low-humidity conditions.

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.

Effects of Deep Convection on Atmospheric Chemistry

NASA Technical Reports Server (NTRS)

Pickering, Kenneth E.

2007-01-01

This presentation will trace the important research developments of the last 20+ years in defining the roles of deep convection in tropospheric chemistry. The role of deep convection in vertically redistributing trace gases was first verified through field experiments conducted in 1985. The consequences of deep convection have been noted in many other field programs conducted in subsequent years. Modeling efforts predicted that deep convection occurring over polluted continental regions would cause downstream enhancements in photochemical ozone production in the middle and upper troposphere due to the vertical redistribution of ozone precursors. Particularly large post-convective enhancements of ozone production were estimated for convection occurring over regions of pollution from biomass burning and urban areas. These estimates were verified by measurements taken downstream of biomass burning regions of South America. Models also indicate that convective transport of pristine marine boundary layer air causes decreases in ozone production rates in the upper troposphere and that convective downdrafts bring ozone into the boundary layer where it can be destroyed more rapidly. Additional consequences of deep convection are perturbation of photolysis rates, effective wet scavenging of soluble species, nucleation of new particles in convective outflow, and the potential fix stratosphere-troposphere exchange in thunderstorm anvils. The remainder of the talk will focus on production of NO by lightning, its subsequent transport within convective clouds . and its effects on downwind ozone production. Recent applications of cloud/chemistry model simulations combined with anvil NO and lightning flash observations in estimating NO Introduction per flash will be described. These cloud-resolving case-study simulations of convective transport and lightning NO production in different environments have yielded results which are directly applicable to the design of lightning parameterizations for global chemical transport models. The range of mean values (factor of 3) of NO production per flash (or per meter of lightning channel length) that have been deduced from the model will be shown and compared with values of production in the literature that have been deduced using other methods, Results show that on a per flash basis, IC flashes are nearly as productive of NO as CG flashes. When combined with the global flash rate of 44 flashes per second from NASA's Optical Transient Detector (OTD) measurements, these estimates and the results from other techniques yield global NO production rates of 2-9 TgN/year. Vertical profiles of lightning NOx mass at the end of the 3-D storm simulations have been summarized to yield suggested profiles for use in global models. Simulations of the photochemistry over the 24 hours following a storm have been performed to determine the additional ozone production which can be attributed to lightning NO.

Measurement of nucleotide exchange rate constants in single rabbit soleus myofibrils during shortening and lengthening using a fluorescent ATP analog.

PubMed Central

Shirakawa, I; Chaen, S; Bagshaw, C R; Sugi, H

2000-01-01

The kinetics of displacement of a fluorescent nucleotide, 2'(3')-O-[N[2-[[Cy3]amido]ethyl]carbamoyl]-adenosine 5'-triphosphate (Cy3-EDA-ATP), bound to rabbit soleus muscle myofibrils were studied using flash photolysis of caged ATP. Use of myofibrils from this slow twitch muscle allowed better resolution of the kinetics of nucleotide exchange than previous studies with psoas muscle myofibrils (, Biophys. J. 73:2033-2042). Soleus myofibrils in the presence of Cy3-EDA-nucleotides (Cy3-EDA-ATP or Cy3-EDA-ADP) showed selective fluorescence staining of the A-band. The K(m) for Cy3-EDA-ATP and the K(d) for Cy3-EDA-ADP binding to the myofibril A-band were 1.9 microM and 3.8 microM, respectively, indicating stronger binding of nucleotide to soleus cross-bridges compared to psoas cross-bridges (2.6 microM and 50 microM, respectively). After flash photolysis of caged ATP, the A-band fluorescence of the myofibril in the Cy3-EDA-ATP solution under isometric conditions decayed exponentially with a rate constant of 0.045 +/- 0.007 s(-1) (n = 32) at 10 degrees C, which was about seven times slower than that for psoas myofibrils. When a myofibril was allowed to shorten with a constant velocity, the nucleotide displacement rate constant increased from 0.066 s(-1) (isometric) to 0.14 s(-1) at 20 degrees C with increasing shortening velocity up to 0.1 myofibril length/s (V(max), the shortening velocity under no load was approximately 0. 2 myofibril lengths/s). The rate constant was not significantly affected by an isovelocity stretch of up to 0.1 myofibril lengths/s. These results suggest that the cross-bridge kinetics are not significantly affected at higher strain during lengthening but depend on the lower strain during shortening. These data also indicate that the interaction distance between a cross-bridge and the actin filament is at least 16 nm for a single cycle of the ATPase. PMID:10653804

The reaction H + C4H2 - Absolute rate constant measurement and implication for atmospheric modeling of Titan

NASA Technical Reports Server (NTRS)

Nava, D. F.; Mitchell, M. B.; Stief, L. J.

1986-01-01

The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity (i.e., the initial H concentration). The rate constant, k, was found to be equal to 1.39 x 10 to the -10th exp (-1184/T) cu cm/s, with an error of one standard deviation. The Arrhenius parameters at the high pressure limit determined here for the H + C4H2 reaction are consistent with those for the corresponding reactions of H with C2H2 and C3H4. Implications of the kinetic carbon chemistry results, particularly those at low temperature, are considered for models of the atmospheric carbon chemistry of Titan. The rate of this reaction, relative to that of the analogous, but slower, reaction of H + C2H2, appears to make H + C4H2 a very feasible reaction pathway for effective conversion of H atoms to molecular hydrogen in the stratosphere of Titan.

Nano- and micro-structuring of fused silica using time-delay adjustable double flash ns-laser radiation

NASA Astrophysics Data System (ADS)

Lorenz, Pierre; Zhao, Xiongtao; Ehrhardt, Martin; Zagoranskiy, Igor; Zimmer, Klaus; Han, Bing

2018-02-01

Large area, high speed, nanopatterning of surfaces by laser ablation is challenging due to the required high accuracy of the optical and mechanical systems fulfilling the precision of nanopatterning process. Utilization of self-organization approaches can provide an alternative decoupling spot precision and field of machining. The laser-induced front side etching (LIFE) and laser-induced back side dry etching (LIBDE) of fused silica were studied using single and double flash nanosecond laser pulses with a wavelength of 532 nm where the time delay Δτ of the double flash laser pulses was adjusted from 50 ns to 10 μs. The fused silica can be etched at both processes assisted by a 10 nm chromium layer where the etching depth Δz at single flash laser pulses is linear to the laser fluence and independent on the number of laser pulses, from 2 to 12 J/cm2, it is Δz = δLIFE/LIBDE . Φ with δLIFE 16 nm/(J/cm2) and δLIBDE 5.2 nm/(J/cm2) 3 . δLIFE. At double flash laser pulses, the Δz is dependent on the time delay Δτ of the laser pulses and the Δz slightly increased at decreasing Δτ. Furthermore, the surface nanostructuring of fused silica using IPSM-LIFE (LIFE using in-situ pre-structured metal layer) method with a single double flash laser pulse was tested. The first pulse of the double flash results in a melting of the metal layer. The surface tension of the liquid metal layer tends in a droplet formation process and dewetting process, respectively. If the liquid phase life time ΔtLF is smaller than the droplet formation time the metal can be "frozen" in an intermediated state like metal bare structures. The second laser treatment results in a evaporation of the metal and in a partial evaporation and melting of the fused silica surface, where the resultant structures in the fused silica surface are dependent on the lateral geometry of the pre-structured metal layer. A successful IPSM-LIFE structuring could be achieved assisted by a 20 nm molybdenum layer at Δτ >= 174 ns. That path the way for the high speed ultra-fast nanostructuring of dielectric surfaces by self-organizing processes. The different surface structures were analyzed by scanning electron microscopy (SEM) and white light interferometry (WLI).

Flash Lamp Integrating Sphere Technique for Measuring the Dynamic Reflectance of Shocked Materials

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

Stevens, Gerald; La Lone, Brandon; Veeser, Lynn

2013-07-08

Accurate reflectance (R) measurements of metals undergoing shock wave compression can benefit high pressure research in several ways. For example, pressure dependent reflectance measurements can be used to deduce electronic band structure, and discrete changes with pressure or temperature may indicate the occurrence of a phase boundary. Additionally, knowledge of the wavelength dependent emissivity (1 -R, for opaque samples) of the metal surface is essential for accurate pyrometric temperature measurement because the radiance is a function of both the temperature and emissivity. We have developed a method for measuring dynamic reflectance in the visible and near IR spectral regions withmore » nanosecond response time and less than 1.5% uncertainty. The method utilizes an integrating sphere fitted with a xenon flash-lamp illumination source. Because of the integrating sphere, the measurements are insensitive to changes in surface curvature or tilt. The in-situ high brightness of the flash-lamp exceeds the sample’s thermal radiance and also enables the use of solid state detectors for recording the reflectance signals with minimal noise. Using the method, we have examined the dynamic reflectance of gallium and tin subjected to shock compression from high explosives. The results suggest significant reflectance changes across phase boundaries for both metals. We have also used the method to determine the spectral emissivity of shock compressed tin at the interface between tin and a LiF window. The results were used to perform emissivity corrections to previous pyrometry data and obtain shock temperatures of the tin/LiF interface with uncertainties of less than 2%.« less

Nanosecond time resolved x-ray diagnostics of relativistic electron beam initiated events

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

Kuswa, Glenn W.; Chang, James

The dynamic behavior of a test sample during aid shortly after it has teen irradiated by an intense relativistic electron beam (REB) is of great interest to the study of team energy deposition. Since the sample densities are far beyond the cutoff in the optical region, flash x-radiography techniques have been developed to diagnose the evolution of the samples. The conventional approach of analyzing the dynamic behavior of solid densities utilizes one or more short x-ray bursts to record images on photographic emulsion. This technique is not useful in the presence of the intense x-rays from the REB interacting withmore » the sample. We report two techniques for isolating the film package from the REB x-ray pulse.« less

Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

Excited-state redox properties of ruthenium(II) phthalocyanine from electron-transfer quenching

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

Prasad, D.R.; Ferraudi, G.

1982-09-30

Electron-transfer reactions between the lowest-lying triplet state, /sup 3/..pi pi../sup */, of ruthenium (phthalocyanine)(pyridine)/sub 2/ and various nitroaromatic compounds have been studied by laser and conventional flash photolysis. Quenching rate constants determined for the oxidation of the excited state have been treated according to the Marcus-Hush theory. A self-exchange rate constant K approx. 10/sup 7/ M/sup -1/ x/sup -1/ was determined for the self-exchange reaction between the /sup 3/..pi pi../sup */ and radical cation, Ru(ph)(py)/sub 2//sup +/. Such a value indicates that the major component to the Franck-Condon reorganizational energy is the outer-sphere contribution. The photochemical properties of the phthalocyaninesmore » are discussed in terms of the redox potentials estimate for various excited states.« less

Kinetics of the addition of olefins to Si-centered radicals: the critical role of dispersion interactions revealed by theory and experiment.

PubMed

Johnson, Erin R; Clarkin, Owen J; Dale, Stephen G; DiLabio, Gino A

2015-06-04

Solution-phase rate constants for the addition of selected olefins to the triethylsilyl and tris(trimethylsilyl)silyl radicals are measured using laser-flash photolysis and competition kinetics. The results are compared with predictions from density functional theory (DFT) calculations, both with and without dispersion corrections obtained from the exchange-hole dipole moment (XDM) model. Without a dispersion correction, the rate constants are consistently underestimated; the errors increase with system size, up to 10(6) s(-1) for the largest system considered. Dispersion interactions preferentially stabilize the transition states relative to the separated reactants and bring the DFT-calculated rate constants into excellent agreement with experiment. Thus, dispersion interactions are found to play a key role in determining the kinetics for addition reactions, particularly those involving sterically bulky functional groups.

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

NASA Technical Reports Server (NTRS)

Margitan, J. J.

1984-01-01

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

DOE R&D Accomplishments Database

Curl, R. F.; Glass, G. P.

1995-06-01

This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

Photosynthetic antenna-reaction center mimicry with a covalently linked monostyryl boron-dipyrromethene-aza-boron-dipyrromethene-C60 triad.

PubMed

Shi, Wen-Jing; El-Khouly, Mohamed E; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K P

2013-08-19

An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP-ADP and ADP-C60 , and the triad BDP-ADP-C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid time-resolved diffraction studies of protein structures using synchrotron radiation

NASA Astrophysics Data System (ADS)

Bartunik, Hans D.; Bartunik, Lesley J.

1992-07-01

The crystal structure of intermediate states in biological reactions of proteins of multi-protein complexes may be studied by time-resolved X-ray diffraction techniques which make use of the high spectral brilliance, continuous wavelength distribution and pulsed time structure of synchrotron radiation. Laue diffraction methods provide a means of investigating intermediate structures with lifetimes in the millisecond time range at presently operational facilities. Third-generation storage rings which are under construction may permit one to reach a time resolution of one microsecond for non-cyclic and one nanosecond for cyclic reactions. The number of individual exposures required for exploring reciprocal space and hence the total time scale strongly depend on the lattice order that may be affected, e.g., by conformational changes. Time-resolved experiments require high population of a specific intermediate which has to be homogeneous over the crystal volume. A number of external excitation techniques have been developed including in situ liberation of active metabolites by laser pulse photolysis of photolabile inactive precursors. First applications to crystal structure analysis of catalytic intermediates of enzymes demonstrate the potential of time-resolved protein crystallography.

Thermochemistry and Kinetics of the Cl+O2 Association Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).

Kinetics of the Reaction of O((sup 3)P) with CF3NO

NASA Technical Reports Server (NTRS)

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

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of O((sup 3)P) with CF3NO (k(2)) as a function of temperature. Our results are described by the Arrhenius expression k(2)(T) = (4.54 +/- 0.70) x 10(exp -l2)exp[(-560 +/- 46)/T] cu cm/molecule.s (243 K is less than or equal to T is less than or equal to 424 K); errors are 2 sigma and represent precision only. The O((sup 3)P) + CF3NO reaction is sufficiently rapid that CF3NO cannot be employed as a selective quencher for O2(alpha(1) Delta-g) in laboratory systems where O((sup 3)P) and O2(alpha 1 Delta g) coexist, and where O((sup 3)P) kinetics are being investigated.

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

NASA Technical Reports Server (NTRS)

Friedl, Randall R.; Sander, Stanley P.

1988-01-01

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire.

PubMed

Morisaki, Yasuhiro; Ueno, Shizue; Saeki, Akinori; Asano, Atsushi; Seki, Shu; Chujo, Yoshiki

2012-04-02

[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dictating photoreactivity through restricted bond rotations: cross-photoaddition of atropisomeric acrylimide derivatives under UV/visible-light irradiation.

PubMed

Iyer, Akila; Jockusch, Steffen; Sivaguru, J

2014-11-13

Nonbiaryl atropisomeric acrylimides underwent facile [2 + 2] photocycloaddition leading to cross-cyclobutane adducts with very high stereospecificity (enantiomeric excess (ee): 99% and diastereomeric excess (de): 99%). The photoreactions proceeded smoothly in isotropic media for both direct and triplet sensitized irradiations. The reactions were also found to be very efficient in the solid state where the same cross-cyclobutane adduct was observed. Photophysical studies enabled us to understand the excited-state photochemistry of acrylimides. The triplet energy was found to be ∼63 kcal/mol. The reactions proceeded predominantly via a singlet excited state upon direct irradiation with very poor intersystem crossing that was ascertained by quantification of the generated singlet oxygen. The reactions progressed smoothly with triplet sensitization with UV or visible-light irradiations. Laser flash photolysis experiments established the triplet transient of atropisomeric acrylimides with a triplet lifetime at room temperature of ∼40 ns.

Structural and electronic properties of extremely long perylene bisimide nanofibers formed through a stoichiometrically mismatched, hydrogen-bonded complexation.

PubMed

Yagai, Shiki; Seki, Tomohiro; Murayama, Haruno; Wakikawa, Yusuke; Ikoma, Tadaaki; Kikkawa, Yoshihiro; Karatsu, Takashi; Kitamura, Akihide; Honsho, Yoshihito; Seki, Shu

2010-12-06

Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks; they co-aggregate in an unexpected stoichiometrically mismatched 1:2 ratio. Various microscopic and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers. The photocarrier generation mechanism in the nanofibers is investigated by time-of-flight (TOF) experiments under electric and magnetic fields, revealing the birth and efficient recombination of singlet geminate electron-hole pairs. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed intrinsic 1D electron mobilities up to 0.6 cm(2) V(-1) s(-1) within nanofibers.

Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

NASA Technical Reports Server (NTRS)

Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

1986-01-01

The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

Femtosecond Laser Microfabrication of an Integrated Device for Optical Release and Sensing of Bioactive Compounds.

PubMed

Ghezzi, Diego; Vazquez, Rebeca Martinez; Osellame, Roberto; Valtorta, Flavia; Pedrocchi, Alessandra; Valle, Giuseppe Della; Ramponi, Roberta; Ferrigno, Giancarlo; Cerullo, Giulio

2008-10-23

Flash photolysis of caged compounds is one of the most powerful approaches to investigate the dynamic response of living cells. Monolithically integrated devices suitable for optical uncaging are in great demand since they greatly simplify the experiments and allow their automation. Here we demonstrate the fabrication of an integrated bio-photonic device for the optical release of caged compounds. Such a device is fabricated using femtosecond laser micromachining of a glass substrate. More in detail, femtosecond lasers are used both to cut the substrate in order to create a pit for cell growth and to inscribe optical waveguides for spatially selective uncaging of the compounds present in the culture medium. The operation of this monolithic bio-photonic device is tested using both free and caged fluorescent compounds to probe its capability of multipoint release and optical sensing. Application of this device to the study of neuronal network activity can be envisaged.

Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D-Printing of Tough Photopolymers without Retardation.

PubMed

Seidler, Konstanze; Griesser, Markus; Kury, Markus; Reghunathan, Harikrishna; Dorfinger, Peter; Koch, Thomas; Svirkova, Anastasiya; Marchetti-Deschmann, Martina; Stampfl, Jürgen; Moszner, Norbert; Gorsche, Christian; Liska, Robert

2018-05-04

Photoinitiated radical polymer network formation is lacking freedom for tailored network design. Resulting inhomogeneous network architectures and brittle material behavior of such glassy-type networks limit the commercial application of photopolymers in 3D printing, biomedicine or microelectronics. An ester-activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate-based networks with nearly no retardation, reduced shrinkage stress, high monomer conversion and improved material toughness. Laser flash photolysis followed by theoretical calculations and photoreactor studies elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit high tensile strength, improved elongation at break and high impact resistance, while maintaining high modulus and hardness at ambient conditions. These findings make EVS an exceptional candidate for the 3D printing of tough photopolymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triplet excited state spectra and dynamics of carotenoids from the thermophilic purple photosynthetic bacterium Thermochromatium tepidum

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

Niedzwiedzki, Dariusz; Kobayashi, Masayuki; Blankenship, R. E.

Light-harvesting complex 2 from the anoxygenic phototrophic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption, fluorescence and flash photolysis spectroscopy. Steady-state absorption and fluorescence measurements show that carotenoids play a negligible role as supportive energy donors and transfer excitation to bacteriochlorophyll-a with low energy transfer efficiency of ~30%. HPLC analysis determined that the dominant carotenoids in the complex are rhodopin and spirilloxanthin. Carotenoid excited triplet state formation upon direct (carotenoid) or indirect (bacteriochlorophyll-a Q{sub x} band) excitation shows that carotenoid triplets are mostly localized on spirilloxanthin. In addition, no triplet excitation transfer between carotenoids was observed. Suchmore » specific carotenoid composition and spectroscopic results strongly suggest that this organism optimized carotenoid composition in the light-harvesting complex 2 in order to maximize photoprotective capabilities of carotenoids but subsequently drastically suppressed their supporting role in light-harvesting process.« less

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

Direct Determination of the Rate Coefficient for the Reaction of OH Radicals with Monoethanol Amine (MEA) from 296 to 510 K.

PubMed

Onel, L; Blitz, M A; Seakins, P W

2012-04-05

Monoethanol amine (H2NCH2CH2OH, MEA) has been proposed for large-scale use in carbon capture and storage. We present the first absolute, temperature-dependent determination of the rate coefficient for the reaction of OH with MEA using laser flash photolysis for OH generation, monitoring OH removal by laser-induced fluorescence. The room-temperature rate coefficient is determined to be (7.61 ± 0.76) × 10(-11) cm(3) molecule(-1) s(-1), and the rate coefficient decreases by about 40% by 510 K. The temperature dependence of the rate coefficient is given by k1= (7.73 ± 0.24) × 10(-11)(T/295)(-(0.79±0.11)) cm(3) molecule(-1) s(-1). The high rate coefficient shows that gas-phase processing in the atmosphere will be competitive with uptake onto aerosols.

New core-pyrene π structure organophotocatalysts usable as highly efficient photoinitiators

PubMed Central

Telitel, Sofia; Dumur, Frédéric; Faury, Thomas; Graff, Bernadette; Tehfe, Mohamad-Ali; Fouassier, Jean-Pierre

2013-01-01

Summary Eleven di- and trifunctional compounds based on a core-pyrene π structure (Co_Py) were synthesized and investigated for the formation of free radicals. The application of two- and three-component photoinitiating systems (different Co_Pys with the addition of iodonium or sulfonium salts, alkyl halide or amine) was investigated in detail for cationic and radical photopolymerization reactions under near-UV–vis light. The proposed compounds can behave as new photocatalysts. Successful results in terms of rates of polymerization and final conversions were obtained. The strong MO coupling between the six different cores and the pyrene moiety was studied by DFT calculations. The different chemical intermediates are characterized by ESR and laser flash photolysis experiments. The mechanisms involved in the initiation step are discussed, and relationships between the core structure, the Co_Py absorption property, and the polymerization ability are tentatively proposed. PMID:23766803

Rate theories and puzzles of hemeprotein kinetics.

PubMed

Frauenfelder, H; Wolynes, P G

1985-07-26

The binding of dioxygen and carbon monoxide to heme proteins such as myoglobin and hemoglobin has been studied with flash photolysis. At temperatures below 200 K, binding occurs from within the heme pocket and, contrary to expectation, with nearly equal rates for both ligands. This observation has led to a reexamination of the theory of the association reaction taking into account friction, protein structure, and the nature of electronic transitions. The rate coefficients for the limiting cases of large and small friction are found with simple arguments that use characteristic lengths and times. The arguments indicate how transition state theory as well as calculations based on nonadiabatic perturbation theory, which is called the Golden Rule, may fail. For ligand-binding reactions the data suggest the existence of intermediate states not directly observed so far. The general considerations may also apply to other biomolecular processes such as electron transport.

A triggered mechanism retrieves membrane in seconds after Ca(2+)- stimulated exocytosis in single pituitary cells

PubMed Central

1994-01-01

In neuroendocrine cells, cytosolic Ca2+ triggers exocytosis in tens of milliseconds, yet known pathways of endocytic membrane retrieval take minutes. To test for faster retrieval mechanisms, we have triggered short bursts of exocytosis by flash photolysis of caged Ca2+, and have tracked subsequent retrieval by measuring the plasma membrane capacitance. We find that a limited amount of membrane can be retrieved with a time constant of 4 s at 21-26 degrees C, and that this occurs partially via structures larger than coated vesicles. This novel mechanism may be arrested at a late step. Incomplete retrieval structures then remain on the cell surface for minutes until the consequences of a renewed increase in cytosolic [Ca2+] disconnect them from the cell surface in < 1 s. Our results provide evidence for a rapid, triggered membrane retrieval pathway in excitable cells. PMID:8120090

CIDEP study on the flash photolysis of benzoin included in β-cyclodextrin

NASA Astrophysics Data System (ADS)

Kitahama, Yasutaka; Murai, Hisao

1996-10-01

The photodissociation reaction of benzoin (Norrish type I) included in a β-cyclodextrin (CD) cavity in the aqueous phase was studied by using time-resolved ESR and Fourier transform ESR methods. The CIDEP (chemically induced dynamic electron polarization) spectra of α-hydroxybenzyl radical and benzoyl radical were carefully investigated in β-CD, in ethanol, in an ethanol/water mixture, and in saturated aqueous solutions. According to these data and the calculations due to an extended Bloch equation, the spin-lattice relaxation time observed in the β-CD system was compared to those in homogeneous solutions. It is concluded that dissociation takes place from the excited triplet state of benzoin and the fragment radicals are easily ejected from the cavity of β-CD to the aqueous phase much faster than the time-resolution (˜ 20 ns) of the present FT-ESR measurement.

Elucidation of the Key Role of [Ru(bpy)3 ](2+) in Photocatalyzed RAFT Polymerization.

PubMed

Christmann, Julien; Ibrahim, Ahmad; Charlot, Vincent; Croutxé-Barghorn, Céline; Ley, Christian; Allonas, Xavier

2016-08-04

Photocatalysis reactions using [Ru(II) (bpy)3 ](2+) were studied on the example of visible-light-sensitized reversible addition-fragmentation chain transfer (RAFT) polymerization. Although both photoinduced electron- and energy-transfer mechanisms are able to describe this interaction, no definitive experimental proof has been presented so far. This paper investigates the actual mechanism governing this reaction. A set of RAFT agents was selected, their redox potentials measured by cyclic voltammetry, and relaxed triplet energies calculated by quantum mechanics. Gibbs free-energy values were calculated for both electron- and energy-transfer mechanisms. Quenching rate constants were determined by laser flash photolysis. The results undoubtedly evidence the involvement of a photoinduced energy-transfer reaction. Controlled photopolymerization experiments are discussed in the light of the primary photochemical process and photodissociation ability of RAFT agent triplet states. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

PubMed

Wentrup, Curt

2017-03-08

Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N 2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N 2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

Factorization of the association rate coefficient in ligand rebinding to heme proteins

NASA Astrophysics Data System (ADS)

Young, Robert D.

1984-01-01

A stochastic theory of ligand migration in biomolecules is used to analyze the recombination of small ligands to heme proteins after flash photolysis. The stochastic theory is based on a generalized sequential barrier model in which a ligand binds by overcoming a series of barriers formed by the solvent protein interface, the protein matrix, and the heme distal histidine system. The stochastic theory shows that the association rate coefficient λon factorizes into three terms λon =γ12Nout, where γ12 is the rate coefficient from the heme pocket to the heme binding site, is the equilibrium pocket occupation factor, and Nout is the fraction of heme proteins which do not undergo geminate recombination of a flashed-off ligand. The factorization of λon holds for any number of barriers and with no assumptions regarding the various rate coefficients so long as the exponential solvent process occurs. Transitions of a single ligand are allowed between any two sites with two crucial exceptions: (i) the heme binding site acts as a trap so that thermal dissociation of a bound ligand does not occur within the time of the measurement; (ii) the final step in the rebinding process always has a ligand in the heme pocket from where the ligand binds to the heme iron.

Measurements of free radicals in a megacity during the Clean Air for London Project

NASA Astrophysics Data System (ADS)

Heard, Dwayne; Whalley, Lisa; Stone, Daniel; Clancy, Noel; Lee, James; Kleffman, Jorg; Laufs, Sebastian; Bandy, Brian

2013-04-01

Free radicals control the photo-oxidative chemistry of the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3, multifunctional species and particulates. Here we present measurements of OH, HO2 and RO2 radicals and OH reactivity recorded at North Kensington, Central London, during two Intensive Operational Periods (IOPs) of the Clear Air for London (Clearflo) project in the summer and winter of 2012. OH and HO2 were measured using laser-induced fluorescence (LIF) spectroscopy at low pressure (the FAGE technique), and RO2 was measured using the recently developed ROXLIF technique, which utilises an external flow-reactor interfaced to FAGE, and which is able to discriminate between HO2 and organic peroxy radicals. Through control of reagent gases we are further able to provide a separate measurement of those RO2 species which are known to give an interference for HO2 measurements (namely alkene, aromatic and large-chain alkane derived RO2). OH reactivity was measured using laser-flash photolysis combined with FAGE. Low concentrations of radicals were observed during the winter IOP, with mixing ratios of [OH] ~ 0.04 pptv, [HO2] ~ 0.4 pptv, and [RO2] ~ 1.6 pptv at noon, all displaying a negative correlation with NO. The photolysis of O3 and subsequent reaction of O(1D) with H2O vapour was only a minor contribution to radical production in winter, with photolysis of HONO a major radical source. The summer IOP coincided with the London Olympic Games, with a number of pollution events, with ozone peaking at 100 ppbv (exceeding EU air quality directives) and elevated radical concentrations (peak [OH] ~ 0.14 pptv, [HO2] ~ 4 pptv, [RO2] ~ 6.4 pptv) being observed. The net rate of ozone production was calculated from radical observations and agreed well with measured ozone production, suggesting that advection/dilution by continental air-masses was not playing a significant role in determining ozone concentrations in London at that time. The ability to partially speciate RO2 enabled the contribution towards ozone production from different types of parent VOCs to be assessed. Steady-state analyses, using OH reactivity measurements to constrain the rate of loss of OH, gave reasonable agreement for [OH] but an additional HO2 sink was required to match [HO2]. The photolysis of HONO and carbonyl species and the decomposition of PAN were the dominant sources of radicals in London in summer.

Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

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

Maulois, Melissa, E-mail: melissa.maulois@laplace.univ-tlse.fr; LAPLACE, 118 Route de Narbonne, 31 062 Toulouse Cedex; CEA/DAM, 46 500 Gramat

2016-04-15

The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N{sub 2} and 20% O{sub 2}) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electronmore » beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 10{sup 13 }cm{sup −3} is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the flash application, the electrons are thermalized and their concentration has decreased from about 10{sup 13 }cm{sup −3} down to about 10{sup 12 }cm{sup −3} leaving positive and negative ionised species and atomic radicals whose recombination characteristic times are much longer.« less

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 states converting the benzazirines to ketenimines were performed. The computational results are in good qualitative and quantitative agreement with the experimental findings.

Subunit dissociation in fish hemoglobins.

PubMed

Edelstein, S J; McEwen, B; Gibson, Q H

1976-12-10

The tetramer-dimer dissociation equilibria (K 4,2) of several fish hemoglobins have been examined by sedimentation velocity measurements with a scanner-computer system for the ultracentrifuge and by flash photolysis measurements using rapid kinetic methods. Samples studied in detail included hemoglobins from a marine teleost, Brevoortia tyrannus (common name, menhaden); a fresh water teleost, Cyprinus carpio, (common name, carp); and an elasmobranch Prionace glauca (common name, blue shark). For all three species in the CO form at pH 7, in 0.1 M phosphate buffer, sedimentation coefficients of 4.3 S (typical of tetrameric hemoglobin) are observed in the micromolar concentration range. In contrast, mammalian hemoglobins dissociate appreciably to dimers under these conditions. The inability to detect dissociation in three fish hemoglobins at the lowest concentrations examined indicates that K 4,2 must have a value of 10(-8) M or less. In flash photolysis experiments on very dilute solutions in long path length cells, two kinetic components were detected with their proportions varying as expected for an equilibrium between tetramers (the slower component) and dimers (the faster component); values of K 4,2 for the three fish hemoglobins in the range 10(-9) to 10(-8) M were calculated from these data. Thus, the values of K 4,2 for liganded forms of the fish hemoglobins appear to be midway between the value for liganded human hemoglobin (K 4,2 approximately 10(-6) M) and unliganded human hemoglobin (K 4,2 approximately 10(-12) M). This conclusion is supported by measurements on solutions containing guanidine hydrochloride to enhance the degree of dissociation. All three fish hemoglobins are appreciably dissociated at guanidine concentrations of about 0.8 M, which is roughly midway between the guanidine concentrations needed to cause comparable dissociation of liganded human hemoglobin (about 0.4 M) and unliganded human hemoglobin (about 1.6 M). Kinetic measurements on solutions containing guanidine hydrochloride indicated that there are changes in both the absolute rates and the proportions of the fast and slow components, which along with other factors complicated the analysis of the data in terms of dissociation constants. Measurements were also made in solutions containing urea to promote dissociation, but with this agent very high concentrations (about 6 M) were required to give measureable dissociation and the fish hemoglobins were unstable under these conditions, with appreciable loss of absorbance spectra in both the sedimentation and kinetic experiments.

Probing the Time Scale of FPOP (Fast Photochemical Oxidation of Proteins): Radical Reactions Extend Over Tens of Milliseconds

NASA Astrophysics Data System (ADS)

Vahidi, Siavash; Konermann, Lars

2016-07-01

Hydroxyl radical (ṡOH) labeling with mass spectrometry detection reports on protein conformations and interactions. Fast photochemical oxidation of proteins (FPOP) involves ṡOH production via H2O2 photolysis by UV laser pulses inside a flow tube. The experiments are conducted in the presence of a scavenger (usually glutamine) that shortens the ṡOH lifetime. The literature claims that FPOP takes place within 1 μs. This ultrafast time scale implies that FPOP should be immune to labeling-induced artifacts that may be encountered with other techniques. Surprisingly, the FPOP time scale has never been validated in direct kinetic measurements. Here we employ flash photolysis for probing oxidation processes under typical FPOP conditions. Bleaching of the reporter dye cyanine-5 (Cy5) served as readout of the time-dependent radical milieu. Surprisingly, Cy5 oxidation extends over tens of milliseconds. This time range is four orders of magnitude longer than expected from the FPOP literature. We demonstrate that the glutamine scavenger generates metastable secondary radicals in the FPOP solution, and that these radicals lengthen the time frame of Cy5 oxidation. Cy5 and similar dyes are widely used for monitoring the radical dose experienced by proteins in solution. The measured Cy5 kinetics thus strongly suggest that protein oxidation in FPOP extends over a much longer time window than previously thought (i.e., many milliseconds instead of one microsecond). The optical approach developed here should be suitable for assessing the performance of future FPOP-like techniques with improved temporal labeling characteristics.

Atmospheric Removal of Very Long-lived Greenhouse Gases in the Mesosphere

NASA Astrophysics Data System (ADS)

Totterdill, A.; Kovacs, T.; Gomez Martin, J.; FENG, W.; Chipperfield, M.; Plane, J. M.

2013-12-01

Chlorofluorocarbons are known to have serious ozone depleting and global warming potentials. Perfluorinated compounds such as SF6, NF3, SF5CF3 and CF3CF2Cl which have very long lifetimes (ranging from a few centuries to over 3000 years) are too stable to affect stratospheric ozone but do have among the highest per molecule radiative forcing of any greenhouse pollutant, making them extremely potent greenhouse gases. Due to the stability of these gases in the lower atmosphere, mesospheric loss processes could significantly reduce their estimated atmospheric lifetimes and hence, overall climate impact. Potential sinks include reactions with metals and energetic particles such as electrons or short wavelength photons already present in the upper atmosphere. The metals, in this instance iron, sodium or potassium, are produced by meteoric ablation, while background and energetic electrons have the continuous source of photoionization and auroral precipitation, respectively. In this study we investigate the removal potentials of four very long lived gases (SF6, NF3, SF5CF3 and CF3CF2Cl). First, by four metals (Fe, Mg, Na and K), where rate coefficients are measured using the Fast Flow Tube and Pulsed Laser Flash Photolysis / Laser Induced Fluorescence techniques. Second, removal by electron attachment was investigated using a quadrupole mass spectrometer. measurements. Third, Lyman-alpha (121.56 nm) photolysis was measured in a VUV absorption cell. The resulting removal rate coefficients are currently being input into the Whole Atmosphere Community Climate Model (WACCM) to obtain lifetime measurements for these species.

Controlled On-chip Stimulation of Quantal Catecholamine Release from Chromaffin Cells Using Photolysis of Caged Ca2+ on Transparent Indium-Tin-Oxide Microchip Electrodes

PubMed Central

Chen, Xiaohui; Gao, Yuanfang; Hossain, Maruf; Gangopadhyay, Shubhra; Gillis, Kevin D.

2008-01-01

Photorelease of caged Ca2+ is a uniquely powerful tool to study the dynamics of Ca2+-triggered exocytosis from individual cells. Using photolithography and other microfabrication techniques, we have developed transparent microchip devices to enable photorelease of caged Ca2+ together with electrochemical detection of quantal catecholamine secretion from individual cells or cell arrays as a step towards developing high-throughput experimental devices. A 100 nm - thick transparent Indium-Tin-Oxide (ITO) film was sputter-deposited onto glass coverslips, which were then patterned into 24 cell-sized working electrodes (∼20 μm by 20 μm). We loaded bovine chromaffin cells with acetoxymethyl (AM) ester derivatives of the Ca2+ cage NP-EGTA and Ca2+ indicator dye Fura-4F, then transferred these cells onto the working ITO electrodes for amperometric recordings. Upon flash photorelease of caged Ca2+, a uniform rise of [Ca2+]i within the target cell leads to quantal release of oxidizable catecholamines measured amperometrically by the underlying ITO electrode. We observed a burst of amperometric spikes upon rapid elevation of [Ca2+]i and a “priming” effect of sub-stimulatory [Ca2+]i on the response of cells to subsequent [Ca2+]i elevation, similar to previous reports using different techniques. We conclude that UV photolysis of caged Ca2+ is a suitable stimulation technique for higher-throughput studies of Ca2+-dependent exocytosis on transparent electrochemical microelectrode arrays. PMID:18094774

Exploring Renner-Teller induced quenching in the reaction H(2S)+NH(a 1Delta): a combined experimental and theoretical study.

PubMed

Adam, L; Hack, W; McBane, G C; Zhu, H; Qu, Z-W; Schinke, R

2007-01-21

Experimental rate coefficients for the removal of NH(a (1)Delta) and ND(a (1)Delta) in collisions with H and D atoms are presented; all four isotope combinations are considered: NH+H, NH+D, ND+H, and ND+D. The experiments were performed in a quasistatic laser-flash photolysis/laser-induced fluorescence system at low pressures. NH(a (1)Delta) and ND(a (1)Delta) were generated by photolysis of HN(3) and DN(3), respectively. The total removal rate coefficients at room temperature are in the range of (3-5)x10(13) cm(3) mol(-1) s(-1). For two isotope combinations, NH+H and NH+D, quenching rate coefficients for the production of NH(X (3)Sigma(-)) or ND(X (3)Sigma(-)) were also determined; they are in the range of 1 x 10(13) cm(3) mol(-1) s(-1). The quenching rate coefficients directly reflect the strength of the Renner-Teller coupling between the (2)A(") and (2)A(') electronic states near linearity and so can be used to test theoretical models for describing this nonadiabatic process. The title reaction was modeled with a simple surface-hopping approach including a single parameter, which was adjusted to reproduce the quenching rate for NH+H; the same parameter value was used for all isotope combinations. The agreement with the measured total removal rate is good for all but one isotope combination. However, the quenching rates for the NH+D combination are only in fair (factor of 2) agreement with the corresponding measured data.

Camera Concepts for the Advanced Gamma-Ray Imaging System (AGIS)

NASA Astrophysics Data System (ADS)

Nepomuk Otte, Adam

2009-05-01

The Advanced Gamma-Ray Imaging System (AGIS) is a concept for the next generation observatory in ground-based very high energy gamma-ray astronomy. Design goals are ten times better sensitivity, higher angular resolution, and a lower energy threshold than existing Cherenkov telescopes. Each telescope is equipped with a camera that detects and records the Cherenkov-light flashes from air showers. The camera is comprised of a pixelated focal plane of blue sensitive and fast (nanosecond) photon detectors that detect the photon signal and convert it into an electrical one. The incorporation of trigger electronics and signal digitization into the camera are under study. Given the size of AGIS, the camera must be reliable, robust, and cost effective. We are investigating several directions that include innovative technologies such as Geiger-mode avalanche-photodiodes as a possible detector and switched capacitor arrays for the digitization.

Photodetectors for the Advanced Gamma-ray Imaging System (AGIS)

NASA Astrophysics Data System (ADS)

Wagner, Robert G.; Advanced Gamma-ray Imaging System AGIS Collaboration

2010-03-01

The Advanced Gamma-Ray Imaging System (AGIS) is a concept for the next generation very high energy gamma-ray observatory. Design goals include an order of magnitude better sensitivity, better angular resolution, and a lower energy threshold than existing Cherenkov telescopes. Each telescope is equipped with a camera that detects and records the Cherenkov-light flashes from air showers. The camera is comprised of a pixelated focal plane of blue sensitive and fast (nanosecond) photon detectors that detect the photon signal and convert it into an electrical one. Given the scale of AGIS, the camera must be reliable and cost effective. The Schwarzschild-Couder optical design yields a smaller plate scale than present-day Cherenkov telescopes, enabling the use of more compact, multi-pixel devices, including multianode photomultipliers or Geiger avalanche photodiodes. We present the conceptual design of the focal plane for the camera and results from testing candidate! focal plane sensors.

Photolysis of Diazo Dye in Aqueous Solutions of Metal Nitrates

NASA Astrophysics Data System (ADS)

Volkova, N. A.; Evstrop'ev, S. K.; Istomina, O. V.; Kolobkova, E. V.

2018-04-01

The photolysis of Chicago Blue Sky diazo dye is studied. It is experimentally shown that the presence of metal nitrates in aqueous solutions changes the photolysis mechanism and sharply increases the photolysis rate.

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.

Absolute rate constants for O + NO + M /= He, Ne, Ar, Kr/ yields NO2 + M from 217-500 K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Payne, W. A.; Whytock, D. A.

1976-01-01

Rate constants for the reaction O + NO + M yields NO2 + M have been obtained at temperatures from 217-500 K in four different rare gases by a method combining flash photolysis with time resolved detection of O(3-P) by resonance fluorescence. The measured rate constants in Arrhenius form are (10.8 plus or minus 1.2) x 10 to the -33rd exp(1040 plus or minus 60/1.987 T) for helium; (9.01 plus or minus 1.16) x 10 to the -33rd exp(1180 plus or minus 70/1.987 T) for argon; (9.33 plus or minus 1.10) x 10 to the -33rd exp(1030 plus or minus 60/1.987 T) for neon; and (9.52 plus or minus 1.10) x 10 to the -33rd exp(1140 plus or minus 70/1.987 T) for krypton in units of cm to the 6th/sq molecule/s.

Electron-transfer quenching vs. exciplex-mediated quenching of the low-lying excited states in phthalocyanines

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

Prasad, D.R.; Ferraudi, G.

1983-05-25

Oxidative electron-transfer quenching of the lowest ligand-centered /sup 3/..pi pi..* of ruthenium (RU) phthalocyanines (pc)L/sub 2/, L = dimethylformamide (dmf) or pyridine (py), by a series of nitroaromatic compounds, viologen salts, and metal complexes has been investigated by laser and conventional flash photolysis. The quenching rate constants, treated according to Marcus-Hush and Rehm-Weller equations, gave self-exchange rate constants, k/sub exch/ approx. 10/sup 7/ M/sup -1/ s/sup -1/, for the electron exchange between the /sup 3/..pi pi..* and the ruthenium(II) ligand radical. The excited states of a number of phthalocyanines, e.g. Ru(pc)(dimethyl sulfoxide(Me/sub 2/SO)/sub 2/), Ru(pc)(dmf)CO, Ru(pc)(py)CO, and Rh(pc)(methanol(CH/sub 3/OH)chloride), undergomore » quenching mediated by exciplex formation. The formation of exciplexes is discussed in terms of the related exciplexes of the porphyrins.« less

Use of side-chain incompatibility for tailoring long-range p/n heterojunctions: photoconductive nanofibers formed by self-assembly of an amphiphilic donor-acceptor dyad consisting of oligothiophene and perylenediimide.

PubMed

Li, Wei-Shi; Saeki, Akinori; Yamamoto, Yohei; Fukushima, Takanori; Seki, Shu; Ishii, Noriyuki; Kato, Kenichi; Takata, Masaki; Aida, Takuzo

2010-07-05

To tailor organic p/n heterojunctions with molecular-level precision, a rational design strategy using side-chain incompatibility of a covalently connected donor-acceptor (D-A) dyad has been successfully carried out. An oligothiophene-perylenediimide dyad, when modified with triethylene glycol side chains at one terminus and dodecyl side chains at the other (2(Amphi)), self-assembles into nanofibers with a long-range D/A heterojunction. In contrast, when the dyad is modified with dodecyl side chains at both termini (2(Lipo)), ill-defined microfibers result. In steady-state measurements using microgap electrodes, a cast film of the nanofiber of 2(Amphi) displays far better photoconducting properties than that of the microfiber of 2(Lipo). Flash-photolysis time-resolved microwave conductivity measurements, in conjunction with transient absorption spectroscopy, clearly indicate that the nanofiber of 2(Amphi) intrinsically allows for better carrier generation and transport properties than the microfibrous assembly of 2(Lipo).

Femtosecond Laser Microfabrication of an Integrated Device for Optical Release and Sensing of Bioactive Compounds

PubMed Central

Ghezzi, Diego; Vazquez, Rebeca Martinez; Osellame, Roberto; Valtorta, Flavia; Pedrocchi, Alessandra; Valle, Giuseppe Della; Ramponi, Roberta; Ferrigno, Giancarlo; Cerullo, Giulio

2008-01-01

Flash photolysis of caged compounds is one of the most powerful approaches to investigate the dynamic response of living cells. Monolithically integrated devices suitable for optical uncaging are in great demand since they greatly simplify the experiments and allow their automation. Here we demonstrate the fabrication of an integrated bio-photonic device for the optical release of caged compounds. Such a device is fabricated using femtosecond laser micromachining of a glass substrate. More in detail, femtosecond lasers are used both to cut the substrate in order to create a pit for cell growth and to inscribe optical waveguides for spatially selective uncaging of the compounds present in the culture medium. The operation of this monolithic bio-photonic device is tested using both free and caged fluorescent compounds to probe its capability of multipoint release and optical sensing. Application of this device to the study of neuronal network activity can be envisaged. PMID:27873888

The interaction of the excited states of safranine-O with low generation carboxyl terminated PAMAM dendrimers in an aqueous medium.

PubMed

Militello, M Paula; Altamirano, Marcela S; Bertolotti, Sonia G; Previtali, Carlos M

2018-05-16

The interaction of the singlet and triplet excited states of the synthetic dye safranine-O with carboxyl-terminated poly(amidoamine) (PAMAM) dendrimers was investigated in a buffer solution at pH 8. Low half-generation PAMAM dendrimers (G -0.5; G +0.5: G 1.5) were employed. The UV-vis absorption spectrum of the dye presents only a very small red shift in the presence of dendrimers. Fluorescence quenching was detected and it was interpreted by a static mechanism in terms of the association of the dye with the dendrimer. Laser flash photolysis experiments were carried out and transient absorption spectra of the triplet and radicals were obtained. The triplet state is quenched by the dendrimers with rate constants well below the diffusional limit. The quenching process was characterized as an electron transfer process and the quantum yield of radicals was estimated. It was found that radicals are formed with a high efficiency in the triplet quenching reaction.

Influence of Arrestin on the Photodecay of Bovine Rhodopsin.

PubMed

Chatterjee, Deep; Eckert, Carl Elias; Slavov, Chavdar; Saxena, Krishna; Fürtig, Boris; Sanders, Charles R; Gurevich, Vsevolod V; Wachtveitl, Josef; Schwalbe, Harald

2015-11-09

Continued activation of the photocycle of the dim-light receptor rhodopsin leads to the accumulation of all-trans-retinal in the rod outer segments (ROS). This accumulation can damage the photoreceptor cell. For retinal homeostasis, deactivation processes are initiated in which the release of retinal is delayed. One of these processes involves the binding of arrestin to rhodopsin. Here, the interaction of pre-activated truncated bovine visual arrestin (Arr(Tr)) with rhodopsin in 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC) micelles is investigated by solution NMR techniques and flash photolysis spectroscopy. Our results show that formation of the rhodopsin-arrestin complex markedly influences partitioning in the decay kinetics of rhodopsin, which involves the simultaneous formation of a meta II and a meta III state from the meta I state. Binding of Arr(Tr) leads to an increase in the population of the meta III state and consequently to an approximately twofold slower release of all-trans-retinal from rhodopsin. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flavylium network of chemical reactions in confined media: modulation of 3',4',7-trihydroxyflavilium reactions by host-guest interactions with cucurbit[7]uril.

PubMed

Basílio, Nuno; Pina, Fernando

2014-08-04

In moderately acidic aqueous solutions, flavylium compounds undergo a pH-, and in some cases, light-dependent array of reversible chemical reactions. This network can be described as a single acid-base reaction involving a flavylium cation (acidic form) and a mixture of basic forms (quinoidal base, hemiketal and cis and trans chalcones). The apparent pK'a of the system and the relative mole fractions of the basic forms can be modulated by the interaction with cucurbit[7]uril. The system is studied by using (1) H NMR spectroscopy, UV/Vis spectroscopy, flash photolysis, and steady-state irradiation. Of all the network species, the flavylium cation possesses the highest affinity for cucurbit[7]uril. The rate of interconversion between flavylium cation and the basic species (where trans-chalcone is dominant) is approximately nine times lower inside the cucurbit[7]uril. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemical reduction of cytochrome c by a 1,4,5,8-naphthalenediimide radical anion.

PubMed

Campos, Ivana B; Nantes, Iseli L; Politi, Mario J; Brochsztain, Sergio

2004-01-01

Steady-state UV irradiation of aqueous solutions containing cytochrome c (cyt c) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (BPNDI), a water-soluble aromatic imide, resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) oxidation state. The reaction kinetics were followed by the increase of the ferrocytochrome c absorbance band at 549 nm. The rate of the photochemical reaction was pH dependent, reaching its maximum values over the pH range 4-7. Addition of electrolyte (NaCl) at pH 5 resulted in a decrease in the reaction rate, as expected for reactions between oppositely charged species. Flash photolysis studies revealed that the actual reductant in the reaction was a photogenerated BPNDI radical anion, which transferred an electron to the cyt c heme iron. The participation of imide radicals in the process was confirmed by the ready reduction of cyt c by BPNDI radicals chemically generated with sodium dithionite.

Measurement of the dipole moments of excited states and photochemical transients by microwave dielectric absorption

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

Fessenden, R.W.; Carton, P.M.; Shimamori, H.

1982-09-16

Time-resolved changes in microwave dielectric absorption have been used to study transients formed by laser flash photolysis. Details of the method and apparatus are given. Applications both to the measurements of the dipole moments of transients and to decay kinetics are given. The dipole moments of the lowest triplet states of a number of aromatic compounds (mostly ketones) have been measured in benzene solution at room temperature. States of n..pi..* character generally possess smaller dipole moments than the corresponding ground states while states of ..pi pi..* character (for example, fluorenone) have larger values than the ground state. The triplets ofmore » 4-(dimethylamino)benzaldehyde and 4,4'-bis(dimethylamino)benzophenone have rather high values of dipole moment (10.5 and 8.4 D, respectively) showing their charge-transfer character. The triplet state of benzil was found to have zero or near-zero dipole moment, thus confirming that the triplet state is of a transstructure. 7 figures, 1 table.« less

Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II.

PubMed

Chararalambidis, Georgios; Das, Shyamal; Trapali, Adelais; Quaranta, Annamaria; Orio, Maylis; Halime, Zakaria; Fertey, Pierre; Guillot, Régis; Coutsolelos, Athanassios; Leibl, Winfried; Aukauloo, Ally; Sircoglou, Marie

2018-05-22

We investigate a biomimetic model of a Tyr Z /His 190 pair, a hydrogen-bonded phenol/imidazole covalently attached to a porphyrin sensitizer. Laser flash photolysis in the presence of an external electron acceptor reveals the need for water molecules to unlock the light-induced oxidation of the phenol through an intramolecular pathway. Kinetics monitoring encompasses two fast phases with distinct spectral properties. The first phase is related to a one-electron transfer from the phenol to the porphyrin radical cation coupled with a domino two-proton transfer leading to the ejection of a proton from the imidazole-phenol pair. The second phase concerns conveying the released proton to the porphyrin N 4 coordinating cavity. Our study provides an unprecedented example of a light-induced electron-transfer process in a Tyr Z /His 190 model of photosystem II, evidencing the movement of both the phenol and imidazole protons along an isoenergetic pathway. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure and temperature dependences of the reaction of OH with nitric acid

NASA Technical Reports Server (NTRS)

Stachnik, R. A.; Molina, L. T.; Molina, M. J.

1986-01-01

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Use of ruthenium dyes for subnanosecond detector fidelity testing in real time transient absorption

NASA Astrophysics Data System (ADS)

Byrdin, Martin; Thiagarajan, Viruthachalam; Villette, Sandrine; Espagne, Agathe; Brettel, Klaus

2009-04-01

Transient absorption spectroscopy is a powerful tool for the study of photoreactions on time scales from femtoseconds to seconds. Typically, reactions slower than ˜1 ns are recorded by the "classical" technique; the reaction is triggered by an excitation flash, and absorption changes accompanying the reaction are recorded in real time using a continuous monitoring light beam and a detection system with sufficiently fast response. The pico- and femtosecond region can be accessed by the more recent "pump-probe" technique, which circumvents the difficulties of real time detection on a subnanosecond time scale. This is paid for by accumulation of an excessively large number of shots to sample the reaction kinetics. Hence, it is of interest to extend the classical real time technique as far as possible to the subnanosecond range. In order to identify and minimize detection artifacts common on a subnanosecond scale, like overshoot, ringing, and signal reflections, rigorous testing is required of how the detection system responds to fast changes of the monitoring light intensity. Here, we introduce a novel method to create standard signals for detector fidelity testing on a time scale from a few picoseconds to tens of nanoseconds. The signals result from polarized measurements of absorption changes upon excitation of ruthenium complexes {[Ru(bpy)3]2+ and a less symmetric derivative} by a short laser flash. Two types of signals can be created depending on the polarization of the monitoring light with respect to that of the excitation flash: a fast steplike bleaching at magic angle and a monoexponentially decaying bleaching for parallel polarizations. The lifetime of the decay can be easily varied via temperature and viscosity of the solvent. The method is applied to test the performance of a newly developed real time transient absorption setup with 300 ps time resolution and high sensitivity.

Intraprotein Electron Transfer in Inducible Nitric Oxide Synthase Holoenzyme

PubMed Central

Feng, Changjian; Dupont, Andrea L.; Nahm, Nickolas J.; Spratt, Donald E.; Hazzard, James T.; Weinberg, J. Brice; Guillemette, J. Guy; Tollin, Gordon; Ghosh, Dipak K.

2008-01-01

Intraprotein electron transfer (IET) from flavin mononucleotide (FMN) to heme is essential in nitric oxide (NO) synthesis by NO synthase (NOS). Our previous laser flash photolysis studies provided a direct determination of the kinetics of the FMN–heme IET in a truncated oxyFMN construct of murine inducible NOS (iNOS), in which only the oxygenase and FMN domains along with the calmodulin (CaM) binding site are present [Feng et al. (2006) J. Am. Chem. Soc. 128, 3808-3811]. Here we report the kinetics of the IET in a human iNOS oxyFMN construct, a human iNOS holoenzyme and a murine iNOS holoenzyme, using CO photolysis in comparative studies on partially reduced NOS and a NOS oxygenase construct that lacks the FMN domain. The IET rate constants for the human and murine iNOS holoenzymes are 34 ± 5 s-1 and 35 ± 3 s-1, respectively, thereby providing a direct measurement of this IET between the catalytically significant redox couples of FMN and heme in the iNOS holoenzyme. These values are approximately an order of magnitude smaller than that in the corresponding iNOS oxyFMN construct, suggesting that in the holoenzyme the rate-limiting step in the IET is the conversion of the shielded electron-accepting (input) state to a new electron-donating (output) state. The fact that there is no rapid IET component in the kinetic traces obtained with the iNOS holoenzyme implies that the enzyme remains mainly in the input state. The IET rate constant value for the iNOS holoenzyme is similar to that obtained for a CaM-bound neuronal NOS (nNOS) holoenzyme, suggesting that CaM activation effectively removes the inhibitory effect of the unique autoregulatory insert in nNOS. PMID:18830722

Determinants of relaxation rate in rabbit skinned skeletal muscle fibres

PubMed Central

Luo, Ye; Davis, Jonathan P; Smillie, Lawrence B; Rall, Jack A

2002-01-01

The influence of Ca2+-activated force, the rate of dissociation of Ca2+ from troponin C (TnC) and decreased crossbridge detachment rate on the time course of relaxation induced by flash photolysis of diazo-2 in rabbit skinned psoas fibres was investigated at 15 °C. The rate of relaxation increased as the diazo-2 chelating capacity (i.e. free [diazo-2]/free [Ca2+]) increased. At a constant diazo-2 chelating capacity, the rate of relaxation was independent of the pre-photolysis Ca2+-activated force in the range 0.3-0.8 of maximum isometric force. A TnC mutant that exhibited increased Ca2+ sensitivity caused by a decreased Ca2+ dissociation rate in solution (M82Q TnC) also increased the Ca2+ sensitivity of steady-state force and decreased the rate of relaxation in fibres by approximately twofold. In contrast, a TnC mutant with decreased Ca2+ sensitivity caused by an increased Ca2+ dissociation rate in solution (NHdel TnC) decreased the Ca2+ sensitivity of steady-state force but did not accelerate relaxation. Decreasing the rate of crossbridge kinetics by reducing intracellular inorganic phosphate concentration ([Pi]) slowed relaxation by approximately twofold and led to two phases of relaxation, a slow linear phase followed by a fast exponential phase. In fibres, M82Q TnC further slowed relaxation in low [Pi] conditions by approximately twofold, whereas NHdel TnC had no significant effect on relaxation. These results are consistent with the interpretation that the Ca2+-dissociation rate and crossbridge detachment rate are similar in fast-twitch skeletal muscle, such that decreasing either rate slows relaxation, but accelerating Ca2+ dissociation has little effect on relaxation. PMID:12482894

OH reactivity at a rural site (Wangdu) in the North China Plain: contributions from OH reactants and experimental OH budget

NASA Astrophysics Data System (ADS)

Fuchs, Hendrik; Tan, Zhaofeng; Lu, Keding; Bohn, Birger; Broch, Sebastian; Brown, Steven S.; Dong, Huabin; Gomm, Sebastian; Häseler, Rolf; He, Lingyan; Hofzumahaus, Andreas; Holland, Frank; Li, Xin; Liu, Ying; Lu, Sihua; Min, Kyung-Eun; Rohrer, Franz; Shao, Min; Wang, Baolin; Wang, Ming; Wu, Yusheng; Zeng, Limin; Zhang, Yinson; Wahner, Andreas; Zhang, Yuanhang

2017-01-01

In 2014, a large, comprehensive field campaign was conducted in the densely populated North China Plain. The measurement site was located in a botanic garden close to the small town Wangdu, without major industry but influenced by regional transportation of air pollution. The loss rate coefficient of atmospheric hydroxyl radicals (OH) was quantified by direct measurements of the OH reactivity. Values ranged between 10 and 20 s-1 for most of the daytime. Highest values were reached in the late night with maximum values of around 40 s-1. OH reactants mainly originated from anthropogenic activities as indicated (1) by a good correlation between measured OH reactivity and carbon monoxide (linear correlation coefficient R2 = 0.33) and (2) by a high contribution of nitrogen oxide species to the OH reactivity (up to 30 % in the morning). Total OH reactivity was measured by a laser flash photolysis-laser-induced fluorescence instrument (LP-LIF). Measured values can be explained well by measured trace gas concentrations including organic compounds, oxygenated organic compounds, CO and nitrogen oxides. Significant, unexplained OH reactivity was only observed during nights, when biomass burning of agricultural waste occurred on surrounding fields. OH reactivity measurements also allow investigating the chemical OH budget. During this campaign, the OH destruction rate calculated from measured OH reactivity and measured OH concentration was balanced by the sum of OH production from ozone and nitrous acid photolysis and OH regeneration from hydroperoxy radicals within the uncertainty of measurements. However, a tendency for higher OH destruction compared to OH production at lower concentrations of nitric oxide is also observed, consistent with previous findings in field campaigns in China.

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...

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

Complex Organics from Laboratory Simulated Interstellar Ices

NASA Technical Reports Server (NTRS)

Dworkin, J. P.

2003-01-01

Many of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. The low temperatures of these ices (T < 50 K) preclude most chemical reactions, but photolysis can drive reactions that produce a suite of new species, many of which are complex organics. We study the UV and proton radiation processing of interstellar ice analogs to explore links between interstellar chemistry, the organics in comets and meteorites, and the origin of life on Earth. The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggest that such links are plausible. Once identified, these species may serve as markers of interstellar heritage of cometary dust and meteorites. Of particular interest are our findings that UV photolysis of interstellar ice analogs produce molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids. Quinones are essential in vital metabolic roles such as electron transport. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are photolyzed in interstellar ices. In the case of anthracene-containing ices, we have observed the production of 9-anthrone and 9,10 anthraquinone, both of which have been observed in the Murchison meteorite. Amphiphiles are also made when mixed molecular ices are photolyzed. These amphiphiles self-assemble into fluorescent vesicles when placed in liquid water, as do Murchison extracts. Both have the ability to trap an ionic dye. Photolysis of plausible ices can also produce alanine, serine, and glycine as well as a number of small alcohols and amines. Flash heating of the room temperature residue generated by such experiments generates mass spectral distributions similar to those of IDPs. The detection of high D/H ratios in some interstellar molecular species, and the knowledge that many of the organics, such as hydroxy and amino acids, in primitive meteorites are D-enriched provides evidence for a connection between intact organic material in the interstellar medium and in meteorites. Thus, some of the oxidized aromatics, amphiphiles, amino acids, hydroxy acids, and other compounds found in meteorites may have had an interstellar ancestry and not solely a product of parent body aqueous alteration. Such compounds should also be targeted for searches of organics in cometary dust.

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.

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.

High Speed Observation of Fragment Impact Initiation of Nitromethane Charges

NASA Astrophysics Data System (ADS)

Cook, M. D.; Briggs, R. I.; Haskins, P. J.; Stennett, C.

1999-06-01

Ultra high speed digital photography has been used to record the onset and build-up of reaction in nitromethane charges that have been impacted by steel fragments. The nitromethane charges were housed in perspex cylinders and back-lit using conventional flash bulbs. Flat plates of aluminium of varying thicknesses were glued to one end of the cylinder and perspex plates to the other. The completed charge was positioned to allow normal impact of the projectiles. The events were filmed using and Imacon 468, ultra high speed digital image system capable of framing at up to 100 million pictures per second, with a minimum interframe time of 10 nanoseconds, and exposure time of between 10ns and 1 millisecond. Using this system it was possible to record detailed photographic information concerning the onset and growth of reaction due to shock initiation of the nitromethane charges. The implications of these results for the ignition and growth process in nitromethane are discussed.

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.

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.

Unraveling the Mechanism of the Photodeprotection Reaction of 8-Bromo- and 8-Chloro-7-hydroxyquinoline Caged Acetates

PubMed Central

Ma, Jiani; Rea, Adam C; An, Huiying; Ma, Chensheng; Guan, Xiangguo; Li, Ming-De; Su, Tao; Yeung, Chi Shun; Harris, Kyle T; Zhu, Yue; Nganga, Jameil L; Fedoryak, Olesya D; Dore, Timothy M; Phillips, David Lee

2012-01-01

Abstract Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming “caged compounds” are a powerful means to regulate the action of physiologically active messengers in vivo through 1-photon excitation (1PE) and 2-photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8-chloro-7-hydroxyquinolin-2-yl)methyl acetate (CHQ-OAc) and (8-bromo-7-hydroxyquinolin-2-yl)methyl acetate (BHQ-OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time-resolved spectroscopic studies using transient emission (ns-EM), transient absorption (ns-TA), transient resonance Raman (ns-TR2), and time-resolved resonance Raman (ns-TR3) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ-OAc, but not CHQ-OAc. A high fluorescence quantum yield and a more efficient excited-state proton transfer (ESPT) in CHQ-OAc compared to BHQ-OAc explain the lower quantum efficiency of CHQ-OAc relative to BHQ-OAc. PMID:22511356

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...

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 ...

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.

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...

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation.

PubMed

Ding, Shi-Ling; Wang, Xi-Kui; Jiang, Wen-Qiang; Meng, Xia; Zhao, Ru-Song; Wang, Chen; Wang, Xia

2013-05-01

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.

Technical brief: Pump-probe paradigm in an integrating cavity to study photodecomposition processes

PubMed Central

Betts-Obregon, Brandi; Tsin, Andrew T.; DeSa, Richard J.

2016-01-01

Purpose Assaying photodecomposition is challenging because light must be used to initiate the photodamage and light must be used to monitor the photodecomposition. The experimental requirements are as follows: 1) During exposure of the actinic beam, continuously monitor the spectral characteristics of the sample, 2) uniformly expose the reactants to the actinic source, 3) obtain informative spectra in the presence of light scatter, and 4) achieve sufficient sensitivity for dilute reactants. Traditional spectrophotometers cannot address these issues due to sample turbidity, the inability to uniformly expose the cuvette contents to the incident beam, the inability to simultaneously perform spectral scans, and inherent low sensitivity. Here, we describe a system that meets these challenges in a practical way. Methods Light access to a 8.6 ml quartz integrating sphere containing 10 µM all-trans retinol in PBS was provided by three ports at right angles allowing for the following: 1) actinic light delivery from light-emitting diodes (LEDs) firing at 100 pulses/sec, 2) entry of a separate scanning beam at 100 scans/sec (10,000 µsec scan time) via an OLIS RSM 1000 ultraviolet/visual (UV/Vis) rapid-scanning spectrophotometer (RSM), and 3) light exit to the detector photomultiplier. The RSM spectral intermediate slit was partially covered to allow for a “dark” period of 2,000 µsec when no scanning light was admitted to the cuvette. During that interval, the LED was flashed, and the photomultiplier was temporarily blocked by a perforated spinning shutter disk. The absorbance per centimeter, which is increased due to the internal reflectance of the integrating sphere compared to a standard 1 cm rectangular cuvette, was calculated according to Fry et al. (2010) Applied Optics 49:575. Retinoid photodecomposition was confirmed with high-performance liquid chromatography (HPLC). Results Using the RSM to trigger the LED flash and photomultiplier shutter closure during the “dark” period allowed actinic flashes to be placed between scans. Exposure of the all-trans retinol to 366 nm flashes resulted in marked reduction in absorbance and a blue shift of the λmax. A white LED, despite its higher photon output, did not support all-trans retinol photolysis. Singular value decomposition (SVD) analysis revealed three spectral intermediates with mechanism, I -> II -> III. HPLC analysis of the reactants at the beginning and the conclusion of the light exposure confirmed the retinol photodecomposition. Conclusions The highly reflecting cavity acts as a multipass cuvette that markedly increased the light path length and, thus, sensitivity. Triggering the LED during a dark period within the scan time allowed the actinic flashes to be interleafed between scans in a pump-probe paradigm. Furthermore, the entire sample was exposed to scan beam and actinic flashes, which is not possible in traditional spectrophotometers. Finally, the integrating cavity cuvette allowed use of turbid samples. SVD was useful for resolving spectral intermediates. Although the identity of the intermediates was not determined here, the ability to define molecular intermediates during photodecomposition reactions will allow future studies to isolate and identify the degradation products and determine the mechanism of light-induced retinoid degradation and that of retinoid-binding protein-mediated photoprotection. PMID:27559291

Impaired Bioenergetics in Mutant Mitochondrial DNA Determines Cell Fate During Seizure-Like Activity.

PubMed

Kovac, Stjepana; Preza, Elisavet; Houlden, Henry; Walker, Matthew C; Abramov, Andrey Y

2018-04-27

Mutations in genes affecting mitochondrial proteins are increasingly recognised in patients with epilepsy, but the factors determining cell fate during seizure activity in these mutations remain unknown. Fluorescent dye imaging techniques were applied to fibroblast cell lines from patients suffering from common mitochondrial mutations and to age-matched controls. Using live cell imaging techniques in fibroblasts, we show that fibroblasts with mutations in the mitochondrial genome had reduced mitochondrial membrane potential and NADH pools and higher redox indices, indicative of respiratory chain dysfunction. Increasing concentrations of ferutinin, a Ca 2+ ionophore, led to oscillatory Ca 2+ signals in fibroblasts resembling dynamic Ca 2+ changes that occur during seizure-like activity. Co-monitoring of mitochondrial membrane potential (ΔΨ m ) changes induced by ferutinin showed accelerated membrane depolarisation and cell collapse in fibroblasts with mutations in the mitochondrial genome when compared to controls. Ca 2+ flash photolysis using caged Ca 2+ confirmed impaired Ca 2+ handling in fibroblasts with mitochondrial mutations. Findings indicate that intracellular Ca 2+ levels cannot be compensated during periods of hyperexcitability, leading to Ca 2+ overload and subsequent cell death in mitochondrial diseases.

Quantitative analysis of time-resolved microwave conductivity data

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

Reid, Obadiah G.; Moore, David T.; Li, Zhen

Flash-photolysis time-resolved microwave conductivity (fp-TRMC) is a versatile, highly sensitive technique for studying the complex photoconductivity of solution, solid, and gas-phase samples. The purpose of this paper is to provide a standard reference work for experimentalists interested in using microwave conductivity methods to study functional electronic materials, describing how to conduct and calibrate these experiments in order to obtain quantitative results. The main focus of the paper is on calculating the calibration factor, K, which is used to connect the measured change in microwave power absorption to the conductance of the sample. We describe the standard analytical formulae that havemore » been used in the past, and compare them to numerical simulations. This comparison shows that the most widely used analytical analysis of fp-TRMC data systematically under-estimates the transient conductivity by ~60%. We suggest a more accurate semi-empirical way of calibrating these experiments. However, we emphasize that the full numerical calculation is necessary to quantify both transient and steady-state conductance for arbitrary sample properties and geometry.« less

Quantitative analysis of time-resolved microwave conductivity data

DOE PAGES

Reid, Obadiah G.; Moore, David T.; Li, Zhen; ...

2017-11-10

Flash-photolysis time-resolved microwave conductivity (fp-TRMC) is a versatile, highly sensitive technique for studying the complex photoconductivity of solution, solid, and gas-phase samples. The purpose of this paper is to provide a standard reference work for experimentalists interested in using microwave conductivity methods to study functional electronic materials, describing how to conduct and calibrate these experiments in order to obtain quantitative results. The main focus of the paper is on calculating the calibration factor, K, which is used to connect the measured change in microwave power absorption to the conductance of the sample. We describe the standard analytical formulae that havemore » been used in the past, and compare them to numerical simulations. This comparison shows that the most widely used analytical analysis of fp-TRMC data systematically under-estimates the transient conductivity by ~60%. We suggest a more accurate semi-empirical way of calibrating these experiments. However, we emphasize that the full numerical calculation is necessary to quantify both transient and steady-state conductance for arbitrary sample properties and geometry.« less

Kinetic studies of halon replacements.

NASA Astrophysics Data System (ADS)

Orkin, Vladimir L.

2013-04-01

Despite their excellence as fire suppressants, the production of halons (bromofluorocarbons) is being phased out because of the danger they pose to the Earth's stratospheric ozone layer. A number of bromine free substances have been proposed and tested, but the effort to find replacements continues to return to bromine-containing compounds because of the properties of bromine as a chemically active flame suppressant. The primary approach to this problem has been to test candidate replacement compounds that have short atmospheric lifetimes or/and lack bromine, the halogen atoms that catalyze ozone destruction. Various chemical classes (alkanes, ethers, alkenes) have been studied both earlier and recently. The reaction with atmospheric hydroxyl radicals dictates the residence time and accumulation in the atmosphere of all potential halon replacements. Therefore, we improved a flash photolysis - resonance fluorescence apparatus to provide the most accurate OH reaction rate constants measured over the atmospheric temperatures. Supplementary UV absorption spectra were measured to allow the estimation of ODPs. Although a thorough 3-D modeling is required to assess ODPs, the simplified estimations can be made based on the compounds lifetimes.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

NASA Astrophysics Data System (ADS)

Zhang, Xian-Fu; Feng, Nan

2018-01-01

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 < δ ≤ 1), and the charge recombination induced the formation of triplet state (Dδ +-Aδ - → D-A (T1). These novel PCT- or PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

A Comparative Study on the Photophysics and Photochemistry of Xanthene Dyes in the Presence of Polyamidoamine (PAMAM) Dendrimers.

PubMed

Arbeloa, Ernesto Maximiliano; Previtali, Carlos Mario; Bertolotti, Sonia Graciela

2018-04-17

The photophysical and photochemical properties of the xanthene dyes Eosin Y, Erythrosin B, and Rose Bengal are evaluated in the presence of amino-terminated polyamidoamine (PAMAM) dendrimers of relatively high generation (G3-G5) in alkaline aqueous solution. UV/Vis absorption and fluorescence spectra of the dyes show bathochromic shifts, which correlate with the size of the dendrimer. Binding constants (K bind ) are calculated from absorption data. The resulting high K bind values indicate strong interactions between both molecules. Triplet-triplet absorption spectra of the dyes are recorded by laser flash photolysis, and a decrease in the triplet lifetimes is observed in the presence of dendrimers. At the same time, an increase in the absorption of the semireduced form of the dyes is observed. Rate constants for triplet quenching ( 3 k q ) and radical quantum yields (Φ R ) are obtained. The results are explained by a very efficient electron-transfer process from PAMAM to xanthene dyes for all of the dye/dendrimer couples that are evaluated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and Computational Studies of the Kinetics of the Reaction of Atomic Hydrogen with Methanethiol.

PubMed

Kerr, Katherine E; Alecu, Ionut M; Thompson, Kristopher M; Gao, Yide; Marshall, Paul

2015-07-16

The overall rate constant for H + CH3SH has been studied over 296-1007 K in an Ar bath gas using the laser flash photolysis method at 193 nm. H atoms were generated from CH3SH and in some cases NH3. They were detected via time-resolved resonance fluorescence. The results are summarized as k = (3.45 ± 0.19) × 10(-11) cm(3) molecule(-1) s(-1) exp(-6.92 ± 0.16 kJ mol(-1)/RT) where the errors in the Arrhenius parameters are the statistical uncertainties at the 2σ level. Overall error limits of ±9% for k are proposed. In the overlapping temperature range there is very good agreement with the resonance fluorescence measurements of Wine et al. Ab initio data and transition state theory yield moderate accord with the total rate constant, but not with prior mass spectrometry measurements of the main product channels leading to CH3S + H2 and CH3 + H2S by Amano et al.

Substituents on Quinone Methides Strongly Modulate Formation and Stability of Their Nucleophilic Adducts

PubMed Central

Weinert, Emily E.; Dondi, Ruggero; Colloredo-Melz, Stefano; Frankenfield, Kristen N.; Mitchell, Charles H.; Freccero, Mauro; Rokita, Steven E.

2008-01-01

Electronic perturbation of quinone methides (QM) greatly influences their stability and in turn alters the kinetics and product profile of QM reaction with deoxynucleosides. Consistent with the electron deficient nature of this reactive intermediate, electron-donating substituents are stabilizing and electron-withdrawing substituents are destabilizing. For example, a dC N3-QM adduct is made stable over the course of observation (7 days) by the presence of an electron-withdrawing ester group that inhibits QM regeneration. Conversely, a related adduct with an electron donating methyl group is very labile and regenerates its QM with a half-life of approximately 5 hr. The generality of these effects is demonstrated with a series of alternative quinone methide precursors (QMP) containing a variety of substituents attached at different positions with respect to the exocyclic methylene. The rates of nucleophilic addition to substituted QMs measured by laser flash photolysis similarly span five orders of magnitude with electron rich species reacting most slowly and electron deficient species reacting most quickly. The reversibility of QM reaction can now be predictably adjusted for any desired application. PMID:16953635

Enhanced Drug Photosafety by Interchromophoric Interaction Owing to Intramolecular Charge Separation.

PubMed

Li, Ming-De; Yan, Zhiping; Zhu, Ruixue; Phillips, David Lee; Aparici-Espert, Isabel; Lhiaubet-Vallet, Virginie; Miranda, Miguel A

2018-05-02

Imatinib is a synthetic tyrosinase inhibitor that is employed for the treatment of some kinds of human cancer. This drug has a low phototoxicity towards DNA, but its pyridylpyrimidine (1) fragment by itself exhibits significant phototoxicitiy. The intrinsic mechanism that leads to the enhanced photosafety of Imatinib is not yet known. Here, the properties of the excited state and interchromophoric interactions of Imatinib have been explored by using ultrafast laser flash photolysis and agarose electrophoresis studies. An intramolecular charge separation was directly observed for the irradiated Imatinib, which accounts for the relaxation of its excited state. An anionic form of pyridylpyrimidine (1) was deduced from the results of time-resolved resonance Raman spectra and by quenching experimental studies on compound 1 and diaminotoluene. In contrast, compound 1 efficiently transformed into triplet excited states with a long lifetime, which explained the phototoxicity associated with this fragment. This work provides insight into how to design drugs with lower phototoxicitiy or improved photostability by using interchromophoric interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct rate constant measurements for the reaction of ground-state atomic oxygen with ethylene, 244-1052 K

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

Klemm, R.B.; Nesbitt, F.L.; Skolnik, E.G.

The rate constant for the reaction of ground-state atomic oxygen with ethylene was determined by using two techniques: flash photolysis-resonance fluorescence (FP-RF, 244-1052 K) and discharge flow-resonance fluorescence (DF-RF, 298-1017 K). Kinetic complications due to the presence of molecular oxygen in the FP-RF experiments at high temperatures (T > 800 K) were overcome by using NO as the photolytic source of the O atoms. The rate constant, k/sub 1/ (T), derived in this study exhibits extreme non-Arrhenius behavior, but it can be successfully fit to the sum of exponentials expression, 244-1052 K, k/sub 1/(T) = (1.02 +/- 0.06) x 10/supmore » -11/ exp(-753 +/- 17 K/T) + (2.75 +/- 0.26) x 10/sup -10/ exp(-4220 +/- 550 K/T), in units of cm/sup 3/ molecule/sup -1/ s/sup -1/. Additionally, a fit of the results of this work to a simple transition-state theory expression and the comparison of these results with those of other workers are discussed.« less

Low charge state heavy ion production with sub-nanosecond laser.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

We have investigated laser ablation plasma of various species using nanosecond and sub-nanosecond lasers for both high and low charge state ion productions. We found that with sub-nanosecond laser, the generated plasma has a long tail which has low charge state ions determined by an electrostatic ion analyzer even under the laser irradiation condition for highly charged ion production. This can be caused by insufficient laser absorption in plasma plume. This property might be suitable for low charge state ion production. We used a nanosecond laser and a sub-nanosecond laser for low charge state ion production to investigate the difference of generated plasma using the Zirconium target.

Low charge state heavy ion production with sub-nanosecond laser

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

Kanesue, T., E-mail: tkanesue@bnl.gov; Okamura, M.; Kumaki, M.

2016-02-15

We have investigated laser ablation plasma of various species using nanosecond and sub-nanosecond lasers for both high and low charge state ion productions. We found that with sub-nanosecond laser, the generated plasma has a long tail which has low charge state ions determined by an electrostatic ion analyzer even under the laser irradiation condition for highly charged ion production. This can be caused by insufficient laser absorption in plasma plume. This property might be suitable for low charge state ion production. We used a nanosecond laser and a sub-nanosecond laser for low charge state ion production to investigate the differencemore » of generated plasma using the Zirconium target.« less

Ozone and dinitrogen monoxide production in atmospheric pressure air dielectric barrier discharge plasma effluent generated by nanosecond pulse superimposed alternating current voltage

NASA Astrophysics Data System (ADS)

Takashima, Keisuke; Kaneko, Toshiro

2017-06-01

The effects of nanosecond pulse superposition to alternating current voltage (NS + AC) on the generation of an air dielectric barrier discharge (DBD) plasma and reactive species are experimentally studied, along with measurements of ozone (O3) and dinitrogen monoxide (N2O) in the exhausted gas through the air DBD plasma (air plasma effluent). The charge-voltage cycle measurement indicates that the role of nanosecond pulse superposition is to induce electrical charge transport and excess charge accumulation on the dielectric surface following the nanosecond pulses. The densities of O3 and N2O in NS + AC DBD are found to be significantly increased in the plasma effluent, compared to the sum of those densities generated in NS DBD and AC DBD operated individually. The production of O3 and N2O is modulated significantly by the phase in which the nanosecond pulse is superimposed. The density increase and modulation effects by the nanosecond pulse are found to correspond with the electrical charge transport and the excess electrical charge accumulation induced by the nanosecond pulse. It is suggested that the electrical charge transport by the nanosecond pulse might result in the enhancement of the nanosecond pulse current, which may lead to more efficient molecular dissociation, and the excess electrical charge accumulation induced by the nanosecond pulse increases the discharge coupling power which would enhance molecular dissociation.

Photochemical attenuation of N-nitrosodimethylamine (NDMA) and other nitrosamines in surface water.

PubMed

Plumlee, Megan H; Reinhard, Martin

2007-09-01

The aqueous photolysis of seven alkyl nitrosamines was studied by irradiation in a solar simulator. Nitrosamines included N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), N-nitrosodi-n-butylamine (NDBA), N-nitrosopiperidine (NPip), and N-nitrosopyrrolidine (NPyr). Direct photolysis at irradiations of 765 W/m2, representing Southern California midsummer, midday sun, resulted in half-lives of 16 min for NDMA and 12-15 min for the other nitrosamines. The quantum yield for NDMA was determined to be phi = 0.41 and phi = 0.43-0.61 for the other nitrosamines. Quantified products of NDMA photolysis included methylamine, dimethylamine, nitrite, nitrate, and formate, with nitrogen and carbon balances exceeding 98 and 79%, respectively. Indirect photolysis of nitrosamines in surface water was not observed; increasing dissolved organic carbon (DOC) slowed the NDMA photolysis rate because of light screening. Removal of NDMA measured in tertiary treated effluent flowing in a shallow, sunlit engineered channel agreed with photolysis rates predicted based on the measured quantum yield and system parameters. Because biodegradation is relatively slow, aquatic photolysis of NDMA is generally expected to be more significant even at relatively low levels of solar irradiation (t(1/2) = 8-38 h at 244-855 W/m2, 51 degrees N latitude, 1 m depth).

Signaling States of Rhodopsin in Rod Disk Membranes Lacking Transducin βγ-Complex

PubMed Central

Lomonosova, Elena; Kolesnikov, Alexander V.; Kefalov, Vladimir J.

2012-01-01

Purpose. To characterize the possible role of transducin Gtβγ-complex in modulating the signaling properties of photoactivated rhodopsin and its lifetime in rod disc membranes and intact rods. Methods. Rhodopsin photolysis was studied using UV-visible spectroscopy and rapid scanning spectroscopy in the presence of hydroxylamine in highly purified wild-type and Gtγ-deficient mouse rod disc membranes. Complex formation between photoactivated rhodopsin and transducin was measured by extra-metarhodopsin (meta) II assay. Recovery of dark current and flash sensitivity in individual intact wild-type and Gtγ-deficient mouse rods was measured by single-cell suction recordings. Results. Photoconversion of rhodopsin to meta I/meta II equilibrium proceeds normally after elimination of the Gtβγ-complex. The meta I/meta II ratio, the rate of meta II decay, the reactivity of meta II toward hydroxylamine, and the rate of meta III formation in Gtγ-deficient rod disc membranes were identical with those observed in wild-type samples. Under low-intensity illumination, the amount of extra–meta II in Gtγ-deficient discs was significantly reduced. The initial rate of dark current recovery after 12% rhodopsin bleach was three times faster in Gtγ-deficient rods, whereas the rate of the late current recovery was largely unchanged. Mutant rods also exhibited faster postbleach recovery of flash sensitivity. Conclusions. Photoactivation and thermal decay of rhodopsin proceed similarly in wild-type and Gtγ-deficient mouse rods, but the complex formation between photoactivated rhodopsin and transducin is severely compromised in the absence of Gtβγ. The resultant lower transduction activation contributes to faster photoresponse recovery after a moderate pigment bleach in Gtγ-deficient rods. PMID:22266510

Calcium regulates vesicle replenishment at the cone ribbon synapse

PubMed Central

Babai, Norbert; Bartoletti, Theodore M.; Thoreson, Wallace B.

2010-01-01

Cones release glutamate-filled vesicles continuously in darkness and changing illumination modulates this release. Because sustained release in darkness is governed by vesicle replenishment rates, we analyzed how cone membrane potential regulates replenishment. Synaptic release from cones was measured by recording post-synaptic currents in Ambystoma tigrinum horizontal or OFF bipolar cells evoked by depolarization of simultaneously voltage-clamped cones. We measured replenishment after attaining a steady-state between vesicle release and replenishment using trains of test pulses. Increasing Ca2+ currents (ICa) by changing the test step from −30 to −10 mV increased replenishment. Lengthening −30 mV test pulses to match the Ca2+ influx during 25 ms test pulses to −10 mV produced similar replenishment rates. Reducing Ca2+ driving force by using test steps to +30 mV slowed replenishment. Using UV flashes to reverse inhibition of ICa by nifedipine accelerated replenishment. Increasing [Ca2+]i by flash photolysis of caged Ca2+ also accelerated replenishment. Replenishment, but not the initial burst of release, was enhanced by using an intracellular Ca2+ buffer of 0.5 mM EGTA rather than 5 mM EGTA, and diminished by 1 mM BAPTA. This suggests that although release and replenishment and release exhibited similar Ca2+-dependencies, release sites are <200 nm from Ca2+ channels but replenishment sites are >200 nm away. Membrane potential thus regulates replenishment by controlling Ca2+ influx, principally by effects on replenishment mechanisms but also by altering releasable pool size. This in turn provides a mechanism for converting changes in light intensity into changes in sustained release at the cone ribbon synapse. PMID:21106825

Caged vanilloid ligands for activation of TRPV1 receptors by 1- and 2-photon excitation†

PubMed Central

Zhao, Jun; Gover, Tony D.; Muralidharan, Sukumaran; Auston, Darryl A.; Weinreich, Daniel; Kao, Joseph P. Y.

2008-01-01

Nociceptive neurons in the peripheral nervous system detect noxious stimuli and report the information to the central nervous system. Most nociceptive neurons express the vanilloid receptor, TRPV1, a non-selective cation channel gated by vanilloid ligands such as capsaicin, the pungent essence of chili peppers. Here, we report the synthesis and biological application of two caged vanilloids—biologically inert precursors that, when photolyzed, release bioactive vanilloid ligands. The two caged vanilloids, Nb-VNA and Nv-VNA, are photoreleased with quantum efficiency of 0.13 and 0.041, respectively. Under flash photolysis conditions, photorelease of Nb-VNA and Nv-VNA is 95% complete in ∼40 μs and ∼125 μs, respectively. Through 1-photon excitation with ultraviolet light (360 nm), or 2-photon excitation with red light (720 nm), the caged vanilloids can be photoreleased in situ to activate TRPV1 receptors on nociceptive neurons. The consequent increase in intracellular free Ca2+ concentration ([Ca2+]i) can be visualized by laser-scanning confocal imaging of neurons loaded with the fluorescent Ca2+ indicator, fluo-3. Stimulation results from TRPV1 receptor activation, because the response is blocked by capsazepine, a selective TRPV1 antagonist. In Ca2+-free extracellular medium, photoreleased vanilloid can still elevate [Ca2+]i, which suggests that TRPV1 receptors also reside on endomembranes in neurons and can mediate Ca2+ release from intracellular stores. Notably, whole-cell voltage clamp measurements showed that flash photorelease of vanilloid can activate TRPV1 channels in < 4 msec at 22°C. In combination with 1- or 2-photon excitation, caged vanilloids are a powerful tool for probing morphologically distinct structures of nociceptive sensory neurons with high spatial and temporal precision. PMID:16605259

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.

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

PubMed

Chen, Ling; Zhou, Hai-Yun; Deng, Qin-Ying

2007-06-01

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

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.

Photodegradation of Polyfluorinated Dibenzo-p-Dioxins in Organic Solvents: Experimental and Theoretical Studies.

PubMed

Zeng, Xiaolan; Qu, Ruijuan; Feng, Mingbao; Chen, Jing; Wang, Liansheng; Wang, Zunyao

2016-08-02

Eighteen polyfluorinated dibenzo-p-dioxins (PFDDs) were synthesized by pyrolysis of fluorophenols. Using a 500 W Xe lamp as the light source, the PFDDs photodegradation kinetics in n-hexane were investigated. The photolysis reactions obeyed the pseudo-first-order rate equation, and higher fluorinated PFDDs tended to photolyze more slowly. Theoretically calculated parameters reflecting the molecular structural properties were used to develop a new model of PFDDs photolysis rates. The results indicated that the substitution pattern for fluorine atoms and the C-O bond length were major factors in the photolysis of PFDDs. We selected octafluorinated dibenzo-p-dioxin (OFDD) as a representative PFDDs to explore the influence of solvent on the photolysis rate of PFDDs, and the results indicated that neither the polarity nor donor hydrogen of organic solvents are independent influencing factors. Mechanistic pathways for the photolysis of OFDD in n-hexane were first studied. The results indicated that photodegradation of OFDD produces octafluorinated dihydroxybiphenyls, octafluorinated phenoxyphenols, and fluorinated phenols. The major pathway for photodegradation of OFDD was C-O bond cleavage. Defluorination reactions did not occur during the photolysis process.

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.

Kinetic and thermochemical studies of the ClO + ClO + M ↔ Cl2O2 + M reaction

NASA Astrophysics Data System (ADS)

Ferracci, V.; Rowley, D. M.

2009-12-01

Chlorine monoxide (ClO) radicals play a crucial role in polar ozone destruction events and the ClO dimer cycle has been identified as one of the most effective ozone-depleting catalytic cycles operating in the polar winter. A recent paper by von Hobe et al.1 highlighted significant inconsistencies between laboratory results, theoretical calculations and field observations concerning the ClO dimer ozone destruction cycle. This work has investigated the temperature dependence of the equilibrium constant of one of the key reactions in this cycle, ClO + ClO + M ↔ Cl2O2 + M (1, -1), by means of laser flash photolysis coupled with time-resolved UV absorption spectroscopy. ClO radicals were generated via laser flash photolysis of Cl2/Cl2O mixtures in synthetic air. The concentration of radicals was monitored via UV absorption spectroscopy: the use of a Charge Coupled Device (CCD) detector allowed time resolution over a broad range of wavelengths. The equilibrium constant Keq was determined as the ratio of the rate constants of the forward and reverse reaction (1, -1) over the T range 256 - 312 K. Second Law and Third Law analytical methods were employed to determine the standard enthalpy and entropy changes of reaction 1, ΔrH° and ΔrS°, from the measured equilibrium constants. The values obtained from the Second Law analysis (ΔrH° = - 80.8 ± 2.2 kJ mol-1; ΔrS° = - 168.4 ± 7.9 J K-1 mol-1) are in good agreement with previous work 2 but greater in magnitude than current NASA recommendations 3. It was also found that, under typical laboratory conditions employed in this work, [ClO] decay exhibits pure second order kinetics at T ≤ 250 K. A higher rate constant for the ClO recombination reaction (1) was also observed in this work (compared to the NASA evaluation 3), implying a higher Keq and a different partitioning between ClO and Cl2O2, shifting towards the dimer. 1. M. Von Hobe, R. J. Salawitch, T. Canty, H. Keller-Rudek, G. K. Moortgat, J.-U. Grooss, R. Müller, F. Stroh, Atmospheric Chemistry and Physics, 2007, 7, 3055 2. S. L. Nickolaisen, R. R. Friedl, S. P. Sander, Journal of Physical Chemistry, 1994, 98, 155 3. S. P. Sander, R. R. Friedl, D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, G. K. Moortgat, A. R. Ravishankara, C. E. Kolb, M. J. Molina, B. J. Finlayson-Pitts, Chemical Kinetics and Photochemical Data for use in Atmospheric Studies, Evaluation No. 14, JPL Publication 02-25, NASA Jet Propulsion Laboratory, Pasadena CA, 2003

Z-scan study of thermal nonlinearities in silicon naphthalocyanine-toluene solution with the excitations of the picosecond pulse train and nanosecond pulse

NASA Astrophysics Data System (ADS)

Yang, Sidney S.; Wei, Tai-Huei; Huang, Tzer-Hsiang; Chang, Yun-Ching

2007-02-01

Using the Z-scan technique, we studied the nonlinear absorption and refraction behaviors of a dilute toluene solution of a silicon naphthalocyanine (Si(OSi(n-hexyl)3)2, SiNc) at 532 nanometer with both a 2.8-nanosecond pulse and a 21-nanosecond (HW1/eM) pulse train containing 11 18-picosecond pulses 7 nanosecond apart. A thermal acoustic model and its steady-state approximation account for the heat generated by the nonradiative relaxations subsequent to the absorption. We found that when the steady-state approximation satisfactorily explained the results obtained with a 21-nanosecond pulse train, only the thermal-acoustic model fit the 2.8-nanosecond experimental results, which supports the approximation criterion established by Kovsh et al.

Transformation of acesulfame in water under natural sunlight: joint effect of photolysis and biodegradation.

PubMed

Gan, Zhiwei; Sun, Hongwen; Wang, Ruonan; Hu, Hongwei; Zhang, Pengfei; Ren, Xinhao

2014-11-01

The transformation of acesulfame in water under environmentally relevant conditions, including direct and indirect photolysis, biodegradation, and hydrolysis, was systematically evaluated. Under natural sunlight, both direct and indirect photolysis of acesulfame were negligible in sterilized systems at neutral or alkaline pH, whereas direct photolysis occurred at pH of 4 with a rate constant of 0.0355 d(-1) in deionized water. No significant reduction in acesulfame contents was found in the dark controls or in the incubation experiments, indicating acesulfame was resistant to hydrolysis and biodegradation. In unsterilized systems, photolysis was substantially enhanced, implying that there was a joint effect of photolysis and biodegradation or that the sterilization process had the secondary effect of inactivating some photosensitizers. The near-surface summer half-life of acesulfame in the water from the Haihe River was 9 d. Specific experiments revealed the involvement of (1)O2/(3)DOM* in acesulfame photolysis, whereas OH exhibited only a slight contribution in the presence of DOM or bicarbonate. As indicated by the total organic carbon data, no significant mineralization occurred in both sterilized and unsterilized systems after acesulfame was irradiated under simulated sunlight for 7 d, suggesting the generation of persistent intermediates. Finally, major degradation intermediates were analyzed, and the degradation pathways of acesulfame under environmentally relevant conditions were proposed for the first time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Numerical Simulation of a Nanosecond Pulse Discharge in Mach 5 Flow

DTIC Science & Technology

2013-01-01

Numerical Simulation of a Nanosecond Pulse Discharge in Mach 5 Flow Jonathan Poggie∗and Nicholas J. Bisek† Air Force Research Laboratory, Wright...was developed for nanosecond- pulse discharges , including real- istic air kinetics, electron energy transport, and compressible bulk gas flow. A reduced...shock waves originating near the sheath edge, consistent with experimental observations. I. Introduction In a nanosecond- pulse discharge , the input

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin.

PubMed

Liang, Chen; Zhao, Huimin; Deng, Minjie; Quan, Xie; Chen, Shuo; Wang, Hua

2015-01-01

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water - dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (OH) and singlet oxygen ((1)O2) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of OH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and (1)O2. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored. Copyright © 2014. Published by Elsevier B.V.

Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C6H6 = HCl + C6H5.

PubMed

Alecu, I M; Gao, Yide; Hsieh, P-C; Sand, Jordan P; Ors, Ahmet; McLeod, A; Marshall, Paul

2007-05-17

The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 x 10(-12) exp(-18.1 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 578-922 K and k(Cl + C6D6) = 6.2 x 10(-12) exp(-22.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 635-922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 x 10(-11) exp(-31.6 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) for 296-922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 x 10(-12) exp(+5.2 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 294-748 K, k(C6H5 + DCl) = 7.7 x 10(-13) exp(+4.9 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 292-546 K, an approximate k(C6H5 + C6H5I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) over 300-750 K, and an upper limit k(Cl + C6H5I) < or = 5.3 x 10(-12) exp(+2.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 300-750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D(298)(C6H5-H) = 472.1 +/- 2.5 kJ mol(-1) and thus the enthalpy of formation Delta(f)H(298)(C6H5) = 337.0 +/- 2.5 kJ mol(-1).

Quantitative production of compound I from a cytochrome P450 enzyme at low temperatures. Kinetics, activation parameters, and kinetic isotope effects for oxidation of benzyl alcohol.

PubMed

Wang, Qin; Sheng, Xin; Horner, John H; Newcomb, Martin

2009-08-05

Cytochrome P450 enzymes are commonly thought to oxidize substrates via an iron(IV)-oxo porphyrin radical cation transient termed Compound I, but kinetic studies of P450 Compounds I are essentially nonexistent. We report production of Compound I from cytochrome P450 119 (CYP119) in high conversion from the corresponding Compound II species at low temperatures in buffer mixtures containing 50% glycerol by photolysis with 365 nm light from a pulsed lamp. Compound I was studied as a reagent in oxidations of benzyl alcohol and its benzylic mono- and dideuterio isotopomers. Pseudo-first-order rate constants obtained at -50 degrees C with concentrations of substrates between 1.0 and 6.0 mM displayed saturation kinetics that gave binding constants for the substrate in the Compound I species (K(bind)) and first-order rate constants for the oxidation reactions (k(ox)). Representative results are K(bind) = 214 M(-1) and k(ox) = 0.48 s(-1) for oxidation of benzyl alcohol. For the dideuterated substrate C(6)H(5)CD(2)OH, kinetics were studied between -50 and -25 degrees C, and a van't Hoff plot for complexation and an Arrhenius plot for the oxidation reaction were constructed. The H/D kinetic isotope effects (KIEs) at -50 degrees C were resolved into a large primary KIE (P = 11.9) and a small, inverse secondary KIE (S = 0.96). Comparison of values extrapolated to 22 degrees C of both the rate constant for oxidation of C(6)H(5)CD(2)OH and the KIE for the nondeuterated and dideuterated substrates to values obtained previously in laser flash photolysis experiments suggested that tunneling could be a significant component of the total rate constant at -50 degrees C.

Experimental studies of Cl-atom reactions at high temperatures: Cl + H{sub 2} {yields} HCl + H from 291 to 1283 K

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

Adusei, G.Y.; Fontijn, A.

1994-12-31

A method is presented for producing Cl atoms for kinetic experiments above 750 K. Combined with a low temperature Cl-atom production technique, rate coefficients for the title reaction have been obtained over a wide temperature range. The Cl atoms were generated by flash photolysis of CCl{sub 4} for the low-temperature measurements and by pulsed laser photolysis of NaCl for the high-temperature measurements. The relative Cl-atom concentrations were monitored by time-resolved resonance fluorescence. The data are well fitted by the expression k{sub 1}(291--1,283 K) = 4.4 {times} 10{sup {minus}11} exp({minus}2568 K/T) cm{sup 3}/molecule, with 2{sigma} precision limits of {+-} 9 {+-}16more » %, depending on temperature, and corresponding 2{sigma} accuracy limits of about {+-} 26 %. There is good agreement between the rate coefficients measured here and those from previous low-temperature studies, leading to the recommendation k{sub 1}(200--1,283 K) = 2.3 {times} 10{sup {minus}16} (T/K){sup 1.63} exp({minus}1592 K/T) cm{sup 3}/molecule s, with a suggested 2{sigma} accuracy limit of {+-}28% for the combined data. A transition state theory calculation base don a semiempirical London-Eyring-Polanyi-Sato (LEPS) potential energy surface gives excellent agreement with the combined experimental results. Extension of their previous recommendation for the reverse reaction to lower temperatures leads to k{sub 2}(200--1,200 K) = 6.6 {times} 10{sup {minus}16} (T/K){sup 1.44} exp({minus}1241 K/T) cm{sup 3}/molecule s, with 2{sigma} accuracy limits within {+-}25 %. There is excellent agreement between the present data and the predicted expression from that reaction and equilibrium data.« less

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%.

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.

Mechanism of Ferric Oxalate Photolysis

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

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Mechanism of Ferric Oxalate Photolysis

DOE PAGES

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr; ...

2017-06-08

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Benefits of Time Correlation Measurements for Passive Screening

NASA Astrophysics Data System (ADS)

Murer, David; Blackie, Douglas; Peerani, Paolo

2014-02-01

The “FLASH Portals Project” is a collaboration between Arktis Radiation Detectors Ltd (CH), the Atomic Weapons Establishment (UK), and the Joint Research Centre (European Commission), supported by the Technical Support Working Group (TSWG). The program's goal was to develop and demonstrate a technology to detect shielded special nuclear materials (SNM) more efficiently and less ambiguously by exploiting time correlation. This study presents experimental results of a two-sided portal monitor equipped with in total 16 4He fast neutron detectors as well as four polyvinyltoluene (PVT) plastic scintillators. All detectors have been synchronized to nanosecond precision, thereby allowing the resolution of time correlations from timescales of tens of microseconds (such as (n, γ) reactions) down to prompt fission correlations directly. Our results demonstrate that such correlations can be detected in a typical radiation portal monitor (RPM) geometry and within operationally acceptable time scales, and that exploiting these signatures significantly improves the performance of the RPM compared to neutron counting. Furthermore, the results show that some time structure remains even in the presence of heavy shielding, thus significantly improving the sensitivity of the detection system to shielded SNM.

Optically trapped atomic resonant devices for narrow linewidth spectral imaging

NASA Astrophysics Data System (ADS)

Qian, Lipeng

This thesis focuses on the development of atomic resonant devices for spectroscopic applications. The primary emphasis is on the imaging properties of optically thick atomic resonant fluorescent filters and their applications. In addition, this thesis presents a new concept for producing very narrow linewidth light as from an atomic vapor lamp pumped by a nanosecond pulse system. This research was motivated by application for missile warning system, and presents an innovative approach to a wide angle, ultra narrow linewidth imaging filter using a potassium vapor cell. The approach is to image onto and collect the fluorescent photons emitted from the surface of an optically thick potassium vapor cell, generating a 2 GHz pass-band imaging filter. This linewidth is narrow enough to fall within a Fraunhefer dark zone in the solar spectrum, thus make the detection solar blind. Experiments are conducted to measure the absorption line shape of the potassium resonant filter, the quantum efficiency of the fluorescent behavior, and the resolution of the fluorescent image. Fluorescent images with different spatial frequency components are analyzed by using a discrete Fourier transform, and the imaging capability of the fluorescent filter is described by its Modulation Transfer Function. For the detection of radiation that is spectrally broader than the linewidth of the potassium imaging filter, the fluorescent image is seen to be blurred by diffuse fluorescence from the slightly off resonant photons. To correct this, an ultra-thin potassium imaging filter is developed and characterized. The imaging property of the ultra-thin potassium imaging cell is tested with a potassium seeded flame, yielding a resolution image of ˜ 20 lines per mm. The physics behind the atomic resonant fluorescent filter is radiation trapping. The diffusion process of the resonant photons trapped in the atomic vapor is theoretically described in this thesis. A Monte Carlo method is used to simulate the absorption and fluorescence. The optimum resolution of the fluorescent image is predicted by simulation. Radiation trapping is also shown to be useful for the generation of ultra-narrow linewidth light from an atomic vapor flash lamp. A 2 nanosecond, high voltage pulse is used to excite low pressure mercury vapor mixed with noble gases, producing high intensity emission at the mercury resonant line at 253.7 nm. With a nanosecond pumping time and high electrical current, the radiation intensity of the mercury discharge is increased significantly compared to a normal glow discharge lamp, while simultaneously suppressing the formation of an arc discharge. By avoiding the arc discharge, discrete spectral lines of mercury were kept at narrow bandwidth. Due to radiation trapping, the emission linewidth from the nanosecond mercury lamp decreases with time and produces ultra-narrow linewidth emission 100 ns after of the excitation, this linewidth is verified by absorption measurements through low pressure mercury absorption filter. The lamp is used along with mercury absorption filters for spectroscopic applications, including Filtered Rayleigh Scattering with different CO2 pressures and Raman scattering from methanol.

FLASH X-RAY (FXR) LINEAR INDUCTION ACCELERATOR (LIA) OPTIMIZATION Sensor Delay Correction

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

Ong, M M; Houck, T L; Kreitzer, B R

2006-05-01

The radiographic goal of the FXR Optimization Project is to generate an x-ray pulse with peak energy of 19 MeV, spot-size of 1.5 mm, a dose of 500 rad, and duration of 60 ns. The electrical objectives are to generate a 3 kA electron-beam and refine our 16 MV accelerator so that the voltage does not vary more than 1%-rms. In a multi-cell linear induction accelerator, like FXR, the timing of the acceleration pulses relative to the beam is critical. The pulses must be timed optimally so that a cell is at full voltage before the beam arrives and doesmore » not drop until the beam passes. In order to stay within the energy-variation budget, the synchronization between the cells and beam arrival must be controlled to a couple of nanoseconds. Therefore, temporal measurements must be accurate to a fraction of a nanosecond. FXR Optimization Project developed a one-giga-sample per second (gs/s) data acquisition system to record beam sensor data. Signal processing algorithms were written to determine cell timing with an uncertainty of a fraction of a nanosecond. However, the uncertainty in the sensor delay was still a few nanoseconds. This error had to be reduced if we are to improve the quality of the electron beam. Two types of sensors are used to align the cell voltage pulse against the beam current. The beam current is measured with resistive-wall sensors. The cell voltages are read with capacitive voltage monitors. Sensor delays can be traced to two mechanisms: (1) the sensors are not co-located at the beam and cell interaction points, and (2) the sensors have different length jumper cables and other components that connect them to the standard-length coaxial cables of the data acquisition system. Using the physical locations and dimensions of the sensor components, and the dielectric constant of the materials, delay times were computed. Relative to the cell voltage, the beam current was theoretically reporting late by 7.7 ns. Two experiments were performed to verify and refine the sensor delay correction. In the first experiment, the beam was allowed to drift through a cell that was not pulsed. The beam induces a potential into the cell that is read by the voltage monitor. Analysis of the data indicated that the beam sensor signal was likely 7.1 ns late. In the second experiment, the beam current is calculated from the injector diode voltage that is the sum of the cell voltages. A 7 ns correction produced a very good match between the signals from the two types of sensors. For simplicity, we selected a correction factor that advanced the current signals by 7 ns. This should reduce the uncertainty in the temporal measurements to less than 1 ns.« less

UV-photodegradation of desipramine: Impact of concentration, pH and temperature on formation of products including their biodegradability and toxicity.

PubMed

Khaleel, Nareman D H; Mahmoud, Waleed M M; Olsson, Oliver; Kümmerer, Klaus

2016-10-01

Desipramine (DMI) is a widely used tricyclic antidepressant, and it is the major metabolite of imipramine (IMI) and lofepramine (LMI); IMI and LMI are two of the most commonly used tricyclic antidepressants. If DMI enters the aquatic environment, it can be transformed by the environmental bacteria or UV radiation. Therefore, photolysis of DMI in water was performed using a simulated sunlight Xenon-lamp and a UV-lamp. Subsequently, the biodegradability of DMI and its photo-transformation products (PTPs) formed during its UV photolysis was studied. The influence of variable conditions, such as initial DMI concentration, solution pH, and temperature, on DMI UV photolysis behavior was also studied. The degree of mineralization of DMI and its PTPs was monitored. A Shimadzu HPLC-UV apparatus was used to follow the kinetic profile of DMI during UV-irradiation; after that, ion-trap and high-resolution mass spectrometry coupled with chromatography were used to monitor and identify the possible PTPs. The environmentally relevant properties and selected toxicity properties of DMI and the non-biodegradable PTPs were predicted using different QSAR models. DMI underwent UV photolysis with first-order kinetics. Quantum yields were very low. DOC values indicated that DMI formed new PTPs and was not completely mineralized. Analysis by means of high-resolution mass spectrometry revealed that the photolysis of DMI followed three main photolysis pathways: isomerization, hydroxylation, and ring opening. The photolysis rate was inversely proportional to initial DMI concentration. The pH showed a significant impact on the photolysis rate of DMI, and on the PTPs in terms of both formation kinetics and mechanisms. Although temperature was expected to increase the photolysis rate, it showed a non-significant impact in this study. Results from biodegradation tests and QSAR analysis revealed that DMI and its PTPs are not readily biodegradable and that some PTPs may be human and/or eco-toxic, so they may pose a risk to the environment. Copyright © 2016 Elsevier B.V. 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.

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.

Role of wetland organic matters as photosensitizer for degradation of micropollutants and metabolites.

PubMed

Lee, Eunkyung; Shon, Ho Kyong; Cho, Jaeweon

2014-07-15

Overall photodegradation of pharmaceuticals, personal care products (PPCPs) and pharmaceutical metabolites were investigated in order to evaluate their photochemical fate in aquatic environments in various natural organic matter (NOM) enriched solutions. Tested PPCPs exhibited different rates of loss during direct and indirect photolysis. Here, only ultraviolet (UV) light source was used for direct photolysis and UV together with (3)DOM(*)for indirect photolysis. Diclofenac and sulfamethoxazole were susceptible to photodegradation, whereas carbamazepine, caffeine, paraxanthine and tri(2-chloroethyl) phosphate (TCEP) showed low levels of photodegradation rate, reflecting their conservative photoreactivity. During indirect photodegradation, in contrast to the hydrophilic autochthonous NOM, allochthonous NOM with relatively high molecular weight (MW), specific ultraviolet absorbance (SUVA) and hydrophobicity (e.g., Suwannee River humic acid (SRHA)) revealed to significantly inhibit the photolysis of target micropollutants. The presence of Typha wetland NOM enhanced the indirect photolysis of well-known conservative micopollutants (carbamazepine and paraxanthine). And atenolol, carbamazepine, glimepiride, and N-acetyl-sulfamethoxazole were found to be sensitive to the triplet excited state of dissolved organic matter ((3)DOM(*)) with Typha wetland NOM under deoxygenated condition. This suggests that photolysis in constructed wetlands connected to the wastewater treatment plant can enhance the degradation of some anthropogenic micropollutants by the interaction with (3)DOM(*) in wetlands. Copyright © 2014 Elsevier B.V. All rights reserved.

Needle-array to Plate DBD Plasma Using Sine AC and Nanosecond Pulse Excitations for Purpose of Improving Indoor Air Quality

PubMed Central

Zhang, Li; Yang, Dezheng; Wang, Wenchun; Wang, Sen; Yuan, Hao; Zhao, Zilu; Sang, Chaofeng; Jia, Li

2016-01-01

In this study, needle-array to plate electrode configuration was employed to generate an atmospheric air diffuse discharge using both nanosecond pulse and sine AC voltage as excitation voltage for the purpose of improving indoor air quality. Different types of voltage sources and electrode configurations are employed to optimize electrical field distribution and improve discharge stability. Discharge images, electrical characteristics, optical emission spectra, and plasma gas temperatures in both sine AC discharge and nanosecond pulse discharge were compared and the discharge stability during long operating time were discussed. Compared with the discharge excited by sine AC voltage, the nanosecond pulsed discharge is more homogenous and stable, besides, the plasma gas temperature of nanosecond pulse discharge is much lower. Using packed-bed structure, where γ- Al2O3 pellets are filled in the electrode gap, has obvious efficacy in the production of homogenous discharge. Furthermore, both sine AC discharge and nanosecond pulse discharge were used for removing formaldehyde from flowing air. It shows that nanosecond pulse discharge has a significant advantage in energy cost. And the main physiochemical processes for the generation of active species and the degradation of formaldehyde were discussed. PMID:27125663

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.

Electron Transfer Activity of a de Novo Designed Copper Center in a Three-Helix Bundle Fold

PubMed Central

Plegaria, Jefferson S.; Herrero, Christian; Quaranta, Annamaria; Pecoraro, Vincent L.

2017-01-01

In this work, we characterized the intermolecular ET property of a de novo designed metallopeptide using laser-flash photolysis. α3D-CH3 is three-helix bundle peptide that was designed to contain a copper ET site found in the β-barrel fold of native cupredoxins. The ET activity of Cuα3D-CH3 was determined using five different photosensitizers. By exhibiting a complete depletion of the photo-oxidant and the successive formation of a Cu(II) species at 400 nm, the transient and generated spectra demonstrated an ET transfer reaction between the photo-oxidant and Cu(I)α3D-CH3. This observation illustrated our success in integrating an ET center within a de novo designed scaffold. From the kinetic traces at 400 nm, first-order and bimolecular rate constants of 105 s−1 and 108 M−1 s−1 were derived. Moreover, a Marcus equation analysis on the rate versus driving force study produced a reorganization energy of 1.1 eV, demonstrating that the helical fold of α3D requires further structural optimization to efficiently perform ET. PMID:26427552

[Photosensitizing properties and antioxidant activity of furagin--an antimicrobial drug that is a derivative of nitrofuran].

PubMed

Makareeva, E N; Lozovskaia, E L; Tatikolov, A S; Sapezhinskiĭ, I I

1997-01-01

Photosensitizing effect of antimicrobial drug nitrofuran derivative--furagin N-(5-nitro-2-furil)-allylidencamino-hydantoin) under irradiation with light longer than 280 nm was found. The method of investigation is based on photochemiluminescence of Gly-Trp peptide in aqueous solution. Maximum photosensitizing efficiency was observed at the furagin concentration 0.08 mM when chemiluminescence yield was 33 times greater than photochemiluminescence of Gly-Trp peptide in absence of drug. It was shown that photochemiluminescence sensitized by furagin occurred via free radical way. Life time of the triplet state of furagin determined by flash photolysis was 40 microseconds. A comparison of experimental data with kinetic calculation allowed us to estimate the rate constant of triplet quenching by oxygen ((2.2 +/- 0.3)10(8) M-1.s-1) and the total rate constants of physical quenching and chemical reaction with Gly-Trp peptide ((2.0 +/- 0.4)10(8) M-1.s-1). It was also found in experiments with photochemiluminescence of Gly-Trp peptide sensitized by riboflavin (irradiation with monochromatic light 436 nm) that furagin possesses antioxidant properties twice reducing the intensity of chemiluminescence at the drug concentration 0.029 mM.

Interaction mechanism between berberine and the enzyme lysozyme

NASA Astrophysics Data System (ADS)

Cheng, Ling-Li; Wang, Mei; Wu, Ming-Hong; Yao, Si-De; Jiao, Zheng; Wang, Shi-Long

2012-11-01

In the present paper, the interaction between model protein lysozyme (Lys) and antitumorigenic berberine (BBR) was investigated by spectroscopic methods, for finding an efficient and safe photosensitizer with highly active transient products using in photodynamic therapy study. The fluorescence data shows that the binding of BBR could change the environment of the tryptophan (Trp) residues of Lys, and form a new complex. Static quenching is the main fluorescence quenching mechanism between Lys and BBR, and there is one binding site in Lys for BBR and the type of binding force between them was determined to be hydrophobic interaction. Furthermore, the possible interaction mechanism between BBR and Lys under the photoexcitation was studied by laser flash photolysis method, the results demonstrated that BBR neutral radicals (BBR(-H)•) react with Trp (K = 3.4 × 109 M-1 s-1) via electron transfer to give the radical cation (Trp/NH•+) and neutral radical of Trp (TrpN•). Additionally BBR selectively oxidize the Trp residues of Lys was also observed by comparing the transient absorption spectra of their reaction products. Through thermodynamic calculation, the reaction mechanisms between 3BBR∗ and Trp or Lys were determined to be electron transfer process.

Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

PubMed

D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

2013-02-01

The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

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

Ghosh, H.N.; Pal, H.; Sapre, A.V.

Photoexcitation of complexes between fullerence C[sub 60] and organic amines in benzene solutions is known to result in charge separation (CS) and subsequent charge recombination (CR) reactions, which lead to varying yields of fullerence triplet formation. Picosecond flash photolysis studies are carried out on C[sub 60]-diphenylamine (DPA), C[sub 60]-triethylamine (TEA), C[sub 60]-diazabicyclooctane (DABCO), and C[sub 60]-triphenylamine (TPA) systems to find out mechanistic details of the triplet formation on CR by inducing heavy atom and polarity effects by using suitable solvents. It is found that in the case of C[sub 60]-DPA, C[sub 60]-TEA, and C[sub 60]-DABCO systems proton transfer from themore » amine cation to the C[sub 60] anion in the ion pair state dominates, leading to poor triplet yields, which improve in heavy atom containing solvents. In TPA, proton transfer is not possible and hence fullerene triplet yields are high. Increase of solvent polarity for this system results in decreased C[sub 60] triplet yields with a consequent increase in the ion dissociation yield. A suitable reaction scheme is proposed to explain the results obtained. 34 refs., 5 figs., 2 tabs.« less

Photoreaction of thioxanthone with indolic and phenolic derivatives of biological relevance: magnetic field effect study.

PubMed

Das, Doyel; Nath, Deb Narayan

2008-11-20

The photoinduced reaction of thioxanthone (TX) with various indolic and phenolic derivatives and amino acids like tryptophan and tyrosine has been monitored in sodium dodecyl sulfate micellar medium. Laser flash photolysis and magnetic field effect (MFE) experiments have been used to study the dynamics of the radical pairs. The quenching rate constant with different quenchers in SDS micellar solution has been measured. For indoles the electron-transfer reaction has been found to be followed by proton transfer from the donor molecule, which gives rise to the TX ketyl radical. On the other hand, the electron-transfer reaction in the case of phenols is preceded with formation of a hydrogen-bonded exciplex. The extent of the MFE and magnitude of the magnetic field corresponding to one-half of the saturation value of MFE ( B 1/2) support the fact that hyperfine mechanism plays the primary role. Quenching of MFE in the presence of gadolinium ions confirms that the radical pair is located near the micellar interface. MFE study has been further extended to protein-like bovine serum albumin in micellar solution. The results indicate loss in mobililty of radical pairs in the protein surfactant complex.

A conserved carboxylic acid group mediates light-dependent proton uptake and signaling by rhodopsin.

PubMed

Arnis, S; Fahmy, K; Hofmann, K P; Sakmar, T P

1994-09-30

A carboxylic acid residue is conserved at the cytoplasmic border of the third transmembrane segment among nearly all G protein-coupled receptors. In the visual receptor rhodopsin, replacement of the conserved Glu134 by a neutral glutamine results in enhanced transducin activation. Here we show that a key event in forming the active state of rhodopsin is proton uptake by Glu134 in the metarhodopsin II (MII) photoproduct. Site-directed mutants E134D and E134Q were studied by flash photolysis, where formation rates of their photoproducts and rates of pH change could be monitored simultaneously. Both mutants showed normal MII formation rates. However, E134D displayed a slowed rate of proton uptake and E134Q displayed a loss of light-induced uptake of two protons from the aqueous phase. Thus, Glu134 mediates light-dependent proton uptake by MII. We propose that receptor activation requires a light-induced conformational change that allows protonation of Glu134 and subsequent protonation of a second group. The strong conservation of Glu134 in G protein-coupled receptors implies a general requirement for a proton acceptor group at this position to allow light- or ligand-dependent receptor activation.

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⁺.

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 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.

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.

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.

Study on Control of NH4 +-N in Surface Water by Photocatalytic

NASA Astrophysics Data System (ADS)

Zuo, Xiaoran; He, Honghua; Yang, Yue; Yan, Chao; Zhou, Ying

2018-01-01

NH4 +-N has become the main pollution factor affecting the surface water quality in China. Based on the theory of photolysis, the feasibility of photolysis removing NH4 +-N in surface water is studied. The effects of pH, CaO2 content and photolysis time on removal rate of NH4 +-N are studied. The actual study is based on Laboratory studies results. Experimental results show: When the pH<7, photolysis can increase the NH4 +-N content. And when pH>8, the photolysis can greatly reduce the NH4 +-N content in water. CaO2 can greatly remove NH4 +-N. The removal rate of NH4 +-N increased with the increase of photocatalytic time. When irradiated with UV light for 108 hours or the sun is irradiated for about 40 days, NH4 +-N content can be reduced from 4mg/L to 0.5mg/L under the optimum experimental conditions. Adjusting the pH of surface water is the most important condition for controlling NH4 +-N content.

Nanosecond pulse lasers for retinal applications.

PubMed

Wood, John P M; Plunkett, Malcolm; Previn, Victor; Chidlow, Glyn; Casson, Robert J

2011-08-01

Thermal lasers are routinely used to treat certain retinal disorders although they cause collateral damage to photoreceptors. The current study evaluated a confined, non-conductive thermal, 3-nanosecond pulse laser in order to determine how to produce the greatest therapeutic range without causing collateral damage. Data were compared with that obtained from a standard thermal laser. Porcine ocular explants were used; apposed neuroretina was also in place for actual laser treatment. After treatment, the retina was removed and a calcein-AM assay was used to assess retinal pigmented epithelium (RPE) cell viability in the explants. Histological methods were also employed to examine lased transverse explant sections. Three nanoseconds pulse lasers with either speckle- or gaussian-beam profile were employed in the study. Comparisons were made with a 100 milliseconds continuous wave (CW) 532 nm laser. The therapeutic energy range ratio was defined as the minimum visible effect threshold (VET) versus the minimum detectable RPE kill threshold. The 3-nanosecond lasers produced markedly lower minimum RPE kill threshold levels than the CW laser (e.g., 36 mJ/cm(2) for speckle-beam and 89 mJ/cm(2) for gaussian-beam profile nanosecond lasers vs. 7,958 mJ/cm(2) for CW laser). VET values were also correspondingly lower for the nanosecond lasers (130 mJ/cm(2) for 3 nanoseconds speckle-beam and 219 mJ/cm(2) for gaussian-beam profile vs. 1,0346 mJ/cm(2) for CW laser). Thus, the therapeutic range ratios obtained with the nanosecond lasers were much more favorable than that obtained by the CW laser: 3.6:1 for the speckle-beam and 2.5:1 for the gaussian-beam profile 3-nanosecond lasers versus 1.3:1 for the CW laser. Nanosecond lasers, particularly with a speckle-beam profile, provide a much wider therapeutic range of energies over which RPE treatment can be performed, without damage to the apposed retina, as compared with conventional CW lasers. These results may have important implications for the treatment of retinal disease. Copyright © 2011 Wiley-Liss, Inc.

Diphosphine is an intermediate in the photolysis of phosphine to phosphorus and hydrogen. [Jupiter atmospheric chemistry

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Benson, R.

1980-01-01

The photolysis of phosphine to red phosphorus (P4) and hydrogen is investigated in light of the potential significance of the reaction in the atmospheric chemistry of Jupiter. It is reported that the photolysis of PH3 at room temperature by a 206.2-nm light source gave rise to a product identified by its UV and IR spectra and gas chromatographic retention time as P2H4, the yield of which is found to increase to a maximum and then decrease to 20% of the maximum value with illumination time. A mechanism for phosphine photolysis including diphosphine formation as an intermediate step is proposed, and it is concluded that P2H4 is a likely constituent of the atmospheres of the Jovian planets.

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 = 4 × 10-4 JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40-60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.

Role of UV photolysis in accelerating the biodegradation of 2,4,6-TCP.

PubMed

Wang, Wenbing; Kirumba, George; Zhang, Yongming; Wu, Yanqing; Rittmann, Bruce E

2015-09-18

2,4,6-TCP, a kind of chlorinated aromatic and aliphatic compound, is difficult to be biodegraded by ordinary microorganisms. UV photolysis and biodegradation of 2,4,6-TCP by Bacillus amyloliquefaciens intimate coupling is a potential means to accelerate its biotransformation. The initial steps of 2,4,6-TCP biodegradation involve mono-oxygenation reactions that have molecular oxygen and an intracellular electron carrier as cosubstrates. It was demonstrated that B. amyloliquefaciens has the 2,4,6-TCP monooxygenase gene tcpA which could encode 2,4,6-TCP monooxygenase (TCP-MO). TCP-MO would catalytically decompose 2,4,6-TCP into 2,6-DCHQ. We employed an internal loop photolytic biofilm reactor for 2,4,6-TCP degradation. Sequentially coupled photolysis and biodegradation experimental results suggested that 2,4,6-TCP removal rate in P + B (TCP(UV) + phenol) protocol was higher by 77 and 103 % when compared to B (TCP + phenol) and B (TCP-only) protocols respectively. The corresponding loss rate coefficient (k) values were 0.069, 0.039, 0.034 mg/L·min -1 respectively. This is because UV photolysis converted 2,4,6-TCP into its intermediates: 2,4-dichlorophenol (2,4-DCP), 4-monochlorophenol (4-MCP), phenol, 2,6-dichloro-p-hydroquinone (2,6-DCHQ), with all displaying less inhibition to bacterial action. In addition, phenol was the crucial UV-photolysis product from 2,4,6-TCP, its catabolic oxidation generating internal electron carriers that may accelerate the initial steps of 2,4,6-TCP biodegradation. Intimately coupled photolysis and biodegradation experimental results suggested that 2,4,6-TCP removal rate in P&B (TCP + phenol) protocol was higher by 166 and 681 % when compared to P&B (TCP-only) and P + B protocols respectively. The corresponding loss rate coefficient (k) values were 0.539, 0.203, 0.069 mg/L·min -1 respectively. It provided sufficient evidence to demonstrate that intimately coupled photolysis and biodegradation accelerated 2,4,6-TCP removal much faster than sequentially coupled photolysis and biodegradation. In addition, oxidation of phenol was the mechanism by which intimately coupled photolysis and biodegradation accelerated rapid 2,4,6-TCP removal producing electron equivalents that stimulated the initial mono-oxygenation reactions for 2,4,6-TCP biodegradation. It is important to note that 2,6-DCHQ (produced from UV-photolysis products or initial mono-oxygenation reactions) would be catalytically decomposed into 6-chlorohydroxyquinol (6-CHQ). Based on this, a tentative reaction mechanism for the photo-biodegradation 2,4,6-TCP was proposed.

Compact nanosecond laser system for the ignition of aeronautic combustion engines

NASA Astrophysics Data System (ADS)

Amiard-Hudebine, G.; Tison, G.; Freysz, E.

2016-12-01

We have studied and developed a compact nanosecond laser system dedicated to the ignition of aeronautic combustion engines. This system is based on a nanosecond microchip laser delivering 6 μJ nanosecond pulses, which are amplified in two successive stages. The first stage is based on an Ytterbium doped fiber amplifier (YDFA) working in a quasi-continuous-wave (QCW) regime. Pumped at 1 kHz repetition rate, it delivers TEM00 and linearly polarized nanosecond pulses centered at 1064 nm with energies up to 350 μJ. These results are in very good agreement with the model we specially designed for a pulsed QCW pump regime. The second amplification stage is based on a compact Nd:YAG double-pass amplifier pumped by a 400 W peak power QCW diode centered at λ = 808 nm and coupled to a 800 μm core multimode fiber. At 10 Hz repetition rate, this system amplifies the pulse delivered by the YDFA up to 11 mJ while preserving its beam profile, polarization ratio, and pulse duration. Finally, we demonstrate that this compact nanosecond system can ignite an experimental combustion chamber.

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.

[Mechanism of ablation with nanosecond pulsed electric field].

PubMed

Cen, Chao; Chen, Xin-hua; Zheng, Shu-sen

2015-11-01

Nanosecond pulsed electric field ablation has been widely applied in clinical cancer treatment, while its molecular mechanism is still unclear. Researchers have revealed that nanosecond pulsed electric field generates nanopores in plasma membrane, leading to a rapid influx of Ca²⁺; it has specific effect on intracellular organelle membranes, resulting in endoplasmic reticulum injuries and mitochondrial membrane potential changes. In addition, it may also change cellular morphology through damage of cytoskeleton. This article reviews the recent research advances on the molecular mechanism of cell membrane and organelle changes induced by nanosecond pulsed electric field ablation.

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

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.

Degradation of methadone by the sunlight/FC process: Kinetics, radical species participation and influence of the water matrix.

PubMed

Hsieh, Ming-Chi; Panchangam, Sri Chandana; Lai, Webber Wei-Po; Lin, Angela Yu-Chen

2018-06-12

Free chlorine sunlight photolysis (sunlight/FC) markedly enhances the degradation rate of methadone, a synthetic opioid used medically, over that obtained using sunlight alone. The pseudo-first-order rate constants of methadone degradation under acidic conditions ([methadone] = 0.2 μM, [free chlorine] = 4 μM, and pH = 4) for sunlight/FC and sunlight photolysis are 7.0 ± 1.1 × 10 -2  min -1 and 1.4 ± 0.2 × 10 -2  min -1 , respectively. The improved methadone degradation can be attributed to the production of HO and reactive chlorine species (RCS) during sunlight/FC photolysis. HO and RCS predominantly accounted for degradation during sunlight/FC photolysis under acidic and neutral conditions, while direct photolysis was the major contributor towards methadone degradation in alkaline conditions. The initial pH (pH 4-11) and free chlorine concentration (1-6 μM) significantly influenced the overall degradation efficiency of methadone. The presence of HCO 3 - , Cl - and dissolved organic matters, which may competitively react with HO and RCS, retard the degradation of methadone in synthetic wastewater. Consequently, a 50% lower methadone degradation rate was observed when deionized (DI) water was replaced with tap water. These results emphasize the need to consider different water matrices when applying sunlight/FC photolysis for water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Nanosecond electric modification of order parameters

NASA Astrophysics Data System (ADS)

Borshch, Volodymyr

In this Dissertation, we study a nanosecond electro-optic response of a nematic liquid crystal in a geometry where an applied electric field E modifies the tensor order parameter but does not change the orientation of the optic axis (director N̂). We use nematics with negative dielectric anisotropy with the electric field applied perpendicularly to N̂. The field changes the dielectric tensor at optical frequencies (optic tensor), due to the following mechanisms: (a) nanosecond creation of biaxial orientational order; (b) uniaxial modification of the orientational order that occurs over the timescales of tens of nanoseconds, and (c) quenching of director fluctuations with a wide range of characteristic times up to milliseconds. We develop a model to describe the dynamics of all three mechanisms. We design the experimental conditions to selectively suppress the contributions from the quenching of director fluctuations (c) and from the biaxial order effect (a) and thus, separate the contributions of the three mechanisms in the electro-optic response. As a result, the experimental data can be well fitted with the model parameters. The analysis provides a rather detailed physical picture of how the liquid crystal responds to a strong electric field, E ˜ 108 V/m, on a timescale of nanoseconds. This work provides a useful guide in the current search of the biaxial nematic phase. Namely, the temperature dependence of the biaxial susceptibility allows one to estimate the temperature of the potential uniaxial-to-biaxial phase transition. An analysis of the quenching of director fluctuations indicates that on a timescale of nanoseconds, the classic model with constant viscoelastic material parameters might reach its limit of validity. The effect of nanosecond electric modification of the order parameter (NEMOP) can be used in applications in which one needs to achieve ultrafast (nanosecond) changes of optical characteristics, such as birefringence.

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.

Water quality parameters controlling the photodegradation of two herbicides in surface waters of the Columbia Basin, Washington.

PubMed

Furman, Olha S; Yu, Miao; Teel, Amy L; Watts, Richard J

2013-11-01

The water quality parameters nitrate-nitrogen, dissolved organic carbon, and suspended solids were correlated with photodegradation rates of the herbicides atrazine and 2,4-D in samples collected from four sites in the Columbia River Basin, Washington, USA. Surface water samples were collected in May, July, and October 2010 and analyzed for the water quality parameters. Photolysis rates for the two herbicides in the surface water samples were then evaluated under a xenon arc lamp. Photolysis rates of atrazine and 2,4-D were similar with rate constants averaging 0.025 h(-1) for atrazine and 0.039 h(-1) for 2,4-D. Based on multiple regression analysis, nitrate-nitrogen was the primary predictor of photolysis for both atrazine and 2,4-D, with dissolved organic carbon also a predictor for some sites. However, at sites where suspended solids concentrations were elevated, photolysis rates of the two herbicides were controlled by the suspended solids concentration. The results of this research provide a basis for evaluating and predicting herbicide photolysis rates in shallow surface waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

The photochemical reaction cycle and photoinduced proton transfer of sensory rhodopsin II (Phoborhodopsin) from Halobacterium salinarum.

PubMed

Tamogami, Jun; Kikukawa, Takashi; Ikeda, Yoichi; Takemura, Ayaka; Demura, Makoto; Kamo, Naoki

2010-04-07

Sensory rhodopsin II (HsSRII, also called phoborhodopsin) is a negative phototaxis receptor of Halobacterium salinarum, a bacterium that avoids blue-green light. In this study, we expressed the protein in Escherichia coli cells, and reconstituted the purified protein with phosphatidylcholine. The reconstituted HsSRII was stable. We examined the photocycle by flash-photolysis spectroscopy in the time range of milliseconds to seconds, and measured proton uptake/release using a transparent indium-tin oxide electrode. The pKa of the counterion of the Schiff base, Asp(73), was 3.0. Below pH 3, the depleted band was observed on flash illumination, but the positive band in the difference spectra was not found. Above pH 3, the basic photocycle was HsSRII (490) --> M (350) --> O (520) --> Y (490) --> HsSRII, where the numbers in parentheses are the maximum wavelengths. The decay rate of O-intermediate and Y-intermediate were pH-independent, whereas the M-intermediate decay was pH-dependent. For 3 < pH < 4.5, the M-decay was one phase, and the rate decreased with an increase in pH. For 4.5 < pH < 6.5, the decay was one phase with pH-independent rates, and azide markedly accelerated the M-decay. These findings suggest the existence of a protonated amino acid residue (X-H) that may serve as a proton relay to reprotonate the Schiff base. Above pH 6.5, the M-decay showed two phases. The fast M-decay was pH-independent and originated from the molecule having a protonated X-H, and the slow M-decay originated from the molecule having a deprotonated X, in which the proton came directly from the outside. The analysis yielded a value of 7.5 for the pKa of X-H. The proton uptake and release occurred during M-decay and O-decay, respectively. Copyright (c) 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Inauguration and first light of the GCT-M prototype for the Cherenkov telescope array

NASA Astrophysics Data System (ADS)

Watson, J. J.; De Franco, A.; Abchiche, A.; Allan, D.; Amans, J.-P.; Armstrong, T. P.; Balzer, A.; Berge, D.; Boisson, C.; Bousquet, J.-J.; Brown, A. M.; Bryan, M.; Buchholtz, G.; Chadwick, P. M.; Costantini, H.; Cotter, G.; Daniel, M. K.; De Frondat, F.; Dournaux, J.-L.; Dumas, D.; Ernenwein, J.-P.; Fasola, G.; Funk, S.; Gironnet, J.; Graham, J. A.; Greenshaw, T.; Hervet, O.; Hidaka, N.; Hinton, J. A.; Huet, J.-M.; Jegouzo, I.; Jogler, T.; Kraus, M.; Lapington, J. S.; Laporte, P.; Lefaucheur, J.; Markoff, S.; Melse, T.; Mohrmann, L.; Molyneux, P.; Nolan, S. J.; Okumura, A.; Osborne, J. P.; Parsons, R. D.; Rosen, S.; Ross, D.; Rowell, G.; Rulten, C. B.; Sato, Y.; Sayède, F.; Schmoll, J.; Schoorlemmer, H.; Servillat, M.; Sol, H.; Stamatescu, V.; Stephan, M.; Stuik, R.; Sykes, J.; Tajima, H.; Thornhill, J.; Tibaldo, L.; Trichard, C.; Vink, J.; White, R.; Yamane, N.; Zech, A.; Zink, A.; Zorn, J.; CTA Consortium

2017-01-01

The Gamma-ray Cherenkov Telescope (GCT) is a candidate for the Small Size Telescopes (SSTs) of the Cherenkov Telescope Array (CTA). Its purpose is to extend the sensitivity of CTA to gamma-ray energies reaching 300 TeV. Its dual-mirror optical design and curved focal plane enables the use of a compact camera of 0.4 m diameter, while achieving a field of view of above 8 degrees. Through the use of the digitising TARGET ASICs, the Cherenkov flash is sampled once per nanosecond contin-uously and then digitised when triggering conditions are met within the analogue outputs of the photosensors. Entire waveforms (typically covering 96 ns) for all 2048 pixels are then stored for analysis, allowing for a broad spectrum of investigations to be performed on the data. Two prototypes of the GCT camera are under development, with differing photosensors: Multi-Anode Photomultipliers (MAPMs) and Silicon Photomultipliers (SiPMs). During November 2015, the GCT MAPM (GCT-M) prototype camera was integrated onto the GCT structure at the Observatoire de Paris-Meudon, where it observed the first Cherenkov light detected by a prototype instrument for CTA.

Microprocessor-controlled, wide-range streak camera

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

Amy E. Lewis, Craig Hollabaugh

Bechtel Nevada/NSTec recently announced deployment of their fifth generation streak camera. This camera incorporates many advanced features beyond those currently available for streak cameras. The arc-resistant driver includes a trigger lockout mechanism, actively monitors input trigger levels, and incorporates a high-voltage fault interrupter for user safety and tube protection. The camera is completely modular and may deflect over a variable full-sweep time of 15 nanoseconds to 500 microseconds. The camera design is compatible with both large- and small-format commercial tubes from several vendors. The embedded microprocessor offers Ethernet connectivity, and XML [extensible markup language]-based configuration management with non-volatile parameter storagemore » using flash-based storage media. The camera’s user interface is platform-independent (Microsoft Windows, Unix, Linux, Macintosh OSX) and is accessible using an AJAX [asynchronous Javascript and XML]-equipped modem browser, such as Internet Explorer 6, Firefox, or Safari. User interface operation requires no installation of client software or browser plug-in technology. Automation software can also access the camera configuration and control using HTTP [hypertext transfer protocol]. The software architecture supports multiple-simultaneous clients, multiple cameras, and multiple module access with a standard browser. The entire user interface can be customized.« less

Microprocessor-controlled wide-range streak camera

NASA Astrophysics Data System (ADS)

Lewis, Amy E.; Hollabaugh, Craig

2006-08-01

Bechtel Nevada/NSTec recently announced deployment of their fifth generation streak camera. This camera incorporates many advanced features beyond those currently available for streak cameras. The arc-resistant driver includes a trigger lockout mechanism, actively monitors input trigger levels, and incorporates a high-voltage fault interrupter for user safety and tube protection. The camera is completely modular and may deflect over a variable full-sweep time of 15 nanoseconds to 500 microseconds. The camera design is compatible with both large- and small-format commercial tubes from several vendors. The embedded microprocessor offers Ethernet connectivity, and XML [extensible markup language]-based configuration management with non-volatile parameter storage using flash-based storage media. The camera's user interface is platform-independent (Microsoft Windows, Unix, Linux, Macintosh OSX) and is accessible using an AJAX [asynchronous Javascript and XML]-equipped modem browser, such as Internet Explorer 6, Firefox, or Safari. User interface operation requires no installation of client software or browser plug-in technology. Automation software can also access the camera configuration and control using HTTP [hypertext transfer protocol]. The software architecture supports multiple-simultaneous clients, multiple cameras, and multiple module access with a standard browser. The entire user interface can be customized.

A trial of ignition innovation of gasoline engine by nanosecond pulsed low temperature plasma ignition

NASA Astrophysics Data System (ADS)

Shiraishi, Taisuke; Urushihara, Tomonori; Gundersen, Martin

2009-07-01

Application of nanosecond pulsed low temperature plasma as an ignition technique for automotive gasoline engines, which require a discharge under conditions of high back pressure, has been studied experimentally using a single-cylinder engine. The nanosecond pulsed plasma refers to the transient (non-equilibrated) phase of a plasma before the formation of an arc discharge; it was obtained by applying a high voltage with a nanosecond pulse (FWHM of approximately 80 or 25 ns) between coaxial cylindrical electrodes. It was confirmed that nanosecond pulsed plasma can form a volumetric multi-channel streamer discharge at an energy consumption of 60 mJ cycle-1 under a high back pressure of 1400 kPa. It was found that the initial combustion period was shortened compared with the conventional spark ignition. The initial flame visualization suggested that the nanosecond pulsed plasma ignition results in the formation of a spatially dispersed initial flame kernel at a position of high electric field strength around the central electrode. It was observed that the electric field strength in the air gap between the coaxial cylindrical electrodes was increased further by applying a shorter pulse. It was also clarified that the shorter pulse improved ignitability even further.

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 photolysis rate of J SOA = 4 × 10 −4 J NO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40–60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.« less

Photodegradation of ibuprofen under UV-Vis irradiation: mechanism and toxicity of photolysis products.

PubMed

Li, Fu Hua; Yao, Kun; Lv, Wen Ying; Liu, Guo Guang; Chen, Ping; Huang, Hao Ping; Kang, Ya Pu

2015-04-01

The photodegradation of ibuprofen (IBP) in aqueous media was studied in this paper. The degradation mechanism, the reaction kinetics and toxicity of the photolysis products of IBP under UV-Vis irradiation were investigated by dissolved oxygen experiments, quenching experiments of reactive oxygen species (ROS), and toxicity evaluation utilizing Vibrio fischeri. The results demonstrated that the IBP degradation process could be fitted by the pseudo first-order kinetics model. The degradation of IBP by UV-Vis irradiation included direct photolysis and self-sensitization via ROS. The presence of dissolved oxygen inhibited the photodegradation of IBP, which indicated that direct photolysis was more rapid than the self-sensitization. The contribution rates of ·OH and (1)O2 were 21.8 % and 38.6 % in self-sensitization, respectively. Ibuprofen generated a number of intermediate products that were more toxic than the base compound during photodegradation.

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.

Photooxidation of carbofuran by a polychromatic UV irradiation without and with hydrogen peroxide

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

Benitez, F.J.; Beltran-Heredia, J.; Gonzalez, T.

The photodegradation of carbofuran aqueous solutions has been conducted with direct photolysis provided by a polychromatic UV radiation source and by the combination of this UV radiation with hydrogen peroxide. In both processes, the decomposition level obtained as a function of the operating variables is reported, and the presence of tert-butyl alcohol, a scavenger of free radicals, is discussed. While the contribution of hydroxyl radicals is negligible in the direct photolysis, its reactions in the UV/H{sub 2}O{sub 2} system clearly increase the carbofuran decomposition and therefore must be taken into account in the reaction rate equation for the total degradation.more » From the mechanisms proposed, the quantum yields for the direct photolysis and the kinetic constants for the reaction between carbofuran and the hydroxyl radicals generated in the H{sub 2}O{sub 2} photolysis in the combined process are respectively evaluated.« less

Wavelength Dependence of Nanosecond IR Laser-Induced Breakdown in Water: Evidence for Multiphoton Initiation via an Intermediate State

DTIC Science & Technology

2015-04-29

bubble generation and shock wave emission in water for femtosecond to nanosecond laser pulses . ...breakdown threshold in water for nanosecond (ns) IR laser pulses . Avalanche ionization (AI) is the most powerful mechanism driving IR ns laser-induced...acknowledged that femtosecond (fs) and picosecond (ps) IR breakdown is initiated by photoionization because ultrashort pulses are sufficiently

Deflagration-to-Detonation Transition Control by Nanosecond Gas Discharges

DTIC Science & Technology

2008-04-07

Report 3. DATES COVERED (From – To) 1 April 2007 - 18 August 09 4. TITLE AND SUBTITLE Deflagration-To- Detonation Transition Control By Nanosecond...SUPPLEMENTARY NOTES 14. ABSTRACT During the current project, an extensive experimental study of detonation initiation by high{voltage...nanosecond gas discharges has been performed in a smooth detonation tube with different discharge chambers and various discharge cell numbers. The chambers

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.

Sunlight photolysis of benzotriazoles - Identification of transformation products and pathways.

PubMed

Weidauer, Cindy; Davis, Caroline; Raeke, Julia; Seiwert, Bettina; Reemtsma, Thorsten

2016-07-01

Benzotriazoles (BTs) are widely used corrosion inhibitors, incompletely removed in municipal wastewater treatment. The photochemical fate of the three BTs 1H-benzotriazole (1H-BT), 4-methyl-1H-benzotriazole (4Me-BT) and 5-methyl-1H-benzotriazole (5Me-BT) and of three microbial metabolites, was studied under simulated sunlight (290-800 nm) at neutral pH in aqueous solution for 24 h. The half-life, the quantum yield and the reaction rate were determined and a total of 36 photolysis products were detected and identified using liquid chromatography-high resolution-mass spectrometry. The half-lives of all six BTs were in the range of 6-24 h under the experimental conditions. Though the quantum yields were comparatively low (0.0007-0.0021), the environmental half-lives ranged from 2.4 to 8 d, suggesting that sunlight photolysis is still a relevant degradation process of BTs in surface waters. The photolysis pathway of 1H-BT under simulated sunlight differed from that suggested for UV-radiation, in that aminophenol is formed directly rather than via aniline. Similar pathways were found for the other BTs, except for 4-hydroxy-1H-benzotriazole (4OH-BT). Most identified transformation products of the BTs showed a high reactivity and appear not to persist in the environment. Upon co-photolysis of BTs with dissolved organic matter (DOM), however, series of reaction products were determined by Fourier transform - ion cyclotron resonance - mass spectrometry (FTICR-MS) which are formed by reaction of photolysis intermediates of the BTs with DOM. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

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

Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

2012-05-17

Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less

Effects of inorganic phosphate and ADP on calcium handling by the sarcoplasmic reticulum in rat skinned cardiac muscles.

PubMed

Xiang, J Z; Kentish, J C

1995-03-01

The aim was to investigate whether, and how, increases in inorganic phosphate (Pi) and ADP, similar to those occurring intracellularly during early myocardial ischaemia, affect the calcium handling of the sarcoplasmic reticulum. Rat ventricular trabeculae were permeabilised with saponin. The physiological process of calcium induced calcium release (CICR) from the muscle sarcoplasmic reticulum was triggered via flash photolysis of the "caged Ca2+", nitr-5. Alternatively, calcium release was induced by rapid application of caffeine to give an estimate of sarcoplasmic reticular calcium loading. The initial rate of sarcoplasmic reticular calcium pumping was also assessed by photolysis of caged ATP at saturating [Ca2+]. Myoplasmic [Ca2+] (using fluo-3) and isometric force were measured. Pi (2-20 mM) significantly depressed the magnitude of CICR and the associated force transient. Sarcoplasmic reticular calcium loading was inhibited even more than CICR by Pi, suggesting that reduced calcium loading could account for all of the inhibitory effect of Pi on CICR and that Pi may slightly activate the calcium release mechanism. The reduced sarcoplasmic reticular calcium loading seemed to be due to a fall in the free energy of ATP hydrolysis (delta GATP) available for the calcium pump, since equal decreases in delta GATP produced by adding both Pi and ADP in various ratios caused similar falls in the calcium loading of the sarcoplasmic reticulum. The caged ATP experiments indicated that Pi (20 mM) did not affect the rate constant of sarcoplasmic reticular calcium uptake. ADP (10 mM) alone, or with 1 mM Pi, inhibited calcium loading. In spite of this, ADP (10 mM) did not alter CICR and, when 1 mM Pi was added, ADP increased CICR above control. An increase in intracellular Pi reduces sarcoplasmic reticular calcium loading and thus depresses the CICR. This could be an important contributing factor in the hypoxic or ischaemic contractile failure of the myocardium. However the detrimental effect of Pi may be offset to some extent by a stimulatory action of ADP on the calcium release mechanism of CICR.

Coexpression of Human α- and Circularly Permuted β-Globins Yields a Hemoglobin with Normal R State but Modified T State Properties†

PubMed Central

Asmundson, Anna L.; Taber, Alexandria M.; van der Walde, Adella; Lin, Danielle H.; Olson, John S.; Anthony-Cahill, Spencer J.

2009-01-01

For the first time, a circularly permuted human β-globin (cpβ) has been coexpressed with human α-globin in bacterial cells and shown to associate to form α-cpβ hemoglobin in solution. Flash photolysis studies of α-cpβ show markedly biphasic CO and O2 kinetics with the amplitudes for the fast association phases being dominant due the presence of large amounts of high-affinity liganded hemoglobin dimers. Extensive dimerization of liganded but not deoxygenated α-cpβ was observed by gel chromatography. The rate constants for O2 and CO binding to the R state forms of α-cpβ are almost identical to those of native HbA (k′R(CO) ≈ 5.0 μM−1 s−1; k′R(O2) ≈ 50 μM−1 s−1), and the rate of O2 dissociation from fully oxygenated α-cpβ is also very similar to that observed for HbA (kR(O2) ≈ 21–28 s−1). When the equilibrium deoxyHb form of α-cpβ is reacted with CO in rapid mixing experiments, the observed time courses are monophasic and the observed bimolecular association rate constant is ∼1.0 μM−1 s−1, which is intermediate between the R state rate measured in partial photolysis experiments (∼5 μM−1 s−1) and that observed for T state deoxyHbA (k′T(CO) ≈ 0.1 to 0.2 μM−1 s−1). Thus the deoxygenated permutated β subunits generate an intermediate, higher affinity, deoxyHb quaternary state. This conclusion is supported by equilibrium oxygen binding measurements in which α-cpβ exhibits a P50 of ∼1.5 mmHg and a low n-value (∼1.3) at pH 7, 20 °C, compared to 8.5 mmHg and n ≈ 2.8 for native HbA under identical, dilute conditions. PMID:19397368

Nanosecond step-scan FT-infrared absorption spectroscopy in photochemistry and catalysis

NASA Astrophysics Data System (ADS)

Frei, H.

1998-06-01

Time-resolved step-scan FT-IR absorption spectroscopy has been expanded to a resolution of 20 nanosecond. Following a description of the experimental set-up, applications in four research areas are presented. In the first project, we discuss a reversible isomerization, namely the bacteriorhodopsin photocycle. Main results are the discovery of 2 processes with distinct kinetics on the nanosecond time scale not detected by previous spectroscopic techniques, and observation of an instantaneous response of the protein environment to chromophore dynamics within the nanosecond laser pulse duration. In a second project, alkane C-H bond activation by a transition metal complex in room temperature solution is investigated and the first measurement of the formation of a C-H insertion product reported (alkyl hydride). Then, a nanosecond study of a pericyclic reaction, the ring-opening of cyclohexadiene, is discussed. The fourth example describes the first observation of a transient molecule in a zeolite matrix, a triplet excited quinone, by time-resolved infrared spectroscopy.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

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...

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

EXPERIMENTAL PROTOCOL FOR DETERMINING PROTOLYSIS REACTION RATE CONSTANTS

EPA Science Inventory

An experimental protocol to determine photolysis rates of chemicals which photolyze relatively rapidly in the gas phase has been developed. This procedure provides a basis for evaluating the relative importance of one atmospheric reaction pathway (i.e., photolysis) for organic su...

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).

A Proposed Time Transfer Experiment Between the USA and the South Pacific

DTIC Science & Technology

1991-12-01

1 nanosecond, The corrected position will be traris~nitted by both the time transfer modem and the existing TV line sync dissemination process...communications satellite (AUSSAT K1) (Figure 5), With after-the- fact ephemeris correction , this is useful to the 20 nanosecond level. The second...spheric corrections will ultimately reduce ephemeris related time transfer errors to the 1 nanosecond level. The corrected position will be transmitted

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.

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.

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.

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).

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 results indicate that this photolytic loss rate would decrease SOA mass by 40-60% for most species after ten days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle, and thus the amount of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales (less than 7 days) that are comparable to wet deposition.

Fluorescence quenching of protonated β-carbolines in water and microemulsions: evidence for heavy-atom and electron-transfer mechanisms.

PubMed

Mousa, Souad A; Douglas, Peter; Burrows, Hugh D; Fonseca, Sofia M

2013-09-01

The fluorescence quenching of protonated β-carbolines has been investigated in acidic aqueous solutions and in w/o microemulsions using I(-), Br(-), Cu(2+), SCN(-), and Pb(2+) as quenchers. It was found that fluorescence quenching by these compounds is much more efficient in water than in microemulsions since quenching in microemulsions depends on the simultaneous occupancy of the water droplets by both fluorophore and quencher. Linear Stern-Volmer plots were obtained in all cases, leading to quenching rate constants of ca. 10(8)-10(10) M(-1) s(-1) in water and ca. 10(7)-10(8) M(-1) s(-1) in microemulsions. In the case of quenching by SCN(-), ns flash photolysis studies indicate formation of (SCN)2(˙-) showing that at least part of the quenching process involves an electron transfer mechanism. This indicates that the singlet excited states of the protonated β-carbolines can act as relatively strong oxidants (E° > 1.6 V), capable of oxidizing many species, including the biologically relevant DNA base guanine. The observation of the (SCN)2(˙-) transient in microemulsions demonstrates that it is possible to have the protonated β-carboline and at least two thiocyanate ions in the same water pool.

A mechanistic study on the potential of quinolinium salts as photocatalysts for the abatement of chlorinated pollutants.

PubMed

Martinez-Haya, Rebeca; Sabater, Consuelo; Castillo, Maria-Ángeles; Miranda, Miguel A; Marin, M Luisa

2018-06-05

Photocatalytic degradation of three highly chlorinated contaminants, namely 2,4,6-trichlorophenol (TCP), 2,4,6-trichloroanisole (TCA) and 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan, TCS) has been investigated in the presence of N-methylquinolinium tetrafluoroborate (NMQ + ), a photocatalyst able to act via Type I or Type II mechanism. Photodegradation of contaminants under aerobic conditions was achieved within hours; and it was accompanied by mineralization, as demonstrated by trapping of the evolved carbon dioxide as barium carbonate. Moreover, a high degree of detoxification, based on % inmobilization of daphnids (Daphnia magna bioassay), was reached after 70 h of irradiation. Quenching of the NMQ + fluorescence by the pollutants was evidenced by a decrease in the emission intensity and lifetime. Detection of the reduced NMQ· by laser flash photolysis in the presence of the pollutants provided an unambigous evidence of the electron transfer process. Quenching of singlet oxygen by the contaminants showed the typical singlet oxygen quenching constants (10 5 -10 6  M -1  s -1 ). Evaluation of the relative contribution of both pathways (Type I vs Type II) point to the photodegradation occurring via a Type I mechanism, being the contribution of Type II mechanism negligible at any concentration range. Copyright © 2018 Elsevier B.V. All rights reserved.

A Micro-Electrode Array device coupled to a laser-based system for the local stimulation of neurons by optical release of glutamate.

PubMed

Ghezzi, Diego; Menegon, Andrea; Pedrocchi, Alessandra; Valtorta, Flavia; Ferrigno, Giancarlo

2008-10-30

Optical stimulation is a promising approach to investigate the local dynamic responses of cultured neurons. In particular, flash photolysis of caged compounds offers the advantage of allowing the rapid change of concentration of either extracellular or intracellular molecules, such as neurotransmitters or second messengers, for the stimulation or modulation of neuronal activity. We describe here the use of an ultra-violet (UV) laser diode coupled to an optical fibre for the local activation of caged compounds combined with a Micro-Electrode Array (MEA) device. Local uncaging was achieved by UV irradiation through the optical fibre previously positioned by using a red laser diode. The size of the stimulation was determined using caged fluorescein, whereas its efficacy was tested by studying the effect of uncaging the neurotransmitter glutamate. Uncaged glutamate evoked neuronal responses that were recorded using either fluorescence measurements or electrophysiological recordings with MEAs, thus showing the ability of our system to induce local neuronal excitation. This method allows overcoming the limitations of the MEA system related to unfocused electrical stimulation and induction of electrical artefacts. In addition, the coupling of a UV laser diode to an optical fibre allows a precise local stimulation and a quick change of the stimulation point.

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.

Photochemical and photocatalytic evaluation of 1D titanate/TiO2 based nanomaterials

NASA Astrophysics Data System (ADS)

Conceição, D. S.; Ferreira, D. P.; Graça, C. A. L.; Júlio, M. F.; Ilharco, L. M.; Velosa, A. C.; Santos, P. F.; Vieira Ferreira, L. F.

2017-01-01

One-dimensional (1D) titanate based nanomaterials were synthesized following an alkaline hydrothermal approach of commercial TiO2 nanopowder. The morphological features of all materials were monitored by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and also Brunauer-Emmett-Teller (BET) technique. In addition the photochemical behaviour of these nanostructured materials were evaluated with the use of laser induced luminescence (LIL), ground-state diffuse reflectance (GSDR), and laser-flash photolysis in diffuse reflectance mode (DRLFP). The mixed titanate/TiO2 nanowires presented the least intense fluorescence spectra, suggesting the presence of surficial defects that can extend the lifetime of the excited charge carriers. A fluorescent 'rhodamine-like' dye was adsorbed onto different materials and examined via photoexcitation in the visible range to study the self-photosensitization mechanism. The presence of the radical cation of the dye and the degradation kinetics, when compared with a neutral substrate-cellulose, provided significant evidences regarding the photoactivity of the different materials. Regarding all the materials under study, the nanowires exhibited a strong photocatalytic efficiency, for the adsorbed fluorescent probe. The photocatalytic mechanism was also considered by studying the photodegradation capability of the titanate based materials in the presence of an herbicide, Amicarbazone, after ultraviolet (UVA) photoexcitation.

Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Thompson, Kristopher M.; Gao, Yide; Marshall, Paul; Wang, Han; Zhou, Linsen; Li, Yongle; Guo, Hua

2017-10-01

The gas-phase kinetics of S(3P) atoms with H2 and D2 have been studied via the laser flash photolysis—resonance fluorescence technique. S atoms were generated by pulsed photolysis of CS2 at 193 nm and monitored by time-resolved fluorescence at 181 nm. The rate coefficients for H2 (k1) and D2 (k2), respectively, are summarized as k1(600-1110 K) = 3.0 × 10-9 exp(-1.317/×105-2.703 ×107K /T 8.314 T /K ) cm3 molecule-1 s-1 and k2(770-1110 K) = 2.2 × 10-14 (T/298 K)3.55 exp(-5420 K/T) cm3 molecule-1 s-1. Error limits are discussed in the text. The rate coefficients for formation of SH(SD) + H(D) on a newly developed triplet potential energy surface were characterized via ring polymer molecular dynamics and canonical variational transition-state theory. There is excellent agreement above about 1000 K between theory and experiment. At lower temperatures, the experimental rate coefficient is substantially larger than the results computed for the adiabatic reaction, suggesting a significant role for intersystem crossing to the singlet potential energy surface at lower temperatures.

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.

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...

Radiation predictions and shielding calculations for RITS-6

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

Maenchen, John Eric; O'Malley, John; Kensek, Ronald Patrick

2005-06-01

The mission of Radiographic Integrated Test Stand-6 (RITS-6) facility is to provide the underlying science and technology for pulsed-power-driven flash radiographic X-ray sources for the National Nuclear Security Administration (NNSA). Flash X-ray radiography is a penetrating diagnostic to discern the internal structure in dynamic experiments. Short (~50 nanosecond (ns) duration) bursts of very high intensity Xrays from mm-scale source sizes are required at a variety of voltages to address this mission. RITS-6 was designed and is used to both develop the accelerator technology needed for these experiments and serves as the principal test stand to develop the high intensity electronmore » beam diodes that generate the required X-ray sources. RITS is currently in operation with three induction cavities (RITS-3) with a maximum voltage output of 5.5 MV and is classified as a low hazard non-nuclear facility in accordance with CPR 400.1.1, Chapter 13, Hazards Identification/Analysis and Risk Management. The facility will be expanded from three to six cavities (RITS-6) effectively doubling the operating voltage. The increase in the operating voltage to above 10 MV has resulted in RITS-6 being classified as an accelerator facility. RITS-6 will come under DOE Order 420.2B, Safety of Accelerator Facilities. The hazards of RITS are detailed in the "Safety Assessment Document for the Radiographic Integrated Test Stand Facility." The principal non-industrial hazard is prompt x-ray radiation. As the operating voltage is increased, both the penetration power and the total amount (dose) of x-rays are increased, thereby increasing the risk to local personnel. Fixed site shielding (predominantly concrete walls and a steel/lead skyshine shield) is used to attenuate these x-rays and mitigate this risk. This SAND Report details the anticipated x-ray doses, the shielding design, and the anticipated x-ray doses external to this shielding structure both in areas where administrative access control restricts occupation and in adjacent uncontrolled areas.« less

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.

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.

Energy efficiency in nanoscale synthesis using nanosecond plasmas.

PubMed

Pai, David Z; Ken Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A; Levchenko, Igor; Laux, Christophe O

2013-01-01

We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO₃ nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges.

A nitric oxide concentration clamp.

PubMed

Zhelyaskov, V R; Godwin, D W

1999-10-01

We report a new method of generating nitric oxide (NO) that possesses several advantages for experimental use. This method consists of a photolysis chamber where NO is released by illuminating photolabile NO donors with light from a xenon lamp, in conjunction with feedback control. Control of the photolysis light was achieved by selectively gating light projected through a shutter before the light was launched into a light guide that conveyed the light to the photolysis chamber. By gating the light in proportion to a sensor that reported nearly instantaneous concentration from the photolysis chamber, a criterion NO concentration could be achieved, which could be easily adjusted to higher or lower criterion levels. To denote the similarity of this process with the electrophysiological process of voltage clamp, we term this process a concentration "clamp." This development enhances the use of the fiber-optic-based system for NO delivery and should enable the execution of experiments where the in situ concentration of NO is particularly critical, such as in biological preparations. Copyright 1999 Academic Press.

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

[Photodegradation of naproxen in aqueous systems by UV irradiation: mechanism and toxicity of photolysis products].

PubMed

Ma, Du-juan; Liu, Guo-guang; Lü, Wen-ying; Yao, Kun; Zhou, Li-hua; Xie, Cheng-ping

2013-05-01

This paper studies the degradation mechanism, the reaction kinetics and the toxicity of photolysis products of naproxen in waters under UV irradiation (120 W mercury lamp) by quenching experiments of reactive oxygen species (ROS), oxygen concentration experiment and toxicity evaluation using Vibrio fischeri bacteria. The results demonstrated that NPX could be degraded effectively by UV irradiation and the photolysis pathways was the sum of the degradation by direct photolysis and self-sensitization via ROS, and the contribution rates of self-sensitized photodegradation were 0.1%, 80.2%, 35.7% via *OH, (1)O2, O2*-, respectively. The effect of oxygen concentration illustrated that dissolved oxygen had an inhibitory effect on the direct photodegradation of NPX, and the higher the oxygen content, the more obvious the inhibitory effect. The toxicity evaluation illustrated the formation of some intermediate products that were more toxic than NPX during the photodegradation of NPX. The process of NPX degradation in all cases could be fitted by the pseudo first-order kinetics model.

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.

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.

Transmembrane molecular transport during versus after extremely large, nanosecond electric pulses.

PubMed

Smith, Kyle C; Weaver, James C

2011-08-19

Recently there has been intense and growing interest in the non-thermal biological effects of nanosecond electric pulses, particularly apoptosis induction. These effects have been hypothesized to result from the widespread creation of small, lipidic pores in the plasma and organelle membranes of cells (supra-electroporation) and, more specifically, ionic and molecular transport through these pores. Here we show that transport occurs overwhelmingly after pulsing. First, we show that the electrical drift distance for typical charged solutes during nanosecond pulses (up to 100 ns), even those with very large magnitudes (up to 10 MV/m), ranges from only a fraction of the membrane thickness (5 nm) to several membrane thicknesses. This is much smaller than the diameter of a typical cell (∼16 μm), which implies that molecular drift transport during nanosecond pulses is necessarily minimal. This implication is not dependent on assumptions about pore density or the molecular flux through pores. Second, we show that molecular transport resulting from post-pulse diffusion through minimum-size pores is orders of magnitude larger than electrical drift-driven transport during nanosecond pulses. While field-assisted charge entry and the magnitude of flux favor transport during nanosecond pulses, these effects are too small to overcome the orders of magnitude more time available for post-pulse transport. Therefore, the basic conclusion that essentially all transmembrane molecular transport occurs post-pulse holds across the plausible range of relevant parameters. Our analysis shows that a primary direct consequence of nanosecond electric pulses is the creation (or maintenance) of large populations of small pores in cell membranes that govern post-pulse transmembrane transport of small ions and molecules. Copyright © 2011 Elsevier Inc. All rights reserved.

Transmembrane molecular transport during versus after extremely large, nanosecond electric pulses

PubMed Central

Smith, Kyle C.; Weaver, James C.

2012-01-01

Recently there has been intense and growing interest in the non-thermal biological effects of nanosecond electric pulses, particularly apoptosis induction. These effects have been hypothesized to result from the widespread creation of small, lipidic pores in the plasma and organelle membranes of cells (supra-electroporation) and, more specifically, ionic and molecular transport through these pores. Here we show that transport occurs overwhelmingly after pulsing. First, we show that the electrical drift distance for typical charged solutes during nanosecond pulses (up to 100 ns), even those with very large magnitudes (up to 10 MV/m), ranges from only a fraction of the membrane thickness (5 nm) to several membrane thicknesses. This is much smaller than the diameter of a typical cell (~16 μm), which implies that molecular drift transport during nanosecond pulses is necessarily minimal. This implication is not dependent on assumptions about pore density or the molecular flux through pores. Second, we show that molecular transport resulting from post-pulse diffusion through minimum-size pores is orders of magnitude larger than electrical drift-driven transport during nanosecond pulses. While field-assisted charge entry and the magnitude of flux favor transport during nanosecond pulses, these effects are too small to overcome the orders of magnitude more time available for post-pulse transport. Therefore, the basic conclusion that essentially all transmembrane molecular transport occurs post-pulse holds across the plausible range of relevant parameters. Our analysis shows that a primary direct consequence of nanosecond electric pulses is the creation (or maintenance) of large populations of small pores in cell membranes that govern post-pulse transmembrane transport of small ions and molecules. PMID:21756883

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1978-01-01

A cyclic process is described for the solar photolysis of water, including a first stage in which water is reduced in the presence of a Eu(+2) photooxidizable reagent producing hydrogen and spent oxidized Eu(+3) reagent. The spent reagent Eu(+3) is reduced by means of a transition metal ligand complex reductant, RuL(+3) in a photoexcited state, such as a ruthenium pyridyl complex. Due to competing reactions between the photolysis and regeneration products, the photooxidation reaction must be separated from the regeneration in space and time by supporting the reagent and/or the reductant on solid supports and utilizing pH, wavelength and flow control to maximize hydrogen and oxygen production.

Production of organic compounds in plasmas - A comparison among electric sparks, laser-induced plasmas, and UV light

NASA Technical Reports Server (NTRS)

Scattergood, Thomas W.; Mckay, Christopher P.; Borucki, William J.; Giver, Lawrence P.; Van Ghyseghem, Hilde

1989-01-01

In order to ascertain the features of organic compound-production in planetary atmospheres under the effects of plasmas and shocks, various mixtures of N2, CH4, and H2 modeling the atmosphere of Titan were subjected to discrete sparks, laser-induced plasmas, and UV radiation. The experimental results obtained suggest that UV photolysis from the plasma is an important organic compound synthesis process, as confirmed by the photolysis of gas samples that were exposed to the light but not to the shock waves emitted by the sparks. The thermodynamic equilibrium theory is therefore incomplete in the absence of photolysis.

Pattern analysis of laser-tattoo interactions for picosecond- and nanosecond-domain 1,064-nm neodymium-doped yttrium-aluminum-garnet lasers in tissue-mimicking phantom.

PubMed

Ahn, Keun Jae; Zheng, Zhenlong; Kwon, Tae Rin; Kim, Beom Joon; Lee, Hye Sun; Cho, Sung Bin

2017-05-08

During laser treatment for tattoo removal, pigment chromophores absorb laser energy, resulting in fragmentation of the ink particles via selective photothermolysis. The present study aimed to outline macroscopic laser-tattoo interactions in tissue-mimicking (TM) phantoms treated with picosecond- and nanosecond-domain lasers. Additionally, high-speed cinematographs were captured to visualize time-dependent tattoo-tissue interactions, from laser irradiation to the formation of photothermal and photoacoustic injury zones (PIZs). In all experimental settings using the nanosecond or picosecond laser, tattoo pigments fragmented into coarse particles after a single laser pulse, and further disintegrated into smaller particles that dispersed toward the boundaries of PIZs after repetitive delivery of laser energy. Particles fractured by picosecond treatment were more evenly dispersed throughout PIZs than those fractured by nanosecond treatment. Additionally, picosecond-then-picosecond laser treatment (5-pass-picosecond treatment + 5-pass-picosecond treatment) induced greater disintegration of tattoo particles within PIZs than picosecond-then-nanosecond laser treatment (5-pass-picosecond treatment + 5-pass-nanosecond treatment). High-speed cinematography recorded the formation of PIZs after repeated reflection and propagation of acoustic waves over hundreds of microseconds to a few milliseconds. The present data may be of use in predicting three-dimensional laser-tattoo interactions and associated reactions in surrounding tissue.

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...

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.

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 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 mechanism and the toxicity assessment in TiO2 photocatalysis and photolysis of parathion.

PubMed

Kim, Tak-Soo; Kim, Jung-Kon; Choi, Kyungho; Stenstrom, Michael K; Zoh, Kyung-Duk

2006-02-01

The photocatalytic degradation of methyl parathion was carried out using a circulating TiO2/UV reactor. The experimental results showed that parathion was more effectively degraded in the photocatalytic condition than the photolysis and TiO2-only condition. With photocatalysis, 10mg/l parathion was completely degraded within 60 min with a TOC decrease exceeding 90% after 150 min. The main ionic byproducts during photocatalysis were measured. The nitrogen from parathion was recovered mainly as NO3-, NO2- and NH4+, 80% of the sulfur as SO4(2-), and less than 5% of the phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and paraoxon were also identified, and these were further degraded. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by photocatalysis and photolysis. A Microtox test using V. fischeri showed that the toxicity, expressed as the relative toxicity (%), was reduced almost completely after 90 min under photocatalysis, whereas only an 83% reduction was achieved with photolysis alone. Another toxicity test using D. magna also showed that the relative toxicity disappeared after 90 min under photocatalysis, whereas there was a 65% reduction in relative toxicity with photolysis alone. The pattern of toxicity reduction parallels the decrease in parathion and TOC concentrations.

Modeling of plasma chemical processes in the artificial ionized layer in the upper atmosphere by the nanosecond corona discharge

NASA Astrophysics Data System (ADS)

Vikharev, A. L.; Gorbachev, A. M.; Ivanov, O. A.; Kolisko, A. L.; Litvak, A. G.

1993-08-01

The plasma chemical processes in the corona discharge formed in air by a series of high voltage pulses of nanosecond duration are investigated experimentally. The experimental conditions (reduced electric field, duration and repetition frequency of the pulses, gas pressure in the chamber) modeled the regime of creation of the artificial ionized layer (AIL) in the upper atmosphere by a nanosecond microwave discharge. It was found that in a nanosecond microwave discharge predominantly generation of ozone occurs, and that the production of nitrogen dioxide is not large. The energy expenditures for the generation of one O 3 molecule were about 15 eV. On the basis of the experimental results the prognosis of the efficiency of ozone generation in AIL was made.

Energy efficiency in nanoscale synthesis using nanosecond plasmas

PubMed Central

Pai, David Z.; (Ken) Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A.; Levchenko, Igor; Laux, Christophe O.

2013-01-01

We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO3 nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges. PMID:23386976

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...

Comparison of two picosecond lasers to a nanosecond laser for treating tattoos: a prospective randomized study on 49 patients.

PubMed

Lorgeou, A; Perrillat, Y; Gral, N; Lagrange, S; Lacour, J-P; Passeron, T

2018-02-01

Q-switched nanosecond lasers demonstrated their efficacy in treating most types of tattoos, but complete disappearance is not always achieved even after performing numerous laser sessions. Picosecond lasers are supposed to be more efficient in clearing tattoos than nanosecond lasers, but prospective comparative data remain limited. To compare on different types of tattoos the efficacy of a nanosecond laser with two types of picosecond lasers. We conducted a prospective randomized study performed from December 2014 to June 2016 on adult patients with all types of tattoos. The tattoos were divided into two halves of equal size. After randomization, half of the tattoo was treated with a picosecond laser and the other half with a nanosecond laser. The evaluation was performed on standardized pictures performed before treatment and 2 months after the last session, by two physicians, not involved in the treatment, blinded on the type of treatments received. The main end point was a clearance above 75% of the tattoos. A total of 49 patients were included. Professional tattoos represented 85.7%, permanent make-up 8.2% and non-professional tattoo 6.1%. The majority were black or blue and 10.2% were polychromatic. No patient was lost during follow-up. A reduction of 75% or more of the colour intensity was obtained for 33% of the tattoos treated with the picosecond lasers compared to 14% with the nanosecond laser (P = 0.008). An improvement superior to 75% was obtained in 34% monochromic black or blue tattoos with the picosecond lasers compared to 9% for the nanosecond laser. Only one of the five polychromic tattoos achieved more than 75% of improvement with the two types of laser. Our results show a statistically significant superiority of the picosecond lasers compared to the nanosecond laser for tattoo clearance. However, they do not show better efficacy for polychromic tattoos and the difference in terms of side-effects was also minimal with a tendency of picosecond lasers to be less painful. © 2017 European Academy of Dermatology and Venereology.

Why Flash Type Matters: A Statistical Analysis

NASA Astrophysics Data System (ADS)

Mecikalski, Retha M.; Bitzer, Phillip M.; Carey, Lawrence D.

2017-09-01

While the majority of research only differentiates between intracloud (IC) and cloud-to-ground (CG) flashes, there exists a third flash type, known as hybrid flashes. These flashes have extensive IC components as well as return strokes to ground but are misclassified as CG flashes in current flash type analyses due to the presence of a return stroke. In an effort to show that IC, CG, and hybrid flashes should be separately classified, the two-sample Kolmogorov-Smirnov (KS) test was applied to the flash sizes, flash initiation, and flash propagation altitudes for each of the three flash types. The KS test statistically showed that IC, CG, and hybrid flashes do not have the same parent distributions and thus should be separately classified. Separate classification of hybrid flashes will lead to improved lightning-related research, because unambiguously classified hybrid flashes occur on the same order of magnitude as CG flashes for multicellular storms.

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.

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.

Formation of various types of nanostructures on germanium surface by nanosecond laser pulses

NASA Astrophysics Data System (ADS)

Mikolutskiy, S. I.; Khasaya, R. R.; Khomich, Yu V.; Yamshchikov, V. A.

2018-03-01

The paper describes the formation of micro- and nanostructures in different parts of irradiation zone on germanium surface by multiple action of nanosecond pulses of ArF-laser. It proposes a simple method using only one laser beam without any optional devices and masks for surface treatment. Hexa- and pentagonal cells with submicron dimensions along the surface were observed in peripheral zone of irradiation spot by atomic-force microscopy. Nanostructures in the form of bulbs with rounded peaks with lateral sizes of 40-120 nm were obtained in peripheral low-intensity region of the laser spot. Considering experimental data on material processing by nanosecond laser pulses, a classification of five main types of surface reliefs formed by nanosecond laser pulses with energy density near or slightly above ablation threshold was proposed.

Mach 5 bow shock control by a nanosecond pulse surface dielectric barrier discharge

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

Nishihara, M.; Takashima, K.; Rich, J. W.

2011-06-15

Bow shock perturbations in a Mach 5 air flow, produced by low-temperature, nanosecond pulse, and surface dielectric barrier discharge (DBD), are detected by phase-locked schlieren imaging. A diffuse nanosecond pulse discharge is generated in a DBD plasma actuator on a surface of a cylinder model placed in air flow in a small scale blow-down supersonic wind tunnel. Discharge energy coupled to the actuator is 7.3-7.8 mJ/pulse. Plasma temperature inferred from nitrogen emission spectra is a few tens of degrees higher than flow stagnation temperature, T = 340 {+-} 30 K. Phase-locked Schlieren images are used to detect compression waves generatedmore » by individual nanosecond discharge pulses near the actuator surface. The compression wave propagates upstream toward the baseline bow shock standing in front of the cylinder model. Interaction of the compression wave and the bow shock causes its displacement in the upstream direction, increasing shock stand-off distance by up to 25%. The compression wave speed behind the bow shock and the perturbed bow shock velocity are inferred from the Schlieren images. The effect of compression waves generated by nanosecond discharge pulses on shock stand-off distance is demonstrated in a single-pulse regime (at pulse repetition rates of a few hundred Hz) and in a quasi-continuous mode (using a two-pulse sequence at a pulse repetition rate of 100 kHz). The results demonstrate feasibility of hypersonic flow control by low-temperature, repetitive nanosecond pulse discharges.« less

LP/LIF STUDY OF THE FORMATION AND CONSUMPTION OF MERCURY (I) CHLORIDE: KINETICS OF MERCURY CHLORINATION

EPA Science Inventory

The laser photolysis/laser induced flourescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) has been detected via LIF at 272 nm from reactions of elemental Hg and Cl atoms generated from the 193 nm photolysis ...

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.

Purification of silane via laser-induced chemistry

DOEpatents

Clark, John H.; Anderson, Robert G.

1979-01-01

Impurities such as PH.sub.3, AsH.sub.3, and B.sub.2 H.sub.6 may be removed from SiH.sub.4 by means of selective photolysis with ultraviolet radiation of the appropriate wavelength. An ArF laser operating at 193 nm provides an efficient and effective radiation source for the photolysis.

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.

Cavity-enhanced measurements of hydrogen peroxide absorption cross sections from 353 to 410 nm.

PubMed

Kahan, Tara F; Washenfelder, Rebecca A; Vaida, Veronica; Brown, Steven S

2012-06-21

We report near-ultraviolet and visible absorption cross sections of hydrogen peroxide (H(2)O(2)) using incoherent broad-band cavity-enhanced absorption spectroscopy (IBBCEAS), a recently developed, high-sensitivity technique. The measurements reported here span the range of 353-410 nm and extend published electronic absorption cross sections by 60 nm to absorption cross sections below 1 × 10(-23) cm(2) molecule(-1). We have calculated photolysis rate constants for H(2)O(2) in the lower troposphere at a range of solar zenith angles by combining the new measurements with previously reported data at wavelengths shorter than 350 nm. We predict that photolysis at wavelengths longer than those included in the current JPL recommendation may account for up to 28% of the total hydroxyl radical (OH) production from H(2)O(2) photolysis under some conditions. Loss of H(2)O(2) via photolysis may be of the same order of magnitude as reaction with OH and dry deposition in the lower atmosphere; these processes have very different impacts on HO(x) loss and regeneration.

State selectivity and dynamics in dissociative electron attachment to CF₃I revealed through velocity slice imaging.

PubMed

Ómarsson, Frímann H; Mason, Nigel J; Krishnakumar, E; Ingólfsson, Oddur

2014-11-03

In light of its substantially more environmentally friendly nature, CF3I is currently being considered as a replacement for the highly potent global-warming gas CF4, which is used extensively in plasma processing. In this context, we have studied the electron-driven dissociation of CF3I to form CF3(-) and I, and we compare this process to the corresponding photolysis channel. By using the velocity slice imaging (VSI) technique we can visualize the complete dynamics of this process and show that electron-driven dissociation proceeds from the same initial parent state as the corresponding photolysis process. However, in contrast to photolysis, which leads nearly exclusively to the (2)P(1/2) excited state of iodine, electron-induced dissociation leads predominantly to the (2)P(3/2) ground state. We believe that the changed spin state of the negative ion allows an adiabatic dissociation through a conical intersection, whereas this path is efficiently repressed by a required spin flip in the photolysis process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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).

Simultaneous high crystallinity and sub-bandgap optical absorptance in hyperdoped black silicon using nanosecond laser annealing

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

Franta, Benjamin, E-mail: bafranta@gmail.com; Pastor, David; Gandhi, Hemi H.

2015-12-14

Hyperdoped black silicon fabricated with femtosecond laser irradiation has attracted interest for applications in infrared photodetectors and intermediate band photovoltaics due to its sub-bandgap optical absorptance and light-trapping surface. However, hyperdoped black silicon typically has an amorphous and polyphasic polycrystalline surface that can interfere with carrier transport, electrical rectification, and intermediate band formation. Past studies have used thermal annealing to obtain high crystallinity in hyperdoped black silicon, but thermal annealing causes a deactivation of the sub-bandgap optical absorptance. In this study, nanosecond laser annealing is used to obtain high crystallinity and remove pressure-induced phases in hyperdoped black silicon while maintainingmore » high sub-bandgap optical absorptance and a light-trapping surface morphology. Furthermore, it is shown that nanosecond laser annealing reactivates the sub-bandgap optical absorptance of hyperdoped black silicon after deactivation by thermal annealing. Thermal annealing and nanosecond laser annealing can be combined in sequence to fabricate hyperdoped black silicon that simultaneously shows high crystallinity, high above-bandgap and sub-bandgap absorptance, and a rectifying electrical homojunction. Such nanosecond laser annealing could potentially be applied to non-equilibrium material systems beyond hyperdoped black silicon.« less

Tailor-made dimensions of diblock copolymer truncated micelles on a solid by UV irradiation.

PubMed

Liou, Jiun-You; Sun, Ya-Sen

2015-09-28

We investigated the structural evolution of truncated micelles in ultrathin films of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, of monolayer thickness on bare silicon substrates (SiOx/Si) upon UV irradiation in air- (UVIA) and nitrogen-rich (UVIN) environments. The structural evolution of micelles upon UV irradiation was monitored using GISAXS measurements in situ, while the surface morphology was probed using atomic force microscopy ex situ and the chemical composition using X-ray photoelectron spectroscopy (XPS). This work provides clear evidence for the interpretation of the relationship between the structural evolution and photochemical reactions in PS-b-P2VP truncated micelles upon UVIA and UVIN. Under UVIA treatment, photolysis and cross-linking reactions coexisted within the micelles; photolysis occurred mainly at the top of the micelles, whereas cross-linking occurred preferentially at the bottom. The shape and size of UVIA-treated truncated micelles were controlled predominantly by oxidative photolysis reactions, which depended on the concentration gradient of free radicals and oxygen along the micelle height. Because of an interplay between photolysis and photo-crosslinking, the scattering length densities (SLD) of PS and P2VP remained constant. In contrast, UVIN treatments enhanced the contrast in SLD between the PS shell and the P2VP core as cross-linking dominated over photolysis in the presence of nitrogen. The enhancement of the SLD contrast was due to the various degrees of cross-linking under UVIN for the PS and P2VP blocks.

Parathion degradation and toxicity reduction in solar photocatalysis and photolysis.

PubMed

Zoh, K D; Kim, T S; Kim, J G; Choi, K; Yi, S M

2006-01-01

The solar photocatalytic degradation of methyl parathion was investigated using a circulating TiO2/solar light reactor. Under solar photocatalysis condition, parathion was more effectively degraded than solar photolysis and TiO2-only conditions. With solar photocatalysis, 20 mg/L of parathion was completely degraded within 60 min with a TOC decrease of 63% after 150 min. The main ionic byproducts during photocatalysis recovered from parathion degradation were mainly as NO3-, NO2- and NH4+, 80% of the sulphur as SO4(2-), and 5% of phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and methyl paraoxon were also identified, and these were further degraded in solar photocatalytic condition. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by solar photocatalysis and photolysis. The Microtox test using V. fischeri showed that the toxicity expressed as EC50 (%) value increased from 5.5% to >82% in solar photocatalysis, indicating that the treated solution is non-toxic, but only increased from 4.9 to 20.5% after 150 min in solar photolysis. The acute toxicity test using D. magna showed that EC50 (%) increased from 0.05 to 1.08% under solar photocatalysis, but only increased to 0.12% after 150 min with solar photolysis, indicating the solution is still toxic. The pattern of toxicity reduction parallels the decrease in TOC and the parathion concentrations.

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.

Nitryl chloride (ClNO2): UV/vis absorption spectrum between 210 and 296 K and O(3P) quantum yield at 193 and 248 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Roberts, James M; Burkholder, James B

2012-06-21

Recent studies have shown that the UV/vis photolysis of nitryl chloride (ClNO2) can be a major source of reactive chlorine in the troposphere. The present work reports measurements of the ClNO2 absorption spectrum and its temperature dependence between 210 and 296 K over the wavelength range 200–475 nm using diode array spectroscopy. The room temperature spectrum obtained in this work was found to be in good agreement with the results from Ganske et al. (J. Geophys. Res. 1992, 97, 7651) over the wavelength range common to both studies (200–370 nm) but differs systematically from the currently recommended spectrum for use in atmospheric models. The present results lead to a decrease in the calculated atmospheric ClNO2 photolysis rate by 30%. Including the temperature dependence of the ClNO2 spectrum decreases the calculated atmospheric photolysis rate at lower temperatures (higher altitudes) even further. A parametrization of the wavelength and temperature dependence of the ClNO2 spectrum is presented. O(3P) quantum yields, Φ(ClNO2)(O), in the photolysis of ClNO2 at 193 and 248 nm were measured at 296 K using pulsed laser photolysis combined with atomic resonance fluorescence detection of O(3P) atoms. Φ(ClNO2)(O)(λ) was found to be 0.67 ± 0.12 and 0.15 ± 0.03 (2σ error limits, including estimated systematic errors) at 193 and 248 nm, respectively, indicating that multiple dissociation channels are active in the photolysis of ClNO2 at these wavelengths. The Φ(ClNO2)(O)(λ) values obtained in this work are discussed in light of previous ClNO2 photodissociation studies and the differences are discussed.

Effects of oil dispersants on photodegradation of parent and alkylated anthracene in seawater.

PubMed

Cai, Zhengqing; Liu, Wen; Fu, Jie; O'Reilly, S E; Zhao, Dongye

2017-10-01

This study investigated effects of three model oil dispersants on photodegradation of two model PAHs (anthracene and 9,10-dimethyanthracene (9,10-DMA)) under simulated sunlight. All three dispersants, i.e. Corexit EC9500A, Corexit EC9527A and SPC 1000, promoted the photolysis rate of 9,10-DMA, following the order of Corexit EC9500A > Corexit EC9527A > SPC 1000. The photodegradation rate was well interpreted by a two-stage, first-order kinetic law with a faster initial photolysis rate in the presence of the dispersants. Span 80, Tween 85 and kerosene were found as the key dispersant components, of which Span 80 and Tween 85 promoted the photodegradation by boosting absorbance of solar irradiation while kerosene by dispersing more PAHs in the upper layer of the water column. Dissolved oxygen (DO) inhibited photolysis of anthracene regardless of dispersant resulting from quenching the excited states of the PAH, while DO facilitated photolysis of 9,10-DMA due to the formation singlet oxygen ( 1 O 2 ) radicals in the presence of oil dispersants. The other ROS, i.e. •O 2 - and •OH, played a negligible role on the photodegradation of anthracene and 9,10-DMA. Fluorescence analysis showed that more anthracene was associated with dispersant than 9,10-DMA, which favored the direct transfer of energy to anthracene, while energy is more likely transferred to oxygen to form 1 O 2 in the case of 9,10-DMA. Direct photolysis dominated the photodegradation of anthracene and 9,10-DMA. Both direct ionization of anthracene and the electron transfer from excited 9,10-DMA to oxygen can lead to formation of the corresponding PAH radical cations. Overall, the oil dispersants accelerated the photolysis rates of the PAHs without altering the degradation pathway. The findings are useful for understanding photochemical weathering of dispersed oil components in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

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-bridges than for positively strained ones. This marked strain dependence of cross-bridge detachment is predicted from the model of A. F. Huxley (1957). 8. In the presence of Ca2+, activation of contraction following photolysis of caged ATP was slowed by inclusion of 20-500 microM-MgADP in the medium. An initial decrease in tension related to cross-bridge detachment by MgATP was markedly suppressed in the presence of MgADP. 9. Ten millimolar Pi partly suppressed active tension generation in the presence of MgADP.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:1886072

New and Advanced Picosecond Lasers for Tattoo Removal.

PubMed

Adatto, Maurice A; Amir, Ruthie; Bhawalkar, Jayant; Sierra, Rafael; Bankowski, Richard; Rozen, Doran; Dierickx, Christine; Lapidoth, Moshe

2017-01-01

Early methods of tattoo removal ultimately resulted in unacceptable cosmetic outcomes. While the introduction of laser technology was an improvement over the existing chemical, mechanical, and surgical procedures, the use of nonselective tattoo removal with carbon dioxide and argon lasers led to scarring. Q-switched lasers with nanosecond (10-9) pulse domains were considered to have revolutionized tattoo treatment, by selectively heating the tattoo particles, while reducing the adverse sequelae to adjacent normal skin. Theoretical considerations of restricting pulse duration, to heat tattoo particles to higher temperatures, proposed the use of sub-nanosecond pulses to target particles with thermal relaxation times lower than the nanosecond pulses in Q-switched lasers. Initial studies demonstrated that picosecond (10-12) pulses were more effective than nanosecond pulses in clearing black tattoos. Advances in picosecond technology led to the development of commercially available lasers, incorporating several different wavelengths, to further refine pigment targeting. © 2017 S. Karger AG, Basel.

Novel denture-cleaning system based on hydroxyl radical disinfection.

PubMed

Kanno, Taro; Nakamura, Keisuke; Ikai, Hiroyo; Hayashi, Eisei; Shirato, Midori; Mokudai, Takayuki; Iwasawa, Atsuo; Niwano, Yoshimi; Kohno, Masahiro; Sasaki, Keiichi

2012-01-01

The purpose of this study was to evaluate a new denture-cleaning device using hydroxyl radicals generated from photolysis of hydrogen peroxide (H2O2). Electron spin resonance analysis demonstrated that the yield of hydroxyl radicals increased with the concentration of H2O2 and light irradiation time. Staphylococcus aureus, Pseudomonas aeruginosa, and methicillin-resistant S aureus were killed within 10 minutes with a > 5-log reduction when treated with photolysis of 500 mM H2O2; Candida albicans was killed within 30 minutes with a > 4-log reduction with photolysis of 1,000 mM H2O2. The clinical test demonstrated that the device could effectively reduce microorganisms in denture plaque by approximately 7-log order within 20 minutes.

Measuring hot flash phenomenonology using ambulatory prospective digital diaries

PubMed Central

Fisher, William I.; Thurston, Rebecca C.

2016-01-01

Objective This study provides the description, protocol, and results from a novel prospective ambulatory digital hot flash phenomenon diary. Methods This study included 152 midlife women with daily hot flashes who completed an ambulatory electronic hot flash diary continuously for the waking hours of 3 consecutive days. In this diary, women recorded their hot flashes and accompanying characteristics and associations as the hot flashes occurred. Results Self-reported hot flash severity on the digital diaries indicated that the majority of hot flashes were rated as mild (41.3%) or moderate (43.7%). Severe (13.1%) and very severe (1.8%) hot flashes were less common. Hot flash bother ratings were rated as mild (43%), or moderate (33.5%), with fewer hot flashes reported bothersome (17.5%) or very bothersome (6%). The majority of hot flashes were reported as occurring on the on the face (78.9%), neck (74.7%), and chest (61.3%). Prickly skin was reported concurrently with 32% of hot flashes, 7% with anxiety and 5% with nausea. A novel finding, 38% of hot flashes were accompanied by a premonitory aura. Conclusion A prospective electronic digital hot flash diary allows for a more precise quantitation of hot flashes while overcoming many of the limitations of commonly employed retrospective questionnaires and paper diaries. Unique insights into the phenomenology, loci and associated characteristics of hot flashes were obtained using this device. The digital hot flash phenomenology diary is recommended for future ambulatory studies of hot flashes as a prospective measure of the hot flash experience. PMID:27404030

Measuring hot flash phenomenonology using ambulatory prospective digital diaries.

PubMed

Fisher, William I; Thurston, Rebecca C

2016-11-01

This study provides the description, protocol, and results from a novel prospective ambulatory digital hot flash phenomenon diary. This study included 152 midlife women with daily hot flashes who completed an ambulatory electronic hot flash diary continuously for the waking hours of three consecutive days. In this diary, women recorded their hot flashes and accompanying characteristics and associations as the hot flashes occurred. Self-reported hot flash severity on the digital diaries indicated that the majority of hot flashes were rated as mild (41.3%) or moderate (43.7%). Severe (13.1%) and very severe (1.8%) hot flashes were less common. Hot flash bother ratings were rated as mild (43%), or moderate (33.5%), with fewer hot flashes reported bothersome (17.5%) or very bothersome (6%). The majority of hot flashes were reported as occurring on the face (78.9%), neck (74.7%), and chest (61.3%). Of all reported hot flashes, 32% occurred concurrently with prickly skin, 7% with anxiety, and 5% with nausea. A novel finding from the study was that 38% of hot flashes were accompanied by a premonitory aura. A prospective electronic digital hot flash diary allows for a more precise quantitation of hot flashes while overcoming many of the limitations of commonly used retrospective questionnaires and paper diaries. Unique insights into the phenomenology, loci, and associated characteristics of hot flashes were obtained using this device. The digital hot flash phenomenology diary is recommended for future ambulatory studies of hot flashes as a prospective measure of the hot flash experience.

A distributed parameter model of transmission line transformer for high voltage nanosecond pulse generation

NASA Astrophysics Data System (ADS)

Li, Jiangtao; Zhao, Zheng; Li, Longjie; He, Jiaxin; Li, Chenjie; Wang, Yifeng; Su, Can

2017-09-01

A transmission line transformer has potential advantages for nanosecond pulse generation including excellent frequency response and no leakage inductance. The wave propagation process in a secondary mode line is indispensable due to an obvious inside transient electromagnetic transition in this scenario. The equivalent model of the transmission line transformer is crucial for predicting the output waveform and evaluating the effects of magnetic cores on output performance. However, traditional lumped parameter models are not sufficient for nanosecond pulse generation due to the natural neglect of wave propagations in secondary mode lines based on a lumped parameter assumption. In this paper, a distributed parameter model of transmission line transformer was established to investigate wave propagation in the secondary mode line and its influential factors through theoretical analysis and experimental verification. The wave propagation discontinuity in the secondary mode line induced by magnetic cores is emphasized. Characteristics of the magnetic core under a nanosecond pulse were obtained by experiments. Distribution and formation of the secondary mode current were determined for revealing essential wave propagation processes in secondary mode lines. The output waveform and efficiency were found to be affected dramatically by wave propagation discontinuity in secondary mode lines induced by magnetic cores. The proposed distributed parameter model was proved more suitable for nanosecond pulse generation in aspects of secondary mode current, output efficiency, and output waveform. In depth, comprehension of underlying mechanisms and a broader view of the working principle of the transmission line transformer for nanosecond pulse generation can be obtained through this research.

A nanosecond pulsed laser heating system for studying liquid and supercooled liquid films in ultrahigh vacuum

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

Xu, Yuntao; Dibble, Collin J.; Petrik, Nikolay G.

2016-04-26

A pulsed laser heating system has been developed that enables investigations of the dynamics and kinetics of nanoscale liquid films and liquid/solid interfaces on the nanosecond timescale in ultrahigh vacuum (UHV). Details of the design, implementation and characterization of a nanosecond pulsed laser system for transiently heating nanoscale films are described. Nanosecond pulses from a Nd:YAG laser are used to rapidly heat thin films of adsorbed water or other volatile materials on a clean, well-characterized Pt(111) crystal in UHV. Heating rates of ~1010 K/s for temperature increases of ~100 – 200 K are obtained. Subsequent rapid cooling (~5 × 109more » K/s) quenches the film, permitting in-situ, post-mortem analysis using a variety of surface science techniques. Lateral variations in the laser pulse energy are ~ ± 3% leading to a temperature uncertainty of ~ ± 5 K for a temperature jump of 200 K. Initial experiments with the apparatus demonstrate that crystalline ice films initially held at 90 K can be rapidly transformed into liquid water films with T > 273 K. No discernable recrystallization occurs during the rapid cooling back to cryogenic temperatures. In contrast, amorphous solid water films heated below the melting point rapidly crystallize. The nanosecond pulsed laser heating system can prepare nanoscale liquid and supercooled liquid films that persist for nanoseconds per heat pulse in an UHV environment, enabling experimental studies of a wide range of phenomena in liquids and at liquid/solid interfaces.« less

A distributed parameter model of transmission line transformer for high voltage nanosecond pulse generation.

PubMed

Li, Jiangtao; Zhao, Zheng; Li, Longjie; He, Jiaxin; Li, Chenjie; Wang, Yifeng; Su, Can

2017-09-01

A transmission line transformer has potential advantages for nanosecond pulse generation including excellent frequency response and no leakage inductance. The wave propagation process in a secondary mode line is indispensable due to an obvious inside transient electromagnetic transition in this scenario. The equivalent model of the transmission line transformer is crucial for predicting the output waveform and evaluating the effects of magnetic cores on output performance. However, traditional lumped parameter models are not sufficient for nanosecond pulse generation due to the natural neglect of wave propagations in secondary mode lines based on a lumped parameter assumption. In this paper, a distributed parameter model of transmission line transformer was established to investigate wave propagation in the secondary mode line and its influential factors through theoretical analysis and experimental verification. The wave propagation discontinuity in the secondary mode line induced by magnetic cores is emphasized. Characteristics of the magnetic core under a nanosecond pulse were obtained by experiments. Distribution and formation of the secondary mode current were determined for revealing essential wave propagation processes in secondary mode lines. The output waveform and efficiency were found to be affected dramatically by wave propagation discontinuity in secondary mode lines induced by magnetic cores. The proposed distributed parameter model was proved more suitable for nanosecond pulse generation in aspects of secondary mode current, output efficiency, and output waveform. In depth, comprehension of underlying mechanisms and a broader view of the working principle of the transmission line transformer for nanosecond pulse generation can be obtained through this research.

A nanosecond pulsed laser heating system for studying liquid and supercooled liquid films in ultrahigh vacuum.

PubMed

Xu, Yuntao; Dibble, Collin J; Petrik, Nikolay G; Smith, R Scott; Joly, Alan G; Tonkyn, Russell G; Kay, Bruce D; Kimmel, Greg A

2016-04-28

A pulsed laser heating system has been developed that enables investigations of the dynamics and kinetics of nanoscale liquid films and liquid/solid interfaces on the nanosecond time scale in ultrahigh vacuum (UHV). Details of the design, implementation, and characterization of a nanosecond pulsed laser system for transiently heating nanoscale films are described. Nanosecond pulses from a Nd:YAG laser are used to rapidly heat thin films of adsorbed water or other volatile materials on a clean, well-characterized Pt(111) crystal in UHV. Heating rates of ∼10(10) K/s for temperature increases of ∼100-200 K are obtained. Subsequent rapid cooling (∼5 × 10(9) K/s) quenches the film, permitting in-situ, post-heating analysis using a variety of surface science techniques. Lateral variations in the laser pulse energy are ∼±2.7% leading to a temperature uncertainty of ∼±4.4 K for a temperature jump of 200 K. Initial experiments with the apparatus demonstrate that crystalline ice films initially held at 90 K can be rapidly transformed into liquid water films with T > 273 K. No discernable recrystallization occurs during the rapid cooling back to cryogenic temperatures. In contrast, amorphous solid water films heated below the melting point rapidly crystallize. The nanosecond pulsed laser heating system can prepare nanoscale liquid and supercooled liquid films that persist for nanoseconds per heat pulse in an UHV environment, enabling experimental studies of a wide range of phenomena in liquids and at liquid/solid interfaces.

Cross-bridge kinetics, cooperativity, and negatively strained cross- bridges in vertebrate smooth muscle. A laser-flash photolysis study

PubMed Central

1988-01-01

The effects of laser-flash photolytic release of ATP from caged ATP [P3- 1(2-nitrophenyl)ethyladenosine-5'-triphosphate] on stiffness and tension transients were studied in permeabilized guinea pig protal vein smooth muscle. During rigor, induced by removing ATP from the relaxed or contracting muscles, stiffness was greater than in relaxed muscle, and electron microscopy showed cross-bridges attached to actin filaments at an approximately 45 degree angle. In the absence of Ca2+, liberation of ATP (0.1-1 mM) into muscles in rigor caused relaxation, with kinetics indicating cooperative reattachment of some cross- bridges. Inorganic phosphate (Pi; 20 mM) accelerated relaxation. A rapid phase of force development, accompanied by a decline in stiffness and unaffected by 20 mM Pi, was observed upon liberation of ATP in muscles that were released by 0.5-1.0% just before the laser pulse. This force increment observed upon detachment suggests that the cross- bridges can bear a negative tension. The second-order rate constant for detachment of rigor cross-bridges by ATP, in the absence of Ca2+, was estimated to be 0.1-2.5 X 10(5) M-1s-1, which indicates that this reaction is too fast to limit the rate of ATP hydrolysis during physiological contractions. In the presence of Ca2+, force development occurred at a rate (0.4 s-1) similar to that of intact, electrically stimulated tissue. The rate of force development was an order of magnitude faster in muscles that had been thiophosphorylated with ATP gamma S before the photochemical liberation of ATP, which indicates that under physiological conditions, in non-thiophosphorylated muscles, light-chain phosphorylation, rather than intrinsic properties of the actomyosin cross-bridges, limits the rate of force development. The release of micromolar ATP or CTP from caged ATP or caged CTP caused force development of up to 40% of maximal active tension in the absence of Ca2+, consistent with cooperative attachment of cross-bridges. Cooperative reattachment of dephosphorylated cross-bridges may contribute to force maintenance at low energy cost and low cross-bridge cycling rates in smooth muscle. PMID:3373178

Kinetics of the Reactions of IO Radicals with NO and NO2

NASA Technical Reports Server (NTRS)

Daykin, E. P.; Wine, P. H.

1997-01-01

A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

p/n-Polarity of thiophene oligomers in photovoltaic cells: role of molecular vs. supramolecular properties.

PubMed

Ghosh, Tanwistha; Gopal, Anesh; Saeki, Akinori; Seki, Shu; Nair, Vijayakumar C

2015-04-28

Molecular and supramolecular properties play key roles in the optoelectronic properties and photovoltaic performances of organic materials. In the present work, we show how small changes in the molecular structure affect such properties, which in turn control the intrinsic and fundamental properties such as the p/n-polarity of organic semiconductors in bulk-heterojunction solar cells. Herein, we designed and synthesized two acceptor-donor-acceptor type semiconducting thiophene oligomers end-functionalized with oxazolone/isoxazolone derivatives (OT1 and OT2 respectively). The HOMO-LUMO energy levels of both derivatives were found to be positioned in such a way that they can act as electron acceptors to P3HT and electron donors to PCBM. However, OT1 functions as a donor (with PCBM) and OT2 as an acceptor (with P3HT) in BHJ photovoltaic cells, and their reverse roles results in either no or poor performance of the cells. Detailed studies using UV-vis absorption and fluorescence spectroscopy, time-correlated single photon counting, UV-photoelectron spectroscopy, density functional theory calculations, X-ray diffraction, and thermal gravimetric analysis proved that both molecular and supramolecular properties contributed equally but in a contrasting manner to the abovementioned observation. The obtained results were further validated by flash-photolysis time-resolved microwave conductivity studies which showed an excellent correlation between the structure, property, and device performances of the materials.

Intraprotein electron transfer between the FMN and heme domains in endothelial nitric oxide synthase holoenzyme

PubMed Central

Feng, Changjian; Taiakina, Valentina; Ghosh, Dipak K.; Guillemette, J. Guy; Tollin, Gordon

2011-01-01

Intraprotein electron transfer (IET) from flavin mononucleotide (FMN) to heme is an essential step in nitric oxide (NO) synthesis by NO synthase (NOS). The IET kinetics in neuronal and inducible NOS (nNOS and iNOS) holoenzymes have been previously determined in our laboratories by laser flash photolysis [reviewed in: C.J. Feng, G. Tollin, Dalton Trans., (2009) 6692-6700]. Here we report the kinetics of the IET in a bovine endothelial NOS (eNOS) holoenzyme in the presence and absence of added calmodulin (CaM). The IET rate constant in the presence of CaM is estimated to be ~ 4.3 s-1. No IET was observed in the absence of CaM, indicating that CaM is the primary factor in controlling the FMN–heme IET in the eNOS enzyme. The IET rate constant value for the eNOS holoenzyme is approximately 10 times smaller than those obtained for the iNOS and CaM-bound nNOS holoenzymes. Possible mechanisms underlying the difference in IET kinetics among the NOS isoforms are discussed. Because the rate-limiting step in the IET process in these enzymes is the conformational change from input state to output state, a slower conformational change (than in the other isoforms) is most likely to cause the slower IET in eNOS. PMID:21864726

Aquatic photochemistry of sulfamethazine: multivariate effects of main water constituents and mechanisms.

PubMed

Li, Yingjie; Liu, Xiangliang; Zhang, Biaojun; Zhao, Qun; Ning, Ping; Tian, Senlin

2018-03-01

The ubiquity of sulfonamides (SAs) in natural waters requires insight into their environmental fate for ecological risk assessment. Extensive studies focused on the effect of univariate water constituents on the photochemical fate of SAs, yet the multivariate effects of water constituents in environmentally relevant concentrations on SA photodegradation are poorly understood. Here, response surface methodology was employed to explore the integrative effects of main water constituents (dissolved organic matter (DOM), NO 3 - , HCO 3 - , Cu 2+ ) on the photodegradation of a representative SA (sulfamethazine). Results showed that besides single factors, interaction of factors also significantly impacted the photodegradation. Radical scavenging experiments indicated that triplet-excited DOM ( 3 DOM*) was responsible for the enhancing effect of DOM on the photodegradation. Additionally, DOM may also quench the 3 DOM*-mediated oxidation intermediate of sulfamethazine causing the inhibiting effect of DOM-DOM interaction. We also found that HCO 3 - was oxidized by triplet-excited sulfamethazine producing CO 3 ˙ - , and the high reactivity of CO 3 ˙ - with sulfamethazine (second-order rate constant 2.2 × 10 8 M -1 s -1 ) determined by laser flash photolysis revealed the enhancing photodegradation mechanism of HCO 3 - . This study is among the first attempts to probe the photodegradation of SAs considering the integrative effects of water constituents, which is important in accurate ecological risk assessment of organic pollutants in the aquatic environment.

Transient Ligand Docking Sites in Cerebratulus lacteus Mini-Hemoglobin

PubMed Central

Deng, Pengchi; Nienhaus, Karin; Palladino, Pasquale; Olson, John S.; Blouin, George; Moens, Luc; Dewilde, Sylvia; Geuens, Eva; Nienhaus, G. Ulrich

2007-01-01

The monomeric hemoglobin of the nemertean worm Cerebratulus lacteus functions as an oxygen storage protein to maintain neural activity under hypoxic conditions. It shares a large, apolar matrix tunnel with other small hemoglobins, which has been implicated as a potential ligand migration pathway. Here we explore ligand migration and binding within the distal heme pocket, to which the tunnel provides access to ligands from the outside. FTIR/TDS experiments performed at cryogenic temperatures reveal the presence of three transient ligand docking sites within the distal pocket, the primary docking site B on top of pyrrole C and secondary sites C and D. Site C is assigned to a cavity adjacent to the distal portion of the heme pocket, surrounded by the B and E helices. It has an opening to the apolar tunnel and is expected to be on the pathway for ligand entry and exit, whereas site D, circumscribed by TyrB10, GlnE7, and the CD corner, most likely is located on a side pathway of ligand migration. Flash photolysis experiments at ambient temperatures indicate that the rate-limiting step for ligand binding to CerHb is migration through the apolar channel to site C. Movement from C to B and iron-ligand bond formation involve low energy barriers and thus are very rapid processes in the wt protein. PMID:17531406

Micellized tris(bipyridine)ruthenium catalysts affording preparative amounts of hydrated electrons with a green light-emitting diode.

PubMed

Naumann, Robert; Lehmann, Florian; Goez, Martin

2018-05-16

We have explored alkyl substitution of the ligands as a means to improve the performance of the title complexes in photoredox catalytic systems that produce synthetically useable amounts of hydrated electrons through photon pooling. Despite generating a superreductant, these electron sources only consume the bioavailable ascorbate and are driven by a green light-emitting diode (LED). The substitutions influence the catalyst activity through the quenching and recombination rates across the micelle-water interface, and the photoionization quantum yield. Laser flash photolysis yields comprehensive information on all these processes and allows quantitative predictions of the activity observed in LED kinetics, but the latter provides the only access to the catalyst stability under illumination on the timescale of the syntheses. The homoleptic complex with dimethylbipyridine ligands emerges as the optimum that combines an activity twice as high with an undiminished stability in relation to the parent compound. With this complex, we have effected dehalogenations of alkyl and aryl chlorides and fluorides, hydrogenations of carbon-carbon double bonds, and self- as well as cross-couplings. All the substrates employed are impervious to ordinary photoredox catalysts but present no problems to the hydrated electron as a super-reductant. A particularly attractive application is selective deuteration with high isotopic purity, which is achieved simply by using heavy water as the solvent. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visible light-driven O2 reduction by a porphyrin-laccase system.

PubMed

Lazarides, Theodore; Sazanovich, Igor V; Simaan, A Jalila; Kafentzi, Maria Chrisanthi; Delor, Milan; Mekmouche, Yasmina; Faure, Bruno; Réglier, Marius; Weinstein, Julia A; Coutsolelos, Athanassios G; Tron, Thierry

2013-02-27

Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.

Summer 2015 measurements of total OH reactivity at a UK coastal site

NASA Astrophysics Data System (ADS)

Woodward-Massey, R.; Cryer, D. R.; Whalley, L. K.; Ingham, T.; Crilley, L.; Kramer, L. J.; Reeves, C.; Forster, G.; Oram, D.; Bandy, B.; Reed, C.; Lee, J. D.; Bloss, W.; Heard, D. E.

2015-12-01

The hydroxyl radical (OH) plays a central role in the day time oxidative removal of pollutants and greenhouse gases in the atmosphere. It is essential that all production and loss pathways of OH are understood and included in computer models in order to accurately predict OH concentrations for a range of environments, and in turn the rate of production of secondary products, for example ozone and organic aerosol. Direct measurement of total OH reactivity, the pseudo first order rate coefficient for OH loss by reaction with its sinks, is a very useful tool to test how complete our knowledge is of OH loss pathways. Comparison with values of total OH reactivity calculated by computer models using concentrations of simultaneously measured OH 'sinks' and unmeasured intermediates enables environments to be identified where there are unidentified 'missing' OH sinks. Total OH reactivity was measured using the laser flash photolysis combined with time-resolved laser-induced fluorescence technique during the ICOZA (Integrated Chemistry of OZone in the Atmosphere) campaign in July 2015 at the Weybourne Atmospheric Observatory (WAO), Norfolk, UK. Air masses sampled ranged from polluted air from the UK or Europe containing processed urban emissions to very clean air of marine origin. Data for measured and calculated OH reactivity will be presented in addition to a discussion of the magnitude of the 'missing' OH sink determined for each type of air mass.

Model studies on the photosensitized isomerization of bixin.

PubMed

Montenegro, Mariana A; Rios, Alessandro de O; Mercadante, Adriana Z; Nazareno, Mónica A; Borsarelli, Claudio D

2004-01-28

The photosensitized isomerization reaction of the natural cis carotenoid bixin (methyl hydrogen 9'-cis-6, 6'-diapocarotene-6, 6'-dioate) with rose bengal or methylene blue as the sensitizer in acetonitrile/methanol (1:1) solution was studied using UV-vis spectroscopy, high-performance liquid chromatography (HPLC), and time-resolved spectroscopic techniques, such as laser-flash photolysis and singlet oxygen phosphorescence detection. In both N(2)- and air-saturated solutions, the main product formed was all-trans-bixin. The observed isomerization rate constants, k(obs), decreased in the presence of air or with increase in the bixin concentration, suggesting the participation of the excited triplet state of bixin, (3)Bix, as precursor of the cis--> trans process. On the other hand, bixin solutions in the absence of sensitizer and/or light did not degrade, indicating that the ground state of bixin is stable to thermal isomerization at room temperature. Time-resolved spectroscopic experiments confirmed the formation of the excited triplet state of bixin and its deactivation by ground state bixin and molecular oxygen quenching processes. The primary isomerization products only degraded in the presence of air and under prolonged illumination conditions, probably due to the formation of oxidation products by reaction with singlet molecular oxygen. An energy-transfer mechanism was used to explain the observed results for the bixin transformations, and the consequences for food color are discussed.

Monitoring light-induced structural changes of Channelrhodopsin-2 by UV-visible and Fourier transform infrared spectroscopy.

PubMed

Ritter, Eglof; Stehfest, Katja; Berndt, Andre; Hegemann, Peter; Bartl, Franz J

2008-12-12

Channelrhodopsin-2 (ChR2) is a microbial type rhodopsin and a light-gated cation channel that controls phototaxis in Chlamydomonas. We expressed ChR2 in COS-cells, purified it, and subsequently investigated this unusual photoreceptor by flash photolysis and UV-visible and Fourier transform infrared difference spectroscopy. Several transient photoproducts of the wild type ChR2 were identified, and their kinetics and molecular properties were compared with those of the ChR2 mutant E90Q. Based on the spectroscopic data we developed a model of the photocycle comprising six distinguishable intermediates. This photocycle shows similarities to the photocycle of the ChR2-related Channelrhodopsin of Volvox but also displays significant differences. We show that molecular changes include retinal isomerization, changes in hydrogen bonding of carboxylic acids, and large alterations of the protein backbone structure. These alterations are stronger than those observed in the photocycle of other microbial rhodopsins like bacteriorhodopsin and are related to those occurring in animal rhodopsins. UV-visible and Fourier transform infrared difference spectroscopy revealed two late intermediates with different time constants of tau = 6 and 40 s that exist during the recovery of the dark state. The carboxylic side chain of Glu(90) is involved in the slow transition. The molecular changes during the ChR2 photocycle are discussed with respect to other members of the rhodopsin family.

Monitoring Light-induced Structural Changes of Channelrhodopsin-2 by UV-visible and Fourier Transform Infrared Spectroscopy*

PubMed Central

Ritter, Eglof; Stehfest, Katja; Berndt, Andre; Hegemann, Peter; Bartl, Franz J.

2008-01-01

Channelrhodopsin-2 (ChR2) is a microbial type rhodopsin and a light-gated cation channel that controls phototaxis in Chlamydomonas. We expressed ChR2 in COS-cells, purified it, and subsequently investigated this unusual photoreceptor by flash photolysis and UV-visible and Fourier transform infrared difference spectroscopy. Several transient photoproducts of the wild type ChR2 were identified, and their kinetics and molecular properties were compared with those of the ChR2 mutant E90Q. Based on the spectroscopic data we developed a model of the photocycle comprising six distinguishable intermediates. This photocycle shows similarities to the photocycle of the ChR2-related Channelrhodopsin of Volvox but also displays significant differences. We show that molecular changes include retinal isomerization, changes in hydrogen bonding of carboxylic acids, and large alterations of the protein backbone structure. These alterations are stronger than those observed in the photocycle of other microbial rhodopsins like bacteriorhodopsin and are related to those occurring in animal rhodopsins. UV-visible and Fourier transform infrared difference spectroscopy revealed two late intermediates with different time constants of τ = 6 and 40 s that exist during the recovery of the dark state. The carboxylic side chain of Glu90 is involved in the slow transition. The molecular changes during the ChR2 photocycle are discussed with respect to other members of the rhodopsin family. PMID:18927082

Irradiation of amelanotic melanoma cells with 532 nm high peak power pulsed laser radiation in the presence of the photothermal sensitizer Cu(II)-hematoporphyrin: a new approach to cell photoinactivation.

PubMed

Soncin, M; Busetti, A; Fusi, F; Jori, G; Rodgers, M A

1999-06-01

Cu(II)-hematoporphyrin (CuHp) was efficiently accumulated by B78H1 amelanotic melanoma cells upon incubation with porphyrin concentrations up to 52 microM. When the cells incubated for 18 h with 13 microM CuHp were irradiated with 532 nm light from a Q-switched Nd: YAG laser operated in a pulsed mode (10 ns pulses, 10 Hz) a significant decrease in cell survival was observed. The cell photoinactivation was not the consequence of a photodynamic process, as CuHp gave no detectable triplet signal upon laser flash photolysis excitation and no decrease in cell survival was observed upon continuous wave irradiation. Thus, it is likely that CuHp sensitization takes place by photothermal pathways. The efficiency of the photoprocess was modulated by different parameters; thus, while varying the amount of added CuHp in the 3.25-26 microM range had little effect, pulse energies larger than 50 mJ and irradiation times of at least 120 s were necessary to induce a cell inactivation of about 50%. The porphyrin-cell incubation time prior to irradiation had a major influence on cell survival, suggesting that the nature of the CuHp microenvironment can control the efficiency of photothermal sensitization.

Photoproduction of hydrated electrons from natural organic solutes in aquatic environments

USGS Publications Warehouse

Zepp, R.G.; Braun, A.M.; Hoigne, J.; Leenheer, J.A.

1987-01-01

Laser flash photolysis was used to investigate the transients formed on absorption of 355-nm light by dissolved organic matter (DOM) from natural water bodies and from soil. Absorption spectra and quenching studies of the transients provided confirming evidence that hydrated electrons were formed by all of the DOM that were studied. The DOM from the Suwannee River in Georgia and from the Greifensee, a Swiss lake, exhibited great variability in light-absorbing properties. Despite this high variability in absorption coefficients, the primary quantum yields for electron ejection from the Greifensee and Suwannee DOM fell in a narrow range (0.005-0.008). Steady-state irradiations (355 nm) of the DOM with 2-chloroethanol (0.02 M) present as an electron scavenger produced chloride ions with quantum yields that were about 2 orders of magnitude lower than the primary quantum yields. This result indicates that most of the photoejected electrons recombine with cations before escaping into bulk solution. Irradiations of DOM solutions under sunlight (April, latitude 34?? N) photoproduced electrons at rates falling in the range of 0.2-0.4 ??mol/[(mg of DOC) h]. These results indicate that hydrated electrons can play a significant role in the environmental photoreduction of persistent, electronegative pollutants but may be relatively unimportant in the environmental production of hydrogen peroxide. ?? 1987 American Chemical Society.

Daily Physical Activity and Hot Flashes in the Study of Women's Health Across the Nation FLASHES Study

PubMed Central

Gibson, Carolyn; Matthews, Karen; Thurston, Rebecca

2014-01-01

Objective To examine the role of physical activity in menopausal hot flashes. Competing models conceptualize physical activity as a risk or protective factor for hot flashes. Few studies have examined this relationship prospectively using physiologic measures of hot flashes and physical activity. Design Over two 48 hour-periods, 51 participants wore a physiologic hot flash monitor and activity monitor, and reported their hot flashes in an electronic diary. Physiologic hot flashes, reported hot flashes and reported hot flashes without physiological corroboration were related to activity changes using hierarchical generalized linear modeling, adjusting for potential confounders. Setting Community. Patients Midlife women. Interventions None. Main Outcome Measures Physiologically-detected hot flashes and reported hot flashes with and without physiologic corroboration. Results Hot flash reports without physiologic corroboration were more likely after activity increases (OR 1.04, 95% CI: 1.00-1.10, p=.01), particularly among women with higher levels of depressive symptoms (interaction p=.02). No other types of hot flashes were related to physical activity. Conclusion Acute increases in physical activity were associated with increased reporting of hot flashes lacking physiologic corroboration, particularly among women with depressive symptoms. Clinicians should consider the role of symptom perception and reporting in relations between physical activity and hot flashes. PMID:24491454

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.

Protein relaxation without a geminate phase in nanosecond photodissociated CO carp hemoglobin

NASA Astrophysics Data System (ADS)

Loupiac, Camille; Kruk, Nicolay; Valat, Pierre; Alpert, Bernard

1999-03-01

Transient heme-protein interactions upon passing from ligated to deligated carp hemoglobin were observed through time-resolved optical spectra following nanosecond CO photodissociation. The spectral evolution of the heme, in the nanosecond and microsecond time ranges, shows a protein conformational relaxation and the absence of a geminate CO recombination in carp hemoglobin. The comparison of the phenomena in carp and human hemoglobin implies that the physical basis of the geminate rebinding in human hemoglobin should involve an out-of-equilibrium protein conformation, close to a dissipative structure defined by the thermodynamics of Prigogine.

Adaptive P300 based control system

PubMed Central

Jin, Jing; Allison, Brendan Z.; Sellers, Eric W.; Brunner, Clemens; Horki, Petar; Wang, Xingyu; Neuper, Christa

2015-01-01

An adaptive P300 brain-computer interface (BCI) using a 12 × 7 matrix explored new paradigms to improve bit rate and accuracy. During online use, the system adaptively selects the number of flashes to average. Five different flash patterns were tested. The 19-flash paradigm represents the typical row/column presentation (i.e., 12 columns and 7 rows). The 9- and 14-flash A & B paradigms present all items of the 12 × 7 matrix three times using either nine or 14 flashes (instead of 19), decreasing the amount of time to present stimuli. Compared to 9-flash A, 9-flash B decreased the likelihood that neighboring items would flash when the target was not flashing, thereby reducing interference from items adjacent to targets. 14-flash A also reduced adjacent item interference and 14-flash B additionally eliminated successive (double) flashes of the same item. Results showed that accuracy and bit rate of the adaptive system were higher than the non-adaptive system. In addition, 9- and 14-flash B produced significantly higher performance than their respective A conditions. The results also show the trend that the 14-flash B paradigm was better than the 19-flash pattern for naïve users. PMID:21474877

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.

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

NF3: UV Absorption Spectrum Temperature Dependence and the Atmospheric and Climate Forcing Implications

NASA Technical Reports Server (NTRS)

Papadimitriou, Vassileios C.; McGillen, Max R.; Fleming, Eric L.; Jackman, Charles H.; Burkholder, James B.

2013-01-01

Nitrogen trifluoride (NF3) is an atmospherically persistent greenhouse gas that is primarily removed by UV photolysis and reaction with O((sup 1)D) atoms. In this work, the NF3 gas-phase UV absorption spectrum, sigma(delta,T), was measured at 16 wavelengths between 184.95 and 250 nm at temperatures between 212 and 296 K. A significant spectrum temperature dependence was observed in the wavelength region most relevant to atmospheric photolysis (200-220 nm) with a decrease in sigma(210 nm,T) of approximately 45 percent between 296 and 212 K. Atmospheric photolysis rates and global annually averaged lifetimes of NF3 were calculated using the Goddard Space Flight Center 2-D model and the sigma(delta,T) parameterization developed in this work. Including the UV absorption spectrum temperature dependence increased the stratospheric photolysis lifetime from 610 to 762 years and the total global lifetime from 484 to 585 years; the NF3 global warming potentials on the 20-, 100-, and 500-year time horizons increased less than 0.3, 1.1, and 6.5 percent to 13,300, 17,700, and 19,700, respectively.

A model assessment of the importance of direct photolysis in the photo-fate of cephalosporins in surface waters: Possible formation of toxic intermediates.

PubMed

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

2015-09-01

The direct and indirect photodegradation of six cephalosporins was predicted using a photochemical model, on the basis of literature values of photochemical reactivity. Environmental photodegradation would be important in surface water bodies with depth ⩽ 2-3m, and/or in deeper waters with low values of the dissolved organic carbon (DOC ⩽ 1 mg C L(-1)). The half-life times would range from a few days to a couple of weeks in summertime. In deeper and higher-DOC waters and/or in different seasons, hydrolysis could prevail over photodegradation. The direct photolysis of cephalosporins is environmentally concerning because it is known to produce toxic intermediates. It would be a major pathway for cefazolin, an important one for amoxicillin and cefotaxime and, at pH<6.5, for cefapirin as well. In contrast, direct photolysis would be negligible for cefradine and cefalexin. The DOC values would influence the fraction of photodegradation accounted for by direct photolysis in shallow water, to a different extent depending on the role of sensitisation by the triplet states of chromophoric dissolved organic matter. Copyright © 2015 Elsevier Ltd. All rights reserved.

Internal loop photo-biodegradation reactor used for accelerated quinoline degradation and mineralization.

PubMed

Chang, Ling; Zhang, Yongming; Gan, Lu; Xu, Hua; Yan, Ning; Liu, Rui; Rittmann, Bruce E

2014-07-01

Biofilm biodegradation was coupled with ultra-violet photolysis using the internal loop photobiodegradation reactor for degradation of quinoline. Three protocols-photolysis alone (P), biodegradation alone (B), and intimately coupled photolysis and biodegradation (P&B)-were used for degradation of quinoline in batch and continuous-flow experiments. For a 1,000 mg/L initial quinoline concentration, the volumetric removal rate for quinoline was 38 % higher with P&B than with B in batch experiments, and the P&B kinetics were the sum of kinetics from the P and B experiments. Continuous-flow experiments with an influent quinoline concentration of 1,000 mg/L also gave significantly greater quinoline removal in P&B, and the quinoline-removal kinetics for P&B were approximately equal to the sum of the removal kinetics for P and B. P&B similarly increased the rate and extent of quinoline mineralization, for which the kinetics for P&B were nearly equal to the sum of kinetics for P and B. These findings support that the rate-limiting step for mineralization was transformation of quinoline, which was accelerated by the simultaneous action of photolysis and biodegradation.

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.

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

PubMed

Liu, Yu-Hai; Ye, Zhao-Lian; Wen, Ying-Pin; Bi, Cheng-Lu

2014-06-01

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

Adverse Effects of Induced Hot Flashes on Objectively Recorded and Subjectively Reported Sleep: Results of a Gonadotropin-Releasing Hormone Agonist Experimental Protocol

PubMed Central

Joffe, Hadine; White, David P.; Crawford, Sybil L.; McCurnin, Kristin E.; Economou, Nicole; Connors, Stephanie; Hall, Janet E.

2013-01-01

Objectives The impact of hot flashes on sleep is of great clinical interest, but results are inconsistent, especially when both hot flashes and sleep are measured objectively. Using objective and subjective measurements, we examined the impact of hot flashes on sleep by inducing hot flashes with a gonadotropin-releasing hormone agonist (GnRHa). Methods The GnRHa leuprolide was administered to 20 healthy premenopausal volunteers without hot flashes or sleep disturbances. Induced hot flashes were assessed objectively (skin-conductance monitor) and subjectively (daily diary) during one-month follow-up. Changes from baseline in objective (actigraphy) and subjective sleep quality (Pittsburgh Sleep Quality Index [PSQI]) were compared between women who did and did not develop objective hot flashes, and, in parallel analyses, subjective hot flashes. Results New-onset hot flashes were recorded in 14 (70%) and reported by 14 (70%) women (80% concordance). Estradiol was universally suppressed. Objective sleep efficiency worsened in women with objective hot flashes and improved in women without objective hot flashes (median decrease 2.6%, increase 4.2%, p=0.005). Subjective sleep quality worsened more in those with than without subjective hot flashes (median increase PSQI 2.5 vs. 1.0, p=0.03). Objective hot flashes were not associated with subjective sleep quality, nor were subjective symptoms linked to objective sleep measures. Conclusions This experimental model of induced hot flashes demonstrates a causal relationship between hot flashes and poor sleep quality. Objective hot flashes result in worse objective sleep efficiency, while subjective hot flashes worsen perceived sleep quality. PMID:23481119

Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

NASA Astrophysics Data System (ADS)

Al-Rubaiey, Najem A.; Walsh, Robin

2017-03-01

Silylenes (silanediyls) have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD) of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2) are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas) at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using Lindemann-Hinshelwood model and Rice, Ramsperger, Kassel and Marcus (RRKM) theory) were also carried out and obtained data fitted the Arrhenius equations.

Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers.

PubMed

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers.

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.

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.

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.

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.

Menopausal hot flashes: Randomness or rhythmicity

NASA Astrophysics Data System (ADS)

Kronenberg, Fredi

1991-10-01

Menopausal hot flashes are episodes of flushing, increased heart rate, skin blood flow and skin temperature, and a sensation of heat. The thermoregulatory and cardiovascular concomitants of hot flashes are associated with peaks in the levels of various hormones and neurotransmitters in the peripheral circulation. Although hot flashes affect about 75% of women, and are the primary reason that women at menopause seek medical attention, the mechanism of hot flashes is still not understood. Hot flashes vary in frequency and intensity both within and between individuals, and have been thought of as occurring randomly. Yet, some women report that their hot flashes are worse at a particular time of day or year. Initial examination of subjects' recordings of their hot flashes showed diurnal patterns of hot flash occurrence. There also seems to be a diurnal rhythm of hot flash intensity. Continuous physiological monitoring of hot flashes is facilitating the analysis of these patterns, which is revealing circadian and ultradian periodicities. The occurrence of hot flashes can be modulated by external and internal factors, including ambient temperature and fever. Rhythms of thermoregulatory and endocrine functions also may influence hot flash patterns. Examination of the interrelationships between the various systems of the body involved in hot flashes, and a multidisciplinary approach to the analysis of hot flash patterns, will aid our understanding of this complex phenomenon.

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; vanDijk, C. A.; Wine, P. H.

1997-01-01

Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the following heats of formation for the RS radicals in units of kcal/mol: Delta-H(sub f)(sub 0)(SH) = 34.07 +/- 0.72, Delta-H(sub f)(sub 298)(SH) = 34.18 +/- 0.68, Delta-H(sub f)(sub 0)(CH3S) = 31.44 +/- 0.54, Delta-H(sub f)(sub 298)(CH3S) = 29.78 +/- 0.44; errors are 2 sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our date is near the low end of the range of previous estimates and is 3-4 kcal/mol lower than values derived from recent molecular beam photofragmentation studies.

Single photon detection and timing in the Lunar Laser Ranging Experiment.

NASA Technical Reports Server (NTRS)

Poultney, S. K.

1972-01-01

The goals of the Lunar Laser Ranging Experiment lead to the need for the measurement of a 2.5 sec time interval to an accuracy of a nanosecond or better. The systems analysis which included practical retroreflector arrays, available laser systems, and large telescopes led to the necessity of single photon detection. Operation under all background illumination conditions required auxiliary range gates and extremely narrow spectral and spatial filters in addition to the effective gate provided by the time resolution. Nanosecond timing precision at relatively high detection efficiency was obtained using the RCA C31000F photomultiplier and Ortec 270 constant fraction of pulse-height timing discriminator. The timing accuracy over the 2.5 sec interval was obtained using a digital interval with analog vernier ends. Both precision and accuracy are currently checked internally using a triggerable, nanosecond light pulser. Future measurements using sub-nanosecond laser pulses will be limited by the time resolution of single photon detectors.

Ablation of aluminum nitride films by nanosecond and femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly; Tzou, Robert; Salakhutdinov, Ildar; Danylyuk, Yuriy; McCullen, Erik; Auner, Gregory

2009-02-01

We present results of comparative study of laser-induced ablation of AlN films with variable content of oxygen as a surface-doping element. The films deposited on sapphire substrate were ablated by a single nanosecond pulse at wavelength 248 nm, and by a single femtosecond pulse at wavelength 775 nm in air at normal pressure. Ablation craters were inspected by AFM and Nomarski high-resolution microscope. Irradiation by nanosecond pulses leads to a significant removal of material accompanied by extensive thermal effects, chemical modification of the films around the ablation craters and formation of specific defect structures next to the craters. Remarkable feature of the nanosecond experiments was total absence of thermo-mechanical fracturing near the edges of ablation craters. The femtosecond pulses produced very gentle ablation removing sub-micrometer layers of the films. No remarkable signs of thermal, thermo-mechanical or chemical effects were found on the films after the femtosecond ablation. We discuss mechanisms responsible for the specific ablation effects and morphology of the ablation craters.

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.

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2014 CFR

2014-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2012 CFR

2012-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2013 CFR

2013-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

The photochemistry of some possible cometary CN parent species

NASA Technical Reports Server (NTRS)

Halpern, Joshua B.

1987-01-01

Laboratory work on the photochemistry of HC3N, C4N2, and CH3CN in relation to their possible role as CN parent molecules in comets is discussed. Photodissociation of HC3N, photolysis of C4N2, and quantum yields of excited CN(B) and CN(A) radicals from the VUV photolysis of CH3CN are considered.

Measurements of 32SO2, 33SO2, 34SO2 and 36SO2 high-resolution cross-sections and isotope effects by SO2 self-shielding

NASA Astrophysics Data System (ADS)

Endo, Y.; Ogawa, M.; Danielache, S. O.; Ueno, Y.

2017-12-01

Archean sulfur mass-independent fractionation (S-MIF) is a unique proxy within the geological and geochemical records for studying the composition of the Archean atmosphere. S-MIF signatures are defined as Δ33S = δ33S - 0.515×δ34S and Δ36S = δ36S - 1.90×δ34S. Archean S-MIF is characterized as Δ36S/Δ33S = -1. Recent SO2 photochemical experiments under specific reducing conditions reproduced the Archean trend for the first time [1]. Self-shielding of SO2 photolysis and intersystem crossing in excited SO2 are probably key mechanisms for explaining Archean S-MIF. Self-shielding is originated from UV spectra changed by upper SO2 own absorption. Because 32S accounts for about 95% of all sulfur isotopes, the photolysis rate constant of only 32SO2 is lower than other isotopologue. Thus, SO2 photolysis in the bottom of the atmosphere undergoes mass-independent fractionation. Fractionation factors by SO2 photolysis reaction can be calculated by absorption cross-sections of 32SO2, 33SO2, 34SO2 and 36SO2 and respective quantum yields. Quantitative estimations self-shielding fractionation factors requires high-spectral resolution cross-sections, but they have not been reported yet. Here we report measurements of high-resolution cross-sections (1cm-1) and fractionation factors by SO2 photolysis including self-shielding. Moreover, because the absorption wavelength varies with each isotopologue, photolysis rate constants of all isotopologues (32S16O2, 32S16O18O, etc) should be different. Then self-shielding may affect the ratio of isotopologues such as clumped-isotopes. We calculated preliminary calculation clumped isotope enrichment in residual species by self-shielding. Reference: [1] Endo, Y., Ueno, Y., Aoyama, S., & Danielache, S. O. (2016). Sulfur isotope fractionation by broadband UV radiation to optically thin SO2 under reducing atmosphere. EPSL, 453, 9-22.

Nanosecond pulse shaping at 780 nm with fiber-based electro-optical modulators and a double-pass tapered amplifier

DOE PAGES

Rogers, III, C. E.; Gould, P. L.

2016-02-01

Here, we describe a system for generating frequency-chirped and amplitude-shaped pulses on time scales from sub-nanosecond to ten nanoseconds. The system starts with cw diode-laser light at 780 nm and utilizes fiber-based electro-optical phase and intensity modulators, driven by an arbitrary waveform generator, to generate the shaped pulses. These pulses are subsequently amplified to several hundred mW with a tapered amplifier in a delayed double-pass configuration. Frequency chirps up to 5 GHz in 2 ns and pulse widths as short as 0.15 ns have been realized.

Nanosecond pulse shaping at 780 nm with fiber-based electro-optical modulators and a double-pass tapered amplifier.

PubMed

Rogers, C E; Gould, P L

2016-02-08

We describe a system for generating frequency-chirped and amplitude-shaped pulses on time scales from sub-nanosecond to ten nanoseconds. The system starts with cw diode-laser light at 780 nm and utilizes fiber-based electro-optical phase and intensity modulators, driven by an arbitrary waveform generator, to generate the shaped pulses. These pulses are subsequently amplified to several hundred mW with a tapered amplifier in a delayed double-pass configuration. Frequency chirps up to 5 GHz in 2 ns and pulse widths as short as 0.15 ns have been realized.

An Analysis of Total Lightning Flash Rates Over Florida

NASA Astrophysics Data System (ADS)

Mazzetti, Thomas O.; Fuelberg, Henry E.

2017-12-01

Although Florida is known as the "Sunshine State", it also contains the greatest lightning flash densities in the United States. Flash density has received considerable attention in the literature, but lightning flash rate has received much less attention. We use data from the Earth Networks Total Lightning Network (ENTLN) to produce a 5 year (2010-2014) set of statistics regarding total flash rates over Florida and adjacent regions. Instead of tracking individual storms, we superimpose a 0.2° × 0.2° grid over the study region and count both cloud-to-ground (CG) and in-cloud (IC) flashes over 5 min intervals. Results show that the distribution of total flash rates is highly skewed toward small values, whereas the greatest rate is 185 flashes min-1. Greatest average annual flash rates ( 3 flashes min-1) are located near Orlando. The southernmost peninsula, North Florida, and the Florida Panhandle exhibit smaller average annual flash rates ( 1.5 flashes min-1). Large flash rates > 100 flashes min-1 can occur during any season, at any time during the 24 h period, and at any location within the domain. However, they are most likely during the afternoon and early evening in East Central Florida during the spring and summer months.

47 CFR 27.1233 - Reimbursement costs of transitioning.

Code of Federal Regulations, 2011 CFR

2011-10-01

... downconverter must not introduce a delta group delay of more than 20 nanoseconds for digital operations or 100 nanoseconds for analog operations over any individual six megahertz MBS channel. (b) Migration of Video... that intends to continue downstream high-power, high-site educational video programming or data...

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.

Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

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

Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu

Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O 3 - and OH-initiated reactions during the day and reactions with NO 3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water,more » 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.« less

Blue light induced free radicals from riboflavin in degradation of crystal violet by microbial viability evaluation.

PubMed

Liang, Ji-Yuan; Yuann, Jeu-Ming P; Hsie, Zong-Jhe; Huang, Shiuh-Tsuen; Chen, Chiing-Chang

2017-09-01

Crystal violet (CV) is applied in daily use mainly as a commercial dye and antimicrobial agent. Waste water containing CV may affect aquatic ecosystems. Riboflavin, also known as vitamin B 2 , is non-toxic and an essential vitamin required for the functions of the human body. Riboflavin is photosensitive to UV and visible light in terms of generating reactive oxygen species. This study investigated the potential application of blue light on riboflavin, so as to come up with an effective way of degrading CV during its treatment. Photosensitivity of CV leading to degradation in the presence of riboflavin was investigated by light intensity, exposure time, and irradiation dosage. The degradation of CV during riboflavin photolysis treatment was studied by a UV/vis spectrometry and chromatography. The effects of CV degradation on microbial viability are relevant when considering the influences on the ecosystem. This study proved that riboflavin photochemical treatment with blue light degrades CV dye by ROS formation. The riboflavin photolysis-treated CV solution appeared to be transparent during conformational transformations of the CV that was rearranged by free radical species generated from riboflavin photolysis. After riboflavin photolysis, colony-forming units (CFUs) were determined for each CV solution. CFU preservation was 85.2% for the CV dissolved riboflavin solution treated with blue light irradiation at 2.0mW/cm 2 for 120min. Degradation of CV by riboflavin photochemical procedures can greatly reduce antimicrobial ability and serve as an environmental friendly waste water treatment method. Our results presented here concerning riboflavin photolysis in degradation of CV provide a novel technique, and a simple and safe practice for environmental decontamination processes. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1996-01-01

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

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.

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.

Behavioral weight loss for the management of menopausal hot flashes: a pilot study.

PubMed

Thurston, Rebecca C; Ewing, Linda J; Low, Carissa A; Christie, Aimee J; Levine, Michele D

2015-01-01

Although adiposity has been considered to be protective against hot flashes, newer data suggest positive relationships between hot flashes and adiposity. No studies have been specifically designed to test whether weight loss reduces hot flashes. This pilot study aimed to evaluate the feasibility, acceptability, and initial efficacy of behavioral weight loss in reducing hot flashes. Forty overweight or obese women with hot flashes (≥ 4 hot flashes/d) were randomized to either behavioral weight loss intervention or wait-list control. Hot flashes were assessed before and after intervention via physiologic monitoring, diary, and questionnaire. Comparisons of changes in hot flashes and anthropometrics between conditions were performed via Wilcoxon tests. Study retention (83%) and intervention satisfaction (93.8%) were high. Most women (74.1%) reported that hot flash reduction was a major motivator for losing weight. Women randomized to the weight loss intervention lost more weight (-8.86 kg) than did women randomized to control (+0.23 kg; P < 0.0001). Women randomized to weight loss also showed greater reductions in questionnaire-reported hot flashes (2-wk hot flashes, -63.0) than did women in the control group (-28.0; P = 0.03)-a difference not demonstrated in other hot flash measures. Reductions in weight and hot flashes were significantly correlated (eg, r = 0.47, P = 0.006). This pilot study shows a behavioral weight loss program that is feasible, acceptable, and effective in producing weight loss among overweight or obese women with hot flashes. Findings indicate the importance of a larger study designed to test behavioral weight loss for hot flash reduction. Hot flash management could motivate women to engage in this health-promoting behavior.

Targeting an efficient target-to-target interval for P300 speller brain–computer interfaces

PubMed Central

Sellers, Eric W.; Wang, Xingyu

2013-01-01

Longer target-to-target intervals (TTI) produce greater P300 event-related potential amplitude, which can increase brain–computer interface (BCI) classification accuracy and decrease the number of flashes needed for accurate character classification. However, longer TTIs requires more time for each trial, which will decrease the information transfer rate of BCI. In this paper, a P300 BCI using a 7 × 12 matrix explored new flash patterns (16-, 18- and 21-flash pattern) with different TTIs to assess the effects of TTI on P300 BCI performance. The new flash patterns were designed to minimize TTI, decrease repetition blindness, and examine the temporal relationship between each flash of a given stimulus by placing a minimum of one (16-flash pattern), two (18-flash pattern), or three (21-flash pattern) non-target flashes between each target flashes. Online results showed that the 16-flash pattern yielded the lowest classification accuracy among the three patterns. The results also showed that the 18-flash pattern provides a significantly higher information transfer rate (ITR) than the 21-flash pattern; both patterns provide high ITR and high accuracy for all subjects. PMID:22350331

DNA Damage in Bone Marrow Cells Induced by Femtosecond and Nanosecond Ultraviolet Laser Pulses.

PubMed

Morkunas, Vaidotas; Gabryte, Egle; Vengris, Mikas; Danielius, Romualdas; Danieliene, Egle; Ruksenas, Osvaldas

2015-12-01

The purpose of this study was to investigate the possible genotoxic impact of new generation 205 nm femtosecond solid-state laser irradiation on the DNA of murine bone marrow cells in vitro, and to compare the DNA damage caused by both femtosecond and nanosecond UV laser pulses. Recent experiments of corneal stromal ablation in vitro and in vivo applying femtosecond UV pulses showed results comparable with or superior to those obtained using nanosecond UV lasers. However, the possible genotoxic effect of ultrashort laser pulses was not investigated. Mouse bone marrow cells were exposed to different doses of 205 nm femtosecond, 213 and 266 nm nanosecond lasers, and 254 nm UV lamp irradiation. The comet assay was used for the evaluation of DNA damage. All types of irradiation demonstrated intensity-dependent genotoxic impact. The DNA damage induced depended mainly upon wavelength rather than on other parameters such as pulse duration, repetition rate, or beam delivery to a target. Both 205 nm femtosecond and clinically applied 213 nm nanosecond lasers' pulses induced a comparable amount of DNA breakage in cells exposed to the same irradiation dose. To further evaluate the suitability of femtosecond UV laser sources for microsurgery, a separate investigation of the genotoxic and mutagenic effects on corneal cells in vitro and, particularly, in vivo is needed.

Spatial-temporal characteristics of lightning flash size in a supercell storm

NASA Astrophysics Data System (ADS)

Zhang, Zhixiao; Zheng, Dong; Zhang, Yijun; Lu, Gaopeng

2017-11-01

The flash sizes of a supercell storm, in New Mexico on October 5, 2004, are studied using the observations from the New Mexico Lightning Mapping Array and the Albuquerque, New Mexico, Doppler radar (KABX). First, during the temporal evolution of the supercell, the mean flash size is anti-correlated with the flash rate, following a unary power function, with a correlation coefficient of - 0.87. In addition, the mean flash size is linearly correlated with the area of reflectivity > 30 dBZ at 5 km normalized by the flash rate, with a correlation coefficient of 0.88. Second, in the horizontal, flash size increases along the direction from the region near the convection zone to the adjacent forward anvil. The region of minimum flash size usually corresponds to the region of maximum flash initiation and extent density. The horizontal correspondence between the mean flash size and the flash extent density can also be fitted by a unary power function, and the correlation coefficient is > 0.5 in 50% of the radar volume scans. Furthermore, the quality of fit is positively correlated to the convective intensity. Third, in the vertical direction, the height of the maximum flash initiation density is close to the height of maximum flash extent density, but corresponds to the height where the mean flash size is relatively small. In the discussion, the distribution of the small and dense charge regions when and where convection is vigorous in the storm, is deduced to be responsible for the relationship that flash size is temporally and spatially anti-correlated with flash rate and density, and the convective intensity.

Method and apparatus for removing and preventing window deposition during photochemical vapor deposition (photo-CVD) processes

DOEpatents

Tsuo, S.; Langford, A.A.

1989-03-28

Unwanted build-up of the film deposited on the transparent light-transmitting window of a photochemical vacuum deposition (photo-CVD) chamber is eliminated by flowing an etchant into the part of the photolysis region in the chamber immediately adjacent the window and remote from the substrate and from the process gas inlet. The respective flows of the etchant and the process gas are balanced to confine the etchant reaction to the part of the photolysis region proximate to the window and remote from the substrate. The etchant is preferably one that etches film deposit on the window, does not etch or affect the window itself, and does not produce reaction by-products that are deleterious to either the desired film deposited on the substrate or to the photolysis reaction adjacent the substrate. 3 figs.

Method and apparatus for removing and preventing window deposition during photochemical vapor deposition (photo-CVD) processes

DOEpatents

Tsuo, Simon; Langford, Alison A.

1989-01-01

Unwanted build-up of the film deposited on the transparent light-transmitting window of a photochemical vacuum deposition (photo-CVD) chamber is eliminated by flowing an etchant into the part of the photolysis region in the chamber immediately adjacent the window and remote from the substrate and from the process gas inlet. The respective flows of the etchant and the process gas are balanced to confine the etchant reaction to the part of the photolysis region proximate to the window and remote from the substrate. The etchant is preferably one that etches film deposit on the window, does not etch or affect the window itself, and does not produce reaction by-products that are deleterious to either the desired film deposited on the substrate or to the photolysis reaction adjacent the substrate.

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.

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

PubMed

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

2015-05-01

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

Flash memory management system and method utilizing multiple block list windows

NASA Technical Reports Server (NTRS)

Chow, James (Inventor); Gender, Thomas K. (Inventor)

2005-01-01

The present invention provides a flash memory management system and method with increased performance. The flash memory management system provides the ability to efficiently manage and allocate flash memory use in a way that improves reliability and longevity, while maintaining good performance levels. The flash memory management system includes a free block mechanism, a disk maintenance mechanism, and a bad block detection mechanism. The free block mechanism provides efficient sorting of free blocks to facilitate selecting low use blocks for writing. The disk maintenance mechanism provides for the ability to efficiently clean flash memory blocks during processor idle times. The bad block detection mechanism provides the ability to better detect when a block of flash memory is likely to go bad. The flash status mechanism stores information in fast access memory that describes the content and status of the data in the flash disk. The new bank detection mechanism provides the ability to automatically detect when new banks of flash memory are added to the system. Together, these mechanisms provide a flash memory management system that can improve the operational efficiency of systems that utilize flash memory.

Perceived control and hot flashes in treatment-seeking breast cancer survivors and menopausal women.

PubMed

Carpenter, Janet S; Wu, Jingwei; Burns, Debra S; Yu, Menggang

2012-01-01

Lower perceived control over hot flashes has been linked to fewer coping strategies, more catastrophizing, and greater hot flash severity and distress in midlife women, yet this important concept has not yet been studied in breast cancer survivors. The aim of this study was to explore perceived control over hot flashes and hot flashes in breast cancer survivors compared with midlife women without cancer. Ninety-nine survivors and 138 midlife women completed questionnaires and a prospective, electronic hot flash diary. All data were collected at a baseline assessment before randomization in a behavioral intervention study. Both groups had moderate perceived control over hot flashes. Control was not significantly related to hot flash frequency but was significantly related to hot flash severity, bother, and interference in both groups. A significantly stronger association between control and hot flash interference was found for survivors than for midlife women. Survivors using hot flash treatments perceived less control than did survivors not using hot flash treatments, whereas the opposite was true in midlife women. Findings extend our knowledge of perceived control over hot flashes in both survivors and midlife women. Findings emphasize the importance of continued menopausal symptom assessment and management, support the importance of continuing nursing care even for survivors who are already using hot flash treatment, and suggest that nursing interventions aimed at improving perceived control over hot flashes may be more helpful for survivors than for midlife women.

Photosynthetic dioxygen formation studied by time-resolved delayed fluorescence measurements--method, rationale, and results on the activation energy of dioxygen formation.

PubMed

Buchta, Joachim; Grabolle, Markus; Dau, Holger

2007-06-01

The analysis of the time-resolved delayed fluorescence (DF) measurements represents an important tool to study quantitatively light-induced electron transfer as well as associated processes, e.g. proton movements, at the donor side of photosystem II (PSII). This method can provide, inter alia, insights in the functionally important inner-protein proton movements, which are hardly detectable by conventional spectroscopic approaches. The underlying rationale and experimental details of the method are described. The delayed emission of chlorophyll fluorescence of highly active PSII membrane particles was measured in the time domain from 10 mus to 60 ms after each flash of a train of nanosecond laser pulses. Focusing on the oxygen-formation step induced by the third flash, we find that the recently reported formation of an S4-intermediate prior to the onset of O-O bond formation [M. Haumann, P. Liebisch, C. Müller, M. Barra, M. Grabolle, H. Dau, Science 310, 1019-1021, 2006] is a multiphasic process, as anticipated for proton movements from the manganese complex of PSII to the aqueous bulk phase. The S4-formation involves three or more likely sequential steps; a tri-exponential fit yields time constants of 14, 65, and 200 mus (at 20 degrees C, pH 6.4). We determine that S4-formation is characterized by a sizable difference in Gibbs free energy of more than 90 meV (20 degrees C, pH 6.4). In the second part of the study, the temperature dependence (-2.7 to 27.5 degrees C) of the rate constant of dioxygen formation (600/s at 20 degrees C) was investigated by analysis of DF transients. If the activation energy is assumed to be temperature-independent, a value of 230 meV is determined. There are weak indications for a biphasicity in the Arrhenius plot, but clear-cut evidence for a temperature-dependent switch between two activation energies, which would point to the existence of two distinct rate-limiting steps, is not obtained.

Synoptic-scale atmospheric conditions associated with flash flooding in watersheds of the Catskill Mountains, New York, USA

NASA Astrophysics Data System (ADS)

Teale, N. G.; Quiring, S. M.

2015-12-01

Understanding flash flooding is important in unfiltered watersheds, such as portions of the New York City water supply system (NYCWSS), as water quality is degraded by turbidity associated with flooding. To further understand flash flooding in watersheds of the NYCWSS, synoptic-scale atmospheric conditions most frequently associated with flash flooding between 1987 and 2013 were examined. Flash floods were identified during this time period using USGS 15-minute discharge data at the Esopus Creek near Allaben, NY and Neversink River at Claryville, NY gauges. Overall, 25 flash floods were detected, occurring over 17 separate flash flood days. These flash flood days were compared to the days on which flash flood warnings encompassing the study area was issued by the National Weather Service. The success rate for which the flash flood warnings for Ulster County coincided with flash flood in the study watershed was 0.09, demonstrating the highly localized nature of flash flooding in the Catskill Mountain region. The synoptic-scale atmospheric patterns influencing the study area were characterized by a principal component analysis and k-means clustering of NCEP/NCAR 500 mb geopotential height reanalysis data. This procedure was executed in Spatial Synoptic Typer Tools 4.0. While 17 unique synoptic patterns were identified, only 3 types were strongly associated with flash flooding events. A strong southwesterly flow suggesting advection of moisture from the Atlantic Ocean and Gulf of Mexico is shown in composites of these 3 types. This multiscalar study thereby links flash flooding in the NYCWSS with synoptic-scale atmospheric circulation.Understanding flash flooding is important in unfiltered watersheds, such as portions of the New York City water supply system (NYCWSS), as water quality is degraded by turbidity associated with flooding. To further understand flash flooding in watersheds of the NYCWSS, synoptic-scale atmospheric conditions most frequently associated with flash flooding between 1987 and 2013 were examined. Flash floods were identified during this time period using USGS 15-minute discharge data at the Esopus Creek near Allaben, NY and Neversink River at Claryville, NY gauges. Overall, 25 flash floods were detected, occurring over 17 separate flash flood days. These flash flood days were compared to the days on which flash flood warnings encompassing the study area was issued by the National Weather Service. The success rate for which the flash flood warnings for Ulster County coincided with flash flood in the study watershed was 0.09, demonstrating the highly localized nature of flash flooding in the Catskill Mountain region. The synoptic-scale atmospheric patterns influencing the study area were characterized by a principal component analysis and k-means clustering of NCEP/NCAR 500 mb geopotential height reanalysis data. This procedure was executed in Spatial Synoptic Typer Tools 4.0. While 17 unique synoptic patterns were identified, only 3 types were strongly associated with flash flooding events. A strong southwesterly flow suggesting advection of moisture from the Atlantic Ocean and Gulf of Mexico is shown in composites of these 3 types. This multiscalar study thereby links flash flooding in the NYCWSS with synoptic-scale atmospheric circulation.

Hot Flashes and Quality of Life Among Breast Cancer Patients

DTIC Science & Technology

2006-08-01

hot flashes, 40.7% report at baseline, having used HRT and 26.8% used exercise to control hot flashes. The 12-month data indicates that 26.5% of the...entire sample who are experiencing hot flashes, tried or are using some form of HRT to control hot flashes with exercise still the most frequently...used approach to manage hot flashes with 44.2% of sample currently exercising . 15. SUBJECT TERMS Breast Cancer, Hot Flashes, Quality of Life

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.

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.

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.

Reaction CH3 + OH studied over the 294-714 K temperature and 1-100 bar pressure ranges.

PubMed

Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N

2012-08-30

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).

Environmental fate of naproxen, carbamazepine and triclosan in wastewater, surface water and wastewater irrigated soil - Results of laboratory scale experiments.

PubMed

Durán-Álvarez, J C; Prado, B; González, D; Sánchez, Y; Jiménez-Cisneros, B

2015-12-15

Lab-scale photolysis, biodegradation and transport experiments were carried out for naproxen, carbamazepine and triclosan in soil, wastewater and surface water from a region where untreated wastewater is used for agricultural irrigation. Results showed that both photolysis and biodegradation occurred for the three emerging pollutants in the tested matrices as follows: triclosan>naproxen>carbamazepine. The highest photolysis rate for the three pollutants was obtained in experiments using surface water, while biodegradation rates were higher in wastewater and soil than in surface water. Carbamazepine showed to be recalcitrant to biodegradation both in soil and water; although photolysis occurred at a higher level than biodegradation, this compound was poorly degraded by natural processes. Transport experiments showed that naproxen was the most mobile compound through the first 30cm of the soil profile; conversely, the mobility of carbamazepine and triclosan through the soil was delayed. Biodegradation of target pollutants occurred within soil columns during transport experiments. Triclosan was not detected either in leachates or the soil in columns, suggesting its complete biodegradation. Data of these experiments can be used to develop more reliable fate-on-the-field and environmental risk assessment studies. Copyright © 2015 Elsevier B.V. All rights reserved.

Physiologically assessed hot flashes and endothelial function among midlife women.

PubMed

Thurston, Rebecca C; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J Richard; von Känel, Roland; Landsittel, Doug P; Matthews, Karen A

2017-08-01

Hot flashes are experienced by most midlife women. Emerging data indicate that they may be associated with endothelial dysfunction. No studies have tested whether hot flashes are associated with endothelial function using physiologic measures of hot flashes. We tested whether physiologically assessed hot flashes were associated with poorer endothelial function. We also considered whether age modified associations. Two hundred seventy-two nonsmoking women reporting either daily hot flashes or no hot flashes, aged 40 to 60 years, and free of clinical cardiovascular disease, underwent ambulatory physiologic hot flash and diary hot flash monitoring; a blood draw; and ultrasound measurement of brachial artery flow-mediated dilation to assess endothelial function. Associations between hot flashes and flow-mediated dilation were tested in linear regression models controlling for lumen diameter, demographics, cardiovascular disease risk factors, and estradiol. In multivariable models incorporating cardiovascular disease risk factors, significant interactions by age (P < 0.05) indicated that among the younger tertile of women in the sample (age 40-53 years), the presence of hot flashes (beta [standard error] = -2.07 [0.79], P = 0.01), and more frequent physiologic hot flashes (for each hot flash: beta [standard error] = -0.10 [0.05], P = 0.03, multivariable) were associated with lower flow-mediated dilation. Associations were not accounted for by estradiol. Associations were not observed among the older women (age 54-60 years) or for self-reported hot flash frequency, severity, or bother. Among the younger women, hot flashes explained more variance in flow-mediated dilation than standard cardiovascular disease risk factors or estradiol. Among younger midlife women, frequent hot flashes were associated with poorer endothelial function and may provide information about women's vascular status beyond cardiovascular disease risk factors and estradiol.

Menopausal Hot Flashes and Carotid Intima Media Thickness Among Midlife Women.

PubMed

Thurston, Rebecca C; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J Richard; Landsittel, Doug P; Santoro, Nanette; von Känel, Roland; Matthews, Karen A

2016-12-01

There has been a longstanding interest in the role of menopause and its correlates in the development of cardiovascular disease (CVD) in women. Menopausal hot flashes are experienced by most midlife women; emerging data link hot flashes to CVD risk indicators. We tested whether hot flashes, measured via state-of-the-art physiologic methods, were associated with greater subclinical atherosclerosis as assessed by carotid ultrasound. We considered the role of CVD risk factors and estradiol concentrations in these associations. A total of 295 nonsmoking women free of clinical CVD underwent ambulatory physiologic hot flash assessments; a blood draw; and carotid ultrasound measurement of intima media thickness and plaque. Associations between hot flashes and subclinical atherosclerosis were tested in regression models controlling for CVD risk factors and estradiol. More frequent physiologic hot flashes were associated with higher carotid intima media thickness (for each additional hot flash: β [SE]=0.004 [0.001]; P=0.0001; reported hot flash: β [SE]=0.008 [0.002]; P=0.002, multivariable) and plaque (eg, for each additional hot flash, odds ratio [95% confidence interval] plaque index ≥2=1.07 [1.003-1.14]; P=0.04, relative to no plaque, multivariable] among women reporting daily hot flashes; associations were not accounted for by CVD risk factors or by estradiol. Among women reporting hot flashes, hot flashes accounted for more variance in intima media thickness than most CVD risk factors. Among women reporting daily hot flashes, frequent hot flashes may provide information about a woman's vascular status beyond standard CVD risk factors and estradiol. Frequent hot flashes may mark a vulnerable vascular phenotype among midlife women. © 2016 American Heart Association, Inc.

Menopausal Hot Flashes and Carotid Intima Media Thickness among Midlife Women

PubMed Central

Thurston, Rebecca C.; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J. Richard; Landsittel, Doug P.; Santoro, Nanette; von Känel, Roland; Matthews, Karen A.

2016-01-01

Background and Purpose There has been a longstanding interest in the role of menopause and its correlates in the development of cardiovascular disease (CVD) in women. Menopausal hot flashes are experienced by most midlife women; emerging data link hot flashes to CVD risk indicators. We tested whether hot flashes, measured via state-of-the-art physiologic methods, were associated with greater subclinical atherosclerosis as assessed by carotid ultrasound. We considered the role of CVD risk factors and estradiol concentrations in these associations. Methods 295 nonsmoking women free of clinical CVD underwent ambulatory physiologic hot flash assessments; a blood draw; and carotid ultrasound measurement of IMT and plaque. Associations between hot flashes and subclinical atherosclerosis were tested in regression models controlling for CVD risk factors and estradiol. Results More frequent physiologic hot flashes were associated with higher carotid intima media thickness [IMT; for each additional hot flash: beta (standard error)=.004(.001), p=.0001; reported hot flash: beta (standard error)=.008(.002), p=.002, multivariable] and plaque [e.g., for each additional hot flash, odds ratio (95% confidence interval) plaque index ≥2=1.07(1.003–1.14, p=.04), relative to no plaque, multivariable] among women reporting daily hot flashes; associations were not accounted for by CVD risk factors or by estradiol. Among women reporting hot flashes, hot flashes accounted for more variance in IMT than most CVD risk factors. Conclusions Among women reporting daily hot flashes, frequent hot flashes may provide information about a woman’s vascular status beyond standard CVD risk factors and estradiol. Frequent hot flashes may mark a vulnerable vascular phenotype among midlife women. PMID:27834746

Behavioral Weight Loss for the Management of Menopausal Hot Flashes: A Pilot Study

PubMed Central

Thurston, Rebecca C.; Ewing, Linda J.; Low, Carissa A.; Christie, Aimee J.; Levine, Michele D.

2014-01-01

Objective Although adiposity has been considered protective against hot flashes, newer data suggest positive relations between flashes and adiposity. No studies have been specifically designed to test whether weight loss reduces hot flashes. This pilot study aimed to evaluate the feasibility, acceptability, and initial efficacy of behavioral weight loss to reduce hot flashes. Methods Forty overweight/obese women with hot flashes (≥4/day) were randomized to a behavioral weight loss intervention or to wait list control. Hot flashes were assessed pre- and post-intervention via physiologic monitor, diary, and questionnaire. Comparisons of changes in hot flashes and anthropometrics between conditions were tested via Wilcoxon tests. Results Study retention (83%) and intervention satisfaction (93.8%) were high. Most women (74.1%) reported that hot flash reduction was a main motivator to lose weight. Women randomized to the weight loss intervention lost more weight (-8.86 kg) than did women randomized to control (+0.23 kg, p<.0001). Women randomized to weight loss also showed greater reductions in questionnaire-reported hot flashes (2-week hot flashes: −63.0) than did women in the control (−28.0, p=.03), a difference not demonstrated in other hot flash measures. Reductions in weight and hot flashes were significantly correlated (e.g., r=.47, p=.006). Conclusions This pilot study showed a behavioral weight loss program to be feasible, acceptable, and effective in producing weight loss among overweight/obese women with hot flashes. Findings indicate the importance of a larger study designed to test behavioral weight loss for hot flash reduction. Hot flash management could motivate women to engage in this health-promoting behavior. PMID:24977456

Photoinduced Reactions of Benzophenone in Biaxially Oriented Polypropylene.

PubMed

Levin, Peter P; Efremkin, Alexei F; Krivandin, Aleksey V; Lomakin, Sergei M; Shatalova, Olga V; Khudyakov, Igor V

2018-05-03

The photoinduced reactions of benzophenone (B) in biaxially oriented polypropylene (BOPP) were studied with nanosecond laser photolysis (N 2 laser, λ337.1 nm). The first observed transient was a triplet state 3 B*. Decay of 3 B* led to formation of a radical pair (RP) of BH • and R • , where R • is a radical formed by hydrogen abstraction from BOPP (RH) by 3 B*. We studied BOPP after the preheating for a short time in a temperature range 298-423 K, which is essentially lower than its melting point of 453 K. All measurements with not-heated and with preheated (annealed) BOPP were made at 298 K. A radical pair (RP) apparently decays as a contact pair 3 [BH • , R • ] in nonheated BOPP. A critical phenomenon takes place: dissociation of RP with a formation of free radicals in the polymer bulk is observed at preheating temperature T crit ≈ 403 K and at a higher T. The physical process of heating and cooling of BOPP apparently resulted in the restructuring of crystallites, their agglomeration, shrinking of the distribution of crystallites according to their sizes in BOPP. Overall BOPP becomes softer which manifests itself in the radical kinetics. The decay kinetics of 3 B* and RP in the cage fits well the first-order law. Rate constants were obtained. Radicals BH • , which exit into the polymer bulk at temperatures of preheating T ≥ 403 K, decay by cross-termination according to the second-order law. A relatively high rate constant ∼10 8 M -1 ·s -1 for this reaction was obtained due to diffusion of BH • enclosed in the soft amorphous phase of BOPP. Properties of BOPP containing B were studied with ESR, DSC, IR, and WAXD.

Karst flash floods: an example from the Dinaric karst (Croatia)

NASA Astrophysics Data System (ADS)

Bonacci, O.; Ljubenkov, I.; Roje-Bonacci, T.

2006-03-01

Flash floods constitute one of the deadliest and costliest natural disasters worldwide. This paper explains the karst flash flood phenomenon, which represents a special kind of flash flood. As the majority of flash floods karst flash floods are caused by intensive short-term precipitation in an area whose surface rarely exceeds a few square kilometres. The characteristics of all flash floods are their short duration, small areal extent, high flood peaks and rapid flows, and heavy loss of life and property. Karst flash floods have specific characteristics due to special conditions for water circulation, which exist in karst terrains. During karst flash floods a sudden rise of groundwater levels occurs, which causes the appearance of numerous, unexpected, abundant and temporary karst springs. This paper presents in detail an example of a karst flash flood in the Marina bay (Dinaric karst region of Croatia), which occurred in December 2004.

A Comprehensive Study on Energy Efficiency and Performance of Flash-based SSD

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

Park, Seon-Yeon; Kim, Youngjae; Urgaonkar, Bhuvan

2011-01-01

Use of flash memory as a storage medium is becoming popular in diverse computing environments. However, because of differences in interface, flash memory requires a hard-disk-emulation layer, called FTL (flash translation layer). Although the FTL enables flash memory storages to replace conventional hard disks, it induces significant computational and space overhead. Despite the low power consumption of flash memory, this overhead leads to significant power consumption in an overall storage system. In this paper, we analyze the characteristics of flash-based storage devices from the viewpoint of power consumption and energy efficiency by using various methodologies. First, we utilize simulation tomore » investigate the interior operation of flash-based storage of flash-based storages. Subsequently, we measure the performance and energy efficiency of commodity flash-based SSDs by using microbenchmarks to identify the block-device level characteristics and macrobenchmarks to reveal their filesystem level characteristics.« less

Multi- and unisensory visual flash illusions.

PubMed

Courtney, Jon R; Motes, Michael A; Hubbard, Timothy L

2007-01-01

The role of stimulus structure in multisensory and unisensory interactions was examined. When a flash (17 ms) was accompanied by multiple tones (each 7 ms, SOA < or =100 ms) multiple flashes were reported, and this effect has been suggested to reflect the role of stimulus continuity in multisensory interactions. In experiments 1 and 2 we examined if stimulus continuity would affect concurrently presented stimuli. When a relatively longer flash (317 ms) was accompanied by multiple tones (each 7 ms), observers reported perceiving multiple flashes. In experiment 3 we tested whether a flash presented near fixation would induce an illusory flash further in the periphery. One flash (17 ms) presented 5 degrees below fixation was reported as multiple flashes if presented with two flashes (each 17 ms, SOA =100 ms) 2 degrees above fixation. The extent to which these data support a phenomenological continuity principle and whether this principle applies to unisensory perception is discussed.

Interactions of numerical and temporal stimulus characteristics on the control of response location by brief flashes of light.

PubMed

Fetterman, J Gregor; Killeen, P Richard

2011-09-01

Pigeons pecked on three keys, responses to one of which could be reinforced after 3 flashes of the houselight, to a second key after 6, and to a third key after 12. The flashes were arranged according to variable-interval schedules. Response allocation among the keys was a function of the number of flashes. When flashes were omitted, transitions occurred very late. Increasing flash duration produced a leftward shift in the transitions along a number axis. Increasing reinforcement probability produced a leftward shift, and decreasing reinforcement probability produced a rightward shift. Intermixing different flash rates within sessions separated allocations: Faster flash rates shifted the functions sooner in real time, but later in terms of flash count, and conversely for slower flash rates. A model of control by fading memories of number and time was proposed.

Flash fire propensity of materials

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Cumming, H. J.

1977-01-01

Flash fire test results on 86 materials, evaluated using the USF flash fire screening test, are presented. The materials which appear least prone to flash fires are PVC, polyphenylene oxide and sulfide, and polyether and polyaryl sulfone; these did not produce flash fires under these particular test conditions. The principal value of these screening tests at the present time is in identifying materials which appear prone to flash fires, and in identifying which formulations of a generic material are more or less prone to flash fires.

The role of nanosecond electric pulse-induced mechanical stress in cellular nanoporation

NASA Astrophysics Data System (ADS)

Roth, Caleb C.

Background: Exposures of cells to very short (less than 1 microsecond) electric pulses in the megavolt/meter range have been shown to cause a multitude of effects, both physical and molecular in nature. Physically, nanosecond electrical pulse exposure can disrupt the plasma membrane, leading to a phenomenon known as nanoporation. Nanoporation is the production of nanometer sized holes (less than 2 nanometers in diameter) that can persist for up to fifteen minutes, allowing the flow of ions into and out of the cell. Nanoporation can lead to secondary physical effects, such as cellular swelling, shrinking and blebbing. Molecularly, nanosecond electrical pulses have been shown to activate signaling pathways, produce oxidative stress, stimulate hormone secretion and induce both apoptotic and necrotic death. The mechanism by which nanosecond electrical pulses cause molecular changes is unknown; however, it is thought the flow of ions, such as calcium, into the cell via nanopores, could be a major cause. The ability of nanosecond electrical pulses to cause membranes to become permeable and to induce apoptosis makes the technology a desirable modality for cancer research; however, the lack of understanding regarding the mechanisms by which nanosecond electrical pulses cause nanoporation impedes further development of this technology. This dissertation documents the genomic and proteomic responses of cells exposed to nanosecond electrical pulses and describes in detail the biophysical effects of these electrical pulses, including the demonstration for the first time of the generation of acoustic pressure transients capable of disrupting plasma membranes and possibly contributing to nanoporation. Methods: Jurkat, clone E6-1 (human lymphocytic cell line), U937 (human lymphocytic cell line), Chinese hamster ovarian cells and adult primary human dermal fibroblasts exposed to nanosecond electrical pulses were subjected to a variety of molecular assays, including flow cytometry, fluorescent confocal microscopy, microarray analysis and or real time polymerase chain reaction. To investigate the physical interaction(s) of the electrical pulse with the aqueous environment, optical techniques such as pump-probe imaging, schlieren imaging, and probe beam deflection were used. Finally, electrochemistry was employed to modify the electrical parameters of the exposures such that different biophysical phenomena could be detected. Results: Approximately 500 genes were selectively up-regulated in each of the assayed cells. Validation of the microarray data indicated genes such as the putative transforming gene of avian sarcoma virus 17, commonly known as jun proto-oncogene, and the Finkel--Biskis--Jinkins murine osteosarcoma viral oncogene homolog were significantly up-regulated in response to the exposure. Many of the genes selectively up-regulated in each cell type are biomarkers of mechanical stress. Proteomic analysis indicated proteins responsible for mitigation of reactive oxygen species were produced in response to nanosecond electrical pulse exposure. Analysis using the Probe Beam Deflection Technique identified the generation of an acoustic pressure transient emanating from the electrodes immediately after the application of the pulse. This acoustic pressure transient traveled at approximately 1500 meters per second, had a frequency bandwidth of 2.5 megahertz and was capable of delivering 13 kilopascals of pressure at 5 millimeters distance from the generating electrodes. Visual confirmation of the acoustic pressure transients was accomplished using pump-probe, schlieren and ultrasonic imaging techniques. Modification of the bathing media in which the cells were exposed indicated that acoustic pressure transient formation was directly dependent on the amount of electrical current induced by the exposure. Confocal microscopy revealed that, in the absence of the acoustic pressure transients, nanoporation, as detected by a green fluorescent carbocyanine nucleic acid stain, was greatly enhanced. Conclusions: We found several genes, some of which are mechanosensitive, were selectively up-regulated due to nanosecond electrical pulse exposure. The source of this apparent mechanical stress was likely the acoustic pressure transients generated by the nanosecond electrical pulse exposure interacting with the plasma membrane of exposed cells. Contrary to our original hypothesis that these acoustic pressure transients enhance nanoporation, it appears that the opposite is true. Acoustic pressure transients generated by nanosecond electrical pulses inhibit nanoporation (or at least are negatively correlated with nanopore formation). This finding is substantiated by other reports in the literature, which indicate shock waves produced by electrical exposures inhibit gene transfection. General Significance: This work provides strong evidence that cells exposed to nanosecond electrical pulses experience a mechanical stress which by some unknown mechanism inhibits nanoporation. The findings in this dissertation are not only poised to cause a paradigm shift in how researchers understand electrical pulses cause electropermeabilization, but also will help fill in a gap in the knowledge concerning this technology, thus enabling its further development as a potential cancer therapy.

Hot flash report and measurement among Bangladeshi migrants, their London neighbors, and their community of origin.

PubMed

Sievert, L L; Begum, K; Sharmeen, T; Murphy, L; Whitcomb, B W; Chowdhury, O; Muttukrishna, S; Bentley, G R

2016-12-01

To examine hot flashes in relation to climate and activity patterns, and to compare subjective and objective hot flashes among Bangladeshi immigrants to London, their white London neighbors, and women still living in their community of origin, Sylhet, Bangladesh ("sedentees"). Ninety-five women, aged 40-55, wore the Biolog ambulatory hot flash monitor. Objective measurements and subjective hot flash reports were examined in relation to demographic, reproductive, anthropometric, and lifestyle variables; temperature and humidity at 12:00 and 18:00; and time spent on housework and cooking. Concordance of objective and subjective hot flashes was assessed by Kappa statistics and by sensitivity of hot flash classification. During the study period, Bangladeshi sedentees reported more subjective hot flashes (p < .05), but there was no difference in number of objective hot flashes. White Londoners were more likely to describe hot flashes on their face and neck compared to Bangladeshis (p < .05). Sedentees were more likely to describe hot flashes on their feet (p < .05). Postmenopausal status, increasing parity, and high levels of housework were significant determinants of subjective hot flashes, while ambient temperature and humidity were not. Measures of subjective/objective concordance were low but similar across groups (10-20%). The proportion of objective hot flashes that were also self-reported was lowest among immigrants. Hot flashes were not associated with warmer temperatures, but were associated with housework and with site-specific patterns of cooking. The number of objective hot flash measures did not differ, but differences in subjective experience suggest the influence of culture. © 2016 Wiley Periodicals, Inc.

Phenomenology of the sound-induced flash illusion.

PubMed

Abadi, Richard V; Murphy, Jonathan S

2014-07-01

Past studies, using pairings of auditory tones and visual flashes, which were static and coincident in space but variable in time, demonstrated errors in judging the temporal patterning of the visual flashes-the sound-induced flash illusion. These errors took one of the two forms: under-reporting (sound-induced fusion) or over-reporting (sound-induced fission) of the flash numbers. Our study had three objectives: to examine the robustness of both illusions and to consider the effects of stimulus set and response bias. To this end, we used an extended range of fixed spatial location flash-tone pairings, examined stimuli that were variable in space and time and measured confidence in judging flash numbers. Our results indicated that the sound-induced flash illusion is a robust percept, a finding underpinned by the confidence measures. Sound-induced fusion was found to be more robust than sound-induced fission and a most likely outcome when high numbers of flashes were incorporated within an incongruent flash-tone pairing. Conversely, sound-induced fission was the most likely outcome for the flash-tone pairing which contained two flashes. Fission was also shown to be strongly driven by stimuli confounds such as categorical boundary conditions (e.g. flash-tone pairings with ≤2 flashes) and compressed response options. These findings suggest whilst both fission and fusion are associated with 'auditory driving', the differences in the occurrence and strength of the two illusions not only reflect the separate neuronal mechanisms underlying audio and visual signal processing, but also the test conditions that have been used to investigate the sound-induced flash illusion.

How self-reported hot flashes may relate to affect, cognitive performance and sleep.

PubMed

Regestein, Quentin; Friebely, Joan; Schiff, Isaac

2015-08-01

To explain the controversy about whether midlife women who self-report hot flashes have relatively increased affective symptoms, poor cognitive performance or worse sleep. Retrospective data from 88 women seeking relief from bothersome day and night hot flashes were submitted to mixed linear regression modeling to find if estimated hot flashes, as measured by Women's Health Questionnaire (WHQ) items, or diary-documented hot flashes recorded daily, were associated with each other, or with affective, cognitive or sleep measures. Subjects averaged 6.3 daytime diary-documented hot flashes and 2.4 nighttime diary-documented hot flashes per 24h. Confounder-controlled diary-documented hot flashes but not estimated hot flashes were associated with increased Leeds anxiety scores (F=4.9; t=2.8; p=0.01) and Leeds depression scores (3.4; 2.5; 0.02), decreased Stroop Color-Word test performance (9.4; 3.5; 0.001), increased subjective sleep disturbance (effect size=0.83) and increased objective sleep disturbance (effect size=0.35). Hot flash effects were small to moderate in size. Univariate but not multivariate analyses revealed that all hot flash measures were associated with all affect measures. Different measures of hot flashes associated differently with affect, cognition and sleep. Only nighttime diary-document hot flash consistently correlated with any affect measures in multivariate analyses. The use of differing measures for hot flashes, affect, cognition and sleep may account for the continually reported inconsistencies in menopause study outcomes. This problem impedes forging a consensus on whether hot flashes correlate with neuropsychological symptoms. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Susceptibility to the Flash-Beep Illusion Is Increased in Children Compared to Adults

ERIC Educational Resources Information Center

Innes-Brown, Hamish; Barutchu, Ayla; Shivdasani, Mohit N.; Crewther, David P.; Grayden, David B.; Paolini, Antonio

2011-01-01

Audio-visual integration was studied in children aged 8-17 (N = 30) and adults (N = 22) using the "flash-beep illusion" paradigm, where the presentation of two beeps causes a single flash to be perceived as two flashes ("fission" illusion), and a single beep causes two flashes to be perceived as one flash ("fusion" illusion). Children reported…

Global Patterns of Lightning Properties Derived by OTD and LIS

NASA Technical Reports Server (NTRS)

Beirle, Steffen; Koshak, W.; Blakeslee, R.; Wagner, T.

2014-01-01

The satellite instruments Optical Transient Detector (OTD) and Lightning Imaging Sensor (LIS) provide unique empirical data about the frequency of lightning flashes around the globe (OTD), and the tropics (LIS), which 5 has been used before to compile a well received global climatology of flash rate densities. Here we present a statistical analysis of various additional lightning properties derived from OTD/LIS, i.e. the number of so-called "events" and "groups" per flash, as well as 10 the mean flash duration, footprint and radiance. These normalized quantities, which can be associated with the flash "strength", show consistent spatial patterns; most strikingly, oceanic flashes show higher values than continental flashes for all properties. Over land, regions with high (Eastern US) 15 and low (India) flash strength can be clearly identified. We discuss possible causes and implications of the observed regional differences. Although a direct quantitative interpretation of the investigated flash properties is difficult, the observed spatial patterns provide valuable information for the 20 interpretation and application of climatological flash rates. Due to the systematic regional variations of physical flash characteristics, viewing conditions, and/or measurement sensitivities, parametrisations of lightning NOx based on total flash rate densities alone are probably affected by regional biases.

Transient thermal effect, nonlinear refraction and nonlinear absorption properties of graphene oxide sheets in dispersion.

PubMed

Zhang, Xiao-Liang; Liu, Zhi-Bo; Li, Xiao-Chun; Ma, Qiang; Chen, Xu-Dong; Tian, Jian-Guo; Xu, Yan-Fei; Chen, Yong-Sheng

2013-03-25

The nonlinear refraction (NLR) properties of graphene oxide (GO) in N, N-Dimethylformamide (DMF) was studied in nanosecond, picosecond and femtosecond time regimes by Z-scan technique. Results show that the dispersion of GO in DMF exhibits negative NLR properties in nanosecond time regime, which is mainly attributed to transient thermal effect in the dispersion. The dispersion also exhibits negative NLR in picosecond and femtosecond time regimes, which are arising from sp(2)- hybridized carbon domains and sp(3)- hybridized matrix in GO sheets. To illustrate the relations between NLR and nonlinear absorption (NLA), NLA properties of the dispersion were also studied in nanosecond, picosecond and femtosecond time regimes.

Observation of laser-driven shock propagation by nanosecond time-resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Yu, Guoyang; Zheng, Xianxu; Song, Yunfei; Zeng, Yangyang; Guo, Wencan; Zhao, Jun; Yang, Yanqiang

2015-01-01

An improved nanosecond time-resolved Raman spectroscopy is performed to observe laser-driven shock propagation in the anthracene/epoxy glue layer. The digital delay instead of optical delay line is introduced for sake of unlimited time range of detection, which enables the ability to observe both shock loading and shock unloading that always lasts several hundred nanoseconds. In this experiment, the peak pressure of shock wave, the pressure distribution, and the position of shock front in gauge layer were determined by fitting Raman spectra of anthracene using the Raman peak shift simulation. And, the velocity of shock wave was calculated by the time-dependent position of shock front.

A scheme for recording a fast process at nanosecond scale by using digital holographic interferometry with continuous wave laser

NASA Astrophysics Data System (ADS)

Wang, Jun; Zhao, Jianlin; Di, Jianglei; Jiang, Biqiang

2015-04-01

A scheme for recording fast process at nanosecond scale by using digital holographic interferometry with continuous wave (CW) laser is described and demonstrated experimentally, which employs delayed-time fibers and angular multiplexing technique and can realize the variable temporal resolution at nanosecond scale and different measured depths of object field at certain temporal resolution. The actual delay-time is controlled by two delayed-time fibers with different lengths. The object field information in two different states can be simultaneously recorded in a composite hologram. This scheme is also suitable for recording fast process at picosecond scale, by using an electro-optic modulator.

Theoretical review of the treatment of pigmented lesions in Asian skin

PubMed Central

Shek, Samantha Y.; Chan, Henry H.L.; Groff, William F.; Imagawa, Kotaro; Akamatsu, Tadashi

2016-01-01

Asian skin has a higher epidermal melanin content, making it more likely to develop adverse pigmentary reactions following laser surgery. The nanosecond lasers are the gold standard for the treatment of pigmented lesions, but the risk of complications, such as post-inflammatory hyperpigmentation, is increased in dark-skinned patients. Intense Pulsed Light (IPL) or long-pulsed lasers are available for treating superficial pigmented lesions, and fewer complications are seen when using these devices compared to the nanosecond lasers. Nanosecond lasers are essential in the treatment of dermal melanosis. Recently, picosecond lasers have been investigated. Picosecond lasers will also play an important role in the treatment of pigmented lesions. PMID:27853342

Nanosecond laser coloration on stainless steel surface.

PubMed

Lu, Yan; Shi, Xinying; Huang, Zhongjia; Li, Taohai; Zhang, Meng; Czajkowski, Jakub; Fabritius, Tapio; Huttula, Marko; Cao, Wei

2017-08-02

In this work, we present laser coloration on 304 stainless steel using nanosecond laser. Surface modifications are tuned by adjusting laser parameters of scanning speed, repetition rate, and pulse width. A comprehensive study of the physical mechanism leading to the appearance is presented. Microscopic patterns are measured and employed as input to simulate light-matter interferences, while chemical states and crystal structures of composites to figure out intrinsic colors. Quantitative analysis clarifies the final colors and RGB values are the combinations of structural colors and intrinsic colors from the oxidized pigments, with the latter dominating. Therefore, the engineering and scientific insights of nanosecond laser coloration highlight large-scale utilization of the present route for colorful and resistant steels.

Integrator Circuitry for Single Channel Radiation Detector

NASA Technical Reports Server (NTRS)

Holland, Samuel D. (Inventor); Delaune, Paul B. (Inventor); Turner, Kathryn M. (Inventor)

2008-01-01

Input circuitry is provided for a high voltage operated radiation detector to receive pulses from the detector having a rise time in the range of from about one nanosecond to about ten nanoseconds. An integrator circuit, which utilizes current feedback, receives the incoming charge from the radiation detector and creates voltage by integrating across a small capacitor. The integrator utilizes an amplifier which closely follows the voltage across the capacitor to produce an integrator output pulse with a peak value which may be used to determine the energy which produced the pulse. The pulse width of the output is stretched to approximately 50 to 300 nanoseconds for use by subsequent circuits which may then use amplifiers with lower slew rates.

GPS common-view time transfer

NASA Technical Reports Server (NTRS)

Lewandowski, W.

1994-01-01

The introduction of the GPS common-view method at the beginning of the 1980's led to an immediate and dramatic improvement of international time comparisons. Since then, further progress brought the precision and accuracy of GPS common-view intercontinental time transfer from tens of nanoseconds to a few nanoseconds, even with SA activated. This achievement was made possible by the use of the following: ultra-precise ground antenna coordinates, post-processed precise ephemerides, double-frequency measurements of ionosphere, and appropriate international coordination and standardization. This paper reviews developments and applications of the GPS common-view method during the last decade and comments on possible future improvements whose objective is to attain sub-nanosecond uncertainty.

Characteristics of Lightning Within Electrified Snowfall Events Using Lightning Mapping Arrays

NASA Astrophysics Data System (ADS)

Schultz, Christopher J.; Lang, Timothy J.; Bruning, Eric C.; Calhoun, Kristin M.; Harkema, Sebastian; Curtis, Nathan

2018-02-01

This study examined 34 lightning flashes within four separate thundersnow events derived from lightning mapping arrays (LMAs) in northern Alabama, central Oklahoma, and Washington DC. The goals were to characterize the in-cloud component of each lightning flash, as well as the correspondence between the LMA observations and lightning data taken from national lightning networks like the National Lightning Detection Network (NLDN). Individual flashes were examined in detail to highlight several observations within the data set. The study results demonstrated that the structures of these flashes were primarily normal polarity. The mean area encompassed by this set of flashes is 375 km2, with a maximum flash extent of 2,300 km2, a minimum of 3 km2, and a median of 128 km2. An average of 2.29 NLDN flashes were recorded per LMA-derived lightning flash. A maximum of 11 NLDN flashes were recorded in association with a single LMA-derived flash on 10 January 2011. Additionally, seven of the 34 flashes in the study contain zero NLDN-identified flashes. Eleven of the 34 flashes initiated from tall human-made objects (e.g., communication towers). In at least six lightning flashes, the NLDN detected a return stroke from the cloud back to the tower and not the initial upward leader. This study also discusses lightning's interaction with the human-built environment and provides an example of lightning within heavy snowfall observed by Geostationary Operational Environmental Satellite-16's Geostationary Lightning Mapper.

Hot flashes in breast cancer survivors: Frequency, severity and impact.

PubMed

Chang, Hao-Yuan; Jotwani, Aparna C; Lai, Yeur-Hur; Jensen, Mark P; Syrjala, Karen L; Fann, Jesse R; Gralow, Julie

2016-06-01

To (1) determine the frequency and severity of hot flashes, (2) examine the associations between hot flash frequency and severity and quality of life, and (3) identify the predictors of hot flash activity in breast cancer survivors. The study used a cross-sectional design and mailed survey of 253 breast cancer survivors recruited from a cancer wellness clinic. Participants provided information regarding cancer history, hot flashes, pain intensity, sleep problems, physical functioning, and psychological functioning. About half of the survivors reported at least one hot flash in the past 24 h (45%) or past week (52%). The average frequency of hot flashes was 1.9 in the past 24 h and 1.8 in the past week. Hot flash severity was usually mild or asymptomatic. However, participants with hot flashes reported significantly more sleep problems and higher pain severity than those reporting no hot flashes. Moreover, the severity of hot flashes was associated with more sleep problems, higher pain severity, and more psychological dysfunction. History of hormonal suppression therapy and younger age predicted hot flash activity in the study sample. In breast cancer survivors, hot flashes are common and are associated with unpleasant symptoms and poor quality of life. Research is needed to determine if treatments that reduce the frequency and severity of hot flashes in breast cancer survivors also result in improvements in symptoms such as sleep problems, pain, and psychological dysfunction. Copyright © 2016 Elsevier Ltd. All rights reserved.