WorldWideScience

Sample records for solvent independent photochemistry

  1. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

    Direct Asymmetric Photochemistry with Circularly Polarized Light, H. RauCoherent Laser Control of the Handedness of Chiral Molecules, P. Brumer and M. ShapiroMagnetochiral Anisotropy in Asymmetric Photochemistry, G.L.J.A.RikkenEnantiodifferentiating Photosensitized Reactions, Y. InoueDiastereodifferentiating Photoreactions, N. Hoffmann and J.-P. PeteChirality in Photochromism, Y. Yokoyama and M. SaitoChiral Photochemistry with Transition Metal Complexes, S. Sakaki and T. HamadaTemplate-Induced Enantioselective Photochemical Reactions in S

  2. 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.

  3. Recent Advances in Photochemistry

    Indian Academy of Sciences (India)

    Unknown

    Photochemistry is considered a thrust area of research activity worldwide. To bring together various researchers and students working in Asian Countries, the first Asian. Photochemistry Conference (APC) was organized at Hong Kong in 1997. The next one was held in Taejon, Korea in 1999. Both the Conferences were ...

  4. Photochemistry of Flavonoids

    Directory of Open Access Journals (Sweden)

    Jan H. Van der Westhuizen

    2010-08-01

    Full Text Available Flavonoids and their photochemical transformations play an important role in biological processes in nature. Synthetic photochemistry allows access to molecules that cannot be obtained via more conventional methods. This review covers all published synthetic photochemical transformations of the different classes of flavonoids. It is first comprehensive review on the photochemistry of flavonoids.

  5. Photochemistry on solid surfaces

    CERN Document Server

    Matsuura, T

    1989-01-01

    The latest developments in photochemistry on solid surfaces, i.e. photochemistry in heterogeneous systems, including liquid crystallines, are brought together for the first time in a single volume. Distinguished photochemists from various fields have contributed to the book which covers a number of important applications: molecular photo-devices for super-memory, photochemical vapor deposition to produce thin-layered electronic semiconducting materials, sensitive optical media, the control of photochemical reactions pathways, etc. Photochemistry on solid surfaces is now a major field and this

  6. Recent Advances in Photochemistry

    Indian Academy of Sciences (India)

    Unknown

    The formation of the Asian and Oceanic Photochemistry Association (APA) was for- mally announced during the APC-2002. This international society will catalyse R&D activities and bring together researchers in various institutions and the industry in differ- ent Asian countries. We take this opportunity to thank the Board of ...

  7. A Device-Independent Evaluation of Carbonyl Emissions from Heated Electronic Cigarette Solvents.

    Science.gov (United States)

    Wang, Ping; Chen, Wenhao; Liao, Jiawen; Matsuo, Toshiki; Ito, Kazuhide; Fowles, Jeff; Shusterman, Dennis; Mendell, Mark; Kumagai, Kazukiyo

    2017-01-01

    To investigate how the two main electronic (e-) cigarette solvents-propylene glycol (PG) and glycerol (GL)-modulate the formation of toxic volatile carbonyl compounds under precisely controlled temperatures in the absence of nicotine and flavor additives. PG, GL, PG:GL = 1:1 (wt/wt) mixture, and two commercial e-cigarette liquids were vaporized in a stainless steel, tubular reactor in flowing air ranging up to 318°C to simulate e-cigarette vaping. Aerosols were collected and analyzed to quantify the amount of volatile carbonyls produced with each of the five e-liquids. Significant amounts of formaldehyde and acetaldehyde were detected at reactor temperatures ≥215°C for both PG and GL. Acrolein was observed only in e-liquids containing GL when reactor temperatures exceeded 270°C. At 318°C, 2.03±0.80 μg of formaldehyde, 2.35±0.87 μg of acetaldehyde, and a trace amount of acetone were generated per milligram of PG; at the same temperature, 21.1±3.80 μg of formaldehyde, 2.40±0.99 μg of acetaldehyde, and 0.80±0.50 μg of acrolein were detected per milligram of GL. We developed a device-independent test method to investigate carbonyl emissions from different e-cigarette liquids under precisely controlled temperatures. PG and GL were identified to be the main sources of toxic carbonyl compounds from e-cigarette use. GL produced much more formaldehyde than PG. Besides formaldehyde and acetaldehyde, measurable amounts of acrolein were also detected at ≥270°C but only when GL was present in the e-liquid. At 215°C, the estimated daily exposure to formaldehyde from e-cigarettes, exceeded United States Environmental Protection Agency (USEPA) and California Office of Environmental Health Hazard Assessment (OEHHA) acceptable limits, which emphasized the need to further examine the potential cancer and non-cancer health risks associated with e-cigarette use.

  8. A Device-Independent Evaluation of Carbonyl Emissions from Heated Electronic Cigarette Solvents.

    Directory of Open Access Journals (Sweden)

    Ping Wang

    Full Text Available To investigate how the two main electronic (e- cigarette solvents-propylene glycol (PG and glycerol (GL-modulate the formation of toxic volatile carbonyl compounds under precisely controlled temperatures in the absence of nicotine and flavor additives.PG, GL, PG:GL = 1:1 (wt/wt mixture, and two commercial e-cigarette liquids were vaporized in a stainless steel, tubular reactor in flowing air ranging up to 318°C to simulate e-cigarette vaping. Aerosols were collected and analyzed to quantify the amount of volatile carbonyls produced with each of the five e-liquids.Significant amounts of formaldehyde and acetaldehyde were detected at reactor temperatures ≥215°C for both PG and GL. Acrolein was observed only in e-liquids containing GL when reactor temperatures exceeded 270°C. At 318°C, 2.03±0.80 μg of formaldehyde, 2.35±0.87 μg of acetaldehyde, and a trace amount of acetone were generated per milligram of PG; at the same temperature, 21.1±3.80 μg of formaldehyde, 2.40±0.99 μg of acetaldehyde, and 0.80±0.50 μg of acrolein were detected per milligram of GL.We developed a device-independent test method to investigate carbonyl emissions from different e-cigarette liquids under precisely controlled temperatures. PG and GL were identified to be the main sources of toxic carbonyl compounds from e-cigarette use. GL produced much more formaldehyde than PG. Besides formaldehyde and acetaldehyde, measurable amounts of acrolein were also detected at ≥270°C but only when GL was present in the e-liquid. At 215°C, the estimated daily exposure to formaldehyde from e-cigarettes, exceeded United States Environmental Protection Agency (USEPA and California Office of Environmental Health Hazard Assessment (OEHHA acceptable limits, which emphasized the need to further examine the potential cancer and non-cancer health risks associated with e-cigarette use.

  9. Photochemistry of interstellar molecules

    Science.gov (United States)

    Stief, L. J.

    1971-01-01

    The photochemistry of two diatomic and eight polyatomic molecules is discussed quantitatively. For an interstellar molecule, the lifetime against photodecomposition depends upon the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. The constant energy density of Habing is used for the unobserved regions of interstellar radiation field, and the field in obscuring clouds is estimated by combining the constant flux with the observed interstellar extinction curve covering the visible and ultraviolet regions. Lifetimes against photodecomposition in the unobscured regions and as a function of increasing optical thickness in obscuring clouds are calculated for the ten species. The results show that, except for CO, all the molecules have comparable lifetimes of less than one hundred years. Thus they can exist only in dense clouds and can never have been exposed to the unobscured radiation. The calculations further show that the lifetimes in clouds of moderate opacity are of the order of one million years.

  10. 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

  11. Photochemistry of Pluto's Atmosphere

    Science.gov (United States)

    Krasnopolsky, Vladimir A.

    1999-01-01

    This work include studies of two problems: (1) Modeling thermal balance, structure. and escape processes in Pluto's upper atmosphere. This study has been completed in full. A new method, of analytic solution for the equation of hydrodynamic flow from in atmosphere been developed. It was found that the ultraviolet absorption by methane which was previously ignored is even more important in Pluto's thermal balance than the extreme ultraviolet absorption by nitrogen. Two basic models of the lower atmosphere have been suggested, with a tropopause and a planetary surface at the bottom of the stellar occultation lightcurve, respectively, Vertical profiles, of temperature, density, gas velocity, and the CH4 mixing ratio have been calculated for these two models at low, mean, and high solar activity (six models). We prove that Pluto' " s atmosphere is restricted to 3060-4500 km, which makes possible a close flyby of future spacecraft. Implication for Pluto's evolution have also been discussed. and (2) Modeling of Pluto's photochemistry. Based on the results of (1), we have made some changes in the basic continuity equation and in the boundary conditions which reflect a unique can of hydrodynamic escape and therefore have not been used in modeling of other planetary atmospheres. We model photochemistry of 44 neutral and 23 ion species. This work required solution of a set of 67 second-order nonlinear ordinary differential equations. Two models have been developed. Each model consists of the vertical profiles for 67 species, their escape and precipitation rates. These models predict the chemical structure and basic chemical processes in the current atmosphere and possible implication of these processes for evolution. This study has also been completed in full.

  12. 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

  13. 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.

  14. Supramolecular photochemistry and solar cells

    Directory of Open Access Journals (Sweden)

    IHA NEYDE YUKIE MURAKAMI

    2000-01-01

    Full Text Available Supramolecular photochemistry as well as solar cells are fascinating topics of current interest in Inorganic Photochemistry and very active research fields which have attracted wide attention in last two decades. A brief outline of the investigations in these fields carried out in our Laboratory of Inorganic Photochemistry and Energy Conversion is given here with no attempt of an exhaustive coverage of the literature. The emphasis is placed on recent work and information on the above mentioned subjects. Three types of supramolecular systems have been the focus of this work: (i cage-type coordination compounds; (ii second-sphere coordination compounds, exemplified by ion-pair photochemistry of cobalt complexes and (iii covalently-linked systems. In the latter, modulation of the photoluminescence and photochemistry of some rhenium complexes are discussed. Solar energy conversion and development of thin-layer photoelectrochemical solar cells based on sensitization of nanocrystalline semiconductor films by some ruthenium polypyridyl complexes are presented as an important application that resulted from specifically engineered artificial assemblies.

  15. 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

  16. 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

  17. 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

  18. 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.

  19. Interfacial photochemistry of retinal proteins

    Science.gov (United States)

    Hong, Felix T.

    1999-09-01

    Retinal proteins are membrane-bound protein pigments that contain vitamin A aldehyde (retinal) as the chromophore. They include the visual pigment rhodopsin and four additional ones in the plasma membrane of Halobacterium salinarium (formerly Halobacterium halobium). These proteins maintain a fixed and asymmetric orientation in the membranes, and respond to a light stimulus by generating vectorial charge movement, which can be detected as an electric potential across the membrane or an electric current through the membrane. These phenomena are collectively called the photoelectric effects, which defy a rigorous quantitative treatment by means of either conventional (solution phase) photochemistry or conventional electrophysiology. As an alternative to the mainstream approach, we utilize the analytic tools of electrochemical surface science and electrophysiology to analyze two molecular models of light-induced charge separation and recombination. Being tutorial in nature, this article demands no prior knowledge about the subject. A parsimonious equivalent circuit model is developed. Data obtained from reconstituted bacteriorhodopsin membranes are used to validate the theoretical model and the analytical approach. Data generated and used by critics to refute our approach is shown to actually support it. The present analysis is sufficiently general to be applicable to other pigment-containing membranes, such as the visual photoreceptor membrane and the chlorophyll-based photosynthetic membranes. It provides a coherent description of a wide range of light-induced phenomena associated with various pigment-containing membranes. In contrast, the mainstream approach has been plagued with self-contradictions and paradoxes. Last, but not least, the alternative bioelectrochemical approach also exhibits a predictive power that has hitherto been generally lacking. Comparison of the photoelectric effects is made with regard to bacteriorhodopsin, rhodopsin, and the chlorophyll

  20. 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

  1. 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.

  2. Synthesis, characterization and photochemistry of a new ...

    Indian Academy of Sciences (India)

    Abstract. The synthesis, crystal structure, redox characteristics and photochemistry of a new heptamolyb- date supported magnesium-aqua coordination complex viz. (hmtH)2[{Mg(H2O)5}2{Mo7O24}]·3H2O 1 (hmt. = hexamethylenetetramine) is reported. The cyclic voltammogram reveals quasireversible redox behaviour.

  3. Synthesis, characterization and photochemistry of a new ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 9. Synthesis, characterization and photochemistry of a new heptamolybdate supported magnesium-aqua coordination complex. Savita S Khandolkar Pallepogu Raghavaiah Bikshandarkoil R Srinivasan. Volume 127 Issue 9 September 2015 pp 1581-1588 ...

  4. 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)

  5. Solvents and solvent effects in organic chemistry

    National Research Council Canada - National Science Library

    Reichardt, C; Welton, T

    2011-01-01

    ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solute-Solvent Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solutions...

  6. Photochemistry of cyclohexane on Cu(111).

    Science.gov (United States)

    Yamaguchi, Dai; Matsumoto, Taketoshi; Watanabe, Kazuya; Takagi, Noriaki; Matsumoto, Yoshiyasu

    2006-01-07

    The photochemistry of cyclohexane on Cu(111) and its excitation mechanism have been studied by temperature-programmed desorption, ultraviolet and X-ray photoelectron spectroscopy. Cyclohexane weakly adsorbed on Cu(111) has been known to show a broadened and redshifted CH stretching band, i.e., CH vibrational mode softening. Although no dehydrogenation takes place thermally on this surface and by the irradiation of photons at 5.0 eV, adsorbed cyclohexane is dissociated to cyclohexyl and hydrogen by the irradiation of photons at 6.4 eV. This is a marked contrast to cyclohexane in the gas phase where the onset of absorption is located at 7 eV. When the surface irradiated by 6.4-eV photons is further annealed, cyclohexyl is dehydrogenated to form cylcohexene that desorbs at 230 K. The systematic measurements of photochemical cross sections at 6.4 eV with linearly polarized light as a function of incident angle indicate that the electronic transition from the highest occupied band of cyclohexane to a partially occupied hybridized band near the Fermi level is responsible for the photochemistry. The hybridized band is formed by the interactions between the electronic states of cyclohexane and the metal substrate. The role of the hybridized band in the photochemistry and the CH vibrational mode softening is discussed.

  7. 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

  8. 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

  9. Trombay symposium on radiation and photochemistry. Preprints volume

    International Nuclear Information System (INIS)

    The Trombay Symposium on Radiation and Photochemistry was held during January 8-12, 1996 in Bombay. The invited lectures as well as contributed papers in the symposium deal with front-line thrust areas in radiation and photochemistry. Papers relevant to INIS are indexed separately. refs., figs., tabs

  10. 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.

  11. 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

  12. 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).

  13. 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)

  14. Deasphalting solvents

    International Nuclear Information System (INIS)

    Carrillo, J. A; Caceres, J; Vela, G; Bueno, H

    1996-01-01

    This paper describes how the deasphalted oil (DMO) or demetalized oil (DMO) quality (CCR, Ni, V end asphaltenes contents) changes with: DAO or DMO yield, solvent/feed ratio, type of vacuum reside (from paraffinic to blends with vis breaking bottoms), extraction temperature and extraction solvent (propane, propylene, n-butane and I butane)

  15. The impact of nonmethane hydrocarbon compounds on tropospheric photochemistry

    NARCIS (Netherlands)

    Houweling, S; Dentener, F; Lelieveld, J

    1998-01-01

    Nonmethane hydrocarbons (NMHC) play an important role in global scale tropospheric photochemistry. The representation of NMHC chemistry in three-dimensional tropospheric chemistry transport models requires a highly parameterized description of only the most important processes, as the number of

  16. 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. .

  17. 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

  18. Solvent substitution

    International Nuclear Information System (INIS)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general ''Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated

  19. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  20. 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

  1. Photochemistry on Pluto - I. Hydrocarbons and aerosols

    Science.gov (United States)

    Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Kammer, Joshua; Hue, Vincent; Hamel, Mark; Filwett, Rachael

    2017-11-01

    In light of the recent New Horizons flyby measurements, we present a coupled ion-neutral-photochemistry model developed for simulating the atmosphere of Pluto. Our model results closely match the observed density profiles of CH4, N2 and the C2 hydrocarbons in the altitude range where available New Horizons measurements are most accurate (above ∼100-200 km). We found a high eddy coefficient of 106 cm2 s-1 from the surface to an altitude of 150 km, and 3 × 106 cm2 s-1 above 150 km for Pluto's atmosphere. Our results demonstrate that C2 hydrocarbons must stick to and be removed by aerosol particles in order to reproduce the C2 profiles observed by New Horizons. Incorporation into aerosols in Pluto's atmosphere is a significantly more effective process than condensation, and we found that condensation alone cannot account for the observed shape of the vertical profiles. We empirically determined the sticking efficiency of C2 hydrocarbons to aerosol particles as a function of altitude, and found that the sticking efficiency of C2 hydrocarbons is inversely related to the aerosol surface area. Aerosols must harden and become less sticky as they age in Pluto's atmosphere. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto's atmosphere. This result is in agreement with the fundamental idea of aerosols hardening as they age, as proposed for Titan's aerosols.

  2. 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.

    2017-09-01

    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 Utqiaġvik, 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.

  3. Solvent substitutes

    International Nuclear Information System (INIS)

    Evanoff, S.P.

    1995-01-01

    The environmental and industrial hygiene regulations promulgated since 1980, most notably the Superfund Amendments and Reauthorization Act (SARA), the Hazardous and Solid Waste Amendments to the Resources Conservation and Recovery Act (RCRA), and the Clean Air Act Amendments of 1990, have brought about an increased emphasis on user exposure, hazardous waste generation, and air emissions. As a result, industry is performing a fundamental reassessment of cleaning solvents, processes, and procedures. The more progressive organizations have made their goal the elimination of solvents that may pose significant potential human health and environmental hazards. This chapter discusses solvent cleaning in metal-finishing, metal-manufacturing, and industrial maintenance applications; precision cleaning; and electronics manufacturing. Nonmetallic cleaning, adhesives, coatings, inks, and aerosols also will be addressed, but in a more cursory manner

  4. 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.

  5. Near-infrared photochemistry at interfaces based on upconverting nanoparticles.

    Science.gov (United States)

    Wu, Si; Butt, Hans-Jürgen

    2017-09-13

    Near-infrared (NIR) light is better suited than ultraviolet (UV) light for biomedical applications because it penetrates deeper into tissue and causes less photodamage to biological systems. The use of NIR light to control biointerfaces has attracted increasing interest. Here, we review NIR photoreactions at interfaces based on upconverting nanoparticles (UCNPs). UCNPs can convert NIR light to UV or visible light, which can then induce photoreactions of photosensitive compounds. This process is referred to as UCNP-assisted photochemistry. Recently, we and others demonstrated UCNP-assisted photochemistry at interfaces to control interfacial properties of nano-carriers, implants, emulsions, and cells. We introduce the fundamentals of UCNP-assisted photochemistry at interfaces, highlight its potential applications, and discuss remaining challenges.

  6. VUV photochemistry simulation of planetary upper atmosphere using synchrotron radiation.

    Science.gov (United States)

    Carrasco, Nathalie; Giuliani, Alexandre; Correia, Jean Jacques; Cernogora, Guy

    2013-07-01

    The coupling of a gas reactor, named APSIS, with a vacuum-ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility, for a photochemistry study of gas mixtures, is reported. The reactor may be irradiated windowless with gas pressures up to hundreds of millibar, and thus allows the effect of energetic photons below 100 nm wavelength to be studied on possibly dense media. This set-up is perfectly suited to atmospheric photochemistry investigations, as illustrated by a preliminary report of a simulation of the upper atmospheric photochemistry of Titan, the largest satellite of Saturn. Titan's atmosphere is mainly composed of molecular nitrogen and methane. Solar VUV irradiation with wavelengths no longer than 100 nm on the top of the atmosphere enables the dissociation and ionization of nitrogen, involving a nitrogen chemistry specific to nitrogen-rich upper atmospheres.

  7. 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.

  8. Fluorine photochemistry in the stratosphere. [effect on ozone

    Science.gov (United States)

    Stolarski, R. S.; Rundel, R. D.

    1975-01-01

    The photochemistry of fluorine in the stratosphere is surveyed in order to estimate the effect on ozone of fluorine atoms released by the breakdown of chlorofluoromethanes. The catalytic efficiency for ozone destruction by fluorine is found to be less than .0001 that of chlorine in the altitude range from 25 to 50 km.

  9. 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.

  10. 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

  11. 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...

  12. Hydrocarbon photochemistry and Lyman alpha albedo of Jupiter

    Science.gov (United States)

    Yung, Y. L.; Strobel, D. F.

    1980-01-01

    A combined study of hydrocarbon and atomic hydrogen photochemistry is made to calculate self-consistently the L alpha albedo of Jupiter. It is shown that the L alpha emissions observed by Voyagers I and II can be explained by resonance scattering of sunlight. Precipitation of energetic particles from the magnetosphere can provide the large required source of atomic hydrogen, although the contribution of direct particle excitation to the disk-averaged brightness is insignificant. The variability of the L alpha brightness inferred from many observations in recent years is examined. The large difference in the brightness of the He 584 A resonance line observed by Pioneer and Voyager is briefly discussed. Driving the photochemistry by solar ultraviolet radiation alone yields a maximum mixing ratio of C2H6 + C2H2 at 0.01 atm of about 4 x 10 to the -6th. The possibility of additional CH4 dissociation from precipitation of magnetospheric particles is discussed. The photochemistry of C2H2 and C2H3 is sufficiently uncertain not to permit accurate calculations of their densities and the ratio C2H6/C2H2.

  13. Hansen Cleaning Solvent Research

    Data.gov (United States)

    National Aeronautics and Space Administration — Environmental regulation will force current baseline precision cleaning solvent (AK-225) to be phased out starting 2015; we plan to develop a new solvent or solvent...

  14. 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.

  15. 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

  16. Trombay symposium on radiation and photochemistry. Preprints vol. 2: contributed papers

    International Nuclear Information System (INIS)

    This volume contains papers on the topics covering radiation and photochemistry presented at the TSRP-94: Trombay symposium on radiation and photochemistry held at Bombay during 17-21 January 1994. The subjects covered include pulse radiolytic techniques, chemical reaction kinetics,and physical and chemical radiation effects. Papers relevant to INIS are indexed separately. (V.R.)

  17. Recent advances in urocanic acid photochemistry, photobiology and photoimmunology.

    Science.gov (United States)

    Gibbs, Neil K; Tye, Joanne; Norval, Mary

    2008-06-01

    Urocanic acid (UCA), produced in the upper layers of mammalian skin, is a major absorber of ultraviolet radiation (UVR). Originally thought to be a 'natural sunscreen', studies conducted a quarter of a century ago proposed that UCA may be a chromophore for the immunosuppression that follows exposure to UVR. With its intriguing photochemistry, its role in immunosuppression and skin cancer development, and skin barrier function, UCA continues to be the subject of intense research effort. This review summarises the photochemical, photobiological and photoimmunological findings regarding UCA, published since 1998.

  18. Ultraviolet photochemistry of cyanoacetylene: Application to Titan. [Abstract only

    Science.gov (United States)

    Clarke, D. W.; Ferris, J. P.

    1994-01-01

    Cyanoacetylene is believed to have had a central role in the formation of the pyrimidines essential for RNA synthesis leading to the origin of life on Earth. Cyanoacetylene has also been detected on Titan, Saturn's largest moon, and the only moon in the solar system that possesses a dense atmosphere. It is generally accepted that photochemistry plays a major role in the formation of the complex organic molecules and aerosols found in Titan's atmosphere. Because of its long wavelength absorption and low dissociation threshold it is expected that cyanoacetylene is an important part of these photochemical processes. Since cyanoacetylene would also have been subject to ultraviolet light in the atmosphere of early Earth, an investigation of cyanoacetylene photochemistry on Titan might lead to a better understanding of both the photochemical reactions occurring on primitive earth and the processes of chemical evolution as they occur in planetary atmospheres. The effects of irradiation wavelength, mixing with Titan's atmospheric gases, reducing the temperature and lowering cyanoacetylene partial pressures on product formation and polymer composition have been determined with the ultimate goal of understanding the chemical transformations taking place in Titan's atmosphere.

  19. Solvents and solvent effects in organic chemistry

    National Research Council Canada - National Science Library

    Reichardt, C; Welton, T

    2011-01-01

    .../guest complexation equilibria and reactions in biphasic solvent systems and neoteric solvents, respectively. More than 900 new references have been added, giving preference to review articles, and many older ones have been deleted. New references either replace older ones or are added to the end of the respective reference list of each chapter. Th...

  20. 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.

  1. Photochemistry of an Urban Region using Observations and Numerical Modeling

    Science.gov (United States)

    Cantrell, C. A.; Mauldin, L.; Mukherjee, A. D.; Flocke, F. M.; Pfister, G.; Apel, E. C.; Bahreini, R.; Blake, D. R.; Blake, N. J.; Campos, T. L.; Cohen, R. C.; Farmer, D.; Fried, A.; Guenther, A. B.; Hall, S. R.; Heikes, B.; Hornbrook, R. S.; Huey, L. G.; Karl, T.; Kaser, L.; Nowak, J. B.; Ortega, J. V.; O'Sullivan, D. W.; Richter, D.; Smith, J. N.; Tanner, D.; Townsend-Small, A.; Ullmann, K.; Walega, J.; Weibring, P.; Weinheimer, A. J.

    2015-12-01

    The chemistry of HOx radicals in the troposphere can lead to the production of secondary products such as ozone and aerosols, while volatile organic compounds are degraded. The production rates and identities of secondary products depend on the abundance of NOx and other parameters. The amounts of VOCs and NOx can also affect the concentrations of OH, HO2 and RO2. Comparison of observations and model-derived values of HOx species can provide one way to assess the completeness and accuracy of model mechanisms. The functional dependence of measure-model agreement on various controlling parameters can also reveal details of current understanding of photochemistry in urban regions. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE), conducted during the summer of 2014, observations from ground-based and airborne platforms were performed to study the evolution of atmospheric composition over the Denver metropolitan area. Of particular interest in FRAPPE was the assessment of the roles of mixing of emissions from oil and gas exploration and extraction, and those from confined animal production operations, with urban emissions (e.g. from transportation, energy production, and industrial processes) on air quality in the metropolitan and surrounding region. Our group made measurements of OH, HO2, and HO2 + RO2 from the NSF/NCAR C-130 aircraft platform using selected ion chemical ionization mass spectrometry. The C-130 was equipped with instrumentation for the observation of a wide variety of photochemical-related species and parameters. These data are used to assess the photochemical regimes encountered during the period of the study, and to quantitatively describe the chemical processes involved in formation of secondary products. One of the tools used is a steady state model for short-lived species such as those that we observed. This presentation summarizes the behavior of species that were measured during FRAPPE and what the observations reveal

  2. 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.

  3. Canyon solvent cleaning

    International Nuclear Information System (INIS)

    Reif, D.J.

    1986-01-01

    The HM Process at the Savannah River Plant (SRP) uses 7.5% tributylphosphate in n-paraffin as an extraction solvent. During use, the solvent is altered due to hydrolysis and radiolysis, forming materials that influence product losses, produce decontamination, and separation efficiencies. Laboratory studies to improve online solvent cleaning have shown the carbonate washing, although removing residual solvent activity does not remove binding ligands that hold fission products in the solvent. Treatment of solvent by an alumina adsorption process removes binding ligands and significantly improves recycle solvent performance. Both laboratory work defining a full-scale alumina adsorption process and the use of the process to clean HM Process first cycle solvent are presented

  4. 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.

  5. Gas-phase experiments on Au(III) photochemistry.

    Science.gov (United States)

    Marcum, Jesse C; Kaufman, Sydney H; Weber, J Mathias

    2011-04-14

    Irradiation of AuCl(4)(-) and AuCl(2)(OH)(2)(-) in the gas-phase using ultraviolet light (220-415 nm) leads to their dissociation. Observed fragment ions for AuCl(4)(-) are AuCl(3)(-) and AuCl(2)(-) and for AuCl(2)(OH)(2)(-) are AuCl(2)(-) and AuClOH(-). All fragment channels correspond to photoreduction of the gold atom to either Au(II) or Au(I) depending on the number of neutral ligands lost. Fragment branching ratios of AuCl(4)(-) are observed to be highly energy dependent and can be explained by comparison of the experimental data to calculated threshold energies obtained using density functional theory. The main observed spectral features are attributed to ligand-to-metal charge transfer transitions. These results are discussed in the context of the molecular-level mechanisms of Au(III) photochemistry.

  6. Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

    Directory of Open Access Journals (Sweden)

    Veronica Vaida

    2008-01-01

    Full Text Available Atmospheric chemical reactions are often initiated by ultraviolet (UV solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical reactions. Experimental and theoretical O–H intensities of several carboxylic acids, alcohols, and peroxides are presented. The importance of combination bands in spectra at chemically relevant energies is examined in the context of atmospheric photochemistry. Candidate systems for overtone-initiated chemistry are provided, and their lowest energy barrier for reaction and the minimum quanta of O–H stretch required for reaction are calculated. We conclude with a discussion of the major pathways available for overtone-induced reactions in the atmosphere.

  7. The photochemistry of carbon-rich circumstellar shells

    Science.gov (United States)

    Huggins, P. J.; Glassgold, A. E.

    1982-01-01

    The effect of ambient ultraviolet photons on the chemical structure of carbon-rich, circumstellar envelopes is investigated with a simple formulation of the time-dependent, photochemical rate equations valid for optically thick shells. Molecules injected into the shielded inner envelope are broken down when they reach the outer regions where ambient ultraviolet photons can penetrate. A quantitative description of the abundance variations is obtained for the case of uniform expansion by detailed consideration of the shielding of the radiation by the dust and molecules of the envelope. Representative results are presented to illustrate the role of shielding in defining the extent of molecular envelopes, the formation of C I and C II shells by photodestruction of carbon-bearing molecules, and the development of layered chemical structures from the photobreakup of polyatomic molecules. Photochemistry makes the outer parts of thick, carbon-rich envelopes into complex regions containing radicals, ions, and atoms which are of considerable observational and theoretical interest.

  8. Exploring Multiple Potential Energy Surfaces: Photochemistry of Small Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Satoshi Maeda

    2012-01-01

    Full Text Available In theoretical studies of chemical reactions involving multiple potential energy surfaces (PESs such as photochemical reactions, seams of intersection among the PESs often complicate the analysis. In this paper, we review our recipe for exploring multiple PESs by using an automated reaction path search method which has previously been applied to single PESs. Although any such methods for single PESs can be employed in the recipe, the global reaction route mapping (GRRM method was employed in this study. By combining GRRM with the proposed recipe, all critical regions, that is, transition states, conical intersections, intersection seams, and local minima, associated with multiple PESs, can be explored automatically. As illustrative examples, applications to photochemistry of formaldehyde and acetone are described. In these examples as well as in recent applications to other systems, the present approach led to discovery of many unexpected nonadiabatic pathways, by which some complicated experimental data have been explained very clearly.

  9. 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.

  10. 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.

    2012-01-01

    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 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 × 108 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 towards 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 to be less favorable than the isomeric MeO-ketenimine. PMID:22568477

  11. Solvent recycle/recovery

    Energy Technology Data Exchange (ETDEWEB)

    Paffhausen, M.W.; Smith, D.L.; Ugaki, S.N.

    1990-09-01

    This report describes Phase I of the Solvent Recycle/Recovery Task of the DOE Chlorinated Solvent Substitution Program for the US Air Force by the Idaho National Engineering Laboratory, EG G Idaho, Inc., through the US Department of Energy, Idaho Operations Office. The purpose of the task is to identify and test recovery and recycling technologies for proposed substitution solvents identified by the Biodegradable Solvent Substitution Program and the Alternative Solvents/Technologies for Paint Stripping Program with the overall objective of minimizing hazardous wastes. A literature search to identify recycle/recovery technologies and initial distillation studies has been conducted. 4 refs.

  12. Method for Predicting Solubilities of Solids in Mixed Solvents

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O'Connell, J. P.

    2009-01-01

    are made for a single parameter characterizing solute/solvent interactions. Comparisons with available data show that the method is successful in describing a variety of observed mixed solvent solubility behavior, including nearly ideal systems with small excess solubilities, systems with solute......-independent excess solubilities, and systems deviating from these simple rules. Successful predictions for new solvent mixtures cat? be made using limited data from other mixtures.......A method is presented for predicting solubilities of solid solutes in mixed solvents, based on excess Henry's law constants. The basis is statistical mechanical fluctuation solution theory for composition derivatives of solute/solvent infinite dilution activity coefficients. Suitable approximations...

  13. Photochemistry on Pluto: part II HCN and nitrogen isotope fractionation

    Science.gov (United States)

    Mandt, Kathleen; Luspay-Kuti, Adrienn; Hamel, Mark; Jessup, Kandis-Lea; Hue, Vincent; Kammer, Josh; Filwett, Rachael

    2017-11-01

    We have converted our Titan one-dimensional photochemical model to simulate the photochemistry of Pluto's atmosphere and include condensation and aerosol trapping in the model. We find that condensation and aerosol trapping are important processes in producing the HCN altitude profile observed by the Atacama Large Millimeter Array (ALMA). The nitrogen isotope chemistry in Pluto's atmosphere does not appear to significantly fractionate the isotope ratio between N2 and HCN as occurs at Titan. However, our simulations only cover a brief period of time in a Pluto year, and thus only a brief portion of the solar forcing conditions that Pluto's atmosphere experiences. More work is needed to evaluate photochemical fractionation over a Pluto year. Condensation and aerosol trapping appear to have a major impact on the altitude profile of the isotope ratio in HCN. Since ALMA did not detect HC15N in Pluto's atmosphere, we conclude that condensation and aerosol trapping must be much more efficient for HC15N compared to HC14N. The large uncertainty in photochemical fractionation makes it difficult to use any potential current measurement of 14N/15N in N2 to determine the origin of Pluto's nitrogen. More work is needed to understand photochemical fractionation and to evaluate how condensation, sublimation and aerosol trapping will fractionate N2 and HCN.

  14. 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.

  15. Hydrocarbon photochemistry in the upper atmosphere of Jupiter

    Science.gov (United States)

    Gladstone, G. R.; Allen, M.; Yung, Y. L.

    1996-01-01

    The hydrocarbon photochemistry in the upper atmosphere of Jupiter is investigated using a one-dimensional, photochemical-diffusive, and diurnally averaged model. The important chemical cycles and pathways among the major species are outlined and a standard model for the North Equatorial Belt region is examined in detail. It is found that several traditionally dominant chemical pathways among the C and C2 species are replaced in importance by cycles involving C-C4 species. The pressure and altitude profiles of mixing ratios for several observable hydrocarbon species are compared with available ultraviolet- and infrared-derived abundances. The results of sensitivity studies on the standard model with respect to variations in eddy diffusion profile, solar flux, atomic hydrogen influx, latitude, temperature, and important chemical reaction rates are presented. Measured and calculated airglow emissions of He at 584 angstroms and H at 1216 angstroms are also used to provide some constraints on the range of model parameters. The relevance of the model results to the upcoming Galileo mission is briefly discussed. The model is subject to considerable improvement; there is a great need for laboratory measurements of basic reaction rates and photodissociation quantum yields, even for such simple species as methylacetylene and allene. Until such laboratory measurements exist there will be considerable uncertainty in the understanding of the C3 and higher hydrocarbons in the atmospheres of the jovian planets.

  16. Photochemistry of Glyoxal in Wet Aerosols: Smog Chamber Study

    Science.gov (United States)

    Lim, Y. B.; Kim, H.; Turpin, B. J.

    2015-12-01

    Aqueous chemistry is an important pathway for the formation of secondary organic aerosol (SOA). Reaction vessel studies provide evidence that in the aqueous phase photooxidation of water soluble organic compounds (e.g., glyoxal, methylglyoxal) form multifunctional organic products and oligomers. In this work, we extend this bulk-phase chemistry to the condensed-phase chemistry that occurs in/on aerosols by conducting smog chamber experiments — photooxidation of ammonium sulfate and sulfuric acid aerosols containing glyoxal and hydrogen peroxide in the presence of NOx under dry/humid conditions. Particles were analyzed using ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). In the irradiated chamber, photooxidation products of glyoxal as seen in reaction vessel experiments (e.g., oxalic acids and tartaric acids) were also formed in both ammonium sulfate aerosols and sulfuric acid aerosols at humid and even dry conditions. However, the major products were organosulfurs (CHOS), organonitrogens (CHON), and nitrooxy-organosulfates (CHONS), which were also dominantly formed in the dark chamber. These products were formed via non-radical reactions, which depend on acidity and humidity. However, the real-time profiles in the dark chamber and the irradiated chamber were very different, suggesting photochemistry substantially affects non-radical formation in the condensed phase.

  17. Surface photochemistry of pesticides containing 4-chlorophenoxyl chromophore.

    Science.gov (United States)

    Da Silva, José P; Vieira Ferreira, Luis F; Osipov, Ivan; Machado, Isabel Ferreira

    2010-07-15

    The surface photochemistry of pesticides containing 4-chlorophenoxyl chromophore was accessed on the model surfaces cellulose and silica, using diffuse reflectance and chromatographic techniques. 4-Chloroanisole was chosen as the model compound and its phototransformation was followed under lamp (254 nm) and sunlight irradiation. The photodegradation rates are faster on cellulose than on silica. The main photodegradation products on cellulose are anisole and dimerization compounds while on silica the formation of 4-hydroxyanisole and dimerization are the main reaction pathways. Transient absorption studies showed the formation of the 4-methoxyphenylperoxyl radical only on cellulose and in the presence of oxygen. The homolytic cleavage of the C-Cl bond, and consequent formation of a triplet radical pair, is the main primary reaction step on both surfaces. The radical pair then diffuses apart or undergoes electron transfer to form phenyl radicals and phenyl cations, respectively. These two reaction intermediates account for reduction, addition, and formation of bonded residues, the main reactions observed on the studied surfaces and also expected to prevail under natural conditions. 2010 Elsevier B.V. All rights reserved.

  18. Surface photochemistry of pesticides containing 4-chlorophenoxyl chromophore

    Energy Technology Data Exchange (ETDEWEB)

    Da Silva, Jose P., E-mail: jpsilva@ualg.pt [FCT, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Vieira Ferreira, Luis F. [Centro de Quimica-Fisica Molecular, Instituto Superior Tecnico, 1049-001 Lisboa (Portugal); Osipov, Ivan [FCT, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Ferreira Machado, Isabel [Centro de Quimica-Fisica Molecular, Instituto Superior Tecnico, 1049-001 Lisboa (Portugal)

    2010-07-15

    The surface photochemistry of pesticides containing 4-chlorophenoxyl chromophore was accessed on the model surfaces cellulose and silica, using diffuse reflectance and chromatographic techniques. 4-Chloroanisole was chosen as the model compound and its phototransformation was followed under lamp (254 nm) and sunlight irradiation. The photodegradation rates are faster on cellulose than on silica. The main photodegradation products on cellulose are anisole and dimerization compounds while on silica the formation of 4-hydroxyanisole and dimerization are the main reaction pathways. Transient absorption studies showed the formation of the 4-methoxyphenylperoxyl radical only on cellulose and in the presence of oxygen. The homolytic cleavage of the C-Cl bond, and consequent formation of a triplet radical pair, is the main primary reaction step on both surfaces. The radical pair then diffuses apart or undergoes electron transfer to form phenyl radicals and phenyl cations, respectively. These two reaction intermediates account for reduction, addition, and formation of bonded residues, the main reactions observed on the studied surfaces and also expected to prevail under natural conditions.

  19. UV and IR Photochemistries of Malonaldehyde Trapped in Cryogenic Matrices.

    Science.gov (United States)

    Trivella, A; Wassermann, T N; Manca Tanner, C; Lüttschwager, N O B; Coussan, S

    2018-03-08

    UV and IR photochemistries of malonaldehyde, the simplest molecule exhibiting an intramolecular proton exchange, have been studied in four cryogenic matrices at 4.3 K, N 2 , Ne, Ar, and Xe. Samples have been irradiated using a UV and IR OPO type tunable laser, and with a broad band UV mercury lamp. UV and IR spectra have been recorded and compared with theoretical calculations carried out at the SAC-CI/6-31++G(d,p) (UV transitions) and B3LYP/6-311++G(2d,2p) (IR spectra) levels of theory. After deposition, the intramolecularly H-bonded form is found exclusively, while several open forms are formed upon UV irradiation. These open forms show ability to interconvert upon UV irradiation too. Some of them are also able to isomerize upon selective IR irradiations. The whole set of results allowed us to identify seven isomers among the eight postulated. The photodynamics of the electronic relaxation of malonaldehyde have also been investigated. By following the decay or rise of suited specific vibrational bands in the IR spectra, and by comparing the results with an earlier study of the homologous acetylacetone, we deduced that the electronic relaxation of malonaldehyde proceeds through singlet states, most probably through a 3-fold conical intersection, as postulated from theoretical calculations. In contrast with acetylacetone, malonaldehyde does not show fragmentation after UV excitation.

  20. 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.

  1. 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.

  2. 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)

  3. Experimental and theoretical simulations of Titan's VUV photochemistry

    Science.gov (United States)

    Peng, Z.; Carrasco, N.; Pernot, P.

    2013-12-01

    A new reactor, named APSIS (Atmospheric Photochemistry SImulated by Synchrotron), has been designed to simulate planetary atmospheric photochemistry [Peng et al. JGR-E. 2013, 118, 778]. We report here a study focusing on Titan's upper atmosphere. A nitrogen-methane gas flow was irradiated by a continuous 60-350 nm VUV beam provided by the DISCO line at SOLEIL synchrotron radiation facility. The production of C2-C4 hydrocarbons as well as several nitriles (HCN, CH3 CN and C2N2) was detected by in situ mass spectrometry, in agreement with Cassini's INMS observations at Titan, and ex situ GC-MS of a cryogenic experiment. We compared the mass spectra with those obtained by a plasma experiment [Carrasco et al. Icarus. 2012, 219, 230] and with another synchrotron-based experiment [Imanaka and Smith. PNAS. 2010, 107, 12423], and with the in situ measurements of the INMS instrument onboard Cassini probing the neutral content of Titan's upper atmosphere. In spite of lower photochemical production efficiency and different environmental conditions, the APSIS reactor seems to simulate Titan's neutral composition rather well. To interpret these experimental data, we developed a fully coupled ion-neutral photochemical model of the reactor, with uncertainty management, based on the neutral model of Hébrard et al. [J. Photochem. Photobiol. A. 2006, 7, 211], the model of ion chemistry of Plessis et al. [J. Chem. Phys. 2010, 133, 134110], and a new representation of photolysis cross-sections and branching ratios [Gans et al. Icarus. 2013, 223, 330]. Compared to the measurements, the production in Cn blocks is in good agreement. Ion chemistry and the full dissociative recombination scheme have been demonstrated to be important features of the model. The photolysis was confirmed to be globally influential by sensivity analysis. We observed the importance of the addition of small (C1 or C2) units in molecular growth, as well as 3 growth families, promoted by C2H2, C2H4 and C2H5/C2H6

  4. THE EFFECT OF H2O ON ICE PHOTOCHEMISTRY

    International Nuclear Information System (INIS)

    Oeberg, Karin I.; Van Dishoeck, Ewine F.; Linnartz, Harold; Andersson, Stefan

    2010-01-01

    UV irradiation of simple ices is proposed to efficiently produce complex organic species during star formation and planet formation. Through a series of laboratory experiments, we investigate the effects of the H 2 O concentration, the dominant ice constituent in space, on the photochemistry of more volatile species, especially CH 4 , in ice mixtures. In the experiments, thin (∼40 ML) ice mixtures, kept at 20-60 K, are irradiated under ultra-high vacuum conditions with a broadband UV hydrogen discharge lamp. Photodestruction cross sections of volatile species (CH 4 and NH 3 ) and production efficiencies of new species (C 2 H 6 , C 2 H 4 , CO, H 2 CO, CH 3 OH, CH 3 CHO, and CH 3 CH 2 OH) in water-containing ice mixtures are determined using reflection-absorption infrared spectroscopy during irradiation and during a subsequent slow warm-up. The four major effects of increasing the H 2 O concentration are: (1) an increase of the destruction efficiency of the volatile mixture constituent by up to an order of magnitude due to a reduction of back reactions following photodissociation, (2) a shift to products rich in oxygen, e.g., CH 3 OH and H 2 CO, (3) trapping of up to a factor of 5 more of the formed radicals in the ice, and (4) a disproportional increase in the diffusion barrier for the OH radical compared with the CH 3 and HCO radicals. The radical diffusion temperature dependencies are consistent with calculated H 2 O-radical bond strengths. All the listed effects are potentially important for the production of complex organics in H 2 O-rich icy grain mantles around protostars and should thus be taken into account when modeling ice chemistry.

  5. Photochemistry of alkyl bromides trapped in water ice films

    Science.gov (United States)

    Schrems, O.; Okaikwei, B.; Bluszcz, Th.

    2012-04-01

    Photochemical reactions of atmospheric trace gases taking place at the surface of atmospheric ice particles and in bulk ice are important in stratospheric and tropospheric chemistry but also in polar and alpine snowpack chemistry. Consequently, the understanding of the uptake und incorporation of atmospheric trace gases in water ice as well as their interactions with water molecules is very important for the understanding of processes which occur in ice particles and at the air/ice interface. Reactive atmospheric trace gases trapped in ice are subject of photochemical reactions when irradiated with solar UV radiation. Among such compounds bromine species are highly interesting due to their potential of depleting ozone both in the stratosphere and troposphere. Organic bromine gases can carry bromine to the stratosphere. Methyl bromide (CH3Br) is the largest bromine carrier to the stratosphere. It has both natural and anthropogenic sources. In this contribution we will present the results of our laboratory studies of alkyl bromides (methyl, bromide (CH3Br), dimethyl bromide (CH2Br2), n-propyl bromide (C3H7Br), 1,2-dibromoethane C2H4Br2)), trapped in water ice. We have simulated the UV photochemistry of these brominated alkanes isolated in ice films kept at 16 K and for comparison in solid argon matrices. The photoproducts formed in the ice have been identified by means of FTIR spectroscopy. Reflection absorption infrared spectroscopy (RAIRS) is especially useful to study nascent ice surfaces, kinetics of adsorption/decomposition, and heterogeneous catalysis. Among the observed photoproducts we could identify carbon monoxide and carbon dioxide for each alkyl bromide studied. The photoproduct HBr is dissociated in the bulk ice. Based on the experimental observations possible reaction mechanisms will be discussed.

  6. Search for HBr and bromine photochemistry on Venus

    Science.gov (United States)

    Krasnopolsky, Vladimir A.; Belyaev, Denis A.

    2017-09-01

    HBr (1-0) R2 2605.8/6.2 cm-1, the strongest line of the strongest band of HBr, was observed when searching for this species on Venus. The observation was conducted using the NASA IRTF and a high-resolution long-slit spectrograph CSHELL with resolving power of 4 × 104. 101 spectra of Venus were analyzed, and the retrieved HBr abundances varied from -8 to + 5 ppb. Their mean value is -1.2 ppb, standard deviation is 2.5 ppb, and uncertainty of the mean is 0.25 ppb. The negative value presumes a systematic error, and the estimated upper limit of the HBr mixing ratio at the cloud tops of Venus is ∼1 ppb. From the simultaneously retrieved CO2 abundances, this corresponds to an altitude of 78 km for the uniform distribution of HBr. A simplified version of the bromine photochemistry is included into the photochemical model (Krasnopolsky 2012, Icarus 218, 230-246). Photolysis of HBr and its reactions with O and H deplete the HBr mixing ratio at 70-80 km relative to that below 60 km by a factor of ≈300. Reanalysis of the observational data with the calculated profile of HBr gives an upper limit of 20-70 ppb for HBr below 60 km and the aerosol optical depth of 0.7 at 70 km and 3.84 μm. The bromine chemistry may be effective on Venus even under the observed upper limit. However, if a Cl/Br ratio in the Venus atmosphere is similar to that in the Solar System, then HBr is ≈1 ppb in the lower atmosphere and the bromine chemistry is insignificant. Thermodynamic calculations based on the chemical kinetic model (Krasnopolsky 2013, Icarus 225, 570-580) predict HBr as a major bromine species in the lower atmosphere.

  7. A computational approach to tuning the photochemistry of platinum(IV) anticancer agents.

    Science.gov (United States)

    Tai, Hui-Chung; Zhao, Yao; Farrer, Nicola J; Anastasi, Anna E; Clarkson, Guy; Sadler, Peter J; Deeth, Robert J

    2012-08-20

    Diazido Pt(IV) complexes are inert stable prodrugs that can be photoactivated to produce Pt(II) species with promising anticancer activity. Our studies of the photochemistry of Pt(IV) complexes, [Pt(X)(2) (Y)(2) (Z)(2) ](0/-1) (X=N-ligands (NH(3) , pyridine, etc.)/S(CH(3) )(2) /H(-) , Y=(pseudo)halogen (N(3) (-) , I(-) ), Z=OR(-) , R=H, Ac) by time-dependent density functional theory (TDDFT) show close agreement with spectroscopic data. Broad exploration of cis/trans geometries, trans influences, the nature of the OR(-) and (pseudo)halogen ligands, electron-withdrawing/donating/delocalising substituents on the N-ligands, and intramolecular H bonds shows that: 1) the design of platinum(IV) complexes with intense bands shifted towards longer wavelengths (from 289 to ∼330 nm) can be achieved by introducing intramolecular H bonds involving the OH ligands and 2-hydroxyquinoline or by iodido ligands; 2) mesomeric electron-withdrawing substituents on pyridine result in low-energy absorption with significant intensity in the visible region; and 3) the distinct makeup of the molecular orbitals involved in the electronic transitions for cis/trans-{Pt(N(3) )(2) } isomers results in different photoproducts. In general, the comparison of the optimised geometries shows that Pt(IV) complexes with longer PtL bonds are more likely to undergo photoreduction with longer-wavelength light. The novel complex trans,trans,trans-[Pt(N(3) )(2) (OH)(2) (NH(3) )(4-nitropyridine)] with predicted absorption in the visible region has been synthesised. The experimental UV/Vis spectrum in aqueous solution correlates well with the intense band in the computed spectrum, whereas the overlay in the low-energy region can be improved by a solvent model. This combined computational and experimental study shows that TDDFT can be used to tune the coordination environment for optimising photoactive Pt(IV) compounds as anticancer agents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGa

  8. 2011 Photochemistry Gordon Research Conference (July10-15, 2011, Stonehill College, Easton, MA)

    Energy Technology Data Exchange (ETDEWEB)

    Prof. Gerald Meyer

    2011-07-15

    Photochemistry has wide implications on fundamental science with technological applications that range from synthetic and mechanistic organic and inorganic chemistry to sensing/manipulation in the biological sciences to viable solar energy conversion assemblies. The 2011 Gordon Research Conference on Photochemistry will highlight recent advances on photochemical reactions, their mechanisms, spectroscopic techniques and applications to materials, organic synthesis, and biology. The conference will continue its long tradition on dynamic discussions on recent advances and unsolved scientific problems. The format of lectures, poster presentations and informal discussions provides an ideal venue for students and post-doctoral fellows to interact with the leaders in the field. These junior scientists will have an opportunity to participate in the Gordon Research Seminar on Photochemistry to be held prior to the GRC. The GRS will focus on photochemical aspects of solar energy conversion. Four abstracts for posters at the GRC and presentations at the GRS will be selected as short talks at the GRC.

  9. Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

    International Nuclear Information System (INIS)

    Hu, Renyu; Seager, Sara

    2014-01-01

    Some super Earths and mini Neptunes will likely have thick atmospheres that are not H 2 -dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H 2 -dominated atmospheres and non-H 2 -dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO 2 rather than CH 4 or CO in a H 2 -depleted water-dominated thick atmosphere and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C 2 H 2 and C 2 H 4 ). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C 2 H 2 features at 1.0 and 1.5 μm in transmission and C 2 H 2 and C 2 H 4 features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.

  10. 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.

  11. 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)

  12. Cleaning without chlorinated solvents

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.M.; Simandl, R.F.

    1994-12-31

    Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92%. The program has been a twofold effort. Vapor degreasers used in batch cleaning-operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting and bonding. Cleaning ability was determined using techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes and swelling of epoxies.

  13. THE ATMOSPHERIC CHEMISTRY OF GJ 1214b: PHOTOCHEMISTRY AND CLOUDS

    International Nuclear Information System (INIS)

    Miller-Ricci Kempton, Eliza; Fortney, Jonathan J.; Zahnle, Kevin

    2012-01-01

    Recent observations of the transiting super-Earth GJ 1214b reveal that its atmosphere may be hydrogen-rich or water-rich in nature, with clouds or hazes potentially affecting its transmission spectrum in the optical and very-near-IR. Here, we further examine the possibility that GJ 1214b does indeed possess a hydrogen-dominated atmosphere, which is the hypothesis that is favored by models of the bulk composition of the planet. We study the effects of non-equilibrium chemistry (photochemistry, thermal chemistry, and mixing) on the planet's transmission spectrum. We furthermore examine the possibility that clouds could play a significant role in attenuating GJ 1214b's transmission spectrum at short wavelengths. We find that non-equilibrium chemistry can have a large effect on the overall chemical composition of GJ 1214b's atmosphere, however these changes mostly take place above the height in the atmosphere that is probed by transmission spectroscopy. The effects of non-equilibrium chemistry on GJ 1214b's transmission spectrum are therefore minimal, with the largest effects taking place if the planet's atmosphere has super-solar metallicity and a low rate of vertical mixing. Interestingly, we find that the best fit to the observations of GJ 1214b's atmosphere in transmission occurs if the planet's atmosphere is deficient in CH 4 , and possesses a cloud layer at a pressure of ∼200 mbar. This is consistent with a picture of efficient methane photolysis, accompanied by formation of organic haze that obscures the lower atmosphere of GJ 1214b at optical wavelengths. However, for methane to be absent from GJ 1214b's transmission spectrum, UV photolysis of this molecule must be efficient at pressures of greater than ∼1 mbar, whereas we find that methane only photolyzes to pressures less than 0.1 mbar, even under the most optimistic assumptions. An alternative explanation of the observations of GJ 1214b is that the atmosphere is water-rich, although this interpretation

  14. Purex process solvent: literature review

    International Nuclear Information System (INIS)

    Geier, R.G.

    1979-10-01

    This document summarizes the data on Purex process solvent presently published in a variety of sources. Extracts from these various sources are presented herein and contain the work done, the salient results obtained, and the original, unaltered conclusions of the author of each paper. Three major areas are addressed: solvent stability, solvent quality testing, and solvent treatment processes. 34 references, 44 tables

  15. Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-20

    Some super Earths and mini Neptunes will likely have thick atmospheres that are not H{sub 2}-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H{sub 2}-dominated atmospheres and non-H{sub 2}-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO{sub 2} rather than CH{sub 4} or CO in a H{sub 2}-depleted water-dominated thick atmosphere and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C{sub 2}H{sub 2} features at 1.0 and 1.5 μm in transmission and C{sub 2}H{sub 2} and C{sub 2}H{sub 4} features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.

  16. 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

  17. 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

  18. 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…

  19. 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

  20. Short review on the acetylene photochemistry in clusters: photofragment caging and reactivity

    Czech Academy of Sciences Publication Activity Database

    Fárník, Michal; Poterya, Viktoriya; Kočišek, Jaroslav; Fedor, Juraj; Slavíček, P.

    2012-01-01

    Roč. 110, 21-22 (2012), s. 2817-2828 ISSN 0026-8976 R&D Projects: GA ČR GA203/09/0422; GA ČR GAP208/11/0161 Institutional support: RVO:61388955 Keywords : acetylene clusters * photochemistry * molecular beams Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.670, year: 2012

  1. Separation by solvent extraction

    Science.gov (United States)

    Holt, Jr., Charles H.

    1976-04-06

    17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

  2. Separation by solvent extraction

    International Nuclear Information System (INIS)

    Holt, C.H. Jr.

    1976-01-01

    In a process for separating fission product values from U and Pu values contained in an aqueous solution, an oxidizing agent is added to the solution to secure U and Pu in their hexavalent state. The aqueous solution is contacted with a substantially water-immiscible organic solvent with agitation while the temperature is maintained at from -1 to -2 0 C until the major part of the water present is frozen. The solid ice phase is continuously separated as it is formed and a remaining aqueous liquid phase containing fission product values and a solvent phase containing Pu and U values are separated from each other. The last obtained part of the ice phase is melted and added to the separated liquid phase. The resulting liquid is treated with a new supply of solvent whereby it is practically depleted of U and Pu

  3. Solvent selection methodology for pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Kumar Tula, Anjan; Gani, Rafiqul

    2016-01-01

    in pharmaceutical processes as well as new solvent swap alternatives. The method takes into account process considerations such as batch distillation and crystallization to achieve the swap task. Rigorous model based simulations of the swap operation are performed to evaluate and compare the performance......A method for the selection of appropriate solvents for the solvent swap task in pharmaceutical processes has been developed. This solvent swap method is based on the solvent selection method of Gani et al. (2006) and considers additional selection criteria such as boiling point difference......, volatility difference, VLE phase diagram analysis, and azeotropic information that are particularly important for the solvent swap task. The method employs a solvent-swap database together with calculation tools for properties–functions of solvents. The database contains solvents that are commonly used...

  4. 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

  5. Organic solvent topical report

    International Nuclear Information System (INIS)

    Cowley, W.L.

    1998-01-01

    This report is the technical basis for the accident and consequence analyses used in the Hanford Tank Farms Basis for Interim Operation. The report also contains the scientific and engineering information and reference material needed to understand the organic solvent safety issue. This report includes comments received from the Chemical Reactions Subcommittee of the Tank Advisory Panel

  6. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-05-13

    This report provides the basis for closing the organic solvent safety issue. Sufficient information is presented to conclude that risk posed by an organic solvent fire is within risk evaluation guidelines. This report updates information contained in Analysis of Consequences of Postulated Solvent Fires in Hanford Site Waste Tanks. WHC-SD-WM-CN-032. Rev. 0A (Cowley et al. 1996). However, this document will not replace Cowley et al (1996) as the primary reference for the Basis for Interim Operation (BIO) until the recently submitted BIO amendment (Hanson 1999) is approved by the US Department of Energy. This conclusion depends on the use of controls for preventing vehicle fuel fires and for limiting the use of flame cutting in areas where hot metal can fall on the waste surface.The required controls are given in the Tank Waste Remediation System Technical Safety Requirements (Noorani 1997b). This is a significant change from the conclusions presented in Revision 0 of this report. Revision 0 of this calcnote concluded that some organic solvent fire scenarios exceeded risk evaluation guidelines, even with controls imposed.

  7. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    Cowley, W.L.

    1998-04-30

    This report is the technical basis for the accident and consequence analyses used in the Hanford Tank Farms Basis for Interim Operation. The report also contains the scientific and engineering information and reference material needed to understand the organic solvent safety issue. This report includes comments received from the Chemical Reactions Subcommittee of the Tank Advisory Panel.

  8. Solvent sorting in (mixed solvent electrolyte) systems: Time-resolved ...

    Indian Academy of Sciences (India)

    Solvent sorting in (mixed solvent electrolyte) systems: Time-resolved ... Mixed solvent systems; electrolyte solutions; dynamic fluorescence measurements; theory. 1. ..... Open and filled triangles represent τs for the other binary mixture in the absence and presence of 1.0 M LiClO4, respectively. exponentially with the mole ...

  9. Independent Directors

    DEFF Research Database (Denmark)

    Ringe, Wolf-Georg

    2013-01-01

    about board independence in Western jurisdictions, a surprising disharmony prevails about the justification, extent and purpose of independence requirements. These considerations lead me to question the benefits of the current system. Instead, this paper proposes a new, ‘functional’ concept of board...

  10. American = Independent?

    Science.gov (United States)

    Markus, Hazel Rose

    2017-09-01

    U.S. American cultures and psyches reflect and promote independence. Devos and Banaji (2005) asked, does American equal White? This article asks, does American equal independent? The answer is that when compared to people in East Asian or South Asian contexts, people in American contexts tend to show an independent psychological signature-a sense of self as individual, separate, influencing others and the world, free from influence, and equal to, if not better than, others (Markus & Conner, 2013). Independence is a reasonable description of the selves of people in the White, middle-class American mainstream. Yet it is a less good characterization of the selves of the majority of Americans who are working-class and/or people of color. A cultural psychological approach reveals that much of North American psychology is still grounded in an independent model of the self and, as such, neglects social contexts and the psychologies of a majority of Americans. Given the prominence of independence in American ideas and institutions, the interdependent tendencies that arise from intersections of national culture with social class, race, and ethnicity go unrecognized and are often misunderstood and stigmatized. This unseen clash of independence and interdependence is a significant factor in many challenges, including those of education, employment, health, immigration, criminal justice, and political polarization.

  11. Solvent extraction columns

    International Nuclear Information System (INIS)

    Middleton, P.; Smith, J.R.

    1979-01-01

    In pulsed columns for use in solvent extraction processes, e.g. the reprocessing of nuclear fuel, the horizontal perforated plates inside the column are separated by interplate spacers manufactured from metallic neutron absorbing material. The spacer may be in the form of a spiral or concentric circles separated by radial limbs, or may be of egg-box construction. Suitable neutron absorbing materials include stainless steel containing boron or gadolinium, hafnium metal or alloys of hafnium. (UK)

  12. Hazardous solvent substitution

    International Nuclear Information System (INIS)

    Twitchell, K.E.

    1995-01-01

    Eliminating hazardous solvents is good for the environment, worker safety, and the bottom line. However, even though we are motivated to find replacements, the big question is 'What can we use as replacements for hazardous solvents?'You, too, can find replacements for your hazardous solvents. All you have to do is search for them. Search through the vendor literature of hundreds of companies with thousands of products. Ponder the associated material safety data sheets, assuming of course that you can obtain them and, having obtained them, that you can read them. You will want to search the trade magazines and other sources for product reviews. You will want to talk to users about how well the product actually works. You may also want to check US Environmental Protection Agency (EPA) and other government reports for toxicity and other safety information. And, of course, you will want to compare the product's constituent chemicals with the many hazardous constituency lists to ensure the safe and legal use of the product in your workplace

  13. Photochemistry and Cytotoxicity Evaluation of Heptamethinecyanine Near Infrared (NIR) Dyes

    Science.gov (United States)

    Conceição, David S.; Ferreira, Diana P.; Vieira Ferreira, Luís F.

    2013-01-01

    The present study investigates the photochemical properties of potential photosensitizers for photodynamic therapy, namely four commercial heptamethinecyanine dyes (IR125, IR780, IR813, IR820). Spectroscopic studies were made by means of laser induced fluorescence and laser flash photolysis in order to obtain fluorescence quantum yields and transient absorption spectra. Fluorescence lifetimes were also determined. The differences encountered were essentially related with the interaction of the sulfonate groups with the solvent, and also regarding the rigidification of the central bridge connecting the two nitrogen-containing heterocyclic groups. Transient absorption studies were performed both in aerated and oxygen free samples, to conclude about the formation of photoisomers and triplet state. For the four dyes under study, a cytotoxic evaluation in the dark and after irradiation was performed using HeLa cells as the model cell line, which revealed significant changes after irradiation mainly in IR125 and IR813 dyes. Confocal microscopy analysis showed that these dyes tend to enter to the intracellular space. PMID:24022690

  14. Proceedings of the Eighteenth DOE Solar Photochemistry Research Conference

    Energy Technology Data Exchange (ETDEWEB)

    1994-07-01

    This annual conference brings together grantees and contractorsof the DOE Division of Chemical Sciences engaged in fundamental research on solar photochemical energy conversion. It provides a focus for a wide spectrum of activities which contribute to providing the knowledge base and concepts needed for the capture and chemical conversion of solar energy. The research will provide the foundations for solar technologies of the future, in which light-induced charge separation processes will be applied to conversion of light energy to chemical energy, e.g., production of alcohols from CO{sub 2}, H{sup 2} from water, NH{sub 3} from atm. N{sub 2}, etc. The plenary lecture addresses photoconversion by nanocrystalline films of oxide semiconductors. The topical sessions feature presentations on charge transfer at semiconductor-liquid electrolyte junctions, long-range vectorial electron transfer in macromolecular arrays, transition metal photophysics, electronic structure and solvent effects on electron transfer processes, artifical assemblies for photosynthesis, and the photosynthetic bacterial reaction center. This volume contains the agenda for the meeting and abstracts of the 30 formal presentations and 56 posters.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Photochemistry of hydrogen bonded heterocycles probed by photodissociation experiments and ab initio methods

    Czech Academy of Sciences Publication Activity Database

    Slavíček, Petr; Fárník, Michal

    2011-01-01

    Roč. 13, č. 26 (2011), s. 12123-12137 ISSN 1463-9076 R&D Projects: GA ČR GA203/09/0422; GA ČR GAP208/11/0161 Institutional research plan: CEZ:AV0Z40400503 Keywords : photochemistry * hydrogen bonded heterocycles * ab initio methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

  1. 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.)

  2. Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

    Science.gov (United States)

    Yeung, Laurence Y.; Murray, Lee T.; Ash, Jeanine L.; Young, Edward D.; Boering, Kristie A.; Atlas, Elliot L.; Schauffler, Sue M.; Lueb, Richard A.; Langenfelds, Ray L.; Krummel, Paul B.; hide

    2016-01-01

    The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as delta36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher delta36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower delta36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-delta36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where delta36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in delta36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a +/-10 percent range since 1978.

  3. 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

  4. Solvent effects in chemistry

    CERN Document Server

    Buncel, Erwin

    2015-01-01

    This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds.  It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as ""green"" chemistry, where ut

  5. 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

  6. Evaluation of some water-miscible organic solvents for spray-drying enzymes and carbohydrates.

    Science.gov (United States)

    Sass, Anke; Lee, Geoffrey

    2014-06-01

    The spray-drying behaviour of 16 water-miscible organic solvents on a bench-scale machine (Büchi B290 with inert loop) was determined under mild-to-moderate process conditions, namely inlet gas temperature of 130 °C and liquid feed flow rate of ≤3 mL/min. The solvents with boiling points below the inlet gas temperature could be fully dried (Group 1 solvents). The two exceptions were DMSO and DMF which despite their higher boiling points could be fully dried. The remaining solvents with boiling points above the inlet gas temperature were not fully dried during passage through the spray-dryer (Group 2 solvents). Trypsin and lysozyme when spray-dried from Group 1 solvent binary mixtures with water showed similar inactivation and residual water content, independent of solvent. The level of residual solvent was, however, strongly dependent on solvent. Trehalose (20%) and mannitol (10%) could be spray-dried from DMSO/water binary mixtures, but the amorphous disaccharide required higher inlet gas temperature. Trehalose/trypsin and mannitol/trypsin formulations showed differing degrees of protection against enzyme inactivation when spray-dried from Group 1 solvent binary mixtures with water. In all solvents the mannitol protected as well, if not better, than the trehalose. This study identifies some suitable organic solvents for spray-drying protein formulations, but also shows the difficulties of remaining organic solvent under the moderate inlet gas temperature used.

  7. Calibration and Propagation of Uncertainty for Independence

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Troy Michael [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Kress, Joel David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Bhat, Kabekode Ghanasham [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-06-30

    This document reports on progress and methods for the calibration and uncertainty quantification of the Independence model developed at UT Austin. The Independence model is an advanced thermodynamic and process model framework for piperazine solutions as a high-performance CO2 capture solvent. Progress is presented in the framework of the CCSI standard basic data model inference framework. Recent work has largely focused on the thermodynamic submodels of Independence.

  8. Solvents level dipole moments.

    Science.gov (United States)

    Liang, Wenkel; Li, Xiaosong; Dalton, Larry R; Robinson, Bruce H; Eichinger, Bruce E

    2011-11-03

    The dipole moments of highly polar molecules measured in solution are usually smaller than the molecular dipole moments that are calculated with reaction field methods, whereas vacuum values are routinely calculated in good agreement with available vapor phase data. Whether from Onsager's theory (or variations thereof) or from quantum mechanical methods, the calculated molecular dipoles in solution are found to be larger than those measured. The reason, of course, is that experiments measure the net dipole moment of solute together with the polarized (perturbed) solvent "cloud" surrounding it. Here we show that the reaction field charges that are generated in the quantum mechanical self-consistent reaction field (SCRF) method give a good estimate of the net dipole moment of the solute molecule together with the moment arising from the reaction field charges. This net dipole is a better description of experimental data than the vacuum dipole moment and certainly better than the bare dipole moment of the polarized solute molecule.

  9. Dispersion of nanoparticles: from organic solvents to polymer solutions.

    Science.gov (United States)

    Nguyen, Van Son; Rouxel, Didier; Vincent, Brice

    2014-01-01

    This work is devoted to a systematic study of nanoparticle dispersion by ultrasonication in different solutions: from organic solvents to polymer solutions. The cluster size of nanoparticles at different concentrations in both organic solvents and polymer solutions were directly characterized by Dynamic Light Scattering to study the effect of solid concentration, surfactant and polymer on the dispersion. It reveals that in stabilized suspensions, the smallest attainable size or aggregate size of nanoparticles is independent of solvent type and solid content over the tested range. Furthermore, nanoparticles in simple solvent and in polymer solutions had the similar evolution of cluster size and almost the same final size, which could be very helpful to optimize the dispersion of nanofillers in polymer solutions and nanocomposites. It is also shown that, with appropriate sonication amplitudes, the dispersion procedure developed for very dilute suspensions could be transferred to higher concentration suspensions or even to polymer suspensions. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. 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.

  11. 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.

  12. 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.

  13. Solvent extraction of Zn and metals in Zn ores by nonphosphorous solvents

    International Nuclear Information System (INIS)

    Auchapt, J.M.; Tostain, Jacqueline.

    1975-07-01

    This bibliography follows a first work on Zn solvent extraction by organo-phosphorous compounds. The other solvents used in Zn extraction, are studied: oxygenated nonphosphorous solvents (ketones, alcohols, carboxylic acids, sulfonates), nitrogenous solvents and hydrocarbons [fr

  14. Small angle neutron scattering study of temperature-independent ...

    Indian Academy of Sciences (India)

    independent and consists of about 25% of ionic surfactants in the mixed system. Contrast variation SANS measurements by contrast matching one of the surfactant components to the solvent suggest homogeneous single mixed micelles of the two ...

  15. Small angle neutron scattering study of temperature-independent ...

    Indian Academy of Sciences (India)

    independent and consists of about 25% of ionic surfactants in the mixed system. Contrast variation SANS measurements by contrast matching one of the surfactant components to the solvent suggest homogeneous single mixed micelles of.

  16. Tyrosinase inactivation in organic solvents.

    Science.gov (United States)

    Warrington, J C; Saville, B A

    1999-11-05

    The inactivation of the catecholase activity of mushroom tyrosinase was investigated under nonaqueous conditions. The enzyme was immobilized on glass beads, and assays were conducted in chloroform, toluene, amyl acetate, isopropyl ether, and butanol. The reaction components were pre-equilibrated for 2 weeks with a saturated salt solution at a water activity of 0.90. The initial reaction velocity varied between 1.3 x 10(3) mol product/((mol enzyme)(min)) in toluene and 8.7 x 10(3) mol product/((mol enzyme)(min)) in amyl acetate. The turnover number varied between 8.1 x 10(3) mol product/mol enzyme in toluene and 7.2 x 10(4) mol product/mol enzyme in amyl acetate. In each solvent, the tyrosinase reaction inactivation parameters were represented by a probabilistic model. Changes in the probability of inactivation were followed throughout the course of the reaction using a second model which relates the reaction velocity to the amount of product formed. These models reveal that the inactivation rate of tyrosinase decreases as the reaction progresses, and that the inactivation kinetics are independent of the quinone concentration in toluene, chloroform, butanol, and amyl acetate. Significant effects of quinone concentration were, however, observed in isopropyl ether. The likelihood of inactivation of the enzyme was found to be greatest toward the beginning of the reaction. In the latter phase of the reaction, inactivation probability was less and tended to remain constant until the completion of the reaction. Copyright 1999 John Wiley & Sons, Inc.

  17. EUV photochemical production of unsaturated hydrocarbons: implications to EUV photochemistry in Titan and Jovian planets.

    Science.gov (United States)

    Imanaka, Hiroshi; Smith, Mark A

    2009-10-22

    The EUV photochemistry of methane is one of the dominant chemical processes in the upper atmospheres of Titan and Jovian planets. The dilution of CH(4) with N(2) significantly changes the subsequent hydrocarbon chemistry initiated by EUV photoionization. At wavelengths below 80 nm, the presence of the dominant N(2) species in a N(2)/CH(4) gas mixture (=95/5) selectively enhances the formation of unsaturated hydrocarbons, such as benzene and toluene, while pure CH(4) gas leads to a wide mixture of saturated/unsaturated hydrocarbon species. This enhanced formation of unsaturated hydrocarbons is most likely initiated by the generation of CH(3)(+) via a dissociative charge-transfer reaction between N(2)(+) and CH(4). This mechanism was further confirmed with the dilution of CH(4) with Ar, which shows similarly enhanced formation of unsaturated species from an Ar/CH(4) (=95/5) gas mixture. In contrast, the depleted generation of unsaturated species from a H(2)/CH(4) gas mixture (=95/5) suggests that the CH(5)(+) ion generated via a proton-transfer reaction is not an important precursor in the production of complex unsaturated hydrocarbons. Therefore, it is the dissociative charge-transfer reaction of CH(4) that initiates the formation of unsaturated complex hydrocarbons through production of C(2)H(5)(+) with subsequent dissociative recombination. Implications regarding photochemistry in the upper atmospheres of Titan and the Jovian planets are discussed.

  18. 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.

  19. 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.

  20. Chemistry and Photochemistry at the Surface of Urban Road Dust and Photoactive Minerals

    Science.gov (United States)

    Styler, S. A.; Abou-Ghanem, M.; Wickware, B.

    2017-12-01

    Each year, over a billion tons of dust are released into the atmosphere from arid regions. After its emission, dust can undergo efficient long-range transport to urban centres, where it can interact with local pollution sources. Another source of dust in urban regions is road dust resuspension, which is the largest anthropogenic source of primary particulate matter in both Canada and the United States. Since dust contains light-absorbing components, including iron- and titanium-containing minerals, dust-catalyzed photochemical processes have the potential to influence both the lifetime of pollutants present at the dust surface and the composition of the surrounding atmosphere. To date, most studies of dust photochemistry have focused on TiO2-mediated processes, and no studies have explored trace gas uptake at the surface of road dust. Here, we present first results from aerosol and coated-wall flow tube investigations of ozone uptake at the surface of a suite of titanium-containing minerals and road dust collected in Edmonton, Alberta. Together, this work represents a significant advance in our understanding of chemistry and photochemistry at realistic environmental interfaces.

  1. UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Asher, Sanford A

    2017-10-19

    Ultraviolet resonance Raman spectroscopy (UVRR) is being developed for standoff trace explosives detection. To accomplish this, it is important to develop a deep understanding of the accompanying UV excited photochemistry of explosives, as well as the impact of reactions on the resulting photoproducts. In the work here we used 229 nm excited UVRR spectroscopy to monitor the photochemistry of pentaerythritol tetranitrate (PETN) in acetonitrile. We find that solutions of PETN in CD 3 CN photodegrade with a quantum yield of 0.08 ± 0.02, as measured by high performance liquid chromatography (HPLC). The initial step in the 229 nm UV photolysis of PETN in CD 3 CN is cleavage of an O-NO 2 bond to form NO 2 . The accompanying photoproduct is pentaerythritol trinitrate (PETriN), (CH 2 ONO 2 ) 3 CCH 2 OH formed by photolysis of a single O-NO 2 . The resulting UVRR spectra show a dominant photoproduct band at ∼1308 cm -1 , which derives from the symmetric stretch of dissolved NO 2 . This photoproduct NO 2 is hydrolyzed by trace amounts of water, which downshifts this 1308 cm -1 NO 2 Raman band due to the formation of molecular HNO 3 . The dissociation of HNO 3 to NO 3 - in the presence of additional water results in an intense NO 3 - symmetric stretching UVRR band at 1044 cm -1 .

  2. 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.

  3. Acetone-based cellulose solvent.

    Science.gov (United States)

    Kostag, Marc; Liebert, Tim; Heinze, Thomas

    2014-08-01

    Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Handbook of organic solvent properties

    CERN Document Server

    Smallwood, Ian

    2012-01-01

    The properties of 72 of the most commonly used solvents are given, tabulated in the most convenient way, making this book a joy for industrial chemists to use as a desk reference. The properties covered are those which answer the basic questions of: Will it do the job? Will it harm the user? Will it pollute the air? Is it easy to handle? Will it pollute the water? Can it be recovered or incinerated? These are all factors that need to be considered at the early stages of choosing a solvent for a new product or process.A collection of the physical properties of most commonly used solvents, their

  5. Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shenggao, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Mathematical Center for Interdiscipline Research, Soochow University, 1 Shizi Street, Jiangsu, Suzhou 215006 (China); Sun, Hui; Cheng, Li-Tien [Department of Mathematics, University of California, San Diego, La Jolla, California 92093-0112 (United States); Dzubiella, Joachim [Soft Matter and Functional Materials, Helmholtz-Zentrum Berlin, 14109 Berlin, Germany and Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin (Germany); Li, Bo, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Quantitative Biology Graduate Program, University of California, San Diego, La Jolla, California 92093-0112 (United States); McCammon, J. Andrew [Department of Chemistry and Biochemistry, Department of Pharmacology, Howard Hughes Medical Institute, University of California, San Diego, La Jolla, California 92093-0365 (United States)

    2016-08-07

    Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the

  6. The femtosecond-to-second photochemistry of red-shifted fast-closing anion channelrhodopsin PsACR1

    NARCIS (Netherlands)

    Hontani, Yusaku; Broser, Matthias; Silapetere, Arita; Krause, Benjamin S.; Hegemann, Peter; Kennis, John T. M.

    2017-01-01

    Anion channelrhodopsins (ACRs) are of great interest due to their ability to inhibit electrical signaling in optogenetic experiments. The photochemistry of ACRs is currently poorly understood and an improved understanding would be beneficial for rational design of ACRs with modified properties.

  7. 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

  8. 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

  9. The Solvent Selection framework: solvents for organic synthesis, separation processes and ionic-organic synthesis

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sansonetti, Sascha; Abildskov, Jens

    2012-01-01

    This paper presents a systematic integrated framework for solvent selection and solvent design. The framework is divided into several modules, which can tackle specific problems in various solvent-based applications. In particular, three modules corresponding to the following solvent selection...... problems are presented: 1) solvent selection and design for organic synthesis, 2) solvent screening and design of solvent mixtures for pharmaceutical applications and 3) ionic liquids selection and design as solvents. The application of the framework is highlighted successfully through case studies...... focusing on solvent replacement problem in organic synthesis and solvent mixture design for ibuprofen respectively....

  10. Laser Photochemistry.

    Science.gov (United States)

    1981-07-01

    HAB + HAA + HABA + HA, (18) where HA and HB are the unperturbed Hamiltonians of the active (A) mode and the bath (B) modes, respectively and HAB is...equations of motion for the average excitation of the active mode in which the many-body effects of the phonon bath modes (HAB and HABA ) and the active...relaxation rates induced by the many-body effects of the Hamiltonians HAA, HAB and HABA ; n is a Bose-Einstein function for the bath modes; and 2c <n> is the

  11. Bactericidal efficiency and mode of action: a comparative study of photochemistry and photocatalysis.

    Science.gov (United States)

    Pigeot-Rémy, S; Simonet, F; Atlan, D; Lazzaroni, J C; Guillard, C

    2012-06-15

    In order to compare the disinfection potential of photocatalysis and photochemistry, the effects of these two processes on bacteria in water were investigated under exposure to UV-A and UV-C. The well-known bacterial model Escherichia coli (E. coli) was used as the experimental organism. Radiation exposure was produced with an HPK 125 W lamp and the standard TiO(2) Degussa P-25 was used as the photocatalyst. Firstly, the impact of photocatalysis and photochemistry on the cultivability of bacterial cells was investigated. UV-A radiation resulted in low deleterious effects on bacterial cultivability but generated colonies of size smaller than average. UV-C photocatalysis demonstrated a greater efficiency than UV-A photocatalysis in altering bacterial cultivability. From a cultivability point of view only, UV-C radiation appeared to be the most deleterious treatment. A rapid epifluorescence staining method using the LIVE/DEAD Bacterial Viability Kit was then used to assess the modifications in bacterial membrane permeability. UV-A radiation did not induce any alterations in bacterial permeability for 420 min of exposure whereas only a few minutes of exposure to UV-C radiation, with the same total radiance intensity, induced total loss of permeability. Moreover, after 20 and 60 min of exposure to UV-C and UV-A photocatalysis respectively, all bacteria lost their membrane integrity, suggesting that the bacterial envelope is the primary target of reactive oxygen species (ROS) generated at the surface of TiO(2) photocatalyst. These results were further confirmed by the formation of malondialdehyde (MDA) during the photocatalytic inactivation of bacterial cells and suggest that destruction of the cell envelope is a key step in the bactericidal action of photocatalysis. The oxidation of bacterial membrane lipids was also correlated with the monitoring of carboxylic acids, which can be considered as representatives of lipid peroxidation by-products. Finally, damages to

  12. Solvent/Non-Solvent Sintering To Make Microsphere Scaffolds

    Science.gov (United States)

    Laurencin, Cato T.; Brown, Justin L.; Nair, Lakshmi

    2011-01-01

    A solvent/non-solvent sintering technique has been devised for joining polymeric microspheres to make porous matrices for use as drug-delivery devices or scaffolds that could be seeded with cells for growing tissues. Unlike traditional sintering at elevated temperature and pressure, this technique is practiced at room temperature and pressure and, therefore, does not cause thermal degradation of any drug, protein, or other biochemical with which the microspheres might be loaded to impart properties desired in a specific application. Also, properties of scaffolds made by this technique are more reproducible than are properties of comparable scaffolds made by traditional sintering. The technique involves the use of two miscible organic liquids: one that is and one that is not a solvent for the affected polymer. The polymeric microspheres are placed in a mold having the size and shape of the desired scaffold, then the solvent/non-solvent mixture is poured into the mold to fill the void volume between the microspheres, then the liquid mixture is allowed to evaporate. Some of the properties of the resulting scaffold can be tailored through choice of the proportions of the liquids and the diameter of the microspheres.

  13. The Ultraviolet Photochemistry and Photobiology of Vegetative Cells and Spores of Bacillus megaterium

    Science.gov (United States)

    Donnellan, J. E.; Stafford, R. S.

    1968-01-01

    The ultraviolet (UV) photochemistry and photobiology of spores and vegetative cells of Bacillus megaterium have been studied. The response of vegetative cells of B. megaterium appears qualitatively similar to those of Escherichia coli, Micrococcus radiodurans, and Bacillus subtilis with respect to photoproduct formation and repair mechanisms. UV irradiation, however, does not produce cyclobutane-type thymine dimers in the DNA of spores, although other thymine photo-products are produced. The photoproducts do not disappear after photoreactivation, but they are eliminated from the DNA by a dark-repair mechanism different from that found for dimers in vegetative cells. Irradiations performed at three wavelengths produce the same amounts of spore photoproduct and give the same survival curves. Variation of the sporulation medium before irradiation results in comparable alterations in the rate of spore photoproduct production and in survival. PMID:4966691

  14. A model for the origin of photosynthesis--III. The ultraviolet photochemistry of uroporphyrinogen

    Science.gov (United States)

    Mercer-Smith, J. A.; Raudino, A.; Mauzerall, D. C.

    1985-01-01

    The photochemical ramifications of the high ultraviolet flux on the primordial earth prior to the formation of the ozone layer have been considered in a study of the ultraviolet photochemistry of uroporphyrinogen (urohexahydroporphyrin), a colorless compound which absorbs strongly at wavelengths less than 220 nanometers. Urohexahydroporphyrin was investigated since it is the first macrocycle formed on the biosynthetic pathway of chlorophyll and can be used to test the hypothesis that the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis. When urohexahydroporphyrin is illuminated in aqueous anaerobic solution, hydrogen gas is produced. More hydrogen gas is produced in the presence of a colloidal platinum catalyst. The products of the photooxidation of urohexahydroporphyrin are urotetrahydroporphyrin (uroporphomethene) and uroporphyrin. This research shows how the oxidation of uroporphyrinogen to uroporphyrin, the first biogenetic porphyrin, could have occurred anaerobically and abiotically on the primordial earth.

  15. Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

    2014-01-01

    We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. Surface photochemistry: alloxazine within nanochannels of Na+ and H + ZSM-5 zeolites.

    Science.gov (United States)

    Ferreira, L F Vieira; Costa, A I; Machado, I Ferreira; do Rego, A M Botelho; Sikorska, E; Sikorskie, M

    2009-07-21

    This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na+ and H+ ZSM-5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine fluorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e. whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig-zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed fluorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest.

  3. Photochemistry of nucleic acid bases and their thio- and aza-analogues in solution.

    Science.gov (United States)

    Pollum, Marvin; Martínez-Fernández, Lara; Crespo-Hernández, Carlos E

    2015-01-01

    The steady-state and time-resolved photochemistry of the natural nucleic acid bases and their sulfur- and nitrogen-substituted analogues in solution is reviewed. Emphasis is given to the experimental studies performed over the last 3-5 years that showcase topical areas of scientific inquiry and those that require further scrutiny. Significant progress has been made toward mapping the radiative and nonradiative decay pathways of nucleic acid bases. There is a consensus that ultrafast internal conversion to the ground state is the primary relaxation pathway in the nucleic acid bases, whereas the mechanism of this relaxation and the level of participation of the (1)πσ*, (1) nπ*, and (3)ππ* states are still matters of debate. Although impressive research has been performed in recent years, the microscopic mechanism(s) by which the nucleic acid bases dissipate excess vibrational energy to their environment, and the role of the N-glycosidic group in this and in other nonradiative decay pathways, are still poorly understood. The simple replacement of a single atom in a nucleobase with a sulfur or nitrogen atom severely restricts access to the conical intersections responsible for the intrinsic internal conversion pathways to the ground state in the nucleic acid bases. It also enhances access to ultrafast and efficient inter-system crossing pathways that populate the triplet manifold in yields close to unity. Determining the coupled nuclear and electronic pathways responsible for the significantly different photochemistry in these nucleic acid base analogues serves as a convenient platform to examine the current state of knowledge regarding the photodynamic properties of the DNA and RNA bases from both experimental and computational perspectives. Further investigations should also aid in forecasting the prospective use of sulfur- and nitrogen-substituted base analogues in photochemotherapeutic applications.

  4. Estimation of diffusion coefficients in bitumen solvent mixtures as derived from low field NMR spectra

    International Nuclear Information System (INIS)

    Wen, Y.; Bryan, J.; Kantzas, A.

    2005-01-01

    Use of solvents for the extraction of heavy oil and bitumen appears to be an increasingly feasible technology. Both vapour extraction and direct solvent injection are considered for conventional exploration and production schemes, while solvent dilution of bitumen is a standard technique in oil sands mining. Mass transfer between solvent and bitumen is a poorly understood process. In some cases, it is totally ignored compared to viscous force effects. In other cases, phenomenological estimations of diffusion and dispersion coefficients are used. Low field NMR has been used successfully in determining both solvent content and viscosity reduction in heavy oil and bitumen mixtures with various solvents. As a solvent comes into contact with a heavy oil or bitumen sample, the mobility of hydrogen bearing molecules of both solvent and oil changes. These changes are detectable through changes in the NMR relaxation characteristics of both solvent and oil. Relaxation changes can then be correlated to mass flux and concentration changes. Based on Fick's Second Law, a diffusion coefficient, which is independent of concentration, was calculated against three oils and six solvents. (author)

  5. Solvents interactions with thermochromic print

    Directory of Open Access Journals (Sweden)

    Mirela Rožić

    2017-12-01

    Full Text Available In this study, the interactions between different solvents (benzene, acetone, cyclohexanone, various alcohols and water and thermochromic printing ink were investigated. Thermochromic printing ink was printed on metal surface. Components of thermochromic printing inks are polymeric microcapsules and classic yellow offset printing ink. Below its activation temperature, dye and developer within the microcapsules form a blue coloured complex. Therefore, thermochromic print is green. By heating above the activation temperature, blue colour of the complex turns into the leuco dye colourless state and the green colour of the prints turns into the yellow colour of the classic offset pigment. The results of the interaction with various solvents show that the thermochromic print is stable in all tested solvents except in ethanol, acetone and cyclohexanone. In ethanol, the green colour of the print becomes yellow. SEM analysis shows that microcapsules are dissolved. In acetone and cyclohexanone, the green colour of the print turns into blue, and the microcapsules become significantly more visible. Thus, the yellow pigment interacts with examined ketones. Based on the obtained interactions it can be concluded that the microcapsules have more polar nature than the classical pigment particles. Solvent-thermocromic print interactions were analysed using Hansen solubility parameters that rank the solvents based on their estimated interaction capabilities.

  6. Multiple sclerosis and organic solvents

    DEFF Research Database (Denmark)

    Mortensen, J T; Brønnum-Hansen, Henrik; Rasmussen, K

    1998-01-01

    We investigated a possible causal relation between exposure to organic solvents in Danish workers (housepainters, typographers/printers, carpenters/cabinetmakers) and onset of multiple sclerosis. Data on men included in the Danish Multiple Sclerosis Register (3,241 men) were linked with data from......, and butchers. Over a follow-up period of 20 years, we observed no increase in the incidence of multiple sclerosis among men presumed to be exposed to organic solvents. It was not possible to obtain data on potential confounders, and the study design has some potential for selection bias. Nevertheless......, the study does not support existing hypotheses regarding an association between occupational exposure to organic solvents and multiple sclerosis....

  7. Solvent sorting in (mixed solvent electrolyte) systems: Time-resolved ...

    Indian Academy of Sciences (India)

    eral studies7–19 that investigated the solvation and rota- tional dynamics either in electrolyte solutions in a sin- gle polar solvent or in binary mixtures in the absence of any electrolyte, similar studies for electrolyte solutions. £For correspondence ..... vent rotation being much faster than the ion translation provides some ...

  8. Risk assessment for halogenated solvents

    International Nuclear Information System (INIS)

    Travis, C.C.

    1988-01-01

    A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

  9. Improved Purex solvent scrubbing methods

    International Nuclear Information System (INIS)

    Mailen, J.C.; Tallent, O.K.

    1984-01-01

    Studies of hydrazine and hydroxylamine salts as solvent scrubbing agents that can be decomposed into gases are summarized. Results from testing of countercurrent scrubbers and solid sorber columns that produce lesser amounts of permanent salts are reported. The status of studies of the acid-degradation of paraffin diluent and the options for removal of long-chain organic acids is given

  10. Multiple sclerosis and organic solvents

    DEFF Research Database (Denmark)

    Mortensen, J T; Brønnum-Hansen, Henrik; Rasmussen, K

    1998-01-01

    We investigated a possible causal relation between exposure to organic solvents in Danish workers (housepainters, typographers/printers, carpenters/cabinetmakers) and onset of multiple sclerosis. Data on men included in the Danish Multiple Sclerosis Register (3,241 men) were linked with data from...

  11. Replacement solvents for use in chemical synthesis

    Science.gov (United States)

    Molnar, Linda K.; Hatton, T. Alan; Buchwald, Stephen L.

    2001-05-15

    Replacement solvents for use in chemical synthesis include polymer-immobilized solvents having a flexible polymer backbone and a plurality of pendant groups attached onto the polymer backbone, the pendant groups comprising a flexible linking unit bound to the polymer backbone and to a terminal solvating moiety. The polymer-immobilized solvent may be dissolved in a benign medium. Replacement solvents for chemical reactions for which tetrahydrofuran or diethyl may be a solvent include substituted tetrahydrofurfuryl ethers and substituted tetrahydro-3-furan ethers. The replacement solvents may be readily recovered from the reaction train using conventional methods.

  12. UV photoprocessing of CO2 ice: a complete quantification of photochemistry and photon-induced desorption processes*

    OpenAIRE

    Martín-Doménech, Rafael; Manzano-Santamaría, J.; Muñoz-Caro, Guillermo M.; Cruz-Díaz, Gustavo A.; Chen, Y.-J.; Herrero, Víctor J.; Tanarro, Isabel

    2015-01-01

    Context. Ice mantles that formed on top of dust grains are photoprocessed by the secondary ultraviolet (UV) field in cold and dense molecular clouds. UV photons induce photochemistry and desorption of ice molecules. Experimental simulations dedicated to ice analogs under astrophysically relevant conditions are needed to understand these processes. Aims. We present UV-irradiation experiments of a pure CO2 ice analog. Calibration of the quadrupole mass spectrometer allowed us to quantify the ph...

  13. 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

  14. Green and Sustainable Solvents in Chemical Processes.

    Science.gov (United States)

    Clarke, Coby J; Tu, Wei-Chien; Levers, Oliver; Bröhl, Andreas; Hallett, Jason P

    2018-01-24

    Sustainable solvents are a topic of growing interest in both the research community and the chemical industry due to a growing awareness of the impact of solvents on pollution, energy usage, and contributions to air quality and climate change. Solvent losses represent a major portion of organic pollution, and solvent removal represents a large proportion of process energy consumption. To counter these issues, a range of greener or more sustainable solvents have been proposed and developed over the past three decades. Much of the focus has been on the environmental credentials of the solvent itself, although how a substance is deployed is as important to sustainability as what it is made from. In this Review, we consider several aspects of the most prominent sustainable organic solvents in use today, ionic liquids, deep eutectic solvents, supercritical fluids, switchable solvents, liquid polymers, and renewable solvents. We examine not only the performance of each class of solvent within the context of the reactions or extractions for which it is employed, but also give consideration to the wider context of the process and system within which the solvent is deployed. A wide range of technical, economic, and environmental factors are considered, giving a more complete picture of the current status of sustainable solvent research and development.

  15. Modeling of a severe dust event and its impacts on ozone photochemistry over the downstream Nanjing megacity of eastern China

    Science.gov (United States)

    Li, Mengmeng; Wang, Tijian; Han, Yong; Xie, Min; Li, Shu; Zhuang, Bingliang; Chen, Pulong

    2017-07-01

    Dust aerosols could affect tropospheric photochemistry by interacting with solar radiation or providing reactive surfaces for heterogeneous reactions. This study examines the effects of a typical springtime dust storm (16-18 March, 2014) on ozone photochemistry over the downstream Nanjing megacity in eastern China. The on-line coupled Weather Research and Forecasting-Chemistry (WRF-Chem) model is used, with the inclusion of eight heterogeneous reactions on dust surfaces. Comparisons with satellite data and visibility record indicate that the model is capable of reproducing the onset time and downstream transport of this dust event. Dust particles act as a sink for all these trace gases examined here. The net decreases of O3, NO2, NO3, N2O5, HNO3, rad OH, HO2rad and H2O2 in the atmosphere are estimated as -6.1%, -16.0%, -37.4%, -13.9%, -47.7%, -6.0%, -9.2% and -29.7%, of which more than 80% can be explained by heterogeneous chemistry on dust surfaces. The decreases in ground photolysis rate and rad OH concentration, along with changes in other weather variables induced by dust aerosols (i.e., radiation and temperature) lead to lower photochemical activity and a small decrease of O3 mixing ratio by roughly 0.5%. This study highlights the importance of dust interaction with ozone photochemistry, and also sets the stage for further investigation of the complicated dust impacts on tropospheric aerosol chemistry.

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

    International Nuclear Information System (INIS)

    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)

  17. Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane.

    Science.gov (United States)

    Farahani, Pooria; Lundberg, Marcus; Lindh, Roland; Roca-Sanjuán, Daniel

    2015-07-28

    Excited-state chemistry is usually ascribed to photo-induced processes, such as fluorescence, phosphorescence, and photochemistry, or to bio- and chemiluminescence, in which light emission originates from a chemical reaction. A third class of excited-state chemistry is, however, possible. It corresponds to the photochemical phenomena produced by chemienergizing certain chemical groups without light - chemiexcitation. By studying Dewar dioxetane, which can be viewed as the combination of 1,2-dioxetane and 1,3-butadiene, we show here how the photo-isomerization channel of 1,3-butadiene can be reached at a later stage after the thermal decomposition of the dioxetane moiety. Multi-reference multiconfigurational quantum chemistry methods and accurate reaction-path computational strategies were used to determine the reaction coordinate of three successive processes: decomposition of the dioxetane moiety, non-adiabatic energy transfer from the ground to the excited state, and finally non-radiative decay of the 1,3-butadiene group. With the present study, we open a new area of research within computational photochemistry to study chemically-induced excited-state chemistry that is difficult to tackle experimentally due to the short-lived character of the species involved in the process. The findings shall be of relevance to unveil "dark" photochemistry mechanisms, which might operate in biological systems under conditions of lack of light. These mechanisms might allow reactions that are typical of photo-induced phenomena.

  18. Iodine removing method in organic solvent

    International Nuclear Information System (INIS)

    Suzuki, Takeo; Sakurai, Manabu

    1988-01-01

    Purpose: To effectively remove iodine in an organic solvent to thereby remove iodine in the solvent that can be re-used or put to purning treatment. Method: Organic solvent formed from wastes of nuclear facilities is mixed with basic lead acetate, or silica gel or activated carbon incorporated with such a compound to adsorb iodine in the organic solvent to the basic lead acetate. Then, iodine in the organic solvent is removed by separating to eliminate the basic lead acetate adsorbing iodine from the organic solvent or by passing the organic solvent through a tower or column charged or pre-coated with silica gel or activated carbon incorporated with lead acetate. By using basic lead acetate as the adsorbents, iodine can effective by adsorbed and eliminated. Thus, the possibility of circumstantial release of iodine can be reduced upon reusing or burning treatment of the organic solvent. (Kamimura, M.)

  19. Computer Aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Conte, Elisa; Abildskov, Jens

    and computer-aided tools and methods for property prediction and computer-aided molecular design (CAMD) principles. This framework is applicable for solvent selection and design in product design as well as process design. The first module of the framework is dedicated to the solvent selection and design...... in terms of: physical and chemical properties (solvent-pure properties); Environment, Health and Safety (EHS) characteristic (solvent-EHS properties); operational properties (solvent–solute properties). 3. Performing the search. The search step consists of two stages. The first is a generation and property...... identification of solvent candidates using special software ProCAMD and ProPred, which are the implementations of computer-aided molecular techniques. The second consists of assigning the RS-indices following the reaction–solvent and then consulting the known solvent database and identifying the set of solvents...

  20. Solvent extraction in nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Chesne, A.

    1980-09-01

    The author reviews the chief aspects of solvent extraction in reprocessing, including choice of the solvent, general description of the Purex process, and extractor technology, while emphasizing the specific character of nuclear fuels

  1. Recent solvent extraction experience at Savannah River

    International Nuclear Information System (INIS)

    Gray, L.W.; Burney, G.A.; Gray, J.H.; Hodges, M.E.; Holt, D.L.; Macafee, I.M.; Reif, D.J.; Shook, H.E.

    1986-01-01

    Tributyl phosphate-based solvent extraction processes have been used at Savannah River for more than 30 years to separate and purify thorium, uranium, neptunium, plutonium, americium, and curium isotopes. This report summarizes the advancement of solvent extraction technology at Savannah River during the 1980's. Topics that are discussed include equipment improvements, solvent treatment, waste reduction, and an improved understanding of the various chemistries in the process streams entering, within, and leaving the solvent extraction processes

  2. Sleep disturbances and exposure to organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Lindelof, B.; Almkvist, O.; Goethe, C. (Huddinge Hospital (Sweden))

    An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

  3. Solute-solvent interaction parameters by gas chromatography.

    Science.gov (United States)

    Kováts, Ervin sz; Fóti, György; Dallos, András

    2004-08-13

    Gas-liquid distribution coefficients at ideal dilution in non-volatile solvents can be measured by gas chromatography. The numerical value of a coefficient depends on the choice of the concentration unit in the solvent and in the gas phase. The relationships between different coefficients characterizing gas-liquid equilibria are discussed and summarized. Coefficients determined at several temperatures permit calculation of the standard chemical potential difference of the solute with the ideal gas phase as reference as a function of temperature, the g-SPOT. Following the proposal of Kirchhoff the latter can be formulated as an equation with three constants. As in the gas phase the molecules of the solute have no interacting partners, the three constants, deltaH, deltaS and deltaC, characterize the interaction between solvent and solute molecules. They will be called the "solute-solvent interaction parameters". In the same system the values of these parameters depend on the choice of the distribution coefficient. Five different distribution coefficients result five sets of interaction parameters. It is shown that conversion of a parameter set to another implies additive corrections independent of the nature of the solute. If g-SPOT-s are measured in a series of solvents, the data may be used to calculate the corresponding liquid-liquid partition coefficients by electing one of the solvents as reference (l-SPOT). The corresponding "relative interaction parameters" can be calculated by simple substraction. In a second chapter the precautions are summarized, necessary for gas chromatographic determination of distribution coefficients and examples are given for interaction parameters in different systems. It is concluded that there are significant differences between g-SPOT-s related to different distribution coefficients. On the other hand, differences between l-SPOT-s are negligible.

  4. Photochemistry-based immune modulation in the treatment of cutaneous leishmaniasis

    Science.gov (United States)

    Akilov, Oleg E.; Kosaka, Sachiko; Hasan, Tayyaba

    2009-06-01

    The destruction of infectious pathogens by photodynamic therapy (PDT) is an emerging modality. We demonstrated the efficacy of PDT for the management of cutaneous leishmaniasis in our previous studies. However, much remains to be done for the improvement of PDT regimens. The modulation of the immune response by photochemistry is an exciting but under-explored area of PDT research. The goal of this study is to understand the mechanisms of the augmentation of the host immune response after PDT of cutaneous leishmaniasis (CL). We found that PDT with phenoxiazine analogues was capable for induction of Th1 immune response due to stimulation of IL- 12 production by dendritic cells. Single PDT treatment facilitated fast healing of the CL lesions due to effective parasite eradication and augmentation of the immune system. Comparative study with different photosensitizers (PS) (porphyrins, pehnoxiazines) demonstrated different immunomodulating properties of PDT depending on chemical class of PS. Knowing the particular profiles and immunomodulating properties of the pertinent PSs allows us to select the optimal PS with regards to both the photodestructive and immunostimulating potential.

  5. 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, NOy 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.

  6. 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

  7. 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.

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

    Science.gov (United States)

    González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

    2016-09-01

    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 % 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.

  9. Prebiotic significance of extraterrestrial ice photochemistry: detection of hydantoin in organic residues.

    Science.gov (United States)

    de Marcellus, Pierre; Bertrand, Marylène; Nuevo, Michel; Westall, Frances; Le Sergeant d'Hendecourt, Louis

    2011-11-01

    The delivery of extraterrestrial organic materials to primitive Earth from meteorites or micrometeorites has long been postulated to be one of the origins of the prebiotic molecules involved in the subsequent apparition of life. Here, we report on experiments in which vacuum UV photo-irradiation of interstellar/circumstellar ice analogues containing H(2)O, CH(3)OH, and NH(3) led to the production of several molecules of prebiotic interest. These were recovered at room temperature in the semi-refractory, water-soluble residues after evaporation of the ice. In particular, we detected small quantities of hydantoin (2,4-imidazolidinedione), a species suspected to play an important role in the formation of poly- and oligopeptides. In addition, hydantoin is known to form under extraterrestrial, abiotic conditions, since it has been detected, along with various other derivatives, in the soluble part of organic matter of primitive carbonaceous meteorites. This result, together with other related experiments reported recently, points to the potential importance of the photochemistry of interstellar "dirty" ices in the formation of organics in Solar System materials. Such molecules could then have been delivered to the surface of primitive Earth, as well as other telluric (exo-) planets, to help trigger first prebiotic reactions with the capacity to lead to some form of primitive biomolecular activity.

  10. 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.

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

    Science.gov (United States)

    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 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. PMID:28066690

  12. 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

    2016-12-13

    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, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

  13. Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

    Science.gov (United States)

    Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

    2009-01-06

    A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

  14. Computer-aided tool for solvent selection in pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; K. Tula, Anjan; Gernaey, Krist V.

    In the pharmaceutical processes, solvents have a multipurpose role since different solvents can be used in different stages (such as chemical reactions, separations and purification) in the multistage active pharmaceutical ingredients (APIs) production process. The solvent swap and selection tasks...... swap solvents is developed and is used to retrieve information for the most commonly used solvent candidates typically found in the pharmaceutical industry. The selection is verified by simulation. The framework for the solvent selection and solvent swap is part of an integrated computer...

  15. Quantitative Framework and Management Expectation Tool for the Selection of Bioremediation Approaches at Chlorinated Solvent Sites

    Science.gov (United States)

    2015-03-19

    Bioremediation Approaches at Chlorinated Solvent Sites March 19, 2015 SERDP & ESTCP Webinar Series (#11) SERDP & ESTCP Webinar Series Welcome and...Expectation Tool for the Selection of Bioremediation Approaches at Chlorinated Solvent Sites Ms. Carmen Lebrón, Independent Consultant (20 minutes + Q&A) Dr...ESTCP Webinar Series Quantitative Framework and Management Expectation Tool for the Selection of Bioremediation Approaches at Chlorinated

  16. Effect of operating parameters on mechanical expression of solvent-soaked soybean-grits.

    Science.gov (United States)

    Sinha, Lalan Kumar; Haldar, Swarrna; Majumdar, Gautam Chandra

    2015-05-01

    Oil from soybean is obtained mostly by solvent extraction of soybean flakes. Legislation banning the use of hexane as solvent for extracting edible vegetable oil has forced a search for an alternative solvent and for developing a suitable oil recovery process. Expellers are being used for obtaining vegetable oil by mechanical means (expression) from oil seeds having oil content higher than 20 %. It was felt, in view of the stiffness of the soybean matrix, a combination of solvent treatment and expression could be a cheaper alternative; thus an attempt has been made here to develop a two stage process constituting soaking of soybean grits in solvent followed by mechanical compression (hydraulic press) of solvent-soaked grits to recover oil. The present work aimed at studying the effect of various process parameters on oil yield from solvent soaked soybean-grits during soaking as well as pressing stages using the solvents: hexane, ethanol (alternative solvent). The process parameters were identified through holistic approach. The dependant variable was oil recovery (expressed as fraction of initial oil content of soybean) whereas the independent parameters were particle size, solvent-bean mass ratio, soaking time, soaking temperature, applied pressure and pressing time. The effect of each of the above parameters on fractional oil recovery (FOR) was studied. The results of the present study indicate that the above parameters have a significant effect on the fractional oil recovery with particle size, soaking temperature, soaking time and pressing time being the most significant factors. The present study also indicates that ethanol can be used as an alternate solvent to hexane by optimizing the factors as discussed in this paper.

  17. SOLVENT EXTRACTION PROCESS FOR PLUTONIUM

    Science.gov (United States)

    Seaborg, G.T.

    1959-04-14

    The separation of plutonium from aqueous inorganic acid solutions by the use of a water immiscible organic extractant liquid is described. The plutonium must be in the oxidized state, and the solvents covered by the patent include nitromethane, nitroethane, nitropropane, and nitrobenzene. The use of a salting out agents such as ammonium nitrate in the case of an aqueous nitric acid solution is advantageous. After contacting the aqueous solution with the organic extractant, the resulting extract and raffinate phases are separated. The plutonium may be recovered by any suitable method.

  18. 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

  19. 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

  20. Vacuum ultraviolet spectroscopy and photochemistry of zinc dihydride and related molecules in low-temperature matrices.

    Science.gov (United States)

    Henchy, Chris; Kilmartin, Una; McCaffrey, John G

    2013-09-26

    Optical absorption spectra of thin film samples, formed by the codeposition of zinc vapor with D2 and CH4, have been recorded with synchrotron radiation. With sufficiently low metal vapor flux, samples deposited at 4 K were found to consist exclusively of isolated zinc atoms for both solids. The atomic absorption bands in the quantum solids D2 and CH4 were found to exhibit large bandwidths, behavior related to the high lattice frequencies of these low mass solids. The reactivity of atomic zinc was promoted with (1)P state photolysis leading to the first recording of electronic absorption spectra for the molecules ZnD2 and CH3ZnH in the vacuum ultraviolet (VUV) region. (3)P state luminescence of atomic zinc observed in the Zn/CH4 system points to the involvement of the spin triplet state in the relaxation of CH3ZnH system as it evolves into the C3v ground state. This state is not involved in the relaxation of the higher symmetry molecule ZnD2. Time dependent density functional theory (TD-DFT) calculations were conducted to predict the electronic transitions of the inserted molecular species. Comparisons with experimental data indicate the predicted transition energies are approximately 0.5 eV less than the recorded values. Possible reasons for the discrepancy are discussed. The molecular photochemistry of ZnD2 and CH3ZnH observed in the VUV was modeled successfully with a simple four-valence electron AH2 Walsh-type diagram.

  1. 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

  2. Impacts of HONO sources on the photochemistry in Mexico City during the MCMA-2006/MILAGO Campaign

    Directory of Open Access Journals (Sweden)

    G. Li

    2010-07-01

    Full Text Available The contribution of HONO sources to the photochemistry in Mexico City is investigated during the MCMA-2006/MILAGO Campaign using the WRF-CHEM model. Besides the homogeneous reaction of NO with OH, four additional HONO sources are considered in the WRF-CHEM model: secondary HONO formation from NO2 heterogeneous reaction with semivolatile organics, NO2 reaction with freshly emitted soot, NO2 heterogeneous reaction on aerosol and ground surfaces. The WRF-CHEM model with the five HONO sources performs reasonably well in tracking the observed diurnal variation of HONO concentrations. The HONO sources included are found to significantly improve the HOx (OH+HO2 simulations during daytime and the partition of NO/NO2 in the morning. The HONO sources also accelerate the accumulation of O3 concentrations in the morning by about 2 h and subsequently result in a noticeable enhancement of O3 concentrations over the course of the day with a midday average of about 6 ppb. Furthermore, these HONO sources play a very important role in the formation of secondary aerosols in the morning. They substantially enhance the secondary organic aerosol concentrations by a factor of 2 on average in the morning, although they contribute less during the rest of the day. The simulated particle-phase nitrate and ammonium are also substantially enhanced in the morning when the four HONO sources are included, in good agreement with the measurements. The impact of the HONO sources on the sulfate aerosols is negligible because of the inefficient conversion of H2SO4 from SO2 reacting with OH.

  3. Provenance effect on carbon assimilation, photochemistry and leaf morphology in Mediterranean Cistus species under chilling stress.

    Science.gov (United States)

    Puglielli, G; Cuevas Román, F J; Catoni, R; Moreno Rojas, J M; Gratani, L; Varone, L

    2017-07-01

    The potential resilience of shrub species to environmental change deserves attention in those areas threatened by climate change, such as the Mediterranean Basin. We asked if leaves produced under different climate conditions through the winter season to spring can highlight the leaf traits involved in determining potential resilience of three Cistus spp. to changing environmental conditions and to what extent intraspecific differences affect such a response. We analysed carbon assimilation, maximum quantum efficiency of PSII photochemistry (F v /F m ) and leaf morphological control of the photosynthetic process in leaves formed through the winter season into spring in C. creticus subsp. eriocephalus (CE), C. salvifolius (CS) and C. monspeliensis (CM) grown from seed of different provenances under common garden conditions. Intraspecific differences were found in F v /F m for CE and CS. Carbon assimilation-related parameters were not affected by provenance. Moreover, our analysis highlighted that the functional relationships investigated can follow seasonal changes and revealed patterns originating from species-specific differences in LMA arising during the favourable period. Cistus spp. have great ability to modify the structure and function of their leaves in the mid-term in order to cope with changing environmental conditions. The F v /F m response to chilling reveals that susceptibility to photoinhibition is a trait under selection in Cistus species. Concerning carbon assimilation, differing ability to control stomatal opening was highlighted between species. Moreover, seasonal changes of the functional relationships investigated can have predictable consequences on species leaf turnover strategies. © 2017 German Botanical Society and The Royal Botanical Society of the Netherlands.

  4. 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.

  5. Photochemistry of Methyl Bromide on the α-Cr2O3(0001) Surface

    International Nuclear Information System (INIS)

    Henderson, Michael A.

    2010-01-01

    The photochemical properties of the Cr-terminated α-Cr 2 O 3 (0001) surface were explored using methyl bromide (CH 3 Br) as a probe molecule. CH 3 Br adsorbed and desorbed molecularly from the Cr-terminated α-Cr 2 O 3 (0001) surface without detectable thermal decomposition. Temperature programmed desorption (TPD) revealed a CH 3 Br desorption state at 240 K for coverages up to 0.5 ML, followed by more weakly bound molecules desorbing at 175 K for coverages up to 1 ML. Multilayer exposures led to desorption at ∼130 K. The CH 3 Br sticking coefficient was unity at 105 K for coverages up to monolayer saturation, but decreased as the multilayer formed. In contrast, pre-oxidation of the surface (using an oxygen plasma source) led to capping of surface Cr 3+ sites and near complete removal of CH 3 Br TPD states above 150 K. The photochemistry of chemisorbed CH 3 Br was explored on the Cr-terminated surface using post-irradiation TPD and photon stimulated desorption (PSD). Irradiation of adsorbed CH 3 Br with broad band light from a Hg arc lamp resulted in both photodesorption and photodecomposition of the parent molecule at a combined cross section of ∼10 -22 cm 2 . Parent PSD was indicative of molecular photodesorption, but CH 3 was also detected in PSD and Br atoms were left on the surface, both reflective of photo-induced CH 3 -Br bond dissociation. Use of a 385 nm cut-off filter effectively shut down the photodissociation pathway but not the parent molecule photodesorption process. From these observations it is inferred that d-to-d transitions in α-Cr 2 O 3 , occurring at photon energies 3 Br. It is unclear to what extent band-to-band versus direct CH 3 Br photolysis play in CH 3 -Br bond dissociation initiated by more energetic photons.

  6. Lysozyme Photochemistry as a Function of Temperature. The Protective Effect of Nanoparticles on Lysozyme Photostability.

    Science.gov (United States)

    Oliveira Silva, Catarina; Petersen, Steffen B; Pinto Reis, Catarina; Rijo, Patrícia; Molpeceres, Jesús; Vorum, Henrik; Neves-Petersen, Maria Teresa

    2015-01-01

    The presence of aromatic residues and their close spatial proximity to disulphide bridges makes hen egg white lysozyme labile to UV excitation. UVB induced photo-oxidation of tryptophan and tyrosine residues leads to photochemical products, such as, kynurenine, N-formylkynurenine and dityrosine and to the disruption of disulphide bridges in proteins. We here report that lysozyme UV induced photochemistry is modulated by temperature, excitation power, illumination time, excitation wavelength and by the presence of plasmonic quencher surfaces, such as gold, and by the presence of natural fluorescence quenchers, such as hyaluronic acid and oleic acid. We show evidence that the photo-oxidation effects triggered by 295 nm at 20°C are reversible and non-reversible at 10°C, 25°C and 30°C. This paper provides evidence that the 295 nm damage threshold of lysozyme lies between 0.1 μW and 0.3 μW. Protein conformational changes induced by temperature and UV light have been detected upon monitoring changes in the fluorescence emission spectra of lysozyme tryptophan residues and SYPRO® Orange. Lysozyme has been conjugated onto gold nanoparticles, coated with hyaluronic acid and oleic acid (HAOA). Steady state and time resolved fluorescence studies of free and conjugated lysozyme onto HAOA gold nanoparticles reveals that the presence of the polymer decreased the rate of the observed photochemical reactions and induced a preference for short fluorescence decay lifetimes. Size and surface charge of the HAOA gold nanoparticles have been determined by dynamic light scattering and zeta potential measurements. TEM analysis of the particles confirms the presence of a gold core surrounded by a HAOA matrix. We conclude that HAOA gold nanoparticles may efficiently protect lysozyme from the photochemical effects of UVB light and this nanocarrier could be potentially applied to other proteins with clinical relevance. In addition, this study confirms that the temperature plays a

  7. 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.

  8. Dimers and organosulfates derived from biogenic oxidation products in aerosols during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in California 2007 and 2009 (Invited)

    Science.gov (United States)

    Glasius, M.; Worton, D. R.; Kristensen, K.; Nguyen, Q.; Surratt, J.; Enggrob, K. L.; Bouvier-Brown, N. C.; Farmer, D.; Docherty, K. S.; Platt, S.; Bilde, M.; Nøjgaard, J. K.; Seinfeld, J.; Jimenez, J. L.; Goldstein, A.

    2010-12-01

    Oxidation products of biogenic volatile organic compounds, such as monoterpenes and isoprene, contribute to biogenic secondary organic aerosol (BSOA). The organosulfate derivatives of these compounds are formed through heterogeneous reactions involving sulphur compounds, with a considerable contribution from anthropogenic sources. Organosulfate derivatives of biogenic oxidation products thus belong to a new group of anthropogenic enhanced biogenic SOA (ABSOA). The Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) during summers of 2007 and 2009 provided an excellent platform at Blodgett Forest, California (a ponderosa pine plantation) for studying ABSOA. Typically, polluted air masses were transported upslope from the California Central Valley during day, while night conditions were influenced by downslope transport of air masses, low local atmospheric mixing and formation of a shallow boundary layer. We collected particle samples (PM2.5) as one nighttime and two daytime samples per day. After extraction of filters in polar organic solvents (i.e. acetonitrile or methanol), organic aerosol constituents were analyzed by HPLC coupled through an electrospray inlet to a quadrupole time-of-flight mass spectrometer (qTOF-MS). Organosulfates and nitrooxy organosulfates derived from oxidation products of α-pinene, β-pinene, limonene and isoprene were identified based on their molecular mass and MS fragmentation patterns. Measurements by High Resolution Time of Flight Aerosol Mass Spectrometry (HR-ToF-AMS) show high mass loadings of nitrate in the night and morning samples with highest levels of the nitrooxy organosulfates with MW 295 and MW 297. This may indicate that elevated levels of nitrate and nitrooxy organosulfates are formed in the same polluted air mass, probably through nitrate radical reactions. Terpenylic acid, diterpenylic acid acetate, and methylbutane tricarboxylic acid were found at concentrations comparable to pinic acid. A dimer of

  9. 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)

  10. An optimized device for UF6 laser isotopic photochemistry using an optical parametric oscillator and a down converter

    International Nuclear Information System (INIS)

    Kupecek, P.; Weulersse, J.M.; Isnard, P.; Alexandre, M.; Clerc, M.

    1983-01-01

    We developped a tunable coherent source near 16 μm for selective photochemistry studies on UF 6 . The device uses a YAG:Nd 3+ pumped lithium niobate optical parametric oscillator coupled with a cadmium selenide frequency down converter. The components and physical parameters have been optimized leading to an overall optical conversion efficiency of about 6.10 -3 , that is a quantum yield of 0.1. The main characteristics such as beam quality and spectral width have been measured, the last one beeing 60 mK at 16 μm, for 1.5mJ pulses [fr

  11. Independence and Product Systems

    OpenAIRE

    Skeide, Michael

    2003-01-01

    Starting from elementary considerations about independence and Markov processes in classical probability we arrive at the new concept of conditional monotone independence (or operator-valued monotone independence). With the help of product systems of Hilbert modules we show that monotone conditional independence arises naturally in dilation theory.

  12. Solvent characterization using the dispersion number

    International Nuclear Information System (INIS)

    Leonard, R.A.

    1993-01-01

    When developing new solvent extraction processes, one often has to evaluate new solvents, new aqueous phases, or both for their ability to work in plant-scale equipment. To facilitate solvent characterization, a simple test is proposed based on the dimensionless dispersion number (N Di ). It allows one to characterize the ability of the solvent to separate from a two-phase dispersion and allows one to estimate process throughput for equipment of a given size. Several ways to carry out the N Di test are given, including a standard test procedure. The N Di test was applied to the performance of solvent extraction equipment with discrete process stages, the leaching of plasticizers from plastic tubing, and the development of a new solvent for the combined extraction of strontium and transuranic elements

  13. Supercritical solvent extraction of oil sand bitumen

    Science.gov (United States)

    Imanbayev, Ye. I.; Ongarbayev, Ye. K.; Tileuberdi, Ye.; Mansurov, Z. A.; Golovko, A. K.; Rudyk, S.

    2017-08-01

    The supercritical solvent extraction of bitumen from oil sand studied with organic solvents. The experiments were performed in autoclave reactor at temperature above 255 °C and pressure 29 atm with stirring for 6 h. The reaction resulted in the formation of coke products with mineral part of oil sands. The remaining products separated into SARA fractions. The properties of the obtained products were studied. The supercritical solvent extraction significantly upgraded extracted natural bitumen.

  14. Photothermal beam deflection calorimetry in solution photochemistry: recent progress and future prospects.

    Science.gov (United States)

    Falvey, D E

    1997-01-01

    Photothermal beam deflection (PBD) calorimetry is a technique that measures changes in the solvent's refractive index that accompanies photothermal heating. This method is capable of extracting both kinetic and thermodynamic information from photochemical reactions. A qualitative description of physical basis of time-resolved PBD is presented. Several recent examples of its application to photochemical and photobiological problems are discussed. Finally, the advantages and limitations of PBD are described.

  15. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...... solubility measurements in aqueous organic solvent mixtures....

  16. Aminosilicone solvent recovery methods and systems

    Energy Technology Data Exchange (ETDEWEB)

    Spiry, Irina Pavlovna; Perry, Robert James; Wood, Benjamin Rue; Singh, Surinder Prabhjot; Farnum, Rachel Lizabeth; Genovese, Sarah Elizabeth

    2018-02-13

    The present invention is directed to aminosilicone solvent recovery methods and systems. The methods and systems disclosed herein may be used to recover aminosilicone solvent from a carbon dioxide containing vapor stream, for example, a vapor stream that leaves an aminosilicone solvent desorber apparatus. The methods and systems of the invention utilize a first condensation process at a temperature from about 80.degree. C. to about 150.degree. C. and a second condensation process at a temperature from about 5.degree. C. to about 75.degree. C. The first condensation process yields recovered aminosilicone solvent. The second condensation process yields water.

  17. Organic solvents in electromembrane extraction: recent insights

    DEFF Research Database (Denmark)

    Huang, Chuixiu; Gjelstad, Astrid; Pedersen-Bjergaard, Stig

    2016-01-01

    the introduction. Under the influence of an electrical field, EME is based on electrokinetic migration of the analytes through a supported liquid membrane (SLM), which is an organic solvent immobilized in the pores of the polymeric membrane, and into the acceptor solution. Up to date, close to 150 research...... articles with focus on EME have been published. The current review summarizes the performance of EME with different organic solvents and discusses several criteria for efficient solvents in EME. In addition, the authors highlight their personal perspective about the most promising organic solvents for EME...

  18. Synthesis, spectroscopy and photochemistry of novel branched fluorescent nitro-stilbene derivatives with benzopheonone groups.

    Science.gov (United States)

    Gao, Fang; Liu, Jian; Peng, Huayong; Hu, Nvdan; Li, Hongru; Zhang, Shengtao

    2010-05-01

    In this article, we presented novel nitro-stilbene derivatives with one or two benzophenone groups as photoinitiators via multi-steps synthesis. The ultraviolet/visible spectroscopy and the emission spectroscopy of the compounds were determined in various solvents. The results showed that the ultraviolet/visible absorption spectroscopy of the derivatives with benzophenone moiety displayed overlap effects of nitro-stilbene and benzophenone parts. In non-polar solvents, the derivatives exhibited strong emission, while they displayed weak emission in modest and strong polar solvents. Dyes-linked benzopheonone groups displayed stronger fluorescence emission than simple chromophore parent molecules. Visible-light photoinitiating effects of the derivatives were investigated extensively. Methyl methacrylate could be photoinitiated efficiently by the derivatives with benzophenone moieties at very low concentration, even at 1 x 10(-5) mol/L. While the photopolymerization efficiency of styrene initiated by the derivatives was lower than that of methyl methacrylate. Our results showed that the dye-linked photoinitators had more efficient photoinitiating than the simple mixture of dye and photoinitator. Furthermore, the derivative with two benzophenone groups displayed more excellent photoiniatiating effects than the derivative with one benzophenone group. Thermodynamics driving for the occurrence of visible-light photoinduced intramolecular electron transfer from chromophore part to benzophenone part was evaluated. Benzopinacol moiety produced in photoreaction was confirmed by nuclear magnetic resonant spectroscopy. Thermal stability of the derivatives was analyzed.

  19. Cleanup of 7.5% tributyl phosphate/n-paraffin solvent-extraction solvent

    International Nuclear Information System (INIS)

    Reif, D.J.

    1987-02-01

    The HM process at the Savannah River Plant uses 7.5% tributyl phosphate in n-paraffin as an extraction solvent. During use, the solvent is altered due to hydrolysis and radiolysis, forming materials which influence product losses, product decontamination, and separation efficiencies. Laboratory studies to improve online solvent cleaning have shown that carbonate washing, although removing residual solvent activity, does not remove binding ligands which hold fission products in the solvent. Treatment of solvent by an alumina adsorption process removes binding ligands and significantly improves recycle solvent performance. Both laboratory work defining a full-scale alumina adsorption process and the use of the process to clean HM process first cycle solvent is discussed

  20. Quantitation of buried contamination by use of solvents. [degradation of silicone polymers by amine solvents

    Science.gov (United States)

    Pappas, S. P.; Hsiao, Y. C.; Hill, L. W.

    1973-01-01

    Spore recovery form cured silicone potting compounds using amine solvents to degrade the cured polymers was investigated. A complete list of solvents and a description of the effect of each on two different silicone polymers is provided.

  1. Implicit solvent simulations of DNA and DNA-protein complexes: Agreement with explicit solvent vs experiment

    Czech Academy of Sciences Publication Activity Database

    Chocholoušová, Jana; Feig, M.

    2006-01-01

    Roč. 110, č. 34 (2006), s. 17240-17251 ISSN 1520-6106 Keywords : implicit solvent * explicit solvent * protein DNA complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.115, year: 2006

  2. 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.

  3. 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

  4. Thermal chemistry and photochemistry of hexafluoroacetone on rutile TiO2(110)

    International Nuclear Information System (INIS)

    Zehr, Robert T.; Henderson, Michael A.

    2010-01-01

    The ultraviolet (UV) photon-induced decomposition of hexafluoroacetone (HFA) adsorbed on the rutile TiO2(110) surface was investigated using photon stimulated desorption (PSD) and temperature programmed desorption (TPD). The initial 0.2 ML coverage of HFA decomposed when adsorbed on the reduced TiO2(110) surface resulting in the formation of trifluoroacetate (evolving in TPD as CO, CO2, and C2F4 near 600 K). Further HFA exposure resulted in molecular adsorption. No evidence for photochemistry was observed on the reduced surface. HFA adsorbed and desorbed molecularly on a pre-oxidized TiO2(110) surface with only a minor amount (∼1%) of thermal decomposition in TPD. A new adsorption state at 350 K was assigned to the reversible formation of a photoactive HFA-diolate species [(CF3)2COO]. UV irradiation depleted the 350 K state and resulted in the formation of surface bound trifluoroacetate. PSD experiments showed that CF3, CO, and CO2 were evolved during irradiation at 95 K. Post-irradiation TPD showed evidence for trifluoroacetate (desorbing as CO, CO2, and C2F4 near 600 K) as surface-bound photodecomposition products. 18O isotope scrambling experiments showed that the origin of the ejected CO2 was from photodecomposition of the HFA-diolate species. CO photodesorption was due to an as-yet unidentified adsorbed HFA species and not due to decomposition of the HFA-diolate. These results are in contrast to the photochemical behavior of acetone, butanone and acetaldehyde on TiO2(110), where UV irradiation resulted in the gas phase ejection of one of the carbonyl substituent groups as well as a stoichiometric amount of carboxylate left on the surface. We conclude that fluorination alters the electronic structure of adsorbed carbonyls on TiO2(110) in such a way as to promote complete fragmentation of the adsorbed carbonyl complex to form gas phase CO2 as well as open up additional photodissociation pathways leading to CO production.

  5. State-resolved photochemistry and spectroscopic characterization of atmospherically relevant hydroperoxides

    Science.gov (United States)

    Matthews, Jamie

    This dissertation focuses on the photodissociation dynamics, thermochemistry, spectroscopy and structure of important hydroperoxide molecules which influence the oxidation capacity of the atmosphere. Since hydroperoxides such as CH 3OOH, HOCH2OOH, HO2NO2 and HOOH species serve as reservoir for the HOx (=HO2 + OH) radicals, a thorough examination of excited state and ground state photochemistry of these species is needed. In this dissertation, the photodissociation dynamics of vibrationally excited HO2NO2 molecule is examined, and its first OH-stretching state dissociation quantum yield is assessed in order to quantify its contribution to the HOx budget. An ab initio study is used to obtain bond dissociation energies, vibrational spectra and absorption cross-sections. The HOONO molecule is an important structural isomer of nitric acid. Studies of HOONO molecule have primarily focused on the vibrational structure, spectra and energetics of vibrational states in the vicinity of the first and second OH-stretching overtones. From these measurements, the heat of formation and vibrational band assignment of cis-cis HOONO are determined. Organic hydroperoxides such as CH3OOH and HOCH2OOH are fundamental systems to explore the flow of energy among different vibrational modes. In HOCH2OOH, the dissociation rates that are extracted from the third OH-stretching overtone suggest that excitation of the alcohol OH-stretch result in dissociation rates that are substantially slower than rates resulting from excitation of the peroxide OH-stretch where IVR is evidently more restricted. Non-statistical behavior is also observed in CH3OOH, where the excitation of HOO-bending mode and CH-stretching modes result in more complete IVR due to strong state-mixing compared with excitation of the OH-stretching modes; as inferred from the quantities of vibrationally excited OH product formed. Enhanced IVR mixing is also observed in HOOH molecule, suggesting mode-selective behavior is a common

  6. Additive diffusion from LDPE slabs into contacting solvents as a function of solvent absorption

    NARCIS (Netherlands)

    Helmroth, I.E.; Dekker, M.; Hankemeier, Th.

    2003-01-01

    This article describes the simultaneous diffusion of a migrant and a solvent in low density polyethylene (LDPE). The migrant (Irganox 1076) moves out of the slab, while the solvent (isooctane, n-heptane or cyclohexane) moves inwards. Solvent absorption was measured separately by following the

  7. Additive Diffusion from LDPE Slabs into Contacting Solvents as a Function of Solvent Absorption

    NARCIS (Netherlands)

    Helmroth, I.E.; Dekker, M.; Hankemeier, T.

    2003-01-01

    This article describes the simultaneous diffusion of a migrant and a solvent in low density polyethylene (LDPE). The migrant (Irganox 1076) moves out of the slab, while the solvent (isooctane, n-heptane or cyclohexane) moves inwards. Solvent absorption was measured separately by following the

  8. Are Independent Fiscal Institutions Really Independent?

    Directory of Open Access Journals (Sweden)

    Slawomir Franek

    2015-08-01

    Full Text Available In the last decade the number of independent fiscal institutions (known also as fiscal councils has tripled. They play an important oversight role over fiscal policy-making in democratic societies, especially as they seek to restore public finance stability in the wake of the recent financial crisis. Although common functions of such institutions include a role in analysis of fiscal policy, forecasting, monitoring compliance with fiscal rules or costing of spending proposals, their roles, resources and structures vary considerably across countries. The aim of the article is to determine the degree of independence of such institutions based on the analysis of the independence index of independent fiscal institutions. The analysis of this index values may be useful to determine the relations between the degree of independence of fiscal councils and fiscal performance of particular countries. The data used to calculate the index values will be derived from European Commission and IMF, which collect sets of information about characteristics of activity of fiscal councils.

  9. Solvents extraction of niobium and tantalum

    International Nuclear Information System (INIS)

    Santos, P.R.G.; Cunha, O.C. da.

    1982-01-01

    The separation process of niobium and tantalum using solvent extraction is evaluated. The use of methyl isobutyl ketone (MIBK) e tributyl phosphate (TBP), and the distribution of two elements between aqueous and organic phases in function of the fluoridric and sulfuric acids, solvent and diluent is analysed. (M.J.C.) [pt

  10. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    The use of proline or any other amino acid in asymmetric annulation reactions in a solid–liquid phase reaction in the absence of solvents to effect an asymmetric synthesis is an important step forward towards cleaner synthesis 2. ... Reports on solvent-free reactions have become increasingly frequent and the field has.

  11. Molecular Thermodynamic Modeling of Mixed Solvent Solubility

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.

    2010-01-01

    A method based on statistical mechanical fluctuation solution theory for composition derivatives of activity coefficients is employed for estimating dilute solubilities of 11 solid pharmaceutical solutes in nearly 70 mixed aqueous and nonaqueous solvent systems. The solvent mixtures range from ne...

  12. Occupational Exposure to Organic Solvents during Bridge Painting

    Science.gov (United States)

    Qian, Hua; Fiedler, Nancy; Moore, Dirk F.; Weisel, Clifford P.

    2010-01-01

    Exposure to volatile organic compounds (VOCs) from bridge painting was measured in New York City and New Jersey during the summer and fall seasons from 2005 to 2007. The effect of painting activities (paint coating layer, confinement setup, and application method) and meteorological conditions (temperature, humidity, and wind speed) on solvent exposure to aromatic, ketone, ester, and alkane compounds were individually evaluated. Mixed-effect models were used to examine the combination effects of these factors on the air concentration of total VOCs as the individual compound groups were not present in all samples. Air concentration associated with spraying was not affected by meteorological conditions since spraying was done in a confined space, thus reducing their impact on solvent air concentration. The mixed models for brushing and rolling samples included two fixed factors, i.e. application method and temperature, and one random factor, i.e. sampling day. An independent dataset (daily air samples) was used to validate the mixed model constructed for brushing and rolling samples. The regression line of the predicted values and actual measurements had a slope of 1.32 ± 0.15 for daily brushing and rolling samples, with almost all points being within the 95% confidence bands. The constructed model provides practical approaches for estimating the solvent exposure from brushing and rolling activities among construction painters. An adjusted mean air concentration derived from the activity-specific spray samples was the best estimate for that painting application. PMID:20354053

  13. Efficient cellulose solvent: quaternary ammonium chlorides.

    Science.gov (United States)

    Kostag, Marc; Liebert, Tim; El Seoud, Omar A; Heinze, Thomas

    2013-10-01

    Pure quaternary tetraalkylammonium chlorides with one long alkyl chain dissolved in various organic solvents constitute a new class of cellulose solvents. The electrolytes are prepared in high yields and purity by Menshutkin quaternization, an inexpensive and easy synthesis route. The pure molten tetraalkylammonium chlorides dissolve up to 15 wt% of cellulose. Cosolvents, including N,N-dimethylacetamide (DMA), may be added in large excess, leading to a system of decreased viscosity. Contrary to the well-established solvent DMA/LiCl, cellulose dissolves in DMA/quaternary ammonium chlorides without any pretreatment. Thus, the use of the new solvent avoids some disadvantages of DMA/LiCl and ionic liquids, the most extensively employed solvents for homogeneous cellulose chemistry. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Solvent distillations studies for a reprocessing plant

    International Nuclear Information System (INIS)

    Ginisty, C.; Guillaume, B.

    1989-01-01

    The substantial amounts of solvent used in large reprocessing plants are such that considerable care must be paid to solvent management to limit the production of organic wastes. The installation of intensive treatment by chemical regeneration serves to increase the service life of the solvent. General solvent management, combined with a distillation unit under reduced pressure also helps to recycle the two components of the solvent at a low activity level. Distillation also serves to remove the heavy degradation products that are generally responsible for poor hydraulic behavior and for the holdup of radioactive products such as plutonium, zirconium and ruthenium. From the safety standpoint, the flashpoint of the distilled diluent tends to rise. It can therefore be recycled without risk

  15. The chemistry of nonaqueous solvents v.4 solution phenomena and aprotic solvents

    CERN Document Server

    Lagowski, J J

    1976-01-01

    The Chemistry of Nonaqueous Solvents, Volume IV: Solution Phenomena and Aprotic Solvents focuses on the chemistry of nonaqueous solvents, with emphasis on solution phenomena and aprotic solvents such as tetramethylurea, inorganic acid chlorides, cyclic carbonates, and sulfolane. This book is organized into seven chapters and begins with an overview of the theory of electrical conductivity and elementary experimental considerations, along with some of the interesting research on nonaqueous solvents. It then turns to a discussion on hydrogen bonding phenomena in nonaqueous systems as probed

  16. Highlights of the Spectroscopy, Photochemistry and Electrochemistry of [M(CO)4(.alfa.-diimine)] Complexes, M=Cr, Mo, W

    Czech Academy of Sciences Publication Activity Database

    Vlček, Antonín

    2002-01-01

    Roč. 230, - (2002), s. 225-242 ISSN 0010-8545 R&D Projects: GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * electrochemistry * photochemistry Subject RIV: CG - Electrochemistry Impact factor: 5.853, year: 2002

  17. Central Bank independence

    Directory of Open Access Journals (Sweden)

    Vasile DEDU

    2012-08-01

    Full Text Available In this paper we present the key aspects regarding central bank’s independence. Most economists consider that the factor which positively influences the efficiency of monetary policy measures is the high independence of the central bank. We determined that the National Bank of Romania (NBR has a high degree of independence. NBR has both goal and instrument independence. We also consider that the hike of NBR’s independence played an important role in the significant disinflation process, as headline inflation dropped inside the targeted band of 3% ± 1 percentage point recently.

  18. Predicting the Solubility of Pharmaceutical Cocrystals in Solvent/Anti-Solvent Mixtures

    Directory of Open Access Journals (Sweden)

    Linda Lange

    2016-05-01

    Full Text Available In this work, the solubilities of pharmaceutical cocrystals in solvent/anti-solvent systems were predicted using PC-SAFT in order to increase the efficiency of cocrystal formation processes. Modeling results and experimental data were compared for the cocrystal system nicotinamide/succinic acid (2:1 in the solvent/anti-solvent mixtures ethanol/water, ethanol/acetonitrile and ethanol/ethyl acetate at 298.15 K and in the ethanol/ethyl acetate mixture also at 310.15 K. The solubility of the investigated cocrystal slightly increased when adding small amounts of anti-solvent to the solvent, but drastically decreased for high anti-solvent amounts. Furthermore, the solubilities of nicotinamide, succinic acid and the cocrystal in the considered solvent/anti-solvent mixtures showed strong deviations from ideal-solution behavior. However, by accounting for the thermodynamic non-ideality of the components, PC-SAFT is able to predict the solubilities in all above-mentioned solvent/anti-solvent systems in good agreement with the experimental data.

  19. Organic Solvent Tolerant Lipases and Applications

    Directory of Open Access Journals (Sweden)

    Shivika Sharma

    2014-01-01

    Full Text Available Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using lipase(s could be performed in water-restricted organic media as organic solvent(s not only improve(s the solubility of substrate and reactant in reaction mixture but also permit(s the reaction in the reverse direction, and often it is easy to recover the product in organic phase in two-phase equilibrium systems. The use of organic solvent tolerant lipase in organic media has exhibited many advantages: increased activity and stability, regiospecificity and stereoselectivity, higher solubility of substrate, ease of products recovery, and ability to shift the reaction equilibrium toward synthetic direction. Therefore the search for organic solvent tolerant enzymes has been an extensive area of research. A variety of fatty acid esters are now being produced commercially using immobilized lipase in nonaqueous solvents. This review describes the organic tolerance and industrial application of lipases. The main emphasis is to study the nature of organic solvent tolerant lipases. Also, the potential industrial applications that make lipases the biocatalysts of choice for the present and future have been presented.

  20. Solvent extraction: projection to the future

    International Nuclear Information System (INIS)

    Ritcey, G.M.

    1983-01-01

    The process of purification of metal-bearing solutions using solvent extraction has proven to be one of the major improvements to the optimization of the metallurgical flowsheet. Numerous improvements have been made throughout the solvent extraction circuit, as well as considerable research on the subject throughout the world which could, if implemented, add considerably to the overall understanding and viability of the process. This paper examines each of the areas in the solvent extraction process and discusses possibilities whereby process modifications could result in significant improvements to a typical flowsheet. Such improvements of interest and concern to the operating plant include economics, energy and environment. 33 references, 12 figures

  1. Solvent Handbook Database System user's manual

    International Nuclear Information System (INIS)

    1993-03-01

    Industrial solvents and cleaners are used in maintenance facilities to remove wax, grease, oil, carbon, machining fluids, solder fluxes, mold release, and various other contaminants from parts, and to prepare the surface of various metals. However, because of growing environmental and worker-safety concerns, government regulations have already excluded the use of some chemicals and have restricted the use of halogenated hydrocarbons because they affect the ozone layer and may cause cancer. The Solvent Handbook Database System lets you view information on solvents and cleaners, including test results on cleaning performance, air emissions, recycling and recovery, corrosion, and non-metals compatibility. Company and product safety information is also available

  2. Chemical reactions in solvents and melts

    CERN Document Server

    Charlot, G

    1969-01-01

    Chemical Reactions in Solvents and Melts discusses the use of organic and inorganic compounds as well as of melts as solvents. This book examines the applications in organic and inorganic chemistry as well as in electrochemistry. Organized into two parts encompassing 15 chapters, this book begins with an overview of the general properties and the different types of reactions, including acid-base reactions, complex formation reactions, and oxidation-reduction reactions. This text then describes the properties of inert and active solvents. Other chapters consider the proton transfer reactions in

  3. Switchable solvents and methods of use thereof

    Science.gov (United States)

    Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

    2011-07-19

    A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

  4. Genomic and Genetic Approaches to Solvent Tolerance

    Energy Technology Data Exchange (ETDEWEB)

    Eleftherios T. Papoutsakis

    2005-06-10

    The proposed research is to understand and exploit the molecular basis that determines tolerance of the industrially important anaerobic clostridia to solvents. Furthermore, we aim to develop general genomic and metabolic engineering strategies for understanding the molecular basis of tolerance to chemicals and for developing tolerant strains. Our hypothesis is that the molecular basis of what makes bacterial cells able to withstand high solvent concentrations can be used to metabolically engineer cells so that they can tolerate higher concentrations of solvents and related chemicals.

  5. Reduction of solvent emissions from vapor degreasing

    Energy Technology Data Exchange (ETDEWEB)

    Buresh, P.

    1989-12-31

    Hutchinson Tehnology, Inc. (HTI) implemented a number of low cost, low technology procedures to reduce emissions and prevent solvent loss from two open-top freon (CFC-113) vapor degreasers (Branson No. 1 and No. 2). HTI is a computer components manufacturer that uses freon vapor degreasing systems to remove fluxes and other residues remaining on the flexible printed circuits from the soldering process. With relatively minor changes in operation, solvent emissions were reduced by an average of 2.8 gallons per day (GDP) for both degreasers combined. It is anticipated that HTI will follow through with installation of an automatic cover, which can result in further solvent emissions reduction.

  6. 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.

  7. A diabatic circulation two-dimensional model with photochemistry - Simulations of ozone and long-lived tracers with surface sources

    Science.gov (United States)

    Stordal, F.; Isaksen, I. S. A.; Horntveth, K.

    1985-01-01

    Numerous studies have been concerned with the possibility of a reduction of the stratospheric ozone layer. Such a reduction could lead to an enhanced penetration of ultraviolet (UV) radiation to the ground, and, as a result, to damage in the case of several biological processes. It is pointed out that the distributions of many trace gases, such as ozone, are governed in part by transport processes. The present investigation presents a two-dimensional photochemistry-transport model using the residual circulation. The global distribution of both ozone and components with ground sources computed in this model is in good agreement with the observations even though slow diffusion is adopted. The agreement is particularly good in the Northern Hemisphere. The results provide additional support for the idea that tracer transport in the stratosphere is mainly of advective nature.

  8. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Ding, Xunliang; Rentzepis, Peter M

    2008-10-07

    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

  9. Compact Solid-State 213 nm Laser Enables Standoff Deep Ultraviolet Raman Spectrometer: Measurements of Nitrate Photochemistry.

    Science.gov (United States)

    Bykov, Sergei V; Mao, Michael; Gares, Katie L; Asher, Sanford A

    2015-08-01

    We describe a new compact acousto-optically Q-switched diode-pumped solid-state (DPSS) intracavity frequency-tripled neodymium-doped yttrium vanadate laser capable of producing ~100 mW of 213 nm power quasi-continuous wave as 15 ns pulses at a 30 kHz repetition rate. We use this new laser in a prototype of a deep ultraviolet (UV) Raman standoff spectrometer. We use a novel high-throughput, high-resolution Echelle Raman spectrograph. We measure the deep UV resonance Raman (UVRR) spectra of solid and solution sodium nitrate (NaNO3) and ammonium nitrate (NH4NO3) at a standoff distance of ~2.2 m. For this 2.2 m standoff distance and a 1 min spectral accumulation time, where we only monitor the symmetric stretching band, we find a solid state NaNO3 detection limit of ~100 μg/cm(2). We easily detect ~20 μM nitrate water solutions in 1 cm path length cells. As expected, the aqueous solutions UVRR spectra of NaNO3 and NH4NO3 are similar, showing selective resonance enhancement of the nitrate (NO3(-)) vibrations. The aqueous solution photochemistry is also similar, showing facile conversion of NO3(-) to nitrite (NO2(-)). In contrast, the observed UVRR spectra of NaNO3 and NH4NO3 powders significantly differ, because their solid-state photochemistries differ. Whereas solid NaNO3 photoconverts with a very low quantum yield to NaNO2, the NH4NO3 degrades with an apparent quantum yield of ~0.2 to gaseous species.

  10. Surface Photochemistry: Benzophenone as a Probe for the Study of Modified Cellulose Fibres

    Directory of Open Access Journals (Sweden)

    L. F. Vieira Ferreira

    2007-01-01

    Full Text Available This work reports the use of benzophenone, a very well characterized probe, to study new hosts (i.e., modified celluloses grafted with alkyl chains bearing 12 carbon atoms by surface esterification. Laser-induced room temperature luminescence of air-equilibrated or argon-purged solid powdered samples of benzophenone adsorbed onto the two modified celluloses, which will be named C12-1500 and C12-1700, revealed the existence of a vibrationally structured phosphorescence emission of benzophenone in the case where ethanol was used for sample preparation, while a nonstructured emission of benzophenone exists when water was used instead of ethanol. The decay times of the benzophenone emission vary greatly with the solvent used for sample preparation and do not change with the alkylation degree in the range of 1500–1700 micromoles of alkyl chains per gram of cellulose. When water was used as a solvent for sample preparation, the shortest lifetime for the benzophenone emission was observed; this result is similar to the case of benzophenone adsorbed onto the “normal” microcrystalline cellulose surface, with this latter case previously reported by Vieira Ferreira et al. in 1995. This is due to the more efficient hydrogen abstraction reaction from the glycoside rings of cellulose when compared with hydrogen abstraction from the alkyl chains of the modified celluloses. Triplet-triplet transient absorption of benzophenone was obtained in both cases and is the predominant absorption immediately after laser pulse, while benzophenone ketyl radical formation occurs in a microsecond time scale both for normal and modified celluloses.

  11. Computer-aided solvent screening for biocatalysis

    NARCIS (Netherlands)

    Abildskov, J.; Leeuwen, van M.B.; Boeriu, C.G.; Broek, van den L.A.M.

    2013-01-01

    A computer-aidedsolventscreening methodology is described and tested for biocatalytic systems composed of enzyme, essential water and substrates/products dissolved in a solvent medium, without cells. The methodology is computationally simple, using group contribution methods for calculating

  12. Computer-Aided Solvent Screening for Biocatalysis

    DEFF Research Database (Denmark)

    Abildskov, Jens; Leeuwen, M.B. van; Boeriu, C.G.

    2013-01-01

    constrained properties related to chemical reaction equilibrium, substrate and product solubility, water solubility, boiling points, toxicity and others. Two examples are provided, covering the screening of solvents for lipase-catalyzed transesterification of octanol and inulin with vinyl laurate...

  13. Green and Bio-Based Solvents.

    Science.gov (United States)

    Calvo-Flores, Francisco G; Monteagudo-Arrebola, María José; Dobado, José A; Isac-García, Joaquín

    2018-04-24

    Chemical reactions and many of the procedures of separation and purification employed in industry, research or chemistry teaching utilize solvents massively. In the last decades, with the birth of Green Chemistry, concerns about the employment of solvents and the effects on human health, as well as its environmental impacts and its dependence on non-renewable raw materials for manufacturing most of them, has drawn the attention of the scientific community. In this work, we review the concept of green solvent and the properties and characteristics to be considered green. Additionally, we discuss the different possible routes to prepare many solvents from biomass, as an alternative way to those methods currently applied in the petrochemical industry.

  14. Solvent induced supramolecular anisotropy in molecular gels

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Michael A., E-mail: mroger09@uoguelph.ca [Department of Food Science, University of Guelph, Guelph, Ontario, N3C3X9 (Canada); Corradini, Maria G. [Department of Food Science, University of Massachusetts Amherst, Amherst, MA, 01003 (United States); Emge, Thomas [Department of Chemistry and Biochemistry, Rutgers University, New Brunswick, NJ, 08901 (United States)

    2017-06-15

    Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

  15. Solvent induced supramolecular anisotropy in molecular gels

    International Nuclear Information System (INIS)

    Rogers, Michael A.; Corradini, Maria G.; Emge, Thomas

    2017-01-01

    Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

  16. [Chemical hazards when working with solvent glues].

    Science.gov (United States)

    Domański, Wojciech; Makles, Zbigniew

    2012-01-01

    Solvent glues are used in a wide variety of industries, e.g., textile, footwear and rubber. The problem of workers' exposure to solvent vapors is rarely tackled within the area of occupational safety and health in small and medium-sized enterprises. In order to assess exposure to solvents, organic solvents emitted by glues were identified in the samples of workplace air. The concentration of acetone, benzene, cyclohexane, ethylbenzene, n-hexane, methylcyclohexane, butyl acetate and toluene were determined. The obtained results evidenced the presence of cyclohexane, ethylbenzene, ethylcyclohexane, heptane, n-hexane, o-xylene, methylcyclohexane, methylcyclopentane, butyl acetate and toluene in workplace air. The concentration of those compounds in workplace air was low, usually below 0.15 of MAC. At some workstations the presence of benzene was also observed. Occupational risk was assessed at workstations where gluing took place. It showed that the risk at those workstations was medium or low.

  17. Hydrogen recovery by novel solvent systems

    Energy Technology Data Exchange (ETDEWEB)

    Shinnar, R.; Ludmer, Z.; Ullmann, A.

    1991-08-01

    The objective of this work is to develop a novel method for purification of hydrogen from coal-derived synthesis gas. The study involved a search for suitable mixtures of solvents for their ability to separate hydrogen from the coal derived gas stream in significant concentration near their critical point of miscibility. The properties of solvent pairs identified were investigated in more detail to provide data necessary for economic evaluation and process development.

  18. Occupational exposure to solvents and bladder cancer

    DEFF Research Database (Denmark)

    Hadkhale, Kishor; Martinsen, Jan Ivar; Weiderpass, Elisabete

    2017-01-01

    The objective of the study was to assess the relationship between exposure to selected solvents and the risk of bladder cancer. This study is based on the Nordic Occupational Cancer (NOCCA) database and comprises 113,343 cases of bladder cancer diagnosed in Finland, Iceland, Norway and Sweden...... of occupational exposure to trichloroethylene, perchloroethylene, aromatic hydrocarbon solvents, benzene and toluene and the risk of bladder cancer....

  19. Accounting for Independent Schools.

    Science.gov (United States)

    Sonenstein, Burton

    The diversity of independent schools in size, function, and mode of operation has resulted in a considerable variety of accounting principles and practices. This lack of uniformity has tended to make understanding, evaluation, and comparison of independent schools' financial statements a difficult and sometimes impossible task. This manual has…

  20. Independence of Internal Auditors.

    Science.gov (United States)

    Montondon, Lucille; Meixner, Wilda F.

    1993-01-01

    A survey of 288 college and university auditors investigated patterns in their appointment, reporting, and supervisory practices as indicators of independence and objectivity. Results indicate a weakness in the positioning of internal auditing within institutions, possibly compromising auditor independence. Because the auditing function is…

  1. Hazardous Solvent Substitution Data System reference manual

    International Nuclear Information System (INIS)

    Branham-Haar, K.A.; Twitchell, K.E.

    1993-07-01

    Concern for the environment, in addition to Federal regulation, mandate the replacement of hazardous solvents with safer cleaning agents. Manufacturers are working to produce these replacement solvents. As these products are developed, potential users need to be informed of their availability. To promote the use of these new products instead of traditional solvents, the Idaho National Engineering Laboratory (INEL) has developed the Hazardous Solvent Substitution Data System (HSSDS). The HSSDS provides a comprehensive system of information on alternatives to hazardous solvents and related subjects, and it makes that information available to solvent users, industrial hygienists, and process engineers. The HSSDS uses TOPIC reg-sign, a text retrieval system produced by Verity, Inc., to allow a user to search for information on a particular subject. TOPIC reg-sign produces a listing of the retrieved documents and allows the use to examine the documents individually and to use the information contained in them. This reference manual does not replace the comprehensive TOPIC reg-sign user documentation (available from Verity, Inc.), or the HSSDS Tutorial (available from the INEL). The purpose of this reference manual is to provide enough instruction on TOPIC reg-sign so the user may begin accessing the data contained in the HSSDS

  2. Microencapsulation of advanced solvents for carbon capture.

    Science.gov (United States)

    Stolaroff, Joshuah K; Ye, Congwang; Oakdale, James S; Baker, Sarah E; Smith, William L; Nguyen, Du T; Spadaccini, Christopher M; Aines, Roger D

    2016-10-20

    Purpose-designed, water-lean solvents have been developed to improve the energy efficiency of CO 2 capture from power plants, including CO 2 -binding organic liquids (CO 2 BOLs) and ionic liquids (ILs). Many of these solvents are highly viscous or change phases, posing challenges for conventional process equipment. Such problems can be overcome by encapsulation. Micro-Encapsulated CO 2 Sorbents (MECS) consist of a CO 2 -absorbing solvent or slurry encased in spherical, CO 2 -permeable polymer shells. The resulting capsules have diameters in the range of 100-600 μm, greatly increasing the surface area and CO 2 absorption rate of the encapsulated solvent. Encapsulating these new solvents requires careful selection of shell materials and fabrication techniques. We find several common classes of polymers are not compatible with MECS production, but we develop two custom formulations, a silicone and an acrylate, that show promise for encapsulating water-lean solvents. We make the first demonstration of an encapsulated IL for CO 2 capture. The rate of CO 2 absorption is enhanced by a factor of 3.5 compared to a liquid film, a value that can be improved by further development of shell materials and fabrication techniques.

  3. Caustic-Side Solvent Extraction: Chemical and Physical Properties of the Optimized Solvent

    Energy Technology Data Exchange (ETDEWEB)

    Delmau, L.H.

    2002-10-08

    This work was undertaken to optimize the solvent used in the Caustic Side Solvent Extraction (CSSX) process and to measure key chemical and physical properties related to its performance in the removal of cesium from the alkaline high-level salt waste stored in tanks at the Savannah River Site. The need to adjust the solvent composition arose from the prior discovery that the previous baseline solvent was supersaturated with respect to the calixarene extractant. The following solvent-component concentrations in Isopar{reg_sign} L diluent are recommended: 0.007 M calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) extractant, 0.75 M 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs-7SB) phase modifier, and 0.003 M tri-n-octylamine (TOA) stripping aid. Criteria for this selection included BOBCalixC6 solubility, batch cesium distribution ratios (D{sub Cs}), calculated flowsheet robustness, third-phase formation, coalescence rate (dispersion numbers), and solvent density. Although minor compromises within acceptable limits were made in flowsheet robustness and solvent density, significant benefits were gained in lower risk of third-phase formation and lower solvent cost. Data are also reported for the optimized solvent regarding the temperature dependence of D{sub Cs} in extraction, scrubbing, and stripping (ESS); ESS performance on recycle; partitioning of BOBCalixC6, Cs-7SB, and TOA to aqueous process solutions; partitioning of organic anions; distribution of metals; solvent phase separation at low temperatures; solvent stability to elevated temperatures; and solvent density and viscosity. Overall, the technical risk of the CSSX process has been reduced by resolving previously identified issues and raising no new issues.

  4. Cl2O photochemistry: ultraviolet/vis absorption spectrum temperature dependence and O(3P) quantum yield at 193 and 248 nm.

    Science.gov (United States)

    Papanastasiou, Dimitrios K; Feierabend, Karl J; Burkholder, James B

    2011-05-28

    The photochemistry of Cl(2)O (dichlorine monoxide) was studied using measurements of its UV/vis absorption spectrum temperature dependence and the O((3)P) atom quantum yield, Φ(Cl(2)O)(O)(λ), in its photolysis at 193 and 248 nm. The Cl(2)O UV/vis absorption spectrum was measured over the temperature range 201-296 K between 200 and 500 nm using diode array spectroscopy. Cl(2)O absorption cross sections, σ(Cl(2)O)(λ,T), at temperatures <296 K were determined relative to its well established room temperature values. A wavelength and temperature dependent parameterization of the Cl(2)O spectrum using the sum of six Gaussian functions, which empirically represent transitions from the ground (1)A(1) electronic state to excited states, is presented. The Gaussian functions are found to correlate well with published theoretically calculated vertical excitation energies. O((3)P) quantum yields in the photolysis of Cl(2)O at 193 and 248 nm were measured using pulsed laser photolysis combined with atomic resonance fluorescence detection of O((3)P) atoms. O((3)P) quantum yields were measured to be 0.85 ± 0.15 for 193 nm photolysis at 296 K and 0.20 ± 0.03 at 248 nm, which was also found to be independent of temperature (220-352 K) and pressure (17 and 28 Torr, N(2)). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. ClO radical temporal profiles obtained following the photolysis of Cl(2)O at 248 nm, as reported previously in Feierabend et al. [J. Phys. Chem. A 114, 12052, (2010)], were interpreted to establish a <5% upper-limit for the O + Cl(2) photodissociation channel, which indicates that O((3)P) is primarily formed in the three-body, O + 2Cl, photodissociation channel at 248 nm. The analysis also indirectly provided a Cl atom quantum yield of 1.2 ± 0.1 at 248 nm. The results from this work are compared with previous studies where possible. © 2011 American Institute of Physics

  5. PSE For Solvent Applications: A Generic Computer-aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sin, Gürkan; Gani, Rafiqul

    Solvents are widely used across a number of industries in many applications such as separation agents, reaction mediums, cleaning agents and product carriers. Selection of optimal solvents in these applications is mostly based on previous experiences and experimental trial and error. A process sy...... group contributionplus models for pure component and mixture property predictions that allow the selection and design of innovative solvent based processes and products. The application of the framework is highlighted with a number of solvent selection problems from industry.......Solvents are widely used across a number of industries in many applications such as separation agents, reaction mediums, cleaning agents and product carriers. Selection of optimal solvents in these applications is mostly based on previous experiences and experimental trial and error. A process...... industry (API solubility), solvents i! ! n formulations and as cleaning agents. The template is expected to guide the average user through the essential and desirable steps in solvent selection and design. The expert may also use the general interface and create their own template for the types of solvent...

  6. Effect of Organic Solvents on the Yield of Solvent-Tolerant Pseudomonas putida S12

    Science.gov (United States)

    Isken, Sonja; Derks, Antoine; Wolffs, Petra F. G.; de Bont, Jan A. M.

    1999-01-01

    Solvent-tolerant microorganisms are useful in biotransformations with whole cells in two-phase solvent-water systems. The results presented here describe the effects that organic solvents have on the growth of these organisms. The maximal growth rate of Pseudomonas putida S12, 0.8 h−1, was not affected by toluene in batch cultures, but in chemostat cultures the solvent decreased the maximal growth rate by nearly 50%. Toluene, ethylbenzene, propylbenzene, xylene, hexane, and cyclohexane reduced the biomass yield, and this effect depended on the concentration of the solvent in the bacterial membrane and not on its chemical structure. The dose response to solvents in terms of yield was linear up to an approximately 200 mM concentration of solvent in the bacterial membrane, both in the wild type and in a mutant lacking an active efflux system for toluene. Above this critical concentration the yield of the wild type remained constant at 0.2 g of protein/g of glucose with increasing concentrations of toluene. The reduction of the yield in the presence of solvents is due to a maintenance higher by a factor of three or four as well as to a decrease of the maximum growth yield by 33%. Therefore, energy-consuming adaptation processes as well as the uncoupling effect of the solvents reduce the yield of the tolerant cells. PMID:10347053

  7. Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.V.

    2002-06-26

    The purpose of this investigation was to determine whether nitrated organic compounds could be formed during operation of the Caustic-Side Solvent Extraction (CSSX) process, and whether such compounds would present a safety concern. The CSSX process was developed to remove cesium from alkaline high-level salt waste stored at the US Department of Energy Savannah River Site (SRS). The solvent is composed of the cesium extractant calix[4]arene-bis-(4-tert-octylbenzo-crown-6) (BOBCalixC6), a fluorinated alcohol phase modifier, tri-n-octylamine (TOA), and an isoparaffinic diluent (Iospar{reg_sign}). During the CSSX process, the solvent is expected to be exposed to high concentrations of nitrate and nitrite dissolved in the alkaline waste feed. The solvent will also be exposed to dilute (50 mM) nitric acid solutions containing low concentrations of nitrite during scrubbing, followed by stripping with 1 mM nitric acid. The solvent is expected to last for one year of plant operation, and the temperatures the solvent may experience during the process could range from as low as 15 C to as high as 35 C. Excursions from standard process conditions could result in the solvent experiencing higher temperatures, as well as concentrations of nitrate, nitrite, and most importantly nitric acid, that exceed normal operating conditions. Accordingly, conditions may exist where nitration reactions involving the solvent components, possibly leading to other chemical reactions stemming from nitration reactions, could occur. To model such nitration reactions, the solvent was exposed to the types of nitrate- and nitrite-containing solutions that might be expected to be encountered during the process (even under off-normal conditions), as a function of time, temperature, and concentration of nitrate, nitrite, and nitric acid. The experiments conducted as part of this report were designed to examine the more specific effect that high nitrite concentrations could have on forming nitrated

  8. Probabilistic conditional independence structures

    CERN Document Server

    Studeny, Milan

    2005-01-01

    Probabilistic Conditional Independence Structures provides the mathematical description of probabilistic conditional independence structures; the author uses non-graphical methods of their description, and takes an algebraic approach.The monograph presents the methods of structural imsets and supermodular functions, and deals with independence implication and equivalence of structural imsets.Motivation, mathematical foundations and areas of application are included, and a rough overview of graphical methods is also given.In particular, the author has been careful to use suitable terminology, and presents the work so that it will be understood by both statisticians, and by researchers in artificial intelligence.The necessary elementary mathematical notions are recalled in an appendix.

  9. Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Neta, P.

    1995-02-01

    The pulse radiolysis technique is applied to the study of electron transfer processes in a variety of chemical systems. Reactive intermediates are produced in solution by electron pulse irradiation and the kinetics of their reactions are followed by time resolved absorption spectrophotometry. Complementary experiments are carried out with excimer laser flash photolysis. These studies are concerned with mechanisms, kinetics, and thermodynamics of reactions of organic and inorganic radicals and unstable oxidation states of metal ions. Reactions are studied in both aqueous and non-aqueous solutions. The studies focus on the unique ability of pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, species that are key intermediates in many chemical processes. A special concern of this work is the study of electron transfer reactions of metalloporphyrins, which permits evaluation of these molecules as intermediates in solar energy conversion. Metalloporphyrins react with free radicals via electron transfer, involving the ligand or the metal center, or via bonding to the metal, leading to a variety of chemical species whose behavior is also investigated. The highlights of the results during the past three years are summarized below under the following sections: (a) electron transfer reactions of peroxyl radicals, concentrating on the characterization of new peroxyl radicals derived from vinyl, phenyl, other aryl, and pyridyl; (b) solvent effects on electron transfer reactions of inorganic and organic peroxyl radicals, including reactions with porphyrins, and (c) electron transfer and alkylation reactions of metalloporphyrins and other complexes.

  10. Photochemistry of phenyl alkyl ketones. The lifetime of the intermediate biradicals

    International Nuclear Information System (INIS)

    Small, R.D. Jr.; Scalano, J.C.

    1977-01-01

    The lifetimes of a number of biradicals produced in the photochemical Norrish type II reaction of phenyl alkyl ketones have been measured. The decay of the biradicals was followed by monitoring the competition with electron transfer to paraquat dications using nanosecond laser techniques. The lifetimes are rather insensitive to changes in temperature, substitution, and solvent, and are typically in the neighborhood of 100 ns. It is concluded that intersystem crossing is the main factor determining the biradical lifetimes. The rate constant for electron transfer to paraquat dications is 3.7 x 10 9 M -1 s -1 in methanol at room temperature for 1,4-ketyl--alkyl biradicals, and considerably higher for diketyl biradicals, apparently reflecting a change in path degeneracy. Oxygen behaves as a biradical scavenger with a rate constant of 6.2 x 10 9 M -1 s -1 in methanol. The lifetimes of the excited ketone triplets have also been determined at room temperature under the experimental conditions employed; this is an important parameter in determining the viability of the measurements of biradical lifetimes by this technique

  11. New Polymeric Membranes for Organic Solvent Nanofiltration

    KAUST Repository

    Aburabie, Jamaliah

    2017-05-01

    The focus of this dissertation was the development, synthesis and modification of polymers for the preparation of membranes for organic solvent nanofiltration. High chemical stability in a wide range of solvents was a key requirement. Membranes prepared from synthesized polymers as well as from commercial polymers were designed and chemically modified to reach OSN requirements. A solvent stable thin-film composite (TFC) membrane is reported, which is fabricated on crosslinked polythiosemicarbazide (PTSC) as substrate. The membranes exhibited high fluxes towards solvents like THF, DMF and DMSO ranging around 20 L/m2 h at 5 bar with a MWCO of around 1000 g/mol. Ultrafiltration PTSC membranes were prepared by non-solvent induced phase separation and crosslinked with GPTMS. The crosslinking reaction was responsible for the formation of an inorganic-type-network that tuned the membrane pore size. The crosslinked membranes acquired high solvent stability in DMSO, DMF and THF with a MWCO above 1300 g/mol. Reaction Induced Phase Separation (RIPS) was introduced as a new method for the preparation of skinned asymmetric membranes. These membranes have two distinctive layers with different morphologies both from the same polymer. The top dense layer is composed of chemically crosslinked polymer chains while the bottom layer is a porous structure formed by non-crosslinked polymer chains. Such membranes were tested for vitamin B12 in solvents after either crosslinking the support or dissolving the support and fixing the freestanding membrane on alumina. Pebax® 1657 was utilized for the preparation of composite membranes by simple coating. Porous PAN membranes were coated with Pebax® 1657 which was then crosslinked using TDI. Crosslinked Pebax® membranes show high stability towards ethanol, propanol and acetone. The membranes were also stable in DMF once crosslinked PAN supports were used. Sodium alginate polymer was investigated for the preparation of thin film composite

  12. Measurement and correlation of solubility of cefmenoxime hydrochloride in pure solvents and binary solvent mixtures

    International Nuclear Information System (INIS)

    Wang, Jinxiu; Xie, Chuang; Yin, Qiuxiang; Tao, Linggang; Lv, Jun; Wang, Yongli; He, Fang; Hao, Hongxun

    2016-01-01

    Highlights: • Solubility of cefmenoxime hydrochloride in pure and binary solvents was determined. • The experimental solubility data were correlated by thermodynamic models. • A model was employed to calculate the melting temperature of cefmenoxime hydrochloride. • Mixing thermodynamic properties of cefmenoxime hydrochloride were calculated. - Abstract: The solubility of cefmenoxime hydrochloride in pure solvents and binary solvent mixtures was measured at temperatures from (283.15 to 313.15) K by using the UV spectroscopic method. The results reveal that the solubility of cefmenoxime hydrochloride increases with increasing temperature in all solvent selected. The solubility of cefmenoxime hydrochloride reaches its maximum value when the mole fraction of isopropanol is 0.2 in the binary solvent mixtures of (isopropanol + water). The modified Apelblat equation and the NRTL model were successfully used to correlate the experimental solubility in pure solvents while the modified Apelblat equation, the CNIBS/R–K model and the Jouyban–Acree model were applied to correlate the solubility in binary solvent mixtures. In addition, the mixing thermodynamic properties of cefmenoxime hydrochloride in different solvents were also calculated based on the NRTL model and experimental solubility data.

  13. Non-aqueous cleaning solvent substitution

    Science.gov (United States)

    Meier, Gerald J.

    1994-01-01

    A variety of environmental, safety, and health concerns exist over use of chlorinated and fluorinated cleaning solvents. Sandia National Laboratories, Lawrence Livermore National Laboratories, and the Kansas City Division of AlliedSignal have combined efforts to focus on finding alternative cleaning solvents and processes which are effective, environmentally safe, and compliant with local, state, and federal regulations. An alternative solvent has been identified, qualified, and implemented into production of complex electronic assemblies, where aqueous and semi-aqueous cleaning processes are not allowed. Extensive compatibility studies were performed with components, piece-parts, and materials. Electrical testing and accelerated aging were used to screen for detrimental, long-term effects. A terpene, d-limonene, was selected as the solvent of choice, and it was found to be compatible with the components and materials tested. A brief history of the overall project will be presented, along with representative cleaning efficiency results, compatibility results, and residual solvent data. The electronics industry is constantly searching for proven methods and environmentally-safe materials to use in manufacturing processes. The information in this presentation will provide another option to consider on future projects for applications requiring high levels of quality, reliability, and cleanliness from non-aqueous cleaning processes.

  14. Ions, solutes and solvents, oh my!

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Daniel David [Iowa State Univ., Ames, IA (United States)

    2009-08-01

    Modern methods in ab initio quantum mechanics have become efficient and accurate enough to study many gas-phase systems. However, chemists often work in the solution phase. The presence of solvent molecules has been shown to affect reaction mechanisms1, lower reaction energy barriers2, participate in energy transfer with the solute3 and change the physical properties of the solute4. These effects would be overlooked in simple gas phase calculations. Careful study of specific solvents and solutes must be done in order to fully understand the chemistry of the solution phase. Water is a key solvent in chemical and biological applications. The properties of an individual water molecule (a monomer) and the behavior of thousands of molecules (bulk solution) are well known for many solvents. Much is also understood about aqueous microsolvation (small clusters containing ten water molecules or fewer) and the solvation characteristics when bulk water is chosen to solvate a solute. However, much less is known about how these properties behave as the cluster size transitions from the microsolvated cluster size to the bulk. This thesis will focus on species solvated with water clusters that are large enough to exhibit the properties of the bulk but small enough to consist of fewer than one hundred solvent molecules. New methods to study such systems will also be presented.

  15. 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.

  16. Solvent-dependent assembly of terphenyl- and quaterphenyldithiol on gold and gallium arsenide.

    Science.gov (United States)

    Krapchetov, Dmitry A; Ma, Hong; Jen, Alex K Y; Fischer, Daniel A; Loo, Yueh-Lin

    2005-06-21

    The assembly of terphenyldithiol (TPDT) and quaterphenyldithiol (QPDT) on gold and gallium arsenide from ethanol (EtOH), tetrahydrofuran (THF), and solutions consisting of both solvents has been characterized by near-edge X-ray absorption fine structure spectroscopy. The surface coverage and the average orientation of both TPDT and QPDT on gold are solvent-independent. These molecules readily form monolayers on gold with an ensemble-average backbone tilt of 30 degrees +/- 3 degrees from the substrate normal. In sharp contrast, the assembly of TPDT and QPDT on gallium arsenide is extremely solvent-sensitive. At high ethanol fractions, both molecules form monolayers with an ensemble-average orientation that is indistinguishable from those on gold substrates. At low ethanol fractions and in pure THF, however, these molecules are disordered on gallium arsenide and the surface coverage is poor.

  17. Recommended methods for purification of solvents and tests for impurities

    CERN Document Server

    Coetzee, J F

    1982-01-01

    Recommended Methods for Purification of Solvents and Tests for Impurities is a compilation of recommended procedures for purification of solvents and tests for solvent impurities. Ten solvents are covered: acetonitrile, sulfolane, propylene carbonate, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoramide, pyridine, ethylenediamine, N-methylacetamide, and N-methylpropionamide. This book is comprised of 12 chapters and opens with an introduction to general aspects of impurity effects. The rationale for the selection of solvent is explained, and the relative reactivities of solutes in di

  18. Green solvents and technologies for oil extraction from oilseeds

    OpenAIRE

    Kumar, S. P. Jeevan; Prasad, S. Rajendra; Banerjee, Rintu; Agarwal, Dinesh K.; Kulkarni, Kalyani S.; Ramesh, K. V.

    2017-01-01

    Oilseeds are crucial for the nutritional security of the global population. The conventional technology used for oil extraction from oilseeds is by solvent extraction. In solvent extraction, n-hexane is used as a solvent for its attributes such as simple recovery, non-polar nature, low latent heat of vaporization (330?kJ/kg) and high selectivity to solvents. However, usage of hexane as a solvent has lead to several repercussions such as air pollution, toxicity and harmfulness that prompted to...

  19. 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.

  20. Hazardous Solvent Substitution Data System tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC{reg_sign} to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications.

  1. Diluent degradation products in the Purex solvent

    International Nuclear Information System (INIS)

    Neace, J.C.

    1983-08-01

    A number of laboratory tests were conducted in which various impurities, known to be present in degraded Purex solvent, were injected into fresh solvent samples and the effects of these impurities tested in an operating miniature pulse column and in batch contactors. Common fission product elements which interfere in the Purex process were spiked with radiotracers and added to the aqueous phase samples with which the test solvents were contacted. Process controls and blanks were used to verify test data. Periodically, samples of the organic phase were withdrawn for analyses by radiochemical means. From the data obtained, a number of theories were postulated on the mechanisms by which diluent degradation products interfere in the Purex process

  2. Hazardous Solvent Substitution Data System tutorial

    International Nuclear Information System (INIS)

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC reg-sign to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications

  3. Alternative Solvents through Green Chemistry Project

    Science.gov (United States)

    Hintze, Paul E.; Quinn, Jacqueline

    2014-01-01

    Components in the aerospace industry must perform with accuracy and precision under extreme conditions, and surface contamination can be detrimental to the desired performance, especially in cases when the components come into contact with strong oxidizers such as liquid oxygen. Therefore, precision cleaning is an important part of a components preparation prior to utilization in aerospace applications. Current cleaning technologies employ a variety of cleaning agents, many of which are halogenated solvents that are either toxic or cause environmental damage. Thus, this project seeks to identify alternative precision cleaning solvents and technologies, including use of less harmful cleaning solvents, ultrasonic and megasonic agitation, low-pressure plasma cleaning techniques, and supercritical carbon dioxide extraction. Please review all data content found in the Public Data tab located at: https:techport.nasa.govview11697public

  4. Solvent extraction studies on cadmium Pt. 1

    International Nuclear Information System (INIS)

    Alian, A.; El-Kot, A.; Badran, A.; El-Bassiouny, M.S.

    1975-01-01

    An extraction study was performed on tracer concentrations of cadmium halides in absence and presence of sulphuric acid. Inert solvents, nitrobenzene, a long chain amine (Amberlite LA-2) and organophosphorus solvents (TBP and HDEHP) have been investigated. The comparative stability of cadmium chloride and bromide TBP solvates were determined. The presence of sulphuric acid was found to enhance considerably the extraction of cadmium halides by nitrobenzene, Amberlite LA-2 and TBP. The mechanism of extraction has been discussed in light of the obtained results. The systems studied involved halide ions (Cl, Br and I), sulphuric and phosphoric acids. In these systems extraction was negligible for all nonpolar solvents, considerable for nitrobenzene and very high for Amberlite LA-2 and TBP. Work has been carried out for both micro and macro scales in case of sulphuric acid system, and only for the microscale in case of phosphoric acid system, because of the limited solubility of cadmium phosphate in aqueous solutions. (T.G.)

  5. Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

    Energy Technology Data Exchange (ETDEWEB)

    Bromberg, S.E.

    1998-05-01

    When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scan FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.

  6. 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.

  7. Distro’: Independent Creativity for Independent Industr

    Directory of Open Access Journals (Sweden)

    Wiwik Sri Wulandari

    2014-11-01

    Full Text Available To shortened this introduction, ‘Distro’ is one of cultural phenomenon in theyoung generation nowadays. The word of ‘Distro’ is the shortened of DistributionOutlet. The phenomenon of ‘Distro’ has been some kind of new trends inproducing and distributing creative design products of goods amongst theyoungsters independently, in an independence industry that open for challengingand competitiveness for everyone. This field research has been done in the city ofYogyakarta, reknown as the second city in creative design products after the cityof Bandung. Yogyakarta is welknown as the students’ city as well as the capital cityof culture of Indonesia. As a students’ city it is normal that Yogyakarta is growingin numbers of young people who pursued to study here and enriched the cultureof the city to become more multicultural and the varieties of pluralism as well.This sociocultural phenomenon not only brought some dynamic changing tosociety, economy and cultural life of the city, but also social problems that needsto be overcome. My first research question then is about how the existence of‘Distro’ in Yogyakarta can be a positive answer for social problems that may arisesfrom the hegemony of globalization markets domestically? My second questionis how the creative product designs are being made and distributed creatively inindependent industry? Lastly, my third question is dealling with the genres ofthe design products and how it can be a new trend in art expression? ‘Distro’ is aproduct of culture and it is also creating cultural change in some aspects of the lifeof the youngsters who are ‘Distro’ enthusiasts. ‘Distro’ phenomenon basically is anoffensive to the hegemony of internationally branded product design which turnsto become more over-dominated to the domestic markets and industry and thus,‘Distro’ has the spirit of survival whilts at the same time producing opportunity ofenterpreneurship

  8. Solvent-resistant microporous polymide membranes

    Science.gov (United States)

    Miller, Warren K.; McCray, Scott B.; Friesen, Dwayne T.

    1998-01-01

    An asymmetric microporous membrane with exceptional solvent resistance and highly desirable permeability is disclosed. The membrane is made by a solution-casting or solution-spinning process from a copolyamic acid comprising the condensation reaction product in a solvent of at least three reactants selected from certain diamines and dianhydrides and post-treated to imidize and in some cases cross-link the copolyamic acid. The membrane is useful as an uncoated membrane for ultrafiltration, microfiltration, and membrane contactor applications, or may be used as a support for a permselective coating to form a composite membrane useful in gas separations, reverse osmosis, nanofiltration, pervaporation, or vapor permeation.

  9. NMR spectroscopy using liquid crystal solvents

    CERN Document Server

    Emsley, JW

    2013-01-01

    NMR Spectroscopy using Liquid Crystal Solvents covers the importance of using a liquid crystal solvent in NMR to derive nuclear dipolar spin-spin coupling constants. This book is composed of ten chapters, and begins with a brief description of the features and benefits of liquid crystal in NMR spectroscopic analysis. The succeeding chapters deal with the mode of operation of nuclear spin Hamiltonian for partially oriented molecules and the analysis of NMR spectra of partially oriented molecules, as well as the determination of rigid molecule structure. These topics are followed by discussions

  10. Solvent-free fluidic organic dye lasers.

    Science.gov (United States)

    Choi, Eun Young; Mager, Loic; Cham, Tran Thi; Dorkenoo, Kokou D; Fort, Alain; Wu, Jeong Weon; Barsella, Alberto; Ribierre, Jean-Charles

    2013-05-06

    We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.

  11. Independent technical review, handbook

    Energy Technology Data Exchange (ETDEWEB)

    1994-02-01

    Purpose Provide an independent engineering review of the major projects being funded by the Department of Energy, Office of Environmental Restoration and Waste Management. The independent engineering review will address questions of whether the engineering practice is sufficiently developed to a point where a major project can be executed without significant technical problems. The independent review will focus on questions related to: (1) Adequacy of development of the technical base of understanding; (2) Status of development and availability of technology among the various alternatives; (3) Status and availability of the industrial infrastructure to support project design, equipment fabrication, facility construction, and process and program/project operation; (4) Adequacy of the design effort to provide a sound foundation to support execution of project; (5) Ability of the organization to fully integrate the system, and direct, manage, and control the execution of a complex major project.

  12. Independent technical review, handbook

    International Nuclear Information System (INIS)

    1994-02-01

    Purpose Provide an independent engineering review of the major projects being funded by the Department of Energy, Office of Environmental Restoration and Waste Management. The independent engineering review will address questions of whether the engineering practice is sufficiently developed to a point where a major project can be executed without significant technical problems. The independent review will focus on questions related to: (1) Adequacy of development of the technical base of understanding; (2) Status of development and availability of technology among the various alternatives; (3) Status and availability of the industrial infrastructure to support project design, equipment fabrication, facility construction, and process and program/project operation; (4) Adequacy of the design effort to provide a sound foundation to support execution of project; (5) Ability of the organization to fully integrate the system, and direct, manage, and control the execution of a complex major project

  13. Influence of solvent on temperature and thermal peak broadening in capillary zone electrophoresis.

    Science.gov (United States)

    Porras, Simo P; Marziali, Ettore; Gas, Bohuslav; Kenndler, Ernst

    2003-05-01

    carried out with solutions of the same initial electric conductivity (about 0.5 S.m(-1) at 25.0 degrees C). Agreement is found for natural convection conditions, and the deviation between theoretical and experimental results for the forced air and circulated liquid cooling systems can be related to the poorly defined thermal conditions of the capillaries in commercial instrumentation (with a part in a thermostated cassette and a part outside). For given conditions the temperature gradients in the organic solvents exceed largely those in water, independent of the type of cooling. As a consequence, the thermal plate height is significantly larger in organic solvents, at least under conditions where the deviation from the Nernst-Einstein limiting case is not too high. However, even for the maximum applicable field strengths the thermal plate height contributions are negligible compared to longitudinal diffusion in all solvents.

  14. Next Generation Solvent Performance in the Modular Caustic Side Solvent Extraction Process - 15495

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Tara E. [Savannah River Remediation, LLC., Aiken, SC (United States); Scherman, Carl [Savannah River Remediation, LLC., Aiken, SC (United States); Martin, David [Savannah River Remediation, LLC., Aiken, SC (United States); Suggs, Patricia [Savannah River Site (SRS), Aiken, SC (United States)

    2015-01-14

    Changes to the Modular Caustic Side Solvent Extraction Unit (MCU) flow-sheet were implemented in the facility. Implementation included changing the scrub and strip chemicals and concentrations, modifying the O/A ratios for the strip, scrub, and extraction contactor banks, and blending the current BoBCalixC6 extractant-based solvent in MCU with clean MaxCalix extractant-based solvent. During the successful demonstration period, the MCU process was subject to rigorous oversight to ensure hydraulic stability and chemical/radionuclide analysis of the key process tanks (caustic wash tank, solvent hold tank, strip effluent hold tank, and decontaminated salt solution hold tank) to evaluate solvent carryover to downstream facilities and the effectiveness of cesium removal from the liquid salt waste. Results indicated the extraction of cesium was significantly more effective with an average Decontamination Factor (DF) of 1,129 (range was 107 to 1,824) and that stripping was effective. The contactor hydraulic performance was stable and satisfactory, as indicated by contactor vibration, contactor rotational speed, and flow stability; all of which remained at or near target values. Furthermore, the Solvent Hold Tank (SHT) level and specific gravity was as expected, indicating that solvent integrity and organic hydraulic stability were maintained. The coalescer performances were in the range of processing results under the BOBCalixC6 flow sheet, indicating negligible adverse impact of NGS deployment. After the Demonstration period, MCU began processing via routine operations. Results to date reiterate the enhanced cesium extraction and stripping capability of the Next Generation Solvent (NGS) flow sheet. This paper presents process performance results of the NGS Demonstration and continued operations of MCU utilizing the blended BobCalixC6-MaxCalix solvent under the NGS flowsheet.

  15. All Those Independent Variables.

    Science.gov (United States)

    Meacham, Merle L.

    This paper presents a case study of a sixth grade remedial math class which illustrates the thesis that only the "experimental attitude," not the "experimental method," is appropriate in the classroom. The thesis is based on the fact that too many independent variables exist in a classroom situation to allow precise measurement. The case study…

  16. Independence of the judiciary

    Directory of Open Access Journals (Sweden)

    Arjana LLANO

    2013-12-01

    Full Text Available There are many factors which influence the independence of the judiciary. In a decision making process, judges, at any rate, must be able to act independently of any direct or indirect restriction, improper influence, inducement, pressure, threatening or obstacle. The law should provide explicit punishment measures against anyone who tries to impose any of the above means upon the judges. Any judge should possess the inviolable freedom of judging impartially, by his/her consciousness and interpretation, and pursuant to law. However, this is often impossible for judges are frequently put under various pressures that should be avoided. I have employed theoretical and practical methods for the purposes of this article. In conclusion, the research results have shown a heavy infringement of the independence of the judiciary in our country. There is a quite frequent tendency to influence the judges’ decisions. Common violations of law and judicial independence, to a large extent, remain unnoticed and unpunished. A considerable number of judges think that such tendencies have no significant influence on the management of justice.

  17. INDEPENDENT AND GROUP LEARNING.

    Science.gov (United States)

    DICKINSON, MARIE B.

    IN CONTRAST TO THE TRADITIONAL EMPHASES ON ROTE LEARNING AND FACT ACCUMULATION, RECENT TRENDS EMERGING FROM EDUCATIONAL RESEARCH STRESS THE DEVELOPMENT OF THINKING PROCESSES SUCH AS THE ABILITY TO REASON ABSTRACTLY AND TO SYNTHESIZE. CHILDREN WORKING INDEPENDENTLY OR IN GROUPS MOVE THROUGH A DISCOVERY LEARNING CURRICULUM IN WHICH THE TEACHER…

  18. Independent for longer

    NARCIS (Netherlands)

    Cretien van Campen; Jurjen Iedema; Marjolein Broese van Groenou; Dorly Deeg

    2017-01-01

    Original title: Langer zelfstandig. The Dutch government's reform of long-term care is intended to reinforce the trend whereby older persons continue to live independently for longer and the need for admission to a care institution is avoided or delayed. Many Dutch citizens aged 65 years and

  19. Independence in appearance

    DEFF Research Database (Denmark)

    Warming-Rasmussen, Bent; Quick, Reiner; Liempd, Dennis van

    2011-01-01

    article presents research contributions to the question whether the auditor is to continue to provide both audit and non-audit services (NAS) to an audit client. Research results show that this double function for the same audit client is a problem for stakeholders' confidence in auditor independence...

  20. Rate independent Kurzweil processes

    Czech Academy of Sciences Publication Activity Database

    Krejčí, Pavel; Liero, M.

    2009-01-01

    Roč. 54, č. 2 (2009), s. 117-145 ISSN 0862-7940 Institutional research plan: CEZ:AV0Z10190503 Keywords : Kurzweil integral * rate independence Subject RIV: BA - General Mathematics Impact factor: 0.410, year: 2009 http://www.dml.cz/bitstream/handle/10338.dmlcz/140355/AplMat_54-2009-2_2.pdf

  1. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    International Nuclear Information System (INIS)

    Clark, Sue B.

    2016-01-01

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  2. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Sue B. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2016-10-31

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  3. Double Solvent for Extracting Rare Earth Concentrate

    International Nuclear Information System (INIS)

    Bintarti, AN; Bambang EHB

    2007-01-01

    An extraction process to rare earth concentrate which contain elements were yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), gadolinium (Gd) and dysprosium (Dy) which were dissolved in to nitric acid has been done. The experiment of the extraction by double solvent in batch to mix 10 ml of the feed with 10 ml solvent contained the pair of solvent was TBP and TOA, D2EHPA and TOA, TBP and D2EHPA in cyclohexane as tinner. It was selected a right pairs of solvent for doing variation such as the acidity of the feed from 2 - 6 M and the time of stirring from 5 - 25 minutes gave the good relatively extraction condition to Dy element such as using 10 % volume of TOA in D2EHPA and cyclohexane, the acidity of the feed 3 M and the time stirring 15 minutes produced coefficient distribution to dysprosium = 0.586 and separation factor Dy-Ce = ∼ (unlimited); Dy-Nd = 4.651. (author)

  4. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    asymmetric annulation reactions in a solid–liquid phase reaction in the absence of solvents to effect an asymmetric synthesis is an important step forward towards cleaner synthesis 2. Environmental and economic pressures are now forcing the chemical community to search for more efficient ways of performing chemical ...

  5. Deposition dynamics of multi-solvent bioinks

    Science.gov (United States)

    Kaneelil, Paul; Pack, Min; Cui, Chunxiao; Han, Li-Hsin; Sun, Ying

    2017-11-01

    Inkjet printing cellular scaffolds using bioinks is gaining popularity due to the advancement of printing technology as well as the growing demands of regenerative medicine. Numerous studies have been conducted on printing scaffolds of biomimetic structures that support the cell production of human tissues. However, the underlying physics of the deposition dynamics of bioinks remains elusive. Of particular interest is the unclear deposition dynamics of multi-solvent bioinks, which is often used to tune the micro-architecture formation. Here we systematically studied the effects of jetting frequency, solvent properties, substrate wettability, and temperature on the three-dimensional deposition patterns of bioinks made of Methacrylated Gelatin and Carboxylated Gelatin. The microflows inside the inkjet-printed picolitre drops were visualized using fluorescence tracer particles to decipher the complex processes of multi-solvent evaporation and solute self-assembly. The evolution of droplet shape was observed using interferometry. With the integrated techniques, the interplay of solvent evaporation, biopolymer deposition, and multi-drop interactions were directly observed for various ink and substrate properties, and printing conditions. Such knowledge enables the design and fabrication of a variety of tissue engineering scaffolds for potential use in regenerative medicine.

  6. Solvent (acetone-butanol: ab) production

    Science.gov (United States)

    This article describes production of butanol [acetone-butanol-ethanol, (also called AB or ABE or solvent)] by fermentation using both traditional and current technologies. AB production from agricultural commodities, such as corn and molasses, was an important historical fermentation. Unfortunately,...

  7. SOLVENT EFFECTS IN THE HYDROXIDE AND ALKOXIDE ...

    African Journals Online (AJOL)

    in purely aqueous medium, methanol and ethanol; and in a series of dioxane- methanol mixtures. The a scale of ... in the rationalization or correlation of solvent effects on reaction rates and activation parameters. ..... R.W. Taft, Jr., in "Ster'ic Effect in Organic Chemistry", M.S. Newman Ed._. Wiley, New York, N."!'., (1985'). I7.

  8. STUDIES ON SOLVENT EXTRACTION OF FREE HYDROGEN ...

    African Journals Online (AJOL)

    control were investigated to obtain an accurate and precise extraction method for the measurement of hydrogen cyanide in Kaduna River, Nigeria. ... KEY WORDS: Solvent extraction; Free hydrogen cyanide; River water ... inhibits over forty enzymes and important metallo-enzymes containing iron, copper, and molybdenum.

  9. Solvation free energies and solvent force constants

    International Nuclear Information System (INIS)

    Fonseca, T.; Ladanyi, B.M.; Hynes, J.T.

    1992-01-01

    A theoretical formulation for the solvent force constant k q , which gauges electrical potential fluctuations for an ion in solution and whose charge dependence is a measure of nonlinear aspects of solvation, is presented in terms of the solute charge (q) variation of the solvation free energy. This formulation allows the calculation of k q via integral equation theories. This is illustrated by a series of calculations for ionic solutes in model dipolar-quadrupolar solvents via the reference hypernetted chain (RHNC) integral equation approach. It is found that the q variation of k q can be comprehended in terms of the cooperative (or competing) contributions of the solvent dipole and quadrupole to the acceleration of the solvation free energy. By contrast, traditional notions of dielectric saturation prove to be of much less direct relevance, due in part to the importance of competing electrostriction effects. The formalism is also applied to available simulation and integral equation solvation free energy studies of aqueous ionic solvation to infer to behavior of k q . The extensions for the formalism to more complex solutes (e.g., ion pairs), to higher order fluctuations (e.g., electric field), and to the solvent frequency and effective mass are briefly indicated. 51 refs., 11 figs., 1 tab

  10. Mixed Solvent Reactive Recrystallization of Sodium Carbonate

    NARCIS (Netherlands)

    Gaertner, R.S.

    2005-01-01

    Investigation of the reactive recrystallization of trona (sodium sesquicarbonate) and sodium bicarbonate to sodium carbonate (soda) in a mixed solvent led to the design of several alternative, less energy consumptive, economically very attractive process routes for the production of soda from all

  11. Solvent-Free Synthesis of Chalcones

    Science.gov (United States)

    Palleros, Daniel R.

    2004-01-01

    The synthesis of twenty different chalcones in the absence of solvent is presented. The results indicated that out of the twenty different chalcones investigated seventeen can be obtained in a matter of minutes by mixing the corresponding benzaldehyde and acetophenone in the presence of solid NaOH in a mortar with pestle.

  12. Heavy oil recovery using solvents and explosives

    Energy Technology Data Exchange (ETDEWEB)

    Heath, L.J.; Johnson, F.S.; Miller, J.S.; Jones, R.A.; McMurtrie, W.D.

    1977-12-01

    Petroleum-recovery techniques are being developed for the many shallow, low-productivity, heavy-oil sand deposits in southeastern Kansas, southwestern Missouri, and northeastern Oklahoma. In 1971, laboratory flooding experiments were conducted to determine optimum field operating conditions for recovery of heavy oil. Concurrently the Research Center began a field experiment in Labette County, Kans., using a recovery method (SolFrac) that combines chemical-explosive fracturing, to create communication with solvent injection, to improve mobility. The general boundaries of heavy-oil deposits are reported, and the areal extent and general characteristics of the reservoir in Labette County are described. The fracturing, injection, and production techniques and the production results from the field experiment are described. About 14% of the solvent injected was not recovered and thus was lost to the formation. Roughly 27 percent of the oil-in-place within the five-spot interwell zone was recovered. Reinjection of the produced solvent-oil mixture was done on a limited basis. Not enough additional oil was picked up during recycling of the solvent to justify this procedure. 9 tables, 21 figures.

  13. 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.

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

    Science.gov (United States)

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

    2017-01-01

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

  15. Solution and Solid Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) Ultraviolet (UV) 229 nm Photochemistry.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Brinzer, Thomas; Asher, Sanford A

    2015-05-01

    We measured the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We also examined the photochemistry of RDX both in solution and solid states. RDX quickly photodegrades with a solution quantum yield of φ ~ 0.35 as measured by high-performance liquid chromatography (HPLC). New spectral features form over time during the photolysis of RDX, indicating photoproduct formation. The photoproduct(s) show stable DUVRR spectra at later irradiation times that allow standoff detection. In the solution-state photolysis, nitrate is a photoproduct that can be used as a signature for detection of RDX even after photolysis. We used high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) and gas chromatography mass spectrometry (GCMS) to determine some of the major solution-state photoproducts. X-ray photoelectron spectroscopy (XPS) was also used to determine photoproducts formed during solid-state RDX photolysis.

  16. A straightforward method of analysis for direct quantum dynamics: application to the photochemistry of a model cyanine.

    Science.gov (United States)

    Allan, Charlotte S M; Lasorne, Benjamin; Worth, Graham A; Robb, Michael A

    2010-08-26

    We present a new way of analyzing direct quantum dynamics simulations based on a Mulliken-type population analysis. This provides a straightforward interpretation of the wavepacket in much the same way as semiclassical trajectories are usually analyzed. The result can be seen as a coupled set of quantum trajectories. We apply this to the study of the photochemistry of a 12-atom model cyanine to explore possibilities for intelligent optimal control. The work presented here builds on previous semiclassical dynamics simulations [ Hunt , P. A. ; Robb , M. A. J. Am. Chem. Soc. 2005 , 127 , 5720 ]. Those calculations suggested that, by controlling the distribution of momentum components in the initial wavepacket, it should be possible to drive the system to a specific region of the conical intersection seam and ultimately control the product distribution. This was confirmed experimentally by optimal control methods [ Dietzek , B. ; Bruggemann , B. ; Pascher , T. ; Yartsev , A. J. Am. Chem. Soc. 2007 , 129 , 13014 ]. This paper aims to demonstrate this in a quantum dynamics context and give further insight into the conditions required for control. Our results show that directly addressing the trans-cis torsional modes is not efficient. Instead, one needs to decrease the momentum in the skeletal deformation coordinates to prompt radiationless decay near the minimum conical intersection at large twist angles.

  17. The long-term changes in summer-time photochemistry due to urban canopy induced meteorological forcing

    Science.gov (United States)

    Huszar, Peter; Karlicky, Jan; Bardachova, Tatsiana; Belda, Michal; Halenka, Tomas

    2017-04-01

    Urban surfaces are clearly distinguished from rural ones and represent a specific forcing on meteorological conditions resulting in higher temperatures (urban heat island - UHI), reduced wind speed, enhanced turbulence, reduced humidity etc. It is straightforward to expect that these effects have further impact on the chemistry over these surfaces. This study intends to evaluate the summertime changes in ozone photo-chemistry due to urban canopy meteorological effects using the regional climate model RegCM4 coupled to the CAMx chemistry transport model. Experiments cover the 2001-2010 period focusing on central Europe. In all experiments, emission are kept the same and only the individual elements of meteorological forcing are varied. The most important ones are considered: changes of temperature, horizontal wind and turbulence. The surface ozone response to the inclusion of urban induced temperature increase is, over urban centers, is rather negative. Decreased wind speeds further contribute to ozone reduction due to suppressed transport of NOx to the surrounding rural areas, which in turn, increases the titration. The enhanced vertical mixing however have a leading impact on ozone levels: stronger vertical eddy transport removes NOx from urban environment and thus supports ozone formation. The combined effect of the individual ones is an increase of ozone. As each of the urban induced meteorological effects (changes of temperature, wind, turbulence) have a clear daily cycle, we examined the daily cycle of the impact on ozone and its precursors as well, and, it is shown that different mechanism become important throughout the day.

  18. Gas separation by composite solvent-swollen membranes

    Science.gov (United States)

    Matson, Stephen L.; Lee, Eric K. L.; Friesen, Dwayne T.; Kelly, Donald J.

    1989-01-01

    There is disclosed a composite immobulized liquid membrane of a solvent-swollen polymer and a microporous organic or inorganic support, the solvent being at least one highly polar solvent containing at least one nitrogen, oxygen, phosphorous or sulfur atom, and having a boiling point of at least 100.degree. C. and a specified solubility parameter. The solvent or solvent mixture is homogeneously distributed through the solvent-swollen polymer from 20% to 95% by weight. The membrane is suitable for acid gas scrubbing and oxygen/nitrogen separation.

  19. Effect of solvent structure on election reactivity

    International Nuclear Information System (INIS)

    Maham, Y.; Freeman, G.R.

    1988-01-01

    The reactivity of solvated electrons (e s - ) with efficient (nitrobenzene, acetone) and inefficient (phenol, toluene) scavengers is affected greatly by the solvent composition in 2-propanol/water mixed solvents. 2-Propanol is the only secondary alcohol that is completely miscible with water. The variation of the nitrobenzene rate constant k 2 with solvent composition displays four viscosity zones, as in primary and tertiary alcohol/water mixtures. In zone (c), where the Stokes-Smoluchowski equation applies, the nitrobenzene k 2 values in the secondary alcohol/water mixtures are situated between those in the primary and tertiary alcohols, due to the relative values of the dielectric permittivity ε. The charge-dipole attraction energy varies at ε -1 . The two water-rich zones (c) and (d) are characterized by a large change of viscosity η and a small change in e s - solvation energy (trap depth) E r ; here k 2 for all the scavengers correlates with the inverse of the viscosity. In the two alcohol-rich zones (a) and (b) the change of η is small but that of E r is large; here k 2 of inefficient scavengers correlates with the inverse of E r , due to the difficulty of electron transfer out of deeper traps. Activation energies E 2 and entropies ΔS 2 ( double dagger) also show composition zone behaviour. The value of ΔS 2 ( double dagger) is more negative for less efficient scavengers; E 2 varies less and does not correlate with reactivity of E r . Electron transfer from solvent to inefficient scavenger is driven by solvent rearrangement around the reaction center, reflected in ΔS 2 ( double dagger)

  20. Solubility of daidzin in different organic solvents and (ethyl alcohol + water) mixed solvents

    International Nuclear Information System (INIS)

    Fan, Jie-Ping; Yang, Dan; Xu, Xiao-Kang; Guo, Xiao-Jie; Zhang, Xue-Hong

    2015-01-01

    Highlights: • The solubilities of daidzin were measured in various solvents. • The solubility data were correlated by three models. • The thermodynamic properties of the dissolution process were also determined. - Abstract: The solubility of daidzin in different organic solvents and (ethyl alcohol + water) mixed solvents was measured by high performance liquid chromatography (HPLC) analysis method from T = (283.2 to 323.2) K at atmosphere pressure. The results show that at higher temperature more daidzin dissolves, and moreover, the solubility increases with the ethyl alcohol mole fraction increase in the (ethyl alcohol + water) mixed solvents. The experimental solubility values were correlated by a simplified thermodynamic equation, λh equation and modified Apelblat equation. Based on the solubility of daidzin, the enthalpy and entropy of solution were also evaluated by van’t Hoff equation. The results illustrated that the dissolution process of daidzin is endothermic and entropy driven

  1. Bayesian Independent Component Analysis

    DEFF Research Database (Denmark)

    Winther, Ole; Petersen, Kaare Brandt

    2007-01-01

    In this paper we present an empirical Bayesian framework for independent component analysis. The framework provides estimates of the sources, the mixing matrix and the noise parameters, and is flexible with respect to choice of source prior and the number of sources and sensors. Inside the engine...... in a Matlab toolbox, is demonstrated for non-negative decompositions and compared with non-negative matrix factorization.......In this paper we present an empirical Bayesian framework for independent component analysis. The framework provides estimates of the sources, the mixing matrix and the noise parameters, and is flexible with respect to choice of source prior and the number of sources and sensors. Inside the engine...

  2. Quantum independent increment processes

    CERN Document Server

    Franz, Uwe

    2005-01-01

    This volume is the first of two volumes containing the revised and completed notes lectures given at the school "Quantum Independent Increment Processes: Structure and Applications to Physics". This school was held at the Alfried-Krupp-Wissenschaftskolleg in Greifswald during the period March 9 – 22, 2003, and supported by the Volkswagen Foundation. The school gave an introduction to current research on quantum independent increment processes aimed at graduate students and non-specialists working in classical and quantum probability, operator algebras, and mathematical physics. The present first volume contains the following lectures: "Lévy Processes in Euclidean Spaces and Groups" by David Applebaum, "Locally Compact Quantum Groups" by Johan Kustermans, "Quantum Stochastic Analysis" by J. Martin Lindsay, and "Dilations, Cocycles and Product Systems" by B.V. Rajarama Bhat.

  3. Quantum independent increment processes

    CERN Document Server

    Franz, Uwe

    2006-01-01

    This is the second of two volumes containing the revised and completed notes of lectures given at the school "Quantum Independent Increment Processes: Structure and Applications to Physics". This school was held at the Alfried-Krupp-Wissenschaftskolleg in Greifswald in March, 2003, and supported by the Volkswagen Foundation. The school gave an introduction to current research on quantum independent increment processes aimed at graduate students and non-specialists working in classical and quantum probability, operator algebras, and mathematical physics. The present second volume contains the following lectures: "Random Walks on Finite Quantum Groups" by Uwe Franz and Rolf Gohm, "Quantum Markov Processes and Applications in Physics" by Burkhard Kümmerer, Classical and Free Infinite Divisibility and Lévy Processes" by Ole E. Barndorff-Nielsen, Steen Thorbjornsen, and "Lévy Processes on Quantum Groups and Dual Groups" by Uwe Franz.

  4. Independent random sampling methods

    CERN Document Server

    Martino, Luca; Míguez, Joaquín

    2018-01-01

    This book systematically addresses the design and analysis of efficient techniques for independent random sampling. Both general-purpose approaches, which can be used to generate samples from arbitrary probability distributions, and tailored techniques, designed to efficiently address common real-world practical problems, are introduced and discussed in detail. In turn, the monograph presents fundamental results and methodologies in the field, elaborating and developing them into the latest techniques. The theory and methods are illustrated with a varied collection of examples, which are discussed in detail in the text and supplemented with ready-to-run computer code. The main problem addressed in the book is how to generate independent random samples from an arbitrary probability distribution with the weakest possible constraints or assumptions in a form suitable for practical implementation. The authors review the fundamental results and methods in the field, address the latest methods, and emphasize the li...

  5. Biodiesel production from ethanolysis of palm oil using deep eutectic solvent (DES) as co-solvent

    Science.gov (United States)

    Manurung, R.; Winarta, A.; Taslim; Indra, L.

    2017-06-01

    Biodiesel produced from ethanolysis is more renewable and have better properties (higher oxidation stability, lower cloud and pour point) compared to methanolysis, but it has a disadvantage such as complicated purification. To improve ethanolysis process, deep eutectic solvent (DES) can be prepared from choline chloride and glycerol and used as co-solvent in ethanolysis. The deep eutectic solvent is formed from a quaternary ammonium salt (choline chloride) and a hydrogen bond donor (Glycerol), it is a non-toxic, biodegradable solvent compared to a conventional volatile organic solvent such as hexane. The deep eutectic solvent is prepared by mixing choline chloride and glycerol with molar ratio 1:2 at temperature 80 °C, stirring speed 300 rpm for 1 hour. The DES is characterized by its density and viscosity. The ethanolysis is performed at a reaction temperature of 70 °C, ethanol to oil molar ratio of 9:1, potassium hydroxide as catalyst concentration of 1.2 wt. DES as co-solvent with concentration 0.5 to 3 wt. stirring speed 400 rpm, and a reaction time 1 hour. The obtained biodiesel is then characterized by its density, viscosity, and ester content. The oil - ethanol phase condition is observed in the reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to without DES, showed that oil and ethanol become more slightly miscible, which favors the reaction. Using DES as co-solvent in ethanolysis showed increasing in yield and easier purification. The esters properties meet the international standards ASTM D6751, with the highest yield achieved 83,67 with 99,77 conversion at DES concentration 2 . Increasing DES concentration above 2 in ethanolysis decrease the conversion and yield, because of the excessive glycerol in the systems makes the reaction equilibrium moves to the reactant side.

  6. International exploration by independents

    International Nuclear Information System (INIS)

    Bertagne, R.G.

    1991-01-01

    Recent industry trends indicate that the smaller US independents are looking at foreign exploration opportunities as one of the alternatives for growth in the new age of exploration. It is usually accepted that foreign finding costs per barrel are substantially lower than domestic because of the large reserve potential of international plays. To get involved overseas requires, however, an adaptation to different cultural, financial, legal, operational, and political conditions. Generally foreign exploration proceeds at a slower pace than domestic because concessions are granted by the government, or are explored in partnership with the national oil company. First, a mid- to long-term strategy, tailored to the goals and the financial capabilities of the company, must be prepared; it must be followed by an ongoing evaluation of quality prospects in various sedimentary basins, and a careful planning and conduct of the operations. To successfully explore overseas also requires the presence on the team of a minimum number of explorationists and engineers thoroughly familiar with the various exploratory and operational aspects of foreign work, having had a considerable amount of onsite experience in various geographical and climatic environments. Independents that are best suited for foreign expansion are those that have been financially successful domestically, and have a good discovery track record. When properly approached foreign exploration is well within the reach of smaller US independents and presents essentially no greater risk than domestic exploration; the reward, however, can be much larger and can catapult the company into the big leagues

  7. International exploration by independents

    International Nuclear Information System (INIS)

    Bertagne, R.G.

    1992-01-01

    Recent industry trends indicate that the smaller U.S. independents are looking at foreign exploration opportunities as one of the alternatives for growth in the new age of exploration. The problems of communications and logistics caused by different cultures and by geographic distances must be carefully evaluated. A mid-term to long-term strategy tailored to the goals and the financial capabilities of the company should be prepared and followed by a careful planning of the operations. This paper addresses some aspects of foreign exploration that should be considered before an independent venture into the foreign field. It also provides some guidelines for conducting successful overseas operations. When properly assessed, foreign exploration is well within the reach of smaller U.S. independents and presents no greater risk than domestic exploration; the rewards, however, can be much larger. Furthermore, the Oil and Gas Journal surveys of the 300 largest U.S. petroleum companies show that companies with a consistent foreign exploration policy have fared better financially during difficult times

  8. TPO-independent megakaryocytopoiesis.

    Science.gov (United States)

    Zheng, Cuiling; Yang, Renchi; Han, Zhongchao; Zhou, Bin; Liang, Lu; Lu, Min

    2008-03-01

    Megakaryocytopoiesis is a continuous developmental process of platelet production. In this process, a complex network of hemopoietic growth factors are involved, among which TPO (thrombopoietin) is the most thoroughly investigated regulator of MKs (megakaryocytes). In addition to TPO, other regulators also have non-negligible effects on megakaryocytopoiesis. The majority of their effects are independent of TPO signaling. To date, TPO-independent megakaryocytopoiesis forms a regulatory system that includes four signals and (an) unknown signaling pathway(s). These four pathways are the gp 130 (glycoprotein 130)-dependent signaling pathway, the Notch pathway, NMDA (N-methyl-d-aspartate) receptor-mediated signaling, and the SDF-1 (stromal cell-derived factor-1)/FGF-4 (fibroblast growth factor-4) paradigm. Understanding of the TPO-independent regulatory system is important because the system may offer additional opportunities to understand the developmental process and the mechanisms of disorders characterized by abnormal MK and platelet production, such as thrombocytopenia and thrombocythemia, and to advance the development of therapeutics.

  9. International exploration by independent

    International Nuclear Information System (INIS)

    Bertragne, R.G.

    1992-01-01

    Recent industry trends indicate that the smaller U.S. independents are looking at foreign exploration opportunities as one of the alternatives for growth in the new age of exploration. Foreign finding costs per barrel usually are accepted to be substantially lower than domestic costs because of the large reserve potential of international plays. To get involved in overseas exploration, however, requires the explorationist to adapt to different cultural, financial, legal, operational, and political conditions. Generally, foreign exploration proceeds at a slower pace than domestic exploration because concessions are granted by a country's government, or are explored in partnership with a national oil company. First, the explorationist must prepare a mid- to long-term strategy, tailored to the goals and the financial capabilities of the company; next, is an ongoing evaluation of quality prospects in various sedimentary basins, and careful planning and conduct of the operations. To successfully explore overseas also requires the presence of a minimum number of explorationists and engineers thoroughly familiar with the various exploratory and operational aspects of foreign work. Ideally, these team members will have had a considerable amount of on-site experience in various countries and climates. Independents best suited for foreign expansion are those who have been financially successful in domestic exploration. When properly approached, foreign exploration is well within the reach of smaller U.S. independents, and presents essentially no greater risk than domestic exploration; however, the reward can be much larger and can catapult the company into the 'big leagues.'

  10. Effective interactions between nanoparticles: Creating temperature-independent solvation environments for self-assembly

    Science.gov (United States)

    Yadav, Hari O. S.; Shrivastav, Gourav; Agarwal, Manish; Chakravarty, Charusita

    2016-06-01

    The extent to which solvent-mediated effective interactions between nanoparticles can be predicted based on structure and associated thermodynamic estimators for bulk solvents and for solvation of single and pairs of nanoparticles is studied here. As a test of the approach, we analyse the strategy for creating temperature-independent solvent environments using a series of homologous chain fluids as solvents, as suggested by an experimental paper [M. I. Bodnarchuk et al., J. Am. Chem. Soc. 132, 11967 (2010)]. Our conclusions are based on molecular dynamics simulations of Au140(SC10H21)62 nanoparticles in n-alkane solvents, specifically hexane, octane, decane and dodecane, using the TraPPE-UA potential to model the alkanes and alkylthiols. The 140-atom gold core of the nanocrystal is held rigid in a truncated octahedral geometry and the gold-thiolate interaction is modeled using a Morse potential. The experimental observation was that the structural and rheological properties of n-alkane solvents are constant over a temperature range determined by equivalent solvent vapour pressures. We show that this is a consequence of the fact that long chain alkane liquids behave to a good approximation as simple liquids formed by packing of monomeric methyl/methylene units. Over the corresponding temperature range (233-361 K), the solvation environment is approximately constant at the single and pair nanoparticle levels under good solvent conditions. However, quantitative variations of the order of 10%-20% do exist in various quantities, such as molar volume of solute at infinite dilution, entropy of solvation, and onset distance for soft repulsions. In the opposite limit of a poor solvent, represented by vacuum in this study, the effective interactions between nanoparticles are no longer temperature-independent with attractive interactions increasing by up to 50% on decreasing the temperature from 361 K to 290 K, accompanied by an increase in emergent anisotropy due to

  11. Generalized Born and Explicit Solvent Models for Free Energy Calculations in Organic Solvents: Cyclodextrin Dimerization.

    Science.gov (United States)

    Zhang, Haiyang; Tan, Tianwei; van der Spoel, David

    2015-11-10

    Evaluation of solvation (binding) free energies with implicit solvent models in different dielectric environments for biological simulations as well as high throughput ligand screening remain challenging endeavors. In order to address how well implicit solvent models approximate explicit ones we examined four generalized Born models (GB(Still), GB(HCT), GB(OBC)I, and GB(OBC)II) for determining the dimerization free energy (ΔG(0)) of β-cyclodextrin monomers in 17 implicit solvents with dielectric constants (D) ranging from 5 to 80 and compared the results to previous free energy calculations with explicit solvents ( Zhang et al. J. Phys. Chem. B 2012 , 116 , 12684 - 12693 ). The comparison indicates that neglecting the environmental dependence of Born radii appears acceptable for such calculations involving cyclodextrin and that the GB(Still) and GB(OBC)I models yield a reasonable estimation of ΔG(0), although the details of binding are quite different from explicit solvents. Large discrepancies between implicit and explicit solvent models occur in high-dielectric media with strong hydrogen bond (HB) interruption properties. ΔG(0) with the GB models is shown to correlate strongly to 2(D-1)/(2D+1) (R(2) ∼ 0.90) in line with the Onsager reaction field ( Onsager J. Am. Chem. Soc. 1936 , 58 , 1486 - 1493 ) but to be very sensitive to D (D J. Chem. Inf. Model . 2015 , 55 , 1192 - 1201 ) reproduce the weak experimental correlations with 2(D-1)/(2D+1) very well.

  12. Organic Solvent Tropical Report [SEC 1 and 2

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    2000-06-21

    This report provides the basis for closing the organic solvent safety issue. Sufficient information is presented to conclude that risk posed by an unmitigated organic solvent fire is within risk evaluation guidelines.

  13. Non-Aqueous Biocatalysis in Homogeneous Solvent Systems

    Directory of Open Access Journals (Sweden)

    Sebastián Torres

    2004-01-01

    Full Text Available Enzymes are highly specific catalysts that typically function in aqueous solvents. However, many enzymes retain their catalytic activities at high concentrations in non- aqueous environments, including neat hydrophilic organic solvents. In fact, enzymes can be used to carry out reactions in organic solvents that are not possible in aqueous systems. Therefore, biocatalysis in homogenous non-aqueous solvents offers possibilities for producing useful chemicals and several synthetic reactions have already been developed using this type of system. The current review discusses factors that influence enzyme catalysis in non-aqueous solvents such us water content, solvent concentration, interaction of solvent with protein structure, stability and activity. Also, new strategies for non-conventional biocatalysis using extremophiles and ionic solvents are mentioned.

  14. Selection and Evaluation of Alternative Solvents for Caprolactam Extraction

    NARCIS (Netherlands)

    van Delden, M.L.; Kuipers, N.J.M.; de Haan, A.B.

    2006-01-01

    Because of the strict legislation for currently applied solvents in the industrial extraction of caprolactam, being benzene, toluene and chlorinated hydrocarbons, a need exists for alternative, environmentally benign solvents. An experimental screening procedure consisting of several steps was used

  15. Occupational exposure to chlorinated and petroleum solvents and mycosis fungoides

    DEFF Research Database (Denmark)

    Morales-Suárez-Varela, Maria M; Olsen, Jørn; Villeneuve, Sara

    2013-01-01

    To evaluate the potential association between occupational exposure to chlorinated and petroleum solvents and mycosis fungoides (MF).......To evaluate the potential association between occupational exposure to chlorinated and petroleum solvents and mycosis fungoides (MF)....

  16. Chemical engineering aspect of solvent extraction in mineral processing

    International Nuclear Information System (INIS)

    Dara, S.S.; Jakkikar, M.S.

    1975-01-01

    Solvent extraction process, types of solvents used, types of extraction, distribution isotherm and McCabe-Thiele diagram for process design, equipment for the process, operating parameters and applications are described. (M.G.B.)

  17. The disposal of radioactive solvent waste

    International Nuclear Information System (INIS)

    Dean, B.; Baker, W.T.

    1976-01-01

    As the use of radioisotope techniques increases, laboratories are faced with the problem of disposing of considerable quantities of organic solvent and aqueous liquid wastes. Incineration or collection by a waste contractor both raise problems. Since most of the radiochemicals are preferentially water soluble, an apparatus for washing the radiochemicals out into water and discharging into the normal drainage system in a high diluted form is described. Despite the disadvantages (low efficiency, high water usuage, loss of solvent in presence of surface active agents, precipitation of phosphors from dioxan based liquids) it is felt that the method has some merit if a suitably improved apparatus can be designed at reasonable cost. (U.K.)

  18. High performance hydrophobic solvent, carbon dioxide capture

    Science.gov (United States)

    Nulwala, Hunaid; Luebke, David

    2017-05-09

    Methods and compositions useful, for example, for physical solvent carbon capture. A method comprising: contacting at least one first composition comprising carbon dioxide with at least one second composition to at least partially dissolve the carbon dioxide of the first composition in the second composition, wherein the second composition comprises at least one siloxane compound which is covalently modified with at least one non-siloxane group comprising at least one heteroatom. Polydimethylsiloxane (PDMS) materials and ethylene-glycol based materials have high carbon dioxide solubility but suffer from various problems. PDMS is hydrophobic but suffers from low selectivity. Ethylene-glycol based systems have good solubility and selectivity, but suffer from high affinity to water. Solvents were developed which keep the desired combinations of properties, and result in a simplified, overall process for carbon dioxide removal from a mixed gas stream.

  19. Model-independent differences

    DEFF Research Database (Denmark)

    Könemann, Patrick

    2009-01-01

    Computing differences (diffs) and merging different versions is well-known for text files, but for models it is a very young field - especially patches for models are still matter of research. Text-based and model-based diffs have different starting points because the semantics of their structure...... is fundamentally different. This paper reports on our ongoing work on model-independent diffs, i.e. a diff that does not directly refer to the models it was created from. Based on that, we present an idea of how the diff could be generalized, e.g. many atomic diffs are merged to a new, generalized diff. One use...

  20. Model-Independent Diffs

    DEFF Research Database (Denmark)

    Könemann, Patrick

    Computing differences (diffs) and merging different versions is wellknown for text files, but for models it is a very young field. Text-based and model-based diffs have different goals and different starting points, because the semantics of their structure is fundamentally different. Text files...... it was created from. We present concepts for model-independent diffs, how it can be created and used. In the end, we present an idea of how the diff could be generalized, e.g. many atomic differences are merged to a new, generalized diff – similar to a patch for text files. The advantage of such a generalized...

  1. Stability and selectivity of alkaline proteases in hydrophilic solvents

    DEFF Research Database (Denmark)

    Pedersen, Lars Haastrup; Ritthitham, Sinthuwat; Pleissner, Daniel

    2008-01-01

    Hydrophilic, organic solvents can be used as co-solvents with water to produce one phase systems sustaining optimal mass transfer of substrates and products of mixed polarity in biocatalysed processes. At concentrations below 50 % hydrophilic solvents can even have a stabilising effect on alkalin...

  2. Permeability of commercial solvents through living human skin

    DEFF Research Database (Denmark)

    Ursin, C; Hansen, C M; Van Dyk, J W

    1995-01-01

    A procedure has been developed for measuring the steady state rate of permeation of commercial solvents through living human skin. To get the most consistent results, it was necessary with some solvents to normalize the solvent permeation rate of a given skin sample with its [3H]water permeation...

  3. Catalytic coal liquefaction with treated solvent and SRC recycle

    Science.gov (United States)

    Garg, Diwakar; Givens, Edwin N.; Schweighardt, Frank K.

    1986-01-01

    A process for the solvent refining of coal to distillable, pentane soluble products using a dephenolated and denitrogenated recycle solvent and a recycled, pentane-insoluble, solvent-refined coal material, which process provides enhanced oil-make in the conversion of coal.

  4. Green solvents and technologies for oil extraction from oilseeds.

    Science.gov (United States)

    Kumar, S P Jeevan; Prasad, S Rajendra; Banerjee, Rintu; Agarwal, Dinesh K; Kulkarni, Kalyani S; Ramesh, K V

    2017-01-01

    Oilseeds are crucial for the nutritional security of the global population. The conventional technology used for oil extraction from oilseeds is by solvent extraction. In solvent extraction, n -hexane is used as a solvent for its attributes such as simple recovery, non-polar nature, low latent heat of vaporization (330 kJ/kg) and high selectivity to solvents. However, usage of hexane as a solvent has lead to several repercussions such as air pollution, toxicity and harmfulness that prompted to look for alternative options. To circumvent the problem, green solvents could be a promising approach to replace solvent extraction. In this review, green solvents and technology like aqueous assisted enzyme extraction are better solution for oil extraction from oilseeds. Enzyme mediated extraction is eco-friendly, can obtain higher yields, cost-effective and aids in obtaining co-products without any damage. Enzyme technology has great potential for oil extraction in oilseed industry. Similarly, green solvents such as terpenes and ionic liquids have tremendous solvent properties that enable to extract the oil in eco-friendly manner. These green solvents and technologies are considered green owing to the attributes of energy reduction, eco-friendliness, non-toxicity and non-harmfulness. Hence, the review is mainly focussed on the prospects and challenges of green solvents and technology as the best option to replace the conventional methods without compromising the quality of the extracted products.

  5. ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

    Science.gov (United States)

    Long, R.L.

    1958-09-30

    A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

  6. Biological Treatment of Solvent-Based Paint

    Science.gov (United States)

    2011-01-01

    COVERED (From - To) Mar 2005- Mar 2010 4. TITLE AND SUBTITLE Biological Treatment of Solvent-Based Paint 5a. CONTRACT NUMBER WP 200520 5b...GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Torres, Tom; Hoffard, Theresa 5d. PROJECT NUMBER WP 200520 Lagerquist, Jenny 5e. TASK...nonhazardous and can be landfarmed, composted , or captured in a filter press and landfilled. Most industrial biological treatment systems will also require

  7. Deep eutectit solvents : properties and biocatalytic applications

    OpenAIRE

    Maugeri, Zaira

    2015-01-01

    Deep eutectic solvents (DES) have emerged over the last decade as a novel class of ionic liquids (ILs). In its broadest sense, DESs are usually formed by mixing a quaternary ammonium salt (typically choline chloride and derivatives) with hydrogen bond donor molecules such as amines, amides, alcohols, carboxylic acids, sugars or polyols. The mixing of these two components upon gentle heating and in a specific molar ratio leads to a depression of the melting point, resulting in most of the case...

  8. Layered microporous polymers by solvent knitting method.

    Science.gov (United States)

    Wang, Shaolei; Zhang, Chengxin; Shu, Yu; Jiang, Shulan; Xia, Qi; Chen, Linjiang; Jin, Shangbin; Hussain, Irshad; Cooper, Andrew I; Tan, Bien

    2017-03-01

    Two-dimensional (2D) nanomaterials, especially 2D organic nanomaterials with unprecedentedly diverse and controlled structure, have attracted decent scientific interest. Among the preparation strategies, the top-down approach is one of the considered low-cost and scalable strategies to obtain 2D organic nanomaterials. However, some factors of their layered counterparts limited the development and potential applications of 2D organic nanomaterials, such as type, stability, and strict synthetic conditions of layered counterparts. We report a class of layered solvent knitting hyper-cross-linked microporous polymers (SHCPs) prepared by improving Friedel-Crafts reaction and using dichloroalkane as an economical solvent, stable electrophilic reagent, and external cross-linker at low temperature, which could be used as layered counterparts to obtain previously unknown 2D SHCP nanosheets by method of ultrasonic-assisted solvent exfoliation. This efficient and low-cost strategy can produce previously unreported microporous organic polymers with layered structure and high surface area and gas storage capacity. The pore structure and surface area of these polymers can be controlled by tuning the chain length of the solvent, the molar ratio of AlCl 3 , and the size of monomers. Furthermore, we successfully obtain an unprecedentedly high-surface area HCP material (3002 m 2 g -1 ), which shows decent gas storage capacity (4.82 mmol g -1 at 273 K and 1.00 bar for CO 2 ; 12.40 mmol g -1 at 77.3 K and 1.13 bar for H 2 ). This finding provides an opportunity for breaking the constraint of former knitting methods and opening up avenues for the design and synthesis of previously unknown layered HCP materials.

  9. Dynamics of solvent-free grafted nanoparticles

    KAUST Repository

    Chremos, Alexandros

    2012-01-01

    The diffusivity and structural relaxation characteristics of oligomer-grafted nanoparticles have been investigated with simulations of a previously proposed coarse-grained model at atmospheric pressure. Solvent-free, polymer-grafted nanoparticles as well as grafted nanoparticles in a melt were compared to a reference system of bare (ungrafted) particles in a melt. Whereas longer chains lead to a larger hydrodynamic radius and lower relative diffusivity for grafted particles in a melt, bulk solvent-free nanoparticles with longer chains have higher relative diffusivities than their short chain counterparts. Solvent-free nanoparticles with short chains undergo a glass transition as indicated by a vanishing diffusivity, diverging structural relaxation time and the formation of body-centered-cubic-like order. Nanoparticles with longer chains exhibit a more gradual increase in the structural relaxation time with decreasing temperature and concomitantly increasing particle volume fraction. The diffusivity of the long chain nanoparticles exhibits a minimum at an intermediate temperature and volume fraction where the polymer brushes of neighboring particles overlap, but must stretch to fill the interparticle space. © 2012 American Institute of Physics.

  10. Reactive nitrogen in Rocky Mountain National Park during the Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ)

    Science.gov (United States)

    Prenni, A. J.; Benedict, K. B.; Evanoski-Cole, A. R.; Zhou, Y.; Sullivan, A.; Day, D.; Sive, B. C.; Zondlo, M. A.; Schichtel, B. A.; Vimont, J.; Collett, J. L., Jr.

    2014-12-01

    The Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) took place in July-August 2014. This collaborative study was aimed at characterizing those processes which control air quality along Colorado's Front Range. Although the study was largely focused on ozone, an additional goal of the study included characterizing contributions from Front Range sources and long-range transport to total reactive nitrogen in Rocky Mountain National Park (ROMO). Import of reactive nitrogen into ROMO and other pristine, high elevation areas has the potential to negatively impact terrestrial and aquatic ecosystems. We present measurements of reactive nitrogen species measured within ROMO during FRAPPÉ, and compare these data to measurements made in the surrounding areas. At our monitoring site in ROMO, co-located with IMPROVE and CASTNet monitoring, measurements of NO, NO2, NOx, NOy, NH3, and total reactive nitrogen (TNx) were made at high time resolution. Additional measurements of NH3, HNO3 and PM2.5 ions were made at hourly resolution using a MARGA and also at 24-hour time resolution using URG denuder-filter pack sampling. Precipitation samples also were collected to quantify wet deposition of ammonium, nitrate, and organic nitrogen. Finally, measurements of organic gases were made using online gas chromatography and proton transfer reaction-mass spectrometry. Preliminary results for ammonia show both a diel pattern, with concentrations increasing each morning, and a strong dependence on wind direction, implicating the importance of transport. Higher concentrations of NOx and NOy also were observed in the daytime, but in general these patterns differed from that of ammonia. Several upslope events were observed during the measurement period during which NOx, NH3, 2-propylnitrate, 2-butylnitrate, ethane, butane, and pentane were observed to increase in concentration along with ozone.

  11. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    Science.gov (United States)

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. 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.

  13. 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

  14. Independent task Fourier filters

    Science.gov (United States)

    Caulfield, H. John

    2001-11-01

    Since the early 1960s, a major part of optical computing systems has been Fourier pattern recognition, which takes advantage of high speed filter changes to enable powerful nonlinear discrimination in `real time.' Because filter has a task quite independent of the tasks of the other filters, they can be applied and evaluated in parallel or, in a simple approach I describe, in sequence very rapidly. Thus I use the name ITFF (independent task Fourier filter). These filters can also break very complex discrimination tasks into easily handled parts, so the wonderful space invariance properties of Fourier filtering need not be sacrificed to achieve high discrimination and good generalizability even for ultracomplex discrimination problems. The training procedure proceeds sequentially, as the task for a given filter is defined a posteriori by declaring it to be the discrimination of particular members of set A from all members of set B with sufficient margin. That is, we set the threshold to achieve the desired margin and note the A members discriminated by that threshold. Discriminating those A members from all members of B becomes the task of that filter. Those A members are then removed from the set A, so no other filter will be asked to perform that already accomplished task.

  15. The Photochemistry of Unprotected DNA and DNA inside Bacillus subtilis Spores Exposed to Simulated Martian Surface Conditions of Atmospheric Composition, Temperature, Pressure, and Solar Radiation.

    Science.gov (United States)

    Nicholson, Wayne L; Schuerger, Andrew C; Douki, Thierry

    2018-03-28

    DNA is considered a potential biomarker for life-detection experiments destined for Mars. Experiments were conducted to examine the photochemistry of bacterial DNA, either unprotected or within Bacillus subtilis spores, in response to exposure to simulated martian surface conditions consisting of the following: temperature (-10°C), pressure (0.7 kPa), atmospheric composition [CO 2 (95.54%), N 2 (2.7%), Ar (1.6%), O 2 (0.13%), and H 2 O (0.03%)], and UV-visible-near IR solar radiation spectrum (200-1100 nm) calibrated to 4 W/m 2 of UVC (200-280 nm). While the majority (99.9%) of viable spores deposited in multiple layers on spacecraft-qualified aluminum coupons were inactivated within 5 min, a detectable fraction survived for up to the equivalent of ∼115 martian sols. Spore photoproduct (SP) was the major lesion detected in spore DNA, with minor amounts of cyclobutane pyrimidine dimers (CPD), in the order TT CPD > TC CPD > CT CPD. In addition, the (6-4)TC, but not the (6-4)TT, photoproduct was detected in spore DNA. When unprotected DNA was exposed to simulated martian conditions, all photoproducts were detected. Surprisingly, the (6-4)TC photoproduct was the major photoproduct, followed by SP ∼ TT CPD > TC CPD > (6-4)TT > CT CPD > CC CPD. Differences in the photochemistry of unprotected DNA and spore DNA in response to simulated martian surface conditions versus laboratory conditions are reviewed and discussed. The results have implications for the planning of future life-detection experiments that use DNA as the target, and for the long-term persistence on Mars of forward contaminants or their DNA. Key Words: Bacillus subtilis-DNA-Mars-Photochemistry-Spore-Ultraviolet. Astrobiology 18, xxx-xxx.

  16. The importance of board independence

    NARCIS (Netherlands)

    Zijl, N.J.M.

    2012-01-01

    Although the attributed importance of board independence is high, a clear definition of independence does not exist. Furthermore, the aim and consequences of independence are the subject of discussion and empirical evidence about the impact of independence is weak and disputable. Despite this lack

  17. Frequency-Dependent Solvent Impedance and Colloid Microelectrophoresis Measurements in Partially Polar Solvents.

    Science.gov (United States)

    Hayden, Edward; Aljabal, Zena; Yethiraj, Anand

    2017-05-16

    We carry out frequency-dependent solvent impedance measurements and alternating current (ac) colloid microelectrophoresis experiments in partially polar solvents in the low-frequency regime (0.25 Hz ≤ f ≤ 10 Hz). Solvent electrode polarization effects are quantified first in partially polar solvent mixtures containing bromocyclohexane (CHB). We find that the polarization capacitance from electrode polarization exhibits a clear power law behavior C p = C p0 f -m with power law exponent m = 0.25 ± 0.04. Once we account for electrode polarization effects, we are able to obtain quantitative mobilities in the low-frequency regime from our ac microelectrophoresis measurements; for these measurements, we use poly(methyl methacrylate colloids that are gravitationally confined to a plane while suspended in a low-polar solvent mixture of cis-trans decahydronapthalene and CHB. We find that the dimensionless electrophoretic mobility is constant, consistent with expectations for frequencies below the ion-diffusion frequency, and has a value E = 1.6 ± 0.4.

  18. Diluent effects in solvent extraction. The Effects of Diluents in Solvent Extraction - a literature study

    International Nuclear Information System (INIS)

    Loefstroem-Engdahl, Elin; Aneheim, Emma; Ekberg, Christian; Foreman, Mark; Skarnemark, Gunnar

    2010-01-01

    The fact that the choice of organic diluent is important for a solvent extraction process goes without saying. Several factors, such as e.g. price, flash point, viscosity, polarity etc. each have their place in the planning of a solvent extraction system. This high number of variables makes the lack of compilations concerning diluent effects to an interesting topic. Often the interest for the research concerning a specific extraction system focuses on the extractant used and the complexes built up during an extraction. The diluents used are often classical ones, even if it has been shown that choice of diluent can affect extraction as well as separation in an extraction system. An attempt to point out important steps in the understanding of diluent effects in solvent extraction is here presented. This large field is, of course, not summarized in this article, but an attempt is made to present important steps in the understanding of diluents effects in solvent extraction. Trying to make the information concerning diluent effects and applications more easily accessible this review offers a selected summarizing of literature concerning diluents effects in solvent extraction. (authors)

  19. Angle-resolved electron and ion spectroscopy apparatus on the soft X-ray photochemistry beamline BL27SU at SPring-8

    CERN Document Server

    Ueda, K; Senba, Y; Okada, K; Shimizu, Y; Chiba, H; Ohashi, H; Tamenori, Y; Okumura, H; Saitô, N; Nagaoka, S; Hiraya, A; Ishiguro, E; Ibuki, T; Suzuki, I H; Koyano, I

    2001-01-01

    We have designed and constructed the apparatus for the angular distribution measurements of photoejected electrons and ions from free molecules, as a part of the endstation of the c-branch of the beamline BL27SU, a soft X-ray photochemistry beamline at SPring-8. The experimental procedures are described in combination with the use of a capability to switch the horizontal and vertical directions of the linear polarization of the light produced by the figure-8 undulator. As a typical example of the experimental results, we present angle-resolved energetic ion yield spectra in the O 1s excitation region of CO sub 2.

  20. Frame independent cosmological perturbations

    Energy Technology Data Exchange (ETDEWEB)

    Prokopec, Tomislav; Weenink, Jan, E-mail: t.prokopec@uu.nl, E-mail: j.g.weenink@uu.nl [Institute for Theoretical Physics and Spinoza Institute, Utrecht University, Leuvenlaan 4, 3585 CE Utrecht (Netherlands)

    2013-09-01

    We compute the third order gauge invariant action for scalar-graviton interactions in the Jordan frame. We demonstrate that the gauge invariant action for scalar and tensor perturbations on one physical hypersurface only differs from that on another physical hypersurface via terms proportional to the equation of motion and boundary terms, such that the evolution of non-Gaussianity may be called unique. Moreover, we demonstrate that the gauge invariant curvature perturbation and graviton on uniform field hypersurfaces in the Jordan frame are equal to their counterparts in the Einstein frame. These frame independent perturbations are therefore particularly useful in relating results in different frames at the perturbative level. On the other hand, the field perturbation and graviton on uniform curvature hypersurfaces in the Jordan and Einstein frame are non-linearly related, as are their corresponding actions and n-point functions.

  1. Emissivity independent optical pyrometer

    Science.gov (United States)

    Earl, Dennis Duncan; Kisner, Roger A.

    2017-04-04

    Disclosed herein are representative embodiments of methods, apparatus, and systems for determining the temperature of an object using an optical pyrometer. Certain embodiments of the disclosed technology allow for making optical temperature measurements that are independent of the surface emissivity of the object being sensed. In one of the exemplary embodiments disclosed herein, a plurality of spectral radiance measurements at a plurality of wavelengths is received from a surface of an object being measured. The plurality of the spectral radiance measurements is fit to a scaled version of a black body curve, the fitting comprising determining a temperature of the scaled version of the black body curve. The temperature is then output. The present disclosure is not to be construed as limiting and is instead directed toward all novel and nonobvious features and aspects of the various disclosed embodiments, alone or in various combinations and subcombinations with one another.

  2. Solvent exchange module for LC-NMR hyphenation using machine vision-controlled droplet evaporation.

    Science.gov (United States)

    Schoonen, Jan-Willem; Vulto, Paul; de Roo, Niels; van Duynhoven, John; van der Linden, Heiko; Hankemeier, Thomas

    2013-06-18

    We report the use of pendant droplet evaporation for exchange of eluents for (1)H nuclear magnetic resonance ((1)H NMR) purposes. Analytes are fed and retained in 500 nL droplets, which are concentrated by evaporation and subsequently redissolved in deuterated solvent. Droplet size is monitored by machine vision (MV), and heating rates are adjusted concordingly to maintain a stable droplet volume. Evaporation control is independent of solvent properties, and the setup handles feed rates up to 7 μL min(-1). The interface is capable of exchanging up to 90% of solvent for deuterated solvent, with a good recovery and repeatability for tomato extracts (Solanum lycopersicum). The system was capable of handling both polar and nonpolar analytes in one run. Volatiles such as formate, acetate, and lactate and the thermosensitive compound epigallocatechin gallate were recovered without significant losses. Ethanol and propionate were recovered with significant losses due to the formation of a minimum boiling azeotrope. The current setup is ideally suited for on- and off-line hyphenation of liquid chromatography and NMR, as it is comprehensive, fully automated, and easy to operate.

  3. Comparison of orange oil and chloroform as gutta- percha solvents in endodontic retreatment.

    Science.gov (United States)

    Rehman, Kiran; Khan, Farhan Raza; Aman, Nadia

    2013-05-01

    To compare the efficacy of gutta-percha removal achieved with simple mechanical technique using two different solvents. It was an in vitro experimental study conducted at the Aga Khan University Hospital, Karachi, Pakistan on 27 extracted human molars divided into two groups by alternate sampling technique. The teeth were prepared by manual filing and obturated with gutta-percha and calcium hydroxide sealer. Two drops of the assigned solvent were placed on the orifice of the obturated canal and Gates Glidden drills #1, 2 and 3 were used for removal of coronal gutta-percha. Manual filing was done for removal of remaining gutta-percha and the solvent was used in drops until needed. Postoperative periapical radiographs were taken to visualize the remaining gutta-percha left in the canals. Descriptive statistics (mean and SD) of the variables such as tooth type, obturation length and canal curvatures were determined. Chi-square and independent sample t-tests were applied and level of significance was set at 0.05. There was 5.19 (3.8) mm of remaining gutta-percha in the orange oil group and 5.37 (4.2) mm in the chloroform group (p=0.90). There is no statistically significant difference between the orange oil and chloroform when used as solvent for removing gutta-percha.

  4. Characterization of molecularly imprinted polymers using a new polar solvent titration method.

    Science.gov (United States)

    Song, Di; Zhang, Yagang; Geer, Michael F; Shimizu, Ken D

    2014-07-01

    A new method of characterizing molecularly imprinted polymers (MIPs) was developed and tested, which provides a more accurate means of identifying and measuring the molecular imprinting effect. In the new polar solvent titration method, a series of imprinted and non-imprinted polymers were prepared in solutions containing increasing concentrations of a polar solvent. The polar solvent additives systematically disrupted the templation and monomer aggregation processes in the prepolymerization solutions, and the extent of disruption was captured by the polymerization process. The changes in binding capacity within each series of polymers were measured, providing a quantitative assessment of the templation and monomer aggregation processes in the imprinted and non-imprinted polymers. The new method was tested using three different diphenyl phosphate imprinted polymers made using three different urea functional monomers. Each monomer had varying efficiencies of templation and monomer aggregation. The new MIP characterization method was found to have several advantages. To independently verify the new characterization method, the MIPs were also characterized using traditional binding isotherm analyses. The two methods appeared to give consistent conclusions. First, the polar solvent titration method is less susceptible to false positives in identifying the imprinting effect. Second, the method is able to differentiate and quantify changes in binding capacity, as measured at a fixed guest and polymer concentration, arising from templation or monomer aggregation processes in the prepolymerization solution. Third, the method was also easy to carry out, taking advantage of the ease of preparing MIPs. Copyright © 2014 John Wiley & Sons, Ltd.

  5. Permeability of commercial solvents through living human skin

    DEFF Research Database (Denmark)

    Ursin, C; Hansen, C M; Van Dyk, J W

    1995-01-01

    A procedure has been developed for measuring the steady state rate of permeation of commercial solvents through living human skin. To get the most consistent results, it was necessary with some solvents to normalize the solvent permeation rate of a given skin sample with its [3H]water permeation...... rate. For other solvents this was not necessary, so the un-normalized data were used. High [3H]water permeation rate also was used as a criterion for "defective" skin samples that gave erroneous permeability rates, especially for solvents having slow permeability. The linearity of the steady state data...... of DMSO and octyl acetate were measured. No octyl acetate was detected and the permeability of DMSO was proportional to its mole fraction in the mixture. The effect of two hours of solvent exposure on the viability of skin (based on DNA synthesis) was measured and found to be very dependent on the solvent....

  6. Single Stage Contactor Testing Of The Next Generation Solvent Blend

    Energy Technology Data Exchange (ETDEWEB)

    Herman, D. T.; Peters, T. B.; Duignan, M. R.; Williams, M. R.; Poirier, M. R.; Brass, E. A.; Garrison, A. G.; Ketusky, E. T.

    2014-01-06

    The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility at the Savannah River Site (SRS) is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent to increase the cesium decontamination factor. To support this integration of NGS into the MCU facility the Savannah River National Laboratory (SRNL) performed testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing utilized a blend of BOBCalixC6 based solvent and the NGS with the new extractant, MaxCalix, as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 liquid-to-liquid centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. The results indicate that hydraulically, the NGS solvent performed hydraulically similar to the current solvent which was expected. For the organic carryover 93% of the solvent is predicted to be recovered from the stripping operation and 96% from the extraction operation. As for the mass transfer, the NGS solvent significantly improved the cesium DF by at least an order of magnitude when extrapolating the One-stage results to actual Seven-stage extraction operation with a stage efficiency of 95%.

  7. Relaxation dynamics of a polar solvent cage around a nonpolar electronically excited solvent probe. A subpicosecond laser study

    International Nuclear Information System (INIS)

    Mialocq, J.C.; Hebert, P.; Baldacchino, G.; Gustavsson, T.

    1993-01-01

    The aim of the present paper is to show that the LDS 751 unsymmetrical cyanine laser dye, highly polar in the ground state and non polar in the fluorescent excited singlet state, is a suitable solvent probe. Excitation of LDS 751 in a polar solvent with an ultrashort laser pulse suddenly annihilates the permanent dipole moment of the solute and suppresses the forces which orientate the nearby solvent molecules. The subpicosecond analysis of the Time-Dependent Fluorescence Stokes Shift (TDFSS) of LDS 751 thus enables to probe the relaxation of polar solvent molecules which can be considered as free of solute-solvent interactions. (author)

  8. Next Generation Solvent Development for Caustic-Side Solvent Extraction of Cesium

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce A. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Birdwell, Joseph F. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Bonnesen, Peter V. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Bruffey, Stephanie [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

    2014-03-01

    This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modular Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University confirmed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Inter laboratory efforts were coordinated with complementary engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation.

  9. Next Generation Solvent (NGS): Development for Caustic-Side Solvent Extraction of Cesium

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Birdwell, Jr, Joseph F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bonnesen, Peter V. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bruffey, Stephanie H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delmau, Laetitia Helene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Duncan, Nathan C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ensor, Dale [Tennessee Technological Univ., Cookeville, TN (United States); Hill, Talon G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lee, Denise L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Rajbanshi, Arbin [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Roach, Benjamin D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Szczygiel, Patricia L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sloop, Jr., Frederick V. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Stoner, Erica L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Williams, Neil J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2014-03-01

    This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modular Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University confirmed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Interlaboratory efforts were coordinated with complementary engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation.

  10. Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

    CERN Document Server

    Marcus, Y; Kertes, A S

    2013-01-01

    Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

  11. Scenarios Evaluation Tool for Chlorinated Solvent MNA

    Energy Technology Data Exchange (ETDEWEB)

    Vangelas, Karen; Michael J. Truex; Charles J. Newell; Brian Looney

    2007-02-28

    Over the past three decades, much progress has been made in the remediation of chlorinated solvents from the subsurface. Yet these pervasive contaminants continue to present a significant challenge to the U.S. Department of Energy (DOE), other federal agencies, and other public and private organizations. The physical and chemical properties of chlorinated solvents make it difficult to rapidly reach the low concentrations typically set as regulatory limits. These technical challenges often result in high costs and long remediation time frames. In 2003, the DOE through the Office of Environmental Management funded a science-based technical project that uses the U.S. Environmental Protection Agency's technical protocol (EPA, 1998) and directives (EPA, 1999) on Monitored Natural Attenuation (MNA) as the foundation on which to introduce supporting concepts and new scientific developments that will support remediation of chlorinated solvents based on natural attenuation processes. This project supports the direction in which many site owners want to move to complete the remediation of their site(s), that being to complete the active treatment portion of the remedial effort and transition into MNA. The overarching objective of the effort was to examine environmental remedies that are based on natural processes--remedies such as Monitored Natural Attenuation (MNA) or Enhanced Attenuation (EA). The research program did identify several specific opportunities for advances based on: (1) mass balance as the central framework for attenuation based remedies, (2) scientific advancements and achievements during the past ten years, (3) regulatory and policy development and real-world experience using MNA, and (4) exploration of various ideas for integrating attenuation remedies into a systematic set of ''combined remedies'' for contaminated sites. These opportunities are summarized herein and are addressed in more detail in referenced project documents and

  12. Face-Dependent Solvent Adsorption: A Comparative Study on the Interfaces of HMX Crystal with Three Solvents.

    Science.gov (United States)

    Liu, Yingzhe; Lai, Weipeng; Ma, Yiding; Yu, Tao; Kang, Ying; Ge, Zhongxue

    2017-07-27

    To understand the crystal-solvent interfacial interactions on the molecular scale, the interfaces between three solvents, that is, acetone, γ-butyrolactone, and cyclohexanone, and three growth faces of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) crystal have been investigated with the aid of theoretical chemistry. The results show that the structural features of crystal faces play a critical role in the energetic, structural, and dynamic properties at the interfaces. For each solvent, the same change trend of some properties among the three faces of HMX crystal is observed, including adsorption affinity, local mass density, and solvent diffusion. For example, the rate of solvent diffusion at the three faces ranks as (011) > (110) > (020) regardless of solvent species. This can be attributed to the similar adsorption sites for solvent incorporation at the same face, which are concentrated at the cavities formed by surficial HMX molecules.

  13. Lessons from independence

    International Nuclear Information System (INIS)

    Hauptfuhrer, R.R.

    1990-01-01

    The recent history of Oryx provides invaluable lessons for those who plan future energy strategies, relates the author of this paper. When Oryx became an independent oil and gas company, its reserves were declining, its stock was selling below asset values, and the price of oil seemed stuck below $15 per barrel. The message from Oryx management to Oryx employees was: We are in charge of our own destiny. We are about to create our own future. Oryx had developed a new, positive corporate culture and the corporate credit required for growth. This paper points to two basic principles that have guided the metamorphosis in Oryx's performance. The first objective was to improve operational efficiency and to identify the right performance indicators to measure this improvement. It states that the most critical performance indicator for an exploration and production company must be replacement and expansion of reserves at a competitive replacement cost. Oryx has cut its finding costs from $12 to $5 per barrel, while the BP acquisition provided proven reserves at a cost of only $4 per barrel. Another performance indicator measures Oryx's standing in the financial markets

  14. Independent student study groups.

    Science.gov (United States)

    Hendry, Graham D; Hyde, Sarah J; Davy, Peter

    2005-07-01

    Teachers and students regulate learning to varying degrees in educational programmes in higher education. We present evidence that students in a student-centred medical programme self- and co-regulate their learning in independently formed study groups. We describe the perceived benefits of study groups and the effect of study group membership on student achievement. Years 1-2 of a 4-year, graduate-entry problem-based medical programme. We surveyed 233 year 2 students about features of their study groups and their study group membership in years 1-2. We compared study group membership with students' scores on a written summative assessment held at the end of their second year. For students who joined 1 study group, the length of time their group stayed together was positively related to achievement in the written summative assessment. There were no differences in summative assessment results between students who had been in a study group and students who had not been in a study group. Effective study groups are supportive, socially cohesive groups who generate mutual trust and loyalty, and self- and co-regulate their learning by giving and receiving explanations and summaries and motivating individual study. Teachers can support the formation of study groups by using small-group teaching/learning activities, providing clear learning outcomes and assessment criteria, minimising competition for grades and allocating room space.

  15. Flash pyrolysis of coal-solvent slurry prepared from the oxidized coal and the coal dissolved in solvent; Ichibu yokaishita sanka kaishitsutan slurry no jinsoku netsubunkai

    Energy Technology Data Exchange (ETDEWEB)

    Maki, T.; Mae, K.; Okutsu, H.; Miura, K. [Kyushu University, Fukuoka (Japan). Faculty of Engineering

    1996-10-28

    In order to develop a high-efficiency coal pyrolysis method, flash pyrolysis was experimented on slurry prepared by using liquid-phase oxidation reformed coal and a methanol-based solvent mixture. Australian Morwell coal was used for the experiment. The oxidized coal, into which carboxyl groups have been introduced, has the condensation structure relaxed largely, and becomes highly fluid slurry by means of the solvent. Char production can be suppressed by making the oxidation-pretreated coal into slurry, resulting in drastically improved pyrolytic conversion. The slurry was divided into dissolved solution, dried substance, extracted residue, and residual slurry, which were pyrolized independently. The dissolved solution showed very high conversion. Improvement in the conversion is contributed by separating the dissolved substances (coal macromolecules) at molecular levels, coagulating the molecules, suppressing cross-link formation, and reducing molecular weight of the dissolved substances. Oxidized coal can be dissolved to 80% or higher by using several kinds of mixed solvents. As a result of the dissolution, a possibility was suggested on pyrolysis which is easy in handling and high in conversion. 7 refs., 6 figs., 2 tabs.

  16. Polyelectrolyte as solvent and reaction medium.

    Science.gov (United States)

    Prescher, Simon; Polzer, Frank; Yang, Yan; Siebenbürger, Miriam; Ballauff, Matthias; Yuan, Jiayin

    2014-01-08

    A poly(ionic liquid) with a rather low glass transition temperature of -57°C was synthesized via free radical polymerization of an acrylate-type ionic liquid monomer. It exhibits fluidic behavior in a wide temperature range from room temperature to the threshold of the thermal decomposition. We demonstrate that it could act as a unique type of macromolecular solvent to dissolve various compounds and polymers and separate substances. In addition, this polyelectrolyte could serve successfully as reaction medium for catalysis and colloid particle synthesis. The synergy in the solvation and stabilization properties is a striking character of this polymer to downsize the in situ generated particles.

  17. 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.

  18. Photochemistry of free and bound Zn-chlorophyll analogues to synthetic peptides depend on the quinone and pH.

    Science.gov (United States)

    Razeghifard, Reza

    2015-11-01

    A synthetic peptide was used as a scaffold to bind Zn-Chlorophyll (ZnChl) analogues through histidine ligation to study their photochemistry in the presence of different type of quinones. The Chl analogues were chlorin e6 (Ce6), chlorin e6 trimethyl ester, pyropheophorbide a, and pheophorbide a while the quinones were PPBQ, DMBQ, NPHQ, DBTQ, DCBQ and PBQ. The binding of each ZnChl analogue to the peptide was verified by native gel electrophoresis. First the photo-stability of the ZnChl analogues were tested under continuous light. The ZnCe6 and ZnCe6TM analogues showed the least stability judged by the loss of optical signal intensity at their Qy band. The photoactivity of each ZnChl analogue was measured in the presence of each of the six quinones using time-resolved EPR spectroscopy. DMBQ was found to be the most efficient electron acceptor when all four ZnChl analogues were compared. The light-induced electron transfer between the ZnChl analogues complexed with the peptide and DMBQ were also measured using time-resolved EPR spectroscopy. The ZnCe6-peptide complex exhibited the highest photoactivity. The electron transfer in the complex was faster and the photoactivity yield was higher than those values obtained for free ZnCe6 and DMBQ. The fast phase of kinetics can be attributed to intra-protein electron transfer in the complex since it was not observed in the presence of DMBQ-glutathione adduct. Unlike free ZnCe6, the ZnCe6-peptide complex was robust and demonstrated very similar photoactivity efficiency in pH values 10, 8.0 and 5.0. The electron transfer kinetics were pH dependent and appeared to be modulated by the peptide charge and possibly fold. The charge recombination rate was slowed by an order of magnitude when the pH value was changed from 10.0 to 5.0. The implications of constructing the photoactive peptide complexes in terms of artificial photosynthesis are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. 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

  20. Commonwealth of (Independent States

    Directory of Open Access Journals (Sweden)

    Vrućinić Dušan

    2013-01-01

    Full Text Available Following the stages from the establishment itself to the present day of the functioning of such a specific regional organization as the Commonwealth of Independent States (CIS, the article seeks to further explain the meaning of its existence, efficiency and functioning. The CIS was created in order to make the dissolution of a major world super-power, which throughout the 20th century together with the USA defined the bipolar world, as painless as possible, especially for the new countries and its nationally and ethnically diverse population. During the early years after the dissolution of the USSR, the CIS played a major role in a more flexible and less severe dissolution of the Soviet empire, alleviating the consequences for its people. A more efficient functioning among the republics in all fields was also one of the tasks of the Commonwealth, to which it was devoted to the extent which was permitted by the then, not too favourable circumstances. Difficult years of economic crisis did not allow the CIS to mutually integrate its members as much as possible on the economy level. Thanks to the economic recovery of the post-Soviet states in the early 21st century, the Commonwealth has also been transformed, reformed, and renewed, and all this in order to achieve better and more fruitful cooperation between the members. The CIS may serve as a proper example of how the former Soviet Union states are inextricably linked by social, security-political, economic, cultural, communication-transport, and other ties, thanks to the centuries-long existence of the peoples of these states in this area, despite both internal and external factors which occasionally, but temporarily halt the post-Soviet integration. Mathematically expressed, the CIS members are naturally predisposed, to be reciprocally depended on each other, just as they also have the capacity for successful cooperation in the future times and epochs brought on by the modern world.

  1. Media independence and dividend policy

    DEFF Research Database (Denmark)

    Farooq, Omar; Dandoune, Salma

    2012-01-01

    independence and dividend policies in emerging markets. Using a dataset from twenty three emerging markets, we show a significantly negative relationship between dividend policies (payout ratio and decision to pay dividend) and media independence. We argue that independent media reduces information asymmetries...... for stock market participants. Consequently, stock market participants in emerging markets with more independent media do not demand as high and as much dividends as their counterparts in emerging markets with less independent media. We also show that press independence is more important in defining......Can media pressurize managers to disgorge excess cash to shareholders? Do firms in countries with more independent media follow different dividend policies than firms with less independent media? This paper seeks to answer these questions and aims to document the relationship between media...

  2. Developing new chemical tools for solvent extraction

    International Nuclear Information System (INIS)

    Moyer, B.A.; Baes, C.F.; Burns, J.H.; Case, G.N.; Sachleben, R.A.; Bryan, S.A.; Lumetta, G.J.; McDowell, W.J.; Sachleben, R.A.

    1993-01-01

    Prospects for innovation and for greater technological impact in the field of solvent extraction (SX) seem as bright as ever, despite the maturation of SX as an economically significant separation method and as an important technique in the laboratory. New industrial, environmental, and analytical problems provide compelling motivation for diversifying the application of SX, developing new solvent systems, and seeking improved properties. Toward this end, basic research must be dedicated to enhancing the tools of SX: physical tools for probing the basis of extraction and molecular tools for developing new SX chemistries. In this paper, the authors describe their progress in developing and applying the general tools of equilibrium analysis and of ion recognition in SX. Nearly half a century after the field of SX began in earnest, coordination chemistry continues to provide the impetus for important advancements in understanding SX systems and in controlling SX chemistry. In particular, the physical tools of equilibrium analysis, X-ray crystallography, and spectroscopy are elucidating the molecular basis of SX in unprecedented detail. Moreover, the principles of ion recognition are providing the molecular tools with which to achieve new selectivities and new applications

  3. Non-Ideal Behavior in Solvent Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Peter Zalupski

    2011-09-01

    This report presents a summary of the work performed to meet FCR&D level 3 milestone M31SW050801, 'Complete the year-end report summarizing FY11 experimental and modeling activities.' This work was carried out under the auspices of the Non-Ideality in Solvent Extraction Systems FCR&D work package. The report summarizes our initial considerations of potential influences that non-ideal chemistry may impose on computational prediction of outcomes in solvent extraction systems. The report is packaged into three separate test cases where a robustness of the prediction by SXFIT program is under scrutiny. The computational exercises presented here emphasize the importance of accurate representation of both an aqueous and organic mixtures when modeling liquid-liquid distribution systems. Case No.1 demonstrates that non-ideal behavior of HDEHP in aliphatic diluents, such as n-dodecane, interferes with the computation. Cases No.2 and No.3 focus on the chemical complexity of aqueous electrolyte mixtures. Both exercises stress the need for an improved thermodynamic model of an aqueous environment present in the europium distribution experiments. Our efforts for year 2 of this project will focus on the improvements of aqueous and non-aqueous solution models using fundamental physical properties of mixtures acquired experimentally in our laboratories.

  4. Solvents, Ethanol, Car Crashes and Tolerance: How Risky is Inhalation of Organic Solvents?

    Science.gov (United States)

    A research program in the National Health and Environmental Effects Research Laboratory of the U.S. EPA has led to some surprising considerations regarding the potential hazard of exposure to low concentrations of solvent vapors. This program involved conducting experiments to ch...

  5. γIrradiation induced formation of PCB-solvent adducts in aliphatic solvents

    International Nuclear Information System (INIS)

    Lepine, F.; Milot, S.; Gagne, N.

    1990-01-01

    γIrradiation induced formation of PCB-solvent adducts was investigated as a model for PCB residues in irradiated food. Formation of cyclohexyl adducts of PCBs was found to be significant when pure PCB congeners and Aroclor mixture were irradiated in cyclohexane and cyclohexene. Reaction pathways were investigated, and the effects of oxygen and electron scavenger were studied

  6. ACTIVE EFFLUX OF ORGANIC SOLVENTS BY PSEUDOMONAS PUTIDA S12 IS INDUCED BY SOLVENTS

    Science.gov (United States)

    Induction of the membrane-associated organic solvent efflux system SrpABC of Pseudomonas putida S12 was examined by cloning a 312-bp DNA fragment, containing the srp promoter, in the broad-host-range reporter vector pKRZ-1. Compounds that are capable of inducing expression of the...

  7. UV-Vis spectroscopic study and DFT calculation on the solvent effect of trimethoprim in neat solvents and aqueous mixtures.

    Science.gov (United States)

    Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E

    2014-08-14

    The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. A new solvent suppression method via radiation damping effect

    Science.gov (United States)

    Cui, Xiao-Hong; Peng, Ling; Zhang, Zhen-Min; Cai, Shu-Hui; Chen, Zhong

    2011-11-01

    Radiation damping effects induced by the dominated solvent in a solution sample can be applied to suppress the solvent signal. The precession pathway and rate back to equilibrium state between solute and solvent spins are different under radiation damping. In this paper, a series of pulse sequences using radiation damping were designed for the solvent suppression in nuclear magnetic resonance (NMR) spectroscopy. Compared to the WATERGATE method, the solute signals adjacent to the solvent would not be influenced by using the radiation damping method. The one-dimensional (1D) 1H NMR, two-dimensional (2D) gCOSY, and J-resolved experimental results show the practicability of solvent suppression via radiation damping effects in 1D and 2D NMR spectroscopy.

  9. Dissolution of organic solvents from painted surfaces into water

    International Nuclear Information System (INIS)

    Wren, J.C.; Jobe, D.J.; Sanipelli, G.G.; Ball, J.M.

    2000-01-01

    The presence of volatile iodine in containment buildings is one of the major safety concerns in the potential event of nuclear reactor accidents. Organic impurities in containment water, originating from various painted structural surfaces and organic materials, could have a significant impact on iodine volatility following an accident. To determine the source and magnitude of organic impurities and their effects on time-dependent iodine volatility, the dissolution for organic constituents from paints used in reactor buildings has been studied under postulated accident conditions. The studies of the organic dissolution from carbon steel coupons coated with zinc-primed vinyl, epoxy-primed polyurethane or epoxy paints over the temperature range 25-90 deg C are reported. Relatively large activation energies were measured for the release of the principal organic compounds from painted surfaces, suggesting it is the release of the solvents from the paint matrix rather than their diffusion through the solution that is the rate determining step for the dissolution mechanism. The similarities in the values of activation energies for the dissolution of different organic compounds from the paints suggest the release rate is independent of the nature of the painted surface or the type of organic being released from the surface. These two observations indicate that it may be possible to write a generalized rate expression for the release of organic compounds from painted surfaces in containment following an accident. The possible implications of these results for predicting iodine volatility in containment are also discussed. (author)

  10. Outcomes Related to the Use of Frozen Plasma or Pooled Solvent/Detergent-Treated Plasma in Critically Ill Children.

    Science.gov (United States)

    Camazine, Maraya N; Karam, Oliver; Colvin, Ryan; Leteurtre, Stephane; Demaret, Pierre; Tucci, Marisa; Muszynski, Jennifer A; Stanworth, Simon; Spinella, Philip C

    2017-05-01

    To determine if the use of fresh frozen plasma/frozen plasma 24 hours compared to solvent detergent plasma is associated with international normalized ratio reduction or ICU mortality in critically ill children. This is an a priori secondary analysis of a prospective, observational study. Study groups were defined as those transfused with either fresh frozen plasma/frozen plasma 24 hours or solvent detergent plasma. Outcomes were international normalized ratio reduction and ICU mortality. Multivariable logistic regression was used to determine independent associations. One hundred one PICUs in 21 countries. All critically ill children admitted to a participating unit were included if they received at least one plasma unit during six predefined 1-week (Monday to Friday) periods. All children were exclusively transfused with either fresh frozen plasma/frozen plasma 24 hours or solvent detergent plasma. None. There were 443 patients enrolled in the study. Twenty-four patients (5%) were excluded because no plasma type was recorded; the remaining 419 patients were analyzed. Fresh frozen plasma/frozen plasma 24 hours group included 357 patients, and the solvent detergent plasma group included 62 patients. The median (interquartile range) age and weight were 1 year (0.2-6.4) and 9.4 kg (4.0-21.1), respectively. There was no difference in reason for admission, severity of illness score, pretransfusion international normalized ratio, or lactate values; however, there was a difference in primary indication for plasma transfusion (p plasma/frozen plasma 24 hours and solvent detergent plasma study groups, -0.2 (-0.4 to 0) and -0.2 (-0.3 to 0), respectively (p = 0.80). ICU mortality was lower in the solvent detergent plasma versus fresh frozen plasma/frozen plasma 24 hours groups, 14.5% versus 29.1%%, respectively (p = 0.02). Upon adjusted analysis, solvent detergent plasma transfusion was independently associated with reduced ICU mortality (odds ratio, 0.40; 95% CI, 0

  11. Effect of Organic Solvent on the Enzyme Bleaching Agent System

    OpenAIRE

    コマツ, エミコ; モリタ, ミユキ; Emiko, KOMATSU; Miyuki, MORITA

    2002-01-01

    The Orange n decoloration reaction in the presence of various organic solvents with the HRP-H_2O_2 system was examined. In 5% organic solvent mixing aqueous solutions, the decoloration rates of Orange n were about 0.9-0.5 times of those in the aqueous solutions. Decoloration rate of Orange II decreased, as the concentration of organic solvent increases. The reaction of Orange n decoloration stopped at the 60% dimethyl sulfoxide concentration.

  12. Structure and dynamics of diblock copolymers in selective incompatible solvents

    Science.gov (United States)

    Stepanek, Petr

    2004-03-01

    When a diblock copolymer A-B is dissolved in a partially miscible mixture of two solvents, where one solvent is selective for block A and the other solvent is selective for block B, periodic multilayered anisotropic nanostructures are formed consisting of periodically arranged domains of the two solvents, stabilized by the block copolymer. We studied diblock copolymers where one block is polystyrene and the second is a polydiene or aliphatic chain, in mixtures of dimethylformamide (DMF), a selectively good solvent for polystyrene, and cyclohexane, a selectively good solvent for the other block. The coexistence curve of the solvent mixture has an upper critical temperature at 48 ^oC. We found that the copolymers formed macroscopically homogeneous, ordered or disordered solutions in a wide range of solvent compositions (2-40 concentrations (up to 20 We have investigated these systems using small angle neutron scattering, dynamic light scattering and pulsed-field gradient NMR. Depending on the composition of the mixed solvent the ordered phases formed below the coexistence curve of the neat solvents had a hexagonal or cubic structure. For selected systems validity of dilution laws has been examined. Analysis of the scattered intensity at large wave vectors q shows that the chains at the interface of the two solvents are not stretched. The dynamics of the ordered systems can be followed over 10 orders of magnitude and include these processes: solvent diffusion, internal relaxations, cooperative diffusion, self-diffusion, and viscoelastic relaxation. We acknowledge support of the Grant Agency of the Czech Republic (203/01/536).

  13. Solvent distillation studies for a purex reprocessing plant

    International Nuclear Information System (INIS)

    Ginisty, C.; Guillaume, B.

    1990-01-01

    A distillation system has been developed for regeneration of Purex solvent and will be implemented for the first time in a reprocessing plant. The results are described and analyzed, with emphasis on laboratory experiments which were made with a radioactive plant solvent. Particularly the distillation provides a good separation of solvent degradation products, which was verified by measurements of interfacial tension and plutonium or ruthenium retention. 16 refs., 3 figs., 5 tabs

  14. Solvent mediated self-assembly of solids

    Energy Technology Data Exchange (ETDEWEB)

    De Yoreo, J.; Wilson, W.D.; Palmore, T.

    1997-12-12

    Solvent-mediated crystallization represents a robust approach to self-assembly of nanostructures and microstructures. In organic systems, the relative ease with which the structure of hydrogen- bonded molecules can be manipulated allows for generation of a wide variety of nanoscale crystal structures. In living organisms, control over the micron-to-millimeter form of inorganic crystals is achieved through introduction of bio-organic molecules. The purpose of this proposal is to understand the interplay between solution chemistry, molecular structure, surface chemistry, and the processes of nucleation and crystal growth in solvent-mediated systems, with the goal of developing the atomic and molecular basis of a solvent-mediated self-assembly technology. We will achieve this purpose by: (1) utilizing an atomic force microscopy (AFM) approach that provides in situ, real time imaging during growth from solutions, (2) by modifying kinetic Monte Carlo (KMC) models to include solution-surface kinetics, (3) by introducing quantum chemistry (QC) calculations of the potentials of the relevant chemical species and the near-surface structure of the solution, and (4) by utilizing molecular dynamics (MD) simulations to identify the minimum energy pathways to the solid state. Our work will focus on two systems chosen to address both the manometer and micron-to-millimeter length scales of assembly, the family of 2,5- diketopiperazines (X-DKPs) and the system of CaCO{sub 3} with amino acids. Using AFM, we will record the evolution of surface morphology, critical lengths, step speeds, and step-step interactions as a function of supersaturation and temperature. In the case of the X-DKPs, these measurements will be repeated as the molecular structure of the growth unit is varied. In the case of CaCO{sub 3}, they will be performed as a function of solution chemistry including pH, ionic strength, and amino acid content. In addition, we will measure nucleation rates and orientations of

  15. A aplicação da fotoquímica inorgânica nas diversas áreas da ciência Application of inorganic photochemistry in the diverse fields of science

    Directory of Open Access Journals (Sweden)

    Rose Maria Carlos

    2007-01-01

    Full Text Available This article provides an overview of the current status of research involving the photochemical behavior of transition metal complexes in the following important areas: medicine, biology and materials science including some of the experiences of the writer. Coverage is selective, generally focusing on highlights and the most recent developments, with the broad aim of showing the interdisciplinary field of inorganic photochemistry.

  16. Theoretical and experimental study of mixed solvent electrolytes

    International Nuclear Information System (INIS)

    Cummings, P.T.; O'Connell, J.P.

    1990-01-01

    In the original proposal to study mixed solvent electrolyte solutions, four major goals were formulated: fundamental modeling of mixed solvent electrolytes using numerically solved integral equation approximation theories; evaluation of intermolecular pair potential models by computer simulation of selected systems for comparison with experiment and the numerical integral equation studies; development of fundamentally based correlations for the thermodynamic properties of mixed solvent electrolyte solutions using analytically solvable statistical mechanical models; and extension of experimental database on mixed solvent electrolytes by performing vapor-liquid equilibrium measurements on selected systems. This paper discusses the progress on these goals

  17. Decontamination of radioactive contaminated protective wear using dry cleaning solvent

    International Nuclear Information System (INIS)

    Muthiah, Pushpa; Chitra, S.; Paul, Biplob

    2013-01-01

    Liquid waste generated by conventional decontamination of radioactive contaminated cotton protective wear using detergent affects the chemical treatment of the plant. To reduce the generation of aqueous detergent waste, dry cleaning of cotton protective wear, highly soiled with oil and grease towards decontamination was tried with organic solvents. Mineral turpentine oil (MTO) among various other organic solvents was identified as a suitable organic solvent. As MTO leaves characteristic odour on the cloth, various commercial fragrances for the removal of the odour were tried. Application of the optimised dry cleaning solvent and commercial fragrance was adopted in plant scale operation. (author)

  18. Re-Refining of Waste Lubricating Oil by Solvent Extraction

    Directory of Open Access Journals (Sweden)

    Hassan Ali Durrani

    2011-04-01

    Full Text Available Re-refining of waste lubricating oil by solvent extraction is one of the potential techniques. The advantages of solvent extraction technique practically offers from environmental and economic points of view have received due attention. In this paper selection of composite solvent and technique to upgrade the used lubricant oil into base oil has been made. The composite solvent 2-propanol, 1-butanol and butanone have two alcohols that make a binary system reasonably effective. This work also attempts to study the performance of the composite solvent in the extraction process for recovering waste lubricating oil. The key parameters considered were vacuum pressure, temperature and the weight ratio of solvent to waste lubricating oil. The performance was investigated on the PSR (Percentage Sludge Removal and POL (Percent Oil Loss. The best results were obtained using composite solvent 25% 2-propanol, 37% 1-butanol and 38% butanone by a solvent to oil ratio of 6:1 at vacuum pressure 600mmHg and distillation temperature 250oC. The vacuum distilled oil pretreated with the composite solvents was matched to the standard base oil 500N and 150N, found in close agreement and could be used for similar purpose.

  19. Recovery of acid-degraded tributyl phosphate by solvent extraction

    International Nuclear Information System (INIS)

    Young, G.C.; Holladay, D.W.

    1981-01-01

    During nuclear fuel reprocessing the organic solvent becomes loaded with various acidic degradation products, which can be effectively removed through solvent extraction. Studies have been made with a small bench-scale solvent extraction system to optimize such parameters as pH of aqueous phase, phase ratio, residence time, flow rates, and temperature. The necessary decontamination factors have been obtained for various degradation products during continuous solvent extraction in one stage, with the aqueous phase being recycled. The aqueous phase contains compounds that can be degraded to gases to minimize waste disposal problems

  20. The Denaturation Transition of DNA in Mixed Solvents

    Science.gov (United States)

    Hammouda, Boualem; Worcester, David

    2006-01-01

    The helix-to-coil denaturation transition in DNA has been investigated in mixed solvents at high concentration using ultraviolet light absorption spectroscopy and small-angle neutron scattering. Two solvents have been used: water and ethylene glycol. The “melting” transition temperature was found to be 94°C for 4% mass fraction DNA/d-water and 38°C for 4% mass fraction DNA/d-ethylene glycol. The DNA melting transition temperature was found to vary linearly with the solvent fraction in the mixed solvents case. Deuterated solvents (d-water and d-ethylene glycol) were used to enhance the small-angle neutron scattering signal and 0.1M NaCl (or 0.0058 g/g mass fraction) salt concentration was added to screen charge interactions in all cases. DNA structural information was obtained by small-angle neutron scattering, including a correlation length characteristic of the inter-distance between the hydrogen-containing (desoxyribose sugar-amine base) groups. This correlation length was found to increase from 8.5 to 12.3 Å across the melting transition. Ethylene glycol and water mixed solvents were found to mix randomly in the solvation region in the helix phase, but nonideal solvent mixing was found in the melted coil phase. In the coil phase, solvent mixtures are more effective solvating agents than either of the individual solvents. Once melted, DNA coils behave like swollen water-soluble synthetic polymer chains. PMID:16815902

  1. Method for Selection of Solvents for Promotion of Organic Reactions

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Jiménez-González, Concepción; Constable, David J.C.

    2005-01-01

    estimates of thermodynamic properties to generate a knowledge base of reaction, solvent and environment related properties that directly or indirectly influence the rate and/or conversion of a given reaction. Solvents are selected using a rules-based procedure where the estimated reaction-solvent properties...... is to produce, for a given reaction, a short list of chemicals that could be considered as potential solvents, to evaluate their performance in the reacting system, and, based on this, to rank them according to a scoring system. Several examples of application are given to illustrate the main features and steps...

  2. Photocyclization reaction of a diarylmaleimide derivative in polar solvents.

    Science.gov (United States)

    Ohsumi, Masato; Hazama, Masaki; Fukaminato, Tuyoshi; Irie, Masahiro

    2008-07-28

    Photochromism of a symmetric diarylmaleimide derivative, having two thiophene rings (1), and a non-symmetric derivative having a S,S-dioxide thiophene ring and a thiophene ring (2) as the aryl moieties, was studied in various solvents. The photocyclization quantum yield of gradually decreased with increasing the solvent polarity and the reaction was not observed in polar solvents, such as ethanol and acetonitrile; on the other hand, such a strong solvent dependence of the photocyclization reaction was not observed for ; the different behavior is attributed to the weaker electron donating ability of the S,S-dioxide thiophene ring.

  3. 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.

  4. Photochemistry in Organized Media.

    Science.gov (United States)

    Fendler, Janos H.

    1983-01-01

    Describes common artificially produced organized media such as colloids, surfactants, and polymers and their usefulness in studying complex biochemical processes. Discusses selected recent photophysical and photochemical exploitations of these systems, including artificial photosynthesis, in situ generation of colloidal gold and platinum,…

  5. Light Quanta and Photochemistry

    Science.gov (United States)

    Baublitz, M.; Hersek, M.; Gross, N. A.; Bansil, A.

    2006-03-01

    For many undergraduate students the photoelectric effect and quantum nature of light seem abstract because of their lack of first-hand experience with these phenomena. This is particularly true for non-science students taking general science courses. At Northeastern University through the Embedded Learning MOdules (ELMO) Project, developed with support from NSF and FIPSE, non-science students take part in experiments [1] related to the photoelectric effect that help them understand photochemical processes and the quantum nature of light. Photosensitive materials are produced by depositing thin layers of silver nitrate on paper, and various light sources and light filters are used that permit light from only a specific part of the spectrum to expose the photosensitive material. The dependence of the silver nitrate's photosensitivity on the color of the incident light provides students with an example that can be understood in terms of the quantum nature of light. [1] M. Hersek, N. A. Gross, E. J. Mason, and A. Bansil, J. College Sci. Teaching (in press); N. A. Gross, M. Hersek, and A. Bansil, Am. J. Phys. 73, 986 (2005)

  6. Photochemistry of planetary atmospheres

    National Research Council Canada - National Science Library

    Yung, Y. L; DeMore, William B

    1999-01-01

    ... intelligent predictions. Data from solar system probes, meanwhile, provide a context in which Earth-based observations can be interpreted. The breadth of material relevant to the field means, however, that there is a dire need for a monograph in which this information is sorted and woven into a comprehensive volume. To fill this void, two ...

  7. Oligoquinolines under Solvent-free Microwave Irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Kwi-Jeon; Kwon, Tae-Woo [Kyungsung University, Busan (Korea, Republic of)

    2015-01-15

    Quinolines are thermally stable and can be used as an excellent n-type semiconducting materials. Since quinolines are also known to be electron acceptor molecules, combination of various electron donor building blocks can be utilized in photonic and electronic organic light-emitting diode (OLED) applications. For example, donor.acceptor systems with phenothiazine (or carbazole) molecules as electron donors and the phenylquinoline group as an electron acceptor provide an efficient approach for the design of new materials exhibiting highly efficient charge-transfer photophysics and electroluminescence in OLEDs. We have described the Friedlander quinoline synthesis between aminobenzophenones and symmetrical diacetyl compounds having phenothiazine, carbazole, biphenyl, and phenyl moieties under solvent-free microwave irradiation in 12.98% isolated yields.

  8. Management of spent solvents of reprocessing origin

    International Nuclear Information System (INIS)

    Manohar, S.; Srinivas, C.; Vincent, T.; Wattal, P.K.

    2001-01-01

    Spent solvents of reprocessing origin constitute a major portion of radioactive liquid organic wastes arising from nuclear activity. An in-depth study of this waste stream has led to the evolution of a complete management option, which addresses not only the concern of radioactivity but also its organic nature. This is based on alkaline hydrolysis of Tri-n-butyl phosphate (TBP), which converts it into aqueous soluble products, viz. sodium salt of dibutyl phosphoric acid and butanol. During the process of alkaline hydrolysis almost all the activity associated with the waste gets transferred into the aqueous phase. The recovered diluent virtually free of activity and TBP can be recycled, and in case of it not meeting reprocessing standards, can be incinerated. The process generated aqueous waste is found compatible with cement and can be immobilized in cement matrix. (author)

  9. Organogels thermodynamics, structure, solvent role, and properties

    CERN Document Server

    Guenet, Jean-Michel

    2016-01-01

    This book provides a physics-oriented introduction to organogels with a comparison to polymer thermoreversible gels whenever relevant. The past decade has seen the development of a wide variety of newly-synthesized molecules that can spontaneously self-assemble or crystallize from their organic or aqueous solutions to produce fibrillar networks, namely organogels, with potential applications in organic electronics, light harvesting, bio-imaging, non-linear optics, and the like. This compact volume presents a detailed outlook of these novel molecular systems with special emphasis upon their thermodynamics, morphology, molecular structure, and rheology. The definition of these complex systems is also tackled, as well as the role of the solvent. The text features numerous temperature-phase diagrams for a variety of organogels as well as illustrations of their structures at the microscopic, mesoscopic and macroscopic level. A review of some potential applications is provided including hybrid functional materials ...

  10. Is Water a Universal Solvent for Life?

    Science.gov (United States)

    Pohorill, Andrew

    2012-01-01

    There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation

  11. Solvent extraction of noble metals by formazans

    International Nuclear Information System (INIS)

    Grote, M.; Hueppe, U.; Kettrup, A.

    1984-01-01

    The extraction properties of ion-pairs composed of quaternary ammonium cations and a sulphonated formazan were compared with those of an unsulphonated formazan, for various solvent media. In dichloromethane the combined system behaves as a 'coloured anion-exchanger', with displacement of the sulphonated formazan, whereas in toluene Pd(II) and Ag(I) are extracted as the metal formazan chelates from aqueous medium. The rates of extraction are remarkably higher than with the simple extractants. Because of the higher stability only the simple chelating extraction systems afford satisfactory separation of Pd(II) from excess of Pt(IV) and of Ag(I) from Cu(II). The extracted metals can be stripped and the extractant regenerated. (author)

  12. Characterization of an organic-solvent-tolerant Brevibacillus agri strain 13 able to stabilize solvent/water emulsion.

    Science.gov (United States)

    Kongpol, Ajiraporn; Pongtharangkul, Thunyarat; Kato, Junichi; Honda, Kohsuke; Ohtake, Hisao; Vangnai, Alisa S

    2009-08-01

    Brevibacillus agri strain 13 was isolated and characterized as a Gram-positive organic-solvent-tolerant bacterium able to grow at 45 degrees C. It can tolerate high concentrations (5% and 20%, v/v) of various organic solvents with a broad range of log P(ow) when the organic solvent was provided as a nonaqueous layer. Although it can tolerate a number of aromatic solvents, it cannot utilize them as a sole carbon source. The surface characteristics of cells exposed to organic solvent were investigated using the bacterial adhesion to hydrocarbon test, a contact angle measurement, zeta potential determination, and fluorescence microscopy analysis and compared with that of nonexposed cells. The results showed that although it has a hydrophilic cell surface, it has a unique indigenous cell surface characteristic in which the cells can stabilize solvent-in-water emulsion by adhering to the solvent-water interface of the solvent droplets. The tolerance and predilection of B. agri strain 13 toward organic solvents may suggest its potential application as a whole-cell biocatalyst for the biotransformation process of water-immiscible substrate(s).

  13. Complete Evaluation of Available Laboratory-scale Data for the Independence Model

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Troy Michael [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Kress, Joel David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Bhat, Kabekode Ghanasham [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-06-30

    Year 1 Objectives (August 2016 – December 2016) – The original Independence model is a sequentially regressed set of parameters from numerous data sets in the Aspen Plus modeling framework. The immediate goal with the basic data model is to collect and evaluate those data sets relevant to the thermodynamic submodels (pure substance heat capacity, solvent mixture heat capacity, loaded solvent heat capacities, and volatility data). These data are informative for the thermodynamic parameters involved in both vapor-liquid equilibrium, and in the chemical equilibrium of the liquid phase.

  14. Boards: Independent and Committed Directors?

    OpenAIRE

    Christophe Volonté

    2011-01-01

    Regulators, proxy advisors and shareholders are regularly calling for independent directors. However, at the same time, independent directors commonly engage in numerous outside activities potentially reducing their time and commitment with the particular firm. Using Tobin's Q as an approximation of market valuation and controlling for endogeneity, our empirical analysis reveals that neither is independence positively related to firm performance nor are outside activities negatively related t...

  15. Nuclear, uranium, reserves, sustainability, independence; Nucleaire, Uranium, reserves, durabilite, independance

    Energy Technology Data Exchange (ETDEWEB)

    Acket, C

    2007-06-15

    In order to evaluate the energy independence concerning the nuclear energy, the author takes the state of the art about the uranium. He details the fuel needs, the reserves on the base of the today available techniques, the reserves on the base of the future techniques and concludes positively on the energy independence for the nuclear. (A.L.B.)

  16. T2 relaxation measurement with solvent suppression and implications to solvent suppression in general.

    Science.gov (United States)

    Hoffmann, Markus M; Sobstyl, Hanna S; Badali, Vincent A

    2009-07-01

    A number of suppression pulse sequences including Excitation Sculpting and WATERGATE were incorporated into the standard Carr-Purcell-Meiboom-Gill (CPMG) program for T(2) measurement and experimentally evaluated. The chosen suppression schemes were of varying complexity encompassing pulse program elements, such as presaturation, gradients, and selective pulses, which are typically utilized for solvent suppression. The quality of the spectral data and the accuracy of T(2) measurements of the investigated suppression schemes were evaluated using three aqueous samples with increasing proton content in the water solvent, i.e. by volume 100% D(2)O, 80/20% D(2)O/H(2)O, and 20/80% D(2)O/H(2)O. For signals removed from the water signal, the T(2) values were generally very consistent between all pulse sequences tested. T(2) measurements can be unreliable for signals too close to the water signal such that they are significantly suppressed as well. Their intensity may actually grow initially through cross relaxation that transfers magnetization back to the solute signal. In turn, this relaxation phenomenon can be exploited to improve the spectral quality of conventional solvent suppression schemes. In favorable cases, even signals that are completely masked by the water signal can be recovered by adding a carefully chosen number of spin echoes with optimized evolution time to conventional water suppression pulse programs, such as Excitation Sculpting or WATERGATE. 2009 John Wiley & Sons, Ltd.

  17. Gravity Independent Compressor, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose to develop and demonstrate a small, gravity independent, vapor compression refrigeration system using a linear motor compressor which effectively...

  18. The influence of granulating solvents on drug release from tablets ...

    African Journals Online (AJOL)

    ... significantly lower than the other wet granulated tablets, but higher than the matrix tablets. The granulating solvent influenced the release of drug which increased with increase in the water content. Key Words: Grewia gum: Granulating solvents; Release mechanisms. Journal of Pharmacy and Bioresources Vol.1(1) 2004: ...

  19. Solvent density mode instability in non-polar solutions

    Indian Academy of Sciences (India)

    1Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National. Centre for Basic Sciences, ... upon excitation mainly drives the solvent reorganization [12,13]. However, the. Stokes shifts ..... process [17] where a solvent density mode with momentum q is scattered to another density mode of ...

  20. Charge-transfer spectra of ferrocene in halocarbon solvents under ...

    Indian Academy of Sciences (India)

    Unknown

    Literature survey has shown that the studies on the change in electronic absorption spectra of ferrocene after photoexcitation (at several wavelengths in the UV region) in halocarbon solvents have received much attention in the past 10–13. Formation of charge-transfer complexes of ferrocene with halocarbon solvents after ...

  1. Effects Of Solvent Composition And Polymer Concentration On Poly ...

    African Journals Online (AJOL)

    Its solution in Phenol: 1,2-dichlorobenzene solvent mixtures of 35%: 65%, 50%: 50%, 65%: 35% by weight was degraded at 143± 2oC. The effects of solvent composition and polymer concentration on poly (ethylene terephthalate) degradation in solution were investigated by dilute solution viscometric method using 0.460, ...

  2. Biocomposites from polyhydroxybutyrate and bio-fillers by solvent ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 40; Issue 2. Biocomposites from polyhydroxybutyrate and bio-fillers by solvent casting method ... alpha cellulose (AC) and cellulose nanofibrils (CNFs) were prepared to investigate the effect of the bio-fillers on the properties of PHB by a solvent casting method.

  3. SAGE 2.0 SOLVENT ALTERNATIVES GUIDE - USER'S GUIDE

    Science.gov (United States)

    The guide provides instruction for using the SAGE (Solvent Alternatives Guide) software system, version 2.O. It assumes that the user is familiar with the fundamentals of operating a personal computer under the Microsoft disk operating system (MS-DOS). AGE recommends solvent repl...

  4. 40 CFR 52.254 - Organic solvent usage.

    Science.gov (United States)

    2010-07-01

    ... contrivances designed for processing continuous web, strip, or wire that emit organic materials in the course... applying any photochemically reactive solvent, as defined in paragraph (k) of this section, or material containing such photochemically reactive solvent, unless said discharge has been reduced by at least 85...

  5. Solvent selection for fatty acid residue analysis of archeologicial artifacts

    Directory of Open Access Journals (Sweden)

    Rosentreter Jeffrey J.

    2017-06-01

    Full Text Available Residue analysis has rapidly become one of the most useful techniques for determining an artifact function and revealing insight into paleodiets. The success of analytical residue analysis often lies with the first preparatory step, where the residue is extracted from the object. Detection of a residue requires effective solvation of the material, and there is a large range of potential solvents. One purpose of this study is to determine the efficiency of various solvents for the extraction of fatty acids from charcoal, a material that is ubiquitous, easily identified, remarkably stable in the archaeological record but, most importantly for this research, retains fats extremely well. This investigation examines the removal efficiency of model fatty acids from carbonized wood samples. The strong affinity of lipids to charcoal makes carbonized wood ideal for retaining them, but also makes their extraction extremely challenging and thus an ideal benchmark for solvent extraction characterization. Several solvents (benzene, chloroform, hexane, methanol and water are used to determine the quantitative extraction efficiency of tripalmitin. While benzene and chloroform perform best for some wood types, neither solvent is better for all carbonized wood. Correlations between the chemical properties of the solvents and the effectiveness of the extraction provide guidance for solvents. Findings indicate solvent characteristics including dipole moment, dielectric constant, hydrogen bonding, and molecular weight all play an important role in extraction of fat from a charcoal matrix. Results presented should provide guidelines to allow for more effective residue extration and more accurate lipid analysis.

  6. Alternative solvents can make preparative liquid chromatography greener

    NARCIS (Netherlands)

    Shen, Y.; Chen, B.; Beek, van T.A.

    2015-01-01

    To make preparative Reversed-Phase High Performance Liquid Chromatography (RP-pHPLC) greener, alternative solvents were considered among others in terms of toxicity, cost, safety, workability, chromatographic selectivity and elution strength. The less toxic solvents ethanol, acetone and ethyl

  7. 25 CFR 11.451 - Abuse of psychotoxic chemical solvents.

    Science.gov (United States)

    2010-04-01

    ... any glue, gasoline, paint, hair spray, Lysol, or other substance containing one or more of the... 25 Indians 1 2010-04-01 2010-04-01 false Abuse of psychotoxic chemical solvents. 11.451 Section 11... OFFENSES AND LAW AND ORDER CODE Criminal Offenses § 11.451 Abuse of psychotoxic chemical solvents. (a) It...

  8. Antinociceptive and Anti-Inflammatory Effects of Solvent Extracts of ...

    African Journals Online (AJOL)

    Erah

    Solvent Extracts of Tagetes erectus Linn (Asteraceae). NV Shinde*, KG Kanase, ... Soxhlet extractor and refluxed continuously for 6 h. The solvent ... of the plant extract. Most of the so-called peripheral analgesics possess anti-inflammatory properties and, in some cases, also antipyretic activity besides analgesia. For many ...

  9. MOLECULAR THERMODYNAMICS IN THE DESIGN OF SUBSTITUTE SOLVENTS

    Science.gov (United States)

    The use of physical properties and fluid behavior from molecular thermodynamics can lead to better decision making in the design of substitute solvents and can greatly reduce the expense and time required to find substitutes compared to designing solvents by experiment. this pape...

  10. Polyethylene glycol: A recyclable solvent system for the synthesis of ...

    Indian Academy of Sciences (India)

    Administrator

    22 as green solvent has also been documented, but ionic liquids safety is still debated and the reactions in water do not give good yields because of the hydrophobic nature of the organic reactants. Recently, polyethylene glycol is found to be an interesting recyclable and eco-friendly solvent system in synthetic chemistry for ...

  11. Solvent effects in the reaction between piperazine and benzyl bromide

    Indian Academy of Sciences (India)

    WINTEC

    analysis indicates that the transition state is more solvated than the reactants due to hydrogen bond dona- tion and polarizability of the solvent while the reactant is more solvated than the transition state due to electrophilicity of the solvent. Study of ... and benzonitrile were all analytical grade and of. Merck or Sd-fine make.

  12. The course of chronic solvent induced encephalopathy: A systematic review

    NARCIS (Netherlands)

    van Valen, Evelien; Wekking, Ellie; Van der Laan, Gert; Sprangers, Mirjam; van Dijk, Frank

    2009-01-01

    Background: Worldwide millions of workers; are exposed to organic solvents. Long term exposure leads in some workers to the development of Chronic Solvent induced Encephalopathy (CSE). The first reports about CSE came from the European Nordic countries in the 1970s. In spite of decades of experience

  13. Temporal epileptic seizures and occupational exposure to solvents

    DEFF Research Database (Denmark)

    Jacobsen, M; Bælum, Jesper; Bonde, J P

    1994-01-01

    exposure to a mixture of organic solvents (mainly cyclohexanone, white spirit, and isopropanol). Epileptic seizures of temporal type were occurring in relation to solvent exposure. The seizures disappeared shortly after stopping exposure but returned just after a short term re-exposure to cyclohexanone...

  14. Method of purifying phosphoric acid after solvent extraction

    International Nuclear Information System (INIS)

    Kouloheris, A.P.; Lefever, J.A.

    1979-01-01

    A method of purifying phosphoric acid after solvent extraction is described. The phosphoric acid is contacted with a sorbent which sorbs or takes up the residual amount of organic carrier and the phosphoric acid separated from the organic carrier-laden sorbent. The method is especially suitable for removing residual organic carrier from phosphoric acid after solvent extraction uranium recovery. (author)

  15. Human solvent exposure. Factors influencing the pharmacokinetics and acute toxicity

    DEFF Research Database (Denmark)

    Bælum, Jesper

    1991-01-01

    of these peaks or of increased physical activity during exposure could be detected. However, the importance of peek concentrations and of workload for the development of chronic solvent encephalopathy is still unknown. The influence of a 9-25 years occupational exposure to solvents was investigated. A group...

  16. Molecular transport behaviour of organic solvents through halloysite ...

    Indian Academy of Sciences (India)

    ... behaviour of three organic solvents was further validated by their crosslink density values. The thermodynamic parameters such as enthalpy, entropy and free energy of sorption were evaluated. The positive values of free energy indicate the non-spontaneity of the sorption of HNTs filled EVA in aromatic solvents at 303 K.

  17. Excited state charge transfer reaction in (mixed solvent+ electrolyte ...

    Indian Academy of Sciences (India)

    The reaction time constant in low polar mixtures, which becomes faster on addition of electrolyte, lengthens on increasing the mole fraction of the relatively less polar solvent component of the mixture. These observations have been qualitatively explained in terms of the measured solvent reorganization energy and reaction ...

  18. Highly Efficient and Reproducible Nonfullerene Solar Cells from Hydrocarbon Solvents

    KAUST Repository

    Wadsworth, Andrew

    2017-06-01

    With chlorinated solvents unlikely to be permitted for use in solution-processed organic solar cells in industry, there must be a focus on developing nonchlorinated solvent systems. Here we report high-efficiency devices utilizing a low-bandgap donor polymer (PffBT4T-2DT) and a nonfullerene acceptor (EH-IDTBR) from hydrocarbon solvents and without using additives. When mesitylene was used as the solvent, rather than chlorobenzene, an improved power conversion efficiency (11.1%) was achieved without the need for pre- or post-treatments. Despite altering the processing conditions to environmentally friendly solvents and room-temperature coating, grazing incident X-ray measurements confirmed that active layers processed from hydrocarbon solvents retained the robust nanomorphology obtained with hot-processed chlorinated solvents. The main advantages of hydrocarbon solvent-processed devices, besides the improved efficiencies, were the reproducibility and storage lifetime of devices. Mesitylene devices showed better reproducibility and shelf life up to 4000 h with PCE dropping by only 8% of its initial value.

  19. SAGE 2.1: SOLVENT ALTERNATIVES GUIDE: USER'S GUIDE

    Science.gov (United States)

    The guide provides instruction for using the SAGE (Solvent Alternatives GuidE) software system, version 2.1. SAGE recommends solvent replacements in cleaning and degreasing operations. It leads the user through a question-and-answer session. The user's responses allow the system ...

  20. Compressed air-assisted solvent extraction (CASX) for metal removal.

    Science.gov (United States)

    Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien

    2008-03-01

    A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.

  1. Physiology of solvent tolerance in Pseudomonas putida S12

    NARCIS (Netherlands)

    Isken, S.

    2000-01-01

    Hydrophobic organic solvents, like toluene, are toxic for living organisms. This toxicity is an important drawback in the environmental biotechnology as well as in the application of solvents in the production of fine chemicals by whole-cell biotransformations. The effects of organic

  2. Active efflux of toluene in a solvent-resistant bacterium.

    OpenAIRE

    Isken, S; de Bont, J A

    1996-01-01

    We investigated the mechanisms behind the organic-solvent resistance of the solvent-tolerant strain Pseudomonas putida S12. By use of 14C-labeled toluene, we obtained evidence that an energy-dependent export system may be responsible for this resistance to toluene.

  3. Organic Synthesis under Solvent-free Condition. An Environmentally ...

    Indian Academy of Sciences (India)

    with particular attention to developing new synthetic procedures and reagents, and ... academic interest in solid-solid reactions have led them in recent times to develop methodologies for solvent-free ... ronment-friendly synthetic procedures has made them turn their attention to minimize or circumvent the use of solvents.

  4. The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction

    Science.gov (United States)

    Bandy, Ralph E.; Lakshminarayan, Chitra; Frost, Rex K.; Zwier, Timothy S.

    1993-01-01

    The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.

  5. Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions

    KAUST Repository

    Rai, Durgesh K.

    2016-05-05

    Mass fractal scaling, reflected in the mass fractal dimension df, is independently impacted by topology, reflected in the connectivity dimension c, and by tortuosity, reflected in the minimum dimension dmin. The mass fractal dimension is related to these other dimensions by df=cdmin. Branched fractal structures have a higher mass fractal dimension compared to linear structures due to a higher c, and extended structures have a lower dimension compared to convoluted self-avoiding and Gaussian walks due to a lower dmin. It is found, in this work, that macromolecules in thermodynamic equilibrium display a fixed mass fractal dimension df under good solvent conditions, regardless of chain topology. These equilibrium structures accommodate changes in chain topology such as branching c by a decrease in chain tortuosity dmin. Symmetric star polymers are used to understand the structure of complex macromolecular topologies. A recently published hybrid Unified scattering function accounts for interarm correlations in symmetric star polymers along with polymer-solvent interaction for chains of arbitrary scaling dimension. Dilute solutions of linear, three-arm and six-arm polyisoprene stars are studied under good solvent conditions in deuterated p-xylene. Reduced chain tortuosity can be viewed as steric straightening of the arms. Steric effects for star topologies are quantified, and it is found that steric straightening of arms is more significant for lower-molecular-weight arms. The observation of constant df is explained through a modification of Flory-Krigbaum theory for branched polymers.

  6. Radiation destruction of vitamin A in lipid solvents

    International Nuclear Information System (INIS)

    Snauwaert, F.; Maes, E.; Tobback, P.; Bhushan, B.

    1978-01-01

    The radiation response of vitamin A alcohol and its acetate derivative was compared in different lipid solvents. In all the solvents vitamin A alcohol exhibited a much higher radiation sensitivity than its ester counterpart. The nature of the solvent and the initial concentration was found to have a great influence on the extent of radiation degradation of vitamin A alcohol. In contrast to a high radiolability in non-polar solvents, vitamin A alcohol exhibited a remarkable stability in isopropanol. In addition, in isopropanol the G(-) relationship with radiation dose showed a reverse trend to that observed for other solvents. A thin-layer chromatographic procedure was developed for separation of the radiation degradation products. (author)

  7. [Vapor-liquid equilibria for multicomponent organic solvents].

    Science.gov (United States)

    Ishidao, Toru; Ishimatsu, Sumiyo; Hori, Hajime

    2004-09-01

    Most organic solvents used in the workplace are mixed solvents consisting of several components. It is therefore very important to know the equilibrated vapor concentrations in order to control the work environment. In this study, the vapor-liquid equilibrium for multicomponent organic solvents is estimated by introducing the activity coefficients, which are calculated with the UNIFAC (Universal Quasichemical Functional Group Activity Coefficient) model. For two-component solvents, that is, the toluene-methanol and o-xylene-methanol systems, the calculated values of the vapor fraction and the equilibrated vapor concentrations are in good agreement with the reference ones. For three- or four-component solvents that are used as thinners, the calculated values are also generally in good agreement with the reference ones.

  8. SCENARIOS EVALUATION TOOL FOR CHLORINATED SOLVENT MNA

    Energy Technology Data Exchange (ETDEWEB)

    Vangelas, K; Brian02 Looney, B; Michael J. Truex; Charles J. Newell

    2006-08-16

    Over the past three decades, much progress has been made in the remediation of chlorinated solvents from the subsurface. Yet these pervasive contaminants continue to present a significant challenge to the U.S. Department of Energy (DOE), other federal agencies, and other public and private organizations. The physical and chemical properties of chlorinated solvents make it difficult to rapidly reach the low concentrations typically set as regulatory limits. These technical challenges often result in high costs and long remediation time frames. In 2003, the DOE through the Office of Environmental Management funded a science-based technical project that uses the U.S. Environmental Protection Agency's technical protocol (EPA, 1998) and directives (EPA, 1999) on Monitored Natural Attenuation (MNA) as the foundation on which to introduce supporting concepts and new scientific developments that will support remediation of chlorinated solvents based on natural attenuation processes. This project supports the direction in which many site owners want to move to complete the remediation of their site(s), that being to complete the active treatment portion of the remedial effort and transition into MNA. The overarching objective of the effort was to examine environmental remedies that are based on natural processes--remedies such as Monitored Natural Attenuation (MNA) or Enhanced Attenuation (EA). The research program did identify several specific opportunities for advances based on: (1) mass balance as the central framework for attenuation based remedies, (2) scientific advancements and achievements during the past ten years, (3) regulatory and policy development and real-world experience using MNA, and (4) exploration of various ideas for integrating attenuation remedies into a systematic set of ''combined remedies'' for contaminated sites. These opportunities are summarized herein and are addressed in more detail in referenced project documents and

  9. 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.

  10. 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

  11. Waste and Solvent Composition Limits for Modular Caustic-Side Solvent Extraction Unit (MCU)

    International Nuclear Information System (INIS)

    Adu-Wusu, Kofi; Waler, Douglas D.; Edwards, Thomas B

    2005-01-01

    This study examined waste feed and solvent limits for the Modular Caustic-Side Solvent Extraction Unit (MCU) currently being designed and built at the Savannah River Site (SRS) to remove cesium from highly alkaline radioactive waste. The study involved proposing ranges for 12 waste feed components (i.e., Na + , K + , Cs + , OH - , NO 3 - , NO 2 - , Cl - , F - , SO 4 2- , PO 4 3- , and CO 3 2- , and AlO 2 - ) through a compilation of SRS waste data. Statistical design methods were used to generate numerous wastes with varying compositions from the proposed ranges. An Oak Ridge National Laboratory (ORNL) model called SXFIT was used to predict the cesium extraction distribution coefficients (D-values) between the organic (solvent) phase and the aqueous waste phase using the waste component concentrations as inputs. The D-values from the SXFIT model were used as input along with MCU base case process parameters to a SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) model to calculate final cesium concentrations for the MCU. The SASSE model was developed at Argonne National Laboratory (ANL). The SXFIT D-value and the waste component concentration data were used to develop a handier alternative model (neural network model) to the SXFIT model that predicts D-values within 15% of the SXFIT D-values. Both the SXFIT and the neural network model revealed the following. The solvent extractant concentration ratios are approximately equal to the corresponding D-value ratios; a useful feature that could be used to predict extraction D-values when the extractant concentration in the solvent changes in the MCU operation. Also, potassium is the only waste component out of the 12 that shows a distinct relationship with the cesium extraction D-values; an indication of potassium's competition with cesium in the Caustic-Side Solvent Extraction (CSSX) process. A waste feed acceptance model suitable for assessing wastes within relatively wide ranges of D-values (0.6-40) and

  12. 40 CFR Table 6 to Subpart Vvvv of... - Default Organic HAP Contents of Petroleum Solvent Groups

    Science.gov (United States)

    2010-07-01

    ... Petroleum Solvent Groups 6 Table 6 to Subpart VVVV of Part 63 Protection of Environment ENVIRONMENTAL... Petroleum Solvent Groups As specified in § 63.5758(a)(6), when detailed organic HAP content data for solvent..., Petroleum Spirits, Petroleum Oil, Petroleum Naphtha, Solvent Naphtha, Solvent Blend.) 3 1% Xylene, 1...

  13. On independence in risk communication

    International Nuclear Information System (INIS)

    Lacronique, J. F.

    2006-01-01

    The term 'independence' is a common key word used by almost all stake holders in the field of nuclear safety regulation. The intention is to persuade the public that it can have more confidence and trust in the persons in charge, if their competence and judgment cannot be altered by any kind of political issue or personal interest. However, it is possible to discuss the reality of this claimed quality: how is it possible to verify that the organization that claim 'independence' really respect it? National expertise Institutions can show that they are independent from the industry, but can they claim total independence from the government? NGO have build a large part of their constituency on 'independence' from industry and governments, but are they independent from the ideological forces -sometimes very powerful - that support them? How can we achieve to make this noble word really meaningful? We will show through different examples, that 'independence' is by definition a fragile and versatile challenge, rather than a durable label. It has to be refreshed regularly and thoroughly. Risk communication, in that context, must respect principles which will build independence as a solid asset, and keep a certain distance with mere marketing purposes or candid wishful thinking

  14. Conflict in Independent Catholic Schools

    Science.gov (United States)

    Guernsey, Dan; Barott, James

    2008-01-01

    Independent Catholic schools are a growing phenomenon in the Catholic Church in America. This article provides a contextualized account of the phenomenon by examining via a field observation the experience of two independent Catholic schools in two different dioceses. These schools were founded in conflict and beset by continued conflict to the…

  15. Solvent effects on lipase-catalyzed esterification of glycerol and fatty acids.

    Science.gov (United States)

    Janssen, A E; Van der Padt, A; Riet, K V

    1993-10-01

    The lipase-catalyzed acylglycerol synthesis with fatty acids of different chain length is studied. Measured ester mole fractions at equilibrium are compared with calculated mole fractions. For these calculations the computer program TREP (Two-phase Reaction Equilibrium Prediction) is used. This program is based on the UNIFAC group contribution method and is developed for nondilute two-phase reaction systems.With one set of equilibrium constants, namely 1.3, 0.8, and 0.6 for monoester, diester, and triester synthesis, respectively, the equilibrium position of the reaction between glycerol and all saturated fatty acids with a chain length from 6 to 18 and oleic acid (cis-9-octadecenoic acid) can be calculated. Deviations, expressed as the ratio between calculated and measured ester mole fractions, usually were between 0.7 and 1.2. In the presence of solvents, the deviations of the monoester mole fractions were higher and rose up to 3. Without addition of a solvent, the ester mole fractions at equilibrium are dependent on the fatty acid chain length. With the short-chain hexanoic acid, the monoester mole fraction is the highest ester mole fraction, while for the long-chain oleic acid, the diester mole fraction is the highest one. The ester mole fractions become independent on the chain length of the fatty acid with a solvent added in a sufficient high concentration. Both reactions, with saturated and unsaturated C(18) fatty acids, lead to the same equilibrium position. The program TREP is found to make good predictions of the equilibrium amounts of ester and fatty acid. However, systematic deviations arise between measured and calculated amounts of water and glycerol in the organic phase. The calculated water and glycerol amounts are always lower than the measured ones. These deviations seem to be highest in nonpolar media and are probably due to deficiencies in the UNIFAC calculation method. Some preliminary experiments show the effect of the choice of solvent on the

  16. Defining and Selecting Independent Directors

    Directory of Open Access Journals (Sweden)

    Eric Pichet

    2017-10-01

    Full Text Available Drawing from the Enlightened Shareholder Theory that the author first developed in 2011, this theoretical paper with practical and normative ambitions achieves a better definition of independent director, while improving the understanding of the roles he fulfils on boards of directors. The first part defines constructs like firms, Governance system and Corporate governance, offering a clear distinction between the latter two concepts before explaining the four main missions of a board. The second part defines the ideal independent director by outlining the objective qualities that are necessary and adding those subjective aspects that have turned this into a veritable profession. The third part defines the ideal process for selecting independent directors, based on nominating committees that should themselves be independent. It also includes ways of assessing directors who are currently in function, as well as modalities for renewing their mandates. The paper’s conclusion presents the Paradox of the Independent Director.

  17. Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures.

    Science.gov (United States)

    Almandoz, M C; Sancho, M I; Blanco, S E

    2014-01-24

    The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π(*)). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Surfactant-Solvent Interaction Effects on the Micellization of Cationic Surfactants in a Carboxylic Acid-Based Deep Eutectic Solvent.

    Science.gov (United States)

    Sanchez-Fernandez, Adrian; Hammond, Oliver S; Jackson, Andrew J; Arnold, Thomas; Doutch, James; Edler, Karen J

    2017-12-19

    Deep eutectic solvents have been demonstrated to support amphiphile self-assembly, providing potential alternatives as structure-directing agents in the synthesis of nanostructures, and drug delivery. Here we have expanded on this recent research to investigate the self-assembly of alkyltrimethylammonium bromide surfactants in choline chloride:malonic acid deep eutectic solvent and mixtures of the solvent with water. Surface tension and small-angle neutron scattering were used to determine the behavior of the amphiphiles. Surfactants were found to remain active in the solvent, and surface tension measurements revealed changes in the behavior of the surfactants with different levels of hydration. Small-angle neutron scattering shows that in this solvent the micelle shape depends on the surfactant chain length, varying from globular micelles (aspect ratio ∼2) for short chain surfactants to elongated micelles (aspect ratio ∼14) for long chain surfactants even at low surfactant concentration. We suggest that the formation of elongated micelles can be explained through the interaction of the solvent with the surfactant headgroup, since ion-ion interactions between surfactant headgroups and solvent may modify the morphology of the micelles. The presence of water in the deep eutectic solvents promotes an increase in the charge density at the micelle interface and therefore the formation of less elongated, globular micelles.

  19. Measurement and prediction of dabigatran etexilate mesylate Form II solubility in mono-solvents and mixed solvents

    International Nuclear Information System (INIS)

    Xiao, Yan; Wang, Jingkang; Wang, Ting; Ouyang, Jinbo; Huang, Xin; Hao, Hongxun; Bao, Ying; Fang, Wen; Yin, Qiuxiang

    2016-01-01

    Highlights: • Solubility of DEM Form II in mono-solvents and binary solvent mixtures was measured. • Regressed UNIFAC model was used to predict the solubility in solvent mixtures. • The experimental solubility data were correlated by different models. - Abstract: UV spectrometer method was used to measure the solubility data of dabigatran etexilate mesylate (DEM) Form II in five mono-solvents (methanol, ethanol, ethane-1,2-diol, DMF, DMAC) and binary solvent mixtures of methanol and ethanol in the temperature range from 287.37 K to 323.39 K. The experimental solubility data in mono-solvents were correlated with modified Apelblat equation, van’t Hoff equation and λh equation. GSM model and Modified Jouyban-Acree model were employed to correlate the solubility data in mixed solvent systems. And Regressed UNIFAC model was used to predict the solubility of DEM Form II in the binary solvent mixtures. Results showed that the predicted data were consistent with the experimental data.

  20. Investigating the role of solvent-solute interaction in crystal nucleation of salicylic acid from organic solvents.

    Science.gov (United States)

    Khamar, Dikshitkumar; Zeglinski, Jacek; Mealey, Donal; Rasmuson, Åke C

    2014-08-20

    In previous work, it has been shown that the crystal nucleation of salicylic acid (SA) in different solvents becomes increasingly more difficult in the order: chloroform, ethyl acetate acetonitrile, acetone, methanol, and acetic acid. In the present work, vibration spectroscopy, calorimetric measurements, and density functional theory (DFT) calculations are used to reveal the underlying molecular mechanisms. Raman and infrared spectra suggest that SA exists predominately as dimers in chloroform, but in the other five solvents there is no clear evidence of dimerization. In all solvents, the shift in the SA carbonyl peak reflecting the strength in the solvent-solute interaction is quite well correlated to the nucleation ranking. This shift is corroborated by DFT calculated energies of binding one solvent molecule to the carboxyl group of SA. An even better correlation of the influence of the solvent on the nucleation is provided by DFT calculated energy of binding the complete first solvation shell to the SA molecule. These solvation shell binding energies are corroborated by the enthalpy of solvent-solute interaction as estimated from experimentally determined enthalpy of solution and calculated enthalpy of cavity formation using the scaled particle theory. The different methods reveal a consistent picture and suggest that the stronger the solvent binds to the SA molecule in solution, the slower the nucleation becomes.

  1. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for Solvents and Solvent Blends 4 Table 4 to Subpart OOOO of Part 63 Protection of Environment ENVIRONMENTAL..., and Dyeing of Fabrics and Other Textiles Pt.63, Subpt. OOOO, Table 4 Table 4 to Subpart OOOO of Part...

  2. Extraction, scrub, and strip test results for the salt waste processing facility caustic side solvent extraction solvent example

    Energy Technology Data Exchange (ETDEWEB)

    Peters, T. B. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-08-01

    An Extraction, Scrub, and Strip (ESS) test was performed on a sample of Salt Waste Processing Facility (SWPF) Caustic-Side Solvent Extraction (CSSX) solvent and salt simulant to determine cesium distribution ratios (D(Cs)), and cesium concentration in the strip effluent (SE) and decontaminated salt solution (DSS) streams; this data will be used by Parsons to help determine if the solvent is qualified for use at the SWPF. The ESS test showed acceptable performance of the solvent for extraction, scrub, and strip operations. The extraction D(Cs) measured 12.9, exceeding the required value of 8. This value is consistent with results from previous ESS tests using similar solvent formulations. Similarly, scrub and strip cesium distribution ratios fell within acceptable ranges.

  3. Extraction, Scrub, and Strip Test Results for the Salt Waste Processing Facility Caustic Side Solvent Extraction Solvent Sample

    Energy Technology Data Exchange (ETDEWEB)

    Peters, T. B. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    An Extraction, Scrub, and Strip (ESS) test was performed on a sample of Salt Waste Processing Facility (SWPF) Caustic-Side Solvent Extraction (CSSX) solvent and salt simulant to determine cesium distribution ratios (D(Cs)), and cesium concentration in the strip effluent (SE) and decontaminated salt solution (DSS) streams; this data will be used by Parsons to help determine if the solvent is qualified for use at the SWPF. The ESS test showed acceptable performance of the solvent for extraction, scrub, and strip operations. The extraction D(Cs) measured 12.5, exceeding the required value of 8. This value is consistent with results from previous ESS tests using similar solvent formulations. Similarly, scrub and strip cesium distribution ratios fell within acceptable ranges. This revision was created to correct an error. The previous revision used an incorrect set of temperature correction coefficients which resulted in slight deviations from the correct D(Cs) results.

  4. SOLVENT EXTRACTION OF GINGER OLEORESIN USING ULTRASOUND

    Directory of Open Access Journals (Sweden)

    Normalina Arpi

    2011-11-01

    Full Text Available The use of ultrasound in extraction process creates novel and interesting methodologies, which are oftencomplementary to conventional extraction methods. In the present study, the use of ultrasound to extract oleoresin fromginger (Zingiber officinale R. was investigated. The extraction was performed by using ethanol as solvent in thepresence of ultrasonic irradiations operating at frequency of 42 kHz at extraction temperature of 60 oC. The oleoresinextracted was in the form of dark thick liquid with specific ginger flavor. Based on GC-MS analysis, the use ofultrasound was not give an effect on alteration of main component in ginger oleoresin. The main component inextracted ginger oleoresin was zingerone. Gingerol as one of the pungent principle of the ginger oleoresin was notdetected due to decomposition of gingerol at a temperature above 45 oC. Extraction rate of ultrasound-assistedextraction was about 1.75 times more rapid than a conventional system based on soxhlet. The scanning electronmicroscopy images provided more evidence for the mechanical effects of ultrasound, mainly appearing on cells’ wallsand shown by the destruction of cells, facilitating the release of their contents.

  5. Solvent effects in the nucleophilic substitutions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate: trichloroethylene as solvent for stereoselective C- and O-glycosylations.

    Science.gov (United States)

    Kendale, Joanna C; Valentín, Elizabeth M; Woerpel, K A

    2014-07-18

    The selectivities of nucleophilic substitution reactions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate depend upon the reaction solvent. Polar solvents favor the formation of S(N)1 products, while nonpolar solvents favor S(N)2 products. Trichloroethylene was identified as the solvent most likely to give S(N)2 products in both C- and O-glycosylation reactions.

  6. Spectroscopic and excited-state properties of tri-9-anthrylborane I: Solvent polarity effects.

    Science.gov (United States)

    Kitamura, Noboru; Sakuda, Eri

    2005-08-25

    Spectroscopic and excited-state properties of tri-9-anthrylborane (TAB), showing unique absorption and fluorescence characteristics originating from p(boron)-pi(anthryl group) orbital interactions, were studied in 12 solvents. Although the absorption maximum energy (nu(a)) of TAB which appeared at around 21 x 10(3) cm(-1) (band I) was almost independent of the solvent polarity parameter, f(X) (f(X) = (D(s) - 1)/(2D(s) + 1) - (n(2) - 1)/(2n(2) + 1) where D(s) and n represent the static dielectric constant and the refractive index of a solvent, respectively), the fluorescence maximum energy (nu(f)) showed a linear correlation with f(X). The f(X) dependence of the value of nu(a) - nu(f) demonstrated that the change in the dipole moment of TAB upon light excitation was approximately 8.0 D, indicating that absorption band I was ascribed to an intramolecular charge-transfer transition in nature. The excited electron of TAB was thus concluded to localize primarily on the p orbital of the boron atom. Furthermore, it was shown that the fluorescence lifetime and quantum yield of TAB varied from 11.8 to 1.1 ns and from 0.41 to 0.02, respectively, with an increase in f(X). The present results indicated that the nonradiative decay rate constant (k(nr)) of TAB was influenced significantly by f(X). Excited-state decay of TAB was understood by intramolecular back-electron (charge) transfer from the p orbital of the boron atom to the pi orbital of the anthryl group, which was discussed in terms of the energy gap dependence of k(nr). Specific solvent interactions of TAB revealed by the present spectroscopic and photophysical studies are also discussed.

  7. Psychomotor Effects of Mixed Organic Solvents on Rubber Workers

    Directory of Open Access Journals (Sweden)

    O Aminian

    2014-04-01

    Full Text Available Background: Exposure to organic solvents is common among workers. Objective: To assess neurobehavioral effects of long-term exposure to organic solvents among rubber workers in Tehran, Iran. Methods: Across-sectional study was conducted on 223 employees of a rubber industry. The participants completed a data collection sheet on their occupational and medical history, and demographic characteristics including age, work experience, education level; they performed 6 psychiatric tests on the neurobehavioral core test battery (NCTB that measure simple reaction time, short-term memory (digit span, Benton, eye-hand coordination (Purdue pegboard, pursuit aiming, and perceptual speed (digit symbol. Results: Workers exposed and not exposed to organic solvents had similar age and education distribution. The mean work experience of the exposed and non-exposed workers was 5.9 and 4.4 years, respectively. The exposed workers had a lower performance compared to non-exposed workers in all psychomotor tests. After controlling for the confounders by logistic regression analysis, it was found that exposure to organic solvents had a significant effect on the results of digit symbols, digit span, Benton, aiming, and simple reaction time tests. No significant effect was observed in pegboard test. Conclusion: Occupational exposure to organic solvent can induce subtle neurobehavioral changes among workers exposed to organic solvents; therefore, periodical evaluation of the central nervous system by objective psychomotor tests is recommended among those who are chronically exposed to organic solvents.

  8. Background Noise Contributes to Organic Solvent Induced Brain Dysfunction.

    Science.gov (United States)

    Guthrie, O'neil W; Wong, Brian A; McInturf, Shawn M; Reboulet, James E; Ortiz, Pedro A; Mattie, David R

    2016-01-01

    Occupational exposure to complex blends of organic solvents is believed to alter brain functions among workers. However, work environments that contain organic solvents are also polluted with background noise which raises the issue of whether or not the noise contributed to brain alterations. The purpose of the current study was to determine whether or not repeated exposure to low intensity noise with and without exposure to a complex blend of organic solvents would alter brain activity. Female Fischer344 rats served as subjects in these experiments. Asynchronous volume conductance between the midbrain and cortex was evaluated with a slow vertex recording technique. Subtoxic solvent exposure, by itself, had no statistically significant effects. However, background noise significantly suppressed brain activity and this suppression was exacerbated with solvent exposure. Furthermore, combined exposure produced significantly slow neurotransmission. These abnormal neurophysiologic findings occurred in the absence of hearing loss and detectable damage to sensory cells. The observations from the current experiment raise concern for all occupations where workers are repeatedly exposed to background noise or noise combined with organic solvents. Noise levels and solvent concentrations that are currently considered safe may not actually be safe and existing safety regulations have failed to recognize the neurotoxic potential of combined exposures.

  9. Solvent effects on lasing characteristics for Rh B laser dye

    Energy Technology Data Exchange (ETDEWEB)

    Peter, Jaison, E-mail: jaison.peter@gmail.com [International School of Photonics, Cochin University of Science and Technology, Cochin 682022 (India); Kumar, Mahesh [Department of Applied Chemistry, Cochin University of Science and Technology, Cochin 682022 (India); Ananad, V.R.; Saleem, Rasool; Sebastian, Ananthu; Radhakrishnan, P.; Nampoori, V.P.N.; Vallabhan, C.P.G. [International School of Photonics, Cochin University of Science and Technology, Cochin 682022 (India); Prabhu, Radhakrishna [School of Engineering, Robert Gordon University, Aberdeen AB10 1FR, Scotland (United Kingdom); Kailasnath, M. [International School of Photonics, Cochin University of Science and Technology, Cochin 682022 (India)

    2016-01-15

    We demonstrate pulsed, photopumped multimode laser emission in the visible spectral range from rhodamine B dye dissolved in various solvents. The laser emission is characterized by a well-defined, low threshold pump power at which the emission spectral intensity dramatically increases and collapsed into several dominant laser modes with reduced mode spacing and spectral width. The modes were found to originate from the subcavities formed by the plane-parallel walls of the cuvette containing the gain medium. The cavity lasing spectral structure and the numbers of longitudinal modes were easily controlled by changing the solvents. A shift in the emission spectra has been also observed by changing the solvents will allow a limited range of tuning of laser emission wavelength. We also determined the gain coefficient and stimulated emission cross-section for the Rh B dye dissolved liquid laser system. A detailed discussion of the solvent effect in the lasing characteristics of Rh B in different solution is explained along with the computational data. - Highlights: • Report multimode laser emission from rhodamine B dye dissolved in various solvents. • Modes are originated from the plane-parallel walls of the cuvette. • Spectral range and the number of modes can be controlled by changing the solvents. • Changing solvents also allows a limited range of tuning of laser emission.

  10. Measurement of oxygen transfer from air into organic solvents

    Science.gov (United States)

    Ramesh, Hemalata; Hobisch, Mathias; Borisov, Sergey; Klimant, Ingo; Krühne, Ulrich; Woodley, John M

    2015-01-01

    Abstract BACKGROUND The use of non‐aqueous organic media is becoming increasingly important in many biotechnological applications in order to achieve process intensification. Such media can be used, for example, to directly extract poorly water‐soluble toxic products from fermentations. Likewise many biological reactions require the supply of oxygen, most normally from air. However, reliable online measurements of oxygen concentration in organic solvents (and hence oxygen transfer rates from air to the solvent) has to date proven impossible due to limitations in the current analytical methods. RESULTS For the first time, online oxygen measurements in non‐aqueous media using a novel optical sensor are demonstrated. The sensor was used to measure oxygen concentration in various organic solvents including toluene, THF, isooctane, DMF, heptane and hexane (which have all been shown suitable for several biological applications). Subsequently, the oxygen transfer rates from air into these organic solvents were measured. CONCLUSION The measurement of oxygen transfer rates from air into organic solvents using the dynamic method was established using the solvent resistant optical sensor. The feasibility of online oxygen measurements in organic solvents has also been demonstrated, paving the way for new opportunities in process control. © 2015 The Authors. Journal of Chemical Technology & Biotechnology published by JohnWiley & Sons Ltd on behalf of Society of Chemical Industry. PMID:27773958

  11. 300 area solvent evaporator interim status closure plan: Revision 2

    International Nuclear Information System (INIS)

    1989-02-01

    This document describes activities for the closure of a hazardous waste tank treatment facility operated by the US Department of Energy-Richland Operations Office (DOE-RL) and co-operated by the Westinghouse Hanford Company (WHC). This treatment facility was a solvent evaporator located in the 300 Area of the Hanford Site, from 1975 to 1985 on behalf of DOE-RL. The 300 Area Solvent Evaporator (300 ASE) was a modified load lugger (dumpster) in which solvent wastes were evaporated. Some of the solvents were radioactively contaminated because they came from a degreaser which processed bare uranium metal billets from the N Reactor Fuel Manufacturing Facility. The waste was composed of perchloroethylene, trichloroethylene, 1,1,1-trichloroethane, ethyl acetate/bromine solution, paint shop solvents and possibly some used oil. Also, small amounts of uranium, copper, zirconium and possibly beryllium were present in the degreaser solvents as particulates. Radioactive and non-radioactive solvents were not segregated in the 300 ASE, and the entire mixture was regarded as mixed waste

  12. Organic solvent modifier and temperature effects in non-aqueous size-exclusion chromatography on reversed-phase columns.

    Science.gov (United States)

    Caltabiano, Anna M; Foley, Joe P; Striegel, André M

    2018-01-05

    Common reversed-phase columns (C 18 , C 4 , phenyl, and cyano) offer inert surfaces suitable for the analysis of polymers by size-exclusion chromatography (SEC). The effect of tetrahydrofuran (THF) solvent and the mixtures of THF with a variety of common solvents used in high performance liquid chromatography (acetonitrile, methanol, dimethylformamide, 2-propanol, ethanol, acetone and chloroform) on reversed-phase stationary phase characteristics relevant to size exclusion were studied. The effect of solvent on the elution of polystyrene (PS) and poly(methyl methacrylate) (PMMA) and the effect of column temperature (within a relatively narrow range corresponding to typical chromatographic conditions, i.e., 10°C-60°C) on the SEC partition coefficients K SEC of PS and PMMA polymers, were also investigated. The bonded phases show remarkable differences in size separations when binary mixtures of THF with other solvents are used as the mobile phase. The solvent impact can be two-fold: (i) change of the polymeric coil size, and possible shape, and (ii) change of the stationary phase pore volume. If the effect of this impact is properly moderated, then the greatest benefit of optimized solute resolution can be achieved. Additionally, this work provides an insight on solvent-stationary phase interactions and their effects on column pore volume. The only effect of temperature observed in our studies was a decreased elution volume of the polymers with increasing temperature. SEC partition coefficients were temperature-independent in the range of 10°C-60°C and therefore, over this temperature range elution of PS and PMMA polymers is by near-ideal SEC on reversed-phase columns. Non-ideal SEC appears to occur for high molar mass PMMA polymers on a cyano column when alcohols are used as mobile phase modifiers. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Parameters Affecting Solvent Production by Clostridium pasteurianum

    OpenAIRE

    Dabrock, Birgit; Bahl, Hubert; Gottschalk, Gerhard

    1992-01-01

    The effect of pH, growth rate, phosphate and iron limitation, carbon monoxide, and carbon source on product formation by Clostridium pasteurianum was determined. Under phosphate limitation, glucose was fermented almost exclusively to acetate and butyrate independently of the pH and growth rate. Iron limitation caused lactate production (38 mol/100 mol) from glucose in batch and continuous culture. At 15% (vol/vol) carbon monoxide in the atmosphere, glucose was fermented to ethanol (24 mol/100...

  14. Centrifugal contractors for laboratory-scale solvent extraction tests

    International Nuclear Information System (INIS)

    Leonard, R.A.; Chamberlain, D.B.; Conner, C.

    1995-01-01

    A 2-cm contactor (minicontactor) was developed and used at Argonne National Laboratory for laboratory-scale testing of solvent extraction flowsheets. This new contactor requires only 1 L of simulated waste feed, which is significantly less than the 10 L required for the 4-cm unit that had previously been used. In addition, the volume requirements for the other aqueous and organic feeds are reduced correspondingly. This paper (1) discusses the design of the minicontactor, (2) describes results from having applied the minicontactor to testing various solvent extraction flowsheets, and (3) compares the minicontactor with the 4-cm contactor as a device for testing solvent extraction flowsheets on a laboratory scale

  15. Concentration of heavy metals by predispersed solvent extraction

    International Nuclear Information System (INIS)

    Beyer, G.H.; Rodarte, A.; Sebba, F.

    1986-01-01

    This paper discusses a new method to recover and purify solutions containing dissolved metals. The method depends upon dispersion of the solvent prior to contacting the solution to be extracted. In the past, minutely subdividing the solvent has proven impractical because of the slow rate at which minute particles rise by buoyancy. Now it has become feasible to transport small globules of solvent by a allowing them to attach to much larger gas bubbles, which rise quickly to the surface and separate cleanly. This technique makes possible the removal of metals down to the parts-per-billion range

  16. Acids and bases solvent effects on acid-base strenght

    CERN Document Server

    Cox, Brian G

    2013-01-01

    Acids and bases are ubiquitous in chemistry. Our understanding of them, however, is dominated by their behaviour in water. Transfer to non-aqueous solvents leads to profound changes in acid-base strengths and to the rates and equilibria of many processes: for example, synthetic reactions involving acids, bases and nucleophiles; isolation of pharmaceutical actives through salt formation; formation of zwitter- ions in amino acids; and chromatographic separation of substrates. This book seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous solvents. The behaviour is related where possible to that in water, but correlations and contrasts between solvents are also presented.

  17. Terpenes as Green Solvents for Extraction of Oil from Microalgae

    Directory of Open Access Journals (Sweden)

    Celine Dejoye Tanzi

    2012-07-01

    Full Text Available Herein is described a green and original alternative procedure for the extraction of oil from microalgae. Extractions were carried out using terpenes obtained from renewable feedstocks as alternative solvents instead of hazardous petroleum solvents such as n-hexane. The described method is achieved in two steps using Soxhlet extraction followed by the elimination of the solvent from the medium using Clevenger distillation in the second step. Oils extracted from microalgae were compared in terms of qualitative and quantitative determination. No significant difference was obtained between each extract, allowing us to conclude that the proposed method is green, clean and efficient.

  18. Terpenes as green solvents for extraction of oil from microalgae.

    Science.gov (United States)

    Dejoye Tanzi, Celine; Abert Vian, Maryline; Ginies, Christian; Elmaataoui, Mohamed; Chemat, Farid

    2012-07-09

    Herein is described a green and original alternative procedure for the extraction of oil from microalgae. Extractions were carried out using terpenes obtained from renewable feedstocks as alternative solvents instead of hazardous petroleum solvents such as n-hexane. The described method is achieved in two steps using Soxhlet extraction followed by the elimination of the solvent from the medium using Clevenger distillation in the second step. Oils extracted from microalgae were compared in terms of qualitative and quantitative determination. No significant difference was obtained between each extract, allowing us to conclude that the proposed method is green, clean and efficient.

  19. Leaching and solvent extraction at Mary Kathleen Uranium Ltd

    International Nuclear Information System (INIS)

    Richmond, G.D.

    1978-01-01

    Mary Kathleen Uranium Ltd. recommenced operations in early 1976 following a twelve year period of care and maintenance. Several sections of the plant were modified or completely changed for the second operation. The most important change was the replacement of ion exchange with solvent extraction as the means of purifying and upgrading uranium rich solutions. Most of the problems experienced in the solvent extraction system originate from the leach liquor which has a strong tendency to form stable emulsions. This has been countered by some careful control of leaching conditions and by closer observation of operations in the solvent extraction area. Most problems have now been resolved and plant recoveries are quite satisfactory

  20. Optimal (Solvent) Mixture Design through a Decomposition Based CAMD methodology

    DEFF Research Database (Denmark)

    Achenie, L.; Karunanithi, Arunprakash T.; Gani, Rafiqul

    2004-01-01

    Computer Aided Molecular/Mixture design (CAMD) is one of the most promising techniques for solvent design and selection. A decomposition based CAMD methodology has been formulated where the mixture design problem is solved as a series of molecular and mixture design sub-problems. This approach is...... is able to overcome most of the difficulties associated with the solution of mixture design problems. The new methodology has been illustrated with the help of a case study involving the design of solvent-anti solvent binary mixtures for crystallization of Ibuprofen....

  1. Algae: America's Pathway to Independence

    National Research Council Canada - National Science Library

    Custer, James

    2007-01-01

    .... Oil dependency is an unacceptable risk to U.S. national strategy. This paper advocates independence from foreign oil by converting the national transportation fleet to biodiesel derived from algae...

  2. Logical independence and quantum randomness

    International Nuclear Information System (INIS)

    Paterek, T; Kofler, J; Aspelmeyer, M; Zeilinger, A; Brukner, C; Prevedel, R; Klimek, P

    2010-01-01

    We propose a link between logical independence and quantum physics. We demonstrate that quantum systems in the eigenstates of Pauli group operators are capable of encoding mathematical axioms and show that Pauli group quantum measurements are capable of revealing whether or not a given proposition is logically dependent on the axiomatic system. Whenever a mathematical proposition is logically independent of the axioms encoded in the measured state, the measurement associated with the proposition gives random outcomes. This allows for an experimental test of logical independence. Conversely, it also allows for an explanation of the probabilities of random outcomes observed in Pauli group measurements from logical independence without invoking quantum theory. The axiomatic systems we study can be completed and are therefore not subject to Goedel's incompleteness theorem.

  3. Logical independence and quantum randomness

    Energy Technology Data Exchange (ETDEWEB)

    Paterek, T; Kofler, J; Aspelmeyer, M; Zeilinger, A; Brukner, C [Institute for Quantum Optics and Quantum Information, Austrian Academy of Sciences, Boltzmanngasse 3, A-1090 Vienna (Austria); Prevedel, R; Klimek, P [Faculty of Physics, University of Vienna, Boltzmanngasse 5, A-1090 Vienna (Austria)], E-mail: tomasz.paterek@univie.ac.at

    2010-01-15

    We propose a link between logical independence and quantum physics. We demonstrate that quantum systems in the eigenstates of Pauli group operators are capable of encoding mathematical axioms and show that Pauli group quantum measurements are capable of revealing whether or not a given proposition is logically dependent on the axiomatic system. Whenever a mathematical proposition is logically independent of the axioms encoded in the measured state, the measurement associated with the proposition gives random outcomes. This allows for an experimental test of logical independence. Conversely, it also allows for an explanation of the probabilities of random outcomes observed in Pauli group measurements from logical independence without invoking quantum theory. The axiomatic systems we study can be completed and are therefore not subject to Goedel's incompleteness theorem.

  4. Uranium extraction from colofanite via organic solvents

    International Nuclear Information System (INIS)

    Ribeiro, Valeria Aparecida Leitao

    2007-01-01

    This work describes the use of pure or combined extractants dissolved in organic solvents for quantitative uranium recovery from colofanite, a fluoroapatite ore, from Itataia, Santa Quiteria, Ceara, Brazil. This ore contains the highest brazilian uranium reserve. The metal is associated to phosphate species. The ore is digested with sulfuric acid (wet process), producing phosphoric acid, which is used for manufacturing of fertilizers and animal food. >From the acid leaching, some systems for uranium recovery were tested. Among them, PC88A (2-ethyl-hexyl phosphonic acid, mono-2-ethyl-hexyl ester) 40% vol. and DEHPA (di(2-ethyl-hexyl)phosphoric acid) 40% vol. in kerosene presented the highest values for the distribution coefficient (D) for uranium. When synergistic systems were employed, the best results were obtained for DEHPA 40%vol. + PC88A 40%vol. and DEHPA 40% vol. + TOPO (trioctylphosphine oxide) 5% vol. in kerosene. 15% wt/v sodium carbonate was the best medium for uranium stripping and separation from iron, the main interfering element. Uranium was precipitated as sodium diuranate by adding sodium hydroxide (5,0 mol L -1 ). Thorium in the raffinate was extracted by TOPO (0,1% vol.) in cyclohexane. The radioactivity level of the final aqueous waste is similar to natural background, according to CNEN-NE 6.05 Norm. After neutralization, the solid can be co-processed, according to the Directory 264 from the National Brazilian Environmental Council (CONAMA), whereas the treated effluent can be discarded according to the Directory 357 from CONAMA. (author)

  5. Independent production and Poisson distribution

    International Nuclear Information System (INIS)

    Golokhvastov, A.I.

    1994-01-01

    The well-known statement of factorization of inclusive cross-sections in case of independent production of particles (or clusters, jets etc.) and the conclusion of Poisson distribution over their multiplicity arising from it do not follow from the probability theory in any way. Using accurately the theorem of the product of independent probabilities, quite different equations are obtained and no consequences relative to multiplicity distributions are obtained. 11 refs

  6. Solvents in Organic Synthesis: Replacement and Multi-step Reaction Systems

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Gómez, Paola Arenas; Folic, Milica

    2008-01-01

    with the principles of green chemistry, highlight the need to minimize and optimize the use of organic solvents as much as possible. One important step in optimizing organic solvent use is the identification of suitable ‘greener' solvents that can help to minimize the environmental, health and safety concerns during...... solvent screening problem, several solvent replacement problems and a multi-stage reaction system. In each example a list of solvent candidates is generated so they may be further investigated experimentally....

  7. Tracking Solvent Distribution in Block Polymer Thin Films with In Situ Solvent Vapor Annealing during Neutron Scattering

    Science.gov (United States)

    Shelton, Cameron; Jones, Ronald; Dura, Joseph; Epps, Thomas

    Solvent vapor annealing (SVA) is a potential route to controlling the self-assembly of block polymer nanostructures in thin film geometries as it harnesses the ability to tune substrate surface, free surface, and polymer-polymer interactions simultaneously. However, the effect of parameters such as solvent preference and solvent partial pressure on nanostructure self-assembly is still poorly understood. Herein, we quantified the degree of preferential segregation of d-benzene into polystyrene domains of cylinder-forming poly(styrene-b-isoprene-b-styrene) as a function of film thickness and solvent partial pressure. Additionally, measurable changes in lateral domain spacing, vertical layer spacing, film thickness, and the number of stacked domains at set partial pressures were used to determine how solvent-polymer interactions affected nanostructure reorganization. These in situ experiments were conducted with a combination of small-angle neutron scattering (SANS) and neutron reflectivity (NR), which allowed us to obtain a 3-D profile of solvent distribution and nanostructure self-assembly. By studying the underlying solvent-polymer interactions, this work provides an improved understanding of the mechanisms responsible for nanostructure reorganization during SVA.

  8. Solvent-assisted electrospray ionization for direct analysis of various compounds (complex) from low/nonpolar solvents and eluents.

    Science.gov (United States)

    Zhang, Jun-Ting; Wang, Hao-Yang; Zhu, Wei; Cai, Ting-Ting; Guo, Yin-Long

    2014-09-16

    Electrospray ionization (ESI) is a powerful ionization technique with a wide range of applications. However, the analytes in low/nonpolar solvents cannot be analyzed directly in electrospray ionization-mass spectrometry (ESI-MS), because low/nonpolar solvents are incompatible with ESI, because of their low conductivity. To circumvent this problem, we introduce an electrospray-based ionization method termed solvent-assisted electrospray ionization (SAESI). With the help of electrospray solvents at the tip of the spray needle, compounds in "non-electrospray ionization-friendly" solvents can be ionized directly using solvent-assisted electrospray ionization-mass spectrometry (SAESI-MS). The key features that the assistant solvent can be chosen flexibly and makes little interference to samples lead to better ionization performance in detection of organic reaction intermediates and real-time analysis of polymers and chiral drugs separated by gel permeation chromatography (GPC) and normal phase liquid chromatography (NPLC). Furthermore, it can achieve online hydrogen/deuterium (H/D) exchange reaction and even mitigate the signal suppression caused by strong acid modifiers in liquid chromatography. In addition, all parts of this device are commercially available and it only requires two parameters to be optimized, which makes SAESI easy to handle.

  9. Water soluble peripheral and non-peripheral tetrasubstituted zinc phthalocyanines: Synthesis, photochemistry and bovine serum albumin binding behavior

    Energy Technology Data Exchange (ETDEWEB)

    Çakır, Volkan; Çakır, Dilek [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Pişkin, Mehmet [Department of Food Technology, Çanakkale Vocational School of Technical Sciences, Çanakkale Onsekiz Mart University, 17100 Çanakkale (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze 41400, Kocaeli (Turkey); Bıyıklıoğlu, Zekeriya, E-mail: zekeriya_61@yahoo.com [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2014-10-15

    The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV–vis, FT-IR, {sup 1}H-NMR, {sup 13}C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS+triton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or non-peripherally) and nature of the solvents (DMSO, PBS or PBS+triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work. - Highlights: • Synthesis of zinc phthalocyanines is performed. • Photophysical and photochemical properties of phthalocyanines are studied. • Photodynamic therapy studies are performed.

  10. Hydrogen-bonded encapsulation complexes in protic solvents.

    Science.gov (United States)

    Amaya, Toru; Rebek, Julius

    2004-11-03

    We describe here the behavior of the hydrogen-bonded capsule 1.1 and its complexes in protic solvents. The kinetics and thermodynamics of the encapsulation process were determined through conventional (1)H NMR methods. The enthalpies and entropies of encapsulation are both positive, indicating a process that liberates solvent molecules. The rates of dissociation-association of the capsule were comparable to the rates for the in-out exchange of large guests, which suggests that guest exchange occurs by complete dissociation of the capsule in protic solvents. The stability of the hydrogen-bonded capsule 1.1 toward protic solvents depends strongly on the guests, with the best guest being dimethylstilbene 8. The results establish guidelines for the properties of capsules that could be accessed in water.

  11. Solvent effects on the magnetic shielding of tertiary butyl alcohol

    African Journals Online (AJOL)

    )4 and tetramethyl ammonium cation N(CH3)4(+) have also been presented. KEY WORDS: Solvent effects, Magnetic shielding, Tertiary butyl alcohol, Tertiary butyl amine, Continuum solvation calculations, Chemical shift estimation methods

  12. Solvent vapor annealing of an insoluble molecular semiconductor

    KAUST Repository

    Amassian, Aram

    2010-01-01

    Solvent vapor annealing has been proposed as a low-cost, highly versatile, and room-temperature alternative to thermal annealing of organic semiconductors and devices. In this article, we investigate the solvent vapor annealing process of a model insoluble molecular semiconductor thin film - pentacene on SiO 2 exposed to acetone vapor - using a combination of optical reflectance and two-dimensional grazing incidence X-ray diffraction measurements performed in situ, during processing. These measurements provide valuable and new insight into the solvent vapor annealing process; they demonstrate that solvent molecules interact mainly with the surface of the film to induce a solid-solid transition without noticeable swelling, dissolving or melting of the molecular material. © 2010 The Royal Society of Chemistry.

  13. Study on electrohydrodynamic jetting performance of organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Soo Hong; Nguyen, Xuan Hung; Gim, Yeong Hyeon; Ko, Han Seo [Sungkyunkwan University, Suwon (Korea, Republic of)

    2015-11-15

    The electrohydrodynamic (EHD) inkjet method is a printing technology using electricity. This technique allows for the printing of EML (Emission layer) materials, usually used for OLED devices, on a substrate. In this study, ejection experiments were performed with various solvents to verify which of them is properly ejected in the EHD method. The solvents employed were dielectric liquids with low viscosity and it was confirmed that among them two solvents, 1,2-Dichlorobenzene (DCB) and 1,2-Dichloroethane (DCE), produced the pulsating cone-Jet mode and stable cone-jet mode well. In addition, experiments were conducted to find out how the voltage and applied flux influence the ejection mode, in order to apply the result to the ejection control. It was found that the selected solvent was easily ejected and printed, due to the free surface charge and charge density determined by the dielectric constant. Finally, a patterning experiment was performed to verify proper printing.

  14. Comparative study of aqueous and solvent methods for cleaning metals

    International Nuclear Information System (INIS)

    Briggs, J.L.; Goad, H.A.

    1976-01-01

    Studies were performed to determine the comparative effectiveness of solvent and aqueous detergent methods for cleaning various metals. The metals investigated included 304L stainless steel, beryllium, uranium-6.5 wt percent niobium alloy, and unalloyed uranium ( 238 U). The studies were initiated in response to governmental regulations restricting the use of some chlorinated solvents. Results showed that aqueous detergent cleaning was more effective than solvents, i.e. trichloroethylene and methyl chloroform, for the removal of light industrial soils. The subsequent adoption of aqueous cleaning at this plant has facilitated waste disposal, which contributed to recorded economic savings. The controlled use of aqueous detergents is environmentally acceptable and has decreased the hazards of fire and toxicity that are generally associated with solvents. 8 tables, 15 figures

  15. Solids Modelling and Capture Simulation of Piperazine in Potassium Solvents

    DEFF Research Database (Denmark)

    Fosbøl, Philip Loldrup; Maribo-Mogensen, Bjørn; Thomsen, Kaj

    2012-01-01

    all parts of the streams, but also during formulation and transport of the solvent.In this work the extended UNIQUAC thermodynamic model is presented with the addition of piperazine (PZ or PIPH2) in combination with the potassium ion of mixtures with CO2 in equilibration with KOH-KHCO3-K2CO3. Phase...... the typical phase behavior will be shown for the PZ solvent with potassium (K2CO3/KHCO3) for CO2 capture. Conclusions are given on a solvent compositions resulting in low heat requirements using the predictive nature of the extended UNIQUAC model. Concentration of a PZ/K2CO3 solvent is suggested with a heat...

  16. Inactivation of yeast inorganic pyrophosphatase by organic solvents

    Directory of Open Access Journals (Sweden)

    Rodrigo Grazinoli-Garrido

    2004-12-01

    Full Text Available A number of application for enzymes in organic solvents have been developed in chemical processing, food related conversions and analyses. The only unsolved problem related to nonaqueous enzymology is the notion that enzymes in organic solvent are mostly far less active than in water. Therefore, studies concerning the mechanisms by which enzymes are inactivated by organic solvents would reveal a clear understanding of the structure-function relationship of this phenomenon. Here we analyzed the effects of a series of alcohols (methanol, ethanol, 1-propanol and 2-propanol and acetone on the activity of yeast inorganic pyrophosphatase. We observed that solvents inactivated the enzyme in a dose-dependent manner. This inactivation is also dependent on the hydrophobicity of the solvent, where the most hydrophobic solvent is also the most effective one. The I50 for inactivation by n-alcohols are 5.9±4, 2.7±1 and 2.5±1 M for methanol, ethanol and 1-propanol, respectively. Inactivation was less effective at 37C than at 5C, when the I50 for inactivation by methanol, ethanol and 1-propanol are 4.5±2, 2.1±2 and 1.7±1 M, respectively. Our proposal is that solvent binds to the enzyme structure promoting the inactivation by stabilizing an unfolded structure, and that this binding is through the hydrophobic regions of either the protein or the solvent.Várias aplicações para a catálise enzimática em solventes orgânicos têm sido desenvolvidas visando processos químicos, industria alimentícia e métodos analíticos. Entretanto, o único problema ainda não resolvido para estas aplicações é o fato que estes catalisadores são bem menos ativos nestas condições que em meio aquoso. Assim, estudos dos mecanismos pelos quais as enzimas são inativadas em solventes orgânicos podem facilitar a compreensão da interrelação estrutura/função da interação entre os catalisadores e o solvente. Neste trabalho, nós analisamos os efeitos de uma s

  17. Fabrication of a thin catalyst layer using organic solvents

    Science.gov (United States)

    Yang, Tae-Hyun; Yoon, Young-Gi; Park, Gu-Gon; Lee, Won-Yong; Kim, Chang-Soo

    The effects of various organic solvents on the performance of polymer electrolyte membrane fuel cell (PEMFC) electrode were investigated. The five catalyst inks were prepared by mixing the 20 wt.% Pt/C, 5 wt.% solubilized Nafion, tetrabutylammonium hydroxide (TBAOH), and different organic solvents such as normal butyl acetate, iso-amyl alcohol, diethyl oxalate, ethylene glycol and ethylene glycol dimethyl ether. Membrane electrode assemblies were prepared by using a transfer method. From the measurements of performances of single cells, the most suitable solvent was selected and the results were discussed in terms of distribution of Nafion ionomer on Pt particles and robustness of the catalyst structure. In addition, reactant transport through electrodes was discussed in relation with decomposition of the solvents.

  18. Influence of solvent on micellar morphologies of semifluorinated block copolymers.

    Science.gov (United States)

    Lee, Min Young; Kim, Sang Jae; Jeong, Yeon Tae; Kim, Joo Hyun; Gal, Yeong-Soon; Lim, Kwon Taek

    2009-12-01

    The influence of solvents on micellar architectures of block copolymers composed of poly(1H,1H-dihydroperfluorooctyl methacrylate) and poly(ethylene oxide) was investigated. In this study, binary solvents with desired proportions were chosen, which had remarkable influence on the morphology of the resulting micelles. With simple adjusting the composition of the binary solvent of chloroform and trichlorofluoromethane, interesting shapes of micelle-like aggregates, such as core-shell, cylinder, worm-like and inverted micelles were formed with sizes of 15, 70, 30 and 250 nm, respectively. In the case of methanol/water system, core-shell spheres and vesicles were produced by varying the proportion of the contents. The morphologies were also tuned to honeycomb-like and bowl-shaped micelles as well as large planar lamellae with holes in DMF and water binary solvent.

  19. Solvent Selection for Recrystallization: An Undergraduate Organic Experiment.

    Science.gov (United States)

    Baumann, Jacob B.

    1979-01-01

    This experiment develops the students' ability to carry out a simple recrystallization effectively, and demonstrates how a solvent may be selected or rejected for the recrystallization of a specific organic compound. (Author/BB)

  20. Extraction of Aromatics from Heavy Naphtha Using Different Solvents

    International Nuclear Information System (INIS)

    EI-Bassuoni, A.A.; Esmael, K.K.

    2004-01-01

    Aromatic hydrocarbons are very important to the petrochemical industry. Among these are benzene, toluene and xylene (BTX), which are basic raw materials for the production of a number of important petrochemicals. There are many processes used to separate aromatic from non aromatic such as fractionation, azeotropic distillation and liquid I liquid extraction, etc. Liquid - liquid extraction is unique, efficiently used for heat sensitive, close boiling components and for separation of components not possible by other unit operations and it could be done at ambient temperature makes it more energy efficient. The choice of solvent depends on the properties and boiling range of the feedstock. Through the years, a lot of selective solvents has been proposed and selected for the physical separation of aromatics in liquid liquid extraction. Among the selection criteria are the stability,. chemical compatibility, availability, environmental hazards and price of the solvent. But the basic solvent properties that make it efficient are selectivity and capacity