Solid state photochemistry. Subpanel A-2(a): Design of molecular precursors for electronic materials

Energy Technology Data Exchange (ETDEWEB)

Wells, R.L. [Duke Univ., Durham, NC (United States)

1996-09-01

Recent achievements of synthetic chemistry in the field of electronic materials are presented in three categories; viz, precursor design for improved processing, new chemistry for selective growth, and new growth techniques. This is followed by a discussion of challenges and opportunities in two general areas designated as composition and structure, and growth and processing.

Microwave Photochemistry II. Photochemistry of 2-tert-butylphenol

Czech Academy of Sciences Publication Activity Database

Církva, Vladimír; Kurfürstová, Jana; Karban, Jindřich; Hájek, Milan

2004-01-01

Roč. 168, č. 3 (2004), s. 197-204 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : microwave photochemistry * electrodeless discharge lamp * 2-tert-Butylphenol Subject RIV: CC - Organic Chemistry Impact factor: 2.235, year: 2004

Radiation and photochemistry section

International Nuclear Information System (INIS)

1991-01-01

The highlights of this past year in the Radiation and Photochemistry Section at Argonne include: (1) picosecond optical studies of radical cations and excited states produced in hydrocarbon radiolysis provided the first kinetic measurements of ion transformation and production of triplet and singlet excited states by ion recombination. (2) studies of radical cations of alkyl-substituted amines and sulfides provided insights into ion-molecule reactions of radical cations in the condensed phase. (3) studies of the behavior of strained alkane radical cations, such as cubane + ·, revealed new rearrangements and remarkable, medium-dependent differences in their structures. (4) H·atom reactions yielding e aq - provided the first reliable measurements of hydrated-electron enthalpy and entropy and forced the revision of some previous thinking about the driving force in aq - reactions

Microwave Photochemistry III. Photochemistry of 4-tert-Butylphenol

Czech Academy of Sciences Publication Activity Database

Církva, Vladimír; Kurfürstová, J.; Karban, Jindřich; Hájek, Milan

2005-01-01

Roč. 174, č. 1 (2005), s. 38-44 ISSN 1010-6030 R&D Projects: GA ČR(CZ) GA203/02/0879; GA AV ČR(CZ) KSK4040110 Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave photochemistry * electrodeless discharge lamp * 4-tert-Butylphenol Subject RIV: CC - Organic Chemistry Impact factor: 2.286, year: 2005

Radiation and Photochemistry Section annual report, October 1990--September 1991

International Nuclear Information System (INIS)

1991-12-01

This report describes the radiation chemistry and photochemistry of reactive intermediates in the condensed phase. The section on the chemistry of ions treats condensed-phase reactions of radical cations, radical cations in zeolite matrices, high energy chemistry, ions and excited states in radiolysis, and photochemistry of the polymer imaging systems. The section on the role of solvent in chemical reactivity describes a study of atomic hydrogen and deuterium in water radiolysis, solvated electron thermodynamics and transport properties, solvent relaxation dynamics, and solvation of an excess electron in an aqueous solution of LiCl. A separate section outlines activities at the 20-MeV linac and the 3-MeV Van de Graaff accelerator

Photochemistry and photophysics concepts, research, applications

CERN Document Server

Balzani , Vincenzo; Juris, Alberto

2014-01-01

This textbook covers the spectrum from basic concepts of photochemistry and photophysics to selected examples of current applications and research.Clearly structured, the first part of the text discusses the formation, properties and reactivity of excited states of inorganic and organic molecules and supramolecular species, as well as experimental techniques. The second part focuses on the photochemical and photophysical processes in nature and artificial systems, using a wealth of examples taken from applications in nature, industry and current research fields, ranging from natural photosynth

Tunable lasers for waste management photochemistry applications

International Nuclear Information System (INIS)

Finch, F.T.

1978-09-01

A review of lasers with potential photochemical applications in waste management indicates that dye lasers, as a class, can provide tunable laser output through the visible and near-uv regions of the spectrum of most interest to photochemistry. Many variables can affect the performance of a specific dye laser, and the interactions of these variables, at the current state of the art, are complex. The recent literature on dye-laser characteristics has been reviewed and summarized, with emphasis on those parameters that most likely will affect the scaling of dye lasers in photochemical applications. Current costs are reviewed and correlated with output power. A new class of efficient uv lasers that appear to be scalable in both energy output and pulse rate, based on rare-gas halide excimers and similar molecules, is certain to find major applications in photochemistry. Because the most important developments are too recent to be adequately described in the literature or are the likely outcome of current experiments, the basic physics underlying the class of excimer lasers is described. Specific cost data are unavailable, but these new gas lasers should reflect costs similar to those of existing gas lasers, in particular, the pulsed CO 2 lasers. To complete the survey of tunable-laser characteristics, the technical characteristics of the various classes of lasers in the ir are summarized. Important developments in ir laser technology are being accelerated by isotope-separation research, but, initially at least, this portion of the spectrum is least likely to receive emphasis in waste-management-oriented photochemistry

Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

Science.gov (United States)

Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

2015-03-17

Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron

Surface-Plasmon-Driven Hot Electron Photochemistry.

Science.gov (United States)

Zhang, Yuchao; He, Shuai; Guo, Wenxiao; Hu, Yue; Huang, Jiawei; Mulcahy, Justin R; Wei, Wei David

2017-11-30

Visible-light-driven photochemistry has continued to attract heightened interest due to its capacity to efficiently harvest solar energy and its potential to solve the global energy crisis. Plasmonic nanostructures boast broadly tunable optical properties coupled with catalytically active surfaces that offer a unique opportunity for solar photochemistry. Resonant optical excitation of surface plasmons produces energetic hot electrons that can be collected to facilitate chemical reactions. This review sums up recent theoretical and experimental approaches for understanding the underlying photophysical processes in hot electron generation and discusses various electron-transfer models on both plasmonic metal nanostructures and plasmonic metal/semiconductor heterostructures. Following that are highlights of recent examples of plasmon-driven hot electron photochemical reactions within the context of both cases. The review concludes with a discussion about the remaining challenges in the field and future opportunities for addressing the low reaction efficiencies in hot-electron-induced photochemistry.

Proceedings of the Nineteenth DOE Solar Photochemistry Research Conference

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-07-01

This document is a compilation of reports presented at the Nineteenth DOE Solar Photochemistry Research Conference. Sessions included photophysical properties of transition metal complexes, cage effects on photochemistry, charge transfer, photo-induced charge separation in biomimetic molecules, photosynthesis, and electron transfer.

A personal perspective on the future of flow photochemistry

NARCIS (Netherlands)

Noël, Timothy

2017-01-01

Photochemistry and photoredox catalysis have witnessed a remarkable comeback in the last decade. Flow chemistry has been of pivotal importance to alleviate some of the classical obstacles associated with photochemistry. Herein, we analyze some of the most exciting features provided by photo flow

Photochemistry of the actinides

International Nuclear Information System (INIS)

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

1979-01-01

It has been found that all three major actinides have a useful variety of photochemical reactions which could be used to achieve a separations process that requires fewer reagents. Several features merit enumerating: (1) Laser photochemistry is not now as uniquely important in fuel reprocessing as it is in isotopic enrichment. The photochemistry can be successfully accomplished with conventional light sources. (2) The easiest place to apply photo-reprocessing is on the three actinides U, Pu, and Np. The solutions are potentially cleaner and more amenable to photoreactions. (3) Organic-phase photoreactions are probably not worth much attention because of the troublesome solvent redox chemistry associated with the photochemical reaction. (4) Upstream process treatment on the raffinate (dissolver solution) may never be too attractive since the radiation intensity precludes the usage of many optical materials and the nature of the solution is such that light transmission into it might be totally impossible

PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. I. PHOTOCHEMISTRY MODEL AND BENCHMARK CASES

Energy Technology Data Exchange (ETDEWEB)

Hu Renyu; Seager, Sara; Bains, William, E-mail: hury@mit.edu [Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

2012-12-20

We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission, and thermal escape of O, H, C, N, and S bearing species, as well as formation and deposition of elemental sulfur and sulfuric acid aerosols. We validate the model by computing the atmospheric composition of current Earth and Mars and find agreement with observations of major trace gases in Earth's and Mars' atmospheres. We simulate several plausible atmospheric scenarios of terrestrial exoplanets and choose three benchmark cases for atmospheres from reducing to oxidizing. The most interesting finding is that atomic hydrogen is always a more abundant reactive radical than the hydroxyl radical in anoxic atmospheres. Whether atomic hydrogen is the most important removal path for a molecule of interest also depends on the relevant reaction rates. We also find that volcanic carbon compounds (i.e., CH{sub 4} and CO{sub 2}) are chemically long-lived and tend to be well mixed in both reducing and oxidizing atmospheres, and their dry deposition velocities to the surface control the atmospheric oxidation states. Furthermore, we revisit whether photochemically produced oxygen can cause false positives for detecting oxygenic photosynthesis, and find that in 1 bar CO{sub 2}-rich atmospheres oxygen and ozone may build up to levels that have conventionally been accepted as signatures of life, if there is no surface emission of reducing gases. The atmospheric scenarios presented in this paper can serve as the

The Electrodeless Discharge Lamp: A Prospective Tool for Photochemistry Part 3. The Microwave Photochemistry Reactor

Czech Academy of Sciences Publication Activity Database

Klán, P.; Hájek, Milan; Církva, Vladimír

2001-01-01

Roč. 140, č. 3 (2001), s. 185-189 ISSN 1010-6030 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * electrodeless discharge lamp * microwave Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 1.038, year: 2001

Proceedings of the Fourteenth DOE solar photochemistry research conference

Energy Technology Data Exchange (ETDEWEB)

1989-01-01

The central themes of this year's Solar Photochemistry Research Conference encompassed initial charge separation in photosynthesis, photoinduced charge separation in other organized assemblies, electron transfer, organic and inorganic photochemistry, and photoelectrochemistry. This volume contains a copy of the program the abstracts of 29 formal presentations and 47 posters, a record of the discussion following each presentation, and an address list for the 96 attendees. Individual projects are processed separately for the databases. .

Proceedings of the Fourteenth DOE solar photochemistry research conference

International Nuclear Information System (INIS)

1989-01-01

The central themes of this year's Solar Photochemistry Research Conference encompassed initial charge separation in photosynthesis, photoinduced charge separation in other organized assemblies, electron transfer, organic and inorganic photochemistry, and photoelectrochemistry. This volume contains a copy of the program the abstracts of 29 formal presentations and 47 posters, a record of the discussion following each presentation, and an address list for the 96 attendees. Individual projects are processed separately for the databases

Effects of climate change on surface-water photochemistry: a review.

Science.gov (United States)

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

2014-10-01

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO3 (·-). However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO3 (·-). Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO3 (·-)). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen ((1)O2) and by the triplet states of chromophoric dissolved organic matter ((3)CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.

VUV spectroscopy and photochemistry of five interstellar and putative prebiotic molecules

Science.gov (United States)

Schwell, M.; Gaie-Levrel, F.; Bénilan, Y.; Gazeau, M.-C.; Fray, N.; Saul, G.; Champion, N.; Leach, S.; Guillemin, J.-C.

2012-02-01

For many years, our group has been investigating the VUV spectroscopy and photochemistry of molecules of astrophysical (Jochims et al. 2006a,b; Leach et al. 2008; Schwell et al. 2012) and prebiotic interest (Schwell et al. 2006). Polyynes and cyano-polyynes that are abundant in the interstellar medium (ISM) and in planetary atmospheres, have been investigated too (e.g. Fray et al. 2010). An aerosol source for reactive and thermo-labile compounds has been developed (Gaie-Levrel et al. 2011) to perform gas-phase measurements. These are necessary to measure intrinsic molecular properties and to compare to quantum chemical calculations. Besides measuring absolute absorption and photoionization cross sections, dissociative channels and their involved excited states are identified for a number of molecules of interstellar interest. Branching ratios of the respective elementary photoreactions are determined in order to understand and model the photochemistry occurring in the ISM. Some very recent results on the dissociative photoionization of methylformate (MF), glycolaldehyde (GA), dimethylether (DIM), aminoacetonitrile (AAC) and cyanoacetylene (CA), are presented here.

Vacuum ultraviolet photochemistry of polymers

International Nuclear Information System (INIS)

Skurat, Vladimir

2003-01-01

The interaction of vacuum UV radiation (wavelength range from 1 to 200 nm) with polymers is interesting for fundamental and applied sciences. This interest is stimulated by various reasons: - Wide applications of polymeric materials in semiconductor technology, where they are used as photoresist materials in combination with VUV light sources (lasers, excimer lamps, synchrotron radiation and others). - Polymers are widely used as spacecraft materials in the last 20 years. On near-Earth orbits, the polymeric materials of spacecraft surfaces are destroyed by solar radiation. - VUV radiation is one of the components of gas discharge plasmas, which are used for treatment of polymer, with the aim of modifying their surface properties. The main features of interaction of VUV radiation with polymers are discussed. The spectra of intrinsic absorption of saturated polymers (polyethylene, polypropylene, polytetrafluoroethylene and others) are situated mainly in the VUV region. The photochemistry of polymers in the VUV region is very different from their photochemistry at wavelengths longer than 200 nm, where the absorption spectra belong to impurities and polymer defects. The polymer photochemistry in the VUV region is wavelength-dependent. At wavelengths longer than about 140 nm, the main role is played by transformations of primary-formed singlet excited molecules. At shorter wavelengths the role of photoionization increases progressively and the main features of VUV photolysis become similar to the picture of radiolysis, with significant contributions of charge pairs and triplet excited molecules. Very important features of VUV light absorption in polymers are high absorption coefficients. Because of this, the surface layers absorb large doses of energy. This leads to very profound transformation of material on the polymer surface. In particular for polymers which are considered destroyed by radiation (for example, perfluoropolymers), this leads to VUV-induced erosion

Photochemistry of psoralen-DNA adducts, biological effects of psoralen-DNA adducts, applications of psoralen-DNA photochemistry

Energy Technology Data Exchange (ETDEWEB)

Shi, Yun-bo

1988-03-01

This thesis consists of three main parts and totally eight chapters. In Part I, The author will present studies on the photochemistry of psoralen-DNA adducts, specifically, the wavelength dependencies for the photoreversals of thymidine-HMT (4'-hydroxymethyl-4, 5', 8-trimenthylpsoralen) monoadducts and diadduct and the same adducts incorporated in DNA helices and the wavelength dependecies for the photocrossslinking of thymidine-HMT monoadducts in double-stranded helices. In Part II, The author will report some biological effects of psoralen-DNA adducts, i.e., the effects on double-stranded DNA stability, DNA structure, and transcription by E. coli and T7 RNA polymerases. Finally, The author will focus on the applications of psoralen-DNA photochemistry to investigation of protein-DNA interaction during transcription, which includes the interaction of E. coli and T7 RNA polymerases with DNA in elongation complexes arrested at specific psoralen-DNA adduct sites as revealed by DNase I footprinting experiments. 123 refs., 52 figs., 12 tabs.

Photochemistry of psoralen-DNA adducts, biological effects of psoralen-DNA adducts, applications of psoralen-DNA photochemistry

International Nuclear Information System (INIS)

Shi, Yun-bo.

1988-03-01

This thesis consists of three main parts and totally eight chapters. In Part I, The author will present studies on the photochemistry of psoralen-DNA adducts, specifically, the wavelength dependencies for the photoreversals of thymidine-HMT (4'-hydroxymethyl-4, 5', 8-trimenthylpsoralen) monoadducts and diadduct and the same adducts incorporated in DNA helices and the wavelength dependecies for the photocrossslinking of thymidine-HMT monoadducts in double-stranded helices. In Part II, The author will report some biological effects of psoralen-DNA adducts, i.e., the effects on double-stranded DNA stability, DNA structure, and transcription by E. coli and T7 RNA polymerases. Finally, The author will focus on the applications of psoralen-DNA photochemistry to investigation of protein-DNA interaction during transcription, which includes the interaction of E. coli and T7 RNA polymerases with DNA in elongation complexes arrested at specific psoralen-DNA adduct sites as revealed by DNase I footprinting experiments. 123 refs., 52 figs., 12 tabs

Photochemistry of modified proteins benzophenone-containing bovine serum albumin

International Nuclear Information System (INIS)

Mariano, P.S.; Glover, G.I.; Wilkinson, T.J.

1976-01-01

The results of exploratory and mechanistic studies of the photochemistry of poly-p-benzoyl-acetimido-bovine serum albumin, a modified protein containing photoreactive and photosensitizing groups, are reported. Specifically described are recent findings concerning (1) the synthesis and characterization of a modified bovine serum albumin that contains benzophenone-like moieties, (2) the photochemistry of this modified protein which appeared to involve photoreductive coupling of the benzophenone chromophores to the protein backbone, and (3) triplet energy transfer from modified bovine serum albumin to small molecule acceptors resulting in quenching of the photoreaction. (author)

Fifteenth DOE solar photochemistry research conference

Energy Technology Data Exchange (ETDEWEB)

1991-01-01

This is a compilation of abstracts from the Fifteenth DOE Solar Photochemistry Research Conference hosted by the Solar Energy Research Institute which took place June 2--6, 1991. A large variety of topics pertinent to solar energy conversion are covered, including photoinduced electron transfer, photochemical energy conversion, and photosynthetic energy conversion. (GHH)

Synthesis, characterization and photochemistry of a new ...

Indian Academy of Sciences (India)

The synthesis, crystal structure, redox characteristics and photochemistry of a new heptamolyb- ... The ability of [Mo7O24]−6 to function as a pure “inor- .... Abbreviations used: bpp = 1,3-bis(4-pyridyl)propane; 2-amp = 2-aminopyridine; DMSO ...

Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

Energy Technology Data Exchange (ETDEWEB)

Kwon, K.D.; Sposito, G.

2010-02-01

Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

Mechanistic reappraisal of early stage photochemistry in the light-driven enzyme protochlorophyllide oxidoreductase.

Directory of Open Access Journals (Sweden)

Derren J Heyes

Full Text Available The light-driven enzyme protochlorophyllide oxidoreductase (POR catalyzes the reduction of protochlorophyllide (Pchlide to chlorophyllide (Chlide. This reaction is a key step in the biosynthesis of chlorophyll. Ultrafast photochemical processes within the Pchlide molecule are required for catalysis and previous studies have suggested that a short-lived excited-state species, known as I675*, is the first catalytic intermediate in the reaction and is essential for capturing excitation energy to drive subsequent hydride and proton transfers. The chemical nature of the I675* excited state species and its role in catalysis are not known. Here, we report time-resolved pump-probe spectroscopy measurements to study the involvement of the I675* intermediate in POR photochemistry. We show that I675* is not unique to the POR-catalyzed photoreduction of Pchlide as it is also formed in the absence of the POR enzyme. The I675* species is only produced in samples that contain both Pchlide substrate and Chlide product and its formation is dependent on the pump excitation wavelength. The rate of formation and the quantum yield is maximized in 50∶50 mixtures of the two pigments (Pchlide and Chlide and is caused by direct energy transfer between Pchlide and neighboring Chlide molecules, which is inhibited in the polar solvent methanol. Consequently, we have re-evaluated the mechanism for early stage photochemistry in the light-driven reduction of Pchlide and propose that I675* represents an excited state species formed in Pchlide-Chlide dimers, possibly an excimer. Contrary to previous reports, we conclude that this excited state species has no direct mechanistic relevance to the POR-catalyzed reduction of Pchlide.

The photochemistry of ring-substituted cinnamyl acetates

International Nuclear Information System (INIS)

Fleming, S.A.; Renault, L.; Grundy, E.C.; Pincock, J.A.

2006-01-01

The photochemistry of the (E)-cinnamyl acetates ((E)-1-aryl-3-propenyl acetates, 8a-8e) with substituents H, 4-CH 3 O, 3-CH 3 O, 4-CF 3 , and 3-CF 3 , respectively, was examined in both cyclohexane and methanol solvents. Alkene isomerization (E to Z) occurred more efficiently than other reactions and evidence is presented that this process occurs from the excited triplet state. In a slower process, 1,3-migration of the acetoxy group led to the rearranged 3-aryl-3-propenyl acetate isomers (9a-9e) as the major pathway, particularly in cylohexane. In methanol, the isomeric ethers 3-aryl-3-methoxypropene (14) and 1-aryl-3-methoxypropene (15) were formed by reaction of methanol with the photochemically generated cation. The combined yield of 14 and 15 (95% and 5%, respectively) was quantitative for the 4-methoxyphenyl compound (8b). Independent irradiations of the isomers 9a-9c demonstrated that the ethers 14 and 15 were primary photoproducts from 8 and not secondary photoproducts from 9. Fluorescence quantum yields and excited singlet state lifetimes indicated that the reactions, other than the E to Z isomerization, are from the excited singlet state. (author)

Proceedings of the Seventeenth DOE Solar Photochemistry Research Conference

Energy Technology Data Exchange (ETDEWEB)

1993-12-31

The Seventeenth DOE Solar Photochemistry Research Conference sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences, is being held June 6--10, 1993, at Cragun`s Lodge and Conference Center, Brainerd, Minnesota The meeting is hosted this year by the Ames Laboratory of Iowa State University. The purpose of the meeting is to foster cooperation, collaboration, and exchange of current research ideas among grantees and contractors of the DOE Division of Chemical Sciences engaged in fundamental research on solar photochemical energy conversion. This conference provides a special opportunity for interaction among investigators from diverse traditional chemistry disciplines who share the common good of providing the knowledge and concepts needed for production of low cost fuels and chemicals or electricity by photochemical conversion of solar energy. Our special guest plenary lecturer is Professor Graham Fleming, of the University of Chicago, who will speak on ultrafast spectroscopic studies of molecular dynamics in the condensed phase. The remaining presentations on Monday will feature further investigations of ultrafast phenomena in solvation, electron transfer, and charge separation at interfaces. These will lead into the topical sessions which follow on photosynthesis, molecular models, photoinduced charge transfer in homogeneous and heterogeneous solutions, inorganic photochemistry, and photoelectrochemistry. As an added feature, the photoelectrochemistry session will include six short introductory lectures for the benefit of nonspecialists on outstanding issues and problems in that field. In this volume may be found a copy of the program, the abstracts of 28 formal presentations and 59 posters, as well as an address listing of the 114 participants.

Selected topics in photochemistry of nucleic acids. Recent results and perspectives

International Nuclear Information System (INIS)

Loeber, G.; Kittler, L.

1977-01-01

Recent results on the following photoreactions of nucleic acids are reported: photochemistry of aza-bases and minor bases, formation of photoproducts of the non-cyclobutane type, formations of furocoumarin-pyrimidine photoadducts, fluorescence of dye-nucleic acid complexes and their role in chromosomal fluorescence staining, and mechanisms of the photochemical reaction. Results are discussed with respect to: (i) photobiological relevance of light-induced defects in nucleic acids; (ii) possibilities of achieving higher selectivity of light-induced defects in nucleic acids; (iii) the use of nucleic acid photochemistry to analyze genetic material. An extensive bibliography is included. (author)

Aerosols from fires: an examination of the effects on ozone photochemistry in the Western United States.

Science.gov (United States)

Jiang, Xiaoyan; Wiedinmyer, Christine; Carlton, Annmarie G

2012-11-06

This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment.

Science.gov (United States)

Cambié, Dario; Bottecchia, Cecilia; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

2016-09-14

Continuous-flow photochemistry in microreactors receives a lot of attention from researchers in academia and industry as this technology provides reduced reaction times, higher selectivities, straightforward scalability, and the possibility to safely use hazardous intermediates and gaseous reactants. In this review, an up-to-date overview is given of photochemical transformations in continuous-flow reactors, including applications in organic synthesis, material science, and water treatment. In addition, the advantages of continuous-flow photochemistry are pointed out and a thorough comparison with batch processing is presented.

Vertical sounding balloons for stratospheric photochemistry

Science.gov (United States)

Pommereau, J. P.

The use of vertical sounding balloons for stratospheric photochemistry studies is illustrated by the use of a vertical piloted gas balloon for the search of NO2 diurnal variations. It is shown that the use of montgolfieres (hot air balloons) can enhance the vertical sounding technique. Particular attention is given to a sun-heated montgolfiere and to the more sophisticated infrared montgolfiere that is able to perform three to four vertical excursions per day and to remain aloft for weeks or months.

Photochemistry of materials in the stratosphere

Energy Technology Data Exchange (ETDEWEB)

Johnston, H.S. [Lawrence Berkeley Laboratories, CA (United States)

1993-12-01

This research is concerned with global change in the atmosphere, including photochemical modeling and, in the past, experimental gas-phase photochemistry involving molecular dynamics and laboratory study of atmospheric chemical reactions. The experimental work on this project concluded in August 1991, but there is a back-log of several journal articles to be written and submitted for publication. The theoretical work involves photochemical modeling in collaboration with Lawrence Livermore National Laboratory (LLNL) and advising the Upper Atmosphere Research Program on Atmospheric Effects of Stratospheric Aircraft, National Aeronautics and Space Administration (NASA).

Proceedings of the twenty-first DOE solar photochemistry research conference

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-06-01

The Solar Photochemistry Research Conference brings together grantees and contractors of the Division of Chemical Sciences who are engaged in fundamental research on solar photochemical energy conversion. The annual conference provides a focus for the program by allowing for the exchange of new information and ideas, identification of needs and opportunities, and fostering of collaborations among investigators of disparate chemistry backgrounds. The synergy that has been achieved is a major strength of the program. The research provides the foundations for future solar technologies, in which light-induced charge separation processes will be applied to conversion of light energy to chemical energy, e.g., production of alcohols from carbon dioxide, hydrogen from water, ammonia from atmospheric nitrogen, or other needed chemicals at lower cost of by using sunlight as the energy source. The program includes topical sessions on semiconductor nanoparticles, nanocrystalline films, and photoinduced charge separation at the semiconductor/liquid interface; photochemistry and photophysics of transition metal complexes; photoinduced charge separation in zeolites and lamellar assemblies; intramolecular charge separation and electron transfer; dynamics of solvation and solution interfaces; and photoconversion via porphyrins and biomimetic constructs. The special guest plenary lecturer is Professor Moungi Bawendi of the Massachusetts Institute of Technology, who spoke on semiconductor nanocrystallites (quantum dots). As an added feature, Tom Surek, the Photovoltaics Technology program manager at NREL, presented a status report on one of the most promising and heavily supported programs in solar energy conversion technology, solid state photovoltaics. This volume contains the agenda for the meeting, abstracts of the 31 formal presentations and 55 posters, as well as an address list for the 111 participants.

Molecular beam studies of stratospheric photochemistry

Science.gov (United States)

Moore, Teresa Anne

1998-12-01

Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm

Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

Science.gov (United States)

Giammanco, Giuseppe E.

We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue

The photochemistry of neptunium in aqueous perchloric acid solutions

International Nuclear Information System (INIS)

Friedman, H.A.; Toth, L.M.; Osborne, M.M.

1979-01-01

The photochemistry of neptunium ions in aqueous perchloric acid has been investigated using 254 and 300 nm UV radiation. In the absence of other reagents, Np(IV) and (V) oxidized to Np(VI), in a stepwise fashion, with individual quantum efficiencies for each step that vary from 0.02 to 0.004. Decreasing acid concentration favors the Np(IV) → Np(V) reaction whereas it hinders the Np(V) → Np(VI) photo-oxidation. When ethanol, acetaldehyde and other mild reducing agents are added to neptunium-perchloric acid solutions which are then photolyzed, the Np species are reduced to Np(III) in a stepwise fashion with individual quantum efficiencies that vary from 0.07 to 0.006. The overall photoredox reactions of neptunium are subject to competing secondary product reactions that become significant as the photolysis products accumulate. Absorption spectrophotometry was used to monitor the changes in Np oxidation states and reference spectra of the various Np oxidation states are given for 1.0 N HClO 4 . The Np species have absorption bands in the 300 to 1320 nm region that obey Beer's law only when they were properly resolved. (author)

Adenine and 2-aminopurine: paradigms of modern theoretical photochemistry.

Science.gov (United States)

Serrano-Andrés, Luis; Merchán, Manuela; Borin, Antonio C

2006-06-06

Distinct photophysical behavior of nucleobase adenine and its constitutional isomer, 2-aminopurine, has been studied by using quantum chemical methods, in particular an accurate ab initio multiconfigurational second-order perturbation theory. After light irradiation, the efficient, ultrafast energy dissipation observed for nonfluorescent 9H-adenine is explained here by the nonradiative internal conversion process taking place along a barrierless reaction path from the initially populated 1(pipi* La) excited state toward a low-lying conical intersection (CI) connected with the ground state. In contrast, the strong fluorescence recorded for 2-aminopurine at 4.0 eV with large decay lifetime is interpreted by the presence of a minimum in the 1(pipi* La) hypersurface lying below the lowest CI and the subsequent potential energy barrier required to reach the funnel to the ground state. Secondary deactivation channels were found in the two systems related to additional CIs involving the 1(pipi* Lb) and 1(npi*) states. Although in 9H-adenine a population switch between both states is proposed, in 7H-adenine this may be perturbed by a relatively larger barrier to access the 1(npi*) state, and, therefore, the 1(pipi* Lb) state becomes responsible for the weak fluorescence measured in aqueous adenine at approximately 4.5 eV. In contrast to previous models that explained fluorescence quenching in adenine, unlike in 2-aminopurine, on the basis of the vibronic coupling of the nearby 1(pipi*) and 1(npi*) states, the present results indicate that the 1(npi*) state does not contribute to the leading photophysical event and establish the prevalence of a model based on the CI concept in modern photochemistry.

An overview of aquatic photochemistry as it relates to microbial production

Energy Technology Data Exchange (ETDEWEB)

Miller, W.L. [Dalhousie Univ., Halifax, NS (Canada). Inst. of Oceanography

2000-07-01

A review of fundamental photochemistry and its potential impact on microbial processes in natural waters was presented. It is a known fact that solar radiation alters chromophoric dissolved organic matter (CDOM) and results in the production of a complex mixture of reactive oxygen species, inorganic nutrients, and carbon photoproducts. In addition, it results in reduced average molecular weight and changes in water optical properties. The largest carbon product results from the direct photo-mineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC), thereby bypassing the microbial web. Other studies demonstrated that growth was enhanced for heterotrophic bacteria in natural samples exposed to sunlight, that bacterial growth was absent when stimulated by photochemistry and that there was a marked reduction in the ability of DOC to support bacterial growth after exposure to ultraviolet radiation B (UV-B). 20 refs., 1 fig.

Atmospheric photochemistry at a fatty acid coated air/water interface

Science.gov (United States)

George, Christian; Rossignol, Stéphanie; Passananti, Monica; Tinel, Liselotte; Perrier, Sebastien; Kong, Lingdong; Brigante, Marcello; Bianco, Angelica; Chen, Jianmin; Donaldson, James

2017-04-01

Over the past 20 years, interfacial processes have become increasingly of interest in the field of atmospheric chemistry, with many studies showing that environmental surfaces display specific chemistry and photochemistry, enhancing certain reactions and acting as reactive sinks or sources for various atmospherically relevant species. Many molecules display a free energy minimum at the air-water interface, making it a favored venue for compound accumulation and reaction. Indeed, surface active molecules have been shown to undergo specific photochemistry at the air-water interface. This presentation will address some recent surprises. Indeed, while fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds (VOCs) are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over monolayer NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet state NA molecules excited by direct absorption of actinic light at the water surface. As fatty acids covered interfaces are ubiquitous in the environment, such photochemical processing will have a significant impact on local ozone and particle formation. In addition, it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds photochemically on various unsaturated fatty acids compounds, and may therefore have a general environmental impact. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could

Atmospheric Photochemistry

Science.gov (United States)

Massey, Harrie; Potter, A. E.

1961-01-01

The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.

LOW POWER UPCONVERSION FOR SOLAR FUELS PHOTOCHEMISTRY

Energy Technology Data Exchange (ETDEWEB)

Castellano, Felix N. [Bowling Green State University

2013-08-05

Earth abundant copper(I) diimine complexes represent a renewable and economically feasible alternative to commonly used heavy metal containing chromophores. In the metal-to-ligand charge transfer (MLCT) excited state, copper(I) diimine complexes typically undergo a significant structural rearrangement, leading to molecules with large Stokes shifts and very short excited state lifetimes, thereby limiting their usefulness as sensitizers in bimolecular electron and triplet energy transfer reactions. Strategically placed bulky substituents on the coordinating phenanthroline ligands have proven useful in restricting the transiently produced excited state Jahn-Teller distortion, leading to longer-lived excited states. By combining bulky sec-butyl groups in the 2- and 9- positions with methyl groups in the 3-,4-, 7-, and 8- positions, a remarkably long-lived (2.8 μs in DCM) copper(I) bis-phenanthroline complex, [Cu(dsbtmp)2]+, has been synthesized and characterized. Unlike other copper(I) diimine complexes, [Cu(dsbtmp)2]+ also retains a μs lifetime in coordinating solvents such as acetonitrile and water as a result of the cooperative sterics inherent in the molecular design. Preliminary results on the use of this complex in hydrogen-forming homogeneous photocatalysis is presented. Photon upconversion based on sensitized triplet-triplet annihilation (TTA) represents a photochemical means to generate high-energy photons (or high-energy chemical products) from low-energy excitation, having potential applications in solar energy conversion and solar fuels producing devices. For the first time, synthetically facile and earth abundant Cu(I) MLCT sensitizers have been successfully incorporated into two distinct photochemical upconversion schemes, affording both red-to-green and orange-to-blue wavelength conversions. Preliminary results on aqueous-based photochemical upconversion as well as intramolecular Sn(IV) porphyrins containing axially coordinated aromatic hydrocarbon

Photochemistry of the α-Al2O3-PETN Interface

Directory of Open Access Journals (Sweden)

Roman V. Tsyshevsky

2016-02-01

Full Text Available Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al2O3-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C5H8N4O12 and a wide band gap aluminum oxide (α-Al2O3 substrate. The first principles modeling is used to deconstruct and interpret the α-Al2O3-PETN absorption spectrum that has distinct peaks attributed to surface F0-centers and surface—PETN transitions. We predict the low energy α-Al2O3 F0-center—PETN transition, producing the excited triplet state, and α-Al2O3 F0-center—PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.

Microwave Photochemistry. Applications in Organic Synthesis

Czech Academy of Sciences Publication Activity Database

Církva, Vladimír; Relich, Stanislav

2011-01-01

Roč. 8, č. 3 (2011), s. 282-293 ISSN 1570-193X Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave * photochemistry * electrodeless discharge lamp Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 2.406, year: 2011 http://www.scopus.com/record/display.url?eid=2-s2.0-79960013317&origin=resultslist&sort=plf-f&src=s&st1=cirkva%2cv&sid=95rFucNho6qr5iGwVeMnh_W%3a150&sot=b&sdt=b&sl=21&s=AUTHOR-NAME%28cirkva%2cv%29&relpos=0&relpos=0&searchTerm=AUTHOR-NAME(cirkva,v)

HIGH-TEMPERATURE PHOTOCHEMISTRY IN THE ATMOSPHERE OF HD 189733b

International Nuclear Information System (INIS)

Line, M. R.; Yung, Y. L.; Liang, M. C.

2010-01-01

Recent infrared spectroscopy of hot exoplanets is beginning to reveal their atmospheric composition. Deep within the planetary atmosphere, the composition is controlled by thermochemical equilibrium. Photochemistry becomes important higher in the atmosphere, at levels above ∼1 bar. These two chemistries compete between ∼1 and 10 bars in hot-Jupiter-like atmospheres, depending on the strength of the eddy mixing and temperature. HD 189733b provides an excellent laboratory in which to study the consequences of chemistry of hot atmospheres. The recent spectra of HD 189733b contain signatures of CH 4 , CO 2 , CO, and H 2 O. Here we identify the primary chemical pathways that govern the abundances of CH 4 , CO 2 , CO, and H 2 O in the cases of thermochemical equilibrium chemistry, photochemistry, and their combination. Our results suggest that the disequilibrium mechanisms can significantly enhance the abundances of these species above their thermochemical equilibrium value, so some caution must be taken when assuming that an atmosphere is in strict thermochemical equilibrium.

Photodynamic Efficiency: From Molecular Photochemistry to Cell Death

Directory of Open Access Journals (Sweden)

Isabel O. L. Bacellar

2015-08-01

Full Text Available Photodynamic therapy (PDT is a clinical modality used to treat cancer and infectious diseases. The main agent is the photosensitizer (PS, which is excited by light and converted to a triplet excited state. This latter species leads to the formation of singlet oxygen and radicals that oxidize biomolecules. The main motivation for this review is to suggest alternatives for achieving high-efficiency PDT protocols, by taking advantage of knowledge on the chemical and biological processes taking place during and after photosensitization. We defend that in order to obtain specific mechanisms of cell death and maximize PDT efficiency, PSes should oxidize specific molecular targets. We consider the role of subcellular localization, how PS photochemistry and photophysics can change according to its nanoenvironment, and how can all these trigger specific cell death mechanisms. We propose that in order to develop PSes that will cause a breakthrough enhancement in the efficiency of PDT, researchers should first consider tissue and intracellular localization, instead of trying to maximize singlet oxygen quantum yields in in vitro tests. In addition to this, we also indicate many open questions and challenges remaining in this field, hoping to encourage future research.

Parents' reported preference scores for childhood atopic dermatitis disease states

Directory of Open Access Journals (Sweden)

Walter Emmanuel B

2004-10-01

Full Text Available Abstract Background We sought to elicit preference weights from parents for health states corresponding to children with various levels of severity of atopic dermatitis. We also evaluated the hypothesis that parents with children who had been diagnosed with atopic dermatitis would assign different preferences to the health state scenarios compared with parents who did not have a child with atopic dermatitis. Methods Subjects were parents of children aged 3 months to 18 years. The sample was derived from the General Panel, Mommies Sub-Panel, and Chronic Illness Sub-Panel of Harris Interactive. Participants rated health scenarios for atopic dermatitis, asthma, and eyeglasses on a visual analog scale, imagining a child was experiencing the described state. Results A total of 3539 parents completed the survey. Twenty-nine percent had a child with a history of atopic dermatitis. Mean preference scores for atopic dermatitis were as follows: mild, 91 (95% confidence interval [CI], 90.7 to 91.5; mild/moderate, 84 (95%CI, 83.5 to 84.4; moderate, 73 (95%CI, 72.5 to 73.6; moderate/severe, 61 (95%CI, 60.6 to 61.8; severe, 49 (95% CI, 48.7 to 50.1; asthma, 58 (95%CI, 57.4 to 58.8; and eyeglasses, 87(95%CI, 86.3 to 87.4. Conclusions Parents perceive that atopic dermatitis has a negative effect on quality of life that increases with disease severity. Estimates of parents' preferences can provide physicians with insight into the value that parents place on their children's treatment and can be used to evaluate new medical therapies for atopic dermatitis.

Photochemistry of Nitrophenol Molecules and Clusters: Intra- vs Intermolecular Hydrogen Bond Dynamics

Czech Academy of Sciences Publication Activity Database

Grygoryeva, Kateřina; Kubečka, J.; Pysanenko, Andriy; Lengyel, Jozef; Slavíček, Petr; Fárník, Michal

2016-01-01

Roč. 120, č. 24 (2016), s. 4139-4146 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GA15-12386S Institutional support: RVO:61388955 Keywords : photochemistry * clusters * laser techniques Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

Applications of continuous-flow photochemistry in organic synthesis, material science, and water treatment

NARCIS (Netherlands)

Cambié, D.; Bottecchia, C.; Straathof, N.J.W.; Hessel, V.; Noël, T.

2016-01-01

Continuous-flow photochemistry in microreactors receives a lot of attention from researchers in academia and industry as this technology provides reduced reaction times, higher selectivities, straightforward scalability, and the possibility to safely use hazardous intermediates and gaseous

Photochemistry of the ozone-water complex in cryogenic neon, argon, and krypton matrixes.

Science.gov (United States)

Tsuge, Masashi; Tsuji, Kazuhide; Kawai, Akio; Shibuya, Kazuhiko

2013-12-12

The photochemistry of ozone-water complexes and the wavelength dependence of the reactions were studied by matrix isolation FTIR spectrometry in neon, argon, and krypton matrixes. Hydrogen peroxide was formed upon the irradiation of UV light below 355 nm. Quantitative analyses of the reactant and product were performed to evaluate the matrix cage effect of the photoreaction. In argon and krypton matrixes, a bimolecular O((1)D) + H2O → H2O2 reaction was found to occur to form hydrogen peroxide, where the O((1)D) atom generated by the photolysis of ozone diffused in the cryogenic solids to encounter water. In a neon matrix, hydrogen peroxide was generated through intracage photoreaction of the ozone-water complex, indicating that a neon matrix medium is most appropriate to study the photochemistry of the ozone-water complex.

2009 Gordon Research Conference on Photochemistry: Formal Schedule and Speaker/Poster Program

Energy Technology Data Exchange (ETDEWEB)

Wasielewski, Michael [Northwestern Univ., Evanston, IL (United States)

2009-07-05

The impact of photochemistry on diverse fields ranging from materials and environmental science to biology and medicine has never been greater. The 2009 Gordon Conference on Photochemistry will highlight recent advances in these key areas while also presenting the latest research on new photochemical reactions and mechanistic studies. Session topics will include: development of new chromophores, light harvesting materials, solar energy conversion, photocontrolled biomolecules, light-triggered amplification reactions, and advanced bioimaging techniques. The Conference will continue its 45 year history of promoting interactions between fundamental and applied scientists, a hallmark of the Gordon Conferences. In addition, oral presentations, poster sessions and informal discussions will provide opportunities for junior scientists and students to present their own work and discuss their results with leaders in the field. Applicants to the Conference are encouraged to submit abstracts for poster presentations in order to gain visibility and feedback on their research. In addition, a number of poster abstracts will be selected for presentation as short talks.

The nature of light. A brief introduction to photochemistry

OpenAIRE

Font, Josep

2017-01-01

The first lecture of the seminar on Light, Darkness and Living Beings, held in Mataró in March 2015, was devoted to explaining the dual nature of light and the interaction of this electromagnetic radiation with matter, considering mainly the photochemical aspects. This article summarizes the lecture, offering a brief description of the basis of photochemistry and giving some examples of reactions that need light in order to occur. Examples related to biological systems (e.g. plant photosynthe...

Photochemistry at high temperatures - potential of ZnO as a high temperature photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Schubnell, M; Beaud, P; Kamber, I [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Direct conversion of solar radiation into useful, storeable and transportable chemical products is the primary goal of solar chemistry. In this paper we discuss some fundamental aspects of photochemistry at elevated temperatures. We show that luminescence can serve as an indicator of the potential use of a system as a photoconverter. As an example we present experimental data on the chemical potential and on the lifetime of the excited states of ZnO. The low luminescence quantum yield together with a lifetime of about 200 ps indicate that an efficient photochemical conversion on ZnO is highly improbable. We believe this to be a general feature of chemical systems based on a semiconductor photocatalyst, in particular of photoreactions at a solid/gas interface. (author) 3 figs., 6 refs

Bond selective photochemistry in CH2BrI through electronic excitation at 210 nm

International Nuclear Information System (INIS)

Butler, L.J.; Hintsa, E.J.; Lee, Y.T.

1986-01-01

To explore the possibility of bond selective photochemistry in an excited electronic state, we have studied the photolysis of CH 2 BrI in a molecular beam at 210 nm. Following the direct local excitation of a repulsive transition on the C--Br bond at 210 nm, the fragments were detected by time-of-flight mass spectrometry. The dominant channel was found to be C--Br fission (60%) releasing an average of 15 kcal/mol into translation with the remainder reacting to form CH 2 +IBr and CH 2 +I+Br. There was no evidence for the primary fission of the C--I bond, making this the first clear example of the selective cleavage of a stronger bond in a molecule over the weakest one

Enhanced photochemistry on metal surfaces

International Nuclear Information System (INIS)

Goncher, G.M.; Parsons, C.A.; Harris, C.B.

1984-01-01

Due to the fast relaxation of molecular excited states in the vicinity of a metal or semiconductor surface, few observations of surface photochemistry have been reported. The following work concerns the surface-enhanced photo-reactions of a variety of physisorbed molecules on roughened Ag surfaces. In summary, photodecomposition leads to a graphitic surface carbon product which is monitored via surface-enhanced Raman scattering. In most cases an initial two-photon molecular absorption step followed by further absorption and fragmentation is thought to occur. Enhancement of the incident fields occurs through roughness-mediated surface plasmon resonances. This mechanism provides the amplified electromagnetic surface fields responsible for the observed photodecomposition. The photodecomposition experiments are performed under ultra-high vacuum. Surface characterization of the roughened surfaces was done by Scanning Electron Microscopy (SEM), and electron-stimulated emission. The SEM revealed morphology on the order of 300-400 A. This size of roughness feature, when modelled as isolated spheres should exhibit the well-known Mie resonances for light of the correct wavelengths. For protrusions existing on a surface these Mie resonances can be thought of as a coupling of the light with the surface plasmon. Experimental verification of these resonances was provided by the electron-stimulated light emission results. These showed that a polished Ag surface emitted only the expected transition radiation at the frequency of the Ag bulk plasmon. Upon roughening, however, a broad range of lower frequencies extending well into the visible are seen from electron irradiation of the surface. Large enhancements are expected for those frequencies which are able to couple into the surface modes

Modeling of synchrotron-based laboratory simulations of Titan's ionospheric photochemistry

Science.gov (United States)

Carrasco, Nathalie; Peng, Zhe; Pernot, Pascal

2014-11-01

The APSIS reactor has been designed to simulate in the laboratory with a VUV synchrotron irradiation the photochemistry occurring in planetary upper atmospheres. A N2-CH4 Titan-like gas mixture has been studied, whose photochemistry in Titan's ionospheric irradiation conditions leads to a coupled chemical network involving both radicals and ions. In the present work, an ion-neutral coupled model is developed to interpret the experimental data, taking into account the uncertainties on the kinetic parameters by Monte Carlo sampling. The model predicts species concentrations in agreement with mass spectrometry measurements of the methane consumption and product blocks intensities. Ion chemistry and in particular dissociative recombination are found to be very important through sensitivity analysis. The model is also applied to complementary environmental conditions, corresponding to Titan's ionospheric average conditions and to another existing synchrotron setup. An innovative study of the correlations between species concentrations identifies two main competitive families, leading respectively to saturated and unsaturated species. We find that the unsaturated growth family, driven by C2H2 , is dominant in Titan's upper atmosphere, as observed by the Cassini INMS. But the saturated species are substantially more intense in the measurements of the two synchrotron experimental setups, and likely originate from catalysis by metallic walls of the reactors.

Studies in organic and physical photochemistry - an interdisciplinary approach.

Science.gov (United States)

Oelgemöller, Michael; Hoffmann, Norbert

2016-08-21

Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

Separation and enrichment of isotopes using laser photochemistry - fundamentals and prospectives

International Nuclear Information System (INIS)

Guesten, H.

1978-01-01

Basic knowledge is summed up on isotope separation by laser photochemistry. The principal prerequisites are explained of the application of atomic and molecular spectroscopy for this purpose. Practical examples are given of isotope separation of uranium, nitrogen, chlorine, carbon, sulfur, and molybdenum showing the application of two basic techniques, i.e., of gradual atom photoionization or gradual molecule photodissociation and of selective photochemical reactions. (L.K.)

Report of the subpanel on long-range planning for the US High-Energy-Physics Program of the High-Energy-Physics Advisory Panel

International Nuclear Information System (INIS)

1982-01-01

The US High Energy Program remains strong, but it faces vigorous competition from other regions of the world. To maintain its vitality and preeminence over the next decade it requires the following major ingredients: (1) strong exploitation of existing facilities; (2) the expeditious completion of construction projects which will expand these facilities over the next few years; (3) the construction of a substantial new facility to be ready for research by the end of the 1980's; and (4) the vigorous pursuit of a wide range of advanced accelerator R and D programs in preparation for the design and construction of a higher energy accelerator which would probably be initiated near the end of this decade. The Subpanel has considered how best to accomplish these goals under two different budgetary assumptions; namely, average yearly support levels of $440M DOE, $35M NSF, and $395M DOE, $34M NSF (FY 1982 dollars). It has also considered the impact of a yet lower support level of $360M DOE and $32M NSF. A description of facilities in high energy physics is given, and facility recommendations and long range plans are discussed. Recommendations for international collaboration are included

Photophysics and Photochemistry of Canonical Nucleobases’ Thioanalogs: From Quantum Mechanical Studies to Time Resolved Experiments

Directory of Open Access Journals (Sweden)

Serra Arslancan

2017-06-01

Full Text Available Interest in understanding the photophysics and photochemistry of thiated nucleobases has been awakened because of their possible involvement in primordial RNA or their potential use as photosensitizers in medicinal chemistry. The interpretation of the photodynamics of these systems, conditioned by their intricate potential energy surfaces, requires the powerful interplay between experimental measurements and state of the art molecular simulations. In this review, we provide an overview on the photophysics of natural nucleobases’ thioanalogs, which covers the last 30 years and both experimental and computational contributions. For all the canonical nucleobase’s thioanalogs, we have compiled the main steady state absorption and emission features and their interpretation in terms of theoretical calculations. Then, we revise the main topographical features, including stationary points and interstate crossings, of their potential energy surfaces based on quantum mechanical calculations and we conclude, by combining the outcome of different spectroscopic techniques and molecular dynamics simulations, with the mechanism by which these nucleobase analogs populate their triplet excited states, which are at the origin of their photosensitizing properties.

Microwave Photochemistry IV: Preparation of the Electrodeless Discharge Lamps for Photochemical Applications

Czech Academy of Sciences Publication Activity Database

Církva, Vladimír; Vlková, Leona; Relich, Stanislav; Hájek, Milan

2006-01-01

Roč. 179, 1-2 (2006), s. 229-233 ISSN 1010-6030 R&D Projects: GA AV ČR KSK4040110; GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave photochemistry * electrodeless discharge lamp * uv/vis source Subject RIV: CC - Organic Chemistry Impact factor: 2.098, year: 2006

The photochemistry of the paleoatmosphere

Science.gov (United States)

Levine, J. S.

1982-01-01

Recent progress in the understanding of the chemistry and photochemistry of the paleoatmosphere is reviewed with emphasis on the application of photochemical models to the investigation of the evolution of the atmosphere. Photochemical calculations are presented which show that a primordial highly reducing atmosphere composed of methane and ammonia, if it formed at all, would be short-lived in the presence of solar ultraviolet radiation, giving way rapidly to a more mildly reducing atmosphere of carbon dioxide and nitrogen. Estimations of O2 produced from the photolysis of water vapor prior to the emergence of photosynthesis range from less than 10 to the -14th to 0.1 times the present atmospheric level, indicating the need for further research. A series of photochemical models of increasing complexity has been developed to study the evolution of atmospheric ozone taking into account reactions with O atoms, hydrogen oxides, nitrogen oxides, and chlorine as well as vertical transport, temperature and tropospheric chemistry so that the total content and vertical distribution of O3 may be determined for a specified level of paleoatmospheric O2.

Evaluation of linear ozone photochemistry parametrizations in a stratosphere-troposphere data assimilation system

Directory of Open Access Journals (Sweden)

A. J. Geer

2007-01-01

Full Text Available This paper evaluates the performance of various linear ozone photochemistry parametrizations using the stratosphere-troposphere data assimilation system of the Met Office. A set of experiments were run for the period 23 September 2003 to 5 November 2003 using the Cariolle (v1.0 and v2.1, LINOZ and Chem2D-OPP (v0.1 and v2.1 parametrizations. All operational meteorological observations were assimilated, together with ozone retrievals from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS. Experiments were validated against independent data from the Halogen Occultation Experiment (HALOE and ozonesondes. Additionally, a simple offline method for comparing the parametrizations is introduced. It is shown that in the upper stratosphere and mesosphere, outside the polar night, ozone analyses are controlled by the photochemistry parametrizations and not by the assimilated observations. The most important factor in getting good results at these levels is to pay attention to the ozone and temperature climatologies in the parametrizations. There should be no discrepancies between the climatologies and the assimilated observations or the model, but there is also a competing demand that the climatologies be objectively accurate in themselves. Conversely, in the lower stratosphere outside regions of heterogeneous ozone depletion, the ozone analyses are dominated by observational increments and the photochemistry parametrizations have little influence. We investigate a number of known problems in LINOZ and Cariolle v1.0 in more detail than previously, and we find discrepancies in Cariolle v2.1 and Chem2D-OPP v2.1, which are demonstrated to have been removed in the latest available versions (v2.8 and v2.6 respectively. In general, however, all the parametrizations work well through much of the stratosphere, helped by the presence of good quality assimilated MIPAS observations.

Solar eclipse demonstrating the importance of photochemistry in new particle formation

OpenAIRE

Jokinen, Tuija; Kontkanen, Jenni; Lehtipalo, Katrianne; Manninen, Hanna E.; Aalto, Juho; Porcar-Castell, Albert; Garmash, Olga; Nieminen, Tuomo; Ehn, Mikael; Kangasluoma, Juha; Junninen, Heikki; Levula, Janne; Duplissy, Jonathan; Ahonen, Lauri R.; Rantala, Pekka

2017-01-01

Solar eclipses provide unique possibilities to investigate atmospheric processes, such as new particle formation (NPF), important to the global aerosol load and radiative balance. The temporary absence of solar radiation gives particular insight into different oxidation and clustering processes leading to NPF. This is crucial because our mechanistic understanding on how NPF is related to photochemistry is still rather limited. During a partial solar eclipse over Finland in 2015, we found that...

On the photophysics and photochemistry of the water dimer

Energy Technology Data Exchange (ETDEWEB)

Segarra-Marti, Javier; Merchan, Manuela [Instituto de Ciencia Molecular, Universitat de Valencia, P.O. Box 22085, 46071 Valencia (Spain); Roca-Sanjuan, Daniel; Lindh, Roland [Department of Chemistry - Angstroem, Theoretical Chemistry Program, Uppsala University, Box 518, 75120 Uppsala (Sweden)

2012-12-28

The photochemistry of the water dimer irradiated by UV light is studied by means of the complete active space perturbation theory//complete active space self-consistent field (CASPT2//CASSCF) method and accurate computational approaches like as minimum energy paths. Both electronic structure computations and ab initio molecular dynamics simulations are carried out. The results obtained show small shifts relative to a single water molecule on the vertical excitation energies of the dimer due to the hydrogen bond placed between the water donor (W{sub D}) and the water acceptor (W{sub A}). A red-shift and a blue-shift are predicted for the W{sub D} and W{sub A}, respectively, supporting previous theoretical and experimental results. The photoinduced chemistry of the water dimer is described as a process occurring between two single water molecules in which the effect of the hydrogen bond plays a minor role. Thus, the photoinduced decay routes correspond to two photodissociation processes, one for each water molecule. The proposed mechanism for the decay channels of the lowest-lying excited states of the system is established as the photochemical production of a hydrogen-bonded H{sub 2}O Horizontal-Ellipsis HO species plus a hydrogen H atom.

Biweekly list of papers on radiation chemistry and photochemistry. Annual cumulation with keyword and author indexes. Volume 16. 1983

International Nuclear Information System (INIS)

Carmichael, I.C.; Helman, W.P.; Hug, G.L.; Ross, A.B.

1983-01-01

The Biweekly List of Papers on Radiation Chemistry and Photochemistry is a current-awareness service published by the Radiation Chemistry Data Center (RCDC), with special emphasis on the kinetics and other properties of transient ions, radicals, and excited species. Papers are included on the radiation chemistry and photochemistry of organic and inorganic systems, biological molecules and polymers, with references to ESR and luminescence studies. Complete coverage is attempted only for those studies which are initiated by light or ionizing radiation, and which provide quantitative physical chemical data such as quantum yields, specific rates, G values, etc. No attempt is made to cover topics such as mechanistic and preparative photochemistry, photosynthesis, photography, and irradiation of metals. The references listed herein are obtained from scanning about 60 current journals as well as Chemical Abstracts, INIS Atomindex and several other publications listing current references. The reference lists, which are issued biweekly, are cumulated annually with the addition of keyword and author indexes. Indexed cumulations were published semiannually for Vol. 4-6 (1971-73) and are published annually for Vol. 7+ (1974+); back copies are available from the National Technical Information Service (NTIS)

Selected Contributions of the 4th International Conference on Semiconductor Photochemistry (5P4) Introduction.

Czech Academy of Sciences Publication Activity Database

Krýsa, J.; Klusoň, Petr; Malato, S.

2014-01-01

Roč. 230, JUL 2014 (2014), s. 1 ISSN 0920-5861 Grant - others:SMEC(ES) CTQ2012-38754-C03-01 Institutional support: RVO:67985858 Keywords : semiconductor photochemistry * catalysis * scientific applications Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.893, year: 2014

On the involvement of single-bond rotation in the primary photochemistry of photoactive yellow protein

NARCIS (Netherlands)

Stahl, A.D.; Hospes, M.; Singhal, K.; van Stokkum, I.; van Grondelle, R.; Groot, M.L.; Hellingwerf, K.J.

2011-01-01

Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid

Automatic generation of active coordinates for quantum dynamics calculations: Application to the dynamics of benzene photochemistry

International Nuclear Information System (INIS)

Lasorne, Benjamin; Sicilia, Fabrizio; Bearpark, Michael J.; Robb, Michael A.; Worth, Graham A.; Blancafort, Lluis

2008-01-01

A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

Science.gov (United States)

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

Science.gov (United States)

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

EUV-VUV photochemistry in the upper atmospheres of Titan and the early Earth

Science.gov (United States)

Imanaka, H.; Smith, M. A.

2010-12-01

Titan, the organic-rich moon of Saturn, possesses a thick atmosphere of nitrogen, globally covered with organic haze layers. The recent Cassini’s INMS and CAPS observations clearly demonstrate the importance of complex organic chemistry in the ionosphere. EUV photon radiation is the major driving energy source there. Our previous laboratory study of the EUV-VUV photolysis of N2/CH4 gas mixtures demonstrates a unique role of nitrogen photoionization in the catalytic formation of complex hydrocarbons in Titan’s upper atmosphere (Imanaka and Smith, 2007, 2009). Such EUV photochemistry could also have played important roles in the formation of complex organic molecules in the ionosphere of the early Earth. It has been suggested that the early Earth atmosphere may have contained significant amount of reduced species (CH4, H2, and CO) (Kasting, 1990, Pavlov et al., 2001, Tian et al., 2005). Recent experimental study, using photon radiation at wavelengths longer than 110 nm, demonstrates that photochemical organic haze could have been generated from N2/CO2 atmospheres with trace amounts of CH4 or H2 (Trainer et al., 2006, Dewitt et al., 2009). However, possible EUV photochemical processes in the ionosphere are not well understood. We have investigated the effect of CO2 in the possible EUV photochemical processes in simulated reduced early Earth atmospheres. The EUV-VUV photochemistry using wavelength-tunable synchrotron light between 50 - 150 nm was investigated for gas mixtures of 13CO2/CH4 (= 96.7/3.3) and N2/13CO2/CH4 (= 90/6.7/3.3). The onsets of unsaturated hydrocarbon formation were observed at wavelengths shorter than the ionization potentials of CO2 and N2, respectively. This correlation indicates that CO2 can play a similar catalytic role to N2 in the formation of heavy organic species, which implies that EUV photochemistry might have significant impact on the photochemical generation of organic haze layers in the upper atmosphere of the early Earth.

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice. II. Near UV/VIS spectroscopy and ionization rates

Science.gov (United States)

Bouwman, J.; Cuppen, H. M.; Steglich, M.; Allamandola, L. J.; Linnartz, H.

2011-05-01

Context. Mid-infrared emission features originating from polycyclic aromatic hydrocarbons (PAHs) are observed towards photon dominated regions in space. Towards dense clouds, however, these emission features are quenched. Observations of dense clouds show that many simple volatile molecules are frozen out on interstellar grains, forming thin layers of ice. Recently, observations have shown that more complex non-volatile species, presumably including PAHs, also freeze out and contribute to the ongoing solid-state chemistry. Aims: The study presented here aims at obtaining reaction rate data that characterize PAH photochemistry upon vacuum ultraviolet (VUV) irradiation in an interstellar H2O ice analogue to explore the potential impact of PAH:H2O ice reactions on overall interstellar ice chemistry. To this end, the experimental results are implemented in a chemical model under simple interstellar cloud conditions. Methods: Time-dependent near-UV/VIS spectroscopy on the VUV photochemistry of anthracene, pyrene, benzo[ghi]perylene and coronene containing interstellar H2O ice analogs is performed at 25 and 125 K, using an optical absorption setup. Results: Near-UV/VIS absorption spectra are presented for these four PAHs and their photoproducts including cationic species trapped in H2O ice. Oscillator strengths of the cation absorption bands are derived relative to the oscillator strength of the neutral parent PAH. The loss of the parent and growth of PAH photoproducts are measured as a function of VUV dose, yielding solid state reaction constants. The rate constants are used in an exploratory astrochemical model, to assess the importance of PAH:H2O ice photoprocessing in UV exposed interstellar environments, compared with the timescales in which PAH molecules are incorporated in interstellar ices. Conclusions: All four PAHs studied here are found to be readily ionized upon VUV photolysis when trapped in H2O ice and exhibit similar rates for ionization at astronomically

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

Science.gov (United States)

Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

2011-08-01

The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

The Elecrodeless Discharge Lamp: A Prospective Tool for Photochemistry Part 5. Fill Material-Dependent Emission Characteristics

Czech Academy of Sciences Publication Activity Database

Müller, P.; Klán, P.; Církva, Vladimír

2005-01-01

Roč. 171, Vol.1 (2005), s. 51-57 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * microwave * spectra Subject RIV: CC - Organic Chemistry Impact factor: 2.286, year: 2005

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

International Nuclear Information System (INIS)

Laursen, S.L.

1990-01-01

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom ''sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

Energy Technology Data Exchange (ETDEWEB)

Laursen, S.L.

1990-01-01

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

Excited state dynamics & optical control of molecular motors

Science.gov (United States)

Wiley, Ted; Sension, Roseanne

2014-03-01

Chiral overcrowded alkenes are likely candidates for light driven rotary molecular motors. At their core, these molecular motors are based on the chromophore stilbene, undergoing ultrafast cis/trans photoisomerization about their central double bond. Unlike stilbene, the photochemistry of molecular motors proceeds in one direction only. This unidirectional rotation is a result of helicity in the molecule induced by steric hindrance. However, the steric hindrance which ensures unidirectional excited state rotation, has the unfortunate consequence of producing large ground state barriers which dramatically decrease the overall rate of rotation. These molecular scale ultrafast motors have only recently been studied by ultrafast spectroscopy. Our lab has studied the photochemistry and photophysics of a ``first generation'' molecular motor with UV-visible transient absorption spectroscopy. We hope to use optical pulse shaping to enhance the efficiency and turnover rate of these molecular motors.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

Energy Technology Data Exchange (ETDEWEB)

Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui [CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

2016-07-07

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2}, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

Science.gov (United States)

Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

2016-07-01

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

International Nuclear Information System (INIS)

Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

2016-01-01

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N 2 , Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

Toward autonomous measurements of photosynthetic electron transport rates: An evaluation of active fluorescence-based measurements of photochemistry

NARCIS (Netherlands)

Silsbe, G.M.; Oxborough, K.; Suggett, D.J.; Forster, R.M.; Ihnken, S.; Komárek, O.; Lawrenz, E.; Prášil, O.; Röttgers, R.; Šicner, M.; Simis, S.G.H.; Van Dijk, M.A.; Kromkamp, J.C.

2015-01-01

This study presents a methods evaluation and intercalibration of active fluorescence-based measurements of the quantum yield ( inline image) and absorption coefficient ( inline image) of photosystem II (PSII) photochemistry. Measurements of inline image, inline image, and irradiance (E) can be

CHEM2D-OPP: A new linearized gas-phase ozone photochemistry parameterization for high-altitude NWP and climate models

Directory of Open Access Journals (Sweden)

J. P. McCormack

2006-01-01

Full Text Available The new CHEM2D-Ozone Photochemistry Parameterization (CHEM2D-OPP for high-altitude numerical weather prediction (NWP systems and climate models specifies the net ozone photochemical tendency and its sensitivity to changes in ozone mixing ratio, temperature and overhead ozone column based on calculations from the CHEM2D interactive middle atmospheric photochemical transport model. We evaluate CHEM2D-OPP performance using both short-term (6-day and long-term (1-year stratospheric ozone simulations with the prototype high-altitude NOGAPS-ALPHA forecast model. An inter-comparison of NOGAPS-ALPHA 6-day ozone hindcasts for 7 February 2005 with ozone photochemistry parameterizations currently used in operational NWP systems shows that CHEM2D-OPP yields the best overall agreement with both individual Aura Microwave Limb Sounder ozone profile measurements and independent hemispheric (10°–90° N ozone analysis fields. A 1-year free-running NOGAPS-ALPHA simulation using CHEM2D-OPP produces a realistic seasonal cycle in zonal mean ozone throughout the stratosphere. We find that the combination of a model cold temperature bias at high latitudes in winter and a warm bias in the CHEM2D-OPP temperature climatology can degrade the performance of the linearized ozone photochemistry parameterization over seasonal time scales despite the fact that the parameterized temperature dependence is weak in these regions.

3D printing of natural organic materials by photochemistry

Science.gov (United States)

Da Silva Gonçalves, Joyce Laura; Valandro, Silvano Rodrigo; Wu, Hsiu-Fen; Lee, Yi-Hsiung; Mettra, Bastien; Monnereau, Cyrille; Schmitt Cavalheiro, Carla Cristina; Pawlicka, Agnieszka; Focsan, Monica; Lin, Chih-Lang; Baldeck, Patrice L.

2016-03-01

In previous works, we have used two-photon induced photochemistry to fabricate 3D microstructures based on proteins, anti-bodies, and enzymes for different types of bio-applications. Among them, we can cite collagen lines to guide the movement of living cells, peptide modified GFP biosensing pads to detect Gram positive bacteria, anti-body pads to determine the type of red blood cells, and trypsin columns in a microfluidic channel to obtain a real time biochemical micro-reactor. In this paper, we report for the first time on two-photon 3D microfabrication of DNA material. We also present our preliminary results on using a commercial 3D printer based on a video projector to polymerize slicing layers of gelatine-objects.

Dust ablation on the giant planets: Consequences for stratospheric photochemistry

Science.gov (United States)

Moses, Julianne I.; Poppe, Andrew R.

2017-11-01

Ablation of interplanetary dust supplies oxygen to the upper atmospheres of Jupiter, Saturn, Uranus, and Neptune. Using recent dynamical model predictions for the dust influx rates to the giant planets (Poppe et al., 2016), we calculate the ablation profiles and investigate the subsequent coupled oxygen-hydrocarbon neutral photochemistry in the stratospheres of these planets. We find that dust grains from the Edgeworth-Kuiper Belt, Jupiter-family comets, and Oort-cloud comets supply an effective oxygen influx rate of 1.0-0.7+2.2 ×107 O atoms cm-2 s-1 to Jupiter, 7.4-5.1+16 ×104 cm-2 s-1 to Saturn, 8.9-6.1+19 ×104 cm-2 s-1 to Uranus, and 7.5-5.1+16 ×105 cm-2 s-1 to Neptune. The fate of the ablated oxygen depends in part on the molecular/atomic form of the initially delivered products, and on the altitude at which it was deposited. The dominant stratospheric products are CO, H2O, and CO2, which are relatively stable photochemically. Model-data comparisons suggest that interplanetary dust grains deliver an important component of the external oxygen to Jupiter and Uranus but fall far short of the amount needed to explain the CO abundance currently seen in the middle stratospheres of Saturn and Neptune. Our results are consistent with the theory that all of the giant planets have experienced large cometary impacts within the last few hundred years. Our results also suggest that the low background H2O abundance in Jupiter's stratosphere is indicative of effective conversion of meteoric oxygen to CO during or immediately after the ablation process - photochemistry alone cannot efficiently convert the H2O into CO on the giant planets.

On the relationship between the greenhouse effect, atmospheric photochemistry, and species distribution

Science.gov (United States)

Callis, L. B.; Boughner, R. E.; Natarajan, M.

1983-01-01

The coupling that exists between infrared opacity changes and tropospheric (and to a lesser extent stratospheric) chemistry is explored in considerable detail, and the effects arising from various perturbations are examined. The studies are carried out with a fully coupled one-dimensional radiative-convective-photochemical model (RCP) that extends from the surface to 53.5 km and has the capability of calculating surface temperature changes due to both chemical and radiative perturbations. The model encompasses contemporary atmospheric chemistry and photochemistry involving the O(x), HO(x), NO(x), and Cl(x) species.

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

Directory of Open Access Journals (Sweden)

M. Vaïtilingom

2011-08-01

Full Text Available The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H₂O₂ as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10⁻¹⁰–10⁻¹¹ M s⁻¹. The chemical composition (marine or continental origin had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5.

In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10⁻¹² M led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10⁻¹⁴ M, microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach.

Combining these two approaches (experimental and theoretical, our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more

High energy chemistry. Modern state and trends in development

International Nuclear Information System (INIS)

Pikaev, A.K.

1990-01-01

In the review modern state of studies in the field of high energy chemistry is considered. The most important achievements and problems of further development of radiation chemistry, plasmochemistry, photochemistry, laser chemistry and some other branches of high energy chemistry are discussed

Modification of porous silicon rugate filters through thiol-yne photochemistry

International Nuclear Information System (INIS)

Soeriyadi, Alexander H.; Zhu, Ying; Gooding, J. Justin; Reece, Peter

2014-01-01

Porous silicon (PSi) has a considerable potential as biosensor platform. In particular, the ability to modify the surface chemistry of porous silicon is of interest. Here we present a generic method to modify the surface of porous silicon through thiol-yne photochemistry initiated by a radical initiator. Firstly, a freshly etched porous silicon substrate is modified through thermal hydrosilylation with 1,8-nonadiyne to passivate the surface and introduce alkyne functionalities. The alkyne functional surface could then be further reacted with thiol species in the presence of a radical initiator and UV light. Functionalization of the PSi rugate filter is followed with optical reflectivity measurements as well as high resolution X-ray photoelectron spectroscopy (XPS)

Soft x-ray photochemistry in solid surfaces

International Nuclear Information System (INIS)

Sekiguchi, Tetsuhiro; Baba, Yuji

2000-01-01

Resent studies on photochemistry using synchrotron soft x-rays in solid surfaces are reviewed. A type of site-selective chemical reaction induced by inner-shell excitation is classified into two model systems that are referred to as 'Element-specific fragmentation' and 'Bonding-site-specific dissociation.' The former system uses difference of core-binding-energies in different elements and the latter is based on the existence of plural unoccupied molecular orbitals with different antibonding character. The selectivity of the reaction in respective systems is discussed in terms of mass-patterns of desorbed fragment-ions and photon-energy dependence of the ion yields. Also discussed are the fragmentation and desorption mechanisms which include intrinsic direct photofragmentation and indirect channels induced by secondary electrons. The latter process reduces the selectivity of the reaction. Furthermore, two experimental approaches, which have recently been performed to estimate the relative magnitude of contribution in the direct and indirect processes to the total yields, are described: (1) the layer-thickness dependence and (2) polarization-angle dependence in the photofragmentation. (author)

The Electrodeless Discharge Lamp: a Prospective Tool for Photochemistry - Part 4. Temperature- and Envelope Material-Dependent Emission Characteristics

Czech Academy of Sciences Publication Activity Database

Müller, P.; Klán, P.; Církva, Vladimír

2003-01-01

Roč. 158, č. 1 (2003), s. 1-5 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * microwave * electrodeless discharge lamp Subject RIV: CC - Organic Chemistry Impact factor: 1.693, year: 2003

Ultrafast Infrared and UV-vis Studies of the Photochemistry of Methoxycarbonylphenyl Azides in Solution

OpenAIRE

Xue, Jiadan; Luk, Hoi Ling; Eswaran, S. V.; Hadad, Christopher M.; Platz, Matthew S.

2012-01-01

The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a) and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitre...

High-Power 365 nm UV LED Mercury Arc Lamp Replacement for Photochemistry and Chemical Photolithography

OpenAIRE

H?lz, K.; Lietard, J.; Somoza, M. M.

2016-01-01

Ultraviolet light emitting diodes (UV LEDs) have become widespread in chemical research as highly efficient light sources for photochemistry and photopolymerization. However, in more complex experimental setups requiring highly concentrated light and highly spatially resolved patterning of the light, high-pressure mercury arc lamps are still widely used because they emit intense UV light from a compact arc volume that can be efficiently coupled into optical systems. Advances in the deposition...

General patterns in the photochemistry of pregna-1,4-dien-3,20-diones.

Science.gov (United States)

Ricci, Andrea; Fasani, Elisa; Mella, Mariella; Albini, Angelo

2003-05-30

The photochemistry of six pregna-1,4-dien-3,20-diones has been compared and found to involve both the cyclohexadienone moiety in ring A and the isolated ketone at C-20. The two reactions take place proportionally to the fraction of light absorbed by each chromophore. The cross-conjugated ketone absorbs predominantly or exclusively at both 254 and 366 nm and undergoes the "lumi" rearrangement to bicyclo[3.1.0]hex-3-en-2-one. The quantum yield of the reaction diminished somewhat with increasing lambda(exc), e.g., for prednisolone Phi(254) (nm) = 0.42, Phi(366) (nm) = 0.3. A much stronger lowering is caused by halogen substitution in position 9 (by a factor of 3 for F, >50 for Cl), apparently due to a shortened triplet lifetime caused by heavy atom effect. At 310 nm, both chromophores absorb to a comparable degree and both may react. The reaction at C(20) ketone involves either quite efficient alpha-cleavage (C(17)-C(20)) for compounds bearing an acetal or hydroxyl function at C(17) or less effective (by a factor of ca. 10) hydrogen abstraction from the 18-methyl group in the other cases (finally resulting in Norrish II fragmentation or Yang cyclization). The results allow generalizing how the substitution pattern surrounding each chromophore affects the photoreactivity at that site and the competition between the two modes, allowing predicting the photochemistry of this family of antiinflammatory drugs.

A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

Directory of Open Access Journals (Sweden)

Erli Sugiono

2013-11-01

Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

Solar photochemistry - twenty years of progress, what`s been accomplished, and where does it lead?

Energy Technology Data Exchange (ETDEWEB)

Blake, D M

1995-01-01

It has been more than 20 years since the first oil embargo. That event created an awareness of the need for alternative sources of energy and renewed interest in combining sunlight and chemistry to produce the chemicals and materials required by industry. This paper will review approaches that have been taken, progress that has been made, and give some projections for the near and longer term prospects for commercialization of solar photochemistry.

Photochemistry and Gas-Phase FTIR Spectroscopy of Formic Acid Interaction with Anatase Ti18O2 Nanoparticles

Czech Academy of Sciences Publication Activity Database

Civiš, Svatopluk; Ferus, Martin; Zukalová, Markéta; Kubát, Pavel; Kavan, Ladislav

2012-01-01

Roč. 116, č. 20 (2012), s. 11200-11205 ISSN 1932-7447 R&D Projects: GA AV ČR IAAX00100903; GA AV ČR IAA400400804; GA AV ČR KAN200100801; GA ČR GAP208/10/1678; GA MŠk OC09044 Institutional support: RVO:61388955 Keywords : photochemistry * FTIR spectroscopy * nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.814, year: 2012

Formation of reactive nitrogen oxides from urban grime photochemistry

Science.gov (United States)

Baergen, Alyson M.; Donaldson, D. James

2016-05-01

Impervious surfaces are ubiquitous in urban environments and constitute a substrate onto which atmospheric constituents can deposit and undergo photochemical and oxidative processing, giving rise to "urban grime" films. HNO3 and N2O5 are important sinks for NOx in the lower atmosphere and may be deposited onto these films, forming nitrate through surface hydrolysis. Although such deposition has been considered as a net loss of NOx from the atmosphere, there is increasing evidence that surface-associated nitrate undergoes further reaction. Here, we examine the gas phase products of the photochemistry of real, field-collected urban grime using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Gas phase nitrogen oxides are emitted upon illumination of grime samples and their production increases with ambient relative humidity (RH) up to 35 % after which the production becomes independent of RH. These results are discussed in the context of water uptake onto and evaporation from grime films.

Photochemistry in Saturn’s Ring-Shadowed Atmosphere: Photochemistry and Haze Observations

Science.gov (United States)

Edgington, Scott G.; Atreya, Sushil K.; Baines, Kevin H.; West, Robert A.; Bjoraker, Gordon L.; Fletcher, Leigh; Momary, Thomas W.; Wilson, Eric; CIRS, ISS, UVIS, VIMS

2017-10-01

After 13 years of observing Saturn, Cassini would have ended nearly a half Saturnian year. During this epoch, the ring shadow has moved from covering much of the northern hemisphere to covering a large swath southern hemisphere. The net effect is that the intensity of both ultraviolet and visible sunlight penetrating through the rings to any particular latitude will vary depending on both Saturn’s axis relative to the Sun and the optical thickness of each ring system. In essence, the rings act like semi-transparent venetian blinds. This effect magnifies the effect due to axial tilt alone and acts to turn off photochemistry and haze generation. This effect is seen in both the presence of a bluish Rayleigh-scattering atmosphere in 2004 in the northern hemisphere and color change to blue in the northern hemisphere.Previous work examined the variation of the solar flux as a function of solar inclination, i.e. for each 7.25-year season at Saturn. We report on the impact of the oscillating ring shadow, in addition to variation due to axial tilt, on photolysis and production rates of hydrocarbons and phosphine in Saturn’s stratosphere and upper troposphere. The impact of these production and loss rates on the abundance of long-lived photochemical products leading to haze formation are explored. We assess their impact on a disequilibrium species whose presence in the upper troposphere can be used as a tracer of convective processes in the deeper atmosphere.We will also present our ongoing analysis of Cassini’s CIRS, UVIS, and VIMS datasets that provide an estimate of the evolving haze content. In particular, we will examine how the region inside Saturn’s famous hexagonal jet stream changes over time from a relatively clear atmosphere to a hazy one. We also explore how the hexagon acts like a barrier to transport, isolating Saturn’s north polar region from outside influences of photochemically-generated molecules and haze.The research described in this paper was

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

Science.gov (United States)

Zahnle, K. J.

1986-01-01

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

United States: From here to 2000

Energy Technology Data Exchange (ETDEWEB)

Anon.

1990-03-15

When it becomes operational, the 87-kilometre Superconducting Supercollider proton ring - SSC - now approved to be built in Ellis County, Texas, will dominate the skyline of US particle physics. However SSC experiments would not get underway in earnest until about the year 2000, and to achieve an orderly transition into the SSC era while maintaining continuity in the 'base' (non-SSC) programme, a special subpanel has been set up by the High Energy Physics Advisory Panel - HEPAP - which counsels the US Department of Energy in its role as major paymaster of US particle physics.

Radiation Chemistry and Photochemistry of Ionic Liquids

International Nuclear Information System (INIS)

Wishart, J.F.; Takahaski, K.

2010-01-01

As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

78 FR 16659 - Pacific Fishery Management Council; Public Meetings

Science.gov (United States)

2013-03-18

... Barotrauma Device Mortality Rates 6. Groundfish Essential Fish Habitat Synthesis Report and Request for...--Essential Fish Habitat Revision 4. Final Action on 2013 Management Measures 5. Methodology Review Process... Delegation 7 a.m. Washington State Delegation 7 a.m. Ecosystem Advisory Subpanel 8 a.m. Essential Fish...

Energy transfer and photochemistry on a metal surface: Mo(CO)6 on Rh(100)

International Nuclear Information System (INIS)

Germer, T.A.; Ho, W.

1989-01-01

The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO) 6 on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO) 6 adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated first layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO) 6 adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface

Secondary Organic Aerosol Formation from Acetylene (C2H2: seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

Directory of Open Access Journals (Sweden)

P. J. Ziemann

2009-03-01

Full Text Available The lightest Non Methane HydroCarbon (NMHC, i.e., acetylene (C2H2 is found to form secondary organic aerosol (SOA. Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

77 FR 7566 - Pacific Fishery Management Council; Public Meetings

Science.gov (United States)

2012-02-13

... Subpanel--8 a.m. Salmon Technical Team--8 a.m. Enforcement Consultants--As Necessary Tribal Policy Group.... Salmon Technical Team--8 a.m. Enforcement Consultants--As Necessary Tribal Policy Group--As Necessary... Subpanel--8 a.m. Salmon Technical Team--8 a.m. Enforcement Consultants--As Necessary Tribal Policy Group...

Fluorescence Spectroscopy, Exciton Dynamics and Photochemistry of Single Allophycocyanin Trimers

International Nuclear Information System (INIS)

Ying, Liming; Xie, Xiaoliang

1998-01-01

We report a study of the spectroscopy and exciton dynamics of the allophycocyanin trimer (APC), a light harvesting protein complex from cyanobacteria, by room-temperature single-molecule measurements of fluorescence spectra, lifetimes, intensity trajectories and polarization modulation. Emission spectra of individual APC trimers are found to be homogeneous on the time scale of seconds. In contrast, their emission lifetimes are found to be widely distributed, because of generation of exciton traps during the course of measurements. The intensity trajectories and polarization modulation experiments indicate reversible ixciton trap formation within the three quasi-independent pairs of strong interacting a84 and B84 chromophores in APC, as well a photobleaching of individual chromophores. Comparison experiments under continuous wave and pulsed excitation reveal a two-photon mechanism for generating exciton traps and/or photobleaching, which involves exciton-exciton annihilation. These single-molecule experiments provide new insights into exciton dynamics and photochemistry of light-harvesting complexes

Use of local noise power spectrum and wavelet analysis in quantitative image quality assurance for EPIDs

Energy Technology Data Exchange (ETDEWEB)

Lee, Soyoung [Department of Radiation Oncology, University Hospitals Case and Medical Center, Cleveland, Ohio 44106 (United States); Yan, Guanghua; Bassett, Philip; Samant, Sanjiv, E-mail: samant@ufl.edu [Department of Radiation Oncology, University of Florida College of Medicine, Gainesville, Florida 32608 (United States); Gopal, Arun [Department of Radiation Oncology, University of Maryland School of Medicine, Baltimore, Maryland 21201 (United States)

2016-09-15

Purpose: To investigate the use of local noise power spectrum (NPS) to characterize image noise and wavelet analysis to isolate defective pixels and inter-subpanel flat-fielding artifacts for quantitative quality assurance (QA) of electronic portal imaging devices (EPIDs). Methods: A total of 93 image sets including custom-made bar-pattern images and open exposure images were collected from four iViewGT a-Si EPID systems over three years. Global quantitative metrics such as modulation transform function (MTF), NPS, and detective quantum efficiency (DQE) were computed for each image set. Local NPS was also calculated for individual subpanels by sampling region of interests within each subpanel of the EPID. The 1D NPS, obtained by radially averaging the 2D NPS, was fitted to a power-law function. The r-square value of the linear regression analysis was used as a singular metric to characterize the noise properties of individual subpanels of the EPID. The sensitivity of the local NPS was first compared with the global quantitative metrics using historical image sets. It was then compared with two commonly used commercial QA systems with images collected after applying two different EPID calibration methods (single-level gain and multilevel gain). To detect isolated defective pixels and inter-subpanel flat-fielding artifacts, Haar wavelet transform was applied on the images. Results: Global quantitative metrics including MTF, NPS, and DQE showed little change over the period of data collection. On the contrary, a strong correlation between the local NPS (r-square values) and the variation of the EPID noise condition was observed. The local NPS analysis indicated image quality improvement with the r-square values increased from 0.80 ± 0.03 (before calibration) to 0.85 ± 0.03 (after single-level gain calibration) and to 0.96 ± 0.03 (after multilevel gain calibration), while the commercial QA systems failed to distinguish the image quality improvement between the two

Isoprene photochemistry over the Amazon rainforest

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.

2016-01-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest. PMID:27185928

Photochemistry of 1,1,1-Trifluoroacetone on Rutile TiO2(110)

International Nuclear Information System (INIS)

Zehr, Robert T.; Deskins, N. Aaron; Henderson, Michael A.

2010-01-01

The ultraviolet (UV) photon-induced photodecomposition of 1,1,1-trifluoroacetone (TFA) adsorbed on the rutile TiO2(110) surface has been investigated with photon stimulated desorption (PSD), temperature programmed desorption (TPD) and density functional theory (DFT). TFA adsorbed molecularly on the reduced surface (8% oxygen vacancies) in states desorbing below 300 K with trace thermal decomposition observed in TPD. Adsorption of TFA on a preoxidized TiO2(110) surface (accomplished by pre-exposure with 20 L O2) led to formation of a new TFA desorption state at 350 K, assigned to decomposition of a TFA-diolate species ((CF3)(CH3)COO). No TFA photochemistry was detected on the reduced surface. UV irradiation of TFA on the oxidized surface depleted TFA in the 350 K state, with TFA molecules in other TPD states unaffected. PSD measurements reveal that both carbonyl substituents (CH3 and CF3), as well as CO, were liberated during UV exposure at 95 K. Post-irradiation TPD showed evidence for both acetate (evolving as ketene at 650 K) and trifluoroacetate (evolving as CO2 at 600 K) as surface-bound photodecomposition products. The CO PSD product was not due to adsorbed CO, to mass spectrometer cracking of a CO-containing PSD product, or from background effects, but originated from complete fragmentation of an unidentified adsorbed TFA species. Thermodynamic analysis using DFT indicated that the photodecomposition of the TFA-diolate was likely not driven by thermodynamics alone as both pathways (CH3+trifluoroacetate and CF3+acetate) were detected when thermodynamics shows a clear preference for only one (CF3+acetate). These observations are in contrast to the photochemical behavior of acetone, butanone and acetaldehyde on TiO2(110), where only one of the two carbonyl substituent groups was observed, with a stoichiometric amount of carboxylate containing the other substituent left on the surface. We conclude that fluorination significantly alters the electronic structure of

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste.

Science.gov (United States)

Redondo-Gómez, Susana; Cox, Lucía; Cornejo, Juan; Figueroa, Enrique

2007-01-01

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.

HEPAP White Paper on planning for U.S. high-energy physics [High Energy Physics Advisory Panel

International Nuclear Information System (INIS)

2000-01-01

High-energy physicists seek to understand what the universe is made of, how it works, and where it has come from. They investigate the most basic particles and the forces between them. Experiments and theoretical insights over the past several decades have made it possible to see the deep connection between apparently unrelated phenomena, and to piece together more of the story of how a rich and complex cosmos could evolve from just a few kinds of elementary particles. The 1998 Subpanel of the High Energy Physics Advisory Panel (HEPAP) laid out a strategy for U.S. high-energy physics for the next decade. That strategy balanced exciting near-term opportunities with preparations for the most important discovery possibilities in the longer-term. Difficult choices were made to end several highly productive programs and to reduce others. This year HEPAP was charged to take the plan given in the Subpanel's report, understand it in the context of worldwide progress, and update it. In response to that charge, this White Paper provides an assessment of where we stand, states the next steps to take in the intermediate term, and serves as input for a longer range planning process involving a new HEPAP subpanel and high-energy physics community evaluation in 2001. Since the 1998 Subpanel, there have been important developments and a number of the Subpanel's recommendations have been implemented. Notably, construction of the B-factory at SLAC, the Main Injector at Fermilab, and the upgrade of CESR at Cornell have all been finished on schedule and on budget. We have gained great confidence in the performance of these accelerators and the associated detectors. The B-factory at SLAC is already operating above design luminosity and plans are in place to reach three times the design in the next few years. In addition, there have been major physics developments that lead us to believe that these completed projects are guaranteed to produce frontier physics results and have an

Photochemistry of pyrene with water at low temperature: study of atmospherical and astrochemical interest.

Science.gov (United States)

Guennoun, Zohra; Aupetit, Christian; Mascetti, Joëlle

2011-03-17

Photochemistry of a polyaromatic hydrocarbon, pyrene C(16)H(10), with water has been investigated at cryogenic temperatures. Photoprocessing of this species, performed at λ > 235 nm, in argon matrices, adsorbed onto amorphous water surfaces, and trapped in solid water, led to the formation of ketonic isomers, C(16)H(10)O, and possibly quinones. These species have been identified for the first time by infrared spectroscopy with the support of isotopic substitution experiments and DFT calculations. These oxidized pyrene-like species, of atmospherical and astrochemical interest, most likely arise from a tautomeric rearrangement of their analogous hydroxylated molecules, these latter being formed by reaction of water with pyrene cations.

Using the Flipchem Photochemistry Model When Fitting Incoherent Scatter Radar Data

Science.gov (United States)

Reimer, A. S.; Varney, R. H.

2017-12-01

The North face Resolute Bay Incoherent Scatter Radar (RISR-N) routinely images the dynamics of the polar ionosphere, providing measurements of the plasma density, electron temperature, ion temperature, and line of sight velocity with seconds to minutes time resolution. RISR-N does not directly measure ionospheric parameters, but backscattered signals, recording them as voltage samples. Using signal processing techniques, radar autocorrelation functions (ACF) are estimated from the voltage samples. A model of the signal ACF is then fitted to the ACF using non-linear least-squares techniques to obtain the best-fit ionospheric parameters. The signal model, and therefore the fitted parameters, depend on the ionospheric ion composition that is used [e.g. Zettergren et. al. (2010), Zou et. al. (2017)].The software used to process RISR-N ACF data includes the "flipchem" model, which is an ion photochemistry model developed by Richards [2011] that was adapted from the Field LineInterhemispheric Plasma (FLIP) model. Flipchem requires neutral densities, neutral temperatures, electron density, ion temperature, electron temperature, solar zenith angle, and F10.7 as inputs to compute ion densities, which are input to the signal model. A description of how the flipchem model is used in RISR-N fitting software will be presented. Additionally, a statistical comparison of the fitted electron density, ion temperature, electron temperature, and velocity obtained using a flipchem ionosphere, a pure O+ ionosphere, and a Chapman O+ ionosphere will be presented. The comparison covers nearly two years of RISR-N data (April 2015 - December 2016). Richards, P. G. (2011), Reexamination of ionospheric photochemistry, J. Geophys. Res., 116, A08307, doi:10.1029/2011JA016613.Zettergren, M., Semeter, J., Burnett, B., Oliver, W., Heinselman, C., Blelly, P.-L., and Diaz, M.: Dynamic variability in F-region ionospheric composition at auroral arc boundaries, Ann. Geophys., 28, 651-664, https

Mousse photochemistry formation; Formacao fotoquimica de mousse

Energy Technology Data Exchange (ETDEWEB)

Rangel, George W.M.; Nicodem, David E. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica]. E-mail: gwallace_iq@yahoo.com.br; nicodem@iq.ufrj.br

2003-07-01

The petroleum, when spilled in the sea it forms an emulsion of water in oil could contain up to 90% of water. This emulsion, called Mousse of Chocolate, it can be very stable, taking to the increase of the environmental impact and impeding the microbiological degradation. It was observed that the petroleum, when irradiated with solar light, it forms Mousse more easily. However, same being known about the importance of the action of the light in the formation of Mousse, little it is known regarding the processes and conditions involved in the formation of Mousse. This project proposes the study of the process of formation of Mousse, in function of the suffered transformations for petroleum after solar irradiation. We will study the relationship between the stability and formation of Mousse and the present amount of asphaltenes in the petroleum as a result of the irradiation. We will develop a methodology for analysis of emulsions of water in petroleum, in way we know her/it the stability of the emulsion in function of the time and the amount of water in the same. We will study the behavior of a sample of Brazilian petroleum of Campos' Basin, already used in other photochemistry studies. We will analyze the effect of the time of irradiation in the asphaltenes formation and Mousse. We will also analyze other types of petroleum, for us to compare results with obtained them in the Brazilian petroleum. (author)

Photosystem II Photochemistry and Phycobiliprotein of the Red Algae Kappaphycus alvarezii and Their Implications for Light Adaptation

OpenAIRE

Guan, Xiangyu; Wang, Jinfeng; Zhu, Jianyi; Yao, Chunyan; Liu, Jianguo; Qin, Song; Jiang, Peng

2013-01-01

Photosystem II photochemistry and phycobiliprotein (PBP) genes of red algae Kappaphycus alvarezii, raw material of κ -carrageenan used in food and pharmaceutical industries, were analyzed in this study. Minimum saturating irradiance (I k ) of this algal species was less than 115  μ mol m−2 s−1. Its actual PSII efficiency (yield II) increased when light intensity enhanced and decreased when light intensity reached 200  μ mol m−2 s−1. Under dim light, yield II declined at first and then increas...

Sunscreen synthesis and their immobilisation on polymethylmethacrylate: an integrated project in organic chemistry, polymer chemistry and photochemistry

International Nuclear Information System (INIS)

Murtinho, Dina Maria B.; Serra, Maria Elisa S.; Pineiro, Marta

2010-01-01

Dibenzalacetone and other aldol condensation products are known sunscreens commonly used in cosmetics. This type of compounds can easily be prepared in an Organic Chemistry Lab by reaction of aldehydes with ketones in basic medium. These compounds can be incorporated in poly(methyl methacrylate) and used as UV light absorbers, for example in sunglasses. This project has the advantage of using inexpensive reagents which are readily available in Chemistry Laboratories. This experiment can also be a base starting point for discussions of organic, polymer and photochemistry topics. (author)

77 FR 15044 - Pacific Fishery Management Council; Public Meetings

Science.gov (United States)

2012-03-14

... Subpanel: 8 a.m. Salmon Technical Team: 8 a.m. Tribal Policy Group: 8 a.m. Tribal and Washington Technical.... Salmon Advisory Subpanel: 8 a.m. Salmon Technical Team: 8 a.m. Tribal Policy Group: 8 a.m. Tribal and... Technical Team: 8 a.m. Tribal Policy Group: 8 a.m. Tribal and Washington Technical Group: 8 a.m. Enforcement...

Impact of lightning-NO on eastern United States photochemistry during the summer of 2006 as determined using the CMAQ model

Directory of Open Access Journals (Sweden)

D. J. Allen

2012-02-01

Full Text Available A lightning-nitrogen oxide (NO algorithm is implemented in the Community Multiscale Air Quality Model (CMAQ and used to evaluate the impact of lightning-NO emissions (LNO_x on tropospheric photochemistry over the United States during the summer of 2006.

For a 500 mole per flash lightning-NO source, the mean summertime tropospheric NO₂ column agrees with satellite-retrieved columns to within −5 to +13%. Temporal fluctuations in the column are moderately well simulated; however, the addition of LNO_x does not lead to a better simulation of day-to-day variability. The contribution of lightning-NO to the model column ranges from ∼10% in the northern US to >45% in the south-central and southeastern US. Lightning-NO adds up to 20 ppbv to upper tropospheric model ozone and 1.5–4.5 ppbv to 8-h maximum surface layer ozone, although, on average, the contribution of LNO_x to model surface ozone is 1–2 ppbv less on poor air quality days. LNO_x increases wet deposition of oxidized nitrogen by 43% and total deposition of nitrogen by 10%. This additional deposition reduces the mean magnitude of the CMAQ low-bias in nitrate wet deposition with respect to National Atmospheric Deposition monitors to near zero.

Differences in urban/rural biases between model and satellite-retrieved NO₂ columns were examined to identify possible problems in model chemistry and/or transport. CMAQ columns were too large over urban areas. Biases at other locations were minor after accounting for the impacts of lightning-NO emissions and the averaging kernel on model columns.

In order to obtain an upper bound on the contribution of uncertainties in NO_y chemistry to upper tropospheric NO_x low biases, sensitivity calculations with updated chemistry were run for the time period of the Intercontinental Chemical Transport Experiment (INTEX-A field campaign (summer 2004

Active molecular iodine photochemistry in the Arctic.

Science.gov (United States)

Raso, Angela R W; Custard, Kyle D; May, Nathaniel W; Tanner, David; Newburn, Matt K; Walker, Lawrence; Moore, Ronald J; Huey, L G; Alexander, Liz; Shepson, Paul B; Pratt, Kerri A

2017-09-19

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2 ) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I - ) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I - measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I - /Na + , consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.

Active molecular iodine photochemistry in the Arctic

Energy Technology Data Exchange (ETDEWEB)

Raso, Angela R.; Custard, Kyle D.; May, Nathaniel W.; Tanner, David; Newburn, Matthew K.; Walker, Lawrence R.; Moore, Ronald J.; Huey, L. G.; Alexander, Lizabeth; Shepson, Paul B.; Pratt, Kerri A.

2017-09-05

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I₂) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I₂ levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I₂ is likely a dominant source of iodine atoms in the Arctic.

Balancing radiation benefits and risks: The needs of an informed public

Energy Technology Data Exchange (ETDEWEB)

1994-04-01

The American public`s perceptions regarding ionizing radiation do not always conform to or correlate with scientific evidence. The ultimate purpose of this coordinated Federal effort and report is to increase the public`s knowledge of the benefits and risks associated with ionizing radiation. This report is divided into five sections. The first section, Introduction, discusses the public`s knowledge of radiation, their perceptions of benefits versus risks, and the Federal government`s role in public education. The section also outlines the charge to the Subpanel. Radiation Issues and Public Reactions discusses several radiation issues important to Federal agencies for which public education programs need to be established or enhanced. Federal Programs describes Federal agencies with public education programs on radiation and the nature of the programs they support. Education Issues and Federal Strategies explores the elements identified by the Subpanel as critical to the development and implementation of an effective Federal program in the area of public education on radiation issues and nuclear technologies. An important issue repeatedly brought up during the public sector presentations to the Subpanel was the perceived lack of Federal credibility on radiation issues in the eyes of the public. To some degree, this concern was factored into all of the recommendations developed by the subpanel. The issues discussed in this section include the fragmented nature of Federal radiation programs and the need to improve credibility, promote agency responsiveness, and support the enhancement of scientific literacy. Finally, under Recommendations, the Subpanel discusses its overall findings and conclusions.

Balancing radiation benefits and risks: The needs of an informed public

International Nuclear Information System (INIS)

1994-04-01

The American public's perceptions regarding ionizing radiation do not always conform to or correlate with scientific evidence. The ultimate purpose of this coordinated Federal effort and report is to increase the public's knowledge of the benefits and risks associated with ionizing radiation. This report is divided into five sections. The first section, Introduction, discusses the public's knowledge of radiation, their perceptions of benefits versus risks, and the Federal government's role in public education. The section also outlines the charge to the Subpanel. Radiation Issues and Public Reactions discusses several radiation issues important to Federal agencies for which public education programs need to be established or enhanced. Federal Programs describes Federal agencies with public education programs on radiation and the nature of the programs they support. Education Issues and Federal Strategies explores the elements identified by the Subpanel as critical to the development and implementation of an effective Federal program in the area of public education on radiation issues and nuclear technologies. An important issue repeatedly brought up during the public sector presentations to the Subpanel was the perceived lack of Federal credibility on radiation issues in the eyes of the public. To some degree, this concern was factored into all of the recommendations developed by the subpanel. The issues discussed in this section include the fragmented nature of Federal radiation programs and the need to improve credibility, promote agency responsiveness, and support the enhancement of scientific literacy. Finally, under Recommendations, the Subpanel discusses its overall findings and conclusions

Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

Directory of Open Access Journals (Sweden)

L. González Palacios

2016-09-01

Full Text Available The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA, including its light-absorbing product imidazole-2-carboxaldehyde (IC. IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT experiments using films of IC and citric acid (CA, an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2 was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1 the [IC]  ×  [CA] concentration product and (2 the photon actinic flux. Additionally, (3 a more complex function of relative humidity (25 %  <  RH  <  63 % and of (4 the O2 ∕ N2 ratio (15 %  <  O2 ∕ N2  <  56 % was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25–55 % RH and at ambient O2 ∕ N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

Surface Photochemistry of Adsorbed Nitrate: The Role of Adsorbed Water in the Formation of Reduced Nitrogen Species on α-Fe2O3 Particle Surfaces

NARCIS (Netherlands)

Nanayakkara, C.E.; Jayaweera, P.M.; Rubasinghege, G; Baltrusaitis, Jonas; Grassian, V.H.

2014-01-01

The surface photochemistry of nitrate, formed from nitric acid adsorption, on hematite (α-Fe2O3) particle surfaces under different environmental conditions is investigated using X-ray photoelectron spectroscopy (XPS). Following exposure of α-Fe2O3 particle surfaces to gas-phase nitric acid, a peak

New concepts in therapeutic photomedicine: photochemistry, optical targeting and the therapeutic window

International Nuclear Information System (INIS)

Parrish, J.A.

1981-01-01

Advances in optics technology, synthetic photochemistry, and the science of photobiology make it possible to think beyond phototherapy and photochemotherapy which is dependent on direct photochemical alteration of metabolites or direct phototoxic insult to cells. This report discusses another gender of photomedicine therapy which includes in vivo photoactivation of medicines, photon-dependent drug delivery, and manipulation of host and exposure source to maximize therapeutic index. These therapeutic manipulations are made possible because the skin is highly overperfused and because non-ionizing electromagnetic radiation that enters skin and blood has adequate photon energy to cause electronic excitation. Radiation of 320-800 nm is not very directly phototoxic, is absorbed by a variety of relatively nontoxic photolabile molecules and has an internal dosimetric depth profile. This radiation can therefore be used to activate, deactivate, bind, release or biotransform medications in vivo in skin or other organs. The photochemist, synthetic chemist and photobiologist can collaborate to significantly increase therapeutic possibilities

Photochemistry of fluorinated 4-iodophenylnitrenes: matrix isolation and spectroscopic characterization of phenylnitrene-4-yls.

Science.gov (United States)

Grote, Dirk; Sander, Wolfram

2009-10-02

The photochemistry of a series of fluorinated p-iodophenyl azides 2 has been investigated using matrix isolation IR and EPR spectroscopy. In all cases, the corresponding phenylnitrenes 1 were formed as primary photoproducts. Further irradiation of the nitrenes 1 resulted in the formation of azirines 3, ketenimines 4, and nitreno radicals 5. The yield of 5 depends on the number of ortho fluorine substituents: with two ortho fluorine atoms the highest yield is observed, whereas without fluorine atoms the yield is too low for IR spectroscopic detection. The interconversion between the isomers 1, 3, and 4 proved to be rather complex. If the fluorine atoms are distributed unsymmetrically, two isomers of azirines 3 and ketenimines 4 can be formed. The yields of these isomers depend critically on the irradiation conditions.

Rice Photosynthetic Productivity and PSII Photochemistry under Nonflooded Irrigation

Directory of Open Access Journals (Sweden)

Haibing He

2014-01-01

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

Photochemistry in the Atmospheres of Denver and Mexico City

Science.gov (United States)

Cantrell, C. A.

2016-12-01

The composition of atmospheres in and downwind of urban centers has been the subject of study for decades. While early campaigns involved measurements exclusively from the ground, more recent studies have included airborne-based observations. Improved understanding has hinged critically on the development of instrumentation for better qualitifcation of pollutants, and measurement of previously unobserved species in the gas and particulate phases. Comprehensive, well-planned studies have, over time, led to more detailed understanding of chemical transformations and thus improved model representations and directions for further research. This presentation focuses on findings from two case studies of urban atmospheres, namely the MILAGRO study in the Mexico City metropolitan area and the FRAPPE study in the Denver metropolitan region. Both studies made use of extensive ground-based networks and multiple aircraft platforms. The data collected during these studies have been combined with numerical models to derive assessments of the evolution of atmospheric composition due to photochemistry, mixing, and surface processes. Here, analysis of MILAGRO data focuses on the evolution of outflow downwind of the urban region. In FRAPPE, the focus is the possible role of oil and gas exploration on urban air quality. These findings are used to assess the accuracy of current numerical models to reproduce observations, and to point toward areas possibly needing further study.

The future of high-energy physics in the United States: Statement for the 1994 HEPAP subpanel

International Nuclear Information System (INIS)

Peoples, J. Jr.

1994-01-01

The United States has a superb capability for forefront research in elementary particle physics for the next decade-but it can be realized only if there is sufficient funding to make efficient use of our existing world-class facilities. Throughout most of the past half century, the US has led the world in making contributions to our growing understanding of elementary particle physics. We are no longer the dominant force in the field, but we are still one of the leaders. The termination of the SSC is an enormous blow, but it need not end our participation in the field. We must first take advantage of what we have -- and that is considerable -- and then use it as the basis for a successful strategy for the first few decades in the next century. The US can make many important contributions to our field for the rest of this decade and for part of the next. But, after that, we will not long remain among the world's leaders unless we have the foresight to preserve and strengthen our capability to construct and operate world-class facilities

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

Science.gov (United States)

de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

2017-10-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

On the determinants of renewable energy consumption: International Evidence

OpenAIRE

Anis Omri; Duc Khuong Nguyen

2014-01-01

Over recent years, renewable energy sources have emerged as an important component of world energy consumption. Little is however known about the determinants of renewable energy consumption. This article tackles this issue for a global panel consisting of 64 countries over the period 1990-2011 by using a dynamic system- GMM panel model. We also consider three homogeneous subpanels which are constructed based on the income level of sample countries (high-, middle-, and low-income subpanels). ...

Combined In Situ Illumination-NMR-UV/Vis Spectroscopy: A New Mechanistic Tool in Photochemistry.

Science.gov (United States)

Seegerer, Andreas; Nitschke, Philipp; Gschwind, Ruth M

2018-06-18

Synthetic applications in photochemistry are booming. Despite great progress in the development of new reactions, mechanistic investigations are still challenging. Therefore, we present a fully automated in situ combination of NMR spectroscopy, UV/Vis spectroscopy, and illumination to allow simultaneous and time-resolved detection of paramagnetic and diamagnetic species. This optical fiber-based setup enables the first acquisition of combined UV/Vis and NMR spectra in photocatalysis, as demonstrated on a conPET process. Furthermore, the broad applicability of combined UVNMR spectroscopy for light-induced processes is demonstrated on a structural and quantitative analysis of a photoswitch, including rate modulation and stabilization of transient species by temperature variation. Owing to the flexibility regarding the NMR hardware, temperature, and light sources, we expect wide-ranging applications of this setup in various research fields. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. II. H{sub 2}S AND SO{sub 2} PHOTOCHEMISTRY IN ANOXIC ATMOSPHERES

Energy Technology Data Exchange (ETDEWEB)

Hu Renyu; Seager, Sara; Bains, William, E-mail: hury@mit.edu [Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

2013-05-20

Sulfur gases are common components in the volcanic and biological emission on Earth, and are expected to be important input gases for atmospheres on terrestrial exoplanets. We study the atmospheric composition and the spectra of terrestrial exoplanets with sulfur compounds (i.e., H{sub 2}S and SO{sub 2}) emitted from their surfaces. We use a comprehensive one-dimensional photochemistry model and radiative transfer model to investigate the sulfur chemistry in atmospheres ranging from reducing to oxidizing. The most important finding is that both H{sub 2}S and SO{sub 2} are chemically short-lived in virtually all types of atmospheres on terrestrial exoplanets, based on models of H{sub 2}, N{sub 2}, and CO{sub 2} atmospheres. This implies that direct detection of surface sulfur emission is unlikely, as their surface emission rates need to be extremely high (>1000 times Earth's volcanic sulfur emission) for these gases to build up to a detectable level. We also find that sulfur compounds emitted from the surface lead to photochemical formation of elemental sulfur and sulfuric acid in the atmosphere, which would condense to form aerosols if saturated. For terrestrial exoplanets in the habitable zone of Sun-like stars or M stars, Earth-like sulfur emission rates result in optically thick haze composed of elemental sulfur in reducing H{sub 2}-dominated atmospheres for a wide range of particle diameters (0.1-1 {mu}m), which is assumed as a free parameter in our simulations. In oxidized atmospheres composed of N{sub 2} and CO{sub 2}, optically thick haze, composed of elemental sulfur aerosols (S{sub 8}) or sulfuric acid aerosols (H{sub 2}SO{sub 4}), will form if the surface sulfur emission is two orders of magnitude more than the volcanic sulfur emission of Earth. Although direct detection of H{sub 2}S and SO{sub 2} by their spectral features is unlikely, their emission might be inferred by observing aerosol-related features in reflected light with future generation

Photochemistry at Interfaces

Energy Technology Data Exchange (ETDEWEB)

Eisenthal, Kenneth B [Columbia Univ., New York, NY (United States)

2015-02-24

We have advanced our capabilities to investigate ultrafast excited state dynamics at a liquid interface using a pump to excite molecules to higher electronic states and then probe the subsequent time evolution of the interfacial molecules with femtosecond time delayed vibrational SFG.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

Energy Technology Data Exchange (ETDEWEB)

De Barros, A. L. F. [Departamento de Física, Centro Federal de Educação Tecnológica Celso Suckow da Fonseca, Av. Maracanã 229, 20271-110 Rio de Janeiro, RJ (Brazil); Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G.A.; Allamandola, L. J. [NASA Ames Research Center, Mail Stop 245-6, Moffett Field, CA 94035-1000 (United States)

2017-10-20

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

International Nuclear Information System (INIS)

De Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G.A.; Allamandola, L. J.

2017-01-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O, and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H + ) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution.

Science.gov (United States)

Xue, Jiadan; Luk, Hoi Ling; Eswaran, S V; Hadad, Christopher M; Platz, Matthew S

2012-06-07

The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).

Photogeneration of reactive transient species upon irradiation of natural water samples: Formation quantum yields in different spectral intervals, and implications for the photochemistry of surface waters.

Science.gov (United States)

Marchisio, Andrea; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-04-15

Chromophoric dissolved organic matter (CDOM) in surface waters is a photochemical source of several transient species such as CDOM triplet states ((3)CDOM*), singlet oxygen ((1)O2) and the hydroxyl radical (OH). By irradiation of lake water samples, it is shown here that the quantum yields for the formation of these transients by CDOM vary depending on the irradiation wavelength range, in the order UVB > UVA > blue. A possible explanation is that radiation at longer wavelengths is preferentially absorbed by the larger CDOM fractions, which show lesser photoactivity compared to smaller CDOM moieties. The quantum yield variations in different spectral ranges were definitely more marked for (3)CDOM* and OH compared to (1)O2. The decrease of the quantum yields with increasing wavelength has important implications for the photochemistry of surface waters, because long-wavelength radiation penetrates deeper in water columns compared to short-wavelength radiation. The average steady-state concentrations of the transients ((3)CDOM*, (1)O2 and OH) were modelled in water columns of different depths, based on the experimentally determined wavelength trends of the formation quantum yields. Important differences were found between such modelling results and those obtained in a wavelength-independent quantum yield scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

Science.gov (United States)

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

Functionalization of the PEG Corona of Nanoparticles by Clip Photochemistry in Water: Application to the Grafting of RGD Ligands on PEGylated USPIO Imaging Agent.

Science.gov (United States)

Pourcelle, Vincent; Laurent, Sophie; Welle, Alexandre; Vriamont, Nicolas; Stanicki, Dimitri; Vander Elst, Luce; Muller, Robert N; Marchand-Brynaert, Jacqueline

2015-05-20

The fast development of nanomedicines requires more and more reliable chemical tools in order to accurately design materials and control the surface properties of the nano-objects used in biomedical applications. In this study we describe a smooth and simple photografting technique, i.e., the clip photochemistry, that allows the introduction of molecules of interest in inert polymers or on stealth nanoparticles directly in aqueous solution. First we developed the methodology on polyethylene glycol (PEG) and looked for critical parameters of the process (irradiation times, concentrations, washings) by using several molecular probes and adapted analytical techniques ((19)F qNMR, EA, LSC). We found that the clip photochemistry in water is a robust and efficient method to functionalize PEG. Second we applied it on PEGylated USPIO (USPIO-PEG) magnetic resonance imaging agent and succeeded in introducing RGD peptide and homemade peptidomimetics on their PEG segments. The magnetic abilities of the conjugated nanoparticles were unchanged by the derivatization process as evidenced by their relaxometric properties and their NMRD profile. When tested on Jurkat lymphocyte T Cells, which express αvβ3 integrins, the USPIO conjugated with RGD ligands leads to an increase of the transverse relaxation rate (R2) by a factor 10 to 14 as compared to USPIO-PEG. Consequently, it makes them good candidates for targeted imaging technology in cancer therapy.

Photochemistry and photophysics of the amino and imino tautomers of 1-methylcytosine: tautomerisation as a side product of the radiationless decay.

Science.gov (United States)

Li, Quansong; Blancafort, Lluís

2013-08-01

The photochemistry and photophysics of the amino-oxo (AO) and imino-oxo (IO) tautomers of 1-methylcytosine are investigated with ab initio calculations, using the CASPT2//CASSCF approach. Our aim is to rationalize recent experimental results which show that the AO tautomer has an excited state lifetime of about 1 ps, similar to cytosine (J.-W. Ho, H.-C. Yen, W.-K. Chou, C.-N. Weng, L.-H. Cheng, H.-Q. Shi, S.-H. Lai and P.-Y. Cheng, J. Phys. Chem. A, 2011, 115, 8406-8418), and that irradiation with wavelengths shorter than 308 nm induces the AO→IO tautomerization (I. Reva, M. J. Nowak, L. Lapinski and R. Fausto, J. Phys. Chem. B, 2012, 116, 5703-5710). For the canonical AO tautomer we find two analogous decay mechanisms to those described previously for cytosine, involving a conical intersection of ethylenic type and one where the amino group is bent out of plane. Decay through these intersections provides an unreactive return path to the AO ground state species. More importantly, we have identified new decay paths that lead from the two intersections to the trans-IO tautomer, without a barrier. These paths provide the possibility of forming the IO tautomer, presumably in small yields, as a side product of the radiationless decay. Thus, we have established for the first time computationally the mechanism of the UV-induced tautomerization, which is compatible with the well-established decay mechanism for cytosine. For the IO tautomer, we also find a mechanism for the excited state interconversion of the cis and trans forms and for efficient radiationless decay through a conical intersection where the imino group is perpendicular to the ring and bent out of the plane. These results are likely to be valid also for cytosine.

The atmosphere simulation chamber SAPHIR: a tool for the investigation of photochemistry.

Science.gov (United States)

Brauers, T.; Bohn, B.; Johnen, F.-J.; Rohrer, R.; Rodriguez Bares, S.; Tillmann, R.; Wahner, A.

2003-04-01

On the campus of the Forschungszentrum Jülich we constructed SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) which was accomplished in fall 2001. The chamber consists of a 280-m^3 double-wall Teflon bag of cylindrical shape that is held by a steel frame. Typically 75% of the outside actinic flux (290~nm~--~420~nm) is available inside the chamber. A louvre system allows switching between full sun light and dark within 40 s giving the opportunity to study relaxation processes of the photo chemical system. The SAPHIR chamber is equipped with a comprehensive set of sensitive instruments including the measurements of OH, HO_2, CO, hydrocarbons, aldehydes, nitrogen-oxides and solar radiation. Moreover, the modular concept of SAPHIR allows fast and flexible integration of new instruments and techniques. In this paper we will show the unique and new features of the SAPHIR chamber, namely the clean air supply and high purity water vapor supply providing a wide range of trace gas concentrations being accessible through the experiments. We will also present examples from the first year of SAPHIR experiment showing the scope of application from high quality instrument inter-comparison and kinetic studies to the simulation of complex mixtures of trace gases at ambient concentrations.

Photochemistry of ethylene: A multireference configuration interaction investigation of the excited-state energy surfaces

International Nuclear Information System (INIS)

Barbatti, M.; Paier, J.; Lischka, H.

2004-01-01

Multireference configuration interaction with singles and doubles (MR-CISD) calculations have been performed for the optimization of conical intersections and stationary points on the ethylene excited-state energy surfaces using recently developed methods for the computation of analytic gradients and nonadiabatic coupling terms. Basis set dependence and the effect of various choices of reference spaces for the MR-CISD calculations have been investigated. The crossing seam between the S 0 and S 1 states has been explored in detail. This seam connects all conical intersections presently known for ethylene. Major emphasis has been laid on the hydrogen-migration path. Starting in the V state of twisted-orthogonal ethylene, a barrierless path to ethylidene was found. The feasibility of ethylidene formation will be important for the explanation of the relative yield of cis and trans H 2 elimination

Photochemistry Saturn's Atmosphere. 2; Effects of an Influx of External Oxygen

Science.gov (United States)

Moses, Julianne I.; Lellouch, Emmanuel; Bezard, Bruno; Gladstone, G. Randall; Allen, Mark

2000-01-01

We use a one-dimensional diurnally averaged model of photochemistry and diffusion in Saturn's stratosphere to investigate the influence of extraplanetary debris on atmospheric chemistry. In particular, we consider the effects of an influx of oxygen from micrometeoroid ablation or from ring-particle diffusion; the contribution from cometary impacts, satellite debris, or ring vapor is deemed to be less important. The photochemical model results are compared directly with Infrared Space Observatory (ISO) observations to constrain the influx of extraplanetary oxygen to Saturn. From the ISO observations, we determine that the column densities of CO2 and H2O above 10 mbar in Saturn's atmosphere are (6.3 +/- 1) x 10(exp 14) and (1.4 +/- 0.4) x 10(exp 15)/ square cm, respectively; our models indicate that a globally averaged oxygen influx of (4+/-2) x 10(exp 6) O atoms /sq cm/s is required to explain these observations. Models with a locally enhanced influx of H20 operating over a small fraction of the projected area do not provide as good a fit to the ISO H2O observations. If volatile oxygen compounds comprise one-third to one-half of the exogenic source by mass, then Saturn is currently being bombarded with (3 +/- 2) x 10(exp -16) g/square cm/s of extraplanetary material. To reproduce the observed CO2/H2O ratio in Saturn's stratosphere, some of the exogenic oxygen must arrive in the form of a carbon-oxygen bonded species such as CO or CO2. An influx consistent with the composition of cometary ices fails to reproduce the high observed CO2/H2O ratio, suggesting that (i) the material has ices that are slightly more carbon-rich than is typical for comets, (ii) a contribution from an organic-rich component is required, or (iii) some of the hydrogen-oxygen bonded material is converted to carbon-oxygen bonded material without photochemistry (e.g., during the ablation process). We have also reanalyzed the 5-micron CO observations of Noll and Larson and determine that the CO

Two case studies on the interaction of large-scale transport, mesoscale photochemistry, and boundary-layer processes on the lower tropospheric ozone dynamics in early spring

Energy Technology Data Exchange (ETDEWEB)

Broennimann, S.; Siegrist, F.C.; Eugster, W.; Cattin, R.; Sidle, C.; Wanner, H. [Inst. of Geography, Univ. of Bern (Switzerland); Hirschberg, M.M. [Lehrstuhl fuer Bioklimatologie und Immissionsforschung, TU Muenchen, Freising-Weihenstephan (Germany); Schneiter, D. [MeteoSwiss, Station Aerologique, Payerne (Switzerland); Perego, S. [IBM Switzerland, Zuerich (Switzerland)

2001-04-01

The vertical distribution of ozone in the lower troposphere over the Swiss Plateau is investigated in detail for two episodes in early spring (February 1998 and March 1999). Profile measurements of boundary-layer ozone performed during two field campaigns with a tethered balloon sounding system and a kite are investigated using regular aerological and ozone soundings from a nearby site, measurements from monitoring stations at various altitudes, backward trajectories, and synoptic analyses of meteorological fields. Additionally, the effect of in situ photochemistry was estimated for one of the episodes employing the Metphomod Eulerian photochemical model. Although the meteorological situations were completely different, both cases had elevated layers with high ozone concentrations, which is not untypical for late winter and early spring. In the February episode, the highest ozone concentrations of 55 to 60 ppb, which were found at around 1100 m asl, were partly advected from Southern France, but a considerable contribution of in situ photochemistry is also predicted by the model. Below that elevation, the local chemical sinks and surface deposition probably overcompensated chemical production, and the vertical ozone distribution was governed by boundary-layer dynamics. In the March episode, the results suggest that ozone-rich air parcels, probably of stratospheric or upper tropospheric origin, were advected aloft the boundary layer on the Swiss Plateau. (orig.)

Differing professional opinions: 1987 Special Review Panel

International Nuclear Information System (INIS)

1987-11-01

In mid-1987, the Executive Director for Operations of the US Nuclear Regulatory Commission appointed a Special Review Panel to review the existing NRC policy for expressing differing professional views and to recommend possible improvements to the policy, if warranted. Through its own efforts and those of three subpanels and three consultants, the Panel developed recommendations for changes and improvements in five major areas. This report presents those recommendations, along with a detailed explanation of the Panel's findings, copies of the reports of the subpanels and consultants, and the results of a survey of NRC non-clerical employees on the issue

Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory

Directory of Open Access Journals (Sweden)

L. K. Xue

2013-09-01

Full Text Available The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l., a baseline station in the northeast part of the Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian subcontinent. A photochemical box model based on the Master Chemical Mechanism (version 3.2 and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO by the hydroperoxyl radical (HO2 dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2, and the ozone is primarily destroyed by photolysis and reactions with the HOx (HOx = OH + HO2 radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2, followed by the photolysis of secondary oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. Overall, the findings of the present study provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.

Non-adiabatic Excited State Molecule Dynamics Modeling of Photochemistry and Photophysics of Materials

Energy Technology Data Exchange (ETDEWEB)

Nelson, Tammie Renee [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tretiak, Sergei [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-01-06

Understanding and controlling excited state dynamics lies at the heart of all our efforts to design photoactive materials with desired functionality. This tailor-design approach has become the standard for many technological applications (e.g., solar energy harvesting) including the design of organic conjugated electronic materials with applications in photovoltaic and light-emitting devices. Over the years, our team has developed efficient LANL-based codes to model the relevant photophysical processes following photoexcitation (spatial energy transfer, excitation localization/delocalization, and/or charge separation). The developed approach allows the non-radiative relaxation to be followed on up to ~10 ps timescales for large realistic molecules (hundreds of atoms in size) in the realistic solvent dielectric environment. The Collective Electronic Oscillator (CEO) code is used to compute electronic excited states, and the Non-adiabatic Excited State Molecular Dynamics (NA-ESMD) code is used to follow the non-adiabatic dynamics on multiple coupled Born-Oppenheimer potential energy surfaces. Our preliminary NA-ESMD simulations have revealed key photoinduced mechanisms controlling competing interactions and relaxation pathways in complex materials, including organic conjugated polymer materials, and have provided a detailed understanding of photochemical products and intermediates and the internal conversion process during the initiation of energetic materials. This project will be using LANL-based CEO and NA-ESMD codes to model nonradiative relaxation in organic and energetic materials. The NA-ESMD and CEO codes belong to a class of electronic structure/quantum chemistry codes that require large memory, “long-queue-few-core” distribution of resources in order to make useful progress. The NA-ESMD simulations are trivially parallelizable requiring ~300 processors for up to one week runtime to reach a meaningful restart point.

The National Spallation Neutron Source Collaboration: Towards a new pulsed neutron source in the United States

International Nuclear Information System (INIS)

Appleton, B.R.; Ball, J.B.; Alonso, J.R.; Gough, R.A.; Weng, W.T.; Jason, A.

1996-01-01

The US Department of Energy has commissioned Oak Ridge National Laboratory to initiate the conceptual design for a next-generation pulsed spallation neutron source. Current expectation is for a construction start in FY 1998, with commencement of operations in 2004. For this project, ORNL has entered into a collaborative arrangement with LBNL, BNL, LANL (and most recently ANL). The conceptual design study is now well underway, building on the strong base of the extensive work already performed by various Laboratories, as well as input from the user community (from special BESAC subpanels). Study progress, including accelerator configuration and plans for resolution of critical issues, is reported in this paper

A novel synthesis of polymeric CO via useful hard X-ray photochemistry

Directory of Open Access Journals (Sweden)

Michael Pravica

2016-12-01

Full Text Available We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC2O4 pressurized to 7 GPa inside a diamond anvil cell (DAC. After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO2 even under ambient conditions with the sample exposed to air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part with dispersed CO2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press without the need for the dangerous and complex loading of toxic CO. A novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.

Differential acclimation of enzymatic antioxidant metabolism and photosystem II photochemistry in tall fescue under drought and heat and the combined stresses

Directory of Open Access Journals (Sweden)

Aoyue eBi

2016-04-01

Full Text Available Quality inferiority in cool-season turfgrass due to drought, heat and a combination of both stresses is predicted to be more prevalent in the future. Understanding the various response to heat and drought stress will assist in the selection and breeding of tolerant grass varieties. The objective of this study was to investigate the behavior of antioxidant metabolism and photosystem II (PSII photochemistry in two tall fescue genotypes (PI 234881 and PI 578718 with various thermotolerance capacities. Wide variations were found between heat-tolerant PI 578718 and heat-sensitive PI 234881 for leaf relative water content, malondialdehyde and electrolyte leakage under drought, high-temperature or a combination of both stresses. The sensitivity of PI 234881 exposed to combined stresses was associated with lower superoxide dismutase activity and higher H2O2 accumulation than that in PI 578718. Various antioxidant enzymes displayed positive correlation with chlorophyll content, but negative with membrane injury index at most of the stages in both tall fescue genotypes. The JIP-test analysis in PI 578718 indicated a significant improvement in ABS/RC, TR0/RC, RE0/RC, RE0/ABS values as compared to the control regime, which indicated that PI 578718 had a high potential to protect the PSII system under drought and high temperature stress. And the PS II photochemistry in PI 234881 was damaged significantly compared with PI578718. Moreover, quantitative RT-PCR revealed that heat and drought stresses deduced the gene expression of psbB and psbC, but induced the expression of psbA. These findings to some extent confirmed that the various adaptations of physiological traits may contribute to breeding in cold-season turfgrass in response to drought, high-temperature and a combination of both stresses.

What do PANs Tell us about VOC-NOx Photochemistry in the Urban/Rural Interface?

Science.gov (United States)

Roberts, J. M.; Flocke, F. M.; Zheng, W.; Bertman, S.; Marchewka, M.; Williams, E.; Lerner, B.; Kuster, W.; Goldan, P.; Gilman, J.; Sommariva, R.; Trainer, M.; Fehsenfeld, F.

2006-12-01

Peroxycarboxylic Nitric Anhydrides (PANs) are co-products of the VOC-NOx photochemistry that is responsible for O3 and secondary organic aerosol (SOA) formation in the troposphere. The relative abundance of the various PAN type compounds can provide important diagnostic information as to the contribution of different VOC sources to these processes. Anthropogenic, biogenic and petrochemical VOC sources have shown distinct profiles of PAN, PPN, MPAN, PiBN, and APAN, which can be analyzed using simple numerical models and compared to the results of detailed chemical mechanisms. One result of these studies is that the PAN compounds can be used to better define the contribution of isoprene to O3 production in the urban/rural interface. Another result is that high relative concentrations of APAN are characteristic of high petrochemical source impact. In addition, changes in the relative abundance of PPN and PAN can indicate the aging of a continental photochemical plume. This paper will present selected results from five field experiments and modeling studies from the Nashville 1999 Southern Oxidant Study up through the TexAQS 2006 study, in and around Houston, TX.

Two case studies on the interaction of large-scale transport, mesoscale photochemistry, and boundary-layer processes on the lower tropospheric ozone dynamics in early spring

Directory of Open Access Journals (Sweden)

S. Brönnimann

2001-04-01

Full Text Available The vertical distribution of ozone in the lower troposphere over the Swiss Plateau is investigated in detail for two episodes in early spring (February 1998 and March 1999. Profile measurements of boundary-layer ozone performed during two field campaigns with a tethered balloon sounding system and a kite are investigated using regular aerological and ozone soundings from a nearby site, measurements from monitoring stations at various altitudes, backward trajectories, and synoptic analyses of meteorological fields. Additionally, the effect of in situ photochemistry was estimated for one of the episodes employing the Metphomod Eulerian photochemical model. Although the meteorological situations were completely different, both cases had elevated layers with high ozone concentrations, which is not untypical for late winter and early spring. In the February episode, the highest ozone concentrations of 55 to 60 ppb, which were found at around 1100 m asl, were partly advected from Southern France, but a considerable contribution of in situ photochemistry is also predicted by the model. Below that elevation, the local chemical sinks and surface deposition probably overcompensated chemical production, and the vertical ozone distribution was governed by boundary-layer dynamics. In the March episode, the results suggest that ozone-rich air parcels, probably of stratospheric or upper tropospheric origin, were advected aloft the boundary layer on the Swiss Plateau.Key words. Atmospheric composition and structure (pollution – urban and regional; troposphere – composition and  chemistry – Meteorology and atmospheric dynamics (mesoscale meteorology

Estimated SAGE II ozone mixing ratios in early 1993 and comparisons with Stratospheric Photochemistry, Aerosols and Dynamic Expedition measurements

Science.gov (United States)

Yue, G. K.; Veiga, R. E.; Poole, L. R.; Zawodny, J. M.; Proffitt, M. H.

1994-01-01

An empirical time-series model for estimating ozone mixing ratios based on Stratospheric Aerosols and Gas Experiment II (SAGE II) monthly mean ozone data for the period October 1984 through June 1991 has been developed. The modeling results for ozone mixing ratios in the 10- to 30- km region in early months of 1993 are presented. In situ ozone profiles obtained by a dual-beam UV-absorption ozone photometer during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) campaign, May 1-14, 1993, are compared with the model results. With the exception of two profiles at altitudes below 16 km, ozone mixing ratios derived by the model and measured by the ozone photometer are in relatively good agreement within their individual uncertainties. The identified discrepancies in the two profiles are discussed.

Time Evolution of the Excimer State of a Conjugated Polymer Laser

Directory of Open Access Journals (Sweden)

Wafa Musa Mujamammi

2017-11-01

Full Text Available An excited dimer is an important complex formed in nano- or pico-second time scales in many photophysics and photochemistry applications. The spectral and temporal profile of the excimer state of a laser from a new conjugated polymer, namely, poly (9,9-dioctylfluorenyl-2,7-diyl (PFO, under several concentrations in benzene were investigated. These solutions were optically pumped by intense pulsed third-harmonic Nd:YAG laser (355-nm to obtain the amplified spontaneous emission (ASE spectra of a monomer and an excimer with bandwidths of 6 and 7 nm, respectively. The monomer and excimer ASEs were dependent on the PFO concentration, pump power, and temperature. Employing a sophisticated picosecond spectrometer, the time evolution of the excimer state of this polymer, which is over 400 ps, can be monitored.

Photochemistry and photobiology of actinic erythema: defensive and reparative cutaneous mechanisms

Directory of Open Access Journals (Sweden)

A.C. Tedesco

1997-05-01

Full Text Available Sunlight is part of our everyday life and most people accept it as beneficial to our health. With the advance of our knowledge in cutaneous photochemistry, photobiology and photomedicine over the past four decades, the terrestrial solar radiation has become a concern of dermatologists and is considered to be a major damaging environmental factor for our skin. Most photobiological effects (e.g., sunburn, suntanning, local and systemic immunosuppression, photoaging or dermatoheliosis, skin cancer and precancer, etc. are attributed to ultraviolet radiation (UVR and more particularly to UVB radiation (290-320 nm. UVA radiation (320-400 nm also plays an important role in the induction of erythema by the photosensitized generation of reactive oxygen species (singlet oxygen (1O2, superoxide (O2.- and hydroxyl radicals (.OH that damage DNA and cellular membranes, and promote carcinogenesis and the changes associated with photoaging. Therefore, research efforts have been directed at a better photochemical and photobiological understanding of the so-called sunburn reaction, actinic or solar erythema. To survive the insults of actinic damage, the skin appears to have different intrinsic defensive mechanisms, among which antioxidants (enzymatic and non-enzymatic systems play a pivotal role. In this paper, we will review the basic aspects of the action of UVR on the skin: a photochemical reactions resulting from photon absorption by endogenous chromophores; b the lipid peroxidation phenomenon, and c intrinsic defensive cutaneous mechanisms (antioxidant systems. The last section will cover the inflammatory response including mediator release after cutaneous UVR exposure and adhesion molecule expression

Photochemistry of comets

International Nuclear Information System (INIS)

Huebner, W.F.

1985-01-01

The classification of comets, chemically rich mixtures of volatile materials and refractory grains, is described. The developments of coma and tails, and the composition and structure of coma, plasma tails, dust, and nucleus are examined. The differences between comets and planetary atmospheres are investigated. Three hypotheses on the origin of comets are proposed; one states that comets formed in the region of the giant planets, the second theory has the development of comets occuring in the outer parts of the solar nebula, and the third states that comets formed in a companion fragment of the nebula. The use of radar, photometric, spectral, and laboratory measurements for modeling comets is discussed. The physics and main photolytic and chemical reaction processes of a collision-dominated coma are analyzed; the influence of the solar wind on the coma is studied. A comparison of the model with observed data is presented; good correlation of data is observed. The features of Halley's Comet and other comets with distinctive characteristics are examined. Future comet exploration missions and the need to improve comet models are discussed. 31 references

Photoexcited singlet and triplet states of a UV absorber ethylhexyl methoxycrylene.

Science.gov (United States)

Kikuchi, Azusa; Hata, Yuki; Kumasaka, Ryo; Nanbu, Yuichi; Yagi, Mikio

2013-01-01

The excited states of UV absorber, ethylhexyl methoxycrylene (EHMCR) have been studied through measurements of UV absorption, fluorescence, phosphorescence and electron paramagnetic resonance (EPR) spectra in ethanol. The energy levels of the lowest excited singlet (S1) and triplet (T1) states of EHMCR were determined. The energy levels of the S1 and T1 states of EHMCR are much lower than those of photolabile 4-tert-butyl-4'-methoxydibenzoylmethane. The energy levels of the S1 and T1 states of EHMCR are lower than those of octyl methoxycinnamate. The weak phosphorescence and EPR B(min) signals were observed and the lifetime was estimated to be 93 ms. These facts suggest that the significant proportion of the S1 molecules undergoes intersystem crossing to the T1 state, and the deactivation process from the T1 state is predominantly radiationless. The photostability of EHMCR arises from the (3)ππ* character in the T1 state. The zero-field splitting (ZFS) parameter in the T1 state is D** = 0.113 cm(-1). © 2012 The Authors Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory

Energy Technology Data Exchange (ETDEWEB)

Valsson, Omar [Department of Chemistry and Applied Biosciences, ETH Zurich and Facoltà di Informatica, Instituto di Scienze Computationali, Università della Svizzera italiana, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Filippi, Claudia, E-mail: c.filippi@utwente.nl [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Casida, Mark E., E-mail: mark.casida@ujf-grenoble.fr [Laboratoire de Chimie Théorique, Département de Chimie Moléculaire (DCM), Institut de Chimie Moléculaire de Grenoble (ICMG), Université Joseph Fourier, Grenoble I, F-3801 Grenoble (France)

2015-04-14

The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

Two case studies on the interaction of large-scale transport, mesoscale photochemistry, and boundary-layer processes on the lower tropospheric ozone dynamics in early spring

Directory of Open Access Journals (Sweden)

S. Brönnimann

Full Text Available The vertical distribution of ozone in the lower troposphere over the Swiss Plateau is investigated in detail for two episodes in early spring (February 1998 and March 1999. Profile measurements of boundary-layer ozone performed during two field campaigns with a tethered balloon sounding system and a kite are investigated using regular aerological and ozone soundings from a nearby site, measurements from monitoring stations at various altitudes, backward trajectories, and synoptic analyses of meteorological fields. Additionally, the effect of in situ photochemistry was estimated for one of the episodes employing the Metphomod Eulerian photochemical model. Although the meteorological situations were completely different, both cases had elevated layers with high ozone concentrations, which is not untypical for late winter and early spring. In the February episode, the highest ozone concentrations of 55 to 60 ppb, which were found at around 1100 m asl, were partly advected from Southern France, but a considerable contribution of in situ photochemistry is also predicted by the model. Below that elevation, the local chemical sinks and surface deposition probably overcompensated chemical production, and the vertical ozone distribution was governed by boundary-layer dynamics. In the March episode, the results suggest that ozone-rich air parcels, probably of stratospheric or upper tropospheric origin, were advected aloft the boundary layer on the Swiss Plateau.

Key words. Atmospheric composition and structure (pollution – urban and regional; troposphere – composition and  chemistry – Meteorology and atmospheric dynamics (mesoscale meteorology

High-Power 365 nm UV LED Mercury Arc Lamp Replacement for Photochemistry and Chemical Photolithography.

Science.gov (United States)

Hölz, K; Lietard, J; Somoza, M M

2017-01-03

Ultraviolet light emitting diodes (UV LEDs) have become widespread in chemical research as highly efficient light sources for photochemistry and photopolymerization. However, in more complex experimental setups requiring highly concentrated light and highly spatially resolved patterning of the light, high-pressure mercury arc lamps are still widely used because they emit intense UV light from a compact arc volume that can be efficiently coupled into optical systems. Advances in the deposition and p -type doping of gallium nitride have recently permitted the manufacture of UV LEDs capable of replacing mercury arc lamps also in these applications. These UV LEDs exceed the spectral radiance of mercury lamps even at the intense I-line at 365 nm. Here we present the successful exchange of a high-pressure mercury arc lamp for a new generation UV LED as a light source in photolithographic chemistry and its use in the fabrication of high-density DNA microarrays. We show that the improved light radiance and efficiency of these LEDs offer substantial practical, economic and ecological advantages, including faster synthesis, lower hardware costs, very long lifetime, an >85-fold reduction in electricity consumption and the elimination of mercury waste and contamination.

Innovative nuclear thermal propulsion technology evaluation: Results of the NASA/DOE Task Team study

International Nuclear Information System (INIS)

Howe, S.; Borowski, S.; Helms, I.; Diaz, N.; Anghaie, S.; Latham, T.

1991-01-01

In response to findings from two NASA/DOE nuclear propulsion workshops held in the summer of 1990, six task teams were formed to continue evaluation of various nuclear propulsion concepts. The Task Team on Nuclear Thermal Propulsion (NTP) created the Innovative Concepts Subpanel to evaluate thermal propulsion concepts which did not utilize solid fuel. The Subpanel endeavored to evaluate each of the concepts on a ''level technological playing field,'' and to identify critical technologies, issues, and early proof-of-concept experiments. The concepts included the liquid core fission, the gas core fission, the fission foil reactors, explosively driven systems, fusion, and antimatter. The results of the studies by the panel will be provided. 13 refs., 6 figs., 2 tabs

High resolution inner-shell spectroscopies of atoms and molecules in gas phase using the soft x-ray photochemistry beamline at SPring-8

International Nuclear Information System (INIS)

Ueda, Kiyoshi

2003-01-01

This article describes recent activities on inner-shell spectroscopies of atoms and molecules on beamline 27SU, nicknamed soft X-ray photochemistry beamline, at SPring-8, an 8-GeV synchrotron radiation facility in Japan. This beamline provides linearly polarized monochromatic soft X-rays at the resolution higher than 10,000. The end station is designed so that one can perform various kinds of excitation and de-excitation spectroscopies as well as coincidence spectroscopies. Following the description of the beamline and the end station, we present recent results for inner-shell spectroscopies on Ne, CO 2 , BF 3 , and CF 4 . Emphasis is given to illustrate the strategy of the research on this beamline and performance of the beamline and the end station. (author)

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-).

Science.gov (United States)

Yempally, Veeranna; Moncho, Salvador; Hasanayn, Faraj; Fan, Wai Yip; Brothers, Edward N; Bengali, Ashfaq A

2017-09-18

The photochemistry of two Mn(bpy)(CO) 3 X complexes (X = PhCC - , Br - ) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO) 2 ] affords the ionic complex [1-(MeCN) 2 ]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br - . Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

How Glassy States Affect Brown Carbon Production?

Science.gov (United States)

Liu, P.; Li, Y.; Wang, Y.; Bateman, A. P.; Zhang, Y.; Gong, Z.; Gilles, M. K.; Martin, S. T.

2015-12-01

Secondary organic material (SOM) can become light-absorbing (i.e. brown carbon) via multiphase reactions with nitrogen-containing species such as ammonia and amines. The physical states of SOM, however, potentially slow the diffusion of reactant molecules in organic matrix under conditions that semisolids or solids prevail, thus inhibiting the browning reaction pathways. In this study, the physical states and the in-particle diffusivity were investigated by measuring the evaporation kinetics of both water and organics from aromatic-derived SOMs using a quartz-crystal-microbalance (QCM). The results indicate that the SOMs derived from aromatic precursors toluene and m-xylene became solid (glassy) and the in particle diffusion was significantly impeded for sufficiently low relative humidity ( toluene-derived SOM after ammonia exposure at varied RHs. The results suggest that the production of light-absorbing nitrogen-containing compounds from multiphase reactions with ammonia was kinetically limited in the glassy organic matrix, which otherwise produce brown carbon. The results of this study have significant implications for production and optical properties of brown carbon in urban atmospheres that ultimately influence the climate and tropospheric photochemistry.

The photochemistry of pyrimidine in realistic astrophysical ices and the production of nucleobases

International Nuclear Information System (INIS)

Nuevo, Michel; Materese, Christopher K.; Sandford, Scott A.

2014-01-01

Nucleobases, together with deoxyribose/ribose and phosphoric acid, are the building blocks of DNA and RNA for all known life. The presence of nucleobase-like compounds in carbonaceous chondrites delivered to the Earth raises the question of an extraterrestrial origin for the molecules that triggered life on our planet. Whether these molecules are formed in interstellar/protostellar environments, in small parent bodies in the solar system, or both, is currently unclear. Recent experiments show that the UV irradiation of pyrimidine (C 4 H 4 N 2 ) in H 2 O-rich ice mixtures that contain NH 3 , CH 3 OH, or CH 4 leads to the formation of the pyrimidine-based nucleobases uracil, cytosine, and thymine. In this work, we discuss the low-temperature UV irradiation of pyrimidine in realistic astrophysical ice mixtures containing H 2 O, CH 3 OH, and NH 3 , with or without CH 4 , to search for the production of nucleobases and other prebiotic compounds. These experiments show the presence of uracil, urea, glycerol, hexamethylenetetramine, small amino acids, and small carboxylic acids in all samples. Cytosine was only found in one sample produced from ices irradiated with a higher UV dose, while thymine was not found in any sample, even after irradiation with a higher UV dose. Results are discussed to evaluate the role of the photochemistry of pyrimidine in the inventory of organic molecules detected in meteorites and their astrophysical/astrobiological implications.

A theoretical investigation of valence and Rydberg electronic states of acrolein

International Nuclear Information System (INIS)

Aquilante, Francesco; Barone, Vincenzo; Roos, Bjoern O.

2003-01-01

The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3 (ππ*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the α,β-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined discrete/continuum approach based on the so called polarizable continuum model. The experimental trends are well reproduced by this approach and a closer degeneracy in the triplet manifold has been detected in solution with respect to gas phase

Committee on Interagency Radiation Research and Policy Coordination 10th anniversary report

International Nuclear Information System (INIS)

1994-06-01

Ten years ago, on April 9, 1984, the Science Advisor to the President, and Director of the Office of Science and Technology Policy, established the Committee on Interagency Radiation Research and Policy Coordination (CIRRPC) to meet the need for an interagency committee to address Congressionally mandated and agency-identified issues related to radiation research and policy. CIRRPC replaced the Committee on Interagency Radiation Policy, a committee of the Federal Coordinating Council for Science, Engineering and Technology, and assumed the responsibilities of the Interagency Radiation Research Committee and the Radiation Policy Council, whose charters had expired. Since then, CIRRPC has been recognized as an effective and respected mechanism for coordinating radiation policy among Federal agencies and as an efficient coordinator and evaluator of Federal efforts on designated radiation research projects. In the last 10 years, CIRRPC has established various Policy and Science Subpanels to undertake the oftentimes difficult task of resolving and coordinating agency policies and responses to issues dealing with radiation. These subpanels addressed such issues as the metrication of radiation units, the policy impact of the radioepidemiological tables, naturally occurring and accelerator-produced radioactive materials, radon protection and health effects, predisaster planning for human health effects research, and ionizing radiation risk assessment. These subpanels and their work represent CIRRPC's continuing effort to seek a common position on issues of national significance and interest

Interfacial photochemistry of biogenic surfactants: a major source of abiotic volatile organic compounds.

Science.gov (United States)

Brüggemann, Martin; Hayeck, Nathalie; Bonnineau, Chloé; Pesce, Stéphane; Alpert, Peter A; Perrier, Sébastien; Zuth, Christoph; Hoffmann, Thorsten; Chen, Jianmin; George, Christian

2017-08-24

Films of biogenic compounds exposed to the atmosphere are ubiquitously found on the surfaces of cloud droplets, aerosol particles, buildings, plants, soils and the ocean. These air/water interfaces host countless amphiphilic compounds concentrated there with respect to in bulk water, leading to a unique chemical environment. Here, photochemical processes at the air/water interface of biofilm-containing solutions were studied, demonstrating abiotic VOC production from authentic biogenic surfactants under ambient conditions. Using a combination of online-APCI-HRMS and PTR-ToF-MS, unsaturated and functionalized VOCs were identified and quantified, giving emission fluxes comparable to previous field and laboratory observations. Interestingly, VOC fluxes increased with the decay of microbial cells in the samples, indicating that cell lysis due to cell death was the main source for surfactants and VOC production. In particular, irradiation of samples containing solely biofilm cells without matrix components exhibited the strongest VOC production upon irradiation. In agreement with previous studies, LC-MS measurements of the liquid phase suggested the presence of fatty acids and known photosensitizers, possibly inducing the observed VOC production via peroxy radical chemistry. Up to now, such VOC emissions were directly accounted to high biological activity in surface waters. However, the results obtained suggest that abiotic photochemistry can lead to similar emissions into the atmosphere, especially in less biologically-active regions. Furthermore, chamber experiments suggest that oxidation (O 3 /OH radicals) of the photochemically-produced VOCs leads to aerosol formation and growth, possibly affecting atmospheric chemistry and climate-related processes, such as cloud formation or the Earth's radiation budget.

Aerosol effects on the photochemistry in Mexico City during MCMA-2006/MILAGRO campaign

Directory of Open Access Journals (Sweden)

G. Li

2011-06-01

Full Text Available In the present study, the impact of aerosols on the photochemistry in Mexico City is evaluated using the WRF-CHEM model for the period from 24 to 29 March during the MCMA-2006/MILAGRO campaign. An aerosol radiative module has been developed with detailed consideration of aerosol size, composition, and mixing. The module has been coupled into the WRF-CHEM model to calculate the aerosol optical properties, including optical depth, single scattering albedo, and asymmetry factor. Calculated aerosol optical properties are in good agreement with the surface observations and aircraft and satellite measurements during daytime. In general, the photolysis rates are reduced due to the absorption by carbonaceous aerosols, particularly in the early morning and late afternoon hours with a long aerosol optical path. However, with the growth of aerosol particles and the decrease of the solar zenith angle around noontime, aerosols can slightly enhance photolysis rates when ultraviolet (UV radiation scattering dominates UV absorption by aerosols at the lower-most model layer. The changes in photolysis rates due to aerosols lead to about 2–17 % surface ozone reduction during daytime in the urban area in Mexico City with generally larger reductions during early morning hours near the city center, resulting in a decrease of OH level by about 9 %, as well as a decrease in the daytime concentrations of nitrate and secondary organic aerosols by 5–6 % on average. In addition, the rapid aging of black carbon aerosols and the enhanced absorption of UV radiation by organic aerosols contribute substantially to the reduction of photolysis rates.

Very large hadron collider (VLHC)

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-09-01

A VLHC informal study group started to come together at Fermilab in the fall of 1995 and at the 1996 Snowmass Study the parameters of this machine took form. The VLHC as now conceived would be a 100 TeV hadron collider. It would use the Fermilab Main Injector (now nearing completion) to inject protons at 150 GeV into a new 3 TeV Booster and then into a superconducting pp collider ring producing 100 TeV c.m. interactions. A luminosity of {approximately}10{sup 34} cm{sup -2}s{sup -1} is planned. Our plans were presented to the Subpanel on the Planning for the Future of US High- Energy Physics (the successor to the Drell committee) and in February 1998 their report stated ``The Subpanel recommends an expanded program of R&D on cost reduction strategies, enabling technologies, and accelerator physics issues for a VLHC. These efforts should be coordinated across laboratory and university groups with the aim of identifying design concepts for an economically and technically viable facility`` The coordination has been started with the inclusion of physicists from Brookhaven National Laboratory (BNL), Lawrence Berkeley National Laboratory (LBNL), and Cornell University. Clearly, this collaboration must expanded internationally as well as nationally. The phrase ``economically and technically viable facility`` presents the real challenge.

Photosystem II photochemistry and phycobiliprotein of the red algae Kappaphycus alvarezii and their implications for light adaptation.

Science.gov (United States)

Guan, Xiangyu; Wang, Jinfeng; Zhu, Jianyi; Yao, Chunyan; Liu, Jianguo; Qin, Song; Jiang, Peng

2013-01-01

Photosystem II photochemistry and phycobiliprotein (PBP) genes of red algae Kappaphycus alvarezii, raw material of κ -carrageenan used in food and pharmaceutical industries, were analyzed in this study. Minimum saturating irradiance (I k) of this algal species was less than 115 μmol m(-2) s(-1). Its actual PSII efficiency (yield II) increased when light intensity enhanced and decreased when light intensity reached 200 μmol m(-2) s(-1). Under dim light, yield II declined at first and then increased on the fourth day. Under high light, yield II retained a stable value. These results indicate that K. alvarezii is a low-light-adapted species but possesses regulative mechanisms in response to both excessive and deficient light. Based on the PBP gene sequences, K. alvarezii, together with other red algae, assembled faster and showed a closer relationship with LL-Prochlorococcus compared to HL-Prochlorococcus. Many amino acid loci in PBP sequences of K. alvarezii were conserved with those of LL-Prochlorococcus. However, loci conserved with HL-Prochlorococcus but divergent with LL-Prochlorococcus were also found. The diversities of PE and PC are proposed to have played some roles during the algal evolution and divergence of light adaption.

Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical Spectroscopy

Science.gov (United States)

McKay, Adam; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Bonev, Boncho; Vervack, Ronald; Gibb, Erika; Roth, Nathan; Kawakita, Hideyo

2018-01-01

Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC'S) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.

Bottom-up excited state dynamics of two cinnamate-based sunscreen filter molecules.

Science.gov (United States)

Peperstraete, Yoann; Staniforth, Michael; Baker, Lewis A; Rodrigues, Natércia D N; Cole-Filipiak, Neil C; Quan, Wen-Dong; Stavros, Vasilios G

2016-10-12

Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2-ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC's and E-EHMC's excited state dynamics upon UV-B photoexcitation to the S 1 (1 1 ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies suggest that the excited state dynamics are driven by non-radiative decay from the 1 1 ππ* to the S 3 (1 1 nπ*) state, followed by de-excitation from the 1 1 nπ* to the ground electronic state (S 0 ). Using both a non-polar-aprotic solvent, cyclohexane, and a polar-protic solvent, methanol, we investigated E-MMC and E-EHMC's photochemistry in a more realistic, 'closer-to-shelf' environment. A stark change to the excited state dynamics in the gas-phase is observed in the solution-phase suggesting that the dynamics are now driven by efficient E/Z isomerisation from the initially photoexcited 1 1 ππ* state to S 0 .

Space Nuclear Thermal Propulsion Test Facilities Subpanel. Final report

International Nuclear Information System (INIS)

Allen, G.C.; Warren, J.W.; Martinell, J.; Clark, J.S.; Perkins, D.

1993-04-01

On 20 Jul. 1989, in commemoration of the 20th anniversary of the Apollo 11 lunar landing, President George Bush proclaimed his vision for manned space exploration. He stated, 'First for the coming decade, for the 1990's, Space Station Freedom, the next critical step in our space endeavors. And next, for the new century, back to the Moon. Back to the future. And this time, back to stay. And then, a journey into tomorrow, a journey to another planet, a manned mission to Mars.' On 2 Nov. 1989, the President approved a national space policy reaffirming the long range goal of the civil space program: to 'expand human presence and activity beyond Earth orbit into the solar system.' And on 11 May 1990, he specified the goal of landing Astronauts on Mars by 2019, the 50th anniversary of man's first steps on the Moon. To safely and ever permanently venture beyond near Earth environment as charged by the President, mankind must bring to bear extensive new technologies. These include heavy lift launch capability from Earth to low-Earth orbit, automated space rendezvous and docking of large masses, zero gravity countermeasures, and closed loop life support systems. One technology enhancing, and perhaps enabling, the piloted Mars missions is nuclear propulsion, with great benefits over chemical propulsion. Asserting the potential benefits of nuclear propulsion, NASA has sponsored workshops in Nuclear Electric Propulsion and Nuclear Thermal Propulsion and has initiated a tri-agency planning process to ensure that appropriate resources are engaged to meet this exciting technical challenge. At the core of this planning process, NASA, DOE, and DOD established six Nuclear Propulsion Technical Panels in 1991 to provide groundwork for a possible tri-agency Nuclear Propulsion Program and to address the President's vision by advocating an aggressive program in nuclear propulsion. To this end the Nuclear Electric Propulsion Technology Panel has focused it energies

Interactive Photochemistry in Earth System Models to Assess Uncertainty in Ozone and Greenhouse Gases. Final report

Energy Technology Data Exchange (ETDEWEB)

Prather, Michael J. [Univ. of California, Irvine, CA (United States); Hsu, Juno [Univ. of California, Irvine, CA (United States); Nicolau, Alex [Univ. of California, Irvine, CA (United States); Veidenbaum, Alex [Univ. of California, Irvine, CA (United States); Smith, Philip Cameron [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bergmann, Dan [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2014-11-07

Atmospheric chemistry controls the abundances and hence climate forcing of important greenhouse gases including N₂O, CH₄, HFCs, CFCs, and O₃. Attributing climate change to human activities requires, at a minimum, accurate models of the chemistry and circulation of the atmosphere that relate emissions to abundances. This DOE-funded research provided realistic, yet computationally optimized and affordable, photochemical modules to the Community Earth System Model (CESM) that augment the CESM capability to explore the uncertainty in future stratospheric-tropospheric ozone, stratospheric circulation, and thus the lifetimes of chemically controlled greenhouse gases from climate simulations. To this end, we have successfully implemented Fast-J (radiation algorithm determining key chemical photolysis rates) and Linoz v3.0 (linearized photochemistry for interactive O₃, N₂O, NO_y and CH₄) packages in LLNL-CESM and for the first time demonstrated how change in O2 photolysis rate within its uncertainty range can significantly impact on the stratospheric climate and ozone abundances. From the UCI side, this proposal also helped LLNL develop a CAM-Superfast Chemistry model that was implemented for the IPCC AR5 and contributed chemical-climate simulations to CMIP5.

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

Science.gov (United States)

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.

DFS-88, 1988 Tri-Service Data Fusion Symposium. Volume I - Technical Proceedings, Johns Hopkins University, Applied Physics Laboratory, Laurel, Maryland, 17 - 19 May 1988

National Research Council Canada - National Science Library

1988-01-01

The 1988 Tri-Service Data Fusion Symposium (DFS-88) was held at Laurel, Maryland on 17-19 May 1988 under the joint sponsorship of the Data Fusion Sub-Panel of the Joint Directors of Laboratories (JDL/DFSP...

Photochemistry of acrylates at 222 nm

International Nuclear Information System (INIS)

Knolle, Wolfgang; Naumov, Sergej; Madani, Mohamed; Sonntag, Clemens von

2005-01-01

Excimer lamps as monochromatic UV sources with an intense short-wavelength emission (especially KrCl * , 222 nm) allow a photoinitiator-free initiation of the acrylate polymerisation. Laser photolysis (KrCl * excimer laser, pulse width 20 ns, up to 5 mJ per pulse) gives rise to similar transient spectra (λ max ∼ 280 nm) for all acrylates studied. As the rather unspecific spectra do not allow conclusions as to the main reaction channel, a product study has been performed by GC-MS following steady-state photolysis of acrylate solutions in acetonitrile, methanol and n-hexane. Somewhat unexpected, α-cleavage seems to be a main reaction channel, and quantum chemical calculations show that such a reaction can occur from either the excited singlet state or the unrelaxed triplet state, but not from the relaxed triplet state that is observed spectroscopically. A reaction scheme accounting for the observed products is presented

VISIBLE LIGHT INDUCED PHOTOCATALYTIC DEGRADATION OF ...

African Journals Online (AJOL)

a

Solar Energy and Photochemistry Laboratory, Department of Chemistry, University College ..... singlet state which then undergo intersystem crossing to their triplet state. ... are removed by the dissolved molecular oxygen to produce superoxide.

Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

KAUST Repository

Snellenburg, Joris J.; Laptenok, Sergey P.; DeSa, Richard J.; Naumov, Pance; Solntsev, Kyril M.

2016-01-01

The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

KAUST Repository

Snellenburg, Joris J.

2016-11-23

The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

Materials irradiation subpanel report to BESAC neutron sources and research panel

International Nuclear Information System (INIS)

Birtcher, R.C.; Goland, A.N.; Lott, R.

1992-01-01

The future success of the nuclear power option in the US (fission and fusion) depends critically on the continued existence of a healthy national materials-irradiation program. Consideration of the requirements for acceptable materials-irradiation systems in a new neutron source has led the subcommittee to identify an advanced steady-state reactor (ANS) as a better choice than a spallation neutron source. However, the subcommittee also hastens to point out that the ANS cannot stand alone as the nation's sole high-flux mixed-spectrum neutron irradiation source in the next century. It must be incorporated in a broader program that includes other currently existing neutron irradiation facilities. Upgrading and continuing support for these facilities must be planned. In particular, serious consideration should be given to converting the HFIR into a dedicated materials test reactor, and long-term support for several university reactors should be established

A Facile Synthesis of Deaza-Analogues of the Bisindole Marine Alkaloid Topsentin

Directory of Open Access Journals (Sweden)

Gianfranco Favi

2013-02-01

Full Text Available A series of substituted ethyl 1-[(tert-butoxycarbonylamino]-2-methyl-5- (1-methyl-1H-indol-3-yl-4-[(1-methyl-1H-indol-3-ylcarbonyl]-1H-pyrrole-3-carboxylates were prepared in excellent yields (82-98% by one-pot reactions between β-dicarbonyl compounds 12a–e and 1,2-diaza-1,3-diene (DD 13. Derivatives 10a,c–e, deazaanalogues of the bis-indole alkaloid topsentin, screened by the National Cancer Institute (Bethesda, MD, USA in the in vitro one dose primary anticancer assay against a panel of about 60 human tumor cell lines, showed no significant activity, with the exception of compound 9e, which showed moderate activity against the HOP-92 cell line of the non small cell lung cancer sub-panel and the SNB-75 cell line of the CNS sub-panel.

Photosystem II Photochemistry and Phycobiliprotein of the Red Algae Kappaphycus alvarezii and Their Implications for Light Adaptation

Directory of Open Access Journals (Sweden)

Xiangyu Guan

2013-01-01

Full Text Available Photosystem II photochemistry and phycobiliprotein (PBP genes of red algae Kappaphycus alvarezii, raw material of κ-carrageenan used in food and pharmaceutical industries, were analyzed in this study. Minimum saturating irradiance (Ik of this algal species was less than 115 μmol m−2 s−1. Its actual PSII efficiency (yield II increased when light intensity enhanced and decreased when light intensity reached 200 μmol m−2 s−1. Under dim light, yield II declined at first and then increased on the fourth day. Under high light, yield II retained a stable value. These results indicate that K. alvarezii is a low-light-adapted species but possesses regulative mechanisms in response to both excessive and deficient light. Based on the PBP gene sequences, K. alvarezii, together with other red algae, assembled faster and showed a closer relationship with LL-Prochlorococcus compared to HL-Prochlorococcus. Many amino acid loci in PBP sequences of K. alvarezii were conserved with those of LL-Prochlorococcus. However, loci conserved with HL-Prochlorococcus but divergent with LL-Prochlorococcus were also found. The diversities of PE and PC are proposed to have played some roles during the algal evolution and divergence of light adaption.

Synthesis of Superparamagnetic Iron Oxide Nanoparticles Modified with MPEG-PEI via Photochemistry as New MRI Contrast Agent

Directory of Open Access Journals (Sweden)

Yancong Zhang

2015-01-01

Full Text Available Novel method for synthesis of superparamagnetic iron oxide nanoparticles (SPIONs coated with polyethylenimine (PEI and modified with poly(ethylene glycol methyl ether (MPEG, MPEG-PEI-SPIONs, was developed. PEI-SPIONs were successfully prepared in aqueous system via photochemistry, and their surface was modified with poly(ethylene glycol methyl ether (MPEG. The so-obtained MPEG-PEI-SPIONs had a uniform hydrodynamic particle size of 34 nm. The successful coating of MPEG-PEI on the SPIONs was ascertained from FT-IR analysis, and the PEI and MPEG fractions in MPEG-PEI-SPIONs were calculated to account for 31% and 12%, respectively. Magnetic measurement revealed that the saturated magnetization of MPEG-PEI-SPIONs reached 46 emu/g and the nanoparticles showed the characteristic of being superparamagnetic. The stability experiment revealed that the MPEG-PEI modification improved the nanoparticles stability greatly. T2 relaxation measurements showed that MPEG-PEI-SPIONs show similar R2 value to the PEI-SPIONs. The T2-weighted magnetic resonance imaging (MRI of MPEG-PEI-SPIONs showed that the magnetic resonance signal was enhanced significantly with increasing nanoparticle concentration in water. These results indicated that the MPEG-PEI-SPIONs had great potential for application in MRI.

Physical Chemistry '98: Fourth International Conference on Fundamental and Applied Aspects of Physical Chemistry - Papers

International Nuclear Information System (INIS)

Ribnikar, S.; Anic, S.

1998-01-01

The proceedings has following chapters: Plenary lectures; Chemical Thermodynamics; Spectroscopy, Molecular Structures, Physical Chemistry of Plasma; Kinetics, Catalysis, Nonlinear Dynamics; Electrochemistry; Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry; Solid State Physical Chemistry, Material Science; Macromolecular Physical Chemistry; Environmental Protection; Phase Boundaries; Complex Compounds; General Physical Chemistry. A separated abstract was prepared for each of the 20 papers selected from the three chapters: Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry. and Environmental Protection. Refs and figs

Ultrafast measurements of chlorine dioxide photochemistry

Energy Technology Data Exchange (ETDEWEB)

Ludowise, P.D.

1997-08-01

Time-resolved mass spectrometry and time-resolved photoelectron spectroscopy are used to study the ultrafast photodissociation dynamics of chlorine dioxide, an important constituent in stratospheric ozone depletion. Chapter 1 introduces these pump/probe techniques, in which a femtosecond pump pulse excites a molecule to a dissociative state. At a later time, a second femtosecond probe pulse ionizes the molecule. The resulting mass and photoelectron spectra are acquired as a function of the delay between the pump and probe pulses, which follows the evolution of the molecule on the excited state. A comparison to other techniques used to study reaction dynamics is discussed. Chapter 2 includes a detailed description of the design and construction of the experimental apparatus, which consists of a femtosecond laser system, a molecular beam time-of-flight spectrometer, and a data acquisition system. The time-of-flight spectrometer is specifically designed to have a short flight distance to maximize the photoelectron collection efficiency without degrading the resolution, which is limited by the bandwidth of the femtosecond laser system. Typical performance of the apparatus is demonstrated in a study of the time-resolved photoelectron spectroscopy of nitric oxide. The results of the time-resolved mass spectrometry experiments of chlorine dioxide are presented in Chapter 3. Upon excitation to the A {sup 2}A{sub 2} state near 3.2 eV, the molecule dissociates through an indirect two-step mechanism. The direct dissociation channel has been predicted to be open, but is not observed. A quantum beat is observed in the OClO{sup +} species, which is described as a vibrational coherence of the optically prepared A {sup 2}A{sub 2} state. Chapter 4 presents the results of the time-resolved photoelectron experiments of chlorine dioxide. At short delay time, the quantum beat of the OClO{sup +} species is observed in the X {sup 1}A{sub 1} state of the ion. At infinite delay, the signal

Photochemistry, mixing and transport in Jupiter's stratosphere constrained by Cassini

Science.gov (United States)

Hue, V.; Hersant, F.; Cavalié, T.; Dobrijevic, M.; Sinclair, J. A.

2018-06-01

In this work, we aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere, using Cassini/CIRS observations published by Nixon et al. (2007,2010). The Cassini-Huygens flyby of Jupiter on December 2000 provided the highest spatially resolved IR observations of Jupiter so far, with the CIRS instrument. The IR spectrum contains the fingerprints of several atmospheric constituents and allows probing the tropospheric and stratospheric composition. In particular, the abundances of C2H2 and C2H6, the main compounds produced by methane photochemistry, can be retrieved as a function of latitude in the pressure range at which CIRS is sensitive to. CIRS observations suggest a very different meridional distribution for these two species. This is difficult to reconcile with their photochemical histories, which are thought to be tightly coupled to the methane photolysis. While the overall abundance of C2H2 decreases with latitude, C2H6 becomes more abundant at high latitudes. In this work, a new 2D (latitude-altitude) seasonal photochemical model of Jupiter is developed. The model is used to investigate whether the addition of stratospheric transport processes, such as meridional diffusion and advection, are able to explain the latitudinal behavior of C2H2 and C2H6. We find that the C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, at the cost of a degradation of the fit to the C2H2 distribution. However, meridional diffusion alone cannot produce the observed increase with latitude of the C2H6 abundance. When adding 2D advective transport between roughly 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can, for the first time, reproduce the C2H6 abundance increase with latitude. In parallel, the fit to the C2H2 distribution is

Tuning Stilbene Photochemistry by Fluorination: State Reordering Leads to Sudden Polarization near the Franck-Condon Region.

Science.gov (United States)

Ioffe, Ilya N; Quick, Martin; Quick, Michael T; Dobryakov, Alexander L; Richter, Celin; Granovsky, Alex A; Berndt, Falko; Mahrwald, Rainer; Ernsting, Nikolaus P; Kovalenko, Sergey A

2017-10-25

Spontaneous polarization of a nonpolar molecule upon photoexcitation (the sudden polarization effect) earlier discussed for 90°-twisted alkenes is observed and calculated for planar ring-fluorinated stilbenes, trans-2,3,5,6,2',3',5',6'-octofluorostilbene (tF2356) and trans-2,3,4,5,6,2',3',4',5',6'-decafluorostilbene (tF23456). Due to the fluorination, Franck-Condon states S 1 FC and S 2 FC are dominated by the quasi-degenerate HOMO-1 → LUMO and HOMO-2 → LUMO excitations, while their interaction gives rise to a symmetry-broken zwitterionic S 1 state. After optical excitation of tF2356, one observes an ultrafast (∼0.06 ps) evolution that reflects relaxation from initial nonpolar S 3 FC to long-lived (1.3 ns in n-hexane and 3.4 ns in acetonitrile) polar S 1 . The polarity of S 1 is evidenced by a solvatochromic shift of its fluorescence band. The experimental results provide a sensitive test for quantum-chemical calculations. In particular, our calculations agree with the experiment, and raise concerns about the applicability of the common TDDFT approach to relatively simple stilbenic systems.

Air emissions in France. Metropolitan area substances implied in acidification, eutrophication and photochemistry; Emissions dans l'air en France. Metropole substances impliquees dans les phenomenes d'acidification, d'eutrophisation et de photochimie

Energy Technology Data Exchange (ETDEWEB)

NONE

2002-04-01

Acidification, eutrophication and photochemistry: SO{sub 2}, NO{sub x}, NH{sub 3}, NMVOCs (total and speciation relating to more than 200 different compounds), CO, acid equivalent index (Aeq) and photochemical ozone creation potential (POCP) are presented. Density ratios relating to population, area, gross product, primary energy consumption, etc. Emissions are presented by the mean of charts for each substance and the main source categories with a five years step until 1990 then yearly beyond. Dates corresponding to the maximum and minimum values are also included. (author)

Genomic prediction applied to high-biomass sorghum for bioenergy production.

Science.gov (United States)

de Oliveira, Amanda Avelar; Pastina, Maria Marta; de Souza, Vander Filipe; da Costa Parrella, Rafael Augusto; Noda, Roberto Willians; Simeone, Maria Lúcia Ferreira; Schaffert, Robert Eugene; de Magalhães, Jurandir Vieira; Damasceno, Cynthia Maria Borges; Margarido, Gabriel Rodrigues Alves

2018-01-01

The increasing cost of energy and finite oil and gas reserves have created a need to develop alternative fuels from renewable sources. Due to its abiotic stress tolerance and annual cultivation, high-biomass sorghum ( Sorghum bicolor L. Moench) shows potential as a bioenergy crop. Genomic selection is a useful tool for accelerating genetic gains and could restructure plant breeding programs by enabling early selection and reducing breeding cycle duration. This work aimed at predicting breeding values via genomic selection models for 200 sorghum genotypes comprising landrace accessions and breeding lines from biomass and saccharine groups. These genotypes were divided into two sub-panels, according to breeding purpose. We evaluated the following phenotypic biomass traits: days to flowering, plant height, fresh and dry matter yield, and fiber, cellulose, hemicellulose, and lignin proportions. Genotyping by sequencing yielded more than 258,000 single-nucleotide polymorphism markers, which revealed population structure between subpanels. We then fitted and compared genomic selection models BayesA, BayesB, BayesCπ, BayesLasso, Bayes Ridge Regression and random regression best linear unbiased predictor. The resulting predictive abilities varied little between the different models, but substantially between traits. Different scenarios of prediction showed the potential of using genomic selection results between sub-panels and years, although the genotype by environment interaction negatively affected accuracies. Functional enrichment analyses performed with the marker-predicted effects suggested several interesting associations, with potential for revealing biological processes relevant to the studied quantitative traits. This work shows that genomic selection can be successfully applied in biomass sorghum breeding programs.

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes.

Science.gov (United States)

Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

2015-09-15

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. Copyright © 2015. Published by Elsevier B.V.

Untitled

Indian Academy of Sciences (India)

Keywords. Organic solid state; topochemistry; crystal engineering; x-ray crystallography; molecular complexes; photochemistry; atom-atom potentials; solid state tautomerism; intercalation. 1. Introduction. How do organic molecules organise themselves in crystals? Can one predict the crystal structure of an organic solid?

Research opportunities in photochemical sciences

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-07-01

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

77 FR 58981 - Fisheries of the South Atlantic and Gulf of Mexico; South Atlantic Fishery Management Council...

Science.gov (United States)

2012-09-25

... (NOAA), Commerce. ACTION: Notice of public meeting. SUMMARY: The SAFMC will hold a meeting of its Social... DEPARTMENT OF COMMERCE National Oceanic and Atmospheric Administration RIN 0648-XC181 Fisheries [email protected] . SUPPLEMENTARY INFORMATION: The SAFMC SEP is a sub-panel that addresses social and economic...

The triplet excited state of Bodipy: formation, modulation and application.

Science.gov (United States)

Zhao, Jianzhang; Xu, Kejing; Yang, Wenbo; Wang, Zhijia; Zhong, Fangfang

2015-12-21

Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were

The U.S. Magnet Development Program Plan

CERN Document Server

Gourlay, Stephen; Zlobin, Alexander; Cooley, Lance; Larbalestier, David

2016-01-01

The 2014 Particle Physics Project Prioritization Panel (P5) Report identified a critical need for transformational high field magnet R&D focused on substantially increasing performance and lowering the cost per T-m. This need was subsequently reiterated in the HEPAP* Accelerator R&D subpanel report. In response, the DOE Office of High Energy Physics has initiated an ambitious program, coordinated by LBNL (see Appendix A), to aggressively pursue the development of superconducting accelerator magnets that operate as closely as possible to the fundamental limits of superconducting materials and at the same time minimize or eliminate magnet training. The U.S. Magnet Development Program (MDP) is based on four goals that summarize the P5 and Subpanel recommendations. These goals will be achieved by focusing on high field dipole development along four elements. The first element aims at the establishment of a baseline design to demonstrate feasibility of 16 T magnets and the development of higher risk innova...

Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices

Science.gov (United States)

Araujo-Andrade, C.; Giuliano, B. M.; Gómez-Zavaglia, A.; Fausto, R.

2012-11-01

In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the Cdbnd N bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-Cdbnd N and Cdbnd N-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (Ndbnd C)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.

Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States

Directory of Open Access Journals (Sweden)

R. Sommariva

2011-07-01

Full Text Available Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM. The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60 % for all species, except acetic acid.

The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28 % and i-propanol (<15 % and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK is mostly produced from the oxidation of n-butane (20–30 % and 3-methylpentane (<40 %. Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23 % and 5–25 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.

Exogenous Calcium Enhances the Photosystem II Photochemistry Response in Salt Stressed Tall Fescue.

Science.gov (United States)

Wang, Guangyang; Bi, Aoyue; Amombo, Erick; Li, Huiying; Zhang, Liang; Cheng, Cheng; Hu, Tao; Fu, Jinmin

2017-01-01

Calcium enhances turfgrass response to salt stress. However, little is known about PSII photochemical changes when exogenous calcium was applied in salinity-stressed turfgrass. Here, we probe into the rearrangements of PSII electron transport and endogenous ion accumulation in tall fescue ( Festuca arundinacea Schreber) treated with exogenous calcium under salt stress. Three-month-old seedlings of genotype "TF133" were subjected to the control (CK), salinity (S), salinity + calcium nitrate (SC), and salinity + ethylene glycol tetraacetic acid (SE). Calcium nitrate and ethylene glycol tetraacetic acid was used as exogenous calcium donor and calcium chelating agent respectively. At the end of a 5-day duration treatment, samples in SC regime had better photochemistry performance on several parameters than salinity only. Such as the Area (equal to the plastoquinone pool size), N (number of [Formula: see text] redox turnovers until F m is reached), ψE 0 , or δRo (Efficiencdy/probability with which a PSII trapped electron is transferred from Q A to Q B or PSI acceptors), ABS/RC (Absorbed photon flux per RC). All the above suggested that calcium enhanced the electron transfer of PSII (especially beyond [Formula: see text]) and prevented reaction centers from inactivation in salt-stressed tall fescue. Furthermore, both grass shoot and root tissues generally accumulated more C, N, Ca 2+ , and K + in the SC regime than S regime. Interrelated analysis indicated that ψE 0 , δRo, ABS/RC, C, and N content in shoots was highly correlated to each other and significantly positively related to Ca 2+ and K + content in roots. Besides, high salt increased ATP6E and CAMK2 transcription level in shoot at 1 and 5 day, respectively while exogenous calcium relieved it. In root, CAMK2 level was reduced by Salinity at 5 day and exogenous calcium recovered it. These observations involved in electron transport capacity and ion accumulation assist in understanding better the protective role

Exogenous Calcium Enhances the Photosystem II Photochemistry Response in Salt Stressed Tall Fescue

Directory of Open Access Journals (Sweden)

Guangyang Wang

2017-11-01

Full Text Available Calcium enhances turfgrass response to salt stress. However, little is known about PSII photochemical changes when exogenous calcium was applied in salinity-stressed turfgrass. Here, we probe into the rearrangements of PSII electron transport and endogenous ion accumulation in tall fescue (Festuca arundinacea Schreber treated with exogenous calcium under salt stress. Three-month-old seedlings of genotype “TF133” were subjected to the control (CK, salinity (S, salinity + calcium nitrate (SC, and salinity + ethylene glycol tetraacetic acid (SE. Calcium nitrate and ethylene glycol tetraacetic acid was used as exogenous calcium donor and calcium chelating agent respectively. At the end of a 5-day duration treatment, samples in SC regime had better photochemistry performance on several parameters than salinity only. Such as the Area (equal to the plastoquinone pool size, N (number of QA- redox turnovers until Fm is reached, ψE0, or δRo (Efficiencdy/probability with which a PSII trapped electron is transferred from QA to QB or PSI acceptors, ABS/RC (Absorbed photon flux per RC. All the above suggested that calcium enhanced the electron transfer of PSII (especially beyond QA- and prevented reaction centers from inactivation in salt-stressed tall fescue. Furthermore, both grass shoot and root tissues generally accumulated more C, N, Ca2+, and K+ in the SC regime than S regime. Interrelated analysis indicated that ψE0, δRo, ABS/RC, C, and N content in shoots was highly correlated to each other and significantly positively related to Ca2+ and K+ content in roots. Besides, high salt increased ATP6E and CAMK2 transcription level in shoot at 1 and 5 day, respectively while exogenous calcium relieved it. In root, CAMK2 level was reduced by Salinity at 5 day and exogenous calcium recovered it. These observations involved in electron transport capacity and ion accumulation assist in understanding better the protective role of exogenous calcium in tall

Structure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argon

Science.gov (United States)

Ismael, A.; Borba, A.; Duarte, L.; Giuliano, B. M.; Gómez-Zavaglia, A.; Cristiano, M. L. S.

2012-10-01

A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(3df,3pd) study of the novel synthesised tetrazole-saccharyl conjugate 2-[1-(1H-tetrazol-5-yl)ethyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide [1-TE-BZT] was performed. In the gas phase, at room temperature, the compound exists as a mixture of six isomeric forms (four conformers of 1H tautomer and two conformers of 2H tautomer). According to theoretical calculations, conformers 1H were the most stable and the relative energies among the three most stable forms are lower than 4 kJ mol-1. These conformers benefit from stabilising intramolecular hydrogen bonds-like interactions involving the 1H of the tetrazole ring and the carbonyl oxygen of the saccharyl moiety. The photochemistry of 1-TE-BZT in solid argon was investigated and theoretical DFT/B3LYP/6-311++G(3df,3pd) calculations also helped in assignment of the experimental bands. A quick consumption of the compound occurred after irradiation of the matrix with UV laser light at λ = 275 nm. Three photofragmentation pathways were proposed, one leading to 2-[1-(1H-diaziren-3-yl)ethyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide and molecular nitrogen, a second one giving 2-(1,1-dioxide-3-oxo-1,2-benzisothiazol-2(3H)-yl)propanenitrile and azide, and a third one involving loss of azide from the tetrazole ring and decarbonylation of the saccharyl ring of 1-TE-BZT to give acrylonitrile and 7-thia-8-azabicyclo[4.2.0] octa-1,3,5-triene 7,7 dioxide. The comparison of the relative intensities of the bands of the photoproducts obtained from the three channels allowed us to consider the latter pathway, involving an unprecedented photocleavage of the benzisothiazole (saccharyl) ring, as the preferred photodegradation channel of 1-TE-BZT.

Ultrafast photochemical dissociation of an equatorial CO ligand from trans(X,X)-[Ru(X)(2)(CO)(2)(bpy)] (X = Cl, Br, I): A picosecond time-resolved infrared spectroscopic and DFT computational study

Czech Academy of Sciences Publication Activity Database

Gabrielsson, A.; Záliš, Stanislav; Vlček, Antonín; Matousek, P.; Towrie, M.

-, - (2003), s. 91-93. ISBN 0902376314. ISSN 1358-6254 Institutional research plan: CEZ:AV0Z4040901 Keywords : transition metal complexes * escited state dynamics * charge-transfer photochemistry Subject RIV: CG - Electrochemistry

Response of atmospheric biomarkers to NO(x)-induced photochemistry generated by stellar cosmic rays for earth-like planets in the habitable zone of M dwarf stars.

Science.gov (United States)

Grenfell, John Lee; Grießmeier, Jean-Mathias; von Paris, Philip; Patzer, A Beate C; Lammer, Helmut; Stracke, Barbara; Gebauer, Stefanie; Schreier, Franz; Rauer, Heike

2012-12-01

Understanding whether M dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar cosmic rays to break up atmospheric molecular nitrogen (N(2)), which leads to production of nitrogen oxides (NO(x)) in the planetary atmosphere, hence affecting biomarkers such as ozone (O(3)). We apply a stationary model, that is, without a time dependence; hence we are calculating the limiting case where the atmospheric chemistry response time of the biomarkers is assumed to be slow and remains constant compared with rapid forcing by the impinging stellar flares. This point should be further explored in future work with time-dependent models. We estimate the NO(x) production using an air shower approach and evaluate the implications using a climate-chemical model of the planetary atmosphere. O(3) formation proceeds via the reaction O+O(2)+M→O(3)+M. At high NO(x) abundances, the O atoms arise mainly from NO(2) photolysis, whereas on Earth this occurs via the photolysis of molecular oxygen (O(2)). For the flaring case, O(3) is mainly destroyed via direct titration, NO+O(3)→NO(2)+O(2), and not via the familiar catalytic cycle photochemistry, which occurs on Earth. For scenarios with low O(3), Rayleigh scattering by the main atmospheric gases (O(2), N(2), and CO(2)) became more important for shielding the planetary surface from UV radiation. A major result of this work is that the biomarker O(3) survived all the stellar-activity scenarios considered except for the strong

Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry.

Science.gov (United States)

Hunault, Myrtille O J Y; Khan, Wilayat; Minár, Jan; Kroll, Thomas; Sokaras, Dimosthenis; Zimmermann, Patric; Delgado-Jaime, Mario U; de Groot, Frank M F

2017-09-18

Metal-metal charge transfer (MMCT) is expected to be the main mechanism that enables the harvesting of solar light by iron-titanium oxides for photocatalysis. We have studied FeTiO 3 as a model compound for MMCT with 1s2pRIXS at the Fe K-edge. The high-energy resolution XANES enables distinguishing five pre-edge features. The three first well distinct RIXS features are assigned to electric quadrupole transitions to the localized Fe* 3d states, shifted to lower energy by the 1s core-hole. Crystal field multiplet calculations confirm the speciation of divalent iron. The contribution of electric dipole absorption due to local p-d mixing allowed by the trigonal distortion of the cation site is supported by DFT and CFM calculations. The two other nonlocal features are assigned to electric dipole transitions to excited Fe* 4p states mixed with the neighboring Ti 3d states. The comparison with DFT calculations demonstrates that MMCT in ilmenite is favored by the hybridization between the Fe 4p and delocalized Ti 3d orbitals via the O 2p orbitals.

75 FR 13731 - National Marine Fisheries Service, Pacific Fishery Management Council (Pacific Council); April 9...

Science.gov (United States)

2010-03-23

... am Salmon Technical Team 8 am Scientific and Statistical Committee 8 am Tribal Policy GroupAs Needed... Groundfish Management Team 8 am Salmon Advisory Subpanel 8 am Salmon Technical Team 8 am Tribal Policy Group... am Salmon Technical Team 8 am Ad Hoc Regulatory Deeming Committee As Needed Tribal Policy Group As...

Photoinduced electron transfer involving eosin-tryptophan conjugates. Long-lived radical pair states for systems incorporating aromatic amino acid side chains

Energy Technology Data Exchange (ETDEWEB)

Jones, G. II; Farahat, C.W.; Oh, C. (Boston Univ., MA (United States))

1994-07-14

The electron-transfer photochemistry of the covalent derivatives of the dye eosin, in which the xanthene dye is covalently attached to the amino acid L-tryptophan via the thiohydantoin derivative, the tryptophan dipeptide, and an ethyl ester derivative, has been investigated. The singlet excited state of the dye is significantly quenched on attachment of the aromatic amino acid residue. Dye triplet states are also intercepted through intramolecular interaction of excited dye and amino acid pendants. Flash photolysis experiments verify that this interaction involves electron transfer from the indole side chains of tryptophan. Rate constants for electron transfer are discussed in terms of the distance relationships for the eosin chromophore and aromatic redox sites on peptide derivatives, the pathway for [sigma]-[pi] through-bond interaction between redox sites, and the multiplicity and state of protonation for electron-transfer intermediates. Selected electron-transfer photoreactions were studied under conditions of binding of the peptide derivatives in a high molecular weight, water-soluble, globular polymer, poly(vinyl-2-pyrrolidinone). 28 refs., 4 figs., 1 tab.

Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

Science.gov (United States)

Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

1985-04-01

Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

Das, Dr Suresh

Indian Academy of Sciences (India)

Specialization: Photochemistry, Photoresponsive Materials, Liquid Crystals, Photosensitizing Dyes, Photoluminiscent Materials and Photo-induced Electron Transfer Address: Executive Vice President, Kerala State Council for Science, Technology and, Environment, Sasthra Bhavan, Pattom, Thiruvananthapuram 695 004, ...

3,4,5,6-Tetrafluorophenylnitren-2-yl: a ground-state quartet triradical.

Science.gov (United States)

Grote, Dirk; Finke, Christopher; Kossmann, Simone; Neese, Frank; Sander, Wolfram

2010-04-19

The photochemistry of 2-iodo-3,4,5,6-tetrafluorophenyl azide (7 d) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1 d. Further irradiation with UV or visible light results in mixtures of 1 d with azirine 5 d', ketenimine 6 d', nitreno radical 2 d, and azirinyl radical 9. The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2 d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high-spin molecules. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photosensitization and phototherapy with furocoumarins: A quantum-chemical study

International Nuclear Information System (INIS)

Serrano-Perez, Juan Jose; Serrano-Andres, Luis; Merchan, Manuela

2008-01-01

The effect of electromagnetic radiation on biological objects extends from heating to complex photochemistry, and includes DNA alteration, that properly modified in damaged cells may entail beneficial effects. In this regard, psoralen + UV-A (PUVA) therapy, in which furocoumarins, psoralen-like chromophores, are used as photosensitizers and photoreactants with DNA bases, is one of the most promising strategies against a plethora of diseases. Understanding the underlying photochemical mechanisms is crucial to design effective drugs without undesired side effects. We have undertaken a quantum-mechanical study on the photophysics and photochemistry of furocoumarins, analyzing firstly the most efficient way in which the lowest excited triplet state, as protagonist of the photosensitizing action, is populated from the initially promoted singlet states, and secondly the basics of the formation of furocoumarin-DNA photoadducts

Response of Atmospheric Biomarkers to NOx-Induced Photochemistry Generated by Stellar Cosmic Rays for Earth-like Planets in the Habitable Zone of M Dwarf Stars

Science.gov (United States)

Grießmeier, Jean-Mathias; von Paris, Philip; Patzer, A. Beate C.; Lammer, Helmut; Stracke, Barbara; Gebauer, Stefanie; Schreier, Franz; Rauer, Heike

2012-01-01

Abstract Understanding whether M dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar cosmic rays to break up atmospheric molecular nitrogen (N2), which leads to production of nitrogen oxides (NOx) in the planetary atmosphere, hence affecting biomarkers such as ozone (O3). We apply a stationary model, that is, without a time dependence; hence we are calculating the limiting case where the atmospheric chemistry response time of the biomarkers is assumed to be slow and remains constant compared with rapid forcing by the impinging stellar flares. This point should be further explored in future work with time-dependent models. We estimate the NOx production using an air shower approach and evaluate the implications using a climate-chemical model of the planetary atmosphere. O3 formation proceeds via the reaction O+O2+M→O3+M. At high NOx abundances, the O atoms arise mainly from NO2 photolysis, whereas on Earth this occurs via the photolysis of molecular oxygen (O2). For the flaring case, O3 is mainly destroyed via direct titration, NO+O3→NO2+O2, and not via the familiar catalytic cycle photochemistry, which occurs on Earth. For scenarios with low O3, Rayleigh scattering by the main atmospheric gases (O2, N2, and CO2) became more important for shielding the planetary surface from UV radiation. A major result of this work is that the biomarker O3 survived all the stellar-activity scenarios considered except for the strong case, whereas the biomarker

On Promoting Rigour in Educational Research: The Example of the RAE

Science.gov (United States)

Stronach, Ian

2007-01-01

This article offers a deconstruction of the RAE Education sub-panel's rubrics, drawing also on the broader RAE regulations, procedures, and associated documentation and research. It seeks to tease out the sorts of covert epistemologising that may (or may not) be likely to take place. The theoretical ambition is to take a Derridean approach to acts…

The impact of urban canopy meteorological forcing on summer photochemistry

Science.gov (United States)

Huszár, Peter; Karlický, Jan; Belda, Michal; Halenka, Tomáš; Pišoft, Petr

2018-03-01

The regional climate model RegCM4.4, including the surface model CLM4.5, was offline coupled to the chemistry transport model CAMx version 6.30 in order to investigate the impact of the urban canopy induced meteorological changes on the longterm summer photochemistry over central Europe for the 2001-2005 period. First, the urban canopy impact on the meteorological conditions was calculated performing a reference experiment without urban landsurface considered and an experiment with urban surfaces modeled with the urban parameterization within the CLM4.5 model. In accordance with expectations, strong increases of urban surface temperatures (up to 2-3 K), decreases of wind speed (up to -1 ms-1) and increases of vertical turbulent diffusion coefficient (up to 60-70 m2s-1) were found. For the impact on chemistry, these three components were considered. Additionally, we accounted for the effect of temperature enhanced biogenic emission increase. Several experiments were performed by adding these effects one-by-one to the total impact: i.e., first, only the urban temperature impact was considered driving the chemistry model; secondly, the wind impact was added and so on. We found that the impact on biogenic emission account for minor changes in the concentrations of ozone (O3), oxides of nitrogen NOx = NO + NO2 and nitric acid (HNO3). On the other hand, the dominating component acting is the increased vertical mixing, resulting in up to 5 ppbv increase of urban ozone concentrations while causing -2 to -3 ppbv decreases and around 1 ppbv increases of NOx and HNO3 surface concentrations, respectively. The temperature impact alone results in reduction of ozone, increase in NO, decrease in NO2 and increases of HNO3. The wind impact leads, over urban areas, to ozone decreases, increases of NOx and a slight increase in HNO3. The overall impact is similar to the impact of increased vertical mixing alone. The Process Analysis (PA) technique implemented in CAMx was adopted to

Taking snapshots of photoexcited molecules in disordered media using pulsed synchrotron x-rays

International Nuclear Information System (INIS)

Chen, L.X.

2004-01-01

Photoexcited molecules are quintessential reactants in photochemistry. Structures of these photoexcited molecules in disordered media in which a majority of photochemical reactions take place remained elusive for decades owing to a lack of suitable X-ray sources, despite their importance in understanding fundamental aspects in photochemistry. As new pulsed X-ray sources become available, short-lived excited-state molecular structures in disordered media can now be captured by using laser-pulse pump, X-ray pulse-probe techniques of third-generation synchrotron sources with time resolutions of 30-100 ps, as demonstrated by examples in this review. These studies provide unprecedented information on structural origins of molecular properties in the excited states. By using other ultrafast X-ray facilities that will be completed in the near future, time-resolution for the excited-state structure measurements should reach the femtosecond timescales, which will make 'molecular movies' of bond breaking or formation, and vibrational relaxation, a reality.

Photodetoxification and purification of water and air

Energy Technology Data Exchange (ETDEWEB)

Anderson, M. [Univ. of Wisconsin, Madison, WI (United States); Blake, D.M. [National Renewable Energy Lab., Golden, CO (United States)

1996-09-01

The scope of interest in this section is basic research in photochemistry that can remove barriers to the development of photochemical technologies for the removal of hazardous chemicals from contaminated air or water (photodetoxification). Photochemistry is be broadly interpreted to include direct photochemistry, indirect photochemistry (sensitized and photocatalytic), photochemistry of species adsorbed on inert surfaces, and complementary effects of high energy radiation photons and particles. These may occur in either homogeneous or heterogeneous media. The photon source may span the range from ionizing radiation to the near infrared.

PHOTOCHEMISTRY IN THE INNER LAYERS OF CLUMPY CIRCUMSTELLAR ENVELOPES: FORMATION OF WATER IN C-RICH OBJECTS AND OF C-BEARING MOLECULES IN O-RICH OBJECTS

International Nuclear Information System (INIS)

Agundez, Marcelino; Cernicharo, Jose; Guelin, Michel

2010-01-01

A mechanism based on the penetration of interstellar ultraviolet photons into the inner layers of clumpy circumstellar envelopes (CSEs) around asymptotic giant branch stars is proposed to explain the non-equilibrium chemistry observed in such objects. We show through a simple modeling approach that in CSEs with a certain degree of clumpiness or with moderately low mass loss rates (a few 10 -7 M sun yr -1 ) a photochemistry can take place in the warm and dense inner layers, inducing important changes in the chemical composition. In carbon-rich objects water vapor and ammonia would be formed with abundances of 10 -8 -10 -6 relative to H 2 , while in oxygen-rich envelopes ammonia and carbon-bearing molecules such as HCN and CS would form with abundances of 10 -9 -10 -7 relative to H 2 . The proposed mechanism would explain the recent observation of warm water vapor in the carbon-rich envelope IRC+10216 with the Herschel Space Observatory and predict that H 2 O should be detectable in other carbon-rich objects.

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

International Nuclear Information System (INIS)

Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

2015-01-01

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t d,E ) and hydroxyl-radical oxidation half-lives (t ·OH,E ) in sunlit surface waters. The t d,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas t ·OH,E ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways

Photophysics and photochemistry of photoreactivation

International Nuclear Information System (INIS)

Sutherland, J.C.

1977-01-01

Photoreactivating enzyme (PRE) monomerizes cyclobutyl pyrimidine dimers formed in DNA by UV light (lambda < 300 nm). The enzyme requires near UV and visible wavelengths (300 < lambda < 600 nm) for activity. Possible mechanisms of action of the PRE are suggested by non-enzymatic processes in which pyrimidine dimers are monomerized by UV and visible light. Two such non-enzymatic processes are (a) photolysis of dimers resulting from direct absorption of UV, and (b) sensitized monomerization involving charge transfer complexes. Several lines of evidence suggest that the mechanism of action of the PRE more closely resembles (b) than (a). Recent experiments on the PRE from E.coli revealed the presence of new long wavelength absorption which may indicate the presence of a ground state complex. The known ability of PRE to monomerize dimers of thymine, cytosine and uracil suggests that the carbonyl groups at 2 position of the pyrimidine ring may be important in the interaction between enzyme and dimer. (author)

Photophysics and photochemistry of photoreactivation

Energy Technology Data Exchange (ETDEWEB)

Sutherland, J C [California Univ., Irvine (USA)

1977-05-01

Photoreactivating enzyme (PRE) monomerizes cyclobutyl pyrimidine dimers formed in DNA by uv light (lambda < 300 nm). The enzyme requires near UV and visible wavelengths (300 < lambda < 600 nm) for activity. Possible mechanisms of action of the PRE are suggested by non-enzymatic processes in which pyrimidine dimers are monomerized by UV and visible light. Two such non-enzymatic processes are (a) photolysis of dimers resulting from direct absorption of UV, and (b) sensitized monomerization involving charge transfer complexes. Several lines of evidence suggest that the mechanism of action of the PRE more closely resembles (b) than (a). Recent experiments on the PRE from E.coli revealed the presence of new long wavelength absorption which may indicate the presence of a ground state complex. The known ability of PRE to monomerize dimers of thymine, cytosine and uracil suggests that the carbonyl groups at 2 position of the pyrimidine ring may be important in the interaction between enzyme and dimer.

US nuclear physics funding

International Nuclear Information System (INIS)

Anon.

1992-01-01

Because of restrictions in the federal budget, US science spending is coming under close scrutiny, with strong implications for the evolution of the nation's physics research. Recently the Witherell subpanel of the Department of Energy's High Energy Physics Advisory Panel (HEPAP) submitted recommendations on how the US research scene could evolve pending commissioning of the SSC Superconducting Supercollider

Unified semiclassical theory for the two-state system: an analytical solution for general nonadiabatic tunneling.

Science.gov (United States)

Zhu, Chaoyuan; Lin, Sheng Hsien

2006-07-28

Unified semiclasical solution for general nonadiabatic tunneling between two adiabatic potential energy surfaces is established by employing unified semiclassical solution for pure nonadiabatic transition [C. Zhu, J. Chem. Phys. 105, 4159 (1996)] with the certain symmetry transformation. This symmetry comes from a detailed analysis of the reduced scattering matrix for Landau-Zener type of crossing as a special case of nonadiabatic transition and nonadiabatic tunneling. Traditional classification of crossing and noncrossing types of nonadiabatic transition can be quantitatively defined by the rotation angle of adiabatic-to-diabatic transformation, and this rotational angle enters the analytical solution for general nonadiabatic tunneling. The certain two-state exponential potential models are employed for numerical tests, and the calculations from the present general nonadiabatic tunneling formula are demonstrated in very good agreement with the results from exact quantum mechanical calculations. The present general nonadiabatic tunneling formula can be incorporated with various mixed quantum-classical methods for modeling electronically nonadiabatic processes in photochemistry.

Detection of photosynthetic performance of Stipa bungeana seedlings under climatic change using chlorophyll fluorescence imaging

Directory of Open Access Journals (Sweden)

Xiliang eSong

2016-01-01

Full Text Available In this study, the impact of future climate change on photosynthetic efficiency as well as energy partitioning in the Stipa bungeana was investigated by using chlorophyll fluorescence imaging (CFI technique. Two thermal regimes (room temperature, T0: 23.0/17.0℃; High temperature, T6: 29.0/23.0℃ and three water conditions (Control, W0; Water deficit, W-30; excess precipitation, W+30 were set up in artificial control chambers. The results showed that excess precipitation had no significant effect on chlorophyll fluorescence parameters, while water deficit decreased the maximal quantum yield of photosystem II (PSII photochemistry for the dark-adapted state (Fv/Fm by 16.7%, with no large change in maximal quantum yield of PSII photochemistry for the light-adapted state (FV'/FM' and coefficient of the photochemical quenching (qP at T0 condition. Under T6 condition, high temperature offset the negative effect of water deficit on Fv/Fm and enhanced the positive effect of excess precipitation on Fv/Fm, Fv'/Fm' and qP, the values of which all increased. This indicates that the temperature higher by 6 ℃ will be beneficial to the photosynthetic performance of S. bungeana. Spatial changes of photosynthetic performance were monitored in three areas of interest (AOIs located on the bottom, middle and upper position of leaf. Chlorophyll fluorescence images (Fv/Fm, actual quantum yield of PSII photochemistry for the light-adapted state (ΦPSII, quantum yield of nonregulated energy dissipation for the light-adapted state (ΦNO at T0 condition, and ΦPSII at T6 condition showed a large spatial variation, with greater value of ΦNO and lower values of Fv/Fm and ΦPSII in the upper position of leaves. Moreover, there was a closer relationship between ΦPSII and ΦNO, suggesting that the energy dissipation by non-regulated quenching mechanisms played a dominant role in the yield of PSII photochemistry. It was also found that, among all measured fluorescence

Programme budget 1980

International Nuclear Information System (INIS)

1979-10-01

The fields of research done in the Hahn-Meitner institute are described. These concern heavy ion physics, radiation and photochemistry, solid state physics, radiochemistry, data processing and nuclear electronics. In addition some facts concerning the infrastructure and financial planning are presented. (HSI)

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria.

Science.gov (United States)

Niedzwiedzki, Dariusz M; Hunter, C Neil; Blankenship, Robert E

2016-11-03

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation-bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

Energy Technology Data Exchange (ETDEWEB)

Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Siyu [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: pzhang@nmemc.org.cn [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Ren, Honglei; Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)

2015-09-15

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t{sub d,E}) and hydroxyl-radical oxidation half-lives (t{sub ·OH,E}) in sunlit surface waters. The t{sub d,E} values range from 0.56 min to 28.8 min at 45° N latitude, whereas t{sub ·OH,E} ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways.

Causal relationships between energy consumption, foreign direct investment and economic growth: Fresh evidence from dynamic simultaneous-equations models

International Nuclear Information System (INIS)

Omri, Anis; Kahouli, Bassem

2014-01-01

This paper examines the interrelationships between energy consumption, foreign direct investment and economic growth using dynamic panel data models in simultaneous-equations for a global panel consisting of 65 countries. The time component of our dataset is 1990–2011 inclusive. To make the panel data analysis more homogenous, we also investigate this interrelationship for a number of sub-panels which are constructed based on the income level of countries. In this way, we end up with three income panels; namely, high income, middle income, and low income panels. In the empirical part, we draw on the growth theory and augment the classical growth model, which consists of capital stock, labor force and inflation, with foreign direct investment and energy. Generally, we show mixed results about the interrelationship between energy consumption, FDI and economic growth. - Highlights: • We examine the energy–FDI–growth nexus for a global panel of 65 countries. • Dynamic simultaneous-equation panel data models are used to address this issue. • We also investigate this nexus for three sub-panels which are constructed based on the income level of countries. • We show mixed results about the interrelationship between the three variables

QM/MM studies on the excited-state relaxation mechanism of a semisynthetic dTPT3 base.

Science.gov (United States)

Guo, Wei-Wei; Zhang, Teng-Shuo; Fang, Wei-Hai; Cui, Ganglong

2018-02-14

Semisynthetic alphabets can potentially increase the genetic information stored in DNA through the formation of unusual base pairs. Recent experiments have shown that near-visible-light irradiation of the dTPT3 chromophore could lead to the formation of a reactive triplet state and of singlet oxygen in high quantum yields. However, the detailed excited-state relaxation paths that populate the lowest triplet state are unclear. Herein, we have for the first time employed the QM(MS-CASPT2//CASSCF)/MM method to explore the spectroscopic properties and excited-state relaxation mechanism of the aqueous dTPT3 chromophore. On the basis of the results, we have found that (1) the S 2 ( 1 ππ*) state of dTPT3 is the initially populated excited singlet state upon near-visible light irradiation; and (2) there are two efficient relaxation pathways to populate the lowest triplet state, i.e. T 1 ( 3 ππ*). In the first one, the S 2 ( 1 ππ*) system first decays to the S 1 ( 1 nπ*) state near the S 2 /S 1 conical intersection, which is followed by an efficient S 1 → T 1 intersystem crossing process at the S 1 /T 1 crossing point; in the second one, an efficient S 2 → T 2 intersystem crossing takes place first, and then, the T 2 ( 3 nπ*) system hops to the T 1 ( 3 ππ*) state through an internal conversion process at the T 2 /T 1 conical intersection. Moreover, an S 2 /S 1 /T 2 intersection region is found to play a vital role in the excited-state relaxation. These new mechanistic insights help in understanding the photophysics and photochemistry of unusual base pairs.

Structural Control of (1)A(2u)-to-(3)A(2u) Intersystem Crossing in Diplatinum(II,II) Complexes

Czech Academy of Sciences Publication Activity Database

Durrell, A. C.; Keller, G. E.; Lam, Y.; Ch.; Sýkora, Jan; Vlček, Antonín; Gray, H. B.

2012-01-01

Roč. 134, č. 34 (2012), s. 14201-14207 ISSN 0002-7863 R&D Projects: GA MŠk(CZ) ME10124 Institutional support: RVO:61388955 Keywords : TRIPLET EXCITED-STATE * BINUCLEAR PLATINUM(II) PHOTOCHEMISTRY * ELECTRON-TRANSFER REACTIONS Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

Photochemistry of Fe:H2O Adducts in Argon Matrixes: A Combined Experimental and Theoretical Study in the Mid-IR and UV-Visible Regions.

Science.gov (United States)

Deguin, Vincent; Mascetti, Joëlle; Simon, Aude; Ben Amor, Nadia; Aupetit, Christian; Latournerie, Sandra; Noble, Jennifer A

2018-01-18

The photochemistry of Fe:H 2 O adducts is of interest in fields as diverse as catalysis and astrochemistry. Industrially, iron can be used as a catalyst to convert H 2 O to H 2 , whereas in the interstellar medium it may be an important component of dust grains, influencing the chemistry on their icy surfaces. This study consisted of the deposition and spectral characterization of binary systems of atomic iron with H 2 O in cryogenic argon matrixes. In this way, we were able to obtain information about the interaction of the two species; we observed the formation of adducts of iron monomers and dimers with water molecules in the mid-IR and UV-visible spectral domains. Upon irradiation with a UV radiation source, the iron species were inserted into the water molecules to form HFeOH and HFe 2 OH, leading in some cases to the formation of FeO possibly accompanied by the production of H 2 . DFT and correlated multireference wave function calculations confirmed our attributions. This combination of IR and UV-visible spectroscopy with theoretical calculations allowed us to determine, for the first time, the spectral characteristics of iron adducts and their photoproducts in the UV-visible and in the OH stretching region of the mid-IR domain.

Photoelectrochemistry, photocatalysis and photoreactors. Fundamentals and developments

Energy Technology Data Exchange (ETDEWEB)

Schiavello, M [ed.

1985-01-01

During this conference 29 lectures were read on following subjects: materials for electrodes and photochemical cells, fundamentals of photochemistry and photocatalysis, design and modelling of photochemical reactors and reactions. The aim was to define the state of the art and of outlining perspectives, developments and practical utilization. (A.V.)

Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion

DEFF Research Database (Denmark)

Brogaard, Rasmus Y.; Sølling, Theis I.; Møller, Klaus Braagaard

2011-01-01

The Norrish Type I reaction in the S1 (nπ*) state of acetone is a prototype case of ketone photochemistry. On the basis of results from time-resolved mass spectrometry (TRMS) and photoelectron spectroscopy (TRPES) experiments, it was recently suggested that after excitation the wave packet travels...

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

Energy Technology Data Exchange (ETDEWEB)

Ravi Kumar, Venkatraman; Ariese, Freek; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in [Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560012 (India)

2016-03-21

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T{sub 1} and T{sub 2} states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S{sub 0} state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S{sub 0}, T{sub 1}, and T{sub 2} states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the nπ{sup ∗} triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents.

High energy physics advisory panel's subpanel on vision for the future of high-energy physics

International Nuclear Information System (INIS)

1994-05-01

This report was requested by the Secretary of Energy to (1) define a long-term program for pursuing the most important high-energy physics goals since the termination of the Superconducting Super Collider (SSC) project, (2) assess the current US high-energy physics program, and (3) make recommendations regarding the future of the field. Subjects on which recommendations were sought and which the report addresses were: high-energy physics funding priorities; facilitating international collaboration for future construction of large high-energy physics facilities; optimizing uses of the investment made in the SSC; how to encourage displaced scientists and engineers to remain in high-energy physics and to attract young scientists to enter the field in the future. The report includes a description of the state of high-energy physics research in the context of history, a summary of the SSC project, and documentation of the report's own origins and development

Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL: implications for NOx release from the Arctic and coastal Antarctic snowpack

Directory of Open Access Journals (Sweden)

A. Saiz-Lopez

2008-08-01

Full Text Available We utilize a multiphase model, CON-AIR (Condensed Phase to Air Transfer Model, to show that the photochemistry of nitrate (NO3− in and on ice and snow surfaces, specifically the quasi-liquid layer (QLL, can account for NOx volume fluxes, concentrations, and [NO]/[NO2] (γ=[NO]/[NO2] measured just above the Arctic and coastal Antarctic snowpack. Maximum gas phase NOx volume fluxes, concentrations and γ simulated for spring and summer range from 5.0×104 to 6.4×105 molecules cm−3 s−1, 5.7×108 to 4.8×109 molecules cm−3, and ~0.8 to 2.2, respectively, which are comparable to gas phase NOx volume fluxes, concentrations and γ measured in the field. The model incorporates the appropriate actinic solar spectrum, thereby properly weighting the different rates of photolysis of NO3− and NO2−. This is important since the immediate precursor for NO, for example, NO2−, absorbs at wavelengths longer than nitrate itself. Finally, one-dimensional model simulations indicate that both gas phase boundary layer NO and NO2 exhibit a negative concentration gradient as a function of height although [NO]/[NO2] are approximately constant. This gradient is primarily attributed to gas phase reactions of NOx with halogens oxides (i.e. as BrO and IO, HOx, and hydrocarbons, such as CH3O2.

Ionizing radiation risk assessment, BEIR IV

International Nuclear Information System (INIS)

1991-10-01

This report of the Subpanel discusses the potential impact on Federal agencies and indicates individual risk factors that could be used by them in risk assessment. The approach used in this CIRRPC report was to consider the risk factors presented in BEIR IV for each radionuclide (or group radioelements) and to make some judgments regarding their validity and/or the uncertainties involved. The coverage of Radon-222 and its progeny dominated the BEIR IV report and this Subpanel felt is was proper to devote more attention to this radionuclide family. This risk factor presented in BEIR IV for radon is 350 cancer deaths per million person-working level months (WLM) of exposure for a lifetime. There is a range of opinions on the conversion from WLM to absorbed dose. As discussed in the text, the use of the WLM concept makes it difficult or infeasible to compare the risk factor for radon with that of other radionuclides which are based on organ dose. This report also includes a discussion of certain fundamental scientific and operational issues that may have decisive effect upon risk factor selection. These adjunct items are dealt with under separate headings and include discussions of threshold dose considerations, extrapolation to low doses, and age at exposure

Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

Energy Technology Data Exchange (ETDEWEB)

Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

2017-01-18

Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O₃^- and OH-initiated reactions during the day and reactions with NO₃ ^{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, 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.}

Ultrafast Photochemical Dissociation of an Equatorial CO Ligand from trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I). A Picosecond Time-Resolved Infrared Spectroscopic and DFT Computational Study

Czech Academy of Sciences Publication Activity Database

Gabrielsson, A.; Záliš, Stanislav; Matousek, P.; Towrie, M.; Vlček, Antonín

2004-01-01

Roč. 43, - (2004), s. 7380-7388 ISSN 0020-1669 R&D Projects: GA MŠk 1P04OCD14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : transition-metal-complexes * excited-state dynamics * charge-transfer photochemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.454, year: 2004

Síntese de fotoprotetores e sua imobilização em poli(metacrilato de metilo: um projeto integrado de química orgânica, química de polímeros e fotoquímica Sunscreen synthesis and their immobilisition on polymethylmethacrylate: an integrated project in organic chemistry, polymer chemistry and photochemistry

Directory of Open Access Journals (Sweden)

Dina Maria B. Murtinho

2010-01-01

Full Text Available Dibenzalacetone and other aldol condensation products are known sunscreens commonly used in cosmetics. This type of compounds can easily be prepared in an Organic Chemistry Lab by reaction of aldehydes with ketones in basic medium. These compounds can be incorporated in poly(methyl methacrylate and used as UV light absorbers, for example in sunglasses. This project has the advantage of using inexpensive reagents which are readily available in Chemistry Laboratories. This experiment can also be a base starting point for discussions of organic, polymer and photochemistry topics.

Laser-enhanced chemical reactions and the liquid state. II. Possible applications to nuclear fuel reprocessing

International Nuclear Information System (INIS)

DePoorter, G.L.; Rofer-DePoorter, C.K.

1976-01-01

Laser photochemistry is surveyed as a possible improvement upon the Purex process for reprocessing spent nuclear fuel. Most of the components of spent nuclear fuel are photochemically active, and lasers can be used to selectively excite individual chemical species. The great variety of chemical species present and the degree of separation that must be achieved present difficulties in reprocessing. Lasers may be able to improve the necessary separations by photochemical reaction or effects on rates and equilibria of reactions

An analysis of fast photochemistry over high northern latitudes during spring and summer using in-situ observations from ARCTAS and TOPSE

Directory of Open Access Journals (Sweden)

J. R. Olson

2012-08-01

Full Text Available Observations of chemical constituents and meteorological quantities obtained during the two Arctic phases of the airborne campaign ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites are analyzed using an observationally constrained steady state box model. Measurements of OH and HO₂ from the Penn State ATHOS instrument are compared to model predictions. Forty percent of OH measurements below 2 km are at the limit of detection during the spring phase (ARCTAS-A. While the median observed-to-calculated ratio is near one, both the scatter of observations and the model uncertainty for OH are at the magnitude of ambient values. During the summer phase (ARCTAS-B, model predictions of OH are biased low relative to observations and demonstrate a high sensitivity to the level of uncertainty in NO observations. Predictions of HO₂ using observed CH₂O and H₂O₂ as model constraints are up to a factor of two larger than observed. A temperature-dependent terminal loss rate of HO₂ to aerosol recently proposed in the literature is shown to be insufficient to reconcile these differences. A comparison of ARCTAS-A to the high latitude springtime portion of the 2000 TOPSE campaign (Tropospheric Ozone Production about the Spring Equinox shows similar meteorological and chemical environments with the exception of peroxides; observations of H₂O₂ during ARCTAS-A were 2.5 to 3 times larger than those during TOPSE. The cause of this difference in peroxides remains unresolved and has important implications for the Arctic HO_x budget. Unconstrained model predictions for both phases indicate photochemistry alone is unable to simultaneously sustain observed levels of CH₂O and H₂O₂; however when the model is constrained with observed CH₂O, H₂O₂ predictions from a range of

Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis

Science.gov (United States)

Keane, Thomas C.

2017-09-01

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

High energy physics advisory panel`s subpanel on vision for the future of high-energy physics

Energy Technology Data Exchange (ETDEWEB)

1994-05-01

This report was requested by the Secretary of Energy to (1) define a long-term program for pursuing the most important high-energy physics goals since the termination of the Superconducting Super Collider (SSC) project, (2) assess the current US high-energy physics program, and (3) make recommendations regarding the future of the field. Subjects on which recommendations were sought and which the report addresses were: high-energy physics funding priorities; facilitating international collaboration for future construction of large high-energy physics facilities; optimizing uses of the investment made in the SSC; how to encourage displaced scientists and engineers to remain in high-energy physics and to attract young scientists to enter the field in the future. The report includes a description of the state of high-energy physics research in the context of history, a summary of the SSC project, and documentation of the report`s own origins and development.

Laser Photochemistry.

Science.gov (United States)

1981-07-01

inverted by the first, i.e., at the moment of time t = T, such that i = (2n+)lT, where 0 is the Rabi frequency (Oraevski et al., 1976). . classical... anisotropic molecule present. CW HeNe, Ar+ and Kr+ lasers are used, and the filter method is necessary because of time-scales lo8 - 10ll Hz. Some general...e.g., truncated harmonic oscillator, square well, spherically symmetric Morse or Lennard-Jones, anisotropic (angle-dependent) Morse or Lennard-Jones

Climate-driven ground-level ozone extreme in the fall over the Southeast United States.

Science.gov (United States)

Zhang, Yuzhong; Wang, Yuhang

2016-09-06

Ground-level ozone is adverse to human and vegetation health. High ground-level ozone concentrations usually occur over the United States in the summer, often referred to as the ozone season. However, observed monthly mean ozone concentrations in the southeastern United States were higher in October than July in 2010. The October ozone average in 2010 reached that of July in the past three decades (1980-2010). Our analysis shows that this extreme October ozone in 2010 over the Southeast is due in part to a dry and warm weather condition, which enhances photochemical production, air stagnation, and fire emissions. Observational evidence and modeling analysis also indicate that another significant contributor is enhanced emissions of biogenic isoprene, a major ozone precursor, from water-stressed plants under a dry and warm condition. The latter finding is corroborated by recent laboratory and field studies. This climate-induced biogenic control also explains the puzzling fact that the two extremes of high October ozone both occurred in the 2000s when anthropogenic emissions were lower than the 1980s and 1990s, in contrast to the observed decreasing trend of July ozone in the region. The occurrences of a drying and warming fall, projected by climate models, will likely lead to more active photochemistry, enhanced biogenic isoprene and fire emissions, an extension of the ozone season from summer to fall, and an increase of secondary organic aerosols in the Southeast, posing challenges to regional air quality management.

Photochemistry of 2-Aminooxazole, a Hypothetical Prebiotic Precursor of RNA Nucleotides

Czech Academy of Sciences Publication Activity Database

Szabla, Rafal; Tuna, D.; Gora, R.W.; Šponer, Jiří; Sobolewski, A. L.; Domcke, W.

2013-01-01

Roč. 4, č. 16 (2013), s. 2785-2788 ISSN 1948-7185 R&D Projects: GA ČR(CZ) GAP208/10/2302; GA ČR ED1.1.00/02.0068 Institutional support: RVO:68081707 Keywords : EXCITED-STATE DYNAMICS * REPULSIVE (1)PI-SIGMA-ASTERISK STATES * CONICAL INTERSECTIONS Subject RIV: BO - Biophysics Impact factor: 6.687, year: 2013

Dynamics and mechanisms of catalytic processes and hot chemistry. Final report, March 1, 1972-October 31, 1984

International Nuclear Information System (INIS)

Spicer, L.D.

1984-10-01

General areas of research addressed are recoil chemistry of halogens, tritium, and sulfur, radiotracer methods for studies of chemical dynamics, thermal and photochemistry of sulfur dioxide, and photochemistry and photoassistance in catalytic systems

Roles of xanthophylls and exogenous ABA in protection against NaCl-induced photodamage in rice (Oryza sativa L) and cabbage (Brassica campestris).

Science.gov (United States)

Zhu, Su-Qin; Chen, Ming-Wei; Ji, Ben-Hua; Jiao, De-Mao; Liang, Jian-Sheng

2011-08-01

Changes in actual efficiency of PS II photochemistry, non-photochemical quenching (NPQ), content of xanthophylls and kinetics of de-epoxidation were studied in ABA-fed and non-ABA-fed leaves of rice and cabbage under NaCl stress. Salt stress induced more progressive decrease in actual efficiency of PS II photochemistry (ФPS II), higher reduction state of PS II, and a small significant increase in NPQ in NaCl-sensitive rice plants as compared with NaCl-tolerant cabbage plants, whereas exogenously supplied ABA alleviated the decrease in actual efficiency of PS II photochemistry (ФPS II), induced a lower reduction state of PS II, and caused higher capacity of NPQ in ABA-fed plants than in non-ABA-fed plants. As a result, there were higher activities of photosynthetic electron transport, higher capacity of energy dissipation, and lower cumulation of excess light in cabbage than in rice plants, and in ABA-fed leaves than in non-ABA-fed leaves. The effect of ABA was more efficient in cabbage than in rice plants. Addition of exogenous ABA resulted in enhancement of the size of the xanthophyll cycle pool, promotion of de-epoxidation of the xanthophyll cycle components, and a rise in the level of NPQ by altering the kinetics of de-epoxidation of the xanthophyll cycle. Protection from photodamage appears to be achieved by coordinated contributions by exogenous ABA and xanthophyll cycle-mediated NPQ. This variety of photoprotective mechanisms may be essential for conferring photodamage tolerance under NaCl stress. © The Author [2011]. Published by Oxford University Press [on behalf of the Society for Experimental Biology]. All rights reserved.

Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis.

Science.gov (United States)

Keane, Thomas C

2017-09-01

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH 3 (ammonia) and C 2 H 2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH 3 CN (acetonitrile), CH 3 CH = N-N = CHCH 3 (acetaldazine), CH 3 CH = N-NH 2 (acetaldehyde hydrazone), C 2 H 5 NH 2 (ethylamine), CH 3 NH 2 (methylamine) and C 2 H 4 (ethene) in the photolysis of NH 3 /C 2 H 2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH 3 CH = N-N = CHCH 3 does not explain all of the results obtained in this study. The formation of CH 3 CH = N-N = CHCH 3 by a radical combination reaction of CH 3 CH = N• was shown in this work to be inconsistent with other experiments where the CH 3 CH = N• radical is thought to form but where no CH 3 CH = N-N = CHCH 3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH 3 CH = N-N = CHCH 3 formation involving nucleophilic reaction

Photophysics and Photochemistry of 2-Aminobenzoic Acid Anion in Aqueous Solution

Science.gov (United States)

Pozdnyakov, Ivan P.; Plyusnin, Victor F.; Grivin, Vjacheslav P.

2009-11-01

Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA-) in aqueous solutions. Excitation of this species gives rise to the ABA- triplet state to the ABA• radical and to the hydrated electron (eaq-). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA- triplet state, the ABA• radical, and eaq- are T-T annihilation, recombination, and capture by the ABA- anion, respectively.

International collaboration

International Nuclear Information System (INIS)

Anon.

1994-01-01

In the wake of the demise of the US Superconducting Supercollider (SSC) project last year which empoverished both US and world science, some rapid scene shifting is going on. The SSC may be dead, but the underlying physics quest lives on. In the US, the 'future vision' subpanel of the High Energy Physics Advisory Board (HEPAP) is at work formulating its recommendations. On the international front, the International Committee for Future Accelerators (ICFA) at a special meeting in Vancouver in January drafted a statement

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

NARCIS (Netherlands)

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

2014-01-01

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

Laser spectroscopy and photochemistry on metal surfaces, pt.2

CERN Document Server

Dai, HL

1995-01-01

Using lasers to induce and probe surface processes has the advantages of quantum state specificity, species selectivity, surface sensitivity, fast time-resolution, high frequency resolution, and accessibility to full pressure ranges. These advantages make it highly desirable to use light to induce, control, or monitor surface chemical and physical processes. Recent applications of laser based techniques in studying surface processes have stimulated new developments and enabled the understanding of fundamental problems in energy transfer and reactions. This volume will include discussions on sp

Laser spectroscopy and photochemistry on metal surfaces, pt.1

CERN Document Server

Dai, HL

1995-01-01

Using lasers to induce and probe surface processes has the advantages of quantum state specificity, species selectivity, surface sensitivity, fast time-resolution, high frequency resolution, and accessibility to full pressure ranges. These advantages make it highly desirable to use light to induce, control, or monitor surface chemical and physical processes. Recent applications of laser based techniques in studying surface processes have stimulated new developments and enabled the understanding of fundamental problems in energy transfer and reactions. This volume will include discussions on sp

Synoptic comparison of major US and UK simulations

Energy Technology Data Exchange (ETDEWEB)

Henderson, D.B.; Oxenham, D.

1994-07-01

The six simulations considered include two from the United Kingdom: The United Kingdom Extended Air Defence Test Bed (UKEADTB) and the Air Defence Test Bed (ADTB). There are two from the Test Bed Product Office of the US Army Space and Strategic Defense Command (USASSDC) in Huntsville, Alabama: The Extended Air Defense Test Bed (EADTB) and the Extended Air Defense Simulation (EADSIM). There are two from the National Test Facility in Colorado Springs, Colorado: The Test Planning Tool (TPT) and the Human in Control Test Bed (HICTB). A seventh, the Brilliant Eyes Simulator (BESim) -- an element simulation and a close family member of the system level TPT -- is included along with TPT by noting exceptions where necessary. The comparisons are designed to be compact and comprehensible, with no table occupying more than a single page. The present report is organized with the tables on the odd numbered pages and some commentary on the facing even numbered pages. While the effort reported is extensive, it needs to be further developed as planned as the Subpanel`s next major undertaking. Analogously with simulations themselves, there remains the question of validation or accreditation. Also analogously, these depend upon the question being served. That is, the responses reported here, while extensive and interesting, need to be explicitly reviewed in the light of any given serious application. Unfortunately, and again analogously with simulations, this accreditation can not be done in the abstract or once and for all.

Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution

International Nuclear Information System (INIS)

Wu Weiqiang; Yang Chunfan; Zhao Hongmei; Liu Kunhui; Su Hongmei

2010-01-01

By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH 2 =CHCHO) in CH 3 CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH 3 CH=C=O with a branching ratio of 0.78 and the less important channel is the α cleavage of C-H bond yielding radical fragments CH 2 =CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet 3 (ππ * ) state rather than the ground S 0 state and the α cleavage of C-H bond is more likely to proceed in the singlet S 1 1 (nπ * ) state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

Radiation and Photochemistry Section annual report, October 1991--September 1992

International Nuclear Information System (INIS)

1992-11-01

A survey is presented of research on reactive intermediates in the condensed phase and chemistry induced by energetic radiation. The survey is presented in two major parts: (1) ions, excited states, and other transients in condensed phase; and (2) role of solvents in chemical reactivity. Accelerator activities (20-MeV linac, 3-MeV Van de Graaff) are summarized

Photochemistry and exciplex of the uranyl ion in aqueous solution

International Nuclear Information System (INIS)

Marcantonatos, M.D.

1980-01-01

The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

Plasma Science Committee (PLSC) and the Panel on Opportunities in Plasma Science and Technology (OPST)

International Nuclear Information System (INIS)

1993-01-01

The Plasma Science Committee (PLSC) of the National Research Council (NRC) is charged with monitoring the health of the field of plasma science in the United States and identifies and examines both broad and specific issues affecting the field. Regular meetings, teleconferences, briefings from agencies and the scientific community, the formation of study panels to prepare reports, and special symposia are among the mechanisms used by the PLSC to meet its charge. During July 1992, the PLSC sponsored a workshop on nonneutral plasmas in traps. Although no written report on the workshop results, was prepared for public distribution, a summary of highlights was provided to the OPST Subpanel on Nonneutral Plasmas. The PLSC also continued its follow-up briefings and discussions on the results of the results of the report Plasma Processing of materials. Scientific and Technological Opportunities. As a result of these activities, the Committee is now working with the NRC Committee on Atomic, Molecular, and Optical Sciences (CAMOS) to organize a symposium on database needs in plasma processing of materials

Water-chromophore electron transfer determines the photochemistry of cytosine and cytidine

Czech Academy of Sciences Publication Activity Database

Szabla, Rafal; Kruse, Holger; Šponer, Jiří; Gora, R.W.

2017-01-01

Roč. 19, č. 27 (2017), s. 17531-17537 ISSN 1463-9076 Institutional support: RVO:68081707 Keywords : driven proton-transfer * excited-state dynamics * potentially prebiotic synthesis Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

In vitro toxicity testing of zinc tetrasulfophthalocyanines in fibroblast and keratinocyte cells for the treatment of melanoma cancer by photodynamic therapy

CSIR Research Space (South Africa)

Maduray, K

2011-05-01

Full Text Available and United States [3]. The standard oncology treatment for melanoma cancer is surgi- Available online xxxx Keywords: Photodynamic therapy Zinc tetrasulfophthalocyanines Melanoma cancer Phthalocyanines 1011-1344/$ - see front matter � 2011 Elsevier B... of cancer, 567 The Lancet Oncology 1 (2000) 4212?4219. 568 [15] K. Plaetzer, B. Krammer, J. Berlanda, F. Berr, T. Kiesslich, Photophysics and 569 photochemistry of photodynamic therapy: fundamental aspects, Laser Medical 570 Science 24 (2009) 259...

On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

International Nuclear Information System (INIS)

Casadesus, Ricard; Vendrell, Oriol; Moreno, Miquel; Lluch, Jose M.; Morokuma, Keiji

2006-01-01

The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S 0 ) and first singlet excited (S 1 ) electronic states. In S 0 the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S 1 . The ab initio configuration interaction singles (CIS) method overestimates the energy of S 1 and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S 1 and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media

On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Casadesus, Ricard [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States); Vendrell, Oriol [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Moreno, Miquel [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)], E-mail: mmf@klingon.uab.es; Lluch, Jose M. [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Morokuma, Keiji [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States)

2006-06-20

The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S{sub 0}) and first singlet excited (S{sub 1}) electronic states. In S{sub 0} the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S{sub 1}. The ab initio configuration interaction singles (CIS) method overestimates the energy of S{sub 1} and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S{sub 1} and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media.

Hydrocarbons in interstellar ice analogues : UV-vis spectroscopy and VUV photochemistry

NARCIS (Netherlands)

Cuylle, Steven Hendrik

2015-01-01

This thesis treats the chemical behaviour of carbonaceous molecules in water-dominated interstellar ices. VUV photons are considered as the chemical trigger to induce solid state chemistry as it is omnipresent. Lyman- radiation occurs even in dense molecular clouds as a result of cosmic ray

Physics through the 1990s: Plasmas and fluids

International Nuclear Information System (INIS)

1986-01-01

This survey of plasma physics and fluid physics briefly describes present activities and recent major accomplishments. It also identifies research areas that are likely to lead to advances during the next decade. Plasma physics is divided into three major areas: general plasma physics, fusion plasma confinement and heating, and space and astrophysical plasmas. Fluid physics is treated as one topic, although it is an extremely diverse research field ranging from biological fluid dynamics to ship and aircraft performance to geological fluid dynamics. Subpanels, chosen for their technical expertise and scientific breadth, reviewed each of the four areas. The entire survey was coordinated and supervised by an Executive Committee, which is also responsible for the Executive Summary of this volume. Wherever possible, input from recent Advisory Committees was used, e.g., from the Magnetic Fusion Advisory Committee, the Space Science Board, and the Astronomy Survey Committee. This volume is organized as follows: An Introduction and Executive Summary that outlines (1) major findings and recommendations; (2) significant research accomplishments during the past decade and likely areas of future research emphasis; and (3) a brief summary of present funding levels, manpower resources, and institutional involvement; and the subpanel reports constitute Fluid Physics, General Plasma Physics, Fusion Plasma Confinement and Heating, and Space and Astrophysical Plasmas. An important conclusion of this survey is that both plasma physics and fluid physics are scientifically and intellectually well developed, and both ares are broad subdisciplines of physics. We therefore recommend that future physics surveys have separate volumes on the physics of plasmas and the physics of fluids

Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution

Science.gov (United States)

Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei

2010-03-01

By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH2CHCHO) in CH3CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH3CHCO with a branching ratio of 0.78 and the less important channel is the α cleavage of CH bond yielding radical fragments CH2CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet (ππ ∗)3 state rather than the ground S0 state and the α cleavage of CH bond is more likely to proceed in the singlet S1 (nπ∗)1 state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

Energy Technology Data Exchange (ETDEWEB)

Ross, F; Ross, A B

1977-01-01

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

Max Planck Institute for Radiation Chemistry, Muelheim a.d. Ruhr

International Nuclear Information System (INIS)

Anon.

1991-01-01

The Institute carriers out research in the field of radiation chemistry, which is understood as a field of science combining photochemistry and radiation chemistry. The research programme focuses on: the radiation chemistry of the deoxyribonucleic acids (DNA), DNA constituents, and DNA model compounds; photobiochemistry and fundamentals of photobiology; organic and organometallic photochemistry, particularly reaction mechanisms and synthesis; photophysics. (orig.) [de

Silver as an electron source for photodissociation of hydronium

Energy Technology Data Exchange (ETDEWEB)

Papas, B. N.; Whitten, J. L. [Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695 (United States)

2011-11-28

The photochemistry of a solvated hydronium ion near a silver surface is investigated using ab initio self-consistent field and configuration interaction theory. Photoinduced electron attachment can occur at energies in the range of 1.1-1.2 eV depending upon the initial orientation of the hydronium relative to the silver surface. Rearrangement of solvating waters considerably reduces transition state barriers to dissociation on the excited-state potential energy surface, such that fast dissociation of the neutralized hydronium would occur with no barrier. Both the H and H{sub 2} product channels are exothermic pathways on the excited state surface and in several instances exothermic compared to the energy of the initial structure.

Selected Contributions of the 4th European Meeting on Solar Chemistry and Photocatalysis. Environmental Applications (SPEA 4)

International Nuclear Information System (INIS)

Malato Rodriguez, S.; Gernjak, W.; Pereze Pena, J.; Dona Rodriguez, J.M.

2007-01-01

session discussions completed the program. The results and discussion sessions provided a very good approximation of the current state-of-the-art of photocatalytic and solar photocatalytic environmental applications. The focus was on photochemical and photocatalytic air, soil and water pollution treatments, and related topics were classified in eleven areas: (1) water treatment and disinfection; (2) air treatment; (3) soil remediation; (4) green synthesis by solar-chemistry, photochemistry and photocatalysis; (5) development of new materials for photochemistry and photocatalysis; (6) developments and perspectives in environmental photochemistry; (7) commercial applications; (8) environmental management; (9) experimental standardization; (10) models for photochemistry and photocatalysis; (11) general questions. The 33 papers included in this Special Issue represent a good overview of the state of the art of photocatalysis, covering a variety of aspects, and involving institutions from all over the world

A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

Science.gov (United States)

Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

2008-11-01

Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

PHOTOLYTIC HAZES IN THE ATMOSPHERE OF 51 ERI B

Energy Technology Data Exchange (ETDEWEB)

Zahnle, K.; Marley, M. S. [NASA Ames Research Center, Moffett Field, CA 94035 (United States); Morley, C. V. [Department of Astronomy and Astrophysics, University of California, Santa Cruz, CA 95064 (United States); Moses, J. I., E-mail: Kevin.J.Zahnle@NASA.gov, E-mail: kzahnle@mail.arc.NASA.gov, E-mail: Mark.S.Marley@NASA.gov, E-mail: cmorley@ucolick.org, E-mail: jmoses@spacescience.org [Space Science Institute, 4750 Walnut Street, Suite 205, Boulder, CO 80301 (United States)

2016-06-20

We use a 1D model to address photochemistry and possible haze formation in the irradiated warm Jupiter, 51 Eridani b. The intended focus was to be carbon, but sulfur photochemistry turns out to be important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If organic hazes form, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the altitudes where methane and water are photolyzed. The more novel result is that photochemistry turns H{sub 2}S into elemental sulfur, here treated as S{sub 8}. In the cooler models, S{sub 8} is predicted to condense in optically thick clouds of solid sulfur particles, while in the warmer models S{sub 8} remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we have discussed is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650–750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.

Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?

Science.gov (United States)

Marley, Mark Scott; Zahnle, Kevin; Moses, J.; Morley, C.

2015-01-01

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

Radiation and Photochemistry Section annual report, October 1992--November 1993

International Nuclear Information System (INIS)

1993-11-01

The research described in this survey is a study of transient intermediates and chemistry induced by energetic radiation in the condensed phase. The survey is presented in two major parts: the first one studies ions, excited states, and other transients in the condensed phase; the second one studies the role of solvents in chemical reactivity. Some highlights of the past year were observations of ion-molecule reactions of excited aromatic cations via flash photolysis and transient dc conductivity; anion solvation study revealing role of solvent molecular structure; zeolite matrix study of C 7 H 8 radical cation chemistry; and H atom reaction with O 2 , I - , and comparison of diffusion of H, D, and muonium in ice. Refs, 25 figs, 5 tabs

Atmospheric photochemistry at a fatty acid-coated air-water interface

Science.gov (United States)

Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D. James; George, Christian

2016-08-01

Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

Charge and Proton Transfer Reactions: Insights from Theory

OpenAIRE

Savarese, Marika

2014-01-01

Photochemistry is a science concerned with structures and dynamical processes resulting from the interaction of the light with molecules. The understanding of molecular processes triggered by the electronic excitation relies on a proper chemical-physical characterization based on a sound theoretical modeling of the photophysics and the photochemistry. From the more strict point of view of the theoretical chemistry, computational methods provide nowadays a powerful tool to analyze and sing...

1992 HEPAP subpanel on the US Program of High Energy Physics Research

International Nuclear Information System (INIS)

1992-04-01

High energy physics seeks an understanding of the fundamental structure of matter and the laws that govern all physical phenomena. The US high energy physics community has many scientific opportunities before it. Discovering the top quark, exploring the origin of particle-antiparticle asymmetry, and elucidating the Higgs mechanism, the source of mass, are some of the most notable. We were charged with laying out programs for US high energy physics through this decade that would accord with three specific budgetary guidelines for the period FY 1994--FY 1997. This report details the scientific, technical, and resource issues involved, recommends a program for each guideline, and discusses the implications of each program. In all our plans we consider construction of the SSC to have the highest priority in the US particle physics program and to be absolutely essential for continued progress in our field into the 21st century

Panel on protection and management of plutonium: Subpanel on safeguards and security

International Nuclear Information System (INIS)

Tape, J.W.

1995-01-01

Nuclear materials safeguards and security systems are described in the context of the nuclear nonproliferation regime. Materials of interest to safeguards, threats, proposals to strengthen International Atomic Energy Agency safeguards, evolving safeguards issues and requirements, system effectiveness, and elements of a global nuclear materials management regime are discussed. Safeguards are seen as an essential element of nuclear materials management, but not a driver for decisions regarding nuclear power or the disposal of excess weapon nuclear materials

Lucifer's Planet: Photolytic Hazes in the Atmosphere of 51 Eri b

Science.gov (United States)

Zahnle, Kevin

2016-01-01

We use a 1D model to address photochemistry and possible haze formation in the irradiated atmosphere of 51 Eri b (2016arXiv160407388Z). The intended focus was to have been on carbon and organic hazes, but sulfur photochemistry turns out to be interesting and possibly more important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If organic hazes form abundantly, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the altitudes where methane and water are photolyzed. The more novel result is that photochemistry turns H2S into elemental sulfur, here treated as S8. In the cooler models, S8 is predicted to condense in optically significant clouds of solid sulfur particles, whilst in the warmer models S8 remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we discuss is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650-750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.

ERM 593 Applied Project_Guidance for Reviewing and Approving a Waste Stream Profile in the Waste Compliance and Tracking System_Final_05-05-15

Energy Technology Data Exchange (ETDEWEB)

Elicio, Andy U. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-05-05

My ERM 593 applied project will provide guidance for the Los Alamos National Laboratory Waste Stream Profile reviewer (i.e. RCRA reviewer) in regards to Reviewing and Approving a Waste Stream Profile in the Waste Compliance and Tracking System. The Waste Compliance and Tracking system is called WCATS. WCATS is a web-based application that “supports the generation, characterization, processing and shipment of LANL radioactive, hazardous, and industrial waste.” The LANL generator must characterize their waste via electronically by filling out a waste stream profile (WSP) in WCATS. Once this process is completed, the designated waste management coordinator (WMC) will perform a review of the waste stream profile to ensure the generator has completed their waste stream characterization in accordance with applicable state, federal and LANL directives particularly P930-1, “LANL Waste Acceptance Criteria,” and the “Waste Compliance and Tracking System User's Manual, MAN-5004, R2,” as applicable. My guidance/applied project will describe the purpose, scope, acronyms, definitions, responsibilities, assumptions and guidance for the WSP reviewer as it pertains to each panel and subpanel of a waste stream profile.

Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

Science.gov (United States)

Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

2013-06-01

Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

Recent Advances in Photochemistry

Indian Academy of Sciences (India)

Unknown

The next one was held in Taejon, Korea in 1999. Both the Conferences were highly successful. The third conference APC-2002 was awarded to India and was organized at the Hotel. Centaur, Juhu Beach, Mumbai, during 6–11 January 2002. Nearly 80 invited and 150 poster contributions were presented at the Conference.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT version 4.2

Directory of Open Access Journals (Sweden)

T. A. M. Pugh

2012-01-01

Full Text Available A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport, which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Collaborative Research: Atmospheric Pressure Microplasma Chemistry-Photon Synergies Final Report

Energy Technology Data Exchange (ETDEWEB)

Graves, David [Univ. of California, Berkeley, CA (United States)

2017-02-07

Combining the effects of low temperature, atmospheric pressure microplasmas and microplasma photon sources shows greatly expanded range of applications of each of them. The plasma sources create active chemical species and these can be activated further by addition of photons and associated photochemistry. There are many ways to combine the effects of plasma chemistry and photochemistry, especially if there are multiple phases present. The project combines construction of appropriate test experimental systems, various spectroscopic diagnostics and mathematical modeling.

A tribute to Stanislao Cannizzaro, chemical informationist and photochemist.

Science.gov (United States)

Roth, Heinz D

2011-12-01

Stanislao Cannizzaro is known widely for the Cannizzaro reaction, the "disproportionation" of benzaldehyde upon reaction with alkali, for his approach to teaching chemistry, "Sunto di un corso di filosofia chimica", which he presented at the Karlsruhe Congress of 1860, and for his work on the photochemistry of santonin. In Cannizzaro's laboratory two research associates, Giacomo Ciamician and Paul Silber, and a senior colleague, Emanuele Paternó, became acquainted with the basic methods of sunlight-inducd photochemistry.

Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

Science.gov (United States)

Hlavacek, Nikolaus C.; McAnally, Michael O.; Drucker, Stephen

2013-02-01

The cavity ringdown absorption spectrum of acrolein (propenal, CH2=CH—CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0^0_0 band of the T1(n, π*) ← S0 system. We analyzed the 0^0_0 rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], 10.1063/1.470569, which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T1(n, π*) inertial constants to the room-temperature contour. The determined values (cm-1), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T1(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T1(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)], 10.1002/qua.21803 used a triple zeta-quality basis set to optimize the T1(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial

Use of BEIR V and UNSCEAR 1988 in radiation risk assessment: Lifetime total cancer mortality risk estimates at low doses and low dose rates for low-LET radiation

International Nuclear Information System (INIS)

1992-12-01

In November 1986, the Department of Defense (DoD) asked the Committee on Interagency Radiation Research and Policy Coordination (CIRRPC) to develop a coordinated Federal position on risk assessment for low levels of ionizing radiation. Since Federal risk assessment activities are based primarily on the scientific data and analyses in authoritative review documents prepared by groups like the National Academy of Sciences' Committee on the Biological Effects of Ionizing Radiation (BEIR), the National Council on Radiation Protection and Measurements (NCRP) and the United Nations' Scientific Committee on the Effects of Atomic Radiation (UNSCEAR), DoD proposed that the CIRRPC Science Panel undertake the task of providing coordinated interagency positions on the use of information in the reports of such groups. The practice has been for individual Federal agencies to interpret and decide independently how to use the information provided in such reports. As a result of its deliberations, the Subpanel recommends two nominal risk estimates for lifetime total cancer mortality following whole-body exposure to low levels of low-LET ionizing radiation, one for the general population and one for the working-age population (see Section II). The recommended risk estimates reflect the general agreement of information in BEIR V and UNSCEAR 1988 for total cancer mortality. The Subpanel's risk estimates and associated statements are intended to meet the needs of the Federal agencies for: (a) values that are current; (b) values that are relevant to the low-dose and low dose-rate ionizing radiation exposures principally encountered in carrying out Federal responsibilities; (c) a statement of the change in the estimates of lifetime total cancer mortality relative to estimates in previous authoritative review documents; and (d) a practical statement on the scientific uncertainty associated with applying the lifetime total cancer mortality values at very low doses

Very thin thermally stable TiO2 blocking layers with enhanced electron transfer for solar cells

Czech Academy of Sciences Publication Activity Database

Kment, Š.; Krýsová, Hana; Hubička, Zdeněk; Kmentová, H.; Kavan, Ladislav; Zbořil, R.

2017-01-01

Roč. 9, DEC 2017 (2017), s. 122-129 ISSN 2352-9407 R&D Projects: GA MŠk(CZ) LM2015073; GA ČR GA13-07724S Grant - others:GA MŠk(CZ) LO1305 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Cyclic voltammetry * Impedance spectroscopy * Photochemistry * Solar cell * TiO blocking layer 2 Subject RIV: CG - Electrochemistry; BM - Solid Matter Physics ; Magnetism (FZU-D) OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis); Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)

Laser studies of chemical reaction and collision processes

Energy Technology Data Exchange (ETDEWEB)

Flynn, G. [Columbia Univ., New York, NY (United States)

1993-12-01

This work has concentrated on several interrelated projects in the area of laser photochemistry and photophysics which impinge on a variety of questions in combustion chemistry and general chemical kinetics. Infrared diode laser probes of the quenching of molecules with {open_quotes}chemically significant{close_quotes} amounts of energy in which the energy transferred to the quencher has, for the first time, been separated into its vibrational, rotational, and translational components. Probes of quantum state distributions and velocity profiles for atomic fragments produced in photodissociation reactions have been explored for iodine chloride.

Does Parmelina tiliacea lichen photosystem II survive at liquid nitrogen temperatures?

Science.gov (United States)

Oukarroum, Abdallah; El Gharous, Mohamed; Strasser, Reto J

2017-02-01

Parmelina tiliacea lichens kept in the wet and dry state were stored in liquid nitrogen for 1 week and the subsequent recovery of their photosynthetic apparatus was followed. The chlorophyll a fluorescence rise and the maximum quantum yield of primary photochemistry φ Po (F V /F M ) were analysed for this purpose. Storage of wet thalli for 1 week in liquid nitrogen led to an impairment of photosystem II and probably the photosynthetic apparatus as a whole, from which the thalli did not recover over time. Thalli exposed in the dry state thalli were far less affected by the treatment and recovered well. These results indicate that the thalli are extremely tolerant to liquid nitrogen temperatures only in the dry state. Copyright © 2016 Elsevier Inc. All rights reserved.

Synchronously Pumped Optical Parametric Oscillator with Intracavity Difference Frequency Mixing

Science.gov (United States)

1998-06-29

departing from the Rrpubbc of Panama when traveling on official orders." * " De eonfortnidad con el Parrafo 5u) del Articulo XVII del Acuerdo para U...isotopic photochemistry using an optical parametric oscillator and a down converter," J. Opt. ( Paris ), , no. 14, pp. 43-48, 1983. [4] J. D. Kafka, M. L...isotopic photochemistry using an optical parametric oscillator and a down converter," J. Opt. ( Paris ), , no. 14, pp. 43-48, 1983. [4] J. D. Kafka, M. L

Internal Targeting and External Control: Phototriggered Targeting in Nanomedicine.

Science.gov (United States)

Arrue, Lily; Ratjen, Lars

2017-12-07

The photochemical control of structure and reactivity bears great potential for chemistry, biology, and life sciences. A key feature of photochemistry is the spatiotemporal control over secondary events. Well-established applications of photochemistry in medicine are photodynamic therapy (PDT) and photopharmacology (PP). However, although both are highly localizable through the application of light, they lack cell- and tissue-specificity. The combination of nanomaterial-based drug delivery and targeting has the potential to overcome limitations for many established therapy concepts. Even more privileged seems the merger of nanomedicine and cell-specific targeting (internal targeting) controlled by light (external control), as it can potentially be applied to many different areas of medicine and pharmaceutical research, including the aforementioned PDT and PP. In this review a survey of the interface of photochemistry, medicine and targeted drug delivery is given, especially focusing on phototriggered targeting in nanomedicine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2014-08-18

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

The importance of charge-transfer interactions in determining chromophoric dissolved organic matter (CDOM) optical and photochemical properties.

Science.gov (United States)

Sharpless, Charles M; Blough, Neil V

2014-04-01

Absorption of sunlight by chromophoric dissolved natural organic matter (CDOM) is environmentally significant because it controls photic zone depth and causes photochemistry that affects elemental cycling and contaminant fate. Both the optics (absorbance and fluorescence) and photochemistry of CDOM display unusual properties that cannot easily be ascribed to a superposition of individual chromophores. These include (i) broad, unstructured absorbance that decreases monotonically well into the visible and near IR, (ii) fluorescence emission spectra that all fall into a single envelope regardless of the excitation wavelength, and (iii) photobleaching and photochemical quantum yields that decrease monotonically with increasing wavelength. In contrast to a simple superposition model, these phenomena and others can be reasonably well explained by a physical model in which charge-transfer interactions between electron donating and accepting chromophores within the CDOM control the optical and photophysical properties. This review summarizes current understanding of the processes underlying CDOM photophysics and photochemistry as well as their physical basis.

The Life of Pi Star: Exploring the Exciting and Forbidden Worlds of the Benzophenone Photophore.

Science.gov (United States)

Dormán, György; Nakamura, Hiroyuki; Pulsipher, Abigail; Prestwich, Glenn D

2016-12-28

The widespread applications of benzophenone (BP) photochemistry in biological chemistry, bioorganic chemistry, and material science have been prominent in both academic and industrial research. BP photophores have unique photochemical properties: upon n-π* excitation at 365 nm, a biradicaloid triplet state is formed reversibly, which can abstract a hydrogen atom from accessible C-H bonds; the radicals subsequently recombine, creating a stable covalent C-C bond. This light-directed covalent attachment process is exploited in many different ways: (i) binding/contact site mapping of ligand (or protein)-protein interactions; (ii) identification of molecular targets and interactome mapping; (iii) proteome profiling; (iv) bioconjugation and site-directed modification of biopolymers; (v) surface grafting and immobilization. BP photochemistry also has many practical advantages, including low reactivity toward water, stability in ambient light, and the convenient excitation at 365 nm. In addition, several BP-containing building blocks and reagents are commercially available. In this review, we explore the "forbidden" (transitions) and excitation-activated world of photoinduced covalent attachment of BP photophores by touring a colorful palette of recent examples. In this exploration, we will see the pros and cons of using BP photophores, and we hope that both novice and expert photolabelers will enjoy and be inspired by the breadth and depth of possibilities.

Source-receptor relationships for atmospheric mercury in urban Detroit, Michigan

Science.gov (United States)

Lynam, Mary M.; Keeler, Gerald J.

Speciated hourly mercury measurements were made in Detroit, Michigan during four sampling campaigns from 2000 to 2002. In addition, other chemical and meteorological parameters were measured concurrently. These data were analyzed using principal components analysis (PCA) in order to develop source receptor relationships for mercury species in urban Detroit. Reactive gaseous mercury (RGM) was found to cluster on two main factors; photochemistry and a coal combustion factor. Particulate phase mercury, Hg p, tended to cluster with RGM on the same factor. The photochemistry factor corroborates previous observations of the presence of RGM in highly oxidizing atmospheres and does not point to a specific source emission type. Instead, it likely represents local emissions and regional transport of photochemically processed air masses. The coal combustion factor is indicative of emissions from coal-fired power plants near the receptor site. Elemental mercury was found on a factor for combustion from automobiles and points to the influence these emissions have on the receptor site, which was located proximate to two major interstate highways and the largest border crossing in the United States. This analysis reveals that the receptor site which is located in an industrialized sector of the city of Detroit experienced impacts from both stationary and point sources of mercury that are both local and regional in nature.

Semiconductor Quantum Dots with Photoresponsive Ligands.

Science.gov (United States)

Sansalone, Lorenzo; Tang, Sicheng; Zhang, Yang; Thapaliya, Ek Raj; Raymo, Françisco M; Garcia-Amorós, Jaume

2016-10-01

Photochromic or photocaged ligands can be anchored to the outer shell of semiconductor quantum dots in order to control the photophysical properties of these inorganic nanocrystals with optical stimulations. One of the two interconvertible states of the photoresponsive ligands can be designed to accept either an electron or energy from the excited quantum dots and quench their luminescence. Under these conditions, the reversible transformations of photochromic ligands or the irreversible cleavage of photocaged counterparts translates into the possibility to switch luminescence with external control. As an alternative to regulating the photophysics of a quantum dot via the photochemistry of its ligands, the photochemistry of the latter can be controlled by relying on the photophysics of the former. The transfer of excitation energy from a quantum dot to a photocaged ligand populates the excited state of the species adsorbed on the nanocrystal to induce a photochemical reaction. This mechanism, in conjunction with the large two-photon absorption cross section of quantum dots, can be exploited to release nitric oxide or to generate singlet oxygen under near-infrared irradiation. Thus, the combination of semiconductor quantum dots and photoresponsive ligands offers the opportunity to assemble nanostructured constructs with specific functions on the basis of electron or energy transfer processes. The photoswitchable luminescence and ability to photoinduce the release of reactive chemicals, associated with the resulting systems, can be particularly valuable in biomedical research and can, ultimately, lead to the realization of imaging probes for diagnostic applications as well as to therapeutic agents for the treatment of cancer.

Excited- and Ground-State Versions of the Tri-.pi.-methane Rearrangement: Mechanistic and Exploratory Organic Photochemistry

Czech Academy of Sciences Publication Activity Database

Zimmerman, H. E.; Církva, Vladimír

2001-01-01

Roč. 66, č. 5 (2001), s. 1839-1851 ISSN 0022-3263 Grant - others:NSF(US) CHE-9709005 Keywords : Tri-.pi.-methane rearrangement * molecular systems * reaction Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 3.280, year: 2001

Surveys of research in the Chemistry Division, Argonne National Laboratory

Energy Technology Data Exchange (ETDEWEB)

Grazis, B.M. [ed.

1992-11-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Surveys of research in the Chemistry Division, Argonne National Laboratory

Energy Technology Data Exchange (ETDEWEB)

Grazis, B.M. (ed.)

1992-01-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Generation and photosensitization properties of the oxidized radical of riboflavin: a laser flash photolysis study

International Nuclear Information System (INIS)

Han Zhenhui; Lu Changyuan; Wang Wenfeng; Lin Weizhen; Yao Side; Lin Nianyun

2000-01-01

Direct excitation of riboflavin with 248 nm laser gives rise to a transient absorption spectrum with contributions from (1) oxidized radical, (2) hydrated electron, (3) triplet state and reduced radical, and distinction between the transient species below 360 nm is difficult for the absorption overlapped. The RF ·+ or RF(-H) · has been clearly produced via direct photoionization by 248 nm laser in aqueous solution, which has been unambiguously identified by SO 4 ·- radical oxidation, although its transient absorption can not be observed clearly for both lower absorption coefficient (ε = 2000 dm 3 mol -1 cm -1 at 640 nm at pH 7.1) and overlap from others. In the present paper, electron transfer from purine and pyrimidine nucleotides to one-electron oxidized radical of riboflavin were observed for the first time in aqueous solution, and the reaction rate constants were determined respectively, which would obviously be of considerable significance in vivo and in vitro. The results clearly demonstrate the importance of oxidized radical of riboflavin in flavin photochemistry and photobiology. These reaction paths are important for the elucidation of the interaction between riboflavin and DNA nucleotides under photoexcitation. When riboflavin was excited, triplet state and oxidized radical can be formed directly or by sequence reactions of triplet state. In the presence of DNA, electron transfer can take place to form a base radical cation, then hole migration to GG step along base-stacking of DNA leads to DNA strand scission, which has been verified by many steady product analysis. This selective cleavage of DNA shows the potential application of riboflavin as a site-specify photonuclease, which has become a highlight' in the currently photochemistry, photomedicine and photobiology areas. The mechanism implies that riboflavin can be applied potentially to photosensitization of oxygen deficient or under high intensity pulsed laser irradiation. (author)

Mapping the Excited State Potential Energy Surface of a Retinal Chromophore Model with Multireference and Equation-of-Motion Coupled-Cluster Methods.

Science.gov (United States)

Gozem, Samer; Melaccio, Federico; Lindh, Roland; Krylov, Anna I; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2013-10-08

The photoisomerization of the retinal chromophore of visual pigments proceeds along a complex reaction coordinate on a multidimensional surface that comprises a hydrogen-out-of-plane (HOOP) coordinate, a bond length alternation (BLA) coordinate, a single bond torsion and, finally, the reactive double bond torsion. These degrees of freedom are coupled with changes in the electronic structure of the chromophore and, therefore, the computational investigation of the photochemistry of such systems requires the use of a methodology capable of describing electronic structure changes along all those coordinates. Here, we employ the penta-2,4-dieniminium (PSB3) cation as a minimal model of the retinal chromophore of visual pigments and compare its excited state isomerization paths at the CASSCF and CASPT2 levels of theory. These paths connect the cis isomer and the trans isomer of PSB3 with two structurally and energetically distinct conical intersections (CIs) that belong to the same intersection space. MRCISD+Q energy profiles along these paths provide benchmark values against which other ab initio methods are validated. Accordingly, we compare the energy profiles of MRPT2 methods (CASPT2, QD-NEVPT2, and XMCQDPT2) and EOM-SF-CC methods (EOM-SF-CCSD and EOM-SF-CCSD(dT)) to the MRCISD+Q reference profiles. We find that the paths produced with CASSCF and CASPT2 are topologically and energetically different, partially due to the existence of a "locally excited" region on the CASPT2 excited state near the Franck-Condon point that is absent in CASSCF and that involves a single bond, rather than double bond, torsion. We also find that MRPT2 methods as well as EOM-SF-CCSD(dT) are capable of quantitatively describing the processes involved in the photoisomerization of systems like PSB3.

Summaries of the 40. Scientific Assembly of Polish Chemical Society and Association of Engineers and Technicians of Chemical Industry

International Nuclear Information System (INIS)

1997-01-01

Annual 40. Scientific Assembly of Polish Chemical Society and Association of Engineers and Technicians of Chemical Industry has been held in Gdansk on 22-26 September 1997. The most valuable scientific results obtained in Polish Laboratories have been presented in 22 main sections and 7 symposia directed especially at following subjects: analytical chemistry, biochemistry, solid state chemistry and material science, physical chemistry, heteroorganic and coordination chemistry, medical and pharmaceutical chemistry, metalorganic chemistry, inorganic and organic chemistry, polymers chemistry, chemistry and environment protection, theoretical chemistry, chemical didactics, photochemistry, radiation chemistry and chemical kinetics, chemical engineering, catalysis, crystallochemistry, chemical technology, electrochemistry, and instrumental methods

Infrared spectroscopy and photochemistry of NCCN+ and CNCN+ trapped in solid neon

International Nuclear Information System (INIS)

Jacox, Marilyn E.; Thompson, Warren E.

2007-01-01

When a Ne:NCCN sample is codeposited at 4.3 K with neon atoms that have been excited in a microwave discharge, the infrared and near infrared spectra of the resulting deposit include a prominent peak at 1799.5 cm -1 , previously assigned to ν 3 of NCCN + , and several new absorptions at higher frequencies which are contributed by combination bands of ground-state NCCN + . The exposure of the deposit to near infrared and red light results in the appearance of two new absorptions which are attributed to CNCN + . The reverse isomerization occurs when the sample is exposed to near ultraviolet radiation, but the two new absorptions are regenerated upon subsequent irradiation with near infrared and red light

Molecular structure, vibrational spectra and photochemistry of 5-mercapto-1-methyltetrazole

Science.gov (United States)

Gómez-Zavaglia, A.; Reva, I. D.; Frija, L.; Cristiano, M. L.; Fausto, R.

2006-04-01

In this work, 5-mercapto-1-methyltetrazole was studied by low temperature matrix-isolation and solid-state infrared spectroscopy, DFT(B3LYP)/6-311++G(d,p) calculations and photochemical methods. In the low temperature neat solid phase and isolated in an argon matrix, the compound was found to exist in the 1-methyl-1,4-dihydro-5 H-tetrazole-5-thione tautomeric form. The infrared spectra of the compound were fully assigned and correlated with structural properties. In situ UV-irradiation ( λ>235 nm) of the matrix-isolated monomer is shown to induce different photochemical processes, all of them involving cleavage of the tetrazole ring: e.g. (1) molecular nitrogen expulsion, with production of 1-methyl-1 H-diazirene-3-thiol, which is produced in two different conformers; (2) ring cleavage leading to production of methyl isothiocyanate and azide; (3) simultaneous elimination of nitrogen and sulphur with production of N-methylcarbodiimide. Following these photoprocesses, subsequent reactions occur, leading to production of methyl diazene, carbon monosulphide and nitrogen hydride. Spectroscopic evidence of the production of the above-mentioned chemical species is provided.

Relaxation Mechanisms of 5-Azacytosine.

Science.gov (United States)

Giussani, Angelo; Merchán, Manuela; Gobbo, João Paulo; Borin, Antonio Carlos

2014-09-09

The photophysics and deactivation pathways of the noncanonical 5-azacytosine nucleobase were studied using the CASPT2//CASSCF protocol. One of the most significant differences with respect to the parent molecule cytosine is the presence of a dark (1)(nNπ*) excited state placed energetically below the bright excited state (1)(ππ*) at the Franck-Condon region. The main photoresponse of the system is a presumably efficient radiationless decay back to the original ground state, mediated by two accessible conical intersections involving a population transfer from the (1)(ππ*) and the (1)(nNπ*) states to the ground state. Therefore, a minor contribution of the triplet states in the photophysics of the system is expected, despite the presence of a deactivation path leading to the lowest (3)(ππ*) triplet state. The global scenario on the photophysics and photochemistry of the 5-azacytosine system gathered on theoretical grounds is consistent with the available experimental data, taking especially into account the low values of the singlet-triplet intersystem crossing and fluorescence quantum yields observed.

Photochemistry and enzymology of photosynthesis

Energy Technology Data Exchange (ETDEWEB)

Radmer, R.

1979-07-30

In the first task, a specially designed mass spectrometer system monitors the gas exchange occurring in response to single short flashes of light. This apparatus will be primarily used to study photosystem II donor reactions, such as the photooxidation of hydroxylamine, hydrazine, and hydrogen peroxide. This technique will also be used to study the light-induced exchange of O/sub 2/ and CO/sub 2/ in algae. The second task, biochemical studies, will focus on the role of chloroplast copper in photosynthesis. We propose to isolate, purify, and characterize the chloroplast copper enzyme polyphenol oxidase, and attempt to elucidate its role in photosynthesis. These studies will be integrated with a new program devoted to the biochemical response of the photosynthetic membrane to stress. The third task is a series of studies on the light-harvesting and electron-transport mechanisms of C/sub 4/ plants. This program will address three basic problems: (1) the effect of different preparative procedures on various photosynthetic reactions, with particular emphasis on photosystem II reactions in corn bundle sheath chloroplasts; (2) the development and testing of photosystem II assays; and (3) studies of the stoichiometry of electron carriers in bundle sheath chloroplasts, and whether cyclic phosphorylation could be a major pathway in this tissue.

Photochemistry in rare gas clusters

International Nuclear Information System (INIS)

Moeller, T.; Haeften, K. von; Pietrowski, R. von

1999-01-01

In this contribution photochemical processes in pure rare gas clusters will be discussed. The relaxation dynamics of electronically excited He clusters is investigated with luminescence spectroscopy. After electronic excitation of He clusters many sharp lines are observed in the visible and infrared spectral range which can be attributed to He atoms and molecules desorbing from the cluster. It turns out that the desorption of electronically excited He atoms and molecules is an important decay channel. The findings for He clusters are compared with results for Ar clusters. While desorption of electronically excited He atoms is observed for all clusters containing up to several thousand atoms a corresponding process in Ar clusters is only observed for very small clusters (N<10). (orig.)

Photochemistry in rare gas clusters

Energy Technology Data Exchange (ETDEWEB)

Moeller, T.; Haeften, K. von; Pietrowski, R. von [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Hamburger Synchrotronstrahlungslabor; Laarman, T. [Universitaet Hamburg, II. Institut fuer Experimentalphysik, Luruper Chaussee 149, D-22761 Hamburg (Germany)

1999-12-01

In this contribution photochemical processes in pure rare gas clusters will be discussed. The relaxation dynamics of electronically excited He clusters is investigated with luminescence spectroscopy. After electronic excitation of He clusters many sharp lines are observed in the visible and infrared spectral range which can be attributed to He atoms and molecules desorbing from the cluster. It turns out that the desorption of electronically excited He atoms and molecules is an important decay channel. The findings for He clusters are compared with results for Ar clusters. While desorption of electronically excited He atoms is observed for all clusters containing up to several thousand atoms a corresponding process in Ar clusters is only observed for very small clusters (N<10). (orig.)

Metallic Carbon Nanotubes and Ag Nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Brus, Louis E

2014-03-04

The goal of this DOE solar energy research was to understand how visible light interacts with matter, and how to make electric excitations evolve into separated electrons and holes in photovoltaic cells, especially in nanoparticles and nanowires. Our specific experiments focused on A) understanding plasmon enhanced spectroscopy and charge-transfer (metal-to-molecule) photochemistry on the surface of metallic particles and B) the spectroscopy and photochemistry of carbon nanotubes and graphene. I also worked closely with R. Friesner on theoretical studies of photo-excited electrons near surfaces of titanium dioxide nanoparticles; this process is relevant to the Gratzel photovoltaic cell.

Gas response behaviour and photochemistry of borondiketonate in acrylic polymer matrices for sensing applications.

Science.gov (United States)

Arias Espinoza, Juan Diego; Sazhnikov, Viacheslav; Smits, Edsger C P; Ionov, Dmirity; Kononevich, Yuriy; Yakimets, Iryna; Alfimov, Mikael; Schoo, Herman F M

2014-11-01

The fluorescent spectra in combination with gas response behavior of acrylic polymers doped with dibenzoyl(methanato)boron difluoride (DBMBF2) were studied by fluorescence spectroscopy and time-resolved fluorescence lifetime. The role of acrylic matrix polarity upon the fluorescence spectra and fluorescence lifetime was analyzed. Changes in emission of the dye doped polymers under exposure to toluene, n-hexane and ethanol were monitored. The fluorescence lifetimes were measured for the singlet excited state as well as the exciplex formed between DBMBF2 and toluene. A reduction of the transition energy to the first singlet-excited state in the four polymers was observed, compared to solution. Reversible exciplex formation, viz. a red shifted fluorescence emission was perceived when exposing the polymers to toluene, while for hexane and ethanol only reversible reduction of the fluorescence occurred. Longer singlet and shorter exciplex lifetimes were observed for non-polar matrixes. The latter mechanism is explained in function of the lower charge transfer character of the exciplex in non-polar matrixes. Additionally, the quantum yield of the dye in the polymer matrix increased almost seventh-fold compared to values for solution.

Internal reflection flash photolysis study of the photochemistry of eosin at TiO sub 2 semiconductor electrodes

Energy Technology Data Exchange (ETDEWEB)

Ryan, M.A.; Fitzgerald, E.C.; Spitler, M.T. (Polaroid Corp., Cambridge, MA (USA))

1989-08-10

It is shown that the photoelectrochemical data on eosin Y sensitized TiO{sub 2} single-crystal electrodes cannot be interpreted unambiguously without concomitant data from flash photolysis measurements on this system. By use of a combination of internal reflection spectroscopy and laser flash photolysis, electron exchange with TiO{sub 2} was observed for the excited singlet state, the triplet state, and the cation radical of the dye. With a temporal resolution of 100 ns, the kinetics of the charge transfer are compared with those of the dye in solution and used to interpret the photoelectrochemistry of the dye at the electrode. Spectroscopic evidence revealed photocurrent production by the triplet state and a reduction of the eosin cation radical by electrons from the TiO{sub 2} conduction band and by hydroquinone.

First Principles Modeling and Interpretation of Ionization-Triggered Charge Migration in Molecules

Science.gov (United States)

Bruner, Adam; Hernandez, Sam; Mauger, Francois; Abanador, Paul; Gaarde, Mette; Schafer, Ken; Lopata, Ken

Modeling attosecond coherent charge migration in molecules is important for understanding initial steps of photochemistry and light harvesting processes. Ionization triggered hole migration can be difficult to characterize and interpret as the dynamics can be convoluted with excited states. Here, we introduce a real-time time-dependent density functional theory (RT-TDDFT) approach for modeling such dynamics from first principles. To isolate the specific hole dynamics from excited states, Fourier transform analysis and orbital occupations are used to provide a spatial hole representation in the frequency domain. These techniques are applied to hole transfer across a thiophene dimer as well as core-hole triggered valence motion in nitrosobenzene. This work was supported by U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0012462.

A importância do estado excitado 3MLCT de compostos de Ru(II, Re(I e Ir(III no desenvolvimento de fotossensores, oleds e fotorredução de CO2

Directory of Open Access Journals (Sweden)

Andressa V. Müller

Full Text Available The photochemistry and photophysics of coordination compounds have been extensively investigated not only because their structure, stability, reactivity dependence on the metal center oxidation state and the coordinated ligand; but also for their electronic transitions in a wide range of visible radiation. The knowledge of light absorption, excited state deactivation, sensitization and quenching processes are crucial to their manipulation aiming the development of systems capable of execute useful functions such as photosensors and/or probes, luminescent devices and molecular systems to convert sunlight into other types of energy. In this review, the progresses and challenges of biomolecules photosensors, organic light emitting diodes and CO2 photoreduction catalysts based on ruthenium(II, rhenium(I or iridium(III coordination compounds are discussed based on their photochemical and photophysical processes.

On the role of the simplest S-nitrosothiol, HSNO, in atmospheric and biological processes

Energy Technology Data Exchange (ETDEWEB)

Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr; Linguerri, Roberto [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Francisco, Joseph S. [Department of Chemistry and Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47906 (United States)

2013-12-21

Using state-of-the-art theoretical methods, we investigate the lowest electronic states of singlet and triplet spin multiplicities of HSNO. These computations are done using configuration interaction ab initio methods and the aug-cc-pV5Z basis set. One-dimensional cuts of the six-dimensional potential energy surfaces of these electronic states along the HS, SN stretches and HSN, SNO bending and torsion coordinates are calculated. Several avoided crossings and conical intersections are found. We computed also radiative lifetimes and spin-orbit couplings of these electronic states. Our work shows that the dynamics on these excited states is very complex, and suggest that multi-step mechanisms will populate the ground state via radiationless processes or lead to predissociation or intramolecular isomerization. For instance, these potentials are used to propose mechanisms for the IR, Vis, and UV light-induced cis-trans interconversions of HSNO and reactivity towards HS + NO and H + SNO products. Our findings are in good agreement with previous experimental studies on the photochemistry of HSNO. The atmospheric implication of HSNO is also discussed.

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

Science.gov (United States)

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.

Coherent Control of Multiphoton Transitions in the Gas and Condensed Phases with Shaped Ultrashort Pulses

International Nuclear Information System (INIS)

Dantus, Marcos

2008-01-01

Controlling laser-molecule interactions has become an integral part of developing devices and applications in spectroscopy, microscopy, optical switching, micromachining and photochemistry. Coherent control of multiphoton transitions could bring a significant improvement of these methods. In microscopy, multi-photon transitions are used to activate different contrast agents and suppress background fluorescence; coherent control could generate selective probe excitation. In photochemistry, different dissociative states are accessed through two, three, or more photon transitions; coherent control could be used to select the reaction pathway and therefore the yield-specific products. For micromachining and processing a wide variety of materials, femtosecond lasers are now used routinely. Understanding the interactions between the intense femtosecond pulse and the material could lead to technologically important advances. Pulse shaping could then be used to optimize the desired outcome. The scope of our research program is to develop robust and efficient strategies to control nonlinear laser-matter interactions using ultrashort shaped pulses in gas and condensed phases. Our systematic research has led to significant developments in a number of areas relevant to the AMO Physics group at DOE, among them: generation of ultrashort phase shaped pulses, coherent control and manipulation of quantum mechanical states in gas and condensed phases, behavior of isolated molecules under intense laser fields, behavior of condensed phase matter under intense laser field and implications on micromachining with ultrashort pulses, coherent control of nanoparticles their surface plasmon waves and their nonlinear optical behavior, and observation of coherent Coulomb explosion processes at 10 16 W/cm 2 . In all, the research has resulted in 36 publications (five journal covers) and nine invention disclosures, five of which have continued on to patenting

76 FR 21712 - Meeting of the Ocean Research and Resources Advisory Industry Sub-Panel

Science.gov (United States)

2011-04-18

... creative problem-solving to overcome impediments to industry progress toward deploying operational projects... held at the Consortium for Ocean Leadership, 1201 New York Avenue, NW., 4th Floor, Washington, DC 20005...

The Fermilab program for the next decade a response to the Gilman HEPAP subpanel

International Nuclear Information System (INIS)

Pordes, S.

1997-10-01

We have divided this description of our plans for the Laboratory program into seven parts. The first five sections describe the ongoing technical work and the broad range of physics opportunities available at Fermilab. These are organized into: our plans for the accelerator complex; our plans for facilities for performing experiments; the program of experiments we presently foresee; our plans for involvement with the LHC; and our plans for R ampersand D towards a future facility which recaptures the energy frontier. The final sections summarize: our priorities and our planning strategy for making choices for the future, and our budget request to support the Fermilab program as we approach the fundamental challenges of elementary particle physics over the next ten years

The Emission, Lifetimes, and Formation Threshold of the Vegard-Kaplan Transition of Solid Nitrogen Exposed to Far-ultraviolet Radiation

Science.gov (United States)

Lu, Hsiao-Chi; Lo, Jen-Iu; Peng, Yu-Chain; Chou, Sheng-Lung; Lin, Meng-Yeh; Cheng, Bing-Ming

2016-11-01

Irradiation of solid nitrogen at 4 K with far-ultraviolet light from a synchrotron caused excitation to the upper state of the Vegard-Kaplan (VK) system; the emission in that system was simultaneously recorded in wavelength region 200-440 nm. The lifetimes of emission lines for VK (0, 1) to (0, 12) transitions were measured in the range of 2.12 ˜ 2.65 s. The threshold wavelength to observe the VK emission was 175.0 ± 3.5 nm, corresponding to energy 7.08 ± 0.14 eV. This investigation of the generation of icy VK nitrogen enhances our understanding of its photochemistry in space.

THE EMISSION, LIFETIMES, AND FORMATION THRESHOLD OF THE VEGARD–KAPLAN TRANSITION OF SOLID NITROGEN EXPOSED TO FAR-ULTRAVIOLET RADIATION

Energy Technology Data Exchange (ETDEWEB)

Lu, Hsiao-Chi; Lo, Jen-Iu; Peng, Yu-Chain; Chou, Sheng-Lung; Lin, Meng-Yeh; Cheng, Bing-Ming, E-mail: bmcheng@nsrrc.org.tw [National Synchrotron Radiation Research Center, No. 101, Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China)

2016-11-20

Irradiation of solid nitrogen at 4 K with far-ultraviolet light from a synchrotron caused excitation to the upper state of the Vegard–Kaplan (VK) system; the emission in that system was simultaneously recorded in wavelength region 200–440 nm. The lifetimes of emission lines for VK (0, 1) to (0, 12) transitions were measured in the range of 2.12 ∼ 2.65 s. The threshold wavelength to observe the VK emission was 175.0 ± 3.5 nm, corresponding to energy 7.08 ± 0.14 eV. This investigation of the generation of icy VK nitrogen enhances our understanding of its photochemistry in space.

THE EMISSION, LIFETIMES, AND FORMATION THRESHOLD OF THE VEGARD–KAPLAN TRANSITION OF SOLID NITROGEN EXPOSED TO FAR-ULTRAVIOLET RADIATION

International Nuclear Information System (INIS)

Lu, Hsiao-Chi; Lo, Jen-Iu; Peng, Yu-Chain; Chou, Sheng-Lung; Lin, Meng-Yeh; Cheng, Bing-Ming

2016-01-01

Irradiation of solid nitrogen at 4 K with far-ultraviolet light from a synchrotron caused excitation to the upper state of the Vegard–Kaplan (VK) system; the emission in that system was simultaneously recorded in wavelength region 200–440 nm. The lifetimes of emission lines for VK (0, 1) to (0, 12) transitions were measured in the range of 2.12 ∼ 2.65 s. The threshold wavelength to observe the VK emission was 175.0 ± 3.5 nm, corresponding to energy 7.08 ± 0.14 eV. This investigation of the generation of icy VK nitrogen enhances our understanding of its photochemistry in space.

Binding of Substrate Locks the Electrochemistry of CRY-DASH into DNA Repair.

Science.gov (United States)

Gindt, Yvonne M; Messyasz, Adriana; Jumbo, Pamela I

2015-05-12

VcCry1, a member of the CRY-DASH family, may serve two diverse roles in vivo, including blue-light signaling and repair of UV-damaged DNA. We have discovered that the electrochemistry of the flavin adenine dinucleotide cofactor of VcCry1 is locked to cycle only between the hydroquinone and neutral semiquinone states when UV-damaged DNA is present. Other potential substrates, including undamaged DNA and ATP, have no discernible effect on the electrochemistry, and the kinetics of the reduction is unaffected by damaged DNA. Binding of the damaged DNA substrate determines the role of the protein and prevents the presumed photochemistry required for blue-light signaling.

Non-thermally activated chemistry

International Nuclear Information System (INIS)

Stiller, W.

1987-01-01

The subject is covered under the following headings: state-of-the art of non-thermally activated chemical processes; basic phenomena in non-thermal chemistry including mechanochemistry, photochemistry, laser chemistry, electrochemistry, photo-electro chemistry, high-field chemistry, magneto chemistry, plasma chemistry, radiation chemistry, hot-atom chemistry, and positronium and muonium chemistry; elementary processes in non-thermal chemistry including nuclear chemistry, interactions of electromagnetic radiations, electrons and heavy particles with matter, ionic elementary processes, elementary processes with excited species, radicalic elementary processes, and energy-induced elementary processes on surfaces and interfaces; and comparative considerations. An appendix with historical data and a subject index is given. 44 figs., 41 tabs., and 544 refs

Laser isotope separation by selective excited state photochemistry. Annual progress report, March 31, 1976--February 28, 1977

International Nuclear Information System (INIS)

Zare, R.N.

1977-03-01

Experimental results are presented providing insight into the mechanisms of photochemical separation of Cd isotopes by selective excitation of ICl in the presence of halogenated olefins. The types of scrambling reactions that can be expected in isotope separation by scavenging are discussed along with strategies for minimizing such reactions. The experimental results are summarized and the reaction mechanisms are represented by graphic equations

Analysis of the isoprene chemistry observed during the New England Air Quality Study (NEAQS) 2002 intensive experiment

Science.gov (United States)

Roberts, James M.; Marchewka, Mathew; Bertman, Steven B.; Goldan, Paul; Kuster, William; de Gouw, Joost; Warneke, Carsten; Williams, Eric; Lerner, Brian; Murphy, Paul; Apel, Eric; Fehsenfeld, Fred C.

2006-12-01

Isoprene and its first and second generation photochemical products, methyl vinyl ketone (MVK), methacrolein (MACR), and peroxymethacrylic nitric anhydride (MPAN), were measured off the coast of New England during the 2002 New England Air Quality Study (NEAQS) on board the NOAA Research Vessel Ronald H. Brown. The results of these measurements were analyzed using a simple sequential reaction model that has been used previously to examine regional oxidant chemistry. The highest isoprene impact was observed in air masses that had passed over an area of high isoprene emission WSW of Boston. The relative concentrations of isoprene and its first generation products show that the photochemistry is consistently "older" than the isoprene photochemistry observed at continental sites. The sequential reaction model was also applied to the aldehyde-PANs (Peroxycarboxylic nitric anhydride) system, and the resulting PPN (peroxypropionic nitric anhydride)/propanal and PAN (peroxyacetic nitric anhydride)/acetaldehyde relationships were consistent with additional sources of PAN in this environment, e.g., isoprene photochemistry. This isoprene source was estimated to result in approximately 1.6 to 4 times more PAN in this environment relative to that produced from anthropogenic VOCs (volatile organic compounds) alone.

A Lagrangian View of Stratospheric Trace Gas Distributions

Science.gov (United States)

Schoeberl, M. R.; Sparling, L.; Dessler, A.; Jackman, C. H.; Fleming, E. L.

1998-01-01

As a result of photochemistry, some relationship between the stratospheric age-of-air and the amount of tracer contained within an air sample is expected. The existence of such a relationship allows inferences about transport history to be made from observations of chemical tracers. This paper lays down the conceptual foundations for the relationship between age and tracer amount, developed within a Lagrangian framework. In general, the photochemical loss depends not only on the age of the parcel but also on its path. We show that under the "average path approximation" that the path variations are less important than parcel age. The average path approximation then allows us to develop a formal relationship between the age spectrum and the tracer spectrum. Using the relation between the tracer and age spectra, tracer-tracer correlations can be interpreted as resulting from mixing which connects parts of the single path photochemistry curve, which is formed purely from the action of photochemistry on an irreducible parcel. This geometric interpretation of mixing gives rise to constraints on trace gas correlations, and explains why some observations are do not fall on rapid mixing curves. This effect is seen in the ATMOS observations.

Chemical Sciences Division annual report, 1990

International Nuclear Information System (INIS)

1991-08-01

This report contains sections on the following topics: photochemistry of materials in the stratosphere, energy transfer and structural studies of molecules on surfaces, crossed molecular beams, molecular interactions, theory of atomic and molecular collision processes, selective photochemistry, photodissociation of free radicals, physical chemistry with emphasis on thermodynamic properties, chemical physics at the high photon energies, high-energy atomic physics, atomic physics, high-energy oxidizers and delocalized-electron solids, catalytic hydrogenation of CO, transition metal-catalyzed conversion of CO, NO, H 2 , and organic molecules to fuels and petrochemicals, formation of oxyacids of sulfur from SO 2 , potentially catalytic and conducting polyorganometallics, actinide chemistry, and molecular thermodynamics for phase equilibria in mixtures

Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme.

Science.gov (United States)

Li, Shaohong L; Truhlar, Donald G

2015-07-14

Time-dependent density functional theory (TDDFT) with conventional local and hybrid functionals such as the local and hybrid generalized gradient approximations (GGA) seriously underestimates the excitation energies of Rydberg states, which limits its usefulness for applications such as spectroscopy and photochemistry. We present here a scheme that modifies the exchange-enhancement factor to improve GGA functionals for Rydberg excitations within the TDDFT framework while retaining their accuracy for valence excitations and for the thermochemical energetics calculated by ground-state density functional theory. The scheme is applied to a popular hybrid GGA functional and tested on data sets of valence and Rydberg excitations and atomization energies, and the results are encouraging. The scheme is simple and flexible. It can be used to correct existing functionals, and it can also be used as a strategy for the development of new functionals.

On the impact of aircraft emitted NO{sub x} on upper troposphere photochemistry

Energy Technology Data Exchange (ETDEWEB)

Wahner, A.; Rohrer, F.; Ehhalt, D.H. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Atmosphaerische Chemie

1997-12-31

The enhanced nitrogen oxide concentrations influence the photochemical production of ozone as well as the steady state concentrations of hydroxyl radicals, OH, in the upper troposphere. That increase is small compared to the impact of NO{sub x} from fossil fuel combustion on boundary layer ozone. A simple quasi 2-D model was used for the latitude band 40 deg - 50 deg N to analyze the reasons for that. The model includes a simplified CH{sub 4} - CO chemistry and the salient sources of upper tropospheric NO{sub x}, namely lightning, stratospheric input, aircraft emissions and fast upward transport of surface emissions. It is shown that the maximum of net O{sub 3} production and OH concentrations occur at much lower NO{sub x} mixing ratios than in the lower troposphere. (author)

On the impact of aircraft emitted NO{sub x} on upper troposphere photochemistry

Energy Technology Data Exchange (ETDEWEB)

Wahner, A; Rohrer, F; Ehhalt, D H [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Atmosphaerische Chemie

1998-12-31

The enhanced nitrogen oxide concentrations influence the photochemical production of ozone as well as the steady state concentrations of hydroxyl radicals, OH, in the upper troposphere. That increase is small compared to the impact of NO{sub x} from fossil fuel combustion on boundary layer ozone. A simple quasi 2-D model was used for the latitude band 40 deg - 50 deg N to analyze the reasons for that. The model includes a simplified CH{sub 4} - CO chemistry and the salient sources of upper tropospheric NO{sub x}, namely lightning, stratospheric input, aircraft emissions and fast upward transport of surface emissions. It is shown that the maximum of net O{sub 3} production and OH concentrations occur at much lower NO{sub x} mixing ratios than in the lower troposphere. (author)

Achievement report on research and development in the Sunshine Project in fiscal 1976. Research and development of water decomposition by using a hybrid cycle composed of thermo-chemistry and photo-chemistry; 1976 nendo netsukagaku oyobi hikari kagaku hybrid cycle ni yoru mizu bunkai no kenkyu kahatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1977-03-01

This paper describes water decomposition by using a hybrid cycle composed of thermo-chemistry and photo-chemistry. Ferric sulfate and HI are obtained from ferrous sulfate and iodine via photo-chemical reaction. This is an endothermic reaction of 10.8 kcal. Then, the photo-chemically reacted aqueous solution is electrolysed to separate HI, while Fe{sup 3+} (ferric ion) is reduced and converted into Fe{sup 2+} (ferrous ion). Oxygen is generated at this time. Since mixed potential is made from iron oxidation and reduction potential and iodine potential, the electrolytic efficiency is greatly influenced by electrode materials. Ideally, an electrode material that causes only the reduction of Fe{sup 3+}, but not other reactions is preferable. The HI is decomposed into hydrogen and iodine by electrolysis. Research is continuing to acquire hydrogen from HI thermo-chemically. Endothermic reaction heat of 7 to 8 kcal has been obtained in photo-chemical reaction, the heat quantity being close to the theoretical value of 10.8. A result close to the theoretical value may be expected if the electrode material problem is solved. The basic research will be continued for a high possibility of linking the research to a pilot plant in the future. (NEDO)

Eighth International Workshop on Desorption Induced by Electronic Transitions

National Research Council Canada - National Science Library

Madey, Theodore

2001-01-01

... DIET processes, femtosecond dynamics, and photo-chemistry. Applications are myriad, including semiconductor processing, beam damage in quantitative surface analysis, photocatalysis, and surface chemistry in interplanetary space...

Studies in chemical dynamics

International Nuclear Information System (INIS)

Kuppermann, A.

1978-01-01

Progress made in the following studies is reported: low-energy electron scattering; variable-angle photoelectron spectroscopy; laser photochemistry and spectroscopy; and collisions in crossed molecular beams

Influence of arbuscular mycorrhizae on photosynthesis and water status of maize plants under salt stress.

Science.gov (United States)

Sheng, Min; Tang, Ming; Chen, Hui; Yang, Baowei; Zhang, Fengfeng; Huang, Yanhui

2008-09-01

The influence of arbuscular mycorrhizal (AM) fungus Glomus mosseae on characteristics of the growth, water status, chlorophyll concentration, gas exchange, and chlorophyll fluorescence of maize plants under salt stress was studied in the greenhouse. Maize plants were grown in sand and soil mixture with five NaCl levels (0, 0.5, 1.0, 1.5, and 2.0 g/kg dry substrate) for 55 days, following 15 days of non-saline pretreatment. Under salt stress, mycorrhizal maize plants had higher dry weight of shoot and root, higher relative chlorophyll content, better water status (decreased water saturation deficit, increased water use efficiency, and relative water content), higher gas exchange capacity (increased photosynthetic rate, stomatal conductance and transpiration rate, and decreased intercellular CO(2) concentration), higher non-photochemistry efficiency [increased non-photochemical quenching values (NPQ)], and higher photochemistry efficiency [increased the maximum quantum yield in the dark-adapted state (Fv/Fm), the maximum quantum yield in the light-adapted sate (Fv'/Fm'), the actual quantum yield in the light-adapted steady state (phiPSII) and the photochemical quenching values (qP)], compared with non-mycorrhizal maize plants. In addition, AM symbiosis could trigger the regulation of the energy biturcation between photochemical and non-photochemical events reflected in the deexcitation rate constants (kN, kN', kP, and kP'). All the results show that G. mosseae alleviates the deleterious effect of salt stress on plant growth, through improving plant water status, chlorophyll concentration, and photosynthetic capacity, while the influence of AM symbiosis on photosynthetic capacity of maize plants can be indirectly affected by soil salinity and mycorrhizae-mediated enhancement of water status, but not by the mycorrhizae-mediated enhancement of chlorophyll concentration and plant biomass.

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

Science.gov (United States)

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

2014-09-01

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

The investigation of molecular mechanisms in photodynamic action and radiobiology with nanosecond flash photolysis and pulse radiolysis: Final report for period April 1, 1972-June 30, 1987

International Nuclear Information System (INIS)

Grossweiner, L.I.

1987-07-01

Laser flash was employed to investigate initial photolysis mechanisms in enzymes and constituent aromatic amino acids. The key role of photoionization and solvated electron generation was demonstrated. The photochemistry of furocoumarins employed for phototherapy of skin diseases was investigated, emphasizing the production and subsequent reactions of singlet molecular oxygen. The photochemistry of porphyrins employed for photodynamic therapy of malignant tumors was studied, emphasizing photosensitization of model membranes, liposomes and resealed red blood cell membranes. Photosensitization in light-scattering media was investigated in a tissue model, consisting of polystyrene microspheres in an aqueous dye solution and analyzed with the diffusion approximation to radiative transfer. The diffusion approximation was employed to develop a dosimetry model for photodynamic therapy

Photoisomerization of Stilbene: The Detailed XMCQDPT2 Treatment.

Science.gov (United States)

Ioffe, I N; Granovsky, A A

2013-11-12

We report the detailed XMCQDPT2/cc-pVTZ study of trans-cis photoisomerization in one of the core systems of both experimental and computational photochemistry-the stilbene molecule. For the first time, the potential energy surface (PES) of the S1 state has been directly optimized and scanned using a multistate multiconfiguration second-order perturbation theory. We characterize the trans-stilbene, pyramidalized (phantom), and DHP-cis-stilbene geometric domains of the S1 state and describe their stationary points including the transition states between them, as well as S1/S0 intersections. Also reported are the minima and the activation barriers in the ground state. Our calculations correctly predict the kinetic isotope effect due to H/D exchange at ethylenic hydrogens, the dynamic behavior of excited cis-stilbene, and trans-cis branching ratio after relaxation to S0 through a rather unsymmetric conical intersection. In general, the XMCQDPT2 results confirm the qualitative adequacy of the TDDFT (especially SF-TDDFT) picture of the excited stilbene but also reveal quantitative discrepancies that deserve further exploration.

Theoretical insights into the photo-protective mechanisms of natural biological sunscreens: building blocks of eumelanin and pheomelanin.

Science.gov (United States)

Marchetti, Barbara; Karsili, Tolga N V

2016-02-07

Eumelanin (EM) and pheomelanin (PM) are ubiquitous in mammalian skin and hair--protecting against harmful radiation from the sun. Their primary roles are to absorb solar radiation and efficiently dissipate the excess excited state energy in the form of heat without detriment to the polymeric structure. EU and PM exist as polymeric chains consisting of exotic arrangements of functionalised heteroaromatic molecules. Here we have used state-of-the-art electronic structure calculations and on-the-fly surface hopping molecular dynamics simulations to study the intrinsic deactivation paths of various building blocks of EU and PM. Ultrafast excited state decay, via electron-driven proton transfer (in EU and PM) and proton-transfer coupled ring-opening (in PM) reactions, have been identified to proceed along hitherto unknown charge-separated states in EU and PM oligomers. These results shed light on the possible relaxation pathways that dominate the photochemistry of natural skin melanins. Extrapolation of such findings could provide a gateway into engineering more effective molecular constituents in commercial sunscreens--with reduced phototoxicity.

Umapathy, Prof. Siva

Indian Academy of Sciences (India)

Otago, New Zealand). Date of birth: 10 June 1959. Specialization: Instrumentation Development, Microspectroscopy, Laser Spectroscopy, Photochemistry and Ultrafast Dynamics Address: Professor, Department of Inorganic & Physical, Chemistry, ...

Chloroplast Redox Imbalance Governs Phenotypic Plasticity: the Grand Design of Photosynthesis Revisited

Directory of Open Access Journals (Sweden)

Norman eHuner

2012-11-01

Full Text Available Sunlight, the ultimate energy source for life on our planet, enters the biosphere as a direct consequence of the evolution of photoautotrophy. Photoautotrophs must balance the light energy absorbed and trapped through extremely fast, temperature-insensitive photochemistry with energy consumed through much slower, temperature-dependent biochemistry and metabolism. The attainment of such a balance in cellular energy flow between chloroplasts, mitochondria and the cytosol is called photostasis. Photoautotrophs sense cellular energy imbalances through modulation of excitation pressure which is a measure of the relative redox state of QA, the first stable quinone electron acceptor of PSII reaction centers. High excitation pressure constitutes a potential stress condition that can be caused either by exposure to an irradiance that exceeds the capacity of C, N and S assimilation to utilize the electrons generated from the absorbed energy or by low temperature or any stress that decreases the capacity of the metabolic pathways downstream of photochemistry to utilize photosynthetically-generated reductants. The similarities and differences in the phenotypic responses between cyanobacteria, green algae, crop plants and variegation mutants of Arabidopsis thaliana as a function of cold acclimation and photoacclimation are reconciled in terms of differential responses to excitation pressure and the predisposition of photoautotrophs to maintain photostasis. The various acclimation strategies associated with green algae and cyanobacteria versus winter cereals and Arabidopsis thaliana are discussed in terms of retrograde regulation and the grand design of photosynthesis originally proposed by Daniel Arnon in 1982.

The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

Science.gov (United States)

Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

2013-12-01

Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

People and things. CERN Courier, November 1980, v. 20(8)

International Nuclear Information System (INIS)

Anon.

1980-01-01

The article reports on achievements of various people, staff changes and position opportunities within the CERN organization and contains news updates on upcoming or past events. Each year the high energy physics programme in the USA is reviewed by a subpanel of the HEPAP (High Energy Physics Advisory Panel) meeting at Woods Hole. Among the speakers at the dedication ceremony for the new PEP electron-positron collider at SLAC on 5 September was Frank Press, President Carter's advisor on science and technology; Discovering exotic nuclear behaviour is something of a speciality at ISOLDE, the CERN on-line isotope separator. From 24-26 September, Argonne National Laboratory sponsored a Conference on the subject of ternary superconductors. Two improved portable radiation monitors have been developed at the Los Alamos Scientific Laboratory and are now being manufactured by outside industry

Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

Science.gov (United States)

Oliver, Thomas A A; Zhang, Yuyuan; Ashfold, Michael N R; Bradforth, Stephen E

2011-01-01

Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

Achievement report on research and development in the Sunshine Project in fiscal 1977. Research and development of water decomposition using mixture cycles composed by thermo-chemistry, photo-chemistry and electrochemistry; 1977 nendo netsukagaku, hikari kagaku, denki kagaku konsei cycle ni yoru suibunkai no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1978-03-01

Discussions are being made on manufacture of hydrogen and oxygen from water decomposition using mixture cycles composed by thermo-chemistry, photo-chemistry and electrochemistry using ferrous sulfate and iodine. Photo-chemical reaction produces Fe(OH)SO{sub 4} and HI, but due to difficulty of isolating Fe(OH)SO{sub 4}, photo-chemical reaction that can obtain the compound as Fe{sub 2}(SO{sub 4}){sub 3} was introduced. A method was introduced that can perform HI isolation simultaneously while performing reaction to reduce Fe{sup 3+} and turn it into Fe{sup 2+} (generating oxygen) by means of electrolysing the liquid after the former reaction. The electrolytic process decomposes HI into hydrogen and iodine (discussions on thermo-chemical decomposition is also continued). Since the photo-chemical reaction can cause reverse reaction, discussions were given on the reaction process in order to suppress the reverse reaction and enhance the conversion efficiency. This paper describes the achievements during fiscal 1977. A quantification method was elucidated on individual iodine components so that it can be used for computerized control (measurement of absorbance of I{sub 3}{sup -}) . An electrolytic tank was discussed that decomposes and isolates photo-chemical reaction products before the reverse reaction occurs. Heat diffusion method was also discussed that isolates hydrogen from HI decomposition products. (NEDO)

The Studsvik Science Research Laboratory. Progress Report 1977

International Nuclear Information System (INIS)

1978-01-01

The research activities during 1977 are reported. The research programme includes neutron physics, neutron absorption and scattering, radiation chemistry and photochemistry, radiation damage, radioactivity, and theory. (L.E.)

Molecular sciences

International Nuclear Information System (INIS)

Anon.

1975-01-01

The research in molecular sciences summarized includes photochemistry, radiation chemistry, geophysics, electromechanics, heavy-element oxidizers , heavy element chemistry collisions, atoms, organic solids. A list of publications is included

Global N Cycle: Fluxes and N2O Mixing Ratios Originating from Human Activity

Data.gov (United States)

National Aeronautics and Space Administration — Nitrogen is a major nutrient in terrestrial ecosystems and an important catalyst in tropospheric photochemistry. Over the last century human activities have...

Global N Cycle: Fluxes and N2O Mixing Ratios Originating from Human Activity

Data.gov (United States)

National Aeronautics and Space Administration — ABSTRACT: Nitrogen is a major nutrient in terrestrial ecosystems and an important catalyst in tropospheric photochemistry. Over the last century human activities...

Isoprene photochemistry over the Amazon rainforest.

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (Amazon rainforest.

The changing photochemistry of the troposhere

Energy Technology Data Exchange (ETDEWEB)

Crutzen, P.J.; Zimmermann, P.H. (Div. of Atmospheric Chemistry, Max-Planck-Institute for Chemistry, Mainz (DE))

1991-01-01

The cemistry of the troposhere is substantially influenced by a wide range of chemical processes which are primarily driven by the action of solar ultraviolet radiation of wavelengths shorter that about 310 nm on ozone and water vapour. This leads to the formation of hydroxyl (OH) radicals which, despite very low troposheric concentrations, remove most gases that are emitted into the atmosphere by natural and anthropogenic processes. Although troposheric ozone only makes up about 10% of all atmospheric ozone, through the formation of OH, it determines the oxidation efficiency of the atmosphere and it is, therefore, of the utmost importance for maintaining the chemical composition of the atmosphere. Due to a variety of human activities, leading especially to increasing emissions of CH{sub 4}, CO and NO{sub x}, it is conceivable that the concentrations of ozone are increasing in polluted and those of hydroxyl decreasing in clean troposheric environments. The result is most likely an overall decrease in the oxidation efficiency of the atmosphere and consequently a buildup of several long-lived trace gases that are primarily removed by reaction with OH. Here we discuss the most important processes that determine the oxidation efficiency of the atmosphere and give some examples of changes in O{sub 3}, CO, and OH concentration distributions that may have occurred as a result of human activities. (au).

Studies on the photochemistry of vision

International Nuclear Information System (INIS)

Broek, A.D.

1982-01-01

The subject of this study is the preparation of 11-cis and 9-cis retinals deuterated at specific positions of the chain with a high deuterium incorporation and a high chemical purity. The reaction of opsin with these compounds gives rhodopsin and isorhodopsin with a deuterium label on the predetermined positions of the chromophore. For the introduction of the deuterium the author has used the conversion of a propargyl alcohol into an ethylenic alcohol by the LiAlH 4 reductive method. (Auth./C.F.)

Photochemistry of DNA containing iodinated cytosine

Energy Technology Data Exchange (ETDEWEB)

Rahn, R O; Stafford, R S [Oak Ridge National Lab., TN (USA)

1979-10-01

Irradiation at 313 nm of compounds containing iodinated cytosine moieties results in the photolysis of iodine. Photolysis occurs with a quantum yield of 0.022-0.024 for 5-iododeoxycytidine and 5-iododeoxycytidine monophosphate, and 0.004-0.008 for iodinated DNA as well as for iodinated polycytidylate. Photodegradation of the cytosine moiety occurs when air is present during irradiation, presumably due to the reaction of oxygen with the cytosyl radical formed when iodine is lost. This oxygen promoted photodegradation destroys the cytosine chromophore and is complete in the monomers but occurs to only a limited extent in the polymers. In the absence of oxygen or in the presence of ethanol, photodegradation is prevented and the loss of iodine leads exclusively to the formation of the cytosine chromophore. In DNA, the loss of iodine is accompanied by the formation of sugar damage and/or chain breaks. As measured by sedimentation in alkaline sucrose gradients, approximately one break is made for every six iodines lost in denatured DNA. The frequency of chain breakage per iodine photolyzed is reduced 2-fold in renatured DNA. Analysis in neutral gradients suggests that half of the breaks observed in alkali are alkali-labile bonds. Both ethanol and cysteamine reduce the number of chain breaks in alkali by approximately 3-fold.

Photochemistry of 4-thiouridine and thymine

International Nuclear Information System (INIS)

Peak, M.J.; Babasick, D.M.; Haugen, D.A.; Midden, W.R.

1988-01-01

When thymine is irradiated in aqueous solution with monochromatic 334-nm UV radiation in the presence of 4-thiouridine a photoproduct of thymine is formed, as shown by thin-layer chromatography and autoradiography. The quantum yield for the formation of thymine photoproduct is greater than that for cytosine photoproduct formation. The identity of the photoproduct is not known: one possibility is the formation of an adduct between the sensitizer and the base yielding a pyrimidine-pyrimidone type of photoproduct. (author)

Symposium on quantum electronics. Extended abstracts of contributed papers

Energy Technology Data Exchange (ETDEWEB)

1981-02-01

Extended abstracts are provided for papers presented in these subject areas: lasers; quantum optics; nonlinear optics; laser photochemistry; laser spectroscopy; laser scattering; laser produced plasma; and laser applications. (GHT)

A physico-chemical study of some areas of fundamental significance to biophysics

International Nuclear Information System (INIS)

McGlynn, S.P.; Kumar, D.

1992-01-01

This report discusses the following topics: Radiation signatures; photoelectron spectroscopy of biologically active molecules; laser optogalvanic effect; magnetic circular dichroism; photochemistry of halogenated molecules; and density effects on high-n rydbergs

What limits photosynthetic energy conversion efficiency in nature? Lessons from the oceans.

Science.gov (United States)

Falkowski, Paul G; Lin, Hanzhi; Gorbunov, Maxim Y

2017-09-26

Constraining photosynthetic energy conversion efficiency in nature is challenging. In principle, two yield measurements must be made simultaneously: photochemistry, fluorescence and/or thermal dissipation. We constructed two different, extremely sensitive and precise active fluorometers: one measures the quantum yield of photochemistry from changes in variable fluorescence, the other measures fluorescence lifetimes in the picosecond time domain. By deploying the pair of instruments on eight transoceanic cruises over six years, we obtained over 200 000 measurements of fluorescence yields and lifetimes from surface waters in five ocean basins. Our results revealed that the average quantum yield of photochemistry was approximately 0.35 while the average quantum yield of fluorescence was approximately 0.07. Thus, closure on the energy budget suggests that, on average, approximately 58% of the photons absorbed by phytoplankton in the world oceans are dissipated as heat. This extraordinary inefficiency is associated with the paucity of nutrients in the upper ocean, especially dissolved inorganic nitrogen and iron. Our results strongly suggest that, in nature, most of the time, most of the phytoplankton community operates at approximately half of its maximal photosynthetic energy conversion efficiency because nutrients limit the synthesis or function of essential components in the photosynthetic apparatus.This article is part of the themed issue 'Enhancing photosynthesis in crop plants: targets for improvement'. © 2017 The Author(s).

Nitrogen Fixation by Photochemistry in the Atmosphere of Titan and Implications for Prebiotic Chemistry

Science.gov (United States)

Balucani, Nadia

The observation of N-containing organic molecules and the composition of the haze aerosols, as determined by the Aerosol Collector and Pyrolyser (ACP) on-board Huygens, are clear indications that some chemistry involving nitrogen active forms and hydrocarbons is operative in the upper atmosphere of Titan. Neutral-neutral reactions involving the first electronically excited state of atomic nitrogen, N(2D), and small hydrocarbons have the right prerequisites to be among the most significant pathways to formation of nitriles, imines and other simple N-containing organic molecules. The closed-shell products methanimine, ethanimine, ketenimine, 2H-azirine and the radical products CH3N, HCCN and CH2NCH can be the intermediate molecular species that, via addition reactions, polymerization and copolymerization form the N-rich organic aerosols of Titan as well as tholins in bulk reactors simulating Titan's atmosphere.

Committee on Interagency Radiation Research and Policy Coordination (CIRRPC)

International Nuclear Information System (INIS)

1994-01-01

Enclosed are proceedings of the workshop on Internal Dosimetry held on Atlanta, Georgia in April 1992. The recommendations from the Workshop were considered by the CIRRPC Subpanel on Occupational Radiation Protection Research in identifying those areas to be undertaken by individual Federal Agencies or in cooperative efforts. This document presents summaries of the following sessions: A.1 Applications and limitations of ICRP and other metabolic models, A.2 Applications and implementation of proposed ICRP lung model, A.3 Estimates of intake from repetitive bioassay data, A.4 Chelation models for plutonium urinalysis data, B.1 Transuranium/uranium registry data, B.2 Autopsy tissue analysis, B.3 Bioassay / Whole body counting, B.4 Data base formatting and availability, C.1 An overview of calculational techniques in use today, C.2 The perfect code, C.3 Dose calculations based on individuals instead of averages, C.4 From macro dosimetry to micro dosimetry

The Radiation Environment of Exoplanet Atmospheres

Directory of Open Access Journals (Sweden)

Jeffrey L. Linsky

2014-10-01

Full Text Available Exoplanets are born and evolve in the radiation and particle environment created by their host star. The host star’s optical and infrared radiation heats the exoplanet’s lower atmosphere and surface, while the ultraviolet, extreme ultraviolet and X-radiation control the photochemistry and mass loss from the exoplanet’s upper atmosphere. Stellar radiation, especially at the shorter wavelengths, changes dramatically as a host star evolves leading to changes in the planet’s atmosphere and habitability. This paper reviews the present state of our knowledge concerning the time-dependent radiation emitted by stars with convective zones, that is stars with spectral types F, G, K, and M, which comprise nearly all of the host stars of detected exoplanets.

A physico-chemical study of some areas of fundamental significance to biophysics: Annual report, 1986-1987

International Nuclear Information System (INIS)

McGlynn, S.P.

1987-01-01

The thirteen (13) titles (Nos. 283 to 295) of the Bibliography for the 1986 to 1987 Annual Report constitute the gist of this document. These titles represent work completed and published (or in process of publication). The scientific report which follows is intended to provide a brief summary of the ongoing research efforts of the Molecular Spectroscopy Group. The titles covered are as follows: Rare Gas Density Effects on High-M Rydberg States, Electric Field Dependence of the Total Excimer Luminescence of Xenon Excited Below the Atomic Ionization Limit, Term Value/Band-Gap Energy Correlations for Solid Rare Gas Excitons, Laser Optogalvanic Spectroscopy of Iodine and Cesium, Photoionization spectroscopy of Highly Polar Aromatics, Photochemistry of Polyatomic Molecules. There are six individual papers listed separately in this report

Materials of the yearly scientific assembly of the Polish Chemical Society - Torun'93: chemistry of new materials

International Nuclear Information System (INIS)

1993-01-01

Scientific conference accompanied the assembly of Polish Chemical Society has been held in 1993 in Torun. The conference has been divided into 12 sections and 4 symposia covering the most important research fields in chemistry. The general view on scientific progress has been presented during the plenary session. Then proceedings have performed in specialist sessions on: contemporary methods in organic chemistry chemistry, chemistry and physico-chemistry of polymers, coordination chemistry state-of-the-art prospects, absorption and absorbents, new chemical technologies of organic compounds, new chemical technologies of inorganic compounds, environment protection, new methods in analytical chemistry, photochemistry and chemical kinetics, crystallochemistry, history of chemistry and didactics, new substances in health protection, membranes and membrane techniques, electroactive organic compounds, zeolites - material properties

Continuous Flow Science in an Undergraduate Teaching Laboratory: Photocatalytic Thiol-Ene Reaction Using Visible Light

Science.gov (United States)

Santandrea, Jeffrey; Kairouz, Vanessa; Collins, Shawn K.

2018-01-01

An undergraduate teaching laboratory experiment involving a continuous flow, photocatalytic thiol-ene reaction using visible-light irradiation is described that allows students to explore concepts of green chemistry, photochemistry, photocatalysis, and continuous flow chemistry.

Matrix isolation and computational study of isodifluorodibromomethane (F2CBr-Br): a route to Br2 formation in CF2Br2 photolysis.

Science.gov (United States)

George, Lisa; Kalume, Aimable; El-Khoury, Patrick Z; Tarnovsky, Alexander; Reid, Scott A

2010-02-28

The photolysis products of dibromodifluoromethane (CF(2)Br(2)) were characterized by matrix isolation infrared and UV/Visible spectroscopy, supported by ab initio calculations. Photolysis at wavelengths of 240 and 266 nm of CF(2)Br(2):Ar samples (approximately 1:5000) held at approximately 5 K yielded iso-CF(2)Br(2) (F(2)CBrBr), a weakly bound isomer of CF(2)Br(2), which is characterized here for the first time. The observed infrared and UV/Visible absorptions of iso-CF(2)Br(2) are in excellent agreement with computational predictions at the B3LYP/aug-cc-pVTZ level. Single point energy calculations at the CCSD(T)/aug-cc-pVDZ level on the B3LYP optimized geometries suggest that the isoform is a minimum on the CF(2)Br(2) potential energy surface, lying some 55 kcal/mol above the CF(2)Br(2) ground state. The energies of various stationary points on the CF(2)Br(2) potential energy surface were characterized computationally; taken with our experimental results, these show that iso-CF(2)Br(2) is an intermediate in the Br+CF(2)Br-->CF(2)+Br(2) reaction. The photochemistry of the isoform was also investigated; excitation into the intense 359 nm absorption band resulted in isomerization to CF(2)Br(2). Our results are discussed in view of the rich literature on the gas-phase photochemistry of CF(2)Br(2), particularly with respect to the existence of a roaming atom pathway leading to molecular products.

Matrix isolation and computational study of isodifluorodibromomethane (F2CBr-Br): A route to Br2 formation in CF2Br2 photolysis

International Nuclear Information System (INIS)

George, Lisa; Kalume, Aimable; Reid, Scott A.; El-Khoury, Patrick Z.; Tarnovsky, Alexander

2010-01-01

The photolysis products of dibromodifluoromethane (CF 2 Br 2 ) were characterized by matrix isolation infrared and UV/Visible spectroscopy, supported by ab initio calculations. Photolysis at wavelengths of 240 and 266 nm of CF 2 Br 2 :Ar samples (∼1:5000) held at ∼5 K yielded iso-CF 2 Br 2 (F 2 CBrBr), a weakly bound isomer of CF 2 Br 2 , which is characterized here for the first time. The observed infrared and UV/Visible absorptions of iso-CF 2 Br 2 are in excellent agreement with computational predictions at the B3LYP/aug-cc-pVTZ level. Single point energy calculations at the CCSD(T)/aug-cc-pVDZ level on the B3LYP optimized geometries suggest that the isoform is a minimum on the CF 2 Br 2 potential energy surface, lying some 55 kcal/mol above the CF 2 Br 2 ground state. The energies of various stationary points on the CF 2 Br 2 potential energy surface were characterized computationally; taken with our experimental results, these show that iso-CF 2 Br 2 is an intermediate in the Br+CF 2 Br→CF 2 +Br 2 reaction. The photochemistry of the isoform was also investigated; excitation into the intense 359 nm absorption band resulted in isomerization to CF 2 Br 2 . Our results are discussed in view of the rich literature on the gas-phase photochemistry of CF 2 Br 2 , particularly with respect to the existence of a roaming atom pathway leading to molecular products.

APPLICATION OF MODULATED CHLOROPHYLL FLUORESCENCE AND MODULATED CHLOROPHYLL FLUORESCENCE IMAGING IN STUDYING ENVIRONMENTAL STRESSES EFFECT

Directory of Open Access Journals (Sweden)

L. Guidi

2016-03-01

Full Text Available Chlorophyll (Chl a fluorescence is a widely used tool to monitor the photosynthetic process in plants subjected to environmental stresses.this review reports the theoretical bases of Chl fluorescence, and the significance of the most important Chl fluorescence parameters. it also reportshow these parameters can be utilised to estimate changes in photosystem ii (PSII photochemistry, linear electron flux and energy dissipationmechanisms. the relation between actual PSII photochemistry and CO2 assimilation is discussed, as is the role of photochemical andnon-photochemical quenching in inducing changes in PSII activity. the application of Chl fluorescence imaging to study heterogeneity on leaflamina is also considered. this review summarises only some of the results obtained by this methodology to study the effects of differentenvironmental stresses, namely water and nutrients availability, pollutants, temperature and salinity.

Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate.

Science.gov (United States)

Tsai, Po-Yu; Chao, Meng-Hsuan; Kasai, Toshio; Lin, King-Chuen; Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo

2014-02-21

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Mimicking the Role of the Antenna in Photosynthetic Photoprotection

Energy Technology Data Exchange (ETDEWEB)

Terazono, Yuichi; Kodis, Gerdenis; Bhushan, Kul; Zaks, Julia; Madden, Christopher; Moore, Ana L.; Moore, Thomas A.; Fleming, Graham R.; Gust, Devens

2011-03-09

One mechanism used by plants to protect against damage from excess sunlight is called nonphotochemical quenching (NPQ). Triggered by low pH in the thylakoid lumen, NPQ leads to conversion of excess excitation energy in the antenna system to heat before it can initiate production of harmful chemical species by photosynthetic reaction centers. Here we report a synthetic hexad molecule that functionally mimics the role of the antenna in NPQ. When the hexad is dissolved in an organic solvent, five zinc porphyrin antenna moieties absorb light, exchange excitation energy, and ultimately decay by normal photophysical processes. Their excited-state lifetimes are long enough to permit harvesting of the excitation energy for photoinduced charge separation or other work. However, when acid is added, a pH-sensitive dye moiety is converted to a form that rapidly quenches the first excited singlet states of all five porphyrins, converting the excitation energy to heat and rendering the porphyrins kinetically incompetent to readily perform useful photochemistry.

Ronald Breslow (1931–2017)

Indian Academy of Sciences (India)

of action of thiamine, commonly known as Vitamin. B1, which acts ... some involving photochemistry and radical reaction processes (e.g. remote functionalization). Another ... freshman chemistry and was an extremely popular instructor. He was ...

Degradation of 4-chlorophenol in aqueous solution photoinduced by Fe(III)-citrate complex

Czech Academy of Sciences Publication Activity Database

Abida, O.; Kolář, Michal; Jirkovský, Jaromír; Mailhot, G.

2012-01-01

Roč. 11, č. 5 (2012), s. 794-802 ISSN 1474-905X Institutional support: RVO:61388955 Keywords : photochemistry * citric acid * hydroxyl radicals Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.923, year: 2012

The Chemistry of Cyclic All-Nitrogen Molecules

National Research Council Canada - National Science Library

Wodtke, Alec M

2006-01-01

..., $474,927, February 15, 2004 - December 31, 2006. During this period, we have extended our preliminary investigations of azide photochemistry, with the aim of demonstrating unambiguously the photochemical production of cyclic-N, and of revealing...

Informal Conference on Photochemistry (15th) Held at Stanford, California on 27 June-1 July 1982

Science.gov (United States)

1982-01-01

spectra and by the kinetics of its thermal transformation to 3.1 Curie law analysis of the esr signal intensity shows this species to be a ground state...Soubeiran, Ann. Ch.m. Phys., 1830, 43, 407. 14. J.B.A. Dumas, Ann. Chim. Phys. 1826, 33, 355. . 15. J. L. Gay Lussac and L. J. Thenard or Ann. Chim. Phys...02CA 3Zu+)], [He] and [Ar] reveals a complex rate law that not only shows a first order dependence on [NO] and [02 (A3Fu+)] but also on [O2]. Such

Report of the Subpanel on Accelerator Research and Development of the High Energy Physics Advisory Panel

International Nuclear Information System (INIS)

1980-06-01

Accelerator R and D in the US High Energy Physics (HEP) program is reviewed. As a result of this study, some shift in priority, particularly as regards long-range accelerator R and D, is suggested to best serve the future needs of the US HEP program. Some specific new directions for the US R and D effort are set forth. 18 figures, 5 tables

Computing for particle physics. Report of the HEPAP subpanel on computer needs for the next decade

International Nuclear Information System (INIS)

1985-08-01

The increasing importance of computation to the future progress in high energy physics is documented. Experimental computing demands are analyzed for the near future (four to ten years). The computer industry's plans for the near term and long term are surveyed as they relate to the solution of high energy physics computing problems. This survey includes large processors and the future role of alternatives to commercial mainframes. The needs for low speed and high speed networking are assessed, and the need for an integrated network for high energy physics is evaluated. Software requirements are analyzed. The role to be played by multiple processor systems is examined. The computing needs associated with elementary particle theory are briefly summarized. Computing needs associated with the Superconducting Super Collider are analyzed. Recommendations are offered for expanding computing capabilities in high energy physics and for networking between the laboratories

Achievement report on research and development in the Sunshine Project in fiscal 1979. Research and development on water decomposition by using mixed cycle of thermo-chemistry, photo-chemistry and electrochemistry; 1979 nendo netsukagaku, hikari kagaku, denki kagaku konsei cycle ni yoru mizu bunkai no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1980-03-01

This paper describes achievements in research and development in the Sunshine Project in fiscal 1979 on water decomposition by using mixed cycle of thermo-chemistry, photo-chemistry and electrochemistry. In research on the light irradiation electrolytic process, with an objective of improving the reaction efficiency, discussions were given by raising light intensity on the irradiated surface as high as 13 times that of the sunlight. The subsequent process is electrolysis of products from photo-chemical reaction, and the product concentration should be high enough to have HI decomposition (hydrogen acquisition) proceed with high efficiency. Experiments were carried out at 0.03 to 0.1M as iodine concentrations (product HI concentration at 3%). A photo-chemical reaction rate of 80% was obtained at light intensity as high as 12 times that of the sunlight, and iodine concentration of 0.07 mM. The efficiency was 15%. Raising temperature causes the reaction rate to decrease, but it can be supplemented by raising the light intensity, where high concentration HI content was obtained. Rate controlling process in the reaction was elucidated from activation energies in the reaction process of each element on the iodine concentrations from 3 to 30 mM used in the photo-chemical reaction. Experiments were performed on HI decomposition (hydrogen acquisition) by using a heat diffusion column. Separation performance in a filled type column was worse than that in an empty type column, which requires future discussions. (NEDO)

State of the States 2016: Arts Education State Policy Summary

Science.gov (United States)

Aragon, Stephanie

2016-01-01

The "State of the States 2016" summarizes state policies for arts education identified in statute or administrative code for all 50 states and the District of Columbia. Information is based on a comprehensive search of state education statute and codes on each state's relevant websites. Complete results from this review are available in…

Effects of Model Chemistry and Data Biases on Stratospheric Ozone Assimilation

National Research Council Canada - National Science Library

Coy, L; Allen, D. R; Eckermann, S. D; McCormack, J. P; Stajner, I; Hogan, T. F

2007-01-01

.... In this study, O-F statistics from the Global Ozone Assimilation Testing System (GOATS) are used to examine how ozone assimilation products and their associated O-F statistics depend on input data biases and ozone photochemistry parameterizations (OPP...

Dhavale, Prof. Dilip Dattatray

Indian Academy of Sciences (India)

Home; Fellowship. Fellow Profile. Elected: 2009 Section: Chemistry. Dhavale, Prof. Dilip Dattatray Ph.D. (Pune), FNASc. Date of birth: 18 February 1956. Specialization: Natural Products Chemistry, Carbohydrate Chemistry, Photochemistry, Reaction Mechanism, Medicinal Chemistry Address: Department of Chemistry, ...

Mittal, Dr Jai Pal

Indian Academy of Sciences (India)

Elected: 1986 Section: Chemistry ... Specialization: Radiation Chemistry & Radiation Biology, Photochemistry ... Address: 11-B, Rohini Co-op. ... The 29th Mid-year meeting of the Academy will be held from 29–30 June 2018 in Infosys, Mysuru ...

Photochemical Synthesis of the Bioconjugate Folic Acid-Gold Nanoparticles

DEFF Research Database (Denmark)

León, John Jairo Castillo; Bertel, Linda; Páez-Mozo, Edgar

2013-01-01

In this paper we present a rapid and simple onepot method to obtain gold nanoparticles functionalized with folic acid using a photochemistry method. The bioconjugate folic acid-gold nanoparticle was generated in one step using a photo-reduction method, mixing hydrogen tetrachloroaurate with folic...... at 4°C prolongs the stability of folic acid-gold nanoparticle suspensions to up to 26 days. Ultraviolet visible and Fourier transform infrared spectroscopy showed a surface plasmon band of around 534nm and fluorescence spectroscopy exhibited a quenching effect on gold nanoparticles in the fluorescence...... emission of folic acid and thus confirmed the conjugation of folic acid to the surface of gold nanoparticles. In this study we demonstrate the use of a photochemistry method to obtain folic acid-gold nanoparticles in a simple and rapid way without the use of surfactants and long reaction times...

Canopy Vegetation Indices from In situ Hyperspectral Data to Assess Plant Water Status of Winter Wheat under Powdery Mildew Stress.

Science.gov (United States)

Feng, Wei; Qi, Shuangli; Heng, Yarong; Zhou, Yi; Wu, Yapeng; Liu, Wandai; He, Li; Li, Xiao

2017-01-01

Plant disease and pests influence the physiological state and restricts the healthy growth of crops. Physiological measurements are considered the most accurate way of assessing plant health status. In this paper, we researched the use of an in situ hyperspectral remote sensor to detect plant water status in winter wheat infected with powdery mildew. Using a diseased nursery field and artificially inoculated open field experiments, we detected the canopy spectra of wheat at different developmental stages and under different degrees of disease severity. At the same time, destructive sampling was carried out for physical tests to investigate the change of physiological parameters under the condition of disease. Selected vegetation indices (VIs) were mostly comprised of green bands, and correlation coefficients between these common VIs and plant water content (PWC) were generally 0.784-0.902 ( p powdery mildew stress. The Photochemical Reflectance Index (PRI) was sensitive to physiological response influenced by powdery mildew, and the relationships of PRI with chlorophyll content, the maximum quantum efficiency of PSII photochemistry (Fv/Fm), and the potential activity of PSII photochemistry (Fv/Fo) were good with R 2 = 0.639, 0.833, 0.808, respectively. Linear regressions showed PRI demonstrated a steady relationship with PWC across different growth conditions, with R 2 = 0.817 and RMSE = 2.17. The acquired PRI model of wheat under the powdery mildew stress has a good compatibility to different experimental fields from booting stage to filling stage compared with the traditional water signal vegetation indices, WBI, FWBI 1 , and FWBI 2 . The verification results with independent data showed that PRI still performed better with R 2 = 0.819 between measured and predicted, and corresponding RE = 8.26%. Thus, PRI is recommended as a potentially reliable indicator of PWC in winter wheat with powdery mildew stress. The results will help to understand the physical state of

Lithium reserves and resources

International Nuclear Information System (INIS)

Evans, R.K.

1978-01-01

As a result of accelerating research efforts in the fields of secondary batteries and thermonuclear power generation, concern has been expressed in certain quarters regarding the availability, in sufficient quantities, of lithium. As part of a recent study by the National Research Council on behalf of the Energy Research and Development Administration, a subpanel was formed to consider the outlook for lithium. Principal areas of concern were reserves, resources and the 'surplus' available for energy applications after allowing for the growth in current lithium applications. Reserves and resources were categorized into four classes ranging from fully proved reserves to resources which are probably dependent upon the marketing of co-products to become economically attractive. Because of the proprietary nature of data on beneficiation and processing recoveries, the tonnages of available lithium are expressed in terms of plant feed. However, highly conservative assumptions have been made concerning mining recoveries and these go a considerable way to accounting for total losses. Western World reserves and resources of all classes are estimated at 10.6 million tonnes Li of which 3.5 million tonnes Li are located in the United States. Current United States capacity, virtually equivalent to Western World capacity, is 4700 tonnes Li and production in 1976 approximated to 3500 tonnes Li. Production for current applications is expected to grow to approx. 10,000 tonnes in year 2000 and 13,000 tonnes a decade later. The massive excess of reserves and resources over that necessary to support conventional requirements has limited the amount of justifiable exploration expenditures; on the last occasion, there was a a major increase in demand (by the USAEA) reserves and capacity were increased rapidly. There are no foreseeable reasons why this shouldn't happen again when the need is clear. (author)

History of Suction-Type Laminar-Flow Control with Emphasis on Flight Resrearch: Monographs in Aerospace History Number 13

Science.gov (United States)

Braslow, A. L.

1999-01-01

The paper contains the following sections: Foreword; Preface; Laminar-Flow Control Concepts and Scope of Monograph; Early Research on Suction-Type Laminar-Flow Control (Research from the 1930s through the War Years; Research from after World War II to the Mid-1960s); Post X-21 Research on Suction-Type Laminar-Flow Control; Status of Laminar-Flow Control Technology in the Mid-1990s; Glossary; Document 1-Aeronautics Panel, AACB, R&D Review, Report of the Subpanel on Aeronautic Energy Conservation/Fuels; Document 2-Report of Review Group on X-21A Laminar Flow Control Program; Document 3-Langley Research Center Announcement, Establishment of Laminar Flow Control Working Group; Document 4-Intercenter Agreement for Laminar Flow Control Leading Edge Glove Flights, LaRC and DFRC; Document 5-Flight Report NLF-144, of AFTIF-111 Aircraft with the TACT Wing Modified by a Natural Laminar Flow Glove; Document 6-Flight Record, F-16XL Supersonic Laminar Flow Control Aircraft; Index; and About the Author.

Annual progress report of the physical chemistry department. Basic research 1987

International Nuclear Information System (INIS)

1988-01-01

Basic research for 1987 in physical chemistry of the French Atomic Energy Commission are reviewed. Topics include molecular chemistry, isotopic geochemistry, molecular photophysics, laser photochemistry, solid and surface physical chemistry. A list of publications and thesis is given [fr

Greener and Sustainable Trends in Synthesis of Organics and Nanomaterials

Science.gov (United States)

Trends in greener and sustainable process development during the past 25 years are abridged involving the use of alternate energy inputs (mechanochemistry, ultrasound- or microwave irradiation), photochemistry, and greener reaction media as applied to synthesis of organics and na...

Understanding pyrography, the photochemistry of 'scorched' decoration.

OpenAIRE

Millis, Susan M.

2013-01-01

This paper examines the discolouration of pyrography artwork applied to three different wood species when exposed to natural light. Samples were 'scorched' in a controlled manner at a range of temperatures to produce different shades from light to dark. This allowed comparisons to be made between different wood species and different temperatures. It was elucidated that pyrography is the result of several processes developed between migrating extractive substances and coloured reaction product...

Solar Photochemistry | Chemistry and Nanoscience Research | NREL

Science.gov (United States)

Generation in Semiconducting Single-Walled Carbon Nanotubes. Nat Comms 2015, 6, 8809. DOI: 10.1038/ncomms9809 . DOI: 10.1038/nchem.2348 Ihly, R.; Mistry, K. S.; Ferguson, A. J.; Clikeman, T. T.; Larson, B. W.; Reid -609. DOI: 10.1038/nchem.2496 Miller, E. M.; Kroupa, D. M.; Zhang, J.; Schulz, P.; Marshall, A. R

Vacuum ultraviolet photochemistry of tetrahydrothiophene and sulfolane

International Nuclear Information System (INIS)

Scala, A.A.; Colon, I.

1979-01-01

The vacuum uv photolysis of tetrahydrothiophene (THT) involves the breaking of the S to α-C bond. Besides ethylene, C 3 H 6 and 1,3-butadiene are also formed. Photolyses of THT, tetrahydrofuran, and pyrrolidine are similar. The vacuum uv photolysis of tetramethylene sulfone (sulfolane) was also studied; products are SO 2 , cyclobutane, 1-butene, and ethylene. No cis-2-butene was observed

Supramolecular photochemistry of drugs in biomolecular environments.

Science.gov (United States)

Monti, Sandra; Manet, Ilse

2014-06-21

In this tutorial review we illustrate how the interaction of photoactive drugs/potential drugs with proteins or DNA in supramolecular complexes can determine the course of the reactions initiated by the drug absorbed photons, evidencing the mechanistic differences with respect to the solution conditions. We focus on photoprocesses, independent of oxygen, that lead to chemical modification of the biomolecules, with formation of new covalent bonds or cleavage of existing bonds. Representative systems are mainly selected from the literature of the last decade. The photoreactivity of some aryl propionic acids, (fluoro)quinolones, furocoumarins, metal coordination complexes, quinine-like compounds, naphthaleneimides and pyrenyl-peptides with proteins or DNA is discussed. The use of light for biomolecule photomodification, historically relevant to biological photosensitization processes and some forms of photochemotherapy, is nowadays becoming more and more important in the development of innovative methods in nanomedicine and biotechnology.

An update of nitrile photochemistry on Titan

Science.gov (United States)

Yung, Yuk L.

1987-01-01

Comparisons are undertaken between laboratory kinetics experiments and Voyager observations in order to shed light on possible chemical reaction pathways to the generation of cyanogen and dicyanoacetylene in Titan's upper atmosphere. The predicted concentrations of the simple nitrile compounds are found to be of a magnitude realistically corresponding to the Voyager observations.

Photochemistry of triarylmethane dyes bound to proteins

Science.gov (United States)

Indig, Guilherme L.

1996-04-01

Triarylmethanes represent a class of cationic dyes whose potential as photosensitizers for use in photodynamic therapy of neoplastic diseases has never been comprehensively evaluated. Here, the laser-induced photodecomposition of three triarylmethane dyes, crystal violet, ethyl violet, and malachite green, non-covalently bound to bovine serum albumin (a model biological target) was investigated. Upon laser excitation at 532 nm, the bleaching of the corresponding dye-protein molecular complexes follows spectroscopic patterns that suggest the formation of reduced forms of the dyes as major reaction photoproducts. That implies that an electron or hydrogen atom transfer from the protein to the dye's moiety within the guest-host complex is the first step of the photobleaching process. Since the availability of dissolved molecular oxygen was not identified as a limiting factor for the phototransformations to occur, these dyes can be seen as potential phototherapeutic agents for use in hypoxic areas of tumors. These triarylmethane dyes strongly absorb at relatively long wavelengths (absorption maximum around 600 nm; (epsilon) max approximately equals 105 M-1 cm-1), and only minor changes in their absorption characteristics are observed upon binding to the protein. However the binding event leads to a remarkable increase in their fluorescence quantum yield and photoreactivity.

State of the States, 2012: Arts Education State Policy Summary

Science.gov (United States)

Arts Education Partnership (NJ1), 2012

2012-01-01

The "State of the States 2012" summarizes state policies for arts education identified in statute or code for all 50 states and the District of Columbia. Information is based primarily on results from the AEP Arts Education State Policy Survey conducted in 2010-11, and updated in April 2012.

Photochemistry of xenon-halogen Van der Waals complexes (X2 = Cl2, Br2, I2): evidence for the intermediate states in the (Xe-X2)*→ XeX* + X reaction

International Nuclear Information System (INIS)

Boivineau, Michel

1987-01-01

This research thesis addresses the reactivity of excited states of xenon-halogen Van der Waals complexes (Cl 2 , Br 2 , I 2 ) submitted to a multi-photonic excitation. The objective of this study is, by means of a specific experimental approach, to highlight the R*+ X 2 *- to better understand the reaction mechanism, and to study the reactivity of rare gas/halogen systems depending on the halogen nature. After having reported a bibliographical study on each studied system, the author describes the experimental system, reports and discusses experimental results obtained on the different complex systems (chlorine-, bromine- or iodine-based). He finally comments a possible and original application of these works in the development of an excimer laser with a new active medium (the rare gas/halogen Van der Waals complex) which would allow a continuous operation and an easy discharge production [fr

Ultrafast deactivation processes in the 2-aminopyridine dimer and the adenine-thymine base pair: Similarities and differences

International Nuclear Information System (INIS)

Ai Yuejie; Zhang Feng; Cui Ganglong; Fang Weihai; Luo Yi

2010-01-01

2-aminopyridine dimer has frequently been used as a model system for studying photochemistry of DNA base pairs. We examine here the relevance of 2-aminopyridine dimer for a Watson-Crick adenine-thymine base pair by studying UV-light induced photodynamics along two main hydrogen bridges after the excitation to the localized 1 ππ* excited-state. The respective two-dimensional potential-energy surfaces have been determined by time-dependent density functional theory with Coulomb-attenuated hybrid exchange-correlation functional (CAM-B3LYP). Different mechanistic aspects of the deactivation pathway have been analyzed and compared in detail for both systems, while the related reaction rates have also be obtained from Monte Carlo kinetic simulations. The limitations of the 2-aminopyridine dimer as a model system for the adenine-thymine base pair are discussed.

Water stress induces overexpression of superoxide dismutases that ...

African Journals Online (AJOL)

SERVER

2007-09-05

Sep 5, 2007 ... Water stress is known to induce active oxygen species in plants. ... photosystem II photochemistry and whole plant growth against oxidative stress in these plants. ..... CO2. Plant Physiol. 110: 393-402. Sen Gupta A, Heinen JL, ...

Electrostatic and Electrochemical Nature of Liquid-Gated Electric-Double-Layer Transistors Based on Oxide Semiconductors

NARCIS (Netherlands)

Yuan, Hongtao; Shimotani, Hidekazu; Ye, Jianting; Yoon, Sungjae; Aliah, Hasniah; Tsukazaki, Atsushi; Kawasaki, Masashi; Iwasa, Yoshihiro

2010-01-01

The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge

Neural-Network Quantum States, String-Bond States, and Chiral Topological States

Science.gov (United States)

Glasser, Ivan; Pancotti, Nicola; August, Moritz; Rodriguez, Ivan D.; Cirac, J. Ignacio

2018-01-01

Neural-network quantum states have recently been introduced as an Ansatz for describing the wave function of quantum many-body systems. We show that there are strong connections between neural-network quantum states in the form of restricted Boltzmann machines and some classes of tensor-network states in arbitrary dimensions. In particular, we demonstrate that short-range restricted Boltzmann machines are entangled plaquette states, while fully connected restricted Boltzmann machines are string-bond states with a nonlocal geometry and low bond dimension. These results shed light on the underlying architecture of restricted Boltzmann machines and their efficiency at representing many-body quantum states. String-bond states also provide a generic way of enhancing the power of neural-network quantum states and a natural generalization to systems with larger local Hilbert space. We compare the advantages and drawbacks of these different classes of states and present a method to combine them together. This allows us to benefit from both the entanglement structure of tensor networks and the efficiency of neural-network quantum states into a single Ansatz capable of targeting the wave function of strongly correlated systems. While it remains a challenge to describe states with chiral topological order using traditional tensor networks, we show that, because of their nonlocal geometry, neural-network quantum states and their string-bond-state extension can describe a lattice fractional quantum Hall state exactly. In addition, we provide numerical evidence that neural-network quantum states can approximate a chiral spin liquid with better accuracy than entangled plaquette states and local string-bond states. Our results demonstrate the efficiency of neural networks to describe complex quantum wave functions and pave the way towards the use of string-bond states as a tool in more traditional machine-learning applications.

SEMI-EMPIRICAL MODELING OF THE PHOTOSPHERE, CHROMOPSHERE, TRANSITION REGION, AND CORONA OF THE M-DWARF HOST STAR GJ 832

Energy Technology Data Exchange (ETDEWEB)

Fontenla, J. M. [NorthWest Research Associates, Boulder, CO 80301 (United States); Linsky, Jeffrey L. [JILA, University of Colorado and NIST, Boulder, CO 80309-0440 (United States); Witbrod, Jesse [University of Colorado Boulder, CO 80309 (United States); France, Kevin [LASP, University of Colorado Boulder, CO 80309-0600 (United States); Buccino, A.; Mauas, Pablo; Vieytes, Mariela [Instituto de Astronomía y Física del Espacio (CONICET-UBA), C.C. 67, Sucursal 28, C1428EHA, Buenos Aires (Argentina); Walkowicz, Lucianne M., E-mail: johnf@digidyna.com, E-mail: jlinsky@jila.colorado.edu, E-mail: jesse.witbrod@colorado.edu, E-mail: kevin.france@lasp.colorado.edu, E-mail: abuccino@iafe.uba.ar, E-mail: pablo@iafe.uba.ar, E-mail: mariela@iafe.uba.ar, E-mail: LWalkowicz@adlerplanetarium.org [The Adler Planetarium, Chicago, IL 60605 (United States)

2016-10-20

Stellar radiation from X-rays to the visible provides the energy that controls the photochemistry and mass loss from exoplanet atmospheres. The important extreme ultraviolet (EUV) region (10–91.2 nm) is inaccessible and should be computed from a reliable stellar model. It is essential to understand the formation regions and physical processes responsible for the various stellar emission features to predict how the spectral energy distribution varies with age and activity levels. We compute a state-of-the-art semi-empirical atmospheric model and the emergent high-resolution synthetic spectrum of the moderately active M2 V star GJ 832 as the first of a series of models for stars with different activity levels. We construct a one-dimensional simple model for the physical structure of the star’s chromosphere, chromosphere-corona transition region, and corona using non-LTE radiative transfer techniques and many molecular lines. The synthesized spectrum for this model fits the continuum and lines across the UV-to-optical spectrum. Particular emphasis is given to the emission lines at wavelengths that are shorter than 300 nm observed with the Hubble Space Telescope , which have important effects on the photochemistry of the exoplanet atmospheres. The FUV line ratios indicate that the transition region of GJ 832 is more biased to hotter material than that of the quiet Sun. The excellent agreement of our computed EUV luminosity with that obtained by two other techniques indicates that our model predicts reliable EUV emission from GJ 832. We find that the unobserved EUV flux of GJ 832, which heats the outer atmospheres of exoplanets and drives their mass loss, is comparable to the active Sun.

A time-resolved study on the photodynamic primary process of ADE. Pt.2: Photochemistry in biomolecular complexes

International Nuclear Information System (INIS)

Pan Jingxi; Lin Weizhen; Han Zhenhui; Miao Jinling; Wang Wenfeng; Yao Side; Lin Nianyun; Zhu Dayuan

2003-01-01

By use of laser flash photolysis and steady state absorption techniques, a systematic study was carried out on the interaction of ADE, which is a kind of model compound of actinomycin D, with DNA and BSA. Non-covalent binding was found between ADE and ssDNA, dsDNA and BSA, and photoinduced electron transfer reaction was observed. These results indicate that actinomycins might be used as type I photodrugs in the future and will be helpful for structure modification of this kind of compound

State-to-state and state-to-all-states reactive scattering angular distributions: F+H 2→HF+H

International Nuclear Information System (INIS)

Emmons, R.W.; Suck, S.H.

1983-01-01

How each state-to-state reactive transition determines nonundulatory ''state-to-all-states'' angular distribution has not yet been investigated. Here we present a complete exposure of state-to-state distorted-wave Born-approximation angular distributions in order to examine how the nonoscillatory and backward-peaked state-to-all-states reactive scattering angular distribution occurs

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. Savita S Khandolkar. Articles written in Journal of Chemical Sciences. Volume 127 Issue 9 September 2015 pp 1581-1588. Synthesis, characterization and photochemistry of a new heptamolybdate supported magnesium-aqua coordination complex · Savita S Khandolkar ...

New Fellows and Honorary Fellow

Indian Academy of Sciences (India)

Home; Fellowship. Fellow Profile. Elected: 2001 Section: Chemistry. Singh, Prof. Anil Kumar Ph.D. (IIT, Kanpur), FNASc. Date of birth: 2 April 1952. Specialization: Bio-organic Chemistry, Photochemistry and Photobiology Address: A-1603, Lake Primerose, Lake Homes, Powai, Mumbai 400 076, Maharashtra Contact:

Sigma*-mediated electronic relaxation in 200nm photoexcited ammonia and heteroaromatics

Directory of Open Access Journals (Sweden)

Evans N. L.

2013-03-01

Full Text Available Time–resolved photoelectron spectra of ammonia display combination bands of the umbrella and stretching modes associated with the N–H coordinate of σ* relaxation. Time–resolved photodissociation studies determine timescales <200fs. Similar σ* photochemistry is found in heteroaromatics

Progress report (1980-1982)

International Nuclear Information System (INIS)

Patel, R.P.; Prithvi Raj

1983-01-01

The research and development (R and D) activities of the Chemistry Division of the Bhabha Atomic Research Centre, Bombay, during the period 1980-1982 are reported in the form of summaries. Basic research activities are being carried out in the areas of inorganic and physical chemistry, radiation and photochemistry, and materials science. Applied research and development work done during the period include chemical treatment for plugging leaks, materials development, studies in radiation and photochemistry, analytical studies, development of biomedical devices and other instruments. Three research projects, namely, advanced research in dynamics of chemical reaction, radiation and photochemical research using electron accelerator and laser, and development of special organic and inorganic materials have been taken up. It is planned to make available in the next two years facilities such as FT NMR, nano and pico second laser kinetic spectrometry, crossed molecular beam apparatus and nano second pulsed electron acceleration. (M.G.B.)

State of the States

Science.gov (United States)

Journal of Education Finance, 2017

2017-01-01

In 2016, a group of school finance scholars and public school practitioners gathered in Jacksonville, Florida, for the National Education Finance Academy's annual conference to discuss, among an array of topics, the state of P-20 finance in all 50 states. At the roundtable discussion, 36 states were represented, and scholars representing 30 states…

Drought induced changes of leaf-to-root relationships in two tomato genotypes.

Science.gov (United States)

Moles, Tommaso Michele; Mariotti, Lorenzo; De Pedro, Leandro Federico; Guglielminetti, Lorenzo; Picciarelli, Piero; Scartazza, Andrea

2018-07-01

Water deficit triggers a dynamic and integrated cross-talk between leaves and roots. Tolerant plants have developed several physiological and molecular mechanisms to establish new cell metabolism homeostasis, avoiding and/or escaping from permanent impairments triggered by drought. Two tomato genotypes (a Southern Italy landrace called Ciettaicale and the well-known commercial cultivar Moneymaker) were investigated at vegetative stage to assess leaf and root metabolic strategies under 20 days of water deficit. Physiological and metabolic changes, in terms of ABA, IAA, proline, soluble sugars and phenols contents, occurred in both tomato genotypes under water stress. Overall, our results pointed out the higher plasticity of Ciettaicale to manage plant water status under drought in order to preserve the source-sink relationships. This aim was achieved by maintaining a more efficient leaf photosystem II (PSII) photochemistry, as suggested by chlorophyll fluorescence parameters, associated with a major investment towards root growth and activity to improve water uptake. On the contrary, the higher accumulation of carbon compounds, resulting from reduced PSII photochemistry and enhanced starch reserve mobilization, in leaves and roots of Moneymaker under drought could play a key role in the osmotic adjustment, although causing a feedback disruption of the source-sink relations. This hypothesis was also supported by the different drought-induced redox unbalance, as suggested by H 2 O 2 and MDA contents. This could affect both PSII photochemistry and root activity, leading to a major involvement of NPQ and antioxidant system in response to drought in Moneymaker than Ciettaicale. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Inertial Confinement Fusion R and D and Nuclear Proliferation

International Nuclear Information System (INIS)

Goldston, Robert J.

2011-01-01

In a few months, or a few years, the National Ignition Facility (NIF) at the Lawrence Livermore National Laboratory may achieve fusion gain using 192 powerful lasers to generate x-rays that will compress and heat a small target containing isotopes of hydrogen. This event would mark a major milestone after decades of research on inertial confinement fusion (ICF). It might also mark the beginning of an accelerated global effort to harness fusion energy based on this science and technology. Unlike magnetic confinement fusion (ITER, 2011), in which hot fusion fuel is confined continuously by strong magnetic fields, inertial confinement fusion involves repetitive fusion explosions, taking advantage of some aspects of the science learned from the design and testing of hydrogen bombs. The NIF was built primarily because of the information it would provide on weapons physics, helping the United States to steward its stockpile of nuclear weapons without further underground testing. The U.S. National Academies' National Research Council is now hosting a study to assess the prospects for energy from inertial confinement fusion. While this study has a classified sub-panel on target physics, it has not been charged with examining the potential nuclear proliferation risks associated with ICF R and D. We argue here that this question urgently requires direct and transparent examination, so that means to mitigate risks can be assessed, and the potential residual risks can be balanced against the potential benefits, now being assessed by the NRC. This concern is not new (Holdren, 1978), but its urgency is now higher than ever before.

Quantum State Engineering Via Coherent-State Superpositions

Science.gov (United States)

Janszky, Jozsef; Adam, P.; Szabo, S.; Domokos, P.

1996-01-01

The quantum interference between the two parts of the optical Schrodinger-cat state makes possible to construct a wide class of quantum states via discrete superpositions of coherent states. Even a small number of coherent states can approximate the given quantum states at a high accuracy when the distance between the coherent states is optimized, e. g. nearly perfect Fock state can be constructed by discrete superpositions of n + 1 coherent states lying in the vicinity of the vacuum state.

Novel biphotonic holographic storage in a side-chain liquid crystalline polyester

DEFF Research Database (Denmark)

Ramanujam, P.S.; Hvilsted, S.; Andruzzi, F.

1993-01-01

We report novel biphotonic holographic storage of text and gratings on unoriented films of a side-chain liquid crystalline polyester capable of high density storage and complete erasure. The holograms have a typical size of 1 mm. The recording utilizes unusual photochemistry involving azo dye...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Synthesis and properties of Oxasmaragdyrins containing one ... Synthesis, crystal structure and photochemistry of Hexakis(butan-1-aminium) heptamolybdate(VI) tetrahydrate ... the active site of catechol oxidase enzyme in acetonitrile medium with a turnover number of 4.788 .... Derivatives through a Facile One-pot Process.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

A comparative study of several compounds charge balanced by the piperazinediium cation is described. Volume 128 Issue 11 November 2016 pp 1737-1744 Regular Article. Synthesis, crystal structure and photochemistry of Hexakis(butan-1-aminium) heptamolybdate(VI) tetrahydrate · SAVITA S KHANDOLKAR ASHISH R ...

A compact spark pre-ionized pulser sustainer TE–CO2 laser

Indian Academy of Sciences (India)

R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

Compact transversely excited atmospheric (TEA) CO2 lasers (Marchetti et al 1983) find numerous scientific and technical applications. These include pulsed laser deposition (PLD). (Sankur et al 1988), photo-chemistry (Baranov 1983), lidar (Killinger & Menyuk 1981), optical pumping of molecular lasers (Midorikawa et al ...

Audiotape Feedback for Essays in Distance Education

NARCIS (Netherlands)

Kirschner, P.A.; Brink, H. van den; Meester, M.

1991-01-01

Students who were required to write three short essays for a university level course on photochemistry at the Open university of the Netherlands received either audio-cassette or written feedback on their essays. The students receiving the audio feedback described their experience as personal,

Detection of treatment success after photodynamic therapy using Dynamic Contrast-Enhanced Magnetic Resonance Imaging

NARCIS (Netherlands)

Schreurs, Tom J.L.; Jacobs, Igor; Nicolay, Klaas; Prompers, Jeanine J.; Strijkers, Gustav J.

2017-01-01

Early evaluation of response to therapy is crucial for selecting the optimal therapeutic follow-up strategy for cancer patients. PDT is a photochemistry-based treatment modality that induces tumor tissue damage by cytotoxic oxygen radicals, generated by a pre-injected photosensitive drug upon light

Effect of application of growth regulators on the physiological and yield parameters of winter wheat under water deficit

Czech Academy of Sciences Publication Activity Database

Barányiová, I.; Klem, Karel

2016-01-01

Roč. 62, č. 3 (2016), s. 114-120 ISSN 1214-1178 R&D Projects: GA MZe QJ1530373 Institutional support: RVO:67179843 Keywords : PSII photochemistry * number of spikes * photosynthesis * spike productivity * water limitation Subject RIV: EH - Ecology, Behaviour Impact factor: 1.225, year: 2016

Radiation chemistry of hydrocarbon and alkyl halide systems. Progress report, August 1, 1980-July 31, 1981

International Nuclear Information System (INIS)

Hanrahan, R.J.

1981-01-01

The results reported here include new measurements on the four systems proposed for study last year. These are pulse radiolysis of alkyl iodide and perfluoaroalkyl iodide systems; gamma radiolysis of H 2 -CO mixtures; photochemistry and mass spectrometry of propane. The work accomplished is described

Photoionization dynamics of glycine adsorbed on a silicon cluster: ''On-the-fly'' simulations

International Nuclear Information System (INIS)

Shemesh, Dorit; Baer, Roi; Seideman, Tamar; Gerber, R. Benny

2005-01-01

Dynamics of glycine chemisorbed on the surface of a silicon cluster is studied for a process that involves single-photon ionization, followed by recombination with the electron after a selected time delay. The process is studied by ''on-the-fly'' molecular dynamics simulations, using the semiempirical parametric method number 3 (PM3) potential energy surface. The system is taken to be in the ground state prior to photoionization, and time delays from 5 to 50 fs before the recombination are considered. The time evolution is computed over 10 ps. The main findings are (1) the positive charge after ionization is initially mostly distributed on the silicon cluster. (2) After ionization the major structural changes are on the silicon cluster. These include Si-Si bond breaking and formation and hydrogen transfer between different silicon atoms. (3) The transient ionization event gives rise to dynamical behavior that depends sensitively on the ion state lifetime. Subsequent to 45 fs evolution in the charged state, the glycine molecule starts to rotate on the silicon cluster. Implications of the results to various processes that are induced by transient transition to a charged state are discussed. These include inelastic tunneling in molecular devices, photochemistry on conducting surfaces, and electron-molecule scattering

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

Science.gov (United States)

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Near-infrared oxygen airglow from the Venus nightside

Science.gov (United States)

Crisp, D.; Meadows, V. S.; Allen, D. A.; Bezard, B.; Debergh, C.; Maillard, J.-P.

1992-01-01

Groundbased imaging and spectroscopic observations of Venus reveal intense near-infrared oxygen airglow emission from the upper atmosphere and provide new constraints on the oxygen photochemistry and dynamics near the mesopause (approximately 100 km). Atomic oxygen is produced by the Photolysis of CO2 on the dayside of Venus. These atoms are transported by the general circulation, and eventually recombine to form molecular oxygen. Because this recombination reaction is exothermic, many of these molecules are created in an excited state known as O2(delta-1). The airglow is produced as these molecules emit a photon and return to their ground state. New imaging and spectroscopic observations acquired during the summer and fall of 1991 show unexpected spatial and temporal variations in the O2(delta-1) airglow. The implications of these observations for the composition and general circulation of the upper venusian atmosphere are not yet understood but they provide important new constraints on comprehensive dynamical and chemical models of the upper mesosphere and lower thermosphere of Venus.

MICMOC/MICMOS: Photochemistry of van der Waals solids and the rise of the organic molecular complexity

Directory of Open Access Journals (Sweden)

Sergeant d’Hendecourt L. Le

2014-02-01

Full Text Available Ices of well-known composition are widely observed in molecular clouds out of which stars, planets and debris (asteroids, comets will form. These ices are naturally subjected to energy input in the form of UV photons and charged cosmic particles which are able to start a very rich radical chemistry in the solid state. These phenomena are simulated in the MICMOC experiment which focuses on the possible prebiotic significance of the organic residues that are formed at room temperature. Further than MICMOC, we propose a general prospective of the evolution of this experiment toward the concept of non-directed experiments that may allow simulating the very first steps from the inanimate molecular world to selective pathways toward self-replicating autocatalytic and heterotrophic molecules that could be considered, for a physicist a template for “minimal” life.

Spectroscopy and photophysics of flavin related compounds: Riboflavin and iso-(6,7)-riboflavin

International Nuclear Information System (INIS)

Sikorska, Ewa; Khmelinskii, Igor; Komasa, Anna; Koput, Jacek; Ferreira, Luis F.V.; Herance, Jose R.; Bourdelande, Jose L.; Williams, Sian L.; Worrall, David R.; Insinska-Rak, MaIgorzata; Sikorski, Marek

2005-01-01

The photochemistry and photophysics of isoalloxazines (10-substituted 2,3,4,10-tetrahydro-benzo[g]pteridine-2,4-diones), and especially flavins (7,8-dimethyl substituted isoalloxazines), are of considerable interest due to the biological relevance of these compounds. In this paper we report data concerning the photophysics of riboflavin and iso-(6,7)-riboflavin (10-(2,3,4,5-tetrahydroxypentyl)-6,7-dimethylbenzo[g]pteridine-2,4(3H,10H) -dione), and correlate the spectroscopic observations with theoretical calculations performed using time-dependent density functional theory. On the basis of these calculations the lowest excited singlet and triplet states are both assigned (π,π*) symmetry, and this result is used to explain the relatively low singlet oxygen quantum yields in comparison with alloxazines. Time-resolved emission studies have indicated 6,7-dimethylalloxazine a photodegradation product of iso-(6,7)-riboflavin

Mutagenicity in Salmonella of a Simulated Urban-Smog Atmosphere Generated Using a Mobile Reaction Chamber

Science.gov (United States)

The EPA Mobile Reaction Chamber (MRC) is a 24-foot trailer containing a 14.3-m3 Teflon lined photochemical chamber used to generate simulated urban atmospheres. Photochemistry in the MRC is catalyzed by 120 fluorescent bulbs evenly mixed with black light bulbs and UV bulbs (300 &...

Spin–Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes

Czech Academy of Sciences Publication Activity Database

Záliš, Stanislav; Lam, Y.; Ch.; Gray, H. B.; Vlček, Antonín

2015-01-01

Roč. 54, č. 7 (2015), s. 3491-3500 ISSN 0020-1669 R&D Projects: GA MŠk LH13015 Institutional support: RVO:61388955 Keywords : BINUCLEAR PLATINUM(II) PHOTOCHEMISTRY * DENSITY-FUNCTIONAL THEORY * SPECTROSCOPIC PROPERTIES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.820, year: 2015

Garry Rumbles | NREL

Science.gov (United States)

. Rumbles' current research interests are in solar energy with a focus on the basic science of solar . His primary research expertise lies in photochemistry and photophysics, with a specialty in kinetics College awards for excellence in teaching. Dr. Rumbles joined NREL as a sabbatical scientist in 2000

Assessing Photosynthesis by Fluorescence Imaging

Science.gov (United States)

Saura, Pedro; Quiles, Maria Jose

2011-01-01

This practical paper describes a novel fluorescence imaging experiment to study the three processes of photochemistry, fluorescence and thermal energy dissipation, which compete during the dissipation of excitation energy in photosynthesis. The technique represents a non-invasive tool for revealing and understanding the spatial heterogeneity in…

Selected Contributions of the 6th European Meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA 6), 13th to 16th June 2010 Introduction

Czech Academy of Sciences Publication Activity Database

Klusoň, Petr; Krýsa, J.; Malato, S.; Oller, I.

2011-01-01

Roč. 161, č. 1 (2011), s. 2-2 ISSN 0920-5861 Grant - others:SMS(ES) CTQ2009-13459-C05-01 Institutional research plan: CEZ:AV0Z40720504 Keywords : solar light * environmental chemistry * photochemistry Subject RIV: CC - Organic Chemistry Impact factor: 3.407, year: 2011

The nitrogen cycle: Atmosphere interactions

Science.gov (United States)

Levine, J. S.

1984-01-01

Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

Experimental simulations of oxidizing conditions and organic decomposition on the surface of Mars

International Nuclear Information System (INIS)

Stoker, C.R.; Mancinelli, R.L.; Mckay, C.P.

1988-01-01

One important scientific objective of a Mars Rover Sample Return mission would be to look for traces of living and extinct life on Mars. An instrument to search for organic carbon may be the simplest instrument that could screen samples which are interesting from a biological point of view. An experimental program is described which would help to understand the nature of the oxidizing soil on Mars and the mechanism responsible for organic degradation on the Martian surface. This is approached by lab simulations of the actual conditions that occur on Mars, particularly the oxidant production by atmospheric photochemistry, and the combined effects of UV light and oxidants in decomposing organic compounds. The results will be used to formulate models of the photochemistry of the atmospheric, the atmosphere-soil interaction, and the diffusion of reactive compounds into the soils. This information will provide insights and constraints on the design of a sampling strategy to search for organic compounds on Mars

Vacuum ultraviolet photochemistry of CH4 and isotopomers. II. Product channel fields and absorption spectra

International Nuclear Information System (INIS)

Wang, Jen-Han; Liu, Kopin; Min, Zhiyuan; Su, Hongmei; Bersohn, Richard; Preses, Jack; Larese, John Z.

2000-01-01

In part I of this work the relative velocities and anisotropies of the atomic H and D fragments from methane photolysis at 10.2 eV were measured. In this paper the relative abundance of the methyl and methylene fragments are reported. A complete set of quantum yields for the different photodissociation channels of each isotopomer is obtained by combining the two sets of data. Previously it was found that H atoms are almost four times more likely than D atoms to be ejected; now it is found that hydrogen molecule photofragments are much richer in H atoms than in D. Overall, the heavier D atoms are more likely than the H atoms to remain attached to the carbon atom. An implication for astrophysics is discussed. The VUV absorption spectra of CH 4 and CH 3 D are almost identical both at room temperature and 75 K. There is, as expected, no variation in the absorption spectrum with temperature. Evidence is given that all or almost all of the methylene is produced in the a 1 A 1 and not in the ground 3 B 1 state. (c) 2000 American Institute of Physics

7 CFR 1220.615 - State and United States.

Science.gov (United States)

2010-01-01

... 7 Agriculture 10 2010-01-01 2010-01-01 false State and United States. 1220.615 Section 1220.615... CONSUMER INFORMATION Procedures To Request a Referendum Definitions § 1220.615 State and United States. State and United States include the 50 States of the United States of America, the District of Columbia...

7 CFR 1220.129 - State and United States.

Science.gov (United States)

2010-01-01

... 7 Agriculture 10 2010-01-01 2010-01-01 false State and United States. 1220.129 Section 1220.129... CONSUMER INFORMATION Soybean Promotion and Research Order Definitions § 1220.129 State and United States. The terms State and United States include the 50 States of the United States of America, the District...

7 CFR 1209.21 - State and United States.

Science.gov (United States)

2010-01-01

... 7 Agriculture 10 2010-01-01 2010-01-01 false State and United States. 1209.21 Section 1209.21... Definitions § 1209.21 State and United States. (a) State means any of the several States, the District of Columbia, and the Commonwealth of Puerto Rico. (b) United States means collectively the several States of...

Optimal resource states for local state discrimination

Science.gov (United States)

Bandyopadhyay, Somshubhro; Halder, Saronath; Nathanson, Michael

2018-02-01

We study the problem of locally distinguishing pure quantum states using shared entanglement as a resource. For a given set of locally indistinguishable states, we define a resource state to be useful if it can enhance local distinguishability and optimal if it can distinguish the states as well as global measurements and is also minimal with respect to a partial ordering defined by entanglement and dimension. We present examples of useful resources and show that an entangled state need not be useful for distinguishing a given set of states. We obtain optimal resources with explicit local protocols to distinguish multipartite Greenberger-Horne-Zeilinger and graph states and also show that a maximally entangled state is an optimal resource under one-way local operations and classical communication to distinguish any bipartite orthonormal basis which contains at least one entangled state of full Schmidt rank.

Formation of secondary organic aerosol coating on black carbon particles near vehicular emissions

Science.gov (United States)

Lee, Alex K. Y.; Chen, Chia-Li; Liu, Jun; Price, Derek J.; Betha, Raghu; Russell, Lynn M.; Zhang, Xiaolu; Cappa, Christopher D.

2017-12-01

Black carbon (BC) emitted from incomplete combustion can result in significant impacts on air quality and climate. Understanding the mixing state of ambient BC and the chemical characteristics of its associated coatings is particularly important to evaluate BC fate and environmental impacts. In this study, we investigate the formation of organic coatings on BC particles in an urban environment (Fontana, California) under hot and dry conditions using a soot-particle aerosol mass spectrometer (SP-AMS). The SP-AMS was operated in a configuration that can exclusively detect refractory BC (rBC) particles and their coatings. Using the -log(NOx / NOy) ratio as a proxy for photochemical age of air masses, substantial formation of secondary organic aerosol (SOA) coatings on rBC particles was observed due to active photochemistry in the afternoon, whereas primary organic aerosol (POA) components were strongly associated with rBC from fresh vehicular emissions in the morning rush hours. There is also evidence that cooking-related organic aerosols were externally mixed from rBC. Positive matrix factorization and elemental analysis illustrate that most of the observed SOA coatings were freshly formed, providing an opportunity to examine SOA coating formation on rBCs near vehicular emissions. Approximately 7-20 wt % of secondary organic and inorganic species were estimated to be internally mixed with rBC on average, implying that rBC is unlikely the major condensation sink of SOA in this study. Comparison of our results to a co-located standard high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement suggests that at least a portion of SOA materials condensed on rBC surfaces were chemically different from oxygenated organic aerosol (OOA) particles that were externally mixed with rBC, although they could both be generated from local photochemistry.

A Model Study of the Photochemical Fate of As(III in Paddy-Water

Directory of Open Access Journals (Sweden)

Luca Carena

2017-03-01

Full Text Available The APEX (Aqueous Photochemistry of Environmentally-occurring Xenobiotics software previously developed by one of us was used to model the photochemistry of As(III in paddy-field water, allowing a comparison with biotic processes. The model included key paddy-water variables, such as the shielding effect of the rice canopy on incident sunlight and its monthly variations, water pH, and the photochemical parameters of the chromophoric dissolved organic matter (CDOM occurring in paddy fields. The half-life times (t1/2 of As(III photooxidation to As(V would be ~20–30 days in May. In contrast, the photochemical oxidation of As(III would be much slower in June and July due to rice-canopy shading of radiation because of plant growth, despite higher sunlight irradiance. At pH < 8 the photooxidation of As(III would mainly be accounted for by reaction with transient species produced by irradiated CDOM (here represented by the excited triplet states 3CDOM*, neglecting the possibly more important reactions with poorly known species such as the phenoxy radicals and, to a lesser extent, with the hydroxyl radicals (HO•. However, the carbonate radicals (CO3•− could be key photooxidants at pH > 8.5 provided that the paddy-water 3CDOM* is sufficiently reactive toward the oxidation of CO32−. In particular, if paddy-water 3CDOM* oxidizes the carbonate anion with a second-order reaction rate constant near (or higher than 106 M−1·s−1, the photooxidation of As(III could be quite fast at pH > 8.5. Such pH conditions can be produced by elevated photosynthetic activity that consumes dissolved CO2.

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade.

Science.gov (United States)

Ben, G Y; Osmond, C B; Sharkey, T D

1987-06-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O(2) electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO(2) saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O(2) per mole photons) was slightly, if at all, affected by mild water stress (>-1.5 megapascals). (c) Severe water stress (<-1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (F(v)/F(m)) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred.

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade 1

Science.gov (United States)

Ben, Gui-Ying; Osmond, C. Barry; Sharkey, Thomas D.

1987-01-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O2 electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO2 saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O2 per mole photons) was slightly, if at all, affected by mild water stress (>−1.5 megapascals). (c) Severe water stress (<−1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (Fv/Fm) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred. PMID:16665465

Minimally conscious state or cortically mediated state?

Science.gov (United States)

Naccache, Lionel

2018-04-01

Durable impairments of consciousness are currently classified in three main neurological categories: comatose state, vegetative state (also recently coined unresponsive wakefulness syndrome) and minimally conscious state. While the introduction of minimally conscious state, in 2002, was a major progress to help clinicians recognize complex non-reflexive behaviours in the absence of functional communication, it raises several problems. The most important issue related to minimally conscious state lies in its criteria: while behavioural definition of minimally conscious state lacks any direct evidence of patient's conscious content or conscious state, it includes the adjective 'conscious'. I discuss this major problem in this review and propose a novel interpretation of minimally conscious state: its criteria do not inform us about the potential residual consciousness of patients, but they do inform us with certainty about the presence of a cortically mediated state. Based on this constructive criticism review, I suggest three proposals aiming at improving the way we describe the subjective and cognitive state of non-communicating patients. In particular, I present a tentative new classification of impairments of consciousness that combines behavioural evidence with functional brain imaging data, in order to probe directly and univocally residual conscious processes.

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3). [applications to spacecraft fuel cells

Science.gov (United States)

Sheridan, P. S.

1980-01-01

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

State laws on tobacco control--United States, 1998.

Science.gov (United States)

Fishman, J A; Allison, H; Knowles, S B; Fishburn, B A; Woollery, T A; Marx, W T; Shelton, D M; Husten, C G; Eriksen, M P

1999-06-25

State laws addressing tobacco use, the leading preventable cause of death in the United States, are summarized. Laws address smoke-free indoor air, minors' access to tobacco products, advertising of tobacco products, and excise taxes on tobacco products. Legislation effective through December 31, 1998. CDC identified laws addressing tobacco control by using an on-line legal research database. CDC's findings were verified with the National Cancer Institute's State Cancer Legislative Database. Since a previous surveillance summary on state tobacco-control laws published in November 1995 (covering legislation effective through June 30, 1995), several states have enacted new restrictions or strengthened existing legislation that addresses smoke-free indoor air, minors' access to tobacco, tobacco advertising, and tobacco taxes. Five states strengthened their smoke-free indoor air legislation. All states and Washington, D.C., continued to prohibit the sale and distribution of tobacco products to minors; however, 21 states expanded minors' access laws by designating enforcement authorities, adding license suspension or revocation for sale to minors, or requiring signage. Since the 1995 report, eight additional states (a total of 19 states and Washington, D.C.) now ban vending machines from areas accessible to minors. Thirteen states restrict advertising of tobacco products, an increase of four states since the 1995 report. Although the number of states that tax cigarettes and smokeless tobacco did not change, 13 states increased excise taxes on cigarettes, and five states increased excise taxes on smokeless tobacco products. The average state excise tax on cigarettes is 38.9 cents per pack, an increase of 7.4 cents compared with the average tax in the 1995 report. State laws addressing tobacco control vary in relation to restrictiveness, enforcement and penalties, preemptions, and exceptions. The data summarizing state tobacco-control laws are available through CDC

Prototype of a Laser-Induced Fluorescence Ground-Based Instrument for Measurements of Atmospheric Iodine Monoxide (IO)

Science.gov (United States)

Thurlow, M. E.; Co, D. T.; Hanisco, T. F.; Lapson, L. B.; Anderson, J. G.

2008-12-01

High abundances of iodine monoxide (IO) are known to exist and to participate in local photochemistry of the marine boundary layer: (1) IO participates in depletion episodes of O3 and in the removal of mercury in the Arctic polar spring by enhancing atomic Br mixing ratios. Recent observations and computer simulations suggest that mercury sequestration is closely tied to halogen photochemistry and that gaseous atomic Hg depletion can be enhanced significantly by the presence of small amounts of iodine-containing compounds. (2) IO and higher- order iodine oxides are involved in the formation of new particles in coastal marine environments. Studies using smog chamber experiments simulating coastal atmospheric conditions have demonstrated that new particles can form from condensable iodine-containing vapors and that their concentrations over the open ocean are sufficient to influence marine particle formation. (3) IO has also been shown to affect the oxidizing capacity of the troposphere by altering the partitioning of NO2/NO and HO2/HO and by activating chlorine and bromine in sea salt aerosols. In the stratosphere, these same processes can lead to enhanced ozone loss rates. Detailed photochemical models that include iodine photochemistry, however, are hampered by the lack of observational data. The distribution of IO in vertical, horizontal, and temporal coordinates is unknown, so the impact of IO on global photochemistry cannot be predicted. The resolution of these important scientific issues requires an in situ IO instrument. A fully functional nanosecond Nd:YAG-pumped Ti:Sapphire laser system and a prototype IO ground-based instrument have been built in our lab. With the current setup, the laser system was situated 10 m from the field station, and the laser light was coupled via an optical fiber. With the use of highly efficient fluorescence detection optics and photon counting techniques, sensitivities of better than 0.1 ppt in 1 s for IO was achieved in the

Multi-electron transfer photochemistry: Caught in the act

Science.gov (United States)

Beiler, Anna M.; Moore, Gary F.

2018-01-01

The accumulation of multiple redox equivalents is essential in photo-driven catalytic reactions such as solar water splitting. However, direct spectroscopic observation of a twice-oxidized species under diffuse illumination has proved elusive until now.

Photochemistry of biogenic emissions over the Amazon forest

Science.gov (United States)

Jacob, Daniel J.; Wofsy, Steven C.

1988-01-01

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

A Bibliography of References in Natural Water Photochemistry

Science.gov (United States)

1984-12-01

Impacto ambiental do la derrama, del Pozo IXTOC-I sobre 91 zooplancton. I.P.N. Falk-Peterson, I.-B., Saethre, L. J. and LUnning, S., 1982. Toxic effects of...larvas, postlarvas, jueveniles y adultos do camaron y adultos do osti6n y pulpo por medio de biosensayos. Cientffica y Ticnica. Universidad de Sonora...spill: Flaking of surface mousse in the Gulf of Mexico . Nature 290: 235-238. Payne, J., 1984.t Physical/chemical weathering of petroleum in the marine

Photochemistry and photopolymerisation activity of novel thioxanthone derivatives

International Nuclear Information System (INIS)

Nik Ghazali Salleh; Allen, N.S.; Edge, M.; Shah, M.; Green, A.

1999-01-01

In this paper, we aim to examine the influence of a range of 4-oxy substituted groups on the photochemical and photopolymerization of 1-chloro- and 1-phenylthio-thioxanhone. Here we have examined the effect of a number of acyloxy groups attached to the ring 4-position. The study includes a spectroscopic and photoinitiated polymerization evaluation using real time infrared and photocalorimetry. The photoactivities of the initiators are compared with those of the standard industrial system such as the 4-n-propoxy derivative and the basic compound like the 1-chloro-4-hydroxyl derivative which was used to synthesise all the derivatives examined here

Transcriptome States Reflect Imaging of Aging States.

Science.gov (United States)

Eckley, D Mark; Coletta, Christopher E; Orlov, Nikita V; Wilson, Mark A; Iser, Wendy; Bastian, Paul; Lehrmann, Elin; Zhang, Yonqing; Becker, Kevin G; Goldberg, Ilya G

2018-06-14

In this study, we describe a morphological biomarker that detects multiple discrete subpopulations (or "age-states") at several chronological ages in a population of nematodes (Caenorhabditis elegans). We determined the frequencies of three healthy adult states and the timing of the transitions between them across the lifespan. We used short-lived and long-lived strains to confirm the general applicability of the state classifier and to monitor state progression. This exploration revealed healthy and unhealthy states, the former being favored in long-lived strains and the latter showing delayed onset. Short-lived strains rapidly transitioned through the putative healthy state. We previously found that age-matched animals in different age-states have distinct transcriptome profiles. We isolated animals at the beginning and end of each identified state and performed microarray analysis (principal component analysis, relative sample to sample distance measurements, and gene set enrichment analysis). In some comparisons, chronologically identical individuals were farther apart than morphologically identical individuals isolated on different days. The age-state biomarker allowed assessment of aging in a novel manner, complementary to chronological age progression. We found hsp70 and some small heat shock protein genes are expressed later in adulthood, consistent with the proteostasis collapse model.

Competing States in the t-J Model: Uniform d-Wave State versus Stripe State versus Stripe State

NARCIS (Netherlands)

Corboz, P.R.; Rice, T.M.; Troyer, M.

2014-01-01

Variational studies of the t-J model on the square lattice based on infinite projected-entangled pair states confirm an extremely close competition between a uniform d-wave superconducting state and different stripe states. The site-centered stripe with an in-phase d-wave order has an equal or only

The association between state attachment security and state Mindfulness.

Directory of Open Access Journals (Sweden)

Christopher A Pepping

Full Text Available Recent research suggests that attachment and mindfulness are related, though the nature of this association is unclear. Here we present two studies examining whether there is a causal relationship between state attachment and state mindfulness. Study 1 investigated the effects of experimentally increasing state mindfulness on state attachment security. State mindfulness was successfully enhanced, but this led to no change in state attachment security. Study 2 investigated the effects of experimentally enhancing state attachment security on state mindfulness. State attachment security was successfully enhanced, but this did not lead to any change in state mindfulness. These findings suggest that there is not a direct, immediate causal relationship between state attachment and state mindfulness as a result of brief experimental manipulations. Future research should examine these associations in longer term interventions.

Abstracts of European Young Investigator Conference 2005

International Nuclear Information System (INIS)

2005-01-01

The conference specially aim at the active participation of all European young investigators, typically consisting of graduate students and postdocs below the age of 35. All participants share an interest in free radical chemistry, radiation chemistry and physics, photochemistry, radiobiology, life sciences and environmentally related topics that cover experimental and theoretical aspects

on Isolated Smooth Muscle Preparation in Rats

African Journals Online (AJOL)

Samuel Olaleye

ABSTRACT. This study investigated the receptor effects of methanolic root extract of ... Phytochemical Analysis: Photochemistry of the methanolic extract was ... mounted with resting tension 0.5g in an organ bath containing .... Effects of extra cellular free Ca2+ and 0.5mM ... isolated smooth muscle by high K+ on the other.

HMI scientific report - chemistry 1988

International Nuclear Information System (INIS)

1989-01-01

Results of the R and D activities are reported, dealing with the following subjects: Interface processes and energy conversion, high-energy photochemistry and radiation chemistry as well as trace elements chemistry. A list of publications and lectures is added and gives a view on results obtained in research and development. (EF) [de

Multiple photon infrared processes in polyatomic molecules

International Nuclear Information System (INIS)

Harrison, R.G.; Butcher, S.R.

1980-01-01

This paper reviews current understanding of the process of multiple photon excitation and dissociation of polyatomic molecules, whereby in the presence of an intense infrared laser field a molecule may absorb upwards of 30 photons. The application of this process to new photochemistry and in particular laser isotope separation is also discussed. (author)

77 FR 47768 - Protection of Stratospheric Ozone: Determination 27 for Significant New Alternatives Policy Program

Science.gov (United States)

2012-08-10

... chemistry of trans-CF3CH=CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O 3 '', Jrnl of Photochemistry and Photobiology A: Chemistry 199 (2008) 92-97; and Wang D., Olsen S., Wuebbles... specified in the MSDS, in American Society for Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE...

Proceedings of the 17. Annual Meeting of the Brazilian Chemistry Society; 7. National Symposium on Inorganic Chemistry. Abstracts

International Nuclear Information System (INIS)

1994-01-01

These 17. Annual Meeting of the Brazilian Chemistry Society and 7. National Symposium on Inorganic Chemistry present several subjects of different interests for the participants, including sections about inorganic chemistry; organic chemistry; environmental chemistry; technological chemistry; electrochemistry; physical chemistry; photochemistry; chemical education; natural products; analytical chemistry and biological chemistry. (C.G.C.)

Teleportations of Mixed States and Multipartite Quantum States

Institute of Scientific and Technical Information of China (English)

YU Chang-Shui; WANG Ya-Hong; SONG He-Shan

2007-01-01

In this paper, we propose a protocol to deterministically teleport an unknown mixed state of qubit by utilizing a maximally bipartite entangled state of qubits as quantum channel. Ifa non-maximally entangled bipartite pure state is employed as quantum channel, the unknown mixed quantum state of qubit can be teleported with 1 - √1 - C2 probability, where C is the concurrence of the quantum channel. The protocol can also be generalized to teleport a mixed state of qudit or a multipartite mixed state. More important purpose is that, on the basis of the protocol, the teleportation of an arbitrary multipartite (pure or mixed) quantum state can be decomposed into the teleportation of each subsystem by employing separate entangled states as quantum channels. In the case of deterministic teleportation,Bob only needs to perform unitary transformations on his single particles in order to recover the initial teleported multipartite quantum state.

Chemistry Division progress report for the period January 1, 1977 - December 31, 1980

International Nuclear Information System (INIS)

Moorthy, P.N.; Ramshesh, V.; Yakhmi, J.V.

1981-01-01

The research and development work of the Chemistry Division of the Bhabha Atomic Research Centre, Bombay, during the period 1977-1980 is reported in the form of individual summaries under the headings: basic research including radiation chemistry, photochemistry, kinetic and electrochemical studies, ion exchange and sorption behaviour, chemistry of metal complexes (in particular, of uranium complexes), radiation damage in solids, heterogeneous catalysts, studies in magnetism, physical properties, solid state studies, theoretical studies, reactor related programmes (including reactor chemistry, lubricants and sealants, surface studies, water chemistry), applied research and development (including materials development, purification and analytical techniques, apolied radiation chemistry etc.), and instrumentation. Work of service facilities such as workshop, analytical se services, and repair and maintenance of instruments is described. Lists of training programmes, staff publications and divisional seminars, are given. At the end a sectionwise list of staff members is also given. (M.G.B.)

Supersqueezed states from squeezed states

International Nuclear Information System (INIS)

Nieto, M.M.

1992-01-01

Using super-Baker-Campbell-Hausdorff relations on the elements of the supergroup OSP(2/2), we derive the supersqueeze operator and the supersqueezed states, which are the supersymmetric generalization of the squeezed states of the harmonic oscillator

Quantum States Transfer by Analogous Bell States

International Nuclear Information System (INIS)

Mei Di; Li Chong; Yang Guohui; Song Heshan

2008-01-01

Transmitting quantum states by channels of analogous Bell states is studied in this paper. We analyze the transmitting process, constructed the probabilitic unitary operator, and gain the largest successful transfer quantum state probability.

Electrochemical studies of ruthenium compounds

International Nuclear Information System (INIS)

Kumar Ghosh, B.; Chakravorty, A.

1989-01-01

In many ways the chemistry of transition metals is the chemistry of multiple oxidation states and the associated redox phenomena. If a particular element were to be singeld out to illustrate this viewpoint, a model choice would be ruthenium - an element that is directly or indirectly the active centre of a plethora of redox phenomena encompassing ten different oxidation states and a breathtaking diversity of structure and bonding. In the present review the authors are primarily concerned with the oxidation states of certain ligands coordinated to ruthenium. This choice is deliberate since this is one area where the unique power of electrochemical methods is splendidly revealed. Without these methods, development in this area would have been greatly hampered. A brief summary of metal oxidation states is also included as a prelude to the main subject of this review. The authors have generally emphasize the information derived which is of chemical interest leaving the details of formal electrochemical arguments in the background. The authors have reviewed the pattern and systematics of ligand redox in ruthenium complexes. The synergistic combination of electrochemical and spectroscopic methods have vastly increased our understanding of ligand phenomena during the last 15 years or so. This in turn has led to better understanding and new developments in other fields. Photophysics and photochemistry could be cited as examples. (author). 176 refs.; 10 figs.; 10 tabs

State-to-State Mode Specificity: Energy Sequestration and Flow Gated by Transition State.

Science.gov (United States)

Zhao, Bin; Sun, Zhigang; Guo, Hua

2015-12-23

Energy flow and sequestration at the state-to-state level are investigated for a prototypical four-atom reaction, H2 + OH → H + H2O, using a transition-state wave packet (TSWP) method. The product state distribution is found to depend strongly on the reactant vibrational excitation, indicating mode specificity at the state-to-state level. From a local-mode perspective, it is shown that the vibrational excitation of the H2O product derives from two different sources, one attributable to the energy flow along the reaction coordinate into the newly formed OH bond and the other due to the sequestration of the vibrational energy in the OH spectator moiety during the reaction. The analysis provided a unified interpretation of some seemingly contradicting experimental observations. It is further shown that the transfer of vibrational energy from the OH reactant to H2O product is gated by the transition state, accomplished coherently by multiple TSWPs with the corresponding OH vibrational excitation.

Report of the High Energy Physics Advisory Panel (HEPAP) subpanel on high energy gamma ray and neutrino astronomy

International Nuclear Information System (INIS)

Gaisser, T.K.; Gordon, H.A.; Melissinos, A.; Rosen, S.P.; Ruderman, M.A.; Turner, M.S.; Zeller, M.

1988-11-01

This report contains information on topics of neutrino and gammay-ray astronomy. Some of the topics discussed are: SN1987A, statistics and variability, background rejection and muons, relation between photon and neutrinos, sensitivity of gamma-ray experiments, comparison of air Cherenkov experiments, air shower experiment, and underground experiments

Noisy teleportation of qubit states via the Greenberger–Horne–Zeilinger state or the W state

International Nuclear Information System (INIS)

Yan-Ling, Li; Mao-Fa, Fang; Xing, Xiao; Chao, Wu; Li-Zhen, Hou

2010-01-01

The effects of distributing entanglement through the amplitude damping channel or the phase damping channel on the teleportation of a single-qubit state via the Greenberger–Horne–Zeilinger state and the W state are discussed. It is found that the average fidelity of teleportation depends on the type and rate of the damping in the channel. For the one-qubit affected case, the Greenberger–Horne–Zeilinger state is as robust as the W state, i.e., the same quantum information is preserved through teleportation. For the two-qubit affected case, the W state is more robust when the entanglement is distributed via the amplitude damping channel; if the entanglement is distributed via the phase damping channel, the W state is more robust when the noisy parameter is small while the Greenberger–Horne–Zeilinger state becomes more robust when it is large. For the three-qubit affected case, the Greenberger–Horne–Zeilinger state is more robust than the W state. (general)

Hydroxyl radical observations during the wintertime in Beijing and comparison with steady state model calculations.

Science.gov (United States)

Slater, E.; Whalley, L.; Woodward-Massey, R.; Ye, C.; Crilley, L.; Kramer, L. J.; Vu, T.; Bloss, W.; Squires, F. A.; Dunmore, R.; Lee, J. D.; Heard, D. E.

2017-12-01

In Beijing poor urban air quality has a demonstrable effect on human health. During the wintertime, anthropogenic emissions from fossil fuel combustion can lead to high aerosol loadings and haze events. A high oxidation capacity on hazy days has previously been inferred from the significant contribution secondary organic aerosol (SOA) make to total PM2.5 (Huang et al., 2014). The hydroxyl radical (OH) mediates virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and SOA. Understanding the sources and sinks of OH in the atmosphere is essential in improving predictions of the lifetimes and chemical processing of pollutants and their transport within urban areas. We will present OH and HO2 measurements made in central Beijing during the recent `An Integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO)' project which took place in November and December 2016. OH measurements were made using the FAGE (Fluorescence Assay by Gas Expansion) technique, with the use of an inlet pre injector (IPI) which provides an alternative method to determine the background by injecting a scavenger (propane) to remove ambient OH. The OH measurements were made over a range of meteorological conditions including a number of haze days, with the average maximum OH concentration measured for the campaign being 2.5 x 106 cm-3 and for haze days the OH concentration reached levels of 3.5 x 106 cm-3 which is comparable to OH levels in non-haze days. We will compare the OH observations to steady state calculations constrained to the total OH reactivity and key OH precursors that were measured alongside OH. Through this comparison we will identify the major OH sources which sustain the wintertime oxidation capacity. The current understanding is that gas-phase oxidation via the OH radical becomes less important in haze events due to lower light and ozone levels, making photochemistry

State nuclear initiatives in the United States

International Nuclear Information System (INIS)

Strauss, P.L.; Stoiber, C.R.

1977-01-01

The paper deals with State nuclear initiatives regarding the role of nuclear power in the energy future of the United States. The question of whether and under what circumstances nuclear facilities should be used to generate electricity was put to the popular vote in several States in 1976. Some general principles of Federal-State relations are discussed with specific reference to nuclear regulations. The initiative mechanism itself is described as well as its legal form and background. The parallel developments in the State and Federal legislative consideration of nuclear issues is reviewed and the suggested reasons for the defeat of the proposals in the seven States concerned are discussed. Finally, the author draws some conclusions on the effects of the 1976 initiatives on future decision-making in the US on energy policy in general and nuclear power in particular. (NEA) [fr

Rates and regimes of photochemical ozone production over Central East China in June 2006: a box model analysis using comprehensive measurements of ozone precursors

Directory of Open Access Journals (Sweden)

Y. Kanaya

2009-10-01

Full Text Available An observation-based box model approach was undertaken to estimate concentrations of OH, HO₂, and RO₂ radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O₃, H₂O, CO, NO, NO₂, hydrocarbon, HCHO, and CH₃CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h⁻¹ as a 6-h average (09:00–15:00 CST, suggesting 58±37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as ~23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once, in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NO_x and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NO_x-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO₂ radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.

Program budget 1979

International Nuclear Information System (INIS)

1978-01-01

This HMI report explains the tasks and activities of the Institute and gives an account of the main research activities in the fields of heavy ion physics, radiation chemistry and photochemistry, solids, nuclear chemistry, data processing and electronics. In addition, a survey is given of the Institute's infrastructure and the financial situation. (HK) [de

Photochemical degradation of dissolved organic matter reduces the availability of phosphorus for aquatic primary producers

Czech Academy of Sciences Publication Activity Database

Porcal, Petr; Kopáček, Jiří

2018-01-01

Roč. 193, FEB (2018), s. 1018-1026 ISSN 0045-6535 R&D Projects: GA ČR GA15-09721S Institutional support: RVO:60077344 Keywords : photochemistry * phosphorus * dissolved organic matter * aluminum * iron Subject RIV: DA - Hydrology ; Limnology OBOR OECD: Environmental sciences (social aspects to be 5.7) Impact factor: 4.208, year: 2016

Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral

Science.gov (United States)

M.J. Alvarado; C.R. Lonsdale; R.J. Yokelson; S.K. Akagi; I.R. Burling; H. Coe; J.S. Craven; E. Fischer; G.R. McMeeking; J.H. Seinfeld; T. Soni; J.W. Taylor; D.R. Weise; C.E. Wold

2015-01-01

Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O3) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air...

[Lawrence Berkeley Laboratory] Chemical Sciences Division annual report 1991

Energy Technology Data Exchange (ETDEWEB)

1992-09-01

Summaries are given of research in the following fields: photochemistry of materials in stratosphere, energy transfer and structural studies of molecules on surfaces, laser sources and techniques, crossed molecular beams, molecular interactions, theory of atomic and molecular collision processes, selective photochemistry, photodissociation of free radicals, physical chemistry with emphasis on thermodynamic properties, chemical physics at high photon energies, high-energy atomic physics, atomic physics, high-energy oxidizers and delocalized-electron solids, catalytic hydrogenation of CO, transition metal-catalyzed conversion of CO, NO, H{sub 2}, and organic molecules to fuels and petrochemicals, formation of oxyacids of sulfur from SO{sub 2}, potentially catalytic and conducting organometallics, actinide chemistry, and molecular thermodynamics for phase equilibria in mixtures. Under exploratory R and D funds, the following are discussed: technical evaluation of beamlines and experimental stations for chemical cynamics applications at the ALS synchrotron, and molecular beam threshold time-of-flight spectroscopy of rare gas atoms. Research on normal and superconducting properties of high-{Tc} systems is reported under work for others. (DLC)

[Lawrence Berkeley Laboratory] Chemical Sciences Division annual report 1991

Energy Technology Data Exchange (ETDEWEB)

1992-09-01

Summaries are given of research in the following fields: photochemistry of materials in stratosphere, energy transfer and structural studies of molecules on surfaces, laser sources and techniques, crossed molecular beams, molecular interactions, theory of atomic and molecular collision processes, selective photochemistry, photodissociation of free radicals, physical chemistry with emphasis on thermodynamic properties, chemical physics at high photon energies, high-energy atomic physics, atomic physics, high-energy oxidizers and delocalized-electron solids, catalytic hydrogenation of CO, transition metal-catalyzed conversion of CO, NO, H[sub 2], and organic molecules to fuels and petrochemicals, formation of oxyacids of sulfur from SO[sub 2], potentially catalytic and conducting organometallics, actinide chemistry, and molecular thermodynamics for phase equilibria in mixtures. Under exploratory R and D funds, the following are discussed: technical evaluation of beamlines and experimental stations for chemical cynamics applications at the ALS synchrotron, and molecular beam threshold time-of-flight spectroscopy of rare gas atoms. Research on normal and superconducting properties of high-[Tc] systems is reported under work for others. (DLC)

[Effects of groundwater level on chlorophyll fluorescence characteristics of Tamarix hispida in lower reaches of Tarim River].

Science.gov (United States)

Zhu, Cheng-gang; Li, Wei-hong; Ma, Jian-xin; Ma, Xiao-dong

2010-07-01

Based on the monitoring data of groundwater level at the typical sections in lower reaches of Tarim River, three survey plots nearby the ecological monitoring wells with groundwater depths > 6 m were selected to investigate the chlorophyll fluorescence characteristics of Tamarix hispida and its photosynthetic activity of PSII under effects of different groundwater depths. With increasing groundwater depth, the chlorophyll fluorescence parameters such as actual photochemical efficiency of PSII in the light (phi(PSII)), electron transport rate (ETR), and photochemistry quenching (q(p)) of T. hispida decreased, while the non-photochemistry quenching (q(N), NPQ) and the yield for dissipation by down-regulation (Y(NPQ)) increased remarkably, and the maximal photochemical efficiency of PSII (Fv/Fm) maintained an optimum value. All the results suggested that the PSII photosynthetic activity of T. hispida under drought stress declined with increasing groundwater depth, and the greater excess energy could result in more risk of photo-inhibition. However, the good adaptability and drought tolerance of T. hispida could make its PSII not seriously damaged, though the drought stress actually existed.

Parameter and State Estimator for State Space Models

Directory of Open Access Journals (Sweden)

Ruifeng Ding

2014-01-01

Full Text Available This paper proposes a parameter and state estimator for canonical state space systems from measured input-output data. The key is to solve the system state from the state equation and to substitute it into the output equation, eliminating the state variables, and the resulting equation contains only the system inputs and outputs, and to derive a least squares parameter identification algorithm. Furthermore, the system states are computed from the estimated parameters and the input-output data. Convergence analysis using the martingale convergence theorem indicates that the parameter estimates converge to their true values. Finally, an illustrative example is provided to show that the proposed algorithm is effective.

31 CFR 515.321 - United States; continental United States.

Science.gov (United States)

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false United States; continental United... General Definitions § 515.321 United States; continental United States. The term United States means the United States and all areas under the jurisdiction or authority thereof, including the Trust Territory of...

31 CFR 500.321 - United States; continental United States.

Science.gov (United States)

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false United States; continental United... General Definitions § 500.321 United States; continental United States. The term United States means the United States and all areas under the jurisdiction or authority thereof, including U.S. trust territories...

31 CFR 535.321 - United States; continental United States.

Science.gov (United States)

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false United States; continental United... General Definitions § 535.321 United States; continental United States. The term United States means the United States and all areas under the jurisdiction or authority thereof including the Trust Territory of...

An alternative laser driven photodissociation mechanism of pyrrole via πσ*1∕S0 conical intersection.

Science.gov (United States)

Nandipati, K R; Lan, Z; Singh, H; Mahapatra, S

2017-06-07

A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S 0 - 1 πσ * (A21) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the πσ*1 state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the πσ*1 photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

An alternative laser driven photodissociation mechanism of pyrrole via π*1σ/S0 conical intersection

Science.gov (United States)

Nandipati, K. R.; Lan, Z.; Singh, H.; Mahapatra, S.

2017-06-01

A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S0-1π σ*(A12) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the π*1σ state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the π*1σ photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

An instant photo-excited electrons relaxation on the photo-degradation properties of TiO2-x films

CSIR Research Space (South Africa)

Nkosi, SS

2014-11-01

Full Text Available of Photochemistry and Photobiology A: Chemistry 293 (2014) 72–80 An instant photo-excited electrons relaxation on the photo- degradation properties of TiO2−x films S.S. Nkosi a,b,∗, I. Kortidis d, D.E. Motaungc,∗, P.R. Makgwanec, O.M. Ndwandwe b, S.S. Rayc, G...