Regional Influences of Marcellus Shale Natural Gas Activity: Back-trajectory Analysis of Baltimore/Washington Ethane Concentrations

NASA Astrophysics Data System (ADS)

Vinciguerra, T.; Chittams, A.; Dadzie, J.; Deskins, T.; Goncalves, V.; M'Bagui Matsanga, C.; Zakaria, R.; Ehrman, S.; Dickerson, R. R.

2015-12-01

Over the past several years, the combined utilization of hydraulic fracturing and horizontal drilling has led to a rapid increase in natural gas production, especially from the Marcellus Shale. To explore the impact of this activity downwind on regions with no natural gas production, the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) Model was used to generate 48-hour back-trajectories for summer, daytime hours from the years 2007-2014 in the Baltimore, MD and Washington, D.C. areas where hourly ethane measurements are available from Photochemical Assessment Monitoring Stations (PAMS). For each of the years investigated, unconventional well counts were obtained for counties in the surrounding states of Pennsylvania, Ohio, West Virginia, and Virginia, and counties exceeding a threshold of 0.05 wells/km2 were designated as counties with a high density of wells. The back-trajectories for each year were separated into two groups: those which passed through counties containing a high density of wells, and those which did not. Back-trajectories passing through high-density counties were further screened by applying a height criterion where trajectories beyond 10% above the mixing layer were excluded. Preliminary results indicate that air parcels with back-trajectories passing within the boundary layer of counties with a high density of unconventional natural gas wells correspond to significantly greater concentrations of observed ethane at these downwind monitors.

Photothermal and photochemical effects of laser light absorption by indocyanine green (ICG)

NASA Astrophysics Data System (ADS)

Yaseen, Mohammad A.; Diagaradjane, Parmeswaran; Pikkula, Brian M.; Yu, Jie; Wong, Michael S.; Anvari, Bahman

2005-04-01

Indocyanine Green (ICG) is clinically used as a fluorescent dye for imaging purposes. Its rapid circulation kinetics and minimal toxicity has prompted investigation into ICG's utility as a photosentitizer for therapeutic applications. Traditionally, optically mediated tumor therapy has focused on photodynamic therapy, which employs a photochemical mechanism resulting from the absorption of low intensity CW laser light by localized photosensitizers such as Photofrin II, Benzoporphyrin Derivative (BPD), ICG. Treatment of cutaneous vascular malformations such as port-wine stains, on the other hand, is based on a photothermal mechanism resulting from the absorption of high intensity pulsed laser light by hemoglobin. In this study, we compared the effectiveness of combining photochemical and photothermal mechanisms during application of ICG in conjunction with laser irradiation with the intention that the combined approach may lead to a reduction in the threshold dose of pulsed laser light required to treat hypervascular malformations. The blood vessels in rabbit ears were used as an in vivo model for targeted vasculature. Irradiation of the ears with IR light (λ=785 nm, Δτ = 3 min, Io = 120 mW) was used to elicit photochemical damage, while photothermal damage was brought about using pulses from a ruby laser (λ=694 nm, τ = 3 ms) with different fluences. For the combined modality, photochemical damage was induced first and followed by photothermal irradiation. This modality was compared with photothermal irradiation alone. The effectiveness of each irradiation scheme was assessed using histopathological analysis. We present preliminary data that suggests that pretreatment with photodynamic therapy before photothermal coagulation results in more severe vascular damage with lower photothermal fluence levels. The results of this study provide the foundation work for further exploration of the therapeutic potentials of photochemical and photothermal effects during application of ICG in conjunction with laser irradiation.

Temporal mapping of photochemical reactions and molecular excited states with carbon specificity

NASA Astrophysics Data System (ADS)

Wang, K.; Murahari, P.; Yokoyama, K.; Lord, J. S.; Pratt, F. L.; He, J.; Schulz, L.; Willis, M.; Anthony, J. E.; Morley, N. A.; Nuccio, L.; Misquitta, A.; Dunstan, D. J.; Shimomura, K.; Watanabe, I.; Zhang, S.; Heathcote, P.; Drew, A. J.

2017-04-01

Photochemical reactions are essential to a large number of important industrial and biological processes. A method for monitoring photochemical reaction kinetics and the dynamics of molecular excitations with spatial resolution within the active molecule would allow a rigorous exploration of the pathway and mechanism of photophysical and photochemical processes. Here we demonstrate that laser-excited muon pump-probe spin spectroscopy (photo-μSR) can temporally and spatially map these processes with a spatial resolution at the single-carbon level in a molecule with a pentacene backbone. The observed time-dependent light-induced changes of an avoided level crossing resonance demonstrate that the photochemical reactivity of a specific carbon atom is modified as a result of the presence of the excited state wavefunction. This demonstrates the sensitivity and potential of this technique in probing molecular excitations and photochemistry.

Thermodynamics and mechanics of photochemcially reacting polymers

NASA Astrophysics Data System (ADS)

Long, Rong; Qi, H. Jerry; Dunn, Martin L.

2013-11-01

We develop a thermodynamics and mechanics theory for polymers that when irradiated with light, undergo photochemical reactions that alter their macromolecular structure, e.g., by bond breaking and/or reformation, and in turn affect their mechanical and physical behavior. This emerging class of highly-engineered active materials shows great promise for myriad applications and is a subset of a broader class of polymers with covalent bonds that can be dynamically tuned with various environmental stimuli. We formulate a general thermodynamic and kinetic framework to model the complex photochemical-thermal-mechanical coupling in these materials. Our theory considers the behavior of a polymer that is subjected to the combination of mechanical and thermal loading while simultaneously irradiated by light with multiple frequency components and directions. We introduce an approach to model the photochemical reactions that can change the network topology, resulting chemical species transport, heat conduction and finite deformation. We describe the interaction of the material with light via a radiometric description and show how it can be linked to a full electromagnetic treatment when appropriate and if desired. Our approach is sufficiently general to permit the modeling of various materials that operate via different photochemical reaction mechanisms. After formulating the general theory, we specialize it to a polymer that when irradiated with light undergoes a series of photochemical reactions that cause chain scission and reformation which continuously rearrange the polymer network into a stress-free configuration. Based on the operant physical mechanisms we develop a constitutive model using a polymer chain decomposition and evolution approach to track the molecular structure changes during simultaneous irradiation and mechanical loading. In the special case of isothermal conditions with monochromatic and unidirectional irradiation, we recover a previous model based on intuitive ad-hoc assumptions and thus put it on strong thermodynamic footing. Finally we use our model to simulate the behavior of a polymer that is biaxially stretched and then irradiated with light from one side. We simulate the process and emphasize the spontaneous bending that occurs due to inhomogeneous photoinduced stress relaxation. From our theory, we obtain an analytical expression of a characteristic time for photo-induced stress relaxation in terms of the dominating system parameters.

A photochemical crosslinking technology for tissue engineering: enhancement of the physico-chemical properties of collagen-based scaffolds

NASA Astrophysics Data System (ADS)

Chan, Barbara P.

2005-04-01

Collagen gel is a natural biomaterial commonly used in tissue engineering because of its close resemblance to nature, negligible immunogenecity and excellent biocompatibility. However, unprocessed collagen gel is mechanically weak, highly water binding and vulnerable to chemical and enzymatic attacks that limits its use in tissue engineering in particular tissues for weight-bearing purposes. The current project aimed to strengthen and stabilize collagen scaffolds using a photochemical crosslinking technique. Photochemical crosslinking is rapid, efficient, non-thermal and does not involve toxic chemicals, comparing with other crosslinking methods such as glutaraldehyde and gamma irradiation. Collagen scaffolds were fabricated using rat-tail tendon collagen. An argon laser was used to process the collagen gel after equilibrating with a photosensitizing reagent. Scanning electronic microscope was used to characterize the surface and cross-sectional morphology of the membranes. Physico-chemical properties of the collagen scaffolds such as water-binding capacity, mechanical properties and thermostability were studied. Photochemical crosslinking significantly reduced the water-binding capacity, a parameter inversely proportional to the extent of crosslinking, of collagen scaffolds. Photochemical crosslinking also significantly increased the ultimate stress and tangent modulus at 90% of the rupture strain of the collagen scaffolds. Differential scanning calorimetry analysis showed a significantly higher shrinkage temperature and absence of the denaturation peak during the thermoscan comparing with the controls. This means greater thermostability in the photochemically crosslinked collagen scaffolds. This study demonstrates that the photochemical crosslinking technology is able to enhance the physicochemical propterties of collagen scaffolds by strengthening, stabilizing and controlling the swelling ratio of the collagen scaffolds so as to enable their use for tissue engineering.

Geckoprinting: assembly of microelectronic devices on unconventional surfaces by transfer printing with isolated gecko setal arrays

PubMed Central

Jeong, Jaeyoung; Kim, Juho; Song, Kwangsun; Autumn, Kellar; Lee, Jongho

2014-01-01

Developing electronics in unconventional forms provides opportunities to expand the use of electronics in diverse applications including bio-integrated or implanted electronics. One of the key challenges lies in integrating semiconductor microdevices onto unconventional substrates without glue, high pressure or temperature that may cause damage to microdevices, substrates or interfaces. This paper describes a solution based on natural gecko setal arrays that switch adhesion mechanically on and off, enabling pick and place manipulation of thin microscale semiconductor materials onto diverse surfaces including plants and insects whose surfaces are usually rough and irregular. A demonstration of functional ‘geckoprinted’ microelectronic devices provides a proof of concept of our results in practical applications. PMID:25056216

Photochemical gas lasers and hybrid (solid/gas) blue-green femtosecond systems

NASA Astrophysics Data System (ADS)

Mikheev, L. D.; Tcheremiskine, V. I.; Uteza, O. P.; Sentis, M. L.

2012-01-01

The review summarizes milestones and major breakthrough results obtained in the course of the development of a photochemical method applied to optical excitation of gas lasers on electronic molecular transitions by radiation from such unconventional pump sources as high-temperature electrical discharges and strong shock waves in gas. It also describes principles and techniques applied in hybrid (solid/gas) high-intensity laser systems emitting in the blue-green spectral region, and discusses wavelength scaling of laser-matter interaction by the example of laser wake-field acceleration (LWFA), high-order harmonic generation (HHG) and “water window” soft X-ray lasers. One of the most significant results of the photochemical method development consists in emerging broad bandwidth lasers (XeF(C-A), Xe2Cl, and Kr2F) operating in the blue-green spectral range, which have potential for amplification of ultra-short (down to 10 fs) optical pulses towards the Petawatt peak power level. The main goal of this review is to argue that the active media of these lasers may provide a basis for the development of fs systems generating super-intense ultrashort laser pulses in the visible spectral range. Some specific hybrid schemes, comprising solid state front-ends and photodissociation XeF(C-A) power boosting amplifiers, are described. They are now under development at the Lasers Plasmas and Photonic Processes (LP3) Laboratory (Marseille, France), the P.N. Lebedev Physical Institute (Moscow, Russia) and the Institute of High-Current Electronics (Tomsk, Russia) with the aim of conducting proof-of-principle experiments. Some consequences of the visible-wavelength laser field interaction with matter are also surveyed to demonstrate advantages of short driver wavelength in the considered examples. One of the most important consequences is the possibility of coherent soft X-ray generation within the “water window” spectral range with the use of short wavelength driver pulses to pump a recombination laser.

Physiological validation of photochemical reflectance index (PRI) as a photosynthetic parameter using Arabidopsis thaliana mutants.

PubMed

Kohzuma, Kaori; Hikosaka, Kouki

2018-03-25

Non-photochemical quenching (NPQ) is the most important photoprotective system in higher plants. NPQ can be divided into several steps according to the timescale of relaxation of chlorophyll fluorescence after reaching a steady state (i.e., the fast phase, qE; middle phase, qZ or qT; and slow phase, qI). The dissipation of excess energy as heat during the xanthophyll cycle, a large component of NPQ, is detectable during the fast to middle phase (sec to min). Although thermal dissipation is primarily investigated using indirect methods such as chlorophyll a fluorescence measurements, such analyses require dark adaptation or the application of a saturating pulse during measurement, making it difficult to continuously monitor this process. Here, we designed an unconventional technique for real-time monitoring of changes in thylakoid lumen pH (as reflected by changes in xanthophyll pigment content) based on the photochemical reflectance index (PRI), which we estimated by measuring light-driven leaf reflectance at 531 nm. We analyzed two Arabidopsis thaliana mutants, npq1 (unable to convert violaxanthin to zeaxanthin due to inhibited violaxanthin de-epoxidase [VDE] activity) and npq4 (lacking PsbS protein), to uncover the regulator of the PRI. The PRI was variable in wild-type and npq4 plants, but not in npq1, indicating that the PRI is related to xanthophyll cycle-dependent thermal energy quenching (qZ) rather than the linear electron transport rate or NPQ. In situ lumen pH substitution using a pH-controlled buffer solution caused a shift in PRI. These results suggest that the PRI reflects only xanthophyll cycle conversion and is therefore a useful parameter for monitoring thylakoid lumen pH (reflecting VDE activity) in vivo. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Multiphoton Absorption is Probably Not the Primary Threshold Damage Mechanism for Femtosecond Laser Pulse Exposures in the Retinal Pigment Epithelium

DTIC Science & Technology

2004-01-01

Tromberg, and E. Gratton, "Two-photon excited lifetime imaging of autofluorescence in cells during UTVA and NIR photostress", J. Micros. 183, pp. 197-204...1996. 4. K. Konig, Y. Liu, G. J. Sonek, M. W. Berns, and B. J. Tromberg, " Autofluorescence spectroscopy of optically trapped cells", Photochem...34, Photochem. Photobiol. 70, pp. 146-151, 1999. 10. R. D. Glickman, "Phototoxicity to the retina : Mechanisms of damage", International Journal of

Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis

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

Zhai, Yueming; DuChene, Joseph S.; Wang, Yi-Chung

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally diferent from its widelymore » accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.« less

Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis

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

Zhai, Yueming; DuChene, Joseph S.; Wang, Yi-Chung

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. In this paper, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different frommore » its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. Finally, these insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.« less

Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis

DOE PAGES

Zhai, Yueming; DuChene, Joseph S.; Wang, Yi-Chung; ...

2016-07-04

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. In this paper, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different frommore » its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. Finally, these insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.« less

Complete Moment Tensor Determination of Induced Seismicity in Unconventional and Conventional Oil/Gas Fields

NASA Astrophysics Data System (ADS)

Gu, C.; Li, J.; Toksoz, M. N.

2013-12-01

Induced seismicity occurs both in conventional oil/gas fields due to production and water injection and in unconventional oil/gas fields due to hydraulic fracturing. Source mechanisms of these induced earthquakes are of great importance for understanding their causes and the physics of the seismic processes in reservoirs. Previous research on the analysis of induced seismic events in conventional oil/gas fields assumed a double couple (DC) source mechanism. However, recent studies have shown a non-negligible percentage of a non-double-couple (non-DC) component of source moment tensor in hydraulic fracturing events (Šílený et al., 2009; Warpinski and Du, 2010; Song and Toksöz, 2011). In this study, we determine the full moment tensor of the induced seismicity data in a conventional oil/gas field and for hydrofrac events in an unconventional oil/gas field. Song and Toksöz (2011) developed a full waveform based complete moment tensor inversion method to investigate a non-DC source mechanism. We apply this approach to the induced seismicity data from a conventional gas field in Oman. In addition, this approach is also applied to hydrofrac microseismicity data monitored by downhole geophones in four wells in US. We compare the source mechanisms of induced seismicity in the two different types of gas fields and explain the differences in terms of physical processes.

Comparison of measured ozone in southeastern Virginia with computer predictions from a photochemical model

NASA Technical Reports Server (NTRS)

Wakelyn, N. T.; Gregory, G. L.

1980-01-01

Data for one day of the 1977 southeastern Virginia urban plume study are compared with computer predictions from a traveling air parcel model using a contemporary photochemical mechanism with a minimal description of nonmethane hydrocarbon (NMHC) constitution and chemistry. With measured initial NOx and O3 concentrations and a current separate estimate of urban source loading input to the model, and for a variation of initial NMHC over a reasonable range, an ozone increase over the day is predicted from the photochemical simulation which is consistent with the flight path averaged airborne data.

Photochemically induced carbon dioxide production as a mechanism for carbon loss from plant litter in arid ecosystems

NASA Astrophysics Data System (ADS)

Brandt, L. A.; Bohnet, C.; King, J. Y.

2009-06-01

We investigated the potential for abiotic mineralization to carbon dioxide (CO2) via photodegradation to account for carbon (C) loss from plant litter under conditions typical of arid ecosystems. We exposed five species of grass and oak litter collected from arid and mesic sites to a factorial design of ultraviolet (UV) radiation (UV pass, UV block), and sterilization under dry conditions in the laboratory. UV pass treatments produced 10 times the amount of CO2 produced in UV block treatments. CO2 production rates were unaffected by litter chemistry or sterilization. We also exposed litter to natural solar radiation outdoors on clear, sunny days close to the summer solstice at midlatitudes and found that UV radiation (280-400 nm) accounted for 55% of photochemically induced CO2 production, while shortwave visible radiation (400-500 nm) accounted for 45% of CO2 production. Rates of photochemically induced CO2 production on a per-unit-mass basis decreased with litter density, indicating that rates depend on litter surface area. We found no evidence for leaching, methane production, or facilitation of microbial decomposition as alternative mechanisms for significant photochemically induced C loss from litter. We conclude that abiotic mineralization to CO2 is the primary mechanism by which C is lost from litter during photodegradation. We estimate that CO2 production via photodegradation could be between 1 and 4 g C m-2 a-1 in arid ecosystems in the southwestern United States. Taken together with low levels of litter production in arid systems, photochemical mineralization to CO2 could account for a significant proportion of annual carbon loss from litter in arid ecosystems.

Tec-kinase-mediated phosphorylation of fibroblast growth factor 2 is essential for unconventional secretion.

PubMed

Ebert, Antje D; Laussmann, Mareike; Wegehingel, Sabine; Kaderali, Lars; Erfle, Holger; Reichert, Jürgen; Lechner, Johannes; Beer, Hans-Dietmar; Pepperkok, Rainer; Nickel, Walter

2010-06-01

Fibroblast growth factor 2 (FGF2) is a potent mitogen that is exported from cells by an endoplasmic reticulum (ER)/Golgi-independent mechanism. Unconventional secretion of FGF2 occurs by direct translocation across plasma membranes, a process that depends on the phosphoinositide phosphatidylinositol 4,5-biphosphate (PI(4,5)P(2)) at the inner leaflet as well as heparan sulfate proteoglycans at the outer leaflet of plasma membranes; however, additional core and regulatory components of the FGF2 export machinery have remained elusive. Here, using a highly effective RNAi screening approach, we discovered Tec kinase as a novel factor involved in unconventional secretion of FGF2. Tec kinase does not affect FGF2 secretion by an indirect mechanism, but rather forms a heterodimeric complex with FGF2 resulting in phosphorylation of FGF2 at tyrosine 82, a post-translational modification shown to be essential for FGF2 membrane translocation to cell surfaces. Our findings suggest a crucial role for Tec kinase in regulating FGF2 secretion under various physiological conditions and, therefore, provide a new perspective for the development of a novel class of antiangiogenic drugs targeting the formation of the FGF2/Tec complex.

UPDATED PHOTOCHEMICAL MODELING FOR CALIFORNIA'S SOUTH COAST AIR BASIN: COMPARISON OF CHEMICAL MECHANISMS AND MOTOR VEHICLE EMISSION INVENTORIES. (R824792)

EPA Science Inventory

Large uncertainties remain in photochemical models used
to relate emissions of VOC and NO_x to ambient
O₃
concentrations. Bias in motor vehicle emission
estimates
for VOC has been a long-standing concern. An improved
Eul...

Breakdown of Landau Fermi liquid theory: Restrictions on the degrees of freedom of quantum electrons

NASA Astrophysics Data System (ADS)

Su, Yue-Hua; Lu, Han-Tao

2018-04-01

One challenge in contemporary condensed matter physics is to understand unconventional electronic physics beyond the paradigm of Landau Fermi-liquid theory. Here, we present a perspective that posits that most such examples of unconventional electronic physics stem from restrictions on the degrees of freedom of quantum electrons in Landau Fermi liquids. Since the degrees of freedom are deeply connected to the system's symmetries and topology, these restrictions can thus be realized by external constraints or by interaction-driven processes via the following mechanisms: (i) symmetry breaking, (ii) new emergent symmetries, and (iii) nontrivial topology. Various examples of unconventional electronic physics beyond the reach of traditional Landau Fermi liquid theory are extensively investigated from this point of view. Our perspective yields basic pathways to study the breakdown of Landau Fermi liquids and also provides a guiding principle in the search for novel electronic systems and devices.

'Beautiful' unconventional synthesis and processing technologies of superconductors and some other materials.

PubMed

Badica, Petre; Crisan, Adrian; Aldica, Gheorghe; Endo, Kazuhiro; Borodianska, Hanna; Togano, Kazumasa; Awaji, Satoshi; Watanabe, Kazuo; Sakka, Yoshio; Vasylkiv, Oleg

2011-02-01

Superconducting materials have contributed significantly to the development of modern materials science and engineering. Specific technological solutions for their synthesis and processing helped in understanding the principles and approaches to the design, fabrication and application of many other materials. In this review, we explore the bidirectional relationship between the general and particular synthesis concepts. The analysis is mostly based on our studies where some unconventional technologies were applied to different superconductors and some other materials. These technologies include spray-frozen freeze-drying, fast pyrolysis, field-assisted sintering (or spark plasma sintering), nanoblasting, processing in high magnetic fields, methods of control of supersaturation and migration during film growth, and mechanical treatments of composite wires. The analysis provides future research directions and some key elements to define the concept of 'beautiful' technology in materials science. It also reconfirms the key position and importance of superconductors in the development of new materials and unconventional synthesis approaches.

H2S and polysulfide metabolism: Conventional and unconventional pathways.

PubMed

Olson, Kenneth R

2018-03-01

It is now well established that hydrogen sulfide (H 2 S) is an effector of a wide variety of physiological processes. It is also clear that many of the effects of H 2 S are mediated through reactions with cysteine sulfur on regulatory proteins and most of these are not mediated directly by H 2 S but require prior oxidation of H 2 S and the formation of per- and polysulfides (H 2 S n , n = 2-8). Attendant with understanding the regulatory functions of H 2 S and H 2 S n is an appreciation of the mechanisms that control, i.e., both increase and decrease, their production and catabolism. Although a number of standard "conventional" pathways have been described and well characterized, novel "unconventional" pathways are continuously being identified. This review summarizes our current knowledge of both the conventional and unconventional. Copyright © 2017 Elsevier Inc. All rights reserved.

Photophysical and photochemical insights into the photodegradation of sulfapyridine in water: A joint experimental and theoretical study.

PubMed

Zhang, Heming; Wei, Xiaoxuan; Song, Xuedan; Shah, Shaheen; Chen, Jingwen; Liu, Jianhui; Hao, Ce; Chen, Zhongfang

2018-01-01

For organic pollutants, photodegradation, as a major abiotic elimination process and of great importance to the environmental fate and risk, involves rather complicated physical and chemical processes of excited molecules. Herein, we systematically studied the photophysical and photochemical processes of a widely used antibiotic, namely sulfapyridine. By means of density functional theory (DFT) computations, we examined the rate constants and the competition of both photophysical and photochemical processes, elucidated the photochemical reaction mechanism, calculated reaction quantum yield (Φ) based on both photophysical and photochemical processes, and subsequently estimated the photodegradation rate constant. We further conducted photolysis experiments to measure the photodegradation rate constant of sulfapyridine. Our computations showed that sulfapyridine at the lowest excited singlet state (S 1 ) mainly undergoes internal conversion to its ground state, and is difficult to transfer to the lowest excited triplet states (T 1 ) via intersystem crossing (ISC) and emit fluorescence. In T 1 state, compared with phosphorescence emission and ISC, chemical reaction is much easier to initiate. Encouragingly, the theoretically predicted photodegradation rate constant is close to the experimentally observed value, indicating that quantum chemistry computation is powerful enough to study photodegradation involving ultra-fast photophysical and photochemical processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic photovoltaic cells based on unconventional electron donor fullerene and electron acceptor copper hexadecafluorophthalocyanine

NASA Astrophysics Data System (ADS)

Yang, J. L.; Sullivan, P.; Schumann, S.; Hancox, I.; Jones, T. S.

2012-01-01

We demonstrate organic discrete heterojunction photovoltaic cells based on fullerene (C60) and copper hexadecafluorophthalocyanine (F16CuPc), in which the C60 and F16CuPc act as the electron donor and the electron acceptor, respectively. The C60/F16CuPc cells fabricated with conventional and inverted architectures both exhibit comparable power conversion efficiencies. Furthermore, we show that the photocurrent in both cells is generated by a conventional exciton dissociation mechanism rather than the exciton recombination mechanism recently proposed for a similar C60/F16ZnPc system [Song et al., J. Am. Chem. Soc. 132, 4554 (2010)]. These results demonstrate that new unconventional material systems are a potential way to fabricate organic photovoltaic cells with inverted as well as conventional architectures.

Summertime C1-C5 alkyl nitrates over Beijing, northern China: Spatial distribution, regional transport, and formation mechanisms

NASA Astrophysics Data System (ADS)

Sun, Jingjing; Li, Zeyuan; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Nie, Wei; Simpson, Isobel J.; Gao, Rui; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

2018-05-01

Alkyl nitrates (RONO2) are an important class of nitrogen oxides reservoirs in the atmosphere and play a key role in tropospheric photochemistry. Despite the increasing concern for photochemical air pollution over China, the knowledge of characteristics and formation mechanisms of alkyl nitrates in this region is limited. We analyzed C1-C5 alkyl nitrates measured in Beijing at a polluted urban site in summer 2008 and at a downwind rural site in summers of both 2005 and 2008. Although the abundances of NOx and hydrocarbons were much lower at the rural site, the mixing ratios of RONO2 were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution. Regional transport of urban plumes governed the elevated RONO2 levels at the rural site. The concentrations of C1-C2 RONO2 were significantly higher at the rural site in 2008 compared to 2005 despite a decline in NOx and anthropogenic VOCs, mainly owing to enhanced contributions from biogenic VOCs. The photochemical formation regimes of RONO2 were evaluated by both a simplified sequential reaction model and a detailed master chemical mechanism box model. The observed C4-C5 RONO2 levels can be well explained by the photochemical degradation of n-butane and n-pentane, while the sources of C1-C3 RONO2 were rather complex. In addition to the C1-C3 alkanes, biogenic VOCs and reactive aromatics were also important precursors of methyl nitrate, and alkenes and long-chain alkanes contributed to the formation of C2-C3 RONO2. This study provides insights into the spatial distribution, inter-annual variation and photochemical formation mechanisms of alkyl nitrate pollution over the Beijing area.

Evaluation of different photosensitizers for use in photochemical gene transfection.

PubMed

Prasmickaite, L; Høgset, A; Berg, K

2001-04-01

Many potentially therapeutic macromolecules, e.g. transgenes used in gene therapy, are taken into the cells by endocytosis, and have to be liberated from endocytic vesicles in order to express a therapeutic function. To achieve this we have developed a new technology, named photochemical internalization (PCI), based on photochemical reactions inducing rupture of endocytic vesicles. The aim of this study was to clarify which properties of photosensitizers are important for obtaining the PCI effect improving gene transfection. The photochemical effect on transfection of human melanoma THX cells has been studied employing photosensitizers with different physicochemical properties and using two gene delivery vectors: the cationic polypeptide polylysine and the cationic lipid 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP). Photochemical treatment by photosensitizers that do not localize in endocytic vesicles (tetra[3-hydroxyphenyl]porphyrin and 5-aminolevulinic acid-induced protoporphyrin IX) do not stimulate transfection, irrespective of the gene delivery vector. In contrast, photosensitizers localized in endocytic vesicles stimulate polylysine-mediated transfection, and amphiphilic photosensitizers (disulfonated aluminium phthalocyanine [AlPcS2a] and meso-tetraphenylporphynes) show the strongest positive effect, inducing approximately 10-fold increase in transfection efficiency. In contrast, DOTAP-mediated transfection is inhibited by all photochemical treatments irrespective of the photosensitizer used. Neither AlPcS2a nor Photofrin affects the uptake of the transfecting DNA over the plasma membrane, therefore photochemical permeabilization of endocytic vesicles seems to be the most likely mechanism responsible for the positive PCI effect on gene transfection.

Potential Chemical Systems for Intramolecular Cycloaddition Cures

DTIC Science & Technology

1979-05-01

allowed electrocyclic photochemical ring closure of stilbene to dihydrophenanthrene is well known (Reference 12). The presence of an oxidant , e.g...CH (c) R 3 0 00 > 0 I I (42) The keto-diynes 36 follow a uniform reaction pathway with chlorotris- ( triphenylphosphine )rhodium[I] to yield the...Irradiation of 36b similarly gives 49. The mechanism proposed for the photochemical reaction involves an initial formation of the reactive cyclobutadiene by

Molecular-beam Studies of Primary Photochemical Processes

DOE R&D Accomplishments Database

Lee, Y. T.

1982-12-01

Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser.

High-Temperature Creep Degradation of the AM1/NiAlPt/EBPVD YSZ System

NASA Astrophysics Data System (ADS)

Riallant, Fanny; Cormier, Jonathan; Longuet, Arnaud; Milhet, Xavier; Mendez, José

2014-01-01

The failure mechanisms of a NiAlPt/electron beam physical vapor deposition yttria-stabilized-zirconia thermal barrier coating system deposited on the AM1 single crystalline substrate have been investigated under pure creep conditions in the temperature range from 1273 K to 1373 K (1000 °C to 1100 °C) and for durations up to 1000 hours. Doubly tapered specimens were used allowing for the analysis of different stress states and different accumulated viscoplastic strains for a given creep condition. Under such experiments, two kinds of damage mechanisms were observed. Under low applied stress conditions ( i.e., long creep tests), microcracking is localized in the vicinity of the thermally grown oxide (TGO). Under high applied stress conditions, an unconventional failure mechanism at the substrate/bond coat interface is observed because of large creep strains and fast creep deformation, hence leading to a limited TGO growth. This unconventional failure mechanism is observed although the interfacial bond coat/top coat TGO thickening is accelerated by the mechanical applied stress beyond a given stress threshold.

Impact of Diurnal Variations of Precursors on the Prediction of Ozone

NASA Astrophysics Data System (ADS)

Hamer, P. D.; Bowman, K. W.; Henze, D. K.; Singh, K.

2009-12-01

Using a photochemical box model and its adjoint, constructed using the Kinetic Pre-Processor, we investigate the impacts of changing observational capacity, observation frequency and quality upon the ability to both understand and predict the nature of peak ozone events within a variety of polluted environments. The model consists of a chemical mechanism based on the Master Chemical Mechanism utilising 171 chemical species and 524 chemical reactions interacting with emissions, dry deposition and mixing schemes. The model was run under a variety of conditions designed to simulate a range of summertime polluted environments spanning a range of NOx and volatile organic compound regimes (VOCs). Using the forward model we were able to generate simulated atmospheric conditions representative of a particular polluted environment, which could in turn be used to generate a set of pseudo observations of key photochemical constituents. The model was then run under somewhat less polluted conditions to generate a background and then perturbed back towards the polluted trajectory using sequential data assimilation and the pseudo observations. Using a combination of the adjoint sensitivity analysis and the sequential data assimilation described here we assess the optimal time of observation and the diversity of observed chemical species required to provide acceptable forecast estimates of ozone concentrations. As the photochemical regime changes depending on NOx and VOC concentrations different observing strategies become favourable. The impact of using remote sensing based observations of the free tropospheric photochemical state are investigated to demonstrate the advantage of gaining knowledge of atmospheric trace gases away from the immediate photochemical environment.

Loss of Functional Photosystem II Reaction Centres in Zooxanthellae of Corals Exposed to Bleaching Conditions: Using Fluorescence Rise Kinetics.

PubMed

Hill, R; Larkum, A W D; Frankart, C; Kühl, M; Ralph, P J

2004-01-01

Mass coral bleaching is linked to elevated sea surface temperatures, 1-2 degrees C above average, during periods of intense light. These conditions induce the expulsion of zooxanthellae from the coral host in response to photosynthetic damage in the algal symbionts. The mechanism that triggers this release has not been clearly established and to further our knowledge of this process, fluorescence rise kinetics have been studied for the first time. Corals that were exposed to elevated temperature (33 degrees C) and light (280 mumol photons m(-2) s(-1)), showed distinct changes in the fast polyphasic induction of chlorophyll-a fluorescence, indicating biophysical changes in the photochemical processes. The fluorescence rise over the first 2000ms was monitored in three species of corals for up to 8 h, with a PEA fluorometer and an imaging-PAM. Pocillopora damicornis showed the least impact on photosynthetic apparatus, while Acropora nobilis was the most sensitive, with Cyphastrea serailia intermediate between the other two species. A. nobilis showed a remarkable capacity for recovery from bleaching conditions. For all three species, a steady decline in the slope of the initial rise and the height of the J-transient was observed, indicating the loss of functional Photosystem II (PS II) centres under elevated-temperature conditions. A significant loss of PS II centres was confirmed by a decline in photochemical quenching when exposed to bleaching stress. Non-photochemical quenching was identified as a significant mechanism for dissipating excess energy as heat under the bleaching conditions. Photophosphorylation could explain this decline in PS II activity. State transitions, a component of non-photochemical quenching, was a probable cause of the high non-photochemical quenching during bleaching and this mechanism is associated with the phosphorylation-induced dissociation of the light harvesting complexes from the PS II reaction centres. This reversible process may account for the coral recovery, particularly in A. nobilis.

Mechanisms and disease relevance of neutrophil extracellular trap formation.

PubMed

Van Avondt, Kristof; Hartl, Dominik

2018-03-15

While the microscopic appearance of neutrophil extracellular traps (NETs) has fascinated basic researchers since its discovery, the (patho)physiological mechanisms triggering NET release, the disease relevance and clinical translatability of this unconventional cellular mechanism remained poorly understood. Here, we summarize and discuss current concepts of the mechanisms and disease relevance of NET formation. © 2018 Stichting European Society for Clinical Investigation Journal Foundation.

Aerosol growth in Titan’s ionosphere

PubMed Central

Lavvas, Panayotis; Yelle, Roger V.; Koskinen, Tommi; Bazin, Axel; Vuitton, Véronique; Vigren, Erik; Galand, Marina; Wellbrock, Anne; Coates, Andrew J.; Wahlund, Jan-Erik; Crary, Frank J.; Snowden, Darci

2013-01-01

Photochemically produced aerosols are common among the atmospheres of our solar system and beyond. Observations and models have shown that photochemical aerosols have direct consequences on atmospheric properties as well as important astrobiological ramifications, but the mechanisms involved in their formation remain unclear. Here we show that the formation of aerosols in Titan’s upper atmosphere is directly related to ion processes, and we provide a complete interpretation of observed mass spectra by the Cassini instruments from small to large masses. Because all planetary atmospheres possess ionospheres, we anticipate that the mechanisms identified here will be efficient in other environments as well, modulated by the chemical complexity of each atmosphere. PMID:23382231

Aerosol growth in Titan's ionosphere.

PubMed

Lavvas, Panayotis; Yelle, Roger V; Koskinen, Tommi; Bazin, Axel; Vuitton, Véronique; Vigren, Erik; Galand, Marina; Wellbrock, Anne; Coates, Andrew J; Wahlund, Jan-Erik; Crary, Frank J; Snowden, Darci

2013-02-19

Photochemically produced aerosols are common among the atmospheres of our solar system and beyond. Observations and models have shown that photochemical aerosols have direct consequences on atmospheric properties as well as important astrobiological ramifications, but the mechanisms involved in their formation remain unclear. Here we show that the formation of aerosols in Titan's upper atmosphere is directly related to ion processes, and we provide a complete interpretation of observed mass spectra by the Cassini instruments from small to large masses. Because all planetary atmospheres possess ionospheres, we anticipate that the mechanisms identified here will be efficient in other environments as well, modulated by the chemical complexity of each atmosphere.

Photodecomposition of Mo(CO)/sub 6/ adsorbed on Si(100)

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

Creighton, J.R.

1985-01-01

The photochemical decomposition of Mo(CO)/sub 6/ layers physisorbed on Si(100) was investigated to determine the feasibility of molybdenum deposition and also to examine the photochemical reaction mechanism and efficiency. Temperature programmed desorption (TPD) was used to investigate the interaction of Mo(CO)/sub 6/ with the silicon surface before and after irradiation. Auger spectroscopy was used to determine surface elemental composition before Mo(CO)/sub 6/ adsorption and after photodecomposition.

Protein disulfide isomerase externalization in endothelial cells follows classical and unconventional routes.

PubMed

Araujo, Thaís L S; Zeidler, Julianna D; Oliveira, Percíllia V S; Dias, Matheus H; Armelin, Hugo A; Laurindo, Francisco R M

2017-02-01

Extracellular protein disulfide isomerase (PDIA1) pool mediates thrombosis and vascular remodeling, however its externalization mechanisms remain unclear. We performed systematic pharmacological screening of secretory pathways affecting extracellular PDIA1 in endothelial cells (EC). We identified cell-surface (csPDIA1) and secreted non-particulated PDIA1 pools in EC. Such Golgi bypass also occurred for secreted PDIA1 in EC at baseline or after PMA, thrombin or ATP stimulation. Inhibitors of Type I, II and III unconventional routes, secretory lysosomes and recycling endosomes, including syntaxin-12 deletion, did not impair EC PDIA1 externalization. This suggests predominantly Golgi-independent unconventional secretory route(s), which were GRASP55-independent. Also, these data reinforce a vesicular-type traffic for PDIA1. We further showed that PDIA1 traffic is ATP-independent, while actin or tubulin cytoskeletal disruption markedly increased EC PDIA1 secretion. Clathrin inhibition enhanced extracellular soluble PDIA1, suggesting dynamic cycling. Externalized PDIA1 represents <2% of intracellular PDIA1. PDIA1 was robustly secreted by physiological levels of arterial laminar shear in EC and supported alpha 5 integrin thiol oxidation. Such results help clarify signaling and homeostatic mechanisms involved in multiple (patho)physiological extracellular PDIA1 functions. Copyright © 2016 Elsevier Inc. All rights reserved.

Probing how initial retinal configuration controls photochemical dynamics in retinal proteins

NASA Astrophysics Data System (ADS)

Wand, A.; Rozin, R.; Eliash, T.; Friedman, N.; Jung, K. H.; Sheves, M.; Ruhman, S.

2013-03-01

The effects of the initial retinal configuration and the active isomerization coordinate on the photochemistry of retinal proteins (RPs) are assessed by comparing photochemical dynamics of two stable retinal ground state configurations (all-trans,15-anti vs. 13-cis,15-syn), within two RPs: Bacteriorhodopsin (BR) and Anabaena Sensory Rhodopsin (ASR). Hyperspectral pump-probe spectroscopy shows that photochemistry starting from 13-cis retinal in both proteins is 3-10 times faster than when started in the all-trans state, suggesting that the hastening is ubiquitous to microbial RPs, regardless of their different biological functions and origin. This may also relate to the known disparity of photochemical rates between microbial RPs and visual pigments. Importance and possible underlying mechanisms are discussed as well.

The Theory of Unconventional Warfare: Win, Lose, and Draw

DTIC Science & Technology

2008-12-01

UNCONVENTIONAL WARFARE MODEL ...................................12 1. Planning Phase...Superiority over Time........................................................................11  Figure 3.  Unconventional Warfare Model ...superiority through the six principles of UW illustrated below in the UW model . . B. THE UNCONVENTIONAL WARFARE MODEL Figure 3. Unconventional

Photochemical activity of a key donor-acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes.

PubMed

Arceo, Elena; Jurberg, Igor D; Alvarez-Fernández, Ana; Melchiorre, Paolo

2013-09-01

Asymmetric catalytic variants of sunlight-driven photochemical processes hold extraordinary potential for the sustainable preparation of chiral molecules. However, the involvement of short-lived electronically excited states inherent to any photochemical reaction makes it challenging for a chiral catalyst to dictate the stereochemistry of the products. Here, we report that readily available chiral organic catalysts, with well-known utility in thermal asymmetric processes, can also confer a high level of stereocontrol in synthetically relevant intermolecular carbon-carbon bond-forming reactions driven by visible light. A unique mechanism of catalysis is proposed, wherein the catalyst is involved actively in both the photochemical activation of the substrates (by inducing the transient formation of chiral electron donor-acceptor complexes) and the stereoselectivity-defining event. We use this approach to enable transformations that are extremely difficult under thermal conditions, such as the asymmetric α-alkylation of aldehydes with alkyl halides, the formation of all-carbon quaternary stereocentres and the control of remote stereochemistry.

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

PubMed

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

2018-01-15

Quantum defects are an emerging class of synthetic single-photon emitters that hold vast potential for near-infrared imaging, chemical sensing, materials engineering, and quantum information processing. Herein, we show that it is possible to optically direct the synthetic creation of molecularly tunable fluorescent quantum defects in semiconducting single-walled carbon nanotube hosts through photochemical reactions. By exciting the host semiconductor with light that resonates with its electronic transition, we find that halide-containing aryl groups can covalently bond to the sp 2 carbon lattice. The introduced quantum defects generate bright photoluminescence that allows tracking of the reaction progress in situ. We show that the reaction is independent of temperature but correlates strongly with the photon energy used to drive the reaction, suggesting a photochemical mechanism rather than photothermal effects. This type of photochemical reactions opens the possibility to control the synthesis of fluorescent quantum defects using light and may enable lithographic patterning of quantum emitters with electronic and molecular precision. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

DOEpatents

Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

2015-02-10

A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

A Framework for Fracture Network Formation in Overpressurised Impermeable Shale: Deformability Versus Diagenesis

NASA Astrophysics Data System (ADS)

Alevizos, Sotiris; Poulet, Thomas; Sari, Mustafa; Lesueur, Martin; Regenauer-Lieb, Klaus; Veveakis, Manolis

2017-03-01

Understanding the formation, geometry and fluid connectivity of nominally impermeable unconventional shale gas and oil reservoirs is crucial for safe unlocking of these vast energy resources. We present a recent discovery of volumetric instabilities of ductile materials that may explain why impermeable formations become permeable. Here, we present the fundamental mechanisms, the critical parameters and the applicability of the novel theory to unconventional reservoirs. We show that for a reservoir under compaction, there exist certain ambient and permeability conditions at which diagenetic (fluid-release) reactions may provoke channelling localisation instabilities. These channels are periodically interspersed in the matrix and represent areas where the excess fluid from the reaction is segregated at high velocity. We find that channelling instabilities are favoured from pore collapse features for extremely low-permeability formations and fluid-release diagenetic reactions, therefore providing a natural, periodic network of efficient fluid pathways in an otherwise impermeable matrix (i.e. fractures). Such an outcome is of extreme importance the for exploration and extraction phases of unconventional reservoirs.

Superconductivity in the vicinity of antiferromagnetic order in CrAs.

PubMed

Wu, Wei; Cheng, Jinguang; Matsubayashi, Kazuyuki; Kong, Panpan; Lin, Fukun; Jin, Changqing; Wang, Nanlin; Uwatoko, Yoshiya; Luo, Jianlin

2014-11-19

One of the common features of unconventional superconducting systems such as the heavy-fermion, high transition-temperature cuprate and iron-pnictide superconductors is that the superconductivity emerges in the vicinity of long-range antiferromagnetically ordered state. In addition to doping charge carriers, the application of external pressure is an effective and clean approach to induce unconventional superconductivity near a magnetic quantum critical point. Here we report on the discovery of superconductivity on the verge of antiferromagnetic order in CrAs via the application of external pressure. Bulk superconductivity with Tc≈2 K emerges at the critical pressure Pc≈8 kbar, where the first-order antiferromagnetic transition at T(N)≈265 K under ambient pressure is completely suppressed. The close proximity of superconductivity to an antiferromagnetic order suggests an unconventional pairing mechanism for CrAs. The present finding opens a new avenue for searching novel superconductors in the Cr and other transition metal-based systems.

Unconventional Protein Secretion in Animal Cells.

PubMed

Ng, Fanny; Tang, Bor Luen

2016-01-01

All eukaryotic cells secrete a range of proteins in a constitutive or regulated manner through the conventional or canonical exocytic/secretory pathway characterized by vesicular traffic from the endoplasmic reticulum, through the Golgi apparatus, and towards the plasma membrane. However, a number of proteins are secreted in an unconventional manner, which are insensitive to inhibitors of conventional exocytosis and use a route that bypasses the Golgi apparatus. These include cytosolic proteins such as fibroblast growth factor 2 (FGF2) and interleukin-1β (IL-1β), and membrane proteins that are known to also traverse to the plasma membrane by a conventional process of exocytosis, such as α integrin and the cystic fibrosis transmembrane conductor (CFTR). Mechanisms underlying unconventional protein secretion (UPS) are actively being analyzed and deciphered, and these range from an unusual form of plasma membrane translocation to vesicular processes involving the generation of exosomes and other extracellular microvesicles. In this chapter, we provide an overview on what is currently known about UPS in animal cells.

Light-activated control of protein channel assembly mediated by membrane mechanics

NASA Astrophysics Data System (ADS)

Miller, David M.; Findlay, Heather E.; Ces, Oscar; Templer, Richard H.; Booth, Paula J.

2016-12-01

Photochemical processes provide versatile triggers of chemical reactions. Here, we use a photoactivated lipid switch to modulate the folding and assembly of a protein channel within a model biological membrane. In contrast to the information rich field of water-soluble protein folding, there is only a limited understanding of the assembly of proteins that are integral to biological membranes. It is however possible to exploit the foreboding hydrophobic lipid environment and control membrane protein folding via lipid bilayer mechanics. Mechanical properties such as lipid chain lateral pressure influence the insertion and folding of proteins in membranes, with different stages of folding having contrasting sensitivities to the bilayer properties. Studies to date have relied on altering bilayer properties through lipid compositional changes made at equilibrium, and thus can only be made before or after folding. We show that light-activation of photoisomerisable di-(5-[[4-(4-butylphenyl)azo]phenoxy]pentyl)phosphate (4-Azo-5P) lipids influences the folding and assembly of the pentameric bacterial mechanosensitive channel MscL. The use of a photochemical reaction enables the bilayer properties to be altered during folding, which is unprecedented. This mechanical manipulation during folding, allows for optimisation of different stages of the component insertion, folding and assembly steps within the same lipid system. The photochemical approach offers the potential to control channel assembly when generating synthetic devices that exploit the mechanosensitive protein as a nanovalve.

Choice of unconventional treatment by patients with cancer.

PubMed

Kimby, Charlotte Kira; Launsø, Laila; Henningsen, Inge; Langgaard, Henrik

2003-08-01

Previous studies conducted on the use of unconventional treatment by patients with cancer have focused on unconventional treatment as a joint group of therapies. The objective of this study is to gather preliminary information about the use of different modes of unconventional cancer treatment by patients with cancer and to describe user profiles of standardized and individualized treatments. Data originate from an ongoing explorative 5-year study of 441 consecutively registered cancer patients who have consulted medical doctors and alternative therapists practicing unconventional treatment in Denmark. This paper is based on data from the first and second of six questionnaires. The unconventional treatments included in this study are categorized into two forms of treatment: standardized and individualized treatment. Four hundred and forty-one (441) Danish patients with cancer who use unconventional cancer treatment. The analysis shows significant correlations between type of treatment and the following variables: gender, education, occupational status, type of cancer, purpose of seeking unconventional treatment, metastatic spread, opinion regarding appropriate unconventional treatment, and simultaneous use of unconventional treatment. The study shows that there are significant differences between patients with cancer choosing standardized and those choosing individualized unconventional treatment. The probability of choosing standardized unconventional treatment is greatest among male participants, patients having shorter school education, and for patients who have recovery as the goal of seeking unconventional treatment. The probability of choosing individualized unconventional treatment is greatest among women, for patients with longer school education, and for patients wanting relief from symptoms, information, and improvement of general condition as the purpose of seeking unconventional cancer treatment. Patients with breast and gynecologic cancer are more inclined to seek individualized treatment than patients with all other cancer diseases. The study points to the fact that it might be essential to differentiate between different forms of unconventional treatment to understand the use by patients with cancer and the outcomes of these treatments.

Purchasing unconventional fuels

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

Doyal, J.

1995-09-01

The reasons to seek unconventional fuels are to either insure a fuel supply or to reduce existing fuel costs. The keys to successfully utilizing unconventional fuel are: (1) build as much flexibility as possible in the variety, quality, quantity and deliverability of the unconventional fuel sources that you can utilize; (2) provide maximum pricing flexibility; (3) fully commit to work with unconventional fuel suppliers; and to (4) consider unconventional fuel operations as a market opportunity. Unconventional fuels operations are well suited to marginal existing operations and can also supplement new startups with uncertain fuel supplies. Unconventional fuel operations can alsomore » help existing facilities generate above market profits for those willing to accommodate the wide market swings inherent in this fledgling industry.« less

Photochemical reactions between mercury (Hg) and dissolved organic matter decrease Hg bioavailability and methylation

DOE PAGES

Luo, Hong-Wei; Yin, Xiangping; Jubb, Aaron M.; ...

2016-11-09

Atmospheric deposition of mercury (Hg) to surface water is one of the dominant sources of Hg in aquatic environments and ultimately drives methylmercury (MeHg) toxin accumulation in fish. It is known that freshly deposited Hg is more readily methylated by microorganisms than aged or preexisting Hg; however the underlying mechanism of this process is unclear. Here we report that Hg bioavailability is decreased by photochemical reactions between Hg and dissolved organic matter (DOM) in water. Photo-irradiation of Hg-DOM complexes results in loss of Sn(II)-reducible (i.e. reactive) Hg and up to an 80% decrease in MeHg production by the methylating bacteriummore » Geobacter sulfurreducens PCA. Loss of reactive Hg proceeded at a faster rate with a decrease in the Hg to DOM ratio and is attributed to the possible formation of mercury sulfide (HgS). Lastly, these results suggest a new pathway of abiotic photochemical formation of HgS in surface water and provide a mechanism whereby freshly deposited Hg is readily methylated but, over time, progressively becomes less available for microbial uptake and methylation.« less

Photochemical reactions between mercury (Hg) and dissolved organic matter decrease Hg bioavailability and methylation

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

Luo, Hong-Wei; Yin, Xiangping; Jubb, Aaron M.

Atmospheric deposition of mercury (Hg) to surface water is one of the dominant sources of Hg in aquatic environments and ultimately drives methylmercury (MeHg) toxin accumulation in fish. It is known that freshly deposited Hg is more readily methylated by microorganisms than aged or preexisting Hg; however the underlying mechanism of this process is unclear. Here we report that Hg bioavailability is decreased by photochemical reactions between Hg and dissolved organic matter (DOM) in water. Photo-irradiation of Hg-DOM complexes results in loss of Sn(II)-reducible (i.e. reactive) Hg and up to an 80% decrease in MeHg production by the methylating bacteriummore » Geobacter sulfurreducens PCA. Loss of reactive Hg proceeded at a faster rate with a decrease in the Hg to DOM ratio and is attributed to the possible formation of mercury sulfide (HgS). Lastly, these results suggest a new pathway of abiotic photochemical formation of HgS in surface water and provide a mechanism whereby freshly deposited Hg is readily methylated but, over time, progressively becomes less available for microbial uptake and methylation.« less

Unified conduction mechanism in unconventional VZnCaFeO glasses

NASA Astrophysics Data System (ADS)

Ahmed, E. M.; Abdel-Wahab, F.

2014-09-01

Unconventional glasses with (70-x)%V2O5 - x%ZnO-10%CaO-20%FeO compositions (where x=0, 2.5, 5, 7.5, 10, 12.5 and 15 mol %) were prepared by a normal melt-quench technique. We investigated the DC and AC conductivities of these glasses as functions of temperature and frequency. We have noted that activation energy and pre-exponential factor of the DC conductivity both vary with composition and satisfy Meyer-Neldel rule (MNR). The AC conductivity exhibited a universal dynamic response: σAC=Aωs. The obtained results of the DC, AC and exponent factor S were discussed in terms of the modified correlated barrier hopping model, which assumes that the relaxation time should contain a Meyer-Neldel rule term. An agreement between experimental and theoretical results suggests that the conduction mechanism could be hopping of polarons over barriers.

Phosphatidylinositol 4,5-Bisphosphate (PI(4,5)P2)-dependent Oligomerization of Fibroblast Growth Factor 2 (FGF2) Triggers the Formation of a Lipidic Membrane Pore Implicated in Unconventional Secretion*

PubMed Central

Steringer, Julia P.; Bleicken, Stephanie; Andreas, Helena; Zacherl, Sonja; Laussmann, Mareike; Temmerman, Koen; Contreras, F. Xabier; Bharat, Tanmay A. M.; Lechner, Johannes; Müller, Hans-Michael; Briggs, John A. G.; García-Sáez, Ana J.; Nickel, Walter

2012-01-01

Fibroblast growth factor 2 (FGF2) is a critical mitogen with a central role in specific steps of tumor-induced angiogenesis. It is known to be secreted by unconventional means bypassing the endoplasmic reticulum/Golgi-dependent secretory pathway. However, the mechanism of FGF2 membrane translocation into the extracellular space has remained elusive. Here, we show that phosphatidylinositol 4,5-bisphosphate-dependent membrane recruitment causes FGF2 to oligomerize, which in turn triggers the formation of a lipidic membrane pore with a putative toroidal structure. This process is strongly up-regulated by tyrosine phosphorylation of FGF2. Our findings explain key requirements of FGF2 secretion from living cells and suggest a novel self-sustained mechanism of protein translocation across membranes with a lipidic membrane pore being a transient translocation intermediate. PMID:22730382

Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)(3)(PR(3))](+) complexes and the properties of their triplet ligand-field excited states.

PubMed

Koike, Kazuhide; Okoshi, Nobuaki; Hori, Hisao; Takeuchi, Koji; Ishitani, Osamu; Tsubaki, Hideaki; Clark, Ian P; George, Michael W; Johnson, Frank P A; Turner, James J

2002-09-25

We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X(2)bpy)(CO)(3)(PR(3))](+) complexes (1) and the properties of their triplet ligand-field ((3)LF) excited states. The reason for the photostability of the rhenium complexes [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X(2)bpy)(CO)(2)(PR(3))(CH(3)CN)](+) (2). Isotope experiments clearly showed that the CO ligand trans to the PR(3) ligand was selectively substituted. The photochemical reactions proceeded via a dissociative mechanism from the (3)LF excited state. The thermodynamical data for the (3)LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer ((3)MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) indicated that the (3)LF states of some 3- and 4-type complexes are probably accessible from the (3)MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR(3), py, and Cl(-) ligands.

Spectroscopy and reactions of molecules important in chemical evolution

NASA Technical Reports Server (NTRS)

Becker, R. S.

1974-01-01

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Time-resolved EPR study on the photochemical reactions of benzil

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

Mukai, Masahiro; Yamnauchi, Seigo; Hirota, Noboru

1992-04-16

TREPR and optical studies on the photochemical reactions of benzil in 2-propanol and benzene-TEA conclude that emissive signals are due to the reaction from T{sub n} produced via the S{sub n} pointing right T{sub n} intersystem crossing process. The free-pair radical-pair mechanism can account for the main features of the slow rise component of the chemically induced dynamic electron polarization signal of the ketyl radical in 2-propanol. 27 refs., 10 figs., 2 tabs.

Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

PubMed

Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

2015-10-27

The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

Photoredox Catalysis: The Need to Elucidate the Photochemical Mechanism.

PubMed

Marchini, Marianna; Bergamini, Giacomo; Cozzi, Pier Giorgio; Ceroni, Paola; Balzani, Vincenzo

2017-10-09

The photocatalytic mechanism reported in a recent Communication to produce the radical anion of pyrenes postulates a highly endergonic electron transfer process. An analysis of the thermodynamics is reported together with the proposal of an alternative thermodynamically feasible mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The photochemical alkylation and reduction of heteroarenes.

PubMed

McCallum, T; Pitre, S P; Morin, M; Scaiano, J C; Barriault, L

2017-11-01

The functionalization of heteroarenes has been integral to the structural diversification of medicinally active molecules such as quinolines, pyridines, and phenanthridines. Electron-deficient heteroarenes are electronically compatible to react with relatively nucleophilic free radicals such as hydroxyalkyl. However, the radical functionalization of such heteroarenes has been marked by the use of transition-metal catalyzed processes that require initiators and stoichiometric oxidants. Herein, we describe the photochemical alkylation of quinolines, pyridines and phenanthridines, where through direct excitation of the protonated heterocycle, alcohols and ethers, such as methanol and THF, can serve as alkylating agents. We also report the discovery of a photochemical reduction of these heteroarenes using only iPrOH and HCl. Mechanistic studies to elucidate the underlying mechanism of these transformations, and preliminary results on catalytic methylations are also reported.

The efficiency of non-photochemical fluorescence quenching by cation radicals in photosystem II reaction centers.

PubMed

Paschenko, V Z; Churin, A A; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Maksimov, E G; Mamedov, M D

2016-12-01

In a direct experiment, the rate constants of photochemical k p and non-photochemical k p + quenching of the chlorophyll fluorescence have been determined in spinach photosystem II (PS II) membrane fragments, oxygen-evolving PS II core, as well as manganese-depleted PS II particles using pulse fluorimetry. In the dark-adapted reaction center(s) (RC), the fluorescence decay kinetics of the antenna were measured at low-intensity picosecond pulsed excitation. To create a "closed" P680 + Q A - state, RCs were illuminated by high-intensity actinic flash 8 ns prior to the measuring flash. The obtained data were approximated by the sum of two decaying exponents. It was found that the antennae fluorescence quenching efficiency by the oxidized photoactive pigment of RC P680 + was about 1.5 times higher than that of the neutral P680 state. These results were confirmed by a single-photon counting technique, which allowed to resolve the additional slow component of the fluorescence decay. Slow component was assigned to the charge recombination of P680 + Pheo - in PS II RC. Thus, for the first time, the ratio k p + /k p  ≅ 1.5 was found directly. The mechanism of the higher efficiency of non-photochemical quenching comparing to photochemical quenching is discussed.

Unexpected effect of catalyst concentration on photochemical CO2 reduction by trans(Cl)–Ru(bpy)(CO)2Cl2: new mechanistic insight into the CO/HCOO– selectivity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc00199d Click here for additional data file.

PubMed Central

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

2015-01-01

Photochemical CO2 reduction catalysed by trans(Cl)–Ru(bpy)(CO)2Cl2 (bpy = 2,2′-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO–) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO–) in the photochemical CO2 reduction: the ratio of CO/HCOO– decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO– is selectively produced by the formation of a Ru(i)–Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru–Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO–. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO– in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)–Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO– formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4′-dimethyl-2,2′-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)–Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6′-dimesityl-2,2′-bipyridine), which bears bulky substituents at the 6,6′-positions in the 2,2′-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work. PMID:28706681

Coiling Phagocytosis of Trypanosomatids and Fungal Cells

PubMed Central

Rittig, M. G.; Schröppel, K.; Seack, K.-H.; Sander, U.; N’Diaye, E.-N.; Maridonneau-Parini, I.; Solbach, W.; Bogdan, C.

1998-01-01

Coiling phagocytosis has previously been studied only with the bacteria Legionella pneumophila and Borrelia burgdorferi, and the results were inconsistent. To learn more about this unconventional phagocytic mechanism, the uptake of various eukaryotic microorganisms by human monocytes, murine macrophages, and murine dendritic cells was investigated in vitro by video and electron microscopy. Unconventional phagocytosis of Leishmania spp. promastigotes, Trypanosoma cruzi trypomastigotes, Candida albicans hyphae, and zymosan particles from Saccharomyces cerevisiae differed in (i) morphology (rotating unilateral pseudopods with the trypanosomatids, overlapping bilateral pseudopods with the fungi), (ii) frequency (high with Leishmania; occasional with the fungi; rare with T. cruzi), (iii) duration (rapid with zymosan; moderate with the trypanosomatids; slow with C. albicans), (iv) localization along the promastigotes (flagellum of Leishmania major and L. aethiopica; flagellum or posterior pole of L. donovani), and (v) dependence on complement (strong with L. major and L. donovani; moderate with the fungi; none with L. aethiopica). All of these various types of unconventional phagocytosis gave rise to similar pseudopod stacks which eventually transformed to a regular phagosome. Further video microscopic studies with L. major provided evidence for a cytosolic localization, synchronized replication, and exocytic release of the parasites, extending traditional concepts about leishmanial infection of host cells. It is concluded that coiling phagocytosis comprises phenotypically similar consequences of various disturbances in conventional phagocytosis rather than representing a single separate mechanism. PMID:9712785

The postman always rings twice: two cases of shotgun deaths associated with an unconventional home security alarm system.

PubMed

Asirdizer, Mahmut; Turkmen, Nursel; Akan, Okan; Yavuz, Mehmet Sunay

2014-06-01

Injury and death cases caused by booby traps are not common in forensic medicine practice. Besides, installation of booby traps including firearms is generally for suicidal and rarely for homicidal purposes. Although few patents were described about home security alarm system that were created by firearms in the United States, 1 sample of injury with a similar unconventional mechanism of home safety system was reported by Asirdizer and Yavuz in 2009. In the published case report, the story of an electrical technician who was invited to a summer house by the homeowner to check the home security alarm system was reported. In the so-called report, he was stated to be injured by the shotgun attached to the unconventional home security alarm system while checking the system. As a result, the homeowner was convicted of a possible intent to cause a life-threatening injury to the technician.The so-called homeowner and his wife died by the same shotgun attached to the same unconventional home security alarm system 4 years on from the first event. In the present case report, we have aimed to present the findings of the crime scene and the autopsies of these unusual 2 deaths and to discuss individual and legal factors in paving the way for the deaths of 2 people.

Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA

NASA Astrophysics Data System (ADS)

Ma, Prettiny K.; Zhao, Yunliang; Robinson, Allen L.; Worton, David R.; Goldstein, Allen H.; Ortega, Amber M.; Jimenez, Jose L.; Zotter, Peter; Prévôt, André S. H.; Szidat, Sönke; Hayes, Patrick L.

2017-08-01

Secondary organic aerosol (SOA) is an important contributor to fine particulate matter (PM) mass in polluted regions, and its modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of intermediate-volatility organic compounds (IVOCs) reported in Zhao et al. (2014) and of semi-volatile organic compounds (SVOCs) reported in Worton et al. (2014) the model is biased high at longer photochemical ages, whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas-phase wall losses in environmental chambers, show model-measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil and non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site. Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model-measurement agreement. However, there are many uncertainties associated with these aging mechanisms. Thus, SOA formation in the model is compared to data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass at short to moderate photochemical ages when the aging mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case has SOA formation rates that are more consistent with observations from the OFR though. Aging mechanisms may still play an important role in SOA chemistry, but the additional mass formed by functionalization reactions during aging would need to be offset by gas-phase fragmentation of SVOCs. All the model cases evaluated in this work show a large majority of the urban SOA (70-83 %) at Pasadena coming from the oxidation of primary SVOCs (P-SVOCs) and primary IVOCs (P-IVOCs). The importance of these two types of precursors is further supported by analyzing the percentage of SOA formed at long photochemical ages (1.5 days) as a function of the precursor rate constant. The P-SVOCs and P-IVOCs have rate constants that are similar to highly reactive VOCs that have been previously found to strongly correlate with SOA formation potential measured by the OFR. Finally, the volatility distribution of the total organic mass (gas and particle phase) in the model is compared against measurements. The total SVOC mass simulated is similar to the measurements, but there are important differences in the measured and modeled volatility distributions. A likely reason for the difference is the lack of particle-phase reactions in the model that can oligomerize and/or continue to oxidize organic compounds even after they partition to the particle phase.

Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions.

PubMed

Derwent, Richard

2017-07-01

The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NO x . Photochemical ozone production rates responded differently to 30% NO x and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NO x and VOCs also produced changes in OH. The responses in OH to 30% reductions in NO x and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NO x reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NO x and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NO x and VOC reductions under consideration. The purpose of this paper is to compare predicted ozone responses to NO x and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their application in the air quality models used for policymaking.

Unconventional medicine in dermatology outpatients in Turkey.

PubMed

Gönül, Müzeyyen; Gül, Ulker; Cakmak, Seray Külcü; Kiliç, Selim

2009-06-01

Many people use unconventional therapies for health problems, but the extent and pattern of this use in dermatology have not been studied in detail. This article reports the first investigation on the use of unconventional therapies in dermatology in Turkey. To determine the prevalence and characteristics of unconventional therapies used by dermatology outpatients in Turkey. A questionnaire was employed to determine the use of unconventional therapies in patients attending a dermatology clinic in Ankara, Turkey. The patients were questioned about the number of attendances at dermatology clinics, whether they had ever used unconventional therapies and/or drugs without the suggestion of a medical doctor for the current dermatologic disorder, and the forms of unconventional therapies employed. The data were compared statistically with the age, sex, and education status of the patients. The respondents included 443 men and 563 women, with a total of 1006 patients. The mean age of the patients was 36.62 +/- 17.55 years. Of the 1006 patients, 337 (33.5%) had used at least one form of unconventional therapy. The most common diagnoses of the patients using unconventional therapy were acne, psoriasis, contact dermatitis, and fungal infections. The most frequent forms of unconventional therapy used by the patients were humectants, cologne, spiritual healing, and herbs. Unconventional therapy use according to the sex, age, and education status of the patients did not show any significant difference. A significant relationship was found between some forms of unconventional therapy and some skin disorders, including: generalized pruritus and application of cologne; warts and spiritual healing; fungal infections and application of henna; psoriasis and herbal therapy or spiritual healing; alopecia areata and application of garlic; acne and application of lemon juice, clay, or cosmetics. Regardless of patient age, sex, and education status, dermatology outpatients use unconventional therapies for their health. Dermatologists should be aware of the tendency of patients to use unconventional therapies and should guide patients towards the use of harmless treatments.

77 FR 10485 - Unconventional Resources Technology Advisory Committee

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2012-02-22

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78 FR 68430 - Unconventional Resources Technology Advisory Committee

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2013-11-14

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75 FR 57743 - Unconventional Resources Technology Advisory Committee

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2010-09-22

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78 FR 58294 - Unconventional Resources Technology Advisory Committee

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2013-09-23

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75 FR 48320 - Unconventional Resources Technology Advisory Committee

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77 FR 59182 - Unconventional Resources Technology Advisory Committee

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2012-09-26

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76 FR 77990 - Unconventional Resources Technology Advisory Committee

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2011-12-15

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76 FR 64923 - Unconventional Resources Technology Advisory Committee

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2011-10-19

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77 FR 53191 - Unconventional Resources Technology Advisory Committee

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2012-08-31

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Photochemical and Spectroscopic Effects Resulting from Excimer Laser Excitation.

NASA Astrophysics Data System (ADS)

Wang, Xuan Xiao

I. Photochemical production of ozone from pure oxygen using excimer lasers. Production of ozone was observed from experiments when oxygen was under a broadband pulsed KrF laser radiation. The production process was found to be autocatalytic. Mechanisms for the ozone formation were proposed. Experimental results over a range of oxygen pressure and laser pulse energy (irradiance) provided evidences in favor of the proposed mechanisms. Experiments were also numerically modeled. Good agreement between the experimental and the numerical results were observed, which provided further evidence to support the proposed mechanisms. Cross sections for some photochemical processes in the mechanisms were estimated. Production of ozone from pure oxygen under a ArF excimer laser radiation (193 nm) was also studied and numerically modeled. Effects of ambient water vapor on ozone production were investigated. Experimental results showed a fast ozone destruction when water vapor was present in the cell. However, numerical results obtained from the well-known OH and HO _2 chain ozone destruction mechanism predicted a slower ozone destruction. Possible reasons for the discrepancy are discussed. II. Resonance-enhanced multiphoton ionization of N_2 at 193 and 248 nm detected by N_sp{2}{+} fluorescence. Using a broadband excimer laser operating at 193 and 248 nm multiphoton ionization at high pressures in air and pure nitrogen has been detected by fluorescence from N_sp{2}{+} in the B-X firstnegative system. Measurements of the fluorescence intensity as a function of beam irradiance indicate resonance in N_2 at the energy of two 193 nm photons (2 + 1 REMPI) and three 248 nm photons (3 + 1 REMPI). Possible intermediate states are discussed. III. Excimer laser-induced fluorescence from some organic solvents. Fluorescence was observed from vapor phase benzene, toluene, p-xylene, benzyl chloride, methyl benzoate, acetic anhydride, ether, methanol, ethyl acetone, acetone, and 2-butanone using a broadband excimer laser operating at 248 nm and 308 nm as the source of excitation. Absolute fluorescence quantum yields for the substances under study were measured at 248 nm using toluene as the fluorescence standard. Fluorescence spectra from species produced from nonlinear photochemical processes were also studied.

Constructing and decoding unconventional ubiquitin chains.

PubMed

Behrends, Christian; Harper, J Wade

2011-05-01

One of the most notable discoveries in the ubiquitin system during the past decade is the extensive use of diverse chain linkages to control signaling networks. Although the utility of Lys48- and Lys63-linked chains in protein turnover and molecular assembly, respectively, are well known, we are only beginning to understand how unconventional chain linkages are formed on target proteins and how such linkages are decoded by specific binding proteins. In this review, we summarize recent efforts to elucidate the machinery and mechanisms controlling assembly of Lys11-linked and linear (or Met1-linked) ubiquitin chains, and describe current models for how these chain types function in immune signaling and cell-cycle control.

Two mechanisms for dissipation of excess light in monomeric and trimeric light-harvesting complexes

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

Dall'Osto, Luca; Cazzaniga, Stefano; Bressan, Mauro

Oxygenic photoautotrophs require mechanisms for rapidly matching the level of chlorophyll excited states from light harvesting with the rate of electron transport from water to carbon dioxide. These photoprotective reactions prevent formation of reactive excited states and photoinhibition. The fastest response to excess illumination is the so-called non-photochemical quenching which, in higher plants, requires the luminal pH sensor PsbS and other yet unidentified components of the photosystem II antenna. Both trimeric light-harvesting complex II (LHCII) and monomeric LHC proteins have been indicated as site(s) of the heat-dissipative reactions. Different mechanisms have been proposed: Energy transfer to a lutein quencher inmore » trimers, formation of a zeaxanthin radical cation in monomers. Here, we report on the construction of a mutant lacking all monomeric LHC proteins but retaining LHCII trimers. Its non-photochemical quenching induction rate was substantially slower with respect to the wild type. A carotenoid radical cation signal was detected in the wild type, although it was lost in the mutant. Here, we conclude that non-photochemical quenching is catalysed by two independent mechanisms, with the fastest activated response catalysed within monomeric LHC proteins depending on both zeaxanthin and lutein and on the formation of a radical cation. Trimeric LHCII was responsible for the slowly activated quenching component whereas inclusion in supercomplexes was not required. Finally, this latter activity does not depend on lutein nor on charge transfer events, whereas zeaxanthin was essential.« less

78 FR 70932 - Unconventional Resources Technology Advisory Committee

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2013-11-27

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77 FR 5246 - Unconventional Resources Technology Advisory Committee

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2012-02-02

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77 FR 63300 - Unconventional Resources Technology Advisory Committee

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2012-10-16

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78 FR 53741 - Unconventional Resources Technology Advisory Committee

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2013-08-30

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Roles of an Unconventional Protein Kinase and Myosin II in Amoeba Osmotic Shock Responses

PubMed Central

Betapudi, Venkaiah; Egelhoff, Thomas T.

2009-01-01

The contractile vacuole (CV) is a dynamic organelle that enables Dictyostelium amoeba and other protist to maintain osmotic homeostasis by expelling excess water. In the present study, we have uncovered a mechanism that coordinates the mechanics of the CV with myosin II, regulated by VwkA, an unconventional protein kinase that is conserved in an array of protozoa. GFP-VwkA fusion proteins localize persistently to the CV during both filling and expulsion phases of water. In vwkA null cells, the established CV marker dajumin still localizes to the CV, but these structures are large, spherical, and severely impaired for discharge. Furthermore, myosin II cortical localization and assembly are abnormal in vwkA null cells. Parallel analysis of wild type cells treated with myosin II inhibitors or of myosin II null cells also results in enlarged CVs with impaired dynamics. We suggest that the myosin II cortical cytoskeleton, regulated by VwkA, serves a critical conserved role in the periodic contractions of the CV, as part of the osmotic protective mechanism of protozoa. PMID:19843280

Status and summary of laser energy conversion. [for space power transmission systems

NASA Technical Reports Server (NTRS)

Lee, G.

1978-01-01

This paper presents a survey of the status of laser energy converters. Since the inception of these devices in the early 1970's, significant advances have been made in understanding the basic conversion processes. Numerous theoretical and experimental studies have indicated that laser energy can be converted at wavelengths from the ultraviolet to the far-infrared. These converters can be classified into five general categories: photovoltaics, heat engines, thermoelectronic, optical diode, and photochemical. The conversion can be directly into electricity (such as the photovoltaic, thermoelectronic, and optical diode) or it can go through an intermediate stage of conversion to mechanical energy, as in the heat engines. The photochemical converters result in storable energy such as hydrogen. Projected conversion efficiencies range from about 30% for the photochemical to nearly 75% for the heat engines.

Light limitation plays a central role in regulating DOM reactions in temperate watersheds

NASA Astrophysics Data System (ADS)

Yoon, B.; Hosen, J. D.; Kyzivat, E.; Fair, J. H.; Weber, L.; Aho, K. S.; Stubbins, A.; Lowenthal, R. S.; Raymond, P. A.

2017-12-01

Biological uptake and photochemical oxidation determine how much dissolved organic matter (DOM) can be removed and exported from inland waters. It is thus critical to understand the control on the biological and photochemical oxidation of DOM, and identify potential synergy between these two DOM removal processes. Yet, the variability of biological and photochemical lability, and the prevalence of priming effects between the two removal mechanisms are poorly understood at larger spatiotemporal scale. To address this knowledge gap, we analyzed the lability of 900 samples collected throughout the Connecticut River across two years (n = 510 for biolability, n=394 for photolability). Furthermore, we measured the effect of photochemical priming for biological removal and of biological priming for photochemical removal (n= 151, n=146, respectively). Our results show that photolability is on average 5 times greater than biolability, and that the mass of photolabile DOM can be predicted from UV absorbance at 254 nm. Photochemical DOM removal also led to additional "unlocking" of previously bio-recalcitrant DOM in 80% of the samples, and increased the biological lability by threefold on average. Scaling further, we extrapolate our model to estimate that the DOM fluxes leaving the Connecticut River and the Mississippi River are 49% and 45% photolabile, respectively. The significant photoreactivity observed across the samples and the subsequent increase in biolability demonstrate that sunlight is a more potent agent of DOM removal than the biological reactions. Yet, the photolability of DOM fluxes leaving the Connecticut River and Mississippi River indicates that the full photo-oxidation potential is not achieved due to light limitation.

Photoactive high explosives: linear and nonlinear photochemistry of petrin tetrazine chloride.

PubMed

Greenfield, Margo T; McGrane, Shawn D; Bolme, Cindy A; Bjorgaard, Josiah A; Nelson, Tammie R; Tretiak, Sergei; Scharff, R Jason

2015-05-21

Pentaerythritol tetranitrate (PETN), a high explosive, initiates with traditional shock and thermal mechanisms. In this study, the tetrazine-substituted derivative of PETN, pentaerythritol trinitrate chlorotetrazine (PetrinTzCl), is being investigated for a photochemical initiation mechanism that could allow control over the chemistry contributing to decomposition leading to initiation. PetrinTzCl exhibits a photochemical quantum yield (QYPC) at 532 nm not evident with PETN. Using static spectroscopic methods, we observe energy absorption on the tetrazine (Tz) ring that results in photodissociation yielding N2, Cl-CN, and Petrin-CN as the major photoproducts. The QYPC was enhanced with increasing irradiation intensity. Experiment and theoretical calculations imply this excitation mechanism follows sequential photon absorption. Dynamic simulations demonstrate that the relaxation mechanism leading to the observed photochemistry in PetrinTzCl is due to vibrational excitation during internal conversion. PetrinTzCl's single photon stability and intensity dependence suggest this material could be stable in ambient lighting, yet possible to initiate with short-pulsed lasers.

77 FR 23105 - Supporting Safe and Responsible Development of Unconventional Domestic Natural Gas Resources

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-17

... Safe and Responsible Development of Unconventional Domestic Natural Gas Resources #0; #0; #0..., 2012 Supporting Safe and Responsible Development of Unconventional Domestic Natural Gas Resources By... and responsible development of unconventional domestic natural gas resources and associated...

Relaxation of the non-photochemical chlorophyll fluorescence quenching in diatoms: kinetics, components and mechanisms

PubMed Central

Roháček, Karel; Bertrand, Martine; Moreau, Brigitte; Jacquette, Boris; Caplat, Christelle; Morant-Manceau, Annick; Schoefs, Benoît

2014-01-01

Diatoms are especially important microorganisms because they constitute the larger group of microalgae. To survive the constant variations of the light environment, diatoms have developed mechanisms aiming at the dissipation of excess energy, such as the xanthophyll cycle and the non-photochemical chlorophyll (Chl) fluorescence quenching. This contribution is dedicated to the relaxation of the latter process when the adverse conditions cease. An original nonlinear regression analysis of the relaxation of non-photochemical Chl fluorescence quenching, qN, in diatoms is presented. It was used to obtain experimental evidence for the existence of three time-resolved components in the diatom Phaeodactylum tricornutum: qNf, qNi and qNs. qNf (s time-scale) and qNs (h time-scale) are exponential in shape. By contrast, qNi (min time-scale) is of sigmoidal nature and is dominant among the three components. The application of metabolic inhibitors (dithiothreitol, ammonium chloride, cadmium and diphenyleneiodonium chloride) allowed the identification of the mechanisms on which each component mostly relies. qNi is linked to the relaxation of the ΔpH gradient and the reversal of the xanthophyll cycle. qNs quantifies the stage of photoinhibition caused by the high light exposure, qNf seems to reflect fast conformational changes within thylakoid membranes in the vicinity of the photosystem II complexes. PMID:24591721

Modeling Photochemical Dynamics in Optically Active Energetic Materials

NASA Astrophysics Data System (ADS)

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R. Jason; Tretiak, Sergei

Most high explosives (HEs) absorb in the UV range, making it difficult to develop HEs that can be excited with standard lasers. The conventional optical initiation mechanisms require high laser intensity and occur via indirect thermal or shock processes. A photochemical initiation mechanism could allow control over the chemistry contributing to decomposition leading to initiation. We combine UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) with Nonadiabatic Excited State Molecular Dynamics (NA-ESMD) to model the photochemical pathways in nitromethane (NM), a low sensitivity HE known to undergo UV photolysis. We investigate the ultrafast photodecomposition of NM from the nπ* state excited at 266 nm. The FSRS photoproduct spectrum points to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of 20 fs were predicted from simulations. Predicted time scales reveal that NO2 dissociation occurs in 81 +/-4 fs and methyl nitrite formation is much slower at 452 +/-9 fs corresponding to the absorption feature in the TA spectrum. The relative time scales are consistent with isomerization by NO2 dissociation and ONO rebinding.

A Road Towards High Temperature Superconductors

DTIC Science & Technology

2013-08-01

several nanometers in size . However the mechanism by which such particles enhance vortex pinning was unclear, because they are much...coherent with the matrix and induce only weak pinning, while vice‐versa particles of the same size and concentration but with a stronger lattice... behavior of the cuprates under applied fields can be made by using an unconventional pinning mechanism directly based on the Bond Contraction

Lightweight bio-composites based on hemp fibres produced by conventional and unconventional processes

NASA Astrophysics Data System (ADS)

Boccarusso, L.; Durante, M.; Formisano, A.; Langella, A.; Minutolo, F. Memola Capece

2017-10-01

Considering that nowadays the interest in the use of bio-composite materials is increasing more and more, this work is focused on the manufacturing of lightweight components based on hemp fibres for future applications, for example as a core for sandwich structures. Three different no-complex processes were used: a conventional hand lay-up, an unconventional infusion process and a hand lay-up process followed by injection moulding. They were used to produce bio-composite structures using an epoxy resin and/or a polyurethane foam as matrix. Depending on the process used for the manufacturing, laminates with different values of density were obtained. A detailed study in terms of both static and dynamic properties was carried out and the different mechanical behaviour for each sample typology was highlighted. The results showed that the process in which both the epoxy resin and the polyurethane foam were used as matrix allowed to obtain laminates with lower density and higher specific mechanical properties.

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

NASA Technical Reports Server (NTRS)

Grannas, A. M.; Jones, A. E.; Dibb, J.; Ammann, M.; Anastasio, C.; Beine, H. J.; Bergin, M.; Bottenheim, J.; Boxe, C. S.; Carver, G.;

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

NASA Astrophysics Data System (ADS)

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

1988-05-01

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

The photochemical alkylation and reduction of heteroarenes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03768f Click here for additional data file.

PubMed Central

McCallum, T.; Pitre, S. P.; Morin, M.

2017-01-01

The functionalization of heteroarenes has been integral to the structural diversification of medicinally active molecules such as quinolines, pyridines, and phenanthridines. Electron-deficient heteroarenes are electronically compatible to react with relatively nucleophilic free radicals such as hydroxyalkyl. However, the radical functionalization of such heteroarenes has been marked by the use of transition-metal catalyzed processes that require initiators and stoichiometric oxidants. Herein, we describe the photochemical alkylation of quinolines, pyridines and phenanthridines, where through direct excitation of the protonated heterocycle, alcohols and ethers, such as methanol and THF, can serve as alkylating agents. We also report the discovery of a photochemical reduction of these heteroarenes using only iPrOH and HCl. Mechanistic studies to elucidate the underlying mechanism of these transformations, and preliminary results on catalytic methylations are also reported. PMID:29163892

Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

PubMed Central

Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

2013-01-01

Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

The future of oil: unconventional fossil fuels.

PubMed

Chew, Kenneth J

2014-01-13

Unconventional fossil hydrocarbons fall into two categories: resource plays and conversion-sourced hydrocarbons. Resource plays involve the production of accumulations of solid, liquid or gaseous hydro-carbons that have been generated over geological time from organic matter in source rocks. The character of these hydrocarbons may have been modified subsequently, especially in the case of solids and extra-heavy liquids. These unconventional hydrocarbons therefore comprise accumulations of hydrocarbons that are trapped in an unconventional manner and/or whose economic exploitation requires complex and technically advanced production methods. This review focuses primarily on unconventional liquid hydro-carbons. The future potential of unconventional gas, especially shale gas, is also discussed, as it is revolutionizing the energy outlook in North America and elsewhere.

Unconventional Cooper pairing results in a pseudogap-like phase in s-wave superconductors

NASA Astrophysics Data System (ADS)

Springer, Daniel; Cheong, Siew Ann

2015-10-01

The impact of disorder on the superconducting (SC) pairing mechanism is the centre of much debate. Some evidence suggests a loss of phase coherence of pairs while others point towards the formation of a competing phase. In our work we show that the two perspectives may be different sides of the same coin. Using an extension of the perturbative renormalization group approach we compare the impact of different disorder-induced interactions on a SC ground state. We find that in the strongly disordered regime an interaction between paired fermions and their respective disordered environment replaces conventional Cooper pairing. For these unconventional Cooper pairs the phase coherence condition, required for the formation of a SC condensate, is not satisfied.

Ocular hazards of light

NASA Technical Reports Server (NTRS)

Sliney, David H.

1994-01-01

The eye is protected against bright light by the natural aversion response to viewing bright light sources. The aversion response normally protects the eye against injury from viewing bright light sources such as the sun, arc lamps and welding arcs, since this aversion limits the duration of exposure to a fraction of a second (about 0.25 s). The principal retinal hazard resulting from viewing bright light sources is photoretinitis, e.g., solar retinitis with an accompanying scotoma which results from staring at the sun. Solar retinitis was once referred to as 'eclipse blindness' and associated 'retinal burn'. Only in recent years has it become clear that photoretinitis results from a photochemical injury mechanism following exposure of the retina to shorter wavelengths in the visible spectrum, i.e., violet and blue light. Prior to conclusive animal experiments at that time, it was thought to be a thermal injury mechanism. However, it has been shown conclusively that an intense exposure to short-wavelength light (hereafter referred to as 'blue light') can cause retinal injury. The product of the dose-rate and the exposure duration always must result in the same exposure dose (in joules-per-square centimeter at the retina) to produce a threshold injury. Blue-light retinal injury (photoretinitis) can result from viewing either an extremely bright light for a short time, or a less bright light for longer exposure periods. This characteristic of photochemical injury mechanisms is termed reciprocity and helps to distinguish these effects from thermal burns, where heat conduction requires a very intense exposure within seconds to cause a retinal coagulation otherwise, surrounding tissue conducts the heat away from the retinal image. Injury thresholds for acute injury in experimental animals for both corneal and retinal effects have been corroborated for the human eye from accident data. Occupational safety limits for exposure to UVR and bright light are based upon this knowledge. As with any photochemical injury mechanism must consider the action spectrum, which describes the relative effectiveness of different wavelengths in causing a photobiological effect. The action spectrum for photochemical retinal injury peaks at approximately 440 nm.

[Tanning lamp radiation-induced photochemical retinal damage].

PubMed

Volkov, V V; Kharitonova, N N; Mal'tsev, D S

2014-01-01

On the basis of original clinical research a rare case of bilateral retinal damage due to tanning lamp radiation exposure is presented. Along with significant decrease of visual acuity and light sensitivity of central visual field as well as color vision impairment, bilateral macular dystrophy was found during an ophthalmoscopy and confirmed by optical coherent tomography and fluorescent angiography. Intensive retinoprotective, vascular, and antioxidant therapy was effective and led to functional improvement and stabilization of the pathologic process associated with photochemical retinal damage. A brief review of literature compares mechanisms of retinal damage by either short or long-wave near visible radiation.

Photochemical transformations of diazocarbonyl compounds: expected and novel reactions

NASA Astrophysics Data System (ADS)

Galkina, O. S.; Rodina, L. L.

2016-05-01

Photochemical reactions of diazocarbonyl compounds are well positioned in synthetic practice as an efficient method for ring contraction and homologation of carboxylic acids and as a carbene generation method. However, interpretation of the observed transformations of diazo compounds in electronically excited states is incomplete and requires a careful study of the fine mechanisms of these processes specific to different excited states of diazo compounds resorting to modern methods of investigation, including laser technology. The review is devoted to analysis of new data in the chemistry of excited states of diazocarbonyl compounds. The bibliography includes 155 references.

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. I - Comparison with AAOE observations

NASA Technical Reports Server (NTRS)

Jones, R. L.; Austin, J.; Mckenna, D. S.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Vedder, J. F.

1989-01-01

Results from the Lagrangian photochemical model integrated along computed air parcel trajectories intersected by the ER-2 aircraft are presented and compared with AAOE observations. According to the model, the BrO observations made from the ER-2 within the dehydrated denitrified region are consistent with there being approximately 5 parts per trillion by volume of BrO(y) at 428 K in spring. Within the high ClO region, ozone destruction rates are expected to exceed 2 percent/d with approximately 80 percent due to the ClO dimer mechanism.

Mechanisms of small molecule–DNA interactions probed by single-molecule force spectroscopy

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Rouzina, Ioulia; Williams, Mark C.

2016-01-01

There is a wide range of applications for non-covalent DNA binding ligands, and optimization of such interactions requires detailed understanding of the binding mechanisms. One important class of these ligands is that of intercalators, which bind DNA by inserting aromatic moieties between adjacent DNA base pairs. Characterizing the dynamic and equilibrium aspects of DNA-intercalator complex assembly may allow optimization of DNA binding for specific functions. Single-molecule force spectroscopy studies have recently revealed new details about the molecular mechanisms governing DNA intercalation. These studies can provide the binding kinetics and affinity as well as determining the magnitude of the double helix structural deformations during the dynamic assembly of DNA–ligand complexes. These results may in turn guide the rational design of intercalators synthesized for DNA-targeted drugs, optical probes, or integrated biological self-assembly processes. Herein, we survey the progress in experimental methods as well as the corresponding analysis framework for understanding single molecule DNA binding mechanisms. We discuss briefly minor and major groove binding ligands, and then focus on intercalators, which have been probed extensively with these methods. Conventional mono-intercalators and bis-intercalators are discussed, followed by unconventional DNA intercalation. We then consider the prospects for using these methods in optimizing conventional and unconventional DNA-intercalating small molecules. PMID:27085806

Photochemical insertion of alkynes into Cp sub 2 Fe sub 2 (CO) sub 2 (. mu. -CO) sub 2 : A mechanistic study by laser flash photolysis

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

Bursten, B.E.; McKee, S.D.; Platz, M.S.

1989-04-26

Cp{sub 2}Fe{sub 2}(CO){sub 2}({mu}-CO){sub 2} (1: Cp = {eta}{sup 5}-C{sub 5}H{sub 5}) has a rich and diverse photochemistry, as evidenced by the plethora of synthetic and mechanistic studies of it in the literature. Early photochemical studies of 1 have demonstrated homolysis to the radical Cp(CO){sub 2}Fe{sup {sm bullet}} (2). Recent work on metal dimers indicates that a dinuclear species is formed concomitantly. Tyler, Schmidt, and Gray (TSG) first proposed that irradiation of 1 leads to the dinuclear species 3, which they suggested was the intermediate responsible for phosphine substitution. Research by other individuals has indicated that the substitutionally active speciesmore » is the CO-loss photoproduct CpFe({mu}-CO){sub 3}FeCp (4). The authors interest in the photochemistry of 1 stemmed from their theoretical studies on piano-stool dimers. One reaction of particular concern is the photochemical insertion of alkynes into 1 to yield dimetallacyclopentenone 5. On the basis of MO calculations, the authors proposed a possible LUMO-controlled mechanism for this reaction that involved alkyne addition to the TSG transition state 3, followed by CO loss. In this contribution, they report initial experimental studies which demonstrate that 4 is the photochemical intermediate responsible for this reaction. They consider this reaction to be a paradigm for photochemical substitution and insertion reaction in such systems.« less

Phototoxicity to the retina: mechanisms of damage.

PubMed

Glickman, Randolph D

2002-01-01

Light damage to the retina occurs through three general mechanisms involving thermal, mechanical, or photochemical effects. The particular mechanism activated depends on the wavelength and exposure duration of the injuring light. The transitions between the various light damage mechanism may overlap to some extent. Energy confinement is a key concept in understanding or predicting the type of damage mechanism produced by a given light exposure. As light energy (either from a laser or an incoherent source) is deposited in the retina, its penetration through, and its absorption in, various tissue compartments is determined by its wavelength. Strongly absorbing tissue components will tend to "concentrate" the light energy. The effect of absorbed light energy largely depends on the rate of energy deposition, which is correlated with the exposure duration. If the rate of energy deposition is too low to produce an appreciable temperature increase in the tissue, then any resulting tissue damage necessarily occurs because of chemical (oxidative) reactions induced by absorption of energetic photons (photochemical damage). If the rate of energy deposition is faster than the rate of thermal diffusion (thermal confinement), then the temperature of the exposed tissue rises. If a critical temperature is reached (typically about 10 degrees C above basal), then thermal damage occurs. If the light energy is deposited faster than mechanical relaxation can occur (stress confinement), then a thermoelastic pressure wave is produced, and tissue is disrupted by shear forces or by cavitation-nonlinear effects. Very recent evidence suggests that ultrashort laser pulses can produce tissue damage through nonlinear and photochemical mechanisms; the latter because of two-photon excitation of cellular chromophores. In addition to tissue damage caused directly by light absorption, light toxicity can be produced by the presence of photosensitizing agents. Drugs excited to reactive states by ultraviolet (UV) or visible light produce damage by type I (free radical) and type II (oxygen dependent) mechanisms. Some commonly used drugs, such as certain antibiotics, nonsteroidal anti-inflammatory drugs (NSAIDs), and psychotherapeutic agents, as well as some popular herbal medicines, can produce ocular phototoxicity. Specific cellular effects and damage end points characteristic of light damage mechanisms are described.

Unconventional Aqueous Humor Outflow: A Review

PubMed Central

Johnson, Mark; McLaren, Jay W.; Overby, Darryl R.

2016-01-01

Aqueous humor flows out of the eye primarily through the conventional outflow pathway that includes the trabecular meshwork and Schlemm's canal. However, a fraction of aqueous humor passes through an alternative or ‘unconventional’ route that includes the ciliary muscle, supraciliary and suprachoroidal spaces. From there, unconventional outflow may drain through two pathways: a uveoscleral pathway where aqueous drains across the sclera to be resorbed by orbital vessels, and a uveovortex pathway where aqueous humor enters the choroid to drain through the vortex veins. We review the anatomy, physiology and pharmacology of these pathways. We also discuss methods to determine unconventional outflow rate, including direct techniques that use radioactive or fluorescent tracers recovered from tissues in the unconventional pathway and indirect methods that estimate unconventional outflow based on total outflow over a range of pressures. Indirect methods are subject to a number of assumptions and generally give poor agreement with tracer measurements. We review the variety of animal models that have been used to study conventional and unconventional outflow. The mouse appears to be a promising model because it captures several aspects of conventional and unconventional outflow dynamics common to humans, although questions remain regarding the magnitude of unconventional outflow in mice. Finally, we review future directions. There is a clear need to develop improved methods for measuring unconventional outflow in both animals and humans. PMID:26850315

Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations.

PubMed

Liu, Lili; Niu, Zhiqiang; Chen, Jun

2016-07-25

As energy storage devices, supercapacitors that are also called electrochemical capacitors possess high power density, excellent reversibility and long cycle life. The recent boom in electronic devices with different functions in transparent LED displays, stretchable electronic systems and artificial skin has increased the demand for supercapacitors to move towards light, thin, integrated macro- and micro-devices with transparent, flexible, stretchable, compressible and/or wearable abilities. The successful fabrication of such supercapacitors depends mainly on the preparation of innovative electrode materials and the design of unconventional supercapacitor configurations. Tremendous research efforts have been recently made to design and construct innovative nanocarbon-based electrode materials and supercapacitors with unconventional configurations. We review here recent developments in supercapacitors from nanocarbon-based electrode materials to device configurations. The advances in nanocarbon-based electrode materials mainly include the assembly technologies of macroscopic nanostructured electrodes with different dimensions of carbon nanotubes/nanofibers, graphene, mesoporous carbon, activated carbon, and their composites. The electrodes with macroscopic nanostructured carbon-based materials overcome the issues of low conductivity, poor mechanical properties, and limited dimensions that are faced by conventional methods. The configurational design of advanced supercapacitor devices is presented with six types of unconventional supercapacitor devices: flexible, micro-, stretchable, compressible, transparent and fiber supercapacitors. Such supercapacitors display unique configurations and excellent electrochemical performance at different states such as bending, stretching, compressing and/or folding. For example, all-solid-state simplified supercapacitors that are based on nanostructured graphene composite paper are able to maintain 95% of the original capacity at a 180° folding state. The progress made so far will guide further developments in the structural design of nanocarbon-based electrode materials and the configurational diversity of supercapacitor devices. Future developments and prospects in the controllable assembly of macroscopic nanostructured electrodes and the innovation of unconventional supercapacitor configurations are also discussed. This should shed light on the R&D of supercapacitors.

Evolution of flexible non-photochemical quenching mechanisms that regulate light harvesting in oxygenic photosynthesis.

PubMed

Niyogi, Krishna K; Truong, Thuy B

2013-06-01

All photosynthetic organisms need to regulate light harvesting for photoprotection. Three types of flexible non-photochemical quenching (NPQ) mechanisms have been characterized in oxygenic photosynthetic cyanobacteria, algae, and plants: OCP-, LHCSR-, and PSBS-dependent NPQ. OCP-dependent NPQ likely evolved first, to quench excess excitation in the phycobilisome (PB) antenna of cyanobacteria. During evolution of eukaryotic algae, PBs were lost in the green and secondary red plastid lineages, while three-helix light-harvesting complex (LHC) antenna proteins diversified, including LHCSR proteins that function in dissipating excess energy rather than light harvesting. PSBS, an independently evolved member of the LHC protein superfamily, seems to have appeared exclusively in the green lineage, acquired a function as a pH sensor that turns on NPQ, and eventually replaced LHCSR in vascular plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Application Of Microbial Enhanced Oil Recovery On Unconventional Oil: A Field Specific Approach

NASA Astrophysics Data System (ADS)

Goodman, Sean; Millar, Andrew; Allison, Heather; McCarthy, Alan

2014-05-01

A substantial amount of the world's recoverable oil reserves are made from unconventional or heavy resources. However, great difficulty has been had in recovering this oil after primary and secondary recovery methods have been employed. Therefore, tertiary methods such as microbial enhanced oil recovery (MEOR) have been employed. MEOR involves the use of bacteria and their metabolic products to alter the oil properties or rock permeability within a reservoir in order to promote the flow of oil. Although MEOR has been trialed in the past with mixed outcomes, its feasibility on heavier oils has not been demonstrated. The aim of this study is to show that MEOR can be successfully applied to unconventional oils. By using an indigenous strain of bacteria isolated from a reservoir of interest and applied to field specific microcosms, we will look into the effect of these bacteria compared to variant inoculums to identify which mechanisms of action the bacteria are using to improve recovery. Using this information, we will be able to identify genes of interest and groups of bacteria that may be beneficial for MEOR and look accurately identify favorable bacteria within a reservoir.

Unconventional thermal cloak hiding an object outside the cloak

NASA Astrophysics Data System (ADS)

Gao, Y.; Huang, J. P.

2013-11-01

All the thermal cloaks reported in the literature can be used to thermally hide an object inside the cloak. However, a common limitation of this kind of thermal cloaks is that the cloaked object cannot feel the external heat flow since it is located inside the cloak; thus we call these cloaks “conventional thermal cloaks”. Here we manage to overcome this limitation by exploiting a class of unconventional thermal cloaks that enable the cloaked object to feel the external heat flow. Our finite-element simulations in two dimensions show the desired cloaking effect. The underlying mechanism originates from the complementary effect of thermal metamaterials with negative thermal conductivities. This work suggests a different method to design thermal devices where heat conduction can be controlled at will.

Effects of temperature and water availability on light energy utilization in photosynthetic processes of Deschampsia antarctica.

PubMed

Sáez, Patricia L; Rivera, Betsy K; Ramírez, Constanza F; Vallejos, Valentina; Cavieres, Lohengrin A; Corcuera, Luis J; Bravo, León A

2018-03-30

Regional climate change in Antarctica would favor the carbon assimilation of Antarctic vascular plants, because rising temperatures are approaching their photosynthetic optimum (10-19°C). This could be detrimental for photoprotection mechanisms, mainly those associated with thermal dissipation, making plants more susceptible to eventual drought predicted by climate change models. With the purpose to study the effect of temperature and water availability on light energy utilization and putative adjustments in photoprotective mechanisms of Deschampsia antarctica Desv., plants were collected from two Antarctic provenances: King George Island and Lagotellerie Island. Plants were cultivated at 5°, 10° and 16°C under well-watered (WW) and water-deficit (WD, at 35% of the field capacity) conditions. Chlorophyll fluorescence, pigment content, and de-epoxidation state were evaluated. Regardless of provenances, D. antarctica showed similar morphological, biochemical, and functional responses to growth temperature. Higher temperature triggered an increase in photochemical activity (i.e. ETR, and photochemical quenching), and a decrease in thermal dissipation capacity (i.e. lower xanthophyll pool, Chl a/b, and β carotene/neoxanthin ratios). LMA was reduced at higher temperature, and was only affected in plants exposed to WD at 16°C and exhibiting lower ETR and chlorophylls. D. antarctica is adapted to frequent freezing events, which may induce a form of physiological water stress. Photoprotective responses observed under WD contribute to maintain a stable photochemical activity. Thus, it is possible that short-term temperature increases could favor the photochemical activity of this species. However, long-term effects will depend on the magnitude of changes and the plant's ability to adjust to new growth temperature. This article is protected by copyright. All rights reserved.

Lasers: A Valuable Tool for Chemists.

ERIC Educational Resources Information Center

Findsen, E. W.; Ondrias, M. R.

1986-01-01

Discusses the properties of laser light, reviews types of lasers, presents operating principles, and considers mechanical aspects of laser light production. Applications reviewed include spectroscopy, photochemical reaction initiation, and investigation of biological processes involving porphyrins. (JM)

The susceptibility of the retina to photochemical damage from visible light

PubMed Central

Hunter, Jennifer J; Morgan, Jessica I W; Merigan, William H; Sliney, David H; Sparrow, Janet R; Williams, David R

2011-01-01

The photoreceptor/RPE complex must maintain a delicate balance between maximizing the absorption of photons for vision and retinal image quality while simultaneously minimizing the risk of photodamage when exposed to bright light. We review the recent discovery of two new effects of light exposure on the photoreceptor/RPE complex in the context of current thinking about the causes of retinal phototoxicity. These effects are autofluorescence photobleaching in which exposure to bright light reduces lipofuscin autofluorescence and, at higher light levels, RPE disruption in which the pattern of autofluorescence is permanently altered following light exposure. Both effects occur following exposure to visible light at irradiances that were previously thought to be safe. Photopigment, retinoids involved in the visual cycle, and bisretinoids in lipofuscin have been implicated as possible photosensitizers for photochemical damage. The mechanism of RPE disruption may follow either of these paths. On the other hand, autofluorescence photobleaching is likely an indicator of photooxidation of lipofuscin. The permanent changes inherent in RPE disruption might require modification of the light safety standards. AF photobleaching recovers after several hours although the mechanisms by which this occurs are not yet clear. Understanding the mechanisms of phototoxicity is all the more important given the potential for increased susceptibility in the presence of ocular diseases that affect either the visual cycle and/or lipofuscin accumulation. In addition, knowledge of photochemical mechanisms can improve our understanding of some disease processes that may be influenced by light exposure, such as some forms of Leber’s congenital amaurosis, and aid in the development of new therapies. Such treatment prior to intentional light exposures, as in ophthalmic examinations or surgeries, could provide an effective preventative strategy. PMID:22085795

Photochemistry of fac-[Re(CO)3(dcbH2)( trans-stpy)]+: New Insights on the Isomerization Mechanism of Coordinated Stilbene-like Ligands.

PubMed

Faustino, Leandro A; Hora Machado, Antonio Eduardo; Patrocinio, Antonio Otavio T

2018-03-05

In this work, a novel complex fac-[Re(CO) 3 (dcbH 2 )( trans-stpy)] + , (dcbH 2 = 4,4'-dicarboxylic acid-2,2'-bipyridine; trans-stpy = trans-4-styrylpyridine) was synthesized and characterized toward its spectroscopic, photochemical, and photophysical properties. The experimental data provide new insights on the mechanism of photochemical trans-to- cis isomerization of the stilbene-like ligand coordinated to Re(I) polypyridyl complexes. The new complex exhibits an unusual and strong dependence of the isomerization quantum yield (Φ t →c ) on the irradiation wavelength. Φ t →c was 0.81 ± 0.08 for irradiation at 365 nm and continuously decreased as the irradiation wavelength is shifted to the visible. At 405 nm irradiation Φ t →c is almost 2 orders of magnitude lower (0.010 ± 0.005) than that observed at 365 nm excitation. This behavior can be explained by the low-lying triplet metal-to-ligand charge-transfer excited state ( 3 MLCT) that hinders the triplet photoreaction mechanism under visible light absorption. Under UV irradiation, direct population of styrylpyridine-centered excited state ( 1 IL) leads to the occurrence of the photoisomerization via a singlet mechanism. Further experiments were performed with the complex immobilized on the surface of TiO 2 and Al 2 O 3 films. The nonoccurrence of isomerization at the oxide surfaces even under UV excitation evidences the role of energy gap between the 1 IL/ 1 MLCT states on the photochemical/photophysical processes. The results establish important relationships between the molecular structure and the photoelectrochemical behavior, which can further contribute to the development of solid-state molecular switches based on Re(I) polypyridyl complexes.

Unconventional Deterrence Strategy

DTIC Science & Technology

2005-06-01

200 words) This thesis examines a largely unexplored area of deterrence theory – unconventional deterrence. Unconventional deterrence is defined...hypothesis of deterrence theory which says that the balance of the opponents’ military capabilities is the basic determinant of successful deterrence...

A plasmaless, photochemical etch process for porous organosilicate glass films

NASA Astrophysics Data System (ADS)

Ryan, E. Todd; Molis, Steven E.

2017-12-01

A plasmaless, photochemical etch process using ultraviolet (UV) light in the presence of NH3 or O2 etched porous organosilicate glass films, also called pSiCOH films, in a two-step process. First, a UV/NH3 or UV/O2 treatment removed carbon (mostly methyl groups bonded to silicon) from a pSiCOH film by demethylation to a depth determined by the treatment exposure time. Second, aqueous HF was used to selectively remove the demethylated layer of the pSiCOH film leaving the methylated layer below. UV in the presence of inert gas or H2 did not demethylate the pSiCOH film. The depth of UV/NH3 demethylation followed diffusion limited kinetics and possible mechanisms of demethylation are presented. Unlike reactive plasma processes, which contain ions that can damage surrounding structures during nanofabrication, the photochemical etch contains no damaging ions. Feasibility of the photochemical etching was shown by comparing it to a plasma-based process to remove the pSiCOH dielectric from between Cu interconnect lines, which is a critical step during air gap fabrication. The findings also expand our understanding of UV photon interactions in pSiCOH films that may contribute to plasma-induced damage to pSiCOH films.

Photochemical alteration of organic carbon draining permafrost soils shifts microbial metabolic pathways and stimulates respiration.

PubMed

Ward, Collin P; Nalven, Sarah G; Crump, Byron C; Kling, George W; Cory, Rose M

2017-10-03

In sunlit waters, photochemical alteration of dissolved organic carbon (DOC) impacts the microbial respiration of DOC to CO 2 . This coupled photochemical and biological degradation of DOC is especially critical for carbon budgets in the Arctic, where thawing permafrost soils increase opportunities for DOC oxidation to CO 2 in surface waters, thereby reinforcing global warming. Here we show how and why sunlight exposure impacts microbial respiration of DOC draining permafrost soils. Sunlight significantly increases or decreases microbial respiration of DOC depending on whether photo-alteration produces or removes molecules that native microbial communities used prior to light exposure. Using high-resolution chemical and microbial approaches, we show that rates of DOC processing by microbes are likely governed by a combination of the abundance and lability of DOC exported from land to water and produced by photochemical processes, and the capacity and timescale that microbial communities have to adapt to metabolize photo-altered DOC.The role of dissolved organic carbon (DOC) photo-alteration in the microbial respiration of DOC to CO 2 is unclear. Here, the authors show that the impact of this mechanism depends on whether photo-alteration of DOC produces or removes molecules used by native microbial communities prior to light exposure.

Photochemical reduction of UO(2)(2+) in the presence of alcohol studied by density functional theory calculations.

PubMed

Tsushima, Satoru

2009-06-01

A well-known photochemical process of U(VI)O(2)(2+) reduction to U(V)O(2)(+) in the presence of alcohols was studied by density functional theory (DFT) calculations. It was found that the first process which takes place is a photoexcitation of the ground-state UO(2)(2+) to the triplet excited state (*UO(2)(2+)) followed by a significant shortening of the *UO(2)(2+)-to-alcohol O(ax)-H distance. A charge transfer from *UO(2)(2+) to alcohol and hydrogen abstraction takes place in the following step. Consequently, U(VI)O(2)(2+) gets reduced to U(V)O(OH)(2+). The photochemical byproduct RCHOH acts further as a reducing agent toward UO(2)(2+) to yield UO(2)(+) and RCHO (aldehyde). Only a combination of these two reactions can explain a high quantum yield of this reaction. In the absence of alcohol, the lowest-lying triplet state exhibits a different character, and photoreduction is unlikely to take place via the same mechanism. The present results agree well with recent experimental finding [J. Am. Chem. Soc. 2006, 128, 14024] and supports the idea that the O(ax)-H linkage between UO(2)(2+) and the solvent molecule is the key to the photochemical reduction process.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides

PubMed Central

Kim, J. Dongun; Yee, Nathan; Nanda, Vikas; Falkowski, Paul G.

2013-01-01

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth’s history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth. PMID:23733945

A one-dimensional photochemical model of the troposphere with planetary boundary-layer parameterization

NASA Technical Reports Server (NTRS)

Fishman, J.; Carney, T. A.

1984-01-01

A time-dependent, one-dimensional photochemical model of the troposphere is used to describe the vertical distribution of atmospheric trace constituents for summer-time conditions at midlatitudes in the Northern Hemisphere. The model incorporates a planetary boundary layer (PBL) parametrization and a detailed chemical mechanism that includes the photochemistry of important nonmethane hydrocarbon species formed during the oxidation process. One result of the parametrized PBL is that the concentrations of some trace species in the free troposphere are 20-30 percent higher than when mixing processes are described by a vertical eddy diffusion coefficient which is held constant with respect to height and time. The lifetime of the oxides of nitrogen against photochemical conversion to nitric acid during summertime conditions is on the order of six hours. This lifetime is short enough to deplete most of the NO(x) in the PBL so that other reactive nitrogen species are more abundant than NO(x) throughout the free troposphere.

UV–Vis Light-induced Aging of Titan’s Haze and Ice

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Piétri, Nathalie; Le Letty, Vincent; Chiavassa, Thierry; Gudipati, Murthy

2018-01-01

The study of the photochemical aging of aerosols is an important tool for understanding Titan’s stratosphere/troposphere composition and evolution, particularly the haze. Laboratory simulations of the photoreactivity of the haze aerosol analogs provide insight into the photochemical evolution of Titan’s atmosphere at and below the haze layers. Here we use experimental simulations to investigate the evolution of the laboratory analogs of these organic aerosols under ultraviolet (UV)–visible (Vis) photons, which make it through the haze layers during their sedimentation process. We present experimental results for the aging of Titan’s aerosol analogs obtained from two dominant nitrogen-containing organics, HC3N and HCN, under simulated Titan atmospheric conditions (photons and temperature). We report that volatile nitriles condensed on haze particles could be incorporated through photochemistry and provide one such sink mechanism for nitrile compounds. We provide laboratory evidence that the organic aerosols could photochemically evolve during their sedimentation through Titan’s atmosphere.

A transthylakoid proton gradient and inhibitors induce a non-photochemical fluorescence quenching in unicellular algae Nannochloropsis sp.

PubMed

Cao, Shaona; Zhang, Xiaowen; Xu, Dong; Fan, Xiao; Mou, Shanli; Wang, Yitao; Ye, Naihao; Wang, Wenqi

2013-05-02

Non-photochemical quenching (NPQ) of chlorophyll fluorescence is thought to be an indicator of an essential regulation and photoprotection mechanism against high-light stress in photosynthetic organisms. In this report, special chemicals were used to perturb the kinetics of the ΔpH build-up and the xanthophyll cycle (XC) in Nannochloropsis sp. We found that NPQ was stimulated rapidly on exposure to high light and relaxed rapidly in darkness. The ΔpH could be obligatory for NPQ and ΔpH alone was not sufficient to induce NPQ. The XC, being strictly mediated by ΔpH, was also essential for NPQ. The results demonstrate that the mechanism of NPQ in Nannochloropsis sp. resembled that of diatoms. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes

PubMed Central

Toma, Francesca M.; Cooper, Jason K.; Kunzelmann, Viktoria; McDowell, Matthew T.; Yu, Jie; Larson, David M.; Borys, Nicholas J.; Abelyan, Christine; Beeman, Jeffrey W.; Yu, Kin Man; Yang, Jinhui; Chen, Le; Shaner, Matthew R.; Spurgeon, Joshua; Houle, Frances A.; Persson, Kristin A.; Sharp, Ian D.

2016-01-01

Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability. PMID:27377305

The molecular mechanism of thermal noise in rod photoreceptors.

PubMed

Gozem, Samer; Schapiro, Igor; Ferré, Nicolas; Olivucci, Massimo

2012-09-07

Spontaneous electrical signals in the retina's photoreceptors impose a limit on visual sensitivity. Their origin is attributed to a thermal, rather than photochemical, activation of the transduction cascade. Although the mechanism of such a process is under debate, the observation of a relationship between the maximum absorption wavelength (λ(max)) and the thermal activation kinetic constant (k) of different visual pigments (the Barlow correlation) indicates that the thermal and photochemical activations are related. Here we show that a quantum chemical model of the bovine rod pigment provides a molecular-level understanding of the Barlow correlation. The transition state mediating thermal activation has the same electronic structure as the photoreceptor excited state, thus creating a direct link between λ(max) and k. Such a link appears to be the manifestation of intrinsic chromophore features associated with the existence of a conical intersection between its ground and excited states.

Atomistic mechanisms of rapid energy transport in light-harvesting molecules

NASA Astrophysics Data System (ADS)

Ohmura, Satoshi; Koga, Shiro; Akai, Ichiro; Shimojo, Fuyuki; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

2011-03-01

Synthetic supermolecules such as π-conjugated light-harvesting dendrimers efficiently harvest energy from sunlight, which is of significant importance for the global energy problem. Key to their success is rapid transport of electronic excitation energy from peripheral antennas to photochemical reaction cores, the atomistic mechanisms of which remains elusive. Here, quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals the key molecular motion that significantly accelerates the energy transport based on the Dexter mechanism.

Making sense of "alternative", "complementary", "unconventional" and "integrative" medicine: exploring the terms and meanings through a textual analysis.

PubMed

Ng, Jeremy Y; Boon, Heather S; Thompson, Alison K; Whitehead, Cynthia R

2016-05-20

Medical pluralism has flourished throughout the Western world in spite of efforts to legitimize Western biomedical healthcare as "conventional medicine" and thereby relegate all non-physician-related forms of healthcare to an "other" category. These "other" practitioners have been referred to as "unconventional", "alternative" and "complementary", among other terms throughout the past half century. This study investigates the discourses surrounding the changes in the terms, and their meanings, used to describe unconventional medicine in North America. Terms identified by the literature as synonymous to unconventional medicine were searched using the Scopus database. A textual analysis following the method described by Kripendorff 2013 was subsequently performed on the five most highly-cited unconventional medicine-related peer-reviewed literature published between 1970 and 2013. Five commonly-used, unconventional medicine-related terms were identified. Authors using "complementary and alternative", "complementary", "alternative", or "unconventional" tended to define them by what they are not (e.g., therapies not taught/used in conventional medicine, therapy demands not met by conventional medicine, and therapies that lack research on safety, efficacy and effectiveness). Authors defined "integrated/integrative" medicine by what it is (e.g., a new model of healthcare, the combining of both conventional and unconventional therapies, accounting for the whole person, and preventative maintenance of health). Authors who defined terms by "what is not" stressed that the purpose of conducting research in this area was solely to create knowledge. Comparatively, authors who defined terms by "what is" sought to advocate for the evidence-based combination of unconventional and conventional medicines. Both author groups used scientific rhetoric to define unconventional medical practices. This emergence of two groups of authors who used two different sets of terms to refer to the concept of "unconventional medicine" may explain why some journals, practitioner associations and research/practice centres may choose to use both "what is not" and "what is" terms in their discourse to attract interest from both groups. Since each of the two groups of terms (and authors who use them) has different meanings and goals, the evolution of this discourse will continue to be an interesting phenomenon to explore in the future.

Photochemical modeling of nonmigrating tides in the 15 μm infrared cooling of the lower thermosphere over one solar cycle and comparison with SABER

NASA Astrophysics Data System (ADS)

Nischal, N.; Oberheide, J.; Mlynczak, M. G.; Hunt, L. A.; Maute, A. I.

2015-12-01

Tidal diagnostics of SABER CO2 15 μm data shows a substantial modulation of the energy budget of the lower thermosphere due to nonmigrating tides: relative amplitudes of the CO2 cooling rates for the DE2 and DE3 components are on the order of 15-50% with respect to the monthly mean emissions. Supporting photochemical tidal modeling using TIME-GCM and the empirical CTMT model reproduces the general amplitude structures and phases. Furthermore, it indicates that the main tidal coupling mechanism is the temperature dependence of the collisional excitation of the CO2 (01101) fundamental band transition (ν2). The response to neutral density variations is as important as temperature above 115 km as such explaining an unexpected tidal phase behavior in the observation. The contribution of vertical advection is comparatively small. In order to test the sensitivity of the modeled DE2 and DE3 CO2 VER tides to the solar cycle and to the specific choice of mean temperature, atomic oxygen, and CO2 density, we extend the modeling by using background from MSIS, SABER, and SCIAMACHY. The results indicate that the current uncertainties in the background temperature and atomic oxygen used for the photochemical modeling do not impact our conclusion about the relative importance of the tidal coupling mechanisms. Our results quantify the response of the CO2 15 μm infrared cooling of the lower thermosphere to tropospheric tides and delineate the coupling mechanisms that lead to the observed strong longitudinal and local time variability.

Hydro-mechanical coupled simulation of hydraulic fracturing using the eXtended Finite Element Method (XFEM)

NASA Astrophysics Data System (ADS)

Youn, Dong Joon

This thesis presents the development and validation of an advanced hydro-mechanical coupled finite element program analyzing hydraulic fracture propagation within unconventional hydrocarbon formations under various conditions. The realistic modeling of hydraulic fracturing is necessarily required to improve the understanding and efficiency of the stimulation technique. Such modeling remains highly challenging, however, due to factors including the complexity of fracture propagation mechanisms, the coupled behavior of fracture displacement and fluid pressure, the interactions between pre-existing natural and initiated hydraulic fractures and the formation heterogeneity of the target reservoir. In this research, an eXtended Finite Element Method (XFEM) scheme is developed allowing for representation of single or multiple fracture propagations without any need for re-meshing. Also, the coupled flows through the fracture are considered in the program to account for their influence on stresses and deformations along the hydraulic fracture. In this research, a sequential coupling scheme is applied to estimate fracture aperture and fluid pressure with the XFEM. Later, the coupled XFEM program is used to estimate wellbore bottomhole pressure during fracture propagation, and the pressure variations are analyzed to determine the geometry and performance of the hydraulic fracturing as pressure leak-off test. Finally, material heterogeneity is included into the XFEM program to check the effect of random formation property distributions to the hydraulic fracture geometry. Random field theory is used to create the random realization of the material heterogeneity with the consideration of mean, standard deviation, and property correlation length. These analyses lead to probabilistic information on the response of unconventional reservoirs and offer a more scientific approach regarding risk management for the unconventional reservoir stimulation. The new stochastic approach combining XFEM and random field is named as eXtended Random Finite Element Method (XRFEM). All the numerical analysis codes in this thesis are written in Fortran 2003, and these codes are applicable as a series of sub-modules within a suite of finite element codes developed by Smith and Griffiths (2004).

Sequence-Mandated, Distinct Assembly of Giant Molecules

DOE PAGES

Zhang, Wei; Lu, Xinlin; Mao, Jialin; ...

2017-10-24

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collectivemore » hydrogen bonding and the sequence-mandated topology of the molecules. Lastly, these results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.« less

Sequence-Mandated, Distinct Assembly of Giant Molecules

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

Zhang, Wei; Lu, Xinlin; Mao, Jialin

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collectivemore » hydrogen bonding and the sequence-mandated topology of the molecules. Lastly, these results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.« less

The unconventional secretion of IL-1β: Handling a dangerous weapon to optimize inflammatory responses.

PubMed

Sitia, Roberto; Rubartelli, Anna

2018-04-04

Interleukin 1β (IL-1β) is a major mediator of inflammation, with a causative role in many diseases. Unlike most other cytokines, however, it lacks a secretory signal sequence, raising intriguing mechanistic, functional and evolutionary questions. Despite decades of strenuous efforts in many laboratories, how IL-1β is secreted is still a matter of intense debate. Here, we summarize the different mechanisms and pathways that have been proposed for IL-1β secretion. At least two of them, namely the endolysosomal vesicle-based and gasdermin D-dependent pathways (types III and I in the recent Rabouille's classification of unconventional protein secretion), can be triggered in monocytes, the main source of IL-1β in humans, according to the type and strength of the pro-inflammatory stimuli. As during the escalation of human conflicts, monocytes deploy secretory mechanisms of increasing efficiency and dangerousness, shifting from the specific and controlled type III pathway to the much faster release of type I. Thus, the different mechanisms are activated depending on the severity of the conditions, from the self-limiting type III pathways in response of low pathogen load or small trauma, to the uncontrolled responses that underlie autoinflammatory disorders and sepsis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Application of particle and lattice codes to simulation of hydraulic fracturing

NASA Astrophysics Data System (ADS)

Damjanac, Branko; Detournay, Christine; Cundall, Peter A.

2016-04-01

With the development of unconventional oil and gas reservoirs over the last 15 years, the understanding and capability to model the propagation of hydraulic fractures in inhomogeneous and naturally fractured reservoirs has become very important for the petroleum industry (but also for some other industries like mining and geothermal). Particle-based models provide advantages over other models and solutions for the simulation of fracturing of rock masses that cannot be assumed to be continuous and homogeneous. It has been demonstrated (Potyondy and Cundall Int J Rock Mech Min Sci Geomech Abstr 41:1329-1364, 2004) that particle models based on a simple force criterion for fracture propagation match theoretical solutions and scale effects derived using the principles of linear elastic fracture mechanics (LEFM). The challenge is how to apply these models effectively (i.e., with acceptable models sizes and computer run times) to the coupled hydro-mechanical problems of relevant time and length scales for practical field applications (i.e., reservoir scale and hours of injection time). A formulation of a fully coupled hydro-mechanical particle-based model and its application to the simulation of hydraulic treatment of unconventional reservoirs are presented. Model validation by comparing with available analytical asymptotic solutions (penny-shape crack) and some examples of field application (e.g., interaction with DFN) are also included.

Non-Photochemical Quenching in Cryptophyte Alga Rhodomonas salina Is Located in Chlorophyll a/c Antennae

PubMed Central

Kaňa, Radek; Kotabová, Eva; Sobotka, Roman; Prášil, Ondřej

2012-01-01

Photosynthesis uses light as a source of energy but its excess can result in production of harmful oxygen radicals. To avoid any resulting damage, phototrophic organisms can employ a process known as non-photochemical quenching (NPQ), where excess light energy is safely dissipated as heat. The mechanism(s) of NPQ vary among different phototrophs. Here, we describe a new type of NPQ in the organism Rhodomonas salina, an alga belonging to the cryptophytes, part of the chromalveolate supergroup. Cryptophytes are exceptional among photosynthetic chromalveolates as they use both chlorophyll a/c proteins and phycobiliproteins for light harvesting. All our data demonstrates that NPQ in cryptophytes differs significantly from other chromalveolates – e.g. diatoms and it is also unique in comparison to NPQ in green algae and in higher plants: (1) there is no light induced xanthophyll cycle; (2) NPQ resembles the fast and flexible energetic quenching (qE) of higher plants, including its fast recovery; (3) a direct antennae protonation is involved in NPQ, similar to that found in higher plants. Further, fluorescence spectroscopy and biochemical characterization of isolated photosynthetic complexes suggest that NPQ in R. salina occurs in the chlorophyll a/c antennae but not in phycobiliproteins. All these results demonstrate that NPQ in cryptophytes represents a novel class of effective and flexible non-photochemical quenching. PMID:22235327

Hsp90/Sec22b promotes unconventional secretion of mature-IL-1β through an autophagosomal carrier in porcine alveolar macrophages during Mycoplasma hyopneumoniae infection.

PubMed

Zhang, Zhenzhen; Wei, Yanna; Liu, Beibei; Wu, Yuzi; Wang, Haiyan; Xie, Xing; Feng, Zhixin; Shao, Guoqing; Xiong, Qiyan

2018-06-20

Interleukin-1β (IL-1β) is a critical inflammatory regulator in response to Mycoplasma hyopneumoniae infection. However, the mechanism involved in the secretion of IL-1β during Mycoplasma hyopneumoniae infection is unclear. In this study, we demonstrated that Mycoplasma hyopneumoniae infection increased the secretion of mature-IL-1β (m-IL-1β), but not pro-IL-1β, in porcine alveolar macrophages. Moreover, Mycoplasma hyopneumoniae infection promoted the generation of autophagosomes, which attributed to the unconventional secretion of m-IL-1β. Further results revealed that Hsp90 was required for the entry of m-IL-1β into autophagosomes during Mycoplasma hyopneumoniae infection. The fusion of m-IL-1β-containing autophagosome and plasma membranes was regulated by Sec22b and independent of lysosomal dysfunction. In conclusion, we provide evidence that Hsp90/Sec22b promotes the unconventional secretion of IL-1β through an autophagosomal carrier during Mycoplasma hyopneumoniae infection. The elucidation of the molecular and cellular machinery in Mycoplasma hyopneumoniae infected mammalian cells in this study suggests avenues for further study and applications and paves the way for novel therapeutic strategies to prevent tissue damage in mycoplasma-associated diseases. Copyright © 2018. Published by Elsevier Ltd.

Noble gas and hydrocarbon tracers in multiphase unconventional hydrocarbon systems: Toward integrated advanced reservoir simulators

NASA Astrophysics Data System (ADS)

Darrah, T.; Moortgat, J.; Poreda, R. J.; Muehlenbachs, K.; Whyte, C. J.

2015-12-01

Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noble gas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

Eta-CMAQ Air Quality Forecasts for O3 and Related Species Using Three Different Photochemical Mechanisms (CB4, CB05, SAPRC-99): Comparisons with Measurements During the 2004 ICARTT Study

EPA Science Inventory

In this study, we compare the CB4, CB05 and SAPRC-99 mechanisms by examining the impact of these different chemical mechanisms on the Eta-CMAQ air quality forecast model simulations for O₃ and its related precursors over the eastern US through comparisons with the inte...

Carbon Disulfide (CS2) Interference in Glucose Metabolism from Unconventional Oil and Gas Extraction and Processing Emissions.

PubMed

Rich, Alisa L; Patel, Jay T; Al-Angari, Samiah S

2016-01-01

Carbon disulfide (CS2) has been historically associated with the manufacturing of rayon, cellophane, and carbon tetrachloride production. This study is one of the first to identify elevated atmospheric levels of CS2 above national background levels and its mechanisms to dysregulate normal glucose metabolism. Interference in glucose metabolism can indirectly cause other complications (diabetes, neurodegenerative disease, and retinopathy), which may be preventable if proper precautions are taken. Rich et al found CS2 and 12 associated sulfide compounds present in the atmosphere in residential areas where unconventional shale oil and gas extraction and processing operations were occurring. Ambient atmospheric concentrations of CS2 ranged from 0.7 parts per billion by volume (ppbv) to 103 ppbv over a continuous 24-hour monitoring period. One-hour ambient atmospheric concentrations ranged from 3.4 ppbv to 504.6 ppbv. Using the U.S. Environmental Protection Agency Urban Air Toxic Monitoring Program study as a baseline comparison for atmospheric CS2 concentrations found in this study, it was determined that CS2 atmospheric levels were consistently elevated in areas where unconventional oil and gas extraction and processing occurred. The mechanisms by which CS2 interferes in normal glucose metabolism by dysregulation of the tryptophan metabolism pathway are presented in this study. The literature review found an increased potential for alteration of normal glucose metabolism in viscose rayon occupational workers exposed to CS2. Occupational workers in the energy extraction industry exposed to CS2 and other sulfide compounds may have an increased potential for glucose metabolism interference, which has been an indicator for diabetogenic effect and other related health impacts. The recommendation of this study is for implementation of regular monitoring of blood glucose levels in CS2-exposed populations as a preventative health measure.

Unconventional Expressions: Productive Syntax in the L2 Acquisition of Formulaic Language

ERIC Educational Resources Information Center

Bardovi-Harlig, Kathleen; Stringer, David

2017-01-01

This article presents a generative analysis of the acquisition of formulaic language as an alternative to current usage-based proposals. One influential view of the role of formulaic expressions in second language (L2) development is that they are a bootstrapping mechanism into the L2 grammar; an initial repertoire of constructions allows for…

Photochemical generation and decay kinetics of superoxide and hydrogen peroxide in the presence of standard humic and fulvic acids.

PubMed

Fujii, Manabu; Otani, Erika

2017-10-15

Reactive oxygen species (ROS) such as superoxide (O 2 - ) and hydrogen peroxide (H 2 O 2 ) can be photochemically generated in aerobic waters containing natural organic matters (NOM) such as humic substances (HS). To investigate the effect of NOM molecular composition on the kinetics and mechanism of ROS transformation, photochemical O 2 - generation and subsequent H 2 O 2 production via catalyzed and uncatalyzed (bimolecular dismutation) O 2 - decay were examined in the presence of 14 types of HS (pH 8.0). By using chemiluminescence and colorimetric techniques, the photochemical O 2 - generation rate, quasi-steady-state O 2 - concentration, catalyzed and uncatalyzed O 2 - decay rates, and H 2 O 2 production rate were found to vary significantly by factors of 72, 18, 14, 320, and 7.7, respectively, depending on the type of HS and degree of photolysis. For more than half of the HS samples, both uncatalyzed and catalyzed reductive decay of photogenerated O 2 - were significantly involved in H 2 O 2 generation, and their rates were comparable to those for O 2 - oxidative decay in which H 2 O 2 is not generated. These results suggest that the chemical quality of HS influenced the H 2 O 2 generation pathway. Correlation analyses indicated that rate constants associated with HS-mediated photochemical O 2 - and H 2 O 2 generation are significantly correlated with HS molecular composition including total and aromatic C contents. In particular, practical indices representing NOM aromaticity including specific ultraviolet absorbance (SUVA) can be useful for predicting NOM-mediated ROS generation and decay kinetics. Overall, the present work suggests that NOM concentration and its quality influence NOM-mediated ROS dynamics in aqueous systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

The chitosan - Porphyrazine hybrid materials and their photochemical properties.

PubMed

Chełminiak-Dudkiewicz, Dorota; Ziegler-Borowska, Marta; Stolarska, Magdalena; Sobotta, Lukasz; Falkowski, Michal; Mielcarek, Jadwiga; Goslinski, Tomasz; Kowalonek, Jolanta; Węgrzynowska-Drzymalska, Katarzyna; Kaczmarek, Halina

2018-04-01

Three magnesium sulfanyl porphyrazines differing in the size of peripheral substituents (3,5-dimethoxybenzylsulfanyl, (3,5-dimethoxybenzyloxy)benzylsulfanyl, 3,5-bis[(3,5-bis[(3,5-dimethoxybenzyloxy)benzyloxy]benzylsulfanyl) were exposed to visible and ultraviolet radiation (UV A + B + C) in order to determine their photochemical properties. The course of photochemical reactions in dimethylformamide solutions and the ability of the systems to generate singlet oxygen were studied by UV-Vis spectroscopy, which additionally gave information on aggregation processes. The porphyrazines were found to be stable upon visible light irradiation conditions, but when exposed to high energy UV radiation, the efficient photodegradation of these macrocycles was observed. Therefore, these three magnesium sulfanyl porphyrazines were incorporated into chitosan matrix. The obtained thin films of chitosan doped with porphyrazines were subjected to polychromatic UV-radiation and studied by spectroscopic methods (UV-Vis, FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Application of chitosan as a polymer matrix for porphyrazines was found to be successful method that effectively stopped the unwelcome degradation of macrocycles, thus worth considering for their photoprotection. In addition, the surface properties of the hybrid material were determined by contact angle measurements and calculation of surface free energy. Intermolecular interactions between these novel porphyrazines and chitosan were detected. The mechanism of photochemical reactions occurring in studied systems has been discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Unconventional Word Segmentation in Emerging Bilingual Students' Writing: A Longitudinal Analysis

ERIC Educational Resources Information Center

Sparrow, Wendy

2014-01-01

This study explores cross-language and longitudinal patterns in unconventional word segmentation in 25 emerging bilingual students' (Spanish/English) writing from first through third grade. Spanish and English writing samples were collected annually and analyzed for two basic types of unconventional word segmentation: hyposegmentation, in…

Unconventionality and Originality: Does Self-Assessed Unconventionality Increase Original Achievement?

ERIC Educational Resources Information Center

Andreas, Stuart F. K.; Zech, Stefan; Coyle, Thomas R.; Rindermann, Heiner

2016-01-01

Creativity is negatively associated with certain personality traits (e.g., conformity) and social influences (e.g., group pressure). In this study, creativity was examined in relation to unconventionality, which was expected to correlate positively with creativity, especially originality. This hypothesis was based on the theory that unconventional…

Geology and assessment of unconventional oil and gas resources of northeastern Mexico

USGS Publications Warehouse

,

2015-01-01

The U.S. Geological Survey, in cooperation with the U.S. Department of State, quantitatively assessed the potential for unconventional oil and gas resources within the onshore portions of the Tampico-Misantla Basin, Burgos Basin, and Sabinas Basin provinces of northeastern Mexico. Unconventional resources of the Veracruz Basin were not quantitatively assessed because of a current lack of required geological information. Unconventional resources include shale gas, shale oil, tight gas, tight oil, and coalbed gas. Undiscovered conventional oil and gas resources were assessed in Mexico in 2012.

Assessment of surface water chloride and conductivity trends in areas of unconventional oil and gas development-Why existing national data sets cannot tell us what we would like to know

USGS Publications Warehouse

Bowen, Zachary H.; Oelsner, Gretchen P.; Cade, Brian S.; Gallegos, Tanya J.; Farag, Aïda M.; Mott, David N.; Potter, Christopher J.; Cinotto, Peter J.; Clark, Melanie L.; Kappel, William M.; Kresse, Timothy M.; Melcher, Cynthia P.; Paschke, Suzanne; Susong, David D.; Varela, Brian A.

2015-01-01

Heightened concern regarding the potential effects of unconventional oil and gas development on regional water quality has emerged, but the few studies on this topic are limited in geographic scope. Here we evaluate the potential utility of national and publicly available water-quality data sets for addressing questions regarding unconventional oil and gas development. We used existing U.S. Geological Survey and U.S. Environmental Protection Agency data sets to increase understanding of the spatial distribution of unconventional oil and gas development in the U.S. and broadly assess surface water quality trends in these areas. Based on sample size limitations, we were able to estimate trends in specific conductance (SC) and chloride (Cl-) from 1970 to 2010 in 16% (n=155) of the watersheds with unconventional oil and gas resources. We assessed these trends relative to spatiotemporal distributions of hydraulically fractured wells. Results from this limited analysis suggest no consistent and widespread trends in surface water quality for SC and Cl- in areas with increasing unconventional oil and gas development and highlight limitations of existing national databases for addressing questions regarding unconventional oil and gas development and water quality.

Ozone in the Atmosphere: II. The Lower Atmosphere.

ERIC Educational Resources Information Center

Phillips, Paul; Pickering, Pam

1991-01-01

Described are the problems caused by the increased concentration of ozone in the lower atmosphere. Photochemical pollution, mechanisms of ozone production, ozone levels in the troposphere, effects of ozone on human health and vegetation, ozone standards, and control measures are discussed. (KR)

Photochemical stability of UV-screening transparent acrylic copolymers of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole

NASA Technical Reports Server (NTRS)

Gupta, A.; Scott, G. W.; Kliger, D.; Vogl, O.

1983-01-01

The mechanism of photodegradation of certain hydroxyphenyl benzotriazole based ultraviolet absorbers has been investigated and a new polymerizable ultraviolet absorber in this group has been synthesized. The photoreactivity is entirely confined at the surface of polymethylmethacrylate films containing the ultraviolet absorbers as pendant groups. A mechanism involving sensitized photooxidation has been proposed to interpret the data.

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models

NASA Technical Reports Server (NTRS)

Rodriquez, Jose M.; Hu, Wenjie; Ko, Malcolm K.W.

1996-01-01

The global three-dimensional measurement of long- and short-lived species from Upper Atmospheric Research Satellite (UARS) provides a unique opportunity to validate chemistry and dynamics mechanisms in the middle atmosphere. During the past three months, we focused on expanding our study of data-model comparisons to whole time periods when Cryogenic Limb Array Etalon Spectrometer (CLAES) instrument were operating.

Unconventional secretion of FABP4 by endosomes and secretory lysosomes.

PubMed

Villeneuve, Julien; Bassaganyas, Laia; Lepreux, Sebastien; Chiritoiu, Marioara; Costet, Pierre; Ripoche, Jean; Malhotra, Vivek; Schekman, Randy

2018-02-05

An appreciation of the functional properties of the cytoplasmic fatty acid binding protein 4 (FABP4) has advanced with the recent demonstration that an extracellular form secreted by adipocytes regulates a wide range of physiological functions. Little, however, is known about the mechanisms that mediate the unconventional secretion of FABP4. Here, we demonstrate that FABP4 secretion is mediated by a membrane-bounded compartment, independent of the conventional endoplasmic reticulum-Golgi secretory pathway. We show that FABP4 secretion is also independent of GRASP proteins, autophagy, and multivesicular bodies but involves enclosure within endosomes and secretory lysosomes. We highlight the physiological significance of this pathway with the demonstration that an increase in plasma levels of FABP4 is inhibited by chloroquine treatment of mice. These findings chart the pathway of FABP4 secretion and provide a potential therapeutic means to control metabolic disorders associated with its dysregulated secretion. © 2018 Villeneuve et al.

Assessment of unconventional oil and gas resources in Northeast Mexico, 2014

USGS Publications Warehouse

Schenk, Christopher J.; Charpentier, Ronald R.; Klett, Timothy R.; Tennyson, Marilyn E.; Gaswirth, Stephanie B.; Brownfield, Michael E.; Pawlewicz, Mark J.; Weaver, Jean Noe

2014-01-01

Using a geology-based assessment methodology, the U.S. Geological Survey estimated means of 0.78 billion barrels of unconventional oil, 23.5 trillion cubic feet of unconventional gas, and 0.88 billion barrels of natural gas liquids in the Sabinas Basin, Burgos Basin, and Tampico-Misantla Basin provinces of northeast Mexico.

Variational method for nonconservative field theories: Formulation and two PT-symmetric case examples

NASA Astrophysics Data System (ADS)

Restrepo, Juan; Ciuti, Cristiano; Favero, Ivan

2014-01-01

This Letter investigates a hybrid quantum system combining cavity quantum electrodynamics and optomechanics. The Hamiltonian problem of a photon mode coupled to a two-level atom via a Jaynes-Cummings coupling and to a mechanical mode via radiation pressure coupling is solved analytically. The atom-cavity polariton number operator commutes with the total Hamiltonian leading to an exact description in terms of tripartite atom-cavity-mechanics polarons. We demonstrate the possibility to obtain cooling of mechanical motion at the single-polariton level and describe the peculiar quantum statistics of phonons in such an unconventional regime.

Near infrared radiation damage mechanism in the lens

NASA Astrophysics Data System (ADS)

Söderberg, Per G.; Talebizadeh, Nooshin; Galichanin, Konstantin; Kronschläger, Martin; Schulmeister, Karl; Yu, Zhaohua

2015-03-01

The current data strongly indicates that there is no photochemical effect of in vivo exposure to 1090 nm near IRR radiation within the pupil. Four groups of 20 Sprague-Dawley rats were unilaterally exposed in vivo to 96 W·cm-2 centered inside the pupil for 10, 18, 33 and 60 min, respectively depending on group belonging. This resulted in radiant exposure doses of 57, 103, 198 and 344 kJ·cm-2. Temperature evolution at the limbus during the exposure and difference of intensity of forward light scattering between the exposed and the contralateral not exposed eye was measured at 1 week after exposure. The temperature at the limbus was found to increase exponentially towards an asymptote with an asymptote temperature of around 7 °C and a time constant (1/k) of around 15 s. No increase of light scattering was found despite that the cumulated radiant exposure dose was [80;250] times the threshold for photochemically induced cataract suggested by previous empirical data. It is concluded that at 1090 nm near IRR there is no photochemical effect.

Unconventional superconductivity in heavy-fermion compounds

DOE PAGES

White, B. D.; Thompson, J. D.; Maple, M. B.

2015-02-27

Over the past 35 years, research on unconventional superconductivity in heavy-fermion systems has evolved from the surprising observations of unprecedented superconducting properties in compounds that convention dictated should not superconduct at all to performing explorations of rich phase spaces in which the delicate interplay between competing ground states appears to support emergent superconducting states. In this article, we review the current understanding of superconductivity in heavy-fermion com- pounds and identify a set of characteristics that is common to their unconventional superconducting states. These core properties are compared with those of other classes of unconventional superconductors such as the cuprates andmore » iron-based superconductors. Lastly, we conclude by speculating on the prospects for future research in this field and how new advances might contribute towards resolving the long-standing mystery of how unconventional superconductivity works.« less

Carbon dioxide storage in unconventional reservoirs workshop: summary of recommendations

USGS Publications Warehouse

Jones, Kevin B.; Blondes, Madalyn S.

2015-01-01

The storage capacity for all unconventional reservoirs may be modeled using a volumetric equation starting with the extent of the rock unit and adjusted using these key factors and reaction terms. The ideas that were developed during this workshop can be used by USGS scientists to develop a methodology to assess the CO2 storage resource in unconventional reservoirs. This methodology could then be released for public comment and peer review. After completing this development process, the USGS could then use the methodology to assess the CO2 storage resource in unconventional reservoirs.

An Unconventional Approach to Photomobile Composite Polymer Films.

PubMed

Castagna, Riccardo; Nucara, Luca; Simoni, Francesco; Greci, Lucedio; Rippa, Massimo; Petti, Lucia; Lucchetta, Daniele E

2017-04-01

Photomobile polymer (Pmp) films are fabricated by using a cheap and fast process. The working mechanism of the Pmp-film motion under illumination is explained. Details concerning the film structure and formation are given. Two related applications regarding light-induced caterpillar-miming motion and photocontrolled electrical switches are proposed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of silvicultural practice and wood type on loblolly pine particleboard and medium density fiberboard properties

Treesearch

Todd F. Shupe; Chung Y. Hse; Elvin T. Choong; Leslie H. Groom

1999-01-01

he objective of this study was to determine the effect of five different silvicultural strategies and wood type on mechanical and physical properties of loblolly pine (Pinus taeda L.) particleboard and fiberboard. The furnish was prepared in an unconventional manner from innerwood and outerwood veneer for each stand. Modulus of rupture (MOR)...

Coupled Thermo-Hydro-Mechanical Numerical Framework for Simulating Unconventional Formations

NASA Astrophysics Data System (ADS)

Garipov, T. T.; White, J. A.; Lapene, A.; Tchelepi, H.

2016-12-01

Unconventional deposits are found in all world oil provinces. Modeling these systems is challenging, however, due to complex thermo-hydro-mechanical processes that govern their behavior. As a motivating example, we consider in situ thermal processing of oil shale deposits. When oil shale is heated to sufficient temperatures, kerogen can be converted to oil and gas products over a relatively short timespan. This phase change dramatically impact both the mechanical and hydrologic properties of the rock, leading to strongly coupled THMC interactions. Here, we present a numerical framework for simulating tightly-coupled chemistry, geomechanics, and multiphase flow within a reservoir simulator (the AD-GPRS General Purpose Research Simulator). We model changes in constitutive behavior of the rock using a thermoplasticity model that accounts for microstructural evolution. The multi-component, multiphase flow and transport processes of both mass and heat are modeled at the macroscopic (e.g., Darcy) scale. The phase compositions and properties are described by a cubic equation of state; Arrhenius-type chemical reactions are used to represent kerogen conversion. The system of partial differential equations is discretized using a combination of finite-volumes and finite-elements, respectively, for the flow and mechanics problems. Fully implicit and sequentially implicit method are used to solve resulting nonlinear problem. The proposed framework is verified against available analytical and numerical benchmark cases. We demonstrate the efficiency, performance, and capabilities of the proposed simulation framework by analyzing near well deformation in an oil shale formation.

An innovative alt-alt telescope for small observatories and amateur astronomers

NASA Astrophysics Data System (ADS)

Riva, M.; Basso, S.; Canestrari, R.; Conconi, P.; Fugazza, D.; Ghigo, M.; Landoni, M.; Pareschi, G.; Spanó, P.; Tomelleri, R.; Zerbi, F. M.

2012-09-01

This paper want to show an innovative amateur oriented telescope with an unconventional alt-alt conguration. The goal is to make a telescope with good optical quality reducing production costs by adopting a gimbal based mounting to develop an alt-alt conguration suitable for a telescope. Reduce costs while preserving the optical quality is a necessary condition to allow small groups of amateur astronomers, schools and cultural clubs, with reduced economic resources, to acquire an astronomical instrument that encourages learning and advancing astrophysical knowledge. This unconventional mechanism for the realization of a telescope alt-alt provides signicant advantages. The traditional rotary motors coupled with expensive precision bearings are replaced with two simple linear actuators coupled to a properly preloaded gimbal joint and the cell becomes the primary structure of the telescope. A second advantage would be secured by mechanical simplicity evident in the easy portability of the instrument. The frame alt-alt has some limitations on the horizon pointing but does not show the zenith blind spot of the alt-az mount. A dedicated alt-alt pointing and tracking model is under development to be compatible with commercial telescope softwares and with the proposed new mounting.

Investigation of the Correlation between Odd Oxygen and Secondary Organic Aerosol in Mexico City and Houston

EPA Science Inventory

Many recent models underpredict secondary organic aerosol (SOA) particulate matter(PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much b...

Effect of light intensity on the degree of ammonia toxicity on PSII activity of Arthrospira platensis and Chlorella vulgaris.

PubMed

Markou, Giorgos; Muylaert, Koenraad

2016-09-01

Herein the effect of increasing light intensity on the degree of ammonia toxicity and its impact on the photosynthetic performance of Arthrospira and Chlorella was investigated using Chl fluorescence as a technique to characterize their photosystem II (PSII) activity. The results revealed that the increase of light intensity amplifies the ammonia toxicity on PSII. Chl fluorescence transients shown that at a given free ammonia (FA) concentration (100mg-N/L), the photochemistry potential decreased by increasing light intensity. The inhibition of the PSII was not reversible either by re-incubating the cells under dark or under decreased FA concentration. Moreover, the decrease of photochemical and non-photochemical quenching (NPQ) of fluorescence suggest that ammonia toxicity decreases the open available PSII centers, as well the inability of PSII to transfer the generated electrons beyond QA. The collapse of NPQ suggests that ammonia toxicity inhibits the photoprotection mechanism(s) and hence renders PSII more sensitive to photoinhibition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes

DOE PAGES

Toma, Francesca M.; Cooper, Jason K.; Kunzelmann, Viktoria; ...

2016-07-05

Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates thatmore » photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.« less

Geology and assessment of unconventional resources of Phitsanulok Basin, Thailand

USGS Publications Warehouse

,

2014-01-01

The U.S. Geological Survey (USGS) quantitatively assessed the potential for unconventional oil and gas resources within the Phitsanulok Basin of Thailand. Unconventional resources for the USGS include shale gas, shale oil, tight gas, tight oil, and coalbed gas. In the Phitsanulok Basin, only potential shale-oil and shale-gas resources were quantitatively assessed.

PHOTOCHEMICAL MODELING APPLIED TO NATURAL WATERS

EPA Science Inventory

The study examines the application of modeling photochemical processes in natural water systems. For many photochemical reactions occurring in natural waters, a simple photochemical model describing reaction rate as a function of intensity, radiation attenuation, reactant absorpt...

Gas-phase Precursors to Anthropogenic SOA: Using the MCM to Probe Detailed Observations of Aromatic Photo-oxidation

NASA Astrophysics Data System (ADS)

Rickard, A. R.; Wyche, K. P.; Metzger, A.; Monks, P. S.; Ellis, A. M.; Baltensperger, U.; Pilling, M. J.; Jenkin, M. E.

2008-12-01

The formation of photochemical ozone and particulate matter are major priorities in the determination of European air quality policies. Predictions of the future state of the atmosphere and the development of appropriate mitigation strategies rely on models, which necessarily incorporate chemistry. The Master Chemical Mechanism (MCM, http://mcm.leeds.ac.uk/MCM) is a near-explicit chemical mechanism originally conceived to model ozone formation in Europe but now also employed as a benchmark mechanism in a wide variety of applications where chemical detail is required. The MCM currently describes the detailed gas- phase tropospheric degradation of a 135 primary emitted volatile organic compounds (VOCs) leading to a mechanism containing ca. 5900 species and 13500 reactions. In order that the MCM continues to be a state-of-the-art resource for the atmospheric science community it resides under a constant regime of evaluation, development and improvement. Individual VOC photochemical mechanisms are evaluated using data obtained, under a variety of atmospheric conditions, from highly instrumented smog chambers. Smog chamber experiments are crucial, not only for mechanism evaluation, but also for mechanism development. Findings obtained from combined model and chamber studies can additionally provide key insight for guiding the directions of future laboratory experiments. Recently, the MCM was updated to MCMv3.1 in order to take into account recent advancements in the understanding of aromatic photo-oxidation, an important class of anthropogenic VOCs. As well as constituting precursors to secondary organic aerosol (SOA), aromatics generally have high photochemical ozone creation potentials (POCPs) and hence contribute significantly towards tropospheric ozone formation. In the work presented, a detailed gas-phase photochemical chamber box model, incorporating the MCMv3.1 degradation mechanism for 1,3,5-trimethylbenzene (TMB), has been used to simulate data measured during a series of chamber experiments carried out at the Paul Scherrer Institute Aerosol Chamber in order to evaluate the mechanism under a variety of VOC/NOx conditions. More specifically, the model was used in the interpretation of data recorded by the University of Leicester's Chemical Ionisation Reaction Time-of- Flight Mass Spectrometer (CIR-TOF-MS), a novel instrument used to provide comprehensive, high (mass and time) resolution measurements of the organic gaseous oxidation products formed from the TMB precursor. Additional supporting gas and aerosol measurements also enable us to explore the "missing link" between the gas and aerosol phases. Model-measurement comparisons have been used to gain an insight into the complex array of oxygenated products formed, including the peroxide bicyclic ring opening products (gamma-dicarbonyls and furanones) and the O2-bridged peroxide bicyclic ring retaining products (diol, ketone and nitrate). To our knowledge this is the first time these O2-bridged species have been identified in the gas-phase. The model was also used to give insights into which gas-phase species were participating in SOA formation, with the primary and secondary peroxide products, formed primarily under NOx-limiting conditions ([NO] approaches zero), identified as likely candidates.

Ultrafast Adiabatic Photodehydration of 2-Hydroxymethylphenol and the Formation of Quinone Methide.

PubMed

Škalamera, Đani; Antol, Ivana; Mlinarić-Majerski, Kata; Vančik, Hrvoj; Phillips, David Lee; Ma, Jiani; Basarić, Nikola

2018-04-20

The photochemical reactivity of 2-hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H 2 O gives QM 2 in its S 1 state and the other by which homolytic cleavage of the phenolic O-H bond produces a phenoxyl radical (S 0 ). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S 1 ) probably deactivates to S 0 through a conical intersection to give QM 2 (S 0 ), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Participation of intracellular and extracellular pH changes in photosynthetic response development induced by variation potential in pumpkin seedlings.

PubMed

Sherstneva, O N; Vodeneev, V A; Katicheva, L A; Surova, L M; Sukhov, V S

2015-06-01

Electrical signals presented in plants by action potential and by variation potential (VP) can induce a reversible inactivation of photosynthesis. Changes in the intracellular and extracellular pH during VP generation are a potential mechanism of photosynthetic response induction; however, this hypothesis requires additional experimental investigation. The purpose of the present work was to analyze the influence of pH changes on induction of the photosynthetic response in pumpkin. It was shown that a burning of the cotyledon induced VP propagation into true leaves of pumpkin seedlings inducing a decrease in the photosynthetic CO2 assimilation and an increase in non-photochemical quenching of fluorescence, whereas respiration was activated insignificantly. The photosynthetic response magnitude depended linearly on the VP amplitude. The intracellular and extracellular concentrations of protons were analyzed using pH-sensitive fluorescent probes, and the VP generation was shown to be accompanied by apoplast alkalization (0.4 pH unit) and cytoplasm acidification (0.3 pH unit). The influence of changes in the incubation medium pH on the non-photochemical quenching of fluorescence of isolated chloroplasts was also investigated. It was found that acidification of the medium stimulated the non-photochemical quenching, and the magnitude of this increase depended on the decrease in pH. Our results confirm the contribution of changes in intracellular and extracellular pH to induction of the photosynthetic response caused by VP. Possible mechanisms of the influence of pH changes on photosynthesis are discussed.

Factors controlling the redox potential of ZnCe6 in an engineered bacterioferritin photochemical 'reaction centre'.

PubMed

Mahboob, Abdullah; Vassiliev, Serguei; Poddutoori, Prashanth K; van der Est, Art; Bruce, Doug

2013-01-01

Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical 'reaction centre' (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics-Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal.

Marcellus Shale Drilling's Impact on the Dairy Industry in Pennsylvania: A Descriptive Report.

PubMed

Finkel, Madelon L; Selegean, Jane; Hays, Jake; Kondamudi, Nitin

2013-01-01

Unconventional natural gas drilling in Pennsylvania has accelerated over the past five years, and is unlikely to abate soon. Dairy farming is a large component of Pennsylvania's agricultural economy. This study compares milk production, number of cows, and production per cow in counties with significant unconventional drilling activity to that in neighboring counties with less unconventional drilling activity, from 1996 through 2011. Milk production and milk cows decreased in most counties since 1996, with larger decreases occurring from 2007 through 2011 (when unconventional drilling increased substantially) in five counties with the most wells drilled compared to six adjacent counties with fewer than 100 wells drilled. While this descriptive study cannot draw a causal association between well drilling and decline in cows or milk production, given the importance of Pennsylvania's dairy industry and the projected increase in unconventional natural gas drilling, further research to prevent unintended economic and public health consequences is imperative.

Integrated Approach to Drilling Project in Unconventional Reservoir Using Reservoir Simulation

NASA Astrophysics Data System (ADS)

Stopa, Jerzy; Wiśniowski, Rafał; Wojnarowski, Paweł; Janiga, Damian; Skrzypaszek, Krzysztof

2018-03-01

Accumulation and flow mechanisms in unconventional reservoir are different compared to conventional. This requires a special approach of field management with drilling and stimulation treatments as major factor for further production. Integrated approach of unconventional reservoir production optimization assumes coupling drilling project with full scale reservoir simulation for determine best well placement, well length, fracturing treatment design and mid-length distance between wells. Full scale reservoir simulation model emulate a part of polish shale - gas field. The aim of this paper is to establish influence of technical factor for gas production from shale gas field. Due to low reservoir permeability, stimulation treatment should be direct towards maximizing the hydraulic contact. On the basis of production scenarios, 15 stages hydraulic fracturing allows boost gas production over 1.5 times compared to 8 stages. Due to the possible interference of the wells, it is necessary to determine the distance between the horizontal parts of the wells trajectories. In order to determine the distance between the wells allowing to maximize recovery factor of resources in the stimulated zone, a numerical algorithm based on a dynamic model was developed and implemented. Numerical testing and comparative study show that the most favourable arrangement assumes a minimum allowable distance between the wells. This is related to the volume ratio of the drainage zone to the total volume of the stimulated zone.

EFFECTS OF PHOTOCHEMICAL OXIDANTS ON PLANTS

EPA Science Inventory

Photochemical oxidants are found in 'photochemical smog' which is a complex mixture of primary and secondary air pollutants. The photochemical oxidants are secondary air pollutants formed by the action of sunlight on nitrogen oxides and reactive hydrocarbons, their precursors. Th...

Paul W. King, Ph.D., M.S. | NREL

Science.gov Websites

converting solar energy into biofuels. Specific areas of interest include using molecular, biochemical and Photochemical Conversion Photobiological Hydrogen Production Education Ph.D., Biochemistry and Molecular Biology , Mechanism, and Maturation," Biochimica et Biophysica Acta-Molecular Cell Research (2015) need_alt "

Framework for comparing ecosystem impacts of developing unconventional energy resources on western US rangelands

Treesearch

Urs P. Kreuter; William E. Fox; John A. Tanaka; Kristie A. Maczko; Daniel W. McCollum; John E. Mitchell; Clifford S. Duke; Lori Hidinger

2012-01-01

More diverse sources of energy are needed for countries to progress toward energy independence and to meet future food production needs. The US Task Force on Strategic Unconventional Fuels concluded that to achieve this objective it is essential to develop a domestic unconventional fuels industry. Rangelands, which cover 50% to 70% of the earth's terrestrial...

13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

NASA Astrophysics Data System (ADS)

Sebree, Joshua A.; Stern, Jennifer C.; Mandt, Kathleen E.; Domagal-Goldman, Shawn D.; Trainer, Melissa G.

2016-05-01

The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

Regional Air Quality Model Application of the Aqueous-Phase ...

EPA Pesticide Factsheets

In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry models use a parameterization of the aqueous-phase reduction of Hg2+ that has been shown to be unlikely under normal ambient conditions or use a non mechanistic value derived to optimize wet deposition results. Recent laboratory experiments have shown that Hg2+ can be photochemically reduced to elemental mercury (Hg) in the aqueous-phase by dissolved organic matter and a mechanism and the rate for Hg2+ photochemical reduction by dicarboxylic acids (DCA) has been proposed. For the first time in a regional scale model, the DCA mechanism has been applied. The HO2-Hg2+ reduction mechanism, the proposed DCA reduction mechanism, and no aqueous-phase reduction (NAR) of Hg2+ are evaluated against weekly wet deposition totals, concentrations and precipitation observations from the Mercury Deposition Network (MDN) using the Community Multiscale Air Quality (CMAQ) model version 4.7.1. Regional scale simulations of mercury wet deposition using a DCA reduction mechanism evaluated well against observations, and reduced the bias in model evaluation by at least 13% over the other schemes evaluated, although summertime deposition estimates were still biased by −31.4% against observations. The use of t

Insights on unconventional natural gas development from shale: an interview with Anthony R. Ingraffea by Adam Law.

PubMed

Ingraffea, Anthony R

2013-01-01

Adam Law, M.D., interviewed Anthony R. Ingraffea, Ph.D., P.E., as part of a series of interviews funded by the Heinz Endowment. Dr. Ingraffea is the Dwight C. Baum Professor of Engineering at Cornell University, and has taught structural mechanics, finite element methods, and fracture mechanics at Cornell for 33 years. He discusses issues related to hydraulic fracturing, including inherent risks, spatial intensity, and the importance of a multi-disciplinary organization in establishing a chain of evidence.

Military Space Mission Design and Analysis in a Multi-Body Environment: An Investigation of High-Altitude Orbits as Alternative Transfer Paths, Parking Orbits for Reconstitution, and Unconventional Mission Orbits

DTIC Science & Technology

2017-03-23

Dynamical Astronomy , vol. 90, no. January 2004, pp. 165–178, 2004. [Online]. Available: https://www.researchgate.net/publication/ 225231299 On The...Celestial Mechanics and Dynamical Astronomy , vol. 32, no. 1, pp. 53–71, 1984. [Online]. Available: https://engineering.purdue.edu/people/kathleen.howell

An Unconventional Approach to Reducing Retinal Degeneration After Traumatic Ocular Injury

DTIC Science & Technology

2017-09-01

AWARD NUMBER: W81XWH-15-1-0138 TITLE: An Unconventional Approach to Reducing Retinal Degeneration After Traumatic Ocular Injury PRINCIPAL...2015 - 30 Jun 2017 4. TITLE AND SUBTITLE An Unconventional Approach to Reducing Retinal Degeneration After Traumatic Ocular Injury 5 a . CONTRACT...optic confocal microscope system , test it, and establish protocols for the first successful in vivo retinal microvessel and pericyte advanced

Acetylation

Treesearch

Roger M. Rowell

2006-01-01

Wood was designed after millions of years of evolution, to perform in a wet environment, and nature is programmed to recycle it, in a timely way, back to the basic building blocks of carbon dioxide and water through biological, thermal, aqueous, photochemical, chemical, and mechanical degredations. We learned to use wood, accepting that it changes dimensions with...

STUDY USING A THREE-DIMENSIONAL SMOG FORMATION MODEL UNDER CONDITIONS OF COMPLEX FLOW

EPA Science Inventory

To clarify the photochemical smog formation mechanisms under conditions of complex flow, the SAI Urban Airshed Model was evaluated using a 1981 field observed data base. In the Tokyo Metropolitan Area higher O3 concentrations are usually observed near the shore in the morning. As...

Highly efficient destruction of squamous carcinoma cells of the head and neck by photochemical internalization of Ranpirnase.

PubMed

Liebers, Nora; Holland-Letz, Tim; Welschof, Mona; Høgset, Anders; Jäger, Dirk; Arndt, Michaela A E; Krauss, Jürgen

2017-11-01

Photochemical Internalization is a novel drug delivery technology for cancer treatment based on the principle of Photodynamic Treatment. Using a photosensitizer that locates in endocytic vesicles membranes of tumor cells, Photochemical internalization enables cytosolic release of endocytosed antitumor agents in a site-specific manner. The purpose of the present in-vitro study was to explore whether Photochemical Internalization is able to enhance the efficacy of Ranpirnase, a cytotoxic amphibian ribonuclease, for eradication of squamous cell carcinoma of the head and neck. Cell viability was measured in 8 primary human cell lines of squamous cell carcinoma of the head and neck after treatment with Ranpirnase and Photochemical Internalization. For Photochemical Internalization the photosensitizer disulfonated tetraphenyl porphine was incubated with tumor cells followed by exposure to blue light (435 nm). Our study demonstrates significant enhancement of antitumor activity of Ranpirnase by Photochemical Internalization. Treatment responses were heterogeneous between the primary cancer cell lines. Combining Photochemical Internalization with Ranpirnase resulted in 4.6 to 1,940-fold increased cytotoxicity when compared with the ribonuclease alone (P < 0.05). Cytotoxicity of Ranpirnase can be markedly enhanced by Photochemical Internalization in squamous cell carcinoma of the head and neck.

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

Code of Federal Regulations, 2011 CFR

2011-07-01

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

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

Code of Federal Regulations, 2010 CFR

2010-07-01

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

Photooxidative degradation of clear ultraviolet absorbing acrylic copolymer surfaces

NASA Technical Reports Server (NTRS)

Gupta, A.; Liang, R. H.; Vogl, O.; Pradellok, W.; Huston, A. L.; Scott, G. W.

1983-01-01

Photodegradation of copolymer of methyl methacrylate and 2(2'-hydroxy 5'vinyl-phenyl) 2H-benzotriazole has been investigated in order to determine the changes in the chemical composition of the surface of the copolymer on photooxidation. An electronic energy transfer mechanism has been postulated in order to interpret the observed photochemical changes in the polymer. Preliminary examination of the photophysical properties of the chromophore provides support for such a mechanism.

Varieties of healing. 2: a taxonomy of unconventional healing practices.

PubMed

Kaptchuk, T J; Eisenberg, D M

2001-08-07

The first of two essays in this issue demonstrated that the United States has had a rich history of medical pluralism. This essay seeks to present an overview of contemporary unconventional medical practices in the United States. No clear definition of "alternative medicine" is offered because it is a residual category composed of heterogeneous healing methods. A descriptive taxonomy of contemporary unconventional healing could be more helpful. Two broad categories of unconventional medicine are described here: a more prominent, "mainstream" complementary and alternative medicine (CAM) and a more culture-bound, "parochial" unconventional medicine. The CAM component can be divided into professional groups, layperson-initiated popular health reform movements, New Age healing, alternative psychological therapies, and non-normative scientific enterprises. The parochial category can be divided into ethno-medicine, religious healing, and folk medicine. A topologic examination of U.S. health care can provide an important conceptual framework through which health care providers can understand the current situation in U.S. medical pluralism.

Environmental baseline conditions for impact assessment of unconventional gas exploitation: the G-Baseline project

NASA Astrophysics Data System (ADS)

Kloppmann, Wolfram; Mayer, Berhard; Millot, Romain; Parker, Beth L.; Gaucher, Eric; Clarkson, Christopher R.; Cherry, John A.; Humez, Pauline; Cahill, Aaron

2015-04-01

A major scientific challenge and an indispensible prerequisite for environmental impact assessment in the context of unconventional gas development is the determination of the baseline conditions against which potential environmental impacts on shallow freshwater resources can be accurately and quantitatively tested. Groundwater and surface water resources overlying the low-permeability hydrocarbon host rocks containing shale gas may be impacted to different extents by naturally occurring saline fluids and by natural gas emanations. Baseline assessments in areas of previous conventional hydrocarbon production may also reveal anthropogenic impacts from these activities not related to unconventional gas development. Once unconventional gas exploitation has started, the baseline may be irrevocably lost by the intricate superposition of geogenic and potential anthropogenic contamination by stray gas, formation waters and chemicals used during hydraulic fracturing. The objective of the Franco-Canadian NSERC-ANR project G-Baseline is to develop an innovative and comprehensive methodology of geochemical and isotopic characterization of the environmental baseline for water and gas samples from all three essential zones: (1) the production zone, including flowback waters, (2) the intermediate zone comprised of overlying formations, and (3) shallow aquifers and surface water systems where contamination may result from diverse natural or human impacts. The outcome will be the establishment of a methodology based on innovative tracer and monitoring techniques, including traditional and non-traditional isotopes (C, H, O, S, B, Sr, Cl, Br, N, U, Li, Cu, Zn, CSIA...) for detecting, quantifying and modeling of potential leakage of stray gas and of saline formation water mixed with flowback fluids into fresh groundwater resources and surface waters taking into account the pathways and mechanisms of fluid and gas migration. Here we present an outline of the project as well as first results from chemical and isotopic analyses on gas, fluid and solid samples collected during a baseline monitoring program at the Carbon Management Canada field research site in south-eastern Alberta, Canada.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

NASA Astrophysics Data System (ADS)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-07-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

Excimer laser induced surface chemical modification of polytetrafluoroethylene

NASA Astrophysics Data System (ADS)

Révész, K.; Hopp, B.; Bor, Z.

1997-02-01

Polytetrafluoroethylene has a notoriously non adhesive and non reactive character. Its successful surface photochemical modification was performed by irradiating the polytetrafluoroethylene/liquid triethylamine interface with an ArF excimer laser (λ=193 nm). Due to the photochemical treatment the polytetrafluoroethylene surface became more hydrophilic. The water receding contact angle decreased from 94° to 43°. The reaction cross section was determined from the decrease of the contact angles. It was found to be as high as 6.4×10-18 cm2. XPS measurements evidenced the removal of fluorine from the polytetrafluoroethylene, incorporation of alkyl carbon and nitrogen. Photochemical dissociation path of the triethylamine makes probable that it bonded to the fluoropolymer backbone via the α-carbon atom of an ethyl group. A radical, or a photoinduced electron transfer mechanism was suggested to describe this reaction. A selective area electroless plating of silver was performed after pretreating the sample with patterned photomodification. The increased adhesion of the sample was proved by gluing with epoxy resin. As a result of the surface modification the tensile strength of gluing increased by 210× and reached 24% of the value characteristic for the bulk material.

Highly uniform resistive switching properties of amorphous InGaZnO thin films prepared by a low temperature photochemical solution deposition method.

PubMed

Hu, Wei; Zou, Lilan; Chen, Xinman; Qin, Ni; Li, Shuwei; Bao, Dinghua

2014-04-09

We report on highly uniform resistive switching properties of amorphous InGaZnO (a-IGZO) thin films. The thin films were fabricated by a low temperature photochemical solution deposition method, a simple process combining chemical solution deposition and ultraviolet (UV) irradiation treatment. The a-IGZO based resistive switching devices exhibit long retention, good endurance, uniform switching voltages, and stable distribution of low and high resistance states. Electrical conduction mechanisms were also discussed on the basis of the current-voltage characteristics and their temperature dependence. The excellent resistive switching properties can be attributed to the reduction of organic- and hydrogen-based elements and the formation of enhanced metal-oxide bonding and metal-hydroxide bonding networks by hydrogen bonding due to UV irradiation, based on Fourier-transform-infrared spectroscopy, X-ray photoelectron spectroscopy, and Field emission scanning electron microscopy analysis of the thin films. This study suggests that a-IGZO thin films have potential applications in resistive random access memory and the low temperature photochemical solution deposition method can find the opportunity for further achieving system on panel applications if the a-IGZO resistive switching cells were integrated with a-IGZO thin film transistors.

Balloon-Borne Measurements of Stratospheric Radicals and their Precursors: Implications for the Production and Loss of Ozone

NASA Technical Reports Server (NTRS)

Osterman, G. B.; Salawitch, R. J.; Sen, B.; Toon, G. C.; Stachnik, R. A.; Pickett, H. M.; Margitan, J. J.; Blavier, J.-F.; Peterson, D. B.

1997-01-01

Measurements of hydrogen, nitrogen and chlorine radicals from a balloon flight on 25 September 1993 from Ft. Sumner, NM provide an opportunity to quantify photochemical production and loss of stratospheric ozone. Ozone loss rates determined using measured radical concentrations agree fairly well with loss rates calculated using a photochemical model. Catalytic cycles involving OH and HO2 are shown to dominate photochemical loss of ozone for altitudes between 44 and 50 km. Reactions involving NO and NO2 are the dominant sink for ozone between 25 and 38 km. The total ozone loss rate determined from the measurements balances calculated production rates for altitudes between 30 and 40 km. However, loss of ozone exceeds production by -35% between 42 and 50 km. The imbalance between production and loss of ozone above 42 km is larger than the uncertainty of any one of the critical kinetic parameters or species concentrations. No single adjustment to any of these parameters can simultaneously resolve the imbalance and satisfy constraints imposed by measured OH, HO2, NO2 and ClO. Our results are consistent with an additional mechanism for ozone production above 40 km other than photolysis of ground state O2.

Unconventional gas development and its effect on forested ecosystems in the Northern Appalachians, USA

NASA Astrophysics Data System (ADS)

Drohan, Patrick; Brittingham, Margaret; Mortensen, David; Barlow, Kathryn; Langlois, Lillie

2017-04-01

Worldwide unconventional shale-gas development has the potential to cause substantial landscape disturbance. The northeastern U.S.A. Appalachian Mountains across the states of Pennsylvania, West Virginia, Ohio, and Kentucky, are experiencing rapid landscape change as unconventional gas development occurs. We highlight several years of our research from this region in order to demonstrate the unique effect unconventional development has had on forested ecosystems. Infrastructure development has had a wide-reaching and varied effect on forested ecosystems and their services, which has resulted in temporary disturbances and long-lasting ones altering habitats and their viability. Corridor disturbances, such as pipelines, are the most spatially extensive disturbance and have substantially fragmented forest cover. Core forest disturbance, especially, in upper watershed positions, has resulted in disproportionate disturbances to forested ecosystems and their wildlife, and suggests a need for adaptive land management strategies to minimize and mitigate the effects of gas development. Soil and water resources are most affected by surface disturbances; however, soil protection and restoration strategies are evolving as the gas play changes economically. Dynamic soil properties related to soil organic matter and water availability respond uniquely to unconventional gas development and new, flexible restoration strategies are required to support long-term ecosystem stability. While the focus of management and research to date has been on acute disturbances to forested ecosystems, unconventional gas development is clearly a greater chronic, long-term disturbance factor in the Appalachian Mountains. Effectively managing ecosystems where unconventional gas development is occurring is a complicated interplay between public, private and corporate interests.

Unconventional natural gas development and birth outcomes in Pennsylvania, USA

PubMed Central

Casey, Joan A.; Savitz, David A.; Rasmussen, Sara G.; Ogburn, Elizabeth L.; Pollak, Jonathan; Mercer, Dione G.; Schwartz, Brian S.

2015-01-01

Background Unconventional natural gas development has expanded rapidly. In Pennsylvania the number of producing wells increased from zero in 2005 to 3689 in 2013. To our knowledge, no prior publications have focused on unconventional natural gas development and birth outcomes. Methods We performed a retrospective cohort study using electronic health record data on 9384 mothers linked to 10946 neonates in the Geisinger Health System from January 2009-January 2013. We estimated cumulative exposure to unconventional natural gas development activity with an inverse-distance squared model that incorporated distance to the mother’s home; dates and durations of well pad development, drilling, and hydraulic fracturing; and production volume during the pregnancy. We used multilevel linear and logistic regression models to examine associations between activity index quartile and term birth weight, preterm birth, low 5 minute Apgar score and small size for gestational age, while controlling for potential confounding variables. Results In adjusted models, there was an association between unconventional natural gas development activity and preterm birth that increased across quartiles, with a fourth quartile odds ratio of 1.4 (95% CI: 1.0-1.9). There were no associations of activity with Apgar score, small for gestational age, or term birth weight (after adjustment for year). In a post-hoc analysis, there was an association with physician-recorded high-risk pregnancy identified from the problem list (fourth vs. first quartile, 1.3 [95% CI: 1.1-1.7]). Conclusion Prenatal residential exposure to unconventional natural gas development activity was associated with two pregnancy outcomes, adding to evidence that unconventional natural gas development may impact health. PMID:26426945

Dispersion and photochemical evolution of reactive pollutants in street canyons

NASA Astrophysics Data System (ADS)

Kwak, Kyung-Hwan; Baik, Jong-Jin; Lee, Kwang-Yeon

2013-05-01

Dispersion and photochemical evolution of reactive pollutants in street canyons with canyon aspect ratios of 1 and 2 are investigated using a computational fluid dynamics (CFD) model coupled with the carbon bond mechanism IV (CBM-IV). Photochemical ages of NOx and VOC are expressed as a function of the NO2-to-NOx and toluene-to-xylene ratios, respectively. These are found to be useful for analyzing the O3 and OH oxidation processes in the street canyons. The OH oxidation process (O3 oxidation process) is more pronounced in the upper (lower) region of the street canyon with a canyon aspect ratio of 2, which is characterized by more (less) aged air. In the upper region of the street canyon, O3 is chemically produced as well as transported downward across the roof level, whereas O3 is chemically reduced in the lower region of the street canyon. The O3 chemical production is generally favorable when the normalized photochemical ages of NOx and VOC are larger than 0.55 and 0.28, respectively. The sensitivities of O3 chemical characteristics to NOx and VOC emission rates, photolysis rate, and ambient wind speed are examined for the lower and upper regions of the street canyon with a canyon aspect ratio of 2. The O3 concentration and the O3 chemical production rate divided by the O3 concentration increase as the NOx emission rate decreases and the VOC emission rate and photolysis rate increase. The O3 concentration is less sensitive to the ambient wind speed than to other factors considered. The relative importance of the OH oxidation process compared to the O3 oxidation process increases with increasing NOx emission rate and photolysis rate and decreasing VOC emission rate. In this study, both O3 and OH oxidation processes are found to be important in street-canyon scale chemistry. The methodology of estimating the photochemical ages can potentially be adopted to neighborhood scale chemistry.

Shale Gas Geomechanics for Development and Performance of Unconventional Reservoirs

NASA Astrophysics Data System (ADS)

Domonik, Andrzej; Łukaszewski, Paweł; Wilczyński, Przemysław; Dziedzic, Artur; Łukasiak, Dominik; Bobrowska, Alicja

2017-04-01

Mechanical properties of individual shale formations are predominantly determined by their lithology, which reflects sedimentary facies distribution, and subsequent diagenetic and tectonic alterations. Shale rocks may exhibit complex elasto-viscoplastic deformation mechanisms depending on the rate of deformation and the amount of clay minerals, also bearing implications for subcritical crack growth and heterogeneous fracture network development. Thus, geomechanics for unconventional resources differs from conventional reservoirs due to inelastic matrix behavior, stress sensitivity, rock anisotropy and low matrix permeability. Effective horizontal drilling and hydraulic fracturing technologies are required to obtain and maintain high performance. Success of these techniques strongly depends on the geomechanical investigations of shales. An inelastic behavior of shales draws increasing attention of investigators [1], due to its role in stress relaxation between fracturing phases. A strong mechanical anisotropy in the vertical plane and a lower and more variable one in the horizontal plane are characteristic for shale rocks. The horizontal anisotropy plays an important role in determining the direction and effectiveness of propagation of technological hydraulic fractures. Non-standard rock mechanics laboratory experiments are being applied in order to obtain the mechanical properties of shales that have not been previously studied in Poland. Novel laboratory investigations were carried out to assess the creep parameters and to determine time-dependent viscoplastic deformation of shale samples, which can provide a limiting factor to tectonic stresses and control stress change caused by hydraulic fracturing. The study was supported by grant no.: 13-03-00-501-90-472946 "An integrated geomechanical investigation to enhance gas extraction from the Pomeranian shale formations", funded by the National Centre for Research and Development (NCBiR). References: Ch. Chang M. D. Zoback. 2009. Viscous creep in room-dried unconsolidated Gulf of Mexico shale (I): Experimental results. Journal of Petroleum Science and Engineering 69: 239-246.

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

PubMed

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

2017-07-25

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

Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism

DOE PAGES

Chambers, Matthew B.; Kurtz, Daniel A.; Pitman, Catherine L.; ...

2016-09-27

Artificial photosynthesis relies on coupling light absorption with chemical fuel generation. A mechanistic study of visible light-driven H 2 production from [Cp*Ir(bpy)H] + (1) has revealed a new, highly efficient pathway for integrating light absorption with bond formation. The net reaction of 1 with a proton source produces H 2, but the rate of excited state quenching is surprisingly acid-independent and displays no observable deuterium kinetic isotopic effect. Time-resolved photoluminescence and labeling studies are consistent with diffusion-limited bimetallic self-quenching by electron transfer. Accordingly, the quantum yield of H 2 release nearly reaches unity as the concentration of 1 increases. Furthermore,more » this unique pathway for photochemical H 2 generation provides insight into transformations catalyzed by 1.« less

Unconventional barometry and rheometry: new quantification approaches for mechanically-controlled microstructures

NASA Astrophysics Data System (ADS)

Tajcmanova, L.; Moulas, E.; Vrijmoed, J.; Podladchikov, Y.

2016-12-01

Estimation of pressure-temperature (P-T) from petrographic observations in metamorphic rocks has become a common practice in petrology studies during the last 50 years. This data often serves as a key input in geodynamic reconstructions and thus directly influences our understanding of lithospheric processes. Such an approach might have led the metamorphic geology field to a certain level of quiescence. In the classical view of metamorphic quantification approaches, fast viscous relaxation (and therefore constant pressure across the rock microstructure) is assumed, with chemical diffusion being the limiting factor in equilibration. Recently, we have focused on the other possible scenario - fast chemical diffusion and slow viscous relaxation - and brings an alternative interpretation of chemical zoning found in high-grade rocks. The aim has been to provide insight into the role of mechanically maintained pressure variations on multi-component chemical zoning in minerals. Furthermore, we used the pressure information from the mechanically-controlled microstructure for rheological constrains. We show an unconventional way of relating the direct microstructural observations in rocks to the nonlinearity of rheology at time scales unattainable by laboratory measurements. Our analysis documents that mechanically controlled microstructures that have been preserved over geological times can be used to deduce flow-law parameters and in turn estimate stress levels of minerals in their natural environment. The development of the new quantification approaches has opened new horizons in understanding the phase transformations in the Earth's lithosphere. Furthermore, the new data generated can serve as a food for thought for the next generation of fully coupled numerical codes that involve reacting materials while respecting conservation of mass, momentum and energy.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

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

PubMed Central

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

2017-01-01

Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in-vitro. Recent developments allow for the estimation of some of these photochemical parameters in-vivo. This review will cover the currently available in-vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT. PMID:28166056

The application of the micronucleus test in Chinese hamster V79 cells to detect drug-induced photogenotoxicity.

PubMed

Kersten, B; Zhang, J; Brendler-Schwaab, S Y; Kasper, P; Müller, L

1999-09-15

Recent reports on the photochemical carcinogenicity and photochemical genotoxicity of fluoroquinolone antibacterials led to an increasing awareness for the need of a standard approach to test for photochemical genotoxicity. In this study the micronucleus test using V79 cells was adapted to photogenotoxicity testing. Results of using different UVA/UVB relationships enabled us to identify a suitable irradiation regimen for the activation of different kinds of photosensitizers. Using this regimen, 8-methoxypsoralen and the fluoroquinolones lomefloxacin, grepafloxacin and Bay Y 3118 were identified to cause micronuclei and toxicity upon photochemical activation. Among the phenothiazines tested, chlorpromazine and 2-chlorophenothiazine, were positive for both endpoints, whereas triflupromazine was only slightly photoclastogenic in the presence of strong phototoxicity. Among the other potential human photosensitizers tested (oxytetracycline, doxycycline, metronidazole, emodin, hypericin, griseofulvin), only hypericin was slightly photogenotoxic. Photochemical toxicity in the absence of photochemical genotoxicity was noted for doxycycline and emodin. With the assay system described, it is possible to determine photochemical toxicity and photochemical genotoxicity concomitantly with sufficient reliability.

Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

NASA Astrophysics Data System (ADS)

Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

2015-12-01

The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

Differential coral bleaching-Contrasting the activity and response of enzymatic antioxidants in symbiotic partners under thermal stress.

PubMed

Krueger, Thomas; Hawkins, Thomas D; Becker, Susanne; Pontasch, Stefanie; Dove, Sophie; Hoegh-Guldberg, Ove; Leggat, William; Fisher, Paul L; Davy, Simon K

2015-12-01

Mass coral bleaching due to thermal stress represents a major threat to the integrity and functioning of coral reefs. Thermal thresholds vary, however, between corals, partly as a result of the specific type of endosymbiotic dinoflagellate (Symbiodinium sp.) they harbour. The production of reactive oxygen species (ROS) in corals under thermal and light stress has been recognised as one mechanism that can lead to cellular damage and the loss of their symbiont population (Oxidative Theory of Coral Bleaching). Here, we compared the response of symbiont and host enzymatic antioxidants in the coral species Acropora millepora and Montipora digitata at 28°C and 33°C. A. millepora at 33°C showed a decrease in photochemical efficiency of photosystem II (PSII) and increase in maximum midday excitation pressure on PSII, with subsequent bleaching (declining photosynthetic pigment and symbiont density). M. digitata exhibited no bleaching response and photochemical changes in its symbionts were minor. The symbiont antioxidant enzymes superoxide dismutase, ascorbate peroxidase, and catalase peroxidase showed no significant upregulation to elevated temperatures in either coral, while only catalase was significantly elevated in both coral hosts at 33°C. Increased host catalase activity in the susceptible coral after 5days at 33°C was independent of antioxidant responses in the symbiont and preceded significant declines in PSII photochemical efficiencies. This finding suggests a potential decoupling of host redox mechanisms from symbiont photophysiology and raises questions about the importance of symbiont-derived ROS in initiating coral bleaching. Copyright © 2015 Elsevier Inc. All rights reserved.

Plant resistance mechanisms to air pollutants: rhythms in ascorbic acid production during growth under ozone stress

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

Lee, E.H.

1991-01-01

Relationships between ozone (O3) tolerance and leaf ascorbic acid concentrations in O3-susceptible (O3-S) 'Hark' and O3-resistant (O3-R) 'Hood' soybean, Glycine max (L.) Merr., cultivars were examined with high-performance liquid chromatography (HPLC). Leaf samples were analyzed at 4 intervals during a 24 h period. Soybean cultivars grown in the greenhouse with charcoal filtered (CF) and nonfiltered (NF) air showed daily oscillations in ascorbic acid production. Highest ascorbic acid levels in leaves during light coincided with highest concentrations of photochemical oxidants in the atmosphere at 2:00 p.m. The resistant genotype produced more ascorbic acid in its trifoliate leaves than did the correspondingmore » susceptible genotype. Under CF air (an O3-reduced environment) O3-S and O3-R cultivars showed rhythms in ascorbic acid production. In NF air (an O3 stress environment) the O3-R cultivar alone showed rhythms in ascorbic acid production. Results indicated that superior O3 tolerance in the Hood soybean cultivar (compared with Hark) was associated with a greater increase in endogenous levels of ascorbic acid. Ascorbic acid may scavenge free radicals and thereby protect cells from injury by O3 or other oxyradical products. Plants defend themselves against photochemical oxidant stress, such as O3, by several mechanisms. Experimental evidence indicates that antioxidant defense systems existing in plant tissues may function to protect cellular components from deleterious effects of photochemical oxidants through endogenous and exogenous controls.« less

Deterrence in the Human Domain: A COIN Framework to Deterring Unconventional Warfare in Shaping Operations

DTIC Science & Technology

2017-05-25

Wilkinson US Army School of Advanced Military Studies United States Army Command and General Staff College Fort Leavenworth, Kansas 2017 Approved for...SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) Advanced Military Studies Program 10. SPONSOR/MONITOR’S ACRONYM(S) 11. SPONSOR/MONITOR’S...adversary’s unconventional threat. To test this framework, this monograph analyzes a case study of how Russia will likely use unconventional forces and

Light and oxygenic photosynthesis: energy dissipation as a protection mechanism against photo-oxidation

PubMed Central

Szabó, Ildikó; Bergantino, Elisabetta; Giacometti, Giorgio Mario

2005-01-01

Efficient photosynthesis is of fundamental importance for plant survival and fitness. However, in oxygenic photosynthesis, the complex apparatus responsible for the conversion of light into chemical energy is susceptible to photodamage. Oxygenic photosynthetic organisms have therefore evolved several protective mechanisms to deal with light energy. Rapidly inducible non-photochemical quenching (NPQ) is a short-term response by which plants and eukaryotic algae dissipate excitation energy as heat. This review focuses on recent advances in the elucidation of the molecular mechanisms underlying this protective quenching pathway in higher plants. PMID:15995679

Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids

PubMed Central

Randel, Jason C.; Niestemski, Francis C.; Botello-Mendez, Andrés R.; Mar, Warren; Ndabashimiye, Georges; Melinte, Sorin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Butova, Ekaterina D.; Fokin, Andrey A.; Schreiner, Peter R.; Charlier, Jean-Christophe; Manoharan, Hari C.

2014-01-01

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p–n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane–C60 conjugate. By linking both sp3 (diamondoid) and sp2 (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane–C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism. PMID:25202942

Unconventional Bose—Einstein Condensations from Spin-Orbit Coupling

NASA Astrophysics Data System (ADS)

Wu, Cong-Jun; Ian, Mondragon-Shem; Zhou, Xiang-Fa

2011-09-01

According to the “no-node" theorem, the many-body ground state wavefunctions of conventional Bose—Einstein condensations (BEC) are positive-definite, thus time-reversal symmetry cannot be spontaneously broken. We find that multi-component bosons with spin-orbit coupling provide an unconventional type of BECs beyond this paradigm. We focus on a subtle case of isotropic Rashba spin-orbit coupling and the spin-independent interaction. In the limit of the weak confining potential, the condensate wavefunctions are frustrated at the Hartree—Fock level due to the degeneracy of the Rashba ring. Quantum zero-point energy selects the spin-spiral type condensate through the “order-from-disorder" mechanism. In a strong harmonic confining trap, the condensate spontaneously generates a half-quantum vortex combined with the skyrmion type of spin texture. In both cases, time-reversal symmetry is spontaneously broken. These phenomena can be realized in both cold atom systems with artificial spin-orbit couplings generated from atom-laser interactions and exciton condensates in semi-conductor systems.

5-FU resistant EMT-like pancreatic cancer cells are hypersensitive to photochemical internalization of the novel endoglin-targeting immunotoxin CD105-saporin.

PubMed

Lund, Kaja; Olsen, Cathrine Elisabeth; Wong, Judith Jing Wen; Olsen, Petter Angell; Solberg, Nina Therese; Høgset, Anders; Krauss, Stefan; Selbo, Pål Kristian

2017-12-19

Development of resistance to 5-fluorouracil (5-FU) is a major problem in treatment of various cancers including pancreatic cancer. In this study, we reveal important resistance mechanisms and photochemical strategies to overcome 5-FU resistance in pancreatic adenocarcinoma. 5-FU resistant (5-FUR), epithelial-to-mesenchymal-like sub-clones of the wild type pancreatic cancer cell line Panc03.27 were previously generated in our lab. We investigated the cytotoxic effect of the endosomal/lysosomal-localizing photosensitizer TPCS 2a (fimaporfin) combined with light (photochemical treatment, PCT) using MTS viability assay, and used fluorescence microscopy to show localization of TPCS 2a and to investigate the effect of photodamage of lysosomes. Flow cytometric analysis was performed to investigate uptake of photosensitizer and to assess intracellular ROS levels. Expression and localization of LAMP1 was assessed using RT-qPCR, western blotting, and structured illumination microscopy. MTS viability assay was used to assess the effect of combinations of 5-FU, chloroquine (CQ), and photochemical treatment. Expression of CD105 was investigated using RT-qPCR, western blotting, flow cytometry, and fluorescence microscopy, and co-localization of TPCS 2a and anti-CD105-saporin was assessed using microscopy. Lastly, the MTS assay was used to investigate cytotoxic effects of photochemical internalization (PCI) of the anti-CD105-immunotoxin. The 5-FUR cell lines display hypersensitivity to PCT, which was linked to increased uptake of TPCS 2a , altered lysosomal distribution, lysosomal photodamage and increased expression of the lysosomal marker LAMP-1 in the 5-FUR cells. We show that inhibition of autophagy induced by either chloroquine or lysosomal photodamage increases the sensitivity to 5-FU in the resistant cells. The three 5-FUR sub-clones overexpress Endoglin (CD105). Treatment with the immunotoxin anti-CD105-saporin alone significantly reduced the viability of the CD105-expressing 5-FUR cells, whereas little effect was seen in the CD105-negative non-resistant parental cancer cell lines. Strikingly, using the intracellular drug delivery method photochemical internalization (PCI) by combining light-controlled activation of the TPCS 2a with nanomolar levels of CD105-saporin resulted in strong cytotoxic effects in the 5-FUR cell population. Our findings suggested that autophagy is an important resistance mechanism against the chemotherapeutic drug 5-FU in pancreatic cancer cells, and that inhibition of the autophagy process, either by CQ or lysosomal photodamage, can contribute to increased sensitivity to 5-FU. For the first time, we demonstrate the promise of PCI-based targeting of CD105 in site-specific elimination of 5-FU resistant pancreatic cancer cells in vitro. In conclusion, PCI-based targeting of CD105 may represent a potent anticancer strategy and should be further evaluated in pre-clinical models.

DE-Cadherin regulates unconventional Myosin ID and Myosin IC in Drosophila left-right asymmetry establishment.

PubMed

Petzoldt, Astrid G; Coutelis, Jean-Baptiste; Géminard, Charles; Spéder, Pauline; Suzanne, Magali; Cerezo, Delphine; Noselli, Stéphane

2012-05-01

In bilateria, positioning and looping of visceral organs requires proper left-right (L/R) asymmetry establishment. Recent work in Drosophila has identified a novel situs inversus gene encoding the unconventional type ID myosin (MyoID). In myoID mutant flies, the L/R axis is inverted, causing reversed looping of organs, such as the gut, spermiduct and genitalia. We have previously shown that MyoID interacts physically with β-Catenin, suggesting a role of the adherens junction in Drosophila L/R asymmetry. Here, we show that DE-Cadherin co-immunoprecipitates with MyoID and is required for MyoID L/R activity. We further demonstrate that MyoIC, a closely related unconventional type I myosin, can antagonize MyoID L/R activity by preventing its binding to adherens junction components, both in vitro and in vivo. Interestingly, DE-Cadherin inhibits MyoIC, providing a protective mechanism to MyoID function. Conditional genetic experiments indicate that DE-Cadherin, MyoIC and MyoID show temporal synchronicity for their function in L/R asymmetry. These data suggest that following MyoID recruitment by β-Catenin at the adherens junction, DE-Cadherin has a twofold effect on Drosophila L/R asymmetry by promoting MyoID activity and repressing that of MyoIC. Interestingly, the product of the vertebrate situs inversus gene inversin also physically interacts with β-Catenin, suggesting that the adherens junction might serve as a conserved platform for determinants to establish L/R asymmetry both in vertebrates and invertebrates.

Deep geothermal: The ‘Moon Landing’ mission in the unconventional energy and minerals space

DOE PAGES

Regenauer-Lieb, Klaus; Bunger, Andrew; Chua, Hui Tong; ...

2015-01-30

Deep geothermal from the hot crystalline basement has remained an unsolved frontier for the geothermal industry for the past 30 years. This poses the challenge for developing a new unconventional geomechanics approach to stimulate such reservoirs. While a number of new unconventional brittle techniques are still available to improve stimulation on short time scales, the astonishing richness of failure modes of longer time scales in hot rocks has so far been overlooked. These failure modes represent a series of microscopic processes: brittle microfracturing prevails at low temperatures and fairly high deviatoric stresses, while upon increasing temperature and decreasing applied stressmore » or longer time scales, the failure modes switch to transgranular and intergranular creep fractures. Accordingly, fluids play an active role and create their own pathways through facilitating shear localization by a process of time-dependent dissolution and precipitation creep, rather than being a passive constituent by simply following brittle fractures that are generated inside a shear zone caused by other localization mechanisms. We lay out a new paradigm for reservoir stimulation by reactivating pre-existing faults at reservoir scale in a reservoir scale aseismic, ductile manner. A side effect of the new “soft” stimulation method is that owing to the design specification of a macroscopic ductile response, the proposed method offers the potential of a safer control over the stimulation process compared to conventional stimulation protocols such as currently employed in shale gas reservoirs.« less

A Molecular Reaction Cycle with a Solvatochromic Merocyanine Dye: An Experiment in Photochemistry, Kinetics, and Catalysis.

ERIC Educational Resources Information Center

Abdel-Kader, M. H.; Steiner, U.

1983-01-01

Three experiments using merocyanine M suitable as an integrated laboratory experience for undergraduates are described. Experiments demonstrate: complete molecular cycle composed of photochemical, thermal, and protolytic reaction steps; kinetics of cis-trans isomerization of the dye; and mechanism of base catalysis for thermal isomerization of the…

Chemical modification

Treesearch

R. M. Rowell

2004-01-01

Wood is a hygroscopic resource that was designed to perform, in nature, in a wet environment. Nature is programmed to recycle wood in a timely way through biological, thermal, aqueous, photochemical, chemical, and mechanical degradations. In simple terms, nature builds wood from carbon dioxide and water and has all the tools to recycle it back to the starting chemicals...

Photochemically Powered AgCl Janus Micromotors as a Model System to Understand Ionic Self-Diffusiophoresis.

PubMed

Zhou, Chao; Zhang, H P; Tang, Jinyao; Wang, Wei

2018-03-13

Micromotors are an emerging class of micromachines that could find potential applications in biomedicine, environmental remediation, and microscale self-assembly. Understanding their propulsion mechanisms holds the key to their future development. This is especially true for a popular category of micromotors that are driven by asymmetric surface photochemical reactions. Many of these micromotors release ionic species and are propelled via a mechanism termed "ionic self-diffusiophoresis". However, exactly how it operates remains vague. To address this fundamental yet important issue, we have developed a dielectric-AgCl Janus micromotor that clearly moves away from the AgCl side when exposed to UV or strong visible light. Taking advantage of numerical simulations and acoustic levitation techniques, we have provided tentative explanations for its speed decay over time as well as its directionality. In addition, photoactive AgCl micromotors demonstrate interesting gravitactic behaviors that hint at three-dimensional transport or sensing applications. The current work presents a well-controlled and easily fabricated model system to understand chemically powered micromotors, highlighting the usefulness of acoustic levitation for studying active matter free from the effect of boundaries.

Mechanism of colour discrimination by a bacterial sensory rhodopsin

NASA Technical Reports Server (NTRS)

Spudich, J. L.; Bogomolni, R. A.

1984-01-01

A photosensitive protein resembling the visual pigments of invertebrates enables phototactic archaebacteria to distinguish color. This protein exists in two spectrally-distinct forms, one of which is a transient photoproduct of the other and each of which undergoes photochemical reactions controlling the cell's swimming behaviour. Activation of a single pigment molecule in the cell is sufficient to signal the flagellar motor. This signal-transduction mechanism makes evident a color-sensing capability inherent in the retinal/protein chromophore.

Water Use for Unconventional Energy Development: How Much, What Kind, and to What Reaction?

NASA Astrophysics Data System (ADS)

Grubert, E.

2017-12-01

Water resources—access to water, protection of water, and allocation of water in particular—are a major priority for Americans, but water use for the energy sector has not previously been well characterized. Water use and management associated with unconventional energy development is of special interest, in part because it is often new to the locations and contexts where it occurs. This presentation focuses on three major questions about water use for unconventional energy development, drawing on both engineering and anthropological research. First, using results from a recent study of water use for energy in the entire United States, how much water does the US use for unconventional energy resources, and how does that compare with water use for more mature fuel cycles? Second, based on that same study, what kind of water is used for these unconventional energy resource fuel cycles? Specifically, where does the water come from, and what is its quality? Finally, drawing on recent case studies in the US and elsewhere, what has the reaction been to these water uses, and why does that matter? Case studies focused on oil and natural gas resources illustrate societal reactions to issues of both water management, particularly related to induced seismicity associated with produced water injection, and water allocation, particularly related to hydraulic fracturing. Overall, recent work finds that public concern about water used for unconventional energy resources is often better explained by observed or anticipated local impacts and the uncertainty surrounding these impacts than by specifics about quantities, allocation, and management techniques. This work provides both quantitative and qualitative characterization of water management and allocation for unconventional energy development.

Unconventional Natural Gas Development and Birth Outcomes in Pennsylvania, USA.

PubMed

Casey, Joan A; Savitz, David A; Rasmussen, Sara G; Ogburn, Elizabeth L; Pollak, Jonathan; Mercer, Dione G; Schwartz, Brian S

2016-03-01

Unconventional natural gas development has expanded rapidly. In Pennsylvania, the number of producing wells increased from 0 in 2005 to 3,689 in 2013. Few publications have focused on unconventional natural gas development and birth outcomes. We performed a retrospective cohort study using electronic health record data on 9,384 mothers linked to 10,946 neonates in the Geisinger Health System from January 2009 to January 2013. We estimated cumulative exposure to unconventional natural gas development activity with an inverse-distance squared model that incorporated distance to the mother's home; dates and durations of well pad development, drilling, and hydraulic fracturing; and production volume during the pregnancy. We used multilevel linear and logistic regression models to examine associations between activity index quartile and term birth weight, preterm birth, low 5-minute Apgar score and small size for gestational age birth, while controlling for potential confounding variables. In adjusted models, there was an association between unconventional natural gas development activity and preterm birth that increased across quartiles, with a fourth quartile odds ratio of 1.4 (95% confidence interval = 1.0, 1.9). There were no associations of activity with Apgar score, small for gestational age birth, or term birth weight (after adjustment for year). In a posthoc analysis, there was an association with physician-recorded high-risk pregnancy identified from the problem list (fourth vs. first quartile, 1.3 [95% confidence interval = 1.1, 1.7]). Prenatal residential exposure to unconventional natural gas development activity was associated with two pregnancy outcomes, adding to evidence that unconventional natural gas development may impact health.See Video Abstract at http://links.lww.com/EDE/B14.

GaN-based light-emitting diodes on various substrates: a critical review.

PubMed

Li, Guoqiang; Wang, Wenliang; Yang, Weijia; Lin, Yunhao; Wang, Haiyan; Lin, Zhiting; Zhou, Shizhong

2016-05-01

GaN and related III-nitrides have attracted considerable attention as promising materials for application in optoelectronic devices, in particular, light-emitting diodes (LEDs). At present, sapphire is still the most popular commercial substrate for epitaxial growth of GaN-based LEDs. However, due to its relatively large lattice mismatch with GaN and low thermal conductivity, sapphire is not the most ideal substrate for GaN-based LEDs. Therefore, in order to obtain high-performance and high-power LEDs with relatively low cost, unconventional substrates, which are of low lattice mismatch with GaN, high thermal conductivity and low cost, have been tried as substitutes for sapphire. As a matter of fact, it is not easy to obtain high-quality III-nitride films on those substrates for various reasons. However, by developing a variety of techniques, distincts progress has been made during the past decade, with high-performance LEDs being successfully achieved on these unconventional substrates. This review focuses on state-of-the-art high-performance GaN-based LED materials and devices on unconventional substrates. The issues involved in the growth of GaN-based LED structures on each type of unconventional substrate are outlined, and the fundamental physics behind these issues is detailed. The corresponding solutions for III-nitride growth, defect control, and chip processing for each type of unconventional substrate are discussed in depth, together with a brief introduction to some newly developed techniques in order to realize LED structures on unconventional substrates. This is very useful for understanding the progress in this field of physics. In this review, we also speculate on the prospects for LEDs on unconventional substrates.

ON A GENERALIZED SELF-SIMILARITY IN THE p-ADIC FIELD

NASA Astrophysics Data System (ADS)

Mukhamedov, Farrukh; Khakimov, Otabek

2016-08-01

In the present paper, we introduce a new set which defines a generalized self-similar set for contractive functions {fi}i=1N on the unit ball ℤp of p-adic numbers. This set is called unconventional limit set. We prove that the unconventional limit set is compact, perfect and uniformly disconnected. Moreover, we provide an example of two contractions for which the corresponding unconventional limiting set is quasi-symmetrically equivalent to the symbolic Cantor set.

U.S. Joint Special Operations Forces: Two Few, Overworked, Young, Homogenous & Macho to Fulfill the Unconventional Demands of the Long War?

DTIC Science & Technology

2008-05-28

OVERWORKED , YOUNG, HOMOGENOUS, & MACHO TO FULFILL THE UNCONVENTIONAL DEMANDS OF THE LONG WAR? SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR...U.S. Joint Special Operations Forces: Two Few, Overworked , Young, Homogenous & Macho to Fulfill the Unconventional Demands of the Long War? 5a...to be the targets of nearly daily mortar, improvised explosive devices (IEDs), and occasional suicide vehicle-borne IED (SVBIED) attacks. It

The composition dependence of the photochemical reactivity of strontium barium titanate

NASA Astrophysics Data System (ADS)

Bhardwaj, Abhilasha

The efficiency of particulate water photolysis catalysts is impractically low due to the recombination of intermediate species and charge carriers. The back reaction can occur easily if the oxidation and reduction sites on the surface of the catalyst are not far enough apart. It is hypothesized that it will be possible to increase the separation of the sites of the two half reactions and reduce the recombination of photogenerated charge carriers by using a ferroelectric material with permanent internal dipolar fields. This separation of the reaction sites may significantly increase the efficiency of the process. The present work compares the photochemical reactivities of ferroelectric and nonferroelectric materials (SrxBa1-xTiO 3, 0.0≤ x ≤1.0) with similar composition and structure. The reactivities are compared by measuring the color change of methylene blue dye after the aqueous dye solution reacts on the surface of ceramic sample pellets as a result of exposure to UV light. The reactivities are also compared by measuring the amount of silver that is formed when an aqueous AgNO3 solution photochemically reacts on the surface. The change in the color of the dye is measured by diffuse reflectance spectroscopy and absorbance measurements. The amount of silver is measured by atomic force microscopy. The photochemical reactivity of SrxBa1-xTiO3 shows a local maximum at the composition of the ferroelectric to non-ferroelectric transition. Also, the reactivities decrease as BaTiO3 and SrTiO3 become less pure. The dominant factors causing this trend in reactivities of SrxBa1-xTiO3 are the dielectric constant and alloy scattering. It is found that higher values of the dielectric constant increase the photochemical reactivity by enlarging the space charge region. The increase in alloy scattering in SrxBa1-xTiO 3 solid solutions as x increases from zero or decreases from 1, has adverse effect on reactivity. There are other factors such as ferroelectric polarization, relative band edge positions and pH of the solution that can influence the reactivity. However, these factors are not significant in determining the composition dependence of the photochemical reactivity of SrxBa 1-xTiO3. The comparison of the surfaces of SrxBa 1-xTiO3 samples imaged by AFM after reaction (with silver nitrate) also showed that the mode of reaction gradually changes from spatially selective reactivity for BaTiO3 to spatially uniform reactivity for SrTiO3. The spatially selective reactivity disappears completely when x in SrxBa1-xTiO3 is greater than or equal to 0.28. The mechanism of the photochemical reaction of methylene blue dye on SrxBa1-xTiO3 was also studied. It is found that the dye reacts by a mechanism similar to that of silver. The methylene blue dye and silver reduce on the surfaces of positively charged domains and the reduced reaction products remain at the reduction reaction site. Extensions of this research would be to experimentally determine the band edges and defect concentrations in SrxBa1-xTiO 3 to get a better understanding of their influence on photochemical reactivity. Since the long term goal of this research is to find a efficient particulate catalyst for photocatalysis of water, the next step in this research is to carry out the photocatalysis of water using SrxBa1-x TiO3 powders. The effect of catalyst particle size should also be analyzed.

Design and life-cycle considerations for unconventional-reservoir wells

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

Miskimins, J.L.

2009-05-15

This paper provides an overview of design and life-cycle considerations for certain unconventional-reservoir wells. An overview of unconventional-reservoir definitions is provided. Well design and life-cycle considerations are addressed from three aspects: upfront reservoir development, initial well completion, and well-life and long-term considerations. Upfront-reservoir-development issues discussed include well spacing, well orientation, reservoir stress orientations, and tubular metallurgy. Initial-well-completion issues include maximum treatment pressures and rates, treatment diversion, treatment staging, flowback and cleanup, and dewatering needs. Well-life and long-term discussions include liquid loading, corrosion, refracturing and associated fracture reorientation, and the cost of abandonment. These design considerations are evaluated with case studiesmore » for five unconventional-reservoir types: shale gas (Barnett shale), tight gas (Jonah feld), tight oil (Bakken play), coalbed methane (CBM) (San Juan basin), and tight heavy oil (Lost Hills field). In evaluating the life cycle and design of unconventional-reservoir wells, 'one size' does not fit all and valuable knowledge and a shortening of the learning curve can be achieved for new developments by studying similar, more-mature fields.« less

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

1988-01-01

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

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

Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.

2014-03-15

The optoelectronic and chemical properties of semiconductor nanocrystals heavily depend on their composition, size, shape and internal structure, surface functionality, etc. Available strategies to alter these properties through traditional colloidal syntheses and ligand exchange methods place a premium on specific reaction conditions and surfactant combinations. In this invited review, we apply a molecular-level understanding of chemical precursor reactivity to reliably control the morphology, composition and intimate architecture (core/shell vs. alloyed) of semiconductor nanocrystals. We also describe our work aimed at achieving highly selective, low-temperature photochemical methods for the synthesis of semiconductor–metal and semiconductor–metal oxide photocatalytic nanocomposites. In addition, we describemore » our work on surface modification of semiconductor nanocrystal quantum dots using new approaches and methods that bypass ligand exchange, retaining the nanocrystal's native ligands and original optical properties, as well as on spectroscopic methods of characterization useful in determining surface ligand organization and chemistry. Using recent examples from our group and collaborators, we demonstrate how these efforts have lead to faster, wider and more systematic application of semiconductor nanocrystal-based materials to biological imaging and tracking, and to photocatalysis of unconventional substrates. We believe techniques and methods borrowed from inorganic chemistry (including coordination, organometallic and solid state chemistry) have much to offer in reaching a better understanding of the synthesis, functionalization and real-life application of such exciting materials as semiconductor nanocrystals (quantum dots, rods, tetrapods, etc.).« less

Methods for the photochemical utilization of solar energy

NASA Technical Reports Server (NTRS)

Schwerzel, R. E.

1978-01-01

The paper considers the 'ground rules' which govern the efficiency of photochemical solar energy conversion and then summarizes the most promising approaches in each of three categories: photochemically assisted thermal systems for the heating and/or cooling of structures; photogalvanic systems for the production of electrical power in applications, such as photorechargeable batteries or inexpensive 'solar cells'; and photochemical formation of fuels for combustion and for use as chemical feedstocks or foods. Three concepts for the photochemical utilization of solar energy in space are found to be particularly promising: (1) photochemical trans-cis isomerization of indigold dyes for photoassisted heating or cooling, (2) the redox stabilized photoelectrolysis cell for the production of hydrogen (and/or oxygen or other useful chemicals), and (3) the liquid-junction photovoltaic cell for the production of electrical power.

The health implications of unconventional natural gas development in Pennsylvania.

PubMed

Peng, Lizhong; Meyerhoefer, Chad; Chou, Shin-Yi

2018-06-01

We investigate the health impacts of unconventional natural gas development of Marcellus shale in Pennsylvania between 2001 and 2013 by merging well permit data from the Pennsylvania Department of Environmental Protection with a database of all inpatient hospital admissions. After comparing changes in hospitalization rates over time for air pollution-sensitive diseases in counties with unconventional gas wells to changes in hospitalization rates in nonwell counties, we find a significant association between shale gas development and hospitalizations for pneumonia among the elderly, which is consistent with higher levels of air pollution resulting from unconventional natural gas development. We note that the lack of any detectable impact of shale gas development on younger populations may be due to unobserved factors contemporaneous with drilling, such as migration. Copyright © 2018 John Wiley & Sons, Ltd.

On the mechanism of non-radiative decay of blue fluorescent protein chromophore: New insight from the excited-state molecular dynamics simulations and potential energy calculations

NASA Astrophysics Data System (ADS)

Zhao, Li; Liu, Jian-Yong; Zhou, Pan-Wang

2017-11-01

A detailed theoretical investigation based on the ab initio on-the-fly surface hopping dynamics simulations and potential energy surfaces calculations has been performed to unveil the mechanism of the photoinduced non-adiabatic relaxation process of the isolated blue fluorescent protein (BFP) chromophore in gas phase. The data analysis presents that the dominant reaction coordinate of the BFP chromophore is driven by a rotation motion around the CC double bridging bond, which is in remarkable difference with a previous result which supports a Hula-Twist rotation pattern. Such behavior is consistent with the double bond rotation pattern of the GFP neutral chromophore. In addition, the dynamics simulations give an estimated decay time of 1.1 ps for the S1 state, which is agrees well with the experimental values measured in proteins. The present work offers a straightforward understanding for the decay mechanism of the BFP chromophore and suggestions of the photochemical properties of analogous protein chromophores. We hope the current work would be helpful for further exploration of the BFP photochemical and photophysical properties in various environments, and can provide guidance and prediction for rational design of the fluorescent proteins catering for different demands.

NIR-Vis-UV Light-Responsive Actuator Films of Polymer-Dispersed Liquid Crystal/Graphene Oxide Nanocomposites.

PubMed

Cheng, Zhangxiang; Wang, Tianjie; Li, Xiao; Zhang, Yihe; Yu, Haifeng

2015-12-16

To take full advantage of sunlight for photomechanical materials, NIR-vis-UV light-responsive actuator films of polymer-dispersed liquid crystal (PDLC)/graphene oxide (GO) nanocomposites were fabricated. The strategy is based on phase transition of LCs from nematic to isotropic phase induced by combination of photochemical and photothermal processes in the PDLC/GO nanocomposites. Upon mechanical stretching of the film, both topological shape change and mesogenic alignment occurred in the separated LC domains, enabling the film to respond to NIR-vis-UV light. The homodispersed GO flakes act as photoabsorbent and nanoscale heat source to transfer NIR or VIS light into thermal energy, heating the film and photothermally inducing phase transition of LC microdomains. By utilizing photochemical phase transition of LCs upon UV-light irradiation, one azobenzene dye was incorporated into the LC domains, endowing the nanocomposite films with UV-responsive property. Moreover, the light-responsive behaviors can be well-controlled by adjusting the elongation ratio upon mechanical treatment. The NIR-vis-UV light-responsive PDLC/GO nanocomposite films exhibit excellent properties of easy fabrication, low-cost, and good film-forming and mechanical features, promising their numerous applications in the field of soft actuators and optomechanical systems driven directly by sunlight.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and unsaturated aldehydes were detected and a reaction pathway, initiated by a H-abstraction of the surfactant by the excited HA*, has been proposed. This mechanism infers that the presence of the surface microlayer will enhance protonation and self-reactions, leading to the formation of dimers as suggested in [6]. These products could explain the formation of the unsaturated products observed. To confirm the hypothesis of an initiative step of H-abstraction, the system was simplified using OH radicals, generated by the photolysis of H2O2, in presence of an artificial organic layer of nonanoic acid. The VOCs produced, monitored by PTR/SRI-TOF-MS in NO+ and H3O+ ionization mode, were less abundant compared to the system with HA, but the same classes of products could be observed, including oxidation products such as aldehydes but also unsatured products like dienes. The underlying water was sampled before and after the experiment and analysed by HR-ESI-MS, showing mostly enrichment of oxidative products, such as hydroxy- and keto-acids immediately derived from the photochemical oxidation of the nonanoic acid layer. These products, showing lower volatility and higher polarity, partition preferentially to the bulk water. The results of this simplified system confirm the reaction mechanism proposed and the role an organic layer can play in the photochemical formation of VOCs, which could influence the marine boundary layer chemistry. 1. Peter S. Liss, R.A.D., ed. Sea Surface and Global Change. 1997, Cambridge University Press: Cambridge. 509. 2. Griffith, E.C. and V. Vaida, In situ observation of peptide bond formation at the water-air interface. Proceedings of the National Academy of Sciences, 2012. 109(39): p. 15697-15701. 3. Sinreich, R., et al., Ship-based detection of glyoxal over the remote tropical Pacific Ocean. Atmospheric Chemistry and Physics, 2010. 10(23): p. 11359-11371. 4. Kieber, R.J., X.L. Zhou, and K. Mopper, Formation of carbonyl-compounds from uv-induced photodegradation of humic substances in natural-waters - fate of riverine carbon in the sea. Limnology and Oceanography, 1990. 35(7): p. 1503-1515. 5. R. Ciuraru, L. Fine, M. van Pinxteren, B. D'Anna, H. Herrmann, C. George, Unravelling new processes at interfaces: chemical isoprene production at the sea surface. submitted. 6. Griffith, E.C., et al., Photoinitiated Synthesis of Self-Assembled Vesicles. Journal of the American Chemical Society, 2014. 136(10): p. 3784-3787.

Theory of disordered unconventional superconductors

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

Keles, A.; Andreev, A. V.; Spivak, B. Z., E-mail: spivak@uw.edu

In contrast to conventional s-wave superconductivity, unconventional (e.g., p- or d-wave) superconductivity is strongly suppressed even by relatively weak disorder. Upon approaching the superconductormetal transition, the order parameter amplitude becomes increasingly inhomogeneous, leading to effective granularity and a phase ordering transition described by the Mattis model of spin glasses. One consequence of this is that at sufficiently low temperatures, between the clean unconventional superconducting and the diffusive metallic phases, there is necessarily an intermediate superconducting phase that exhibits s-wave symmetry on macroscopic scales.

PerSEUS: Ultra-Low-Power High Performance Computing for Plasma Simulations

NASA Astrophysics Data System (ADS)

Doxas, I.; Andreou, A.; Lyon, J.; Angelopoulos, V.; Lu, S.; Pritchett, P. L.

2017-12-01

Peta-op SupErcomputing Unconventional System (PerSEUS) aims to explore the use for High Performance Scientific Computing (HPC) of ultra-low-power mixed signal unconventional computational elements developed by Johns Hopkins University (JHU), and demonstrate that capability on both fluid and particle Plasma codes. We will describe the JHU Mixed-signal Unconventional Supercomputing Elements (MUSE), and report initial results for the Lyon-Fedder-Mobarry (LFM) global magnetospheric MHD code, and a UCLA general purpose relativistic Particle-In-Cell (PIC) code.

Comparison of Direct and Indirect Photolysis in Imazosulfuron Photodegradation.

PubMed

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

2017-04-19

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

Enhancing the efficacy of cytotoxic agents for cancer therapy using photochemical internalisation

PubMed Central

Moore, Caroline M.; Loizidou, Marilena; MacRobert, Alexander J.; Woodhams, Josephine H.

2016-01-01

Photochemical internalisation (PCI) is a technique for improving cellular delivery of certain bioactive agents which are prone to sequestration within endolysosomes. There is a wide range of agents suitable for PCI‐based delivery including toxins, oligonucleotides, genes and immunoconjugates which demonstrates the versatility of this technique. The basic mechanism of PCI involves triggering release of the agent from endolysosomes within the target cells using a photosensitiser which is selectively retained with the endolysosomal membranes. Excitation of the photosensitiser by visible light leads to disruption of the membranes via photooxidative damage thereby releasing the agent into the cytosol. This treatment enables the drugs to reach their intended subcellular target more efficiently and improves their efficacy. In this review we summarise the applications of this technique with the main emphasis placed on cancer chemotherapy. PMID:25758607

Chemical degradation of proteins in the solid state with a focus on photochemical reactions.

PubMed

Mozziconacci, Olivier; Schöneich, Christian

2015-10-01

Protein pharmaceuticals comprise an increasing fraction of marketed products but the limited solution stability of proteins requires considerable research effort to prepare stable formulations. An alternative is solid formulation, as proteins in the solid state are thermodynamically less susceptible to degradation. Nevertheless, within the time of storage a large panel of kinetically controlled degradation reactions can occur such as, e.g., hydrolysis reactions, the formation of diketopiperazine, condensation and aggregation reactions. These mechanisms of degradation in protein solids are relatively well covered by the literature. Considerably less is known about oxidative and photochemical reactions of solid proteins. This review will provide an overview over photolytic and non-photolytic degradation reactions, and specially emphasize mechanistic details on how solid structure may affect the interaction of protein solids with light. Copyright © 2014 Elsevier B.V. All rights reserved.

Recent Advances in the Synthesis of Cyclobutanes by Olefin [2 + 2] Photocycloaddition Reactions

PubMed Central

2016-01-01

The [2 + 2] photocycloaddition is undisputedly the most important and most frequently used photochemical reaction. In this review, it is attempted to cover all recent aspects of [2 + 2] photocycloaddition chemistry with an emphasis on synthetically relevant, regio-, and stereoselective reactions. The review aims to comprehensively discuss relevant work, which was done in the field in the last 20 years (i.e., from 1995 to 2015). Organization of the data follows a subdivision according to mechanism and substrate classes. Cu(I) and PET (photoinduced electron transfer) catalysis are treated separately in sections 2 and 4, whereas the vast majority of photocycloaddition reactions which occur by direct excitation or sensitization are divided within section 3 into individual subsections according to the photochemically excited olefin. PMID:27018601

Biological applications and effects of optical masers

NASA Astrophysics Data System (ADS)

Ham, William T., Jr.; Mueller, Harold A.; Guerry, R. Kennon; Guerry, Dupont, III; Cleary, Stephen F.

1989-10-01

Research was continued on basic mechanisms involving photochemical events in mammalian retina by injecting superoxide dismutase (SOD) and catalase (CAT) into vitreous of monkey eye before and after exposure to blue light. Intravitreal injection plus exposure to blue light proved toxic to the eye and no information on oxygen radicals was obtained. The argon krypton laser line at 488 nm was acoustically modulated at 1, 10, and 20 MHz for 1000s exposures of the monkey retina. Threshold radiant exposures at 20 MHz were 3 times lower than those at 1 MHz. The oxygen effect (high PO2 arterial blood-oxygen) on retinal damage was investigated at 3 wavelengths (540, 640, 840 nm). Lack of an appreciable O2 effect at 640 nm and none at 840 nm provides evidence that photochemical toxicity is confined primarily to wavelengths below 640 nm.

Investigating operation at geometrically unconventional intersections.

DOT National Transportation Integrated Search

2014-08-01

This report documents the development of decision assistance curves (DAC) for unconventional intersections, particularly : median U-turns (MUT), continuous flow intersections (CFI), and jughandles. The operational measure of effectiveness : such as d...

Unconventional Hydrocarbon Development Hazards Within the Central United States. Report 1: Overview and Potential Risk to Infrastructure

DTIC Science & Technology

2015-08-01

of the injection purpose, i.e., secondary oil and gas recovery, disposal of waste fluids, geothermal energy, and/or UHP hydraulic fracturing...activities such as reservoir impoundment, mining, wastewater injection, geothermal systems and CO2 capture have been linked directly to induced...activities, e.g., deep fluid injection, geothermal injection, and/or UHP wells, that critically affect deep lithologies and alter the existing mechanical

The Arrhenius Law and Storage of Food in a Freezer

NASA Astrophysics Data System (ADS)

Leenson, I. A.

1999-04-01

This article contains a brief review of some "unconventional" applications of the Arrhenius law. One such example is proposed as a problem concerning the shelf-life of frozen food (Italian pizza) at temperatures ranging from 0 to -18 °C. The effective activation energy (180 kJ/mole) calculated from the information presented by the manufacturer implies that the most probable mechanism of pizza deterioration on storage is enzyme and microbial destruction.

Mass-dependent and Mass-independent Sulphur Isotope Fractionation Accompanying Thermal- and Photo-chemical Decomposition of Sulphur Bearing Organic Compounds

NASA Astrophysics Data System (ADS)

Oduro, Harry; Izon, Gareth; Ono, Shuhei

2014-05-01

The bimodal S-isotope record, specifically the transition from mass independent (MIF) to mass dependent fractionation (MDF), is perhaps the most widely cited line of evidence for an irreversible rise in atmospheric oxygen at ca. 2.4Ga. The production and preservation of S-MIF, manifested in both Δ33S and Δ36S, within the geological record are linked to atmospheric O2 via a number of arguments. However, to date, the only mechanism capable of generating S-MIF consistent with the Archaean sedimentary records involves gas-phase ultraviolet irradiation of SO21 photolysis. More recently, Δ33S S-MIF trends have been reported from en vitro thermochemical sulphate reduction (TSR) experiments, prompting authors to question the importance of S-MIF as a proxy for Earth oxidation2. Importantly, whilst emerging TSR experiments3,4 affirm the reported Δ33S trends2, these experiments fail to identify correlated S-MIF between Δ33S and Δ36S values3,4. Realization that S-MIF is confined to Δ33S during TSR, precludes TSR as a mechanism responsible for the origin of the Archaean S-MIF record but strongly suggests the effect originating from a magnetic isotope effect (MIE) associated with 33S nucleus3,4. Clearly, photochemical and thermochemical processes impart different Δ36S/Δ33S trends with significant variation in δ34S; however, a complete experimental elucidation of mechanisms responsible for the S-MIF and S-MIE signatures is lacking. Interestingly, a complete understanding of the S-isotope chemistry during thermal- and photo-chemical decomposition may reveal wavelength and thermal dependence archived in the sedimentary record. Here we extend the experimental database to explore the magnitude and sign of Δ36S/Δ33S and δ34S produced during both photo- and thermochemical processes. Here the organic sulphur compounds (OSC) utilized in these experiments carries diagnostic Δ36S/Δ33S patterns that differ from those reported from photolysis experiment SO2 and from the Archaean sedimentary record. Further thermal decomposition of several sulphur containing compounds with; 1) an aliphatic-S (e.g., diphenyl disulphide), 2) tri-substituted aromatic-S (trithiane), and S-amino acids (e.g., cysteine, methionine, taurine, and glutathionine) were tested for four S-isotope fractionation under vacuum. Among these, aromatic trithiane produced anomalous 33S up to 1.3‰, indicating thermal decomposition through radical chemistry, producing S-MIE. While taurine with sulphonic acid (R-SO2OH) functional groups yielded S-MDF up to 15‰ (between the AVS and the residual OSC), which is consistent with estimated zero-point energy shifts for thiol (R-SH), and thiyl (R-S-CH3) groups of cysteine and methionine, respectively. These results suggest that OSC might undergo either thermal or photochemical decomposition and the S-MIF, S-MDF, and S-MIE signatures may be archived in the geologic record. The emerging mechanisms responsible for these isotope signals and their implications will be discussed in more detail. Ultimately this work offers a framework where these signals can be used as a diagnostic marker to distinguish between thermo- and photochemical processes. References: 1. Farquhar et al., Science 2000 2. Watanabe et al., Science 2010; 3. Oduro et al., PNAS 2011; 4. Kopf and Ono, GCA 2012.

Chemical modification of wood

Treesearch

Roger M. Rowell

2007-01-01

After millions of years of evolution, wood was designed to perform in a wet environment, and nature is programmed to recycle it, in a timely way, back to the basic building blocks of carbon dioxide and water through biological, thermal, aqueous, photochemical, chemical, and mechanical degradation. The properties of wood are, for the most part, a result of the chemistry...

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide.

PubMed

Kirkegaard, Marie C; Miskowiec, Andrew; Ambrogio, Michael W; Anderson, Brian B

2018-05-21

We have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.

Unconventional Oil and Gas Extraction Effluent Guidelines

EPA Pesticide Factsheets

Overview and documents for the Unconventional Oil and Gas Extraction Pretreatment Standards final rule (6/28/2016), direct final rule (Sept. 2016) and proposed rule (Sept. 2016). 40 CFR Part 435, Subpart C.

Quantity of flowback and produced waters from unconventional oil and gas exploration.

PubMed

Kondash, Andrew J; Albright, Elizabeth; Vengosh, Avner

2017-01-01

The management and disposal of flowback and produced waters (FP water) is one of the greatest challenges associated with unconventional oil and gas development. The development and production of unconventional natural gas and oil is projected to increase in the coming years, and a better understanding of the volume and quality of FP water is crucial for the safe management of the associated wastewater. We analyzed production data using multiple statistical methods to estimate the total FP water generated per well from six of the major unconventional oil and gas formations in the United States. The estimated median volume ranges from 1.7 to 14.3millionL (0.5 to 3.8milliongal) of FP per well over the first 5-10years of production. Using temporal volume production and water quality data, we show a rapid increase of the salinity associated with a decrease of FP production rates during the first months of unconventional oil and gas production. Based on mass-balance calculations, we estimate that only 4-8% of FP water is composed of returned hydraulic fracturing fluids, while the remaining 92-96% of FP water is derived from naturally occurring formation brines that is extracted together with oil and gas. The salinity and chemical composition of the formation brines are therefore the main limiting factors for beneficial reuse of unconventional oil and gas wastewater. Copyright © 2016 Elsevier B.V. All rights reserved.

A Comparison of the Impacts of Wind Energy and Unconventional Gas Development on Land-use and Ecosystem Services: An Example from the Anadarko Basin of Oklahoma, USA.

PubMed

Davis, Kendall M; Nguyen, Michael N; McClung, Maureen R; Moran, Matthew D

2018-05-01

The United States energy industry is transforming with the rapid development of alternative energy sources and technological advancements in fossil fuels. Two major changes include the growth of wind turbines and unconventional oil and gas. We measured land-use impacts and associated ecosystem services costs of unconventional gas and wind energy development within the Anadarko Basin of the Oklahoma Woodford Shale, an area that has experienced large increases in both energy sectors. Unconventional gas wells developed three times as much land compared to wind turbines (on a per unit basis), resulting in higher ecosystem services costs for gas. Gas wells had higher impacts on intensive agricultural lands (i.e., row crops) compared to wind turbines that had higher impacts on natural grasslands/pastures. Because wind turbines produced on average less energy compared to gas wells, the average land-use-related ecosystem cost per gigajoule of energy produced was almost the same. Our results demonstrate that both unconventional gas and wind energy have substantial impacts on land use, which likely affect wildlife populations and land-use-related ecosystem services. Although wind energy does not have the associated greenhouse gas emissions, we suggest that the direct impacts on ecosystems in terms of land use are similar to unconventional fossil fuels. Considering the expected rapid global expansion of these two forms of energy production, many ecosystems are likely to be at risk.

Hidden magnetism and quantum criticality in the heavy fermion superconductor CeRhIn5.

PubMed

Park, Tuson; Ronning, F; Yuan, H Q; Salamon, M B; Movshovich, R; Sarrao, J L; Thompson, J D

2006-03-02

With only a few exceptions that are well understood, conventional superconductivity does not coexist with long-range magnetic order (for example, ref. 1). Unconventional superconductivity, on the other hand, develops near a phase boundary separating magnetically ordered and magnetically disordered phases. A maximum in the superconducting transition temperature T(c) develops where this boundary extrapolates to zero Kelvin, suggesting that fluctuations associated with this magnetic quantum-critical point are essential for unconventional superconductivity. Invariably, though, unconventional superconductivity masks the magnetic phase boundary when T < T(c), preventing proof of a magnetic quantum-critical point. Here we report specific-heat measurements of the pressure-tuned unconventional superconductor CeRhIn5 in which we find a line of quantum-phase transitions induced inside the superconducting state by an applied magnetic field. This quantum-critical line separates a phase of coexisting antiferromagnetism and superconductivity from a purely unconventional superconducting phase, and terminates at a quantum tetracritical point where the magnetic field completely suppresses superconductivity. The T --> 0 K magnetic field-pressure phase diagram of CeRhIn5 is well described with a theoretical model developed to explain field-induced magnetism in the high-T(c) copper oxides, but in which a clear delineation of quantum-phase boundaries has not been possible. These experiments establish a common relationship among hidden magnetism, quantum criticality and unconventional superconductivity in copper oxides and heavy-electron systems such as CeRhIn5.

Catalysis of Photochemical Reactions.

ERIC Educational Resources Information Center

Albini, A.

1986-01-01

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

Chromophore Protonation State Controls Photoswitching of the Fluoroprotein asFP595

PubMed Central

Schäfer, Lars V.; Groenhof, Gerrit; Boggio-Pasqua, Martial; Robb, Michael A.; Grubmüller, Helmut

2008-01-01

Fluorescent proteins have been widely used as genetically encodable fusion tags for biological imaging. Recently, a new class of fluorescent proteins was discovered that can be reversibly light-switched between a fluorescent and a non-fluorescent state. Such proteins can not only provide nanoscale resolution in far-field fluorescence optical microscopy much below the diffraction limit, but also hold promise for other nanotechnological applications, such as optical data storage. To systematically exploit the potential of such photoswitchable proteins and to enable rational improvements to their properties requires a detailed understanding of the molecular switching mechanism, which is currently unknown. Here, we have studied the photoswitching mechanism of the reversibly switchable fluoroprotein asFP595 at the atomic level by multiconfigurational ab initio (CASSCF) calculations and QM/MM excited state molecular dynamics simulations with explicit surface hopping. Our simulations explain measured quantum yields and excited state lifetimes, and also predict the structures of the hitherto unknown intermediates and of the irreversibly fluorescent state. Further, we find that the proton distribution in the active site of the asFP595 controls the photochemical conversion pathways of the chromophore in the protein matrix. Accordingly, changes in the protonation state of the chromophore and some proximal amino acids lead to different photochemical states, which all turn out to be essential for the photoswitching mechanism. These photochemical states are (i) a neutral chromophore, which can trans-cis photoisomerize, (ii) an anionic chromophore, which rapidly undergoes radiationless decay after excitation, and (iii) a putative fluorescent zwitterionic chromophore. The overall stability of the different protonation states is controlled by the isomeric state of the chromophore. We finally propose that radiation-induced decarboxylation of the glutamic acid Glu215 blocks the proton transfer pathways that enable the deactivation of the zwitterionic chromophore and thus leads to irreversible fluorescence. We have identified the tight coupling of trans-cis isomerization and proton transfers in photoswitchable proteins to be essential for their function and propose a detailed underlying mechanism, which provides a comprehensive picture that explains the available experimental data. The structural similarity between asFP595 and other fluoroproteins of interest for imaging suggests that this coupling is a quite general mechanism for photoswitchable proteins. These insights can guide the rational design and optimization of photoswitchable proteins. PMID:18369426

Enhanced expression of Rubisco activase splicing variants differentially affects Rubisco activity during low temperature treatment in Lolium perenne.

PubMed

Jurczyk, Barbara; Pociecha, Ewa; Grzesiak, Maciej; Kalita, Katarzyna; Rapacz, Marcin

2016-07-01

Alternative splicing of the Rubisco activase gene was shown to be a point for optimization of photosynthetic carbon assimilation. It can be expected to be a stress-regulated event that depends on plant freezing tolerance. The aim of the study was to examine the relationships among Rubisco activity, the expression of two Rubisco activase splicing variants and photoacclimation to low temperature. The experiment was performed on two Lolium perenne genotypes with contrasting levels of freezing tolerance. The study investigated the effect of pre-hardening (15°C) and cold acclimation (4°C) on net photosynthesis, photosystem II photochemical activity, Rubisco activity and the expression of two splicing variants of the Rubisco activase gene. The results showed an induction of Rubisco activity at both 15°C and 4°C only in a highly freezing-tolerant genotype. The enhanced Rubisco activity after pre-hardening corresponded to increased expression of the splicing variant representing the large isoform, while the increase in Rubisco activity during cold acclimation was due to the activation of both transcript variants. These boosts in Rubisco activity also corresponded to an activation of non-photochemical mechanism of photoacclimation induced at low temperature exclusively in the highly freezing-tolerant genotype. In conclusion, enhanced expression of Rubisco activase splicing variants caused an increase in Rubisco activity during pre-hardening and cold acclimation in the more freezing-tolerant Lolium perenne genotype. The induction of the transcript variant representing the large isoform may be an important element of increasing the carbon assimilation rate supporting the photochemical mechanism of photosynthetic acclimation to cold. Copyright © 2016 Elsevier GmbH. All rights reserved.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

NASA Astrophysics Data System (ADS)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-01-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

A New Pathway for Protein Haptenation by β-Lactams.

PubMed

Pérez-Ruíz, Raúl; Lence, Emilio; Andreu, Inmaculada; Limones-Herrero, Daniel; González-Bello, Concepción; Miranda, Miguel A; Jiménez, M Consuelo

2017-10-09

The covalent binding of β-lactams to proteins upon photochemical activation has been demonstrated by using an integrated approach that combines photochemical, proteomic and computational studies, selecting human serum albumin (HSA) as a target protein and ezetimibe (1) as a probe. The results have revealed a novel protein haptenation pathway for this family of drugs that is an alternative to the known nucleophilic ring opening of β-lactams by the free amino group of lysine residues. Thus, photochemical ring splitting of the β-lactam ring, following a formal retro-Staudinger reaction, gives a highly reactive ketene intermediate that is trapped by the neighbouring lysine residues, leading to an amide adduct. For the investigated 1/HSA system, covalent modification of residues Lys414 and Lys525, which are located in sub-domains IIIA and IIIB, respectively, occurs. The observed photobinding may constitute the key step in the sequence of events leading to photoallergy. Docking and molecular dynamics simulation studies provide an insight into the molecular basis of the selectivity of 1 for these HSA sub-domains and the covalent modification mechanism. Computational studies also reveal positive cooperative binding of sub-domain IIIB that explains the experimentally observed modification of Lys414, which is located in a barely accessible pocket (sub-domain IIIA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

on the growth and photochemical efficiency of Acropora cervicornis

NASA Astrophysics Data System (ADS)

Enochs, I. C.; Manzello, D. P.; Carlton, R.; Schopmeyer, S.; van Hooidonk, R.; Lirman, D.

2014-06-01

The effects of light and elevated pCO2 on the growth and photochemical efficiency of the critically endangered staghorn coral, Acropora cervicornis, were examined experimentally. Corals were subjected to high and low treatments of CO2 and light in a fully crossed design and monitored using 3D scanning and buoyant weight methodologies. Calcification rates, linear extension, as well as colony surface area and volume of A. cervicornis were highly dependent on light intensity. At pCO2 levels projected to occur by the end of the century from ocean acidification (OA), A. cervicornis exhibited depressed calcification, but no change in linear extension. Photochemical efficiency ( F v / F m ) was higher at low light, but unaffected by CO2. Amelioration of OA-depressed calcification under high-light treatments was not observed, and we suggest that the high-light intensity necessary to reach saturation of photosynthesis and calcification in A. cervicornis may limit the effectiveness of this potentially protective mechanism in this species. High CO2 causes depressed skeletal density, but not linear extension, illustrating that the measurement of extension by itself is inadequate to detect CO2 impacts. The skeletal integrity of A. cervicornis will be impaired by OA, which may further reduce the resilience of the already diminished populations of this endangered species.

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

PubMed Central

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

2016-01-01

The photochemical reflectance index (PRI) is a proxy for the activity of the photoprotective xanthophyll cycle and photosynthetic light use efficiency (LUE) in plants. Evergreen conifers downregulate photosynthesis in autumn in response to low temperature and shorter photoperiod, and the dynamic xanthophyll cycle-mediated non-photochemical quenching (NPQ) is replaced by sustained NPQ. We hypothesized that this shift in xanthophyll cycle-dependent energy partitioning during the autumn is the cause for variations in the PRI–LUE relationship. In order to test our hypothesis, we characterized energy partitioning and pigment composition during a simulated summer–autumn transition in a conifer and assessed the effects of temperature and photoperiod on the PRI–LUE relationship. We measured gas exchange, chlorophyll fluorescence and leaf reflectance during the photosynthetic downregulation in Pinus strobus L. seedlings exposed to low temperature/short photoperiod or elevated temperature/short photoperiod conditions. Shifts in energy partitioning during simulated autumn were observed when the pools of chlorophylls decreased and pools of photoprotective carotenoids increased. On a seasonal timescale, PRI was controlled by carotenoid pool sizes rather than xanthophyll cycle dynamics. Photochemical reflectance index variation under cold autumn conditions mainly reflected long-term pigment pool adjustments associated with sustained NPQ, which impaired the PRI–LUE relationship. Exposure to warm autumn conditions prevented the induction of sustained NPQ but still impaired the PRI–LUE relationship. We therefore conclude that alternative zeaxanthin-independent NPQ mechanisms, which remain undetected by the PRI, are present under both cold and warm autumn conditions, contributing to the discrepancy in the PRI–LUE relationship during autumn. PMID:26846980

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

PubMed

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

2016-03-01

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

Photochemical conversion of tin-oxo cage compounds studied using hard x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Yu; Haitjema, Jarich; Liu, Xiaomeng; Johansson, Fredrik; Lindblad, Andreas; Castellanos, Sonia; Ottosson, Niklas; Brouwer, Albert M.

2017-03-01

Several metal-containing molecular inorganic materials are currently considered as photoresists for extreme ultraviolet lithography (EUVL). This is primarily due to their high EUV absorption cross section and small building block size, properties which potentially allow both high sensitivity and resolution as well as low line-edge roughness. The photochemical reaction mechanisms that allow these kinds of materials to function as photoresists, however, are still poorly understood. As a step in this direction, we here discuss photochemical reactions upon deep UV (DUV) irradiation of a model negative-tone EUV photoresist material, namely the well-defined molecular tin-oxo cage compound [(SnR)12O14(OH)6]X2 (R = organic group; X = anion) which is spin coated to thin layers of 20 nm. The core electronic structure (Sn 3d, O 1s and C 1s) of fresh and DUV exposed films were then investigated using synchrotron radiationbased hard X-ray photoelectron spectroscopy (HAXPES). This method provides information about the structure and chemical state of the respective atoms in the material. We performed a comparative HAXPES study of the composition of the tin-oxo cage compound [(SnR)12O14(OH)6](OH)2, either fresh directly after spin-coated vs. DUV-exposed materials under either ambient condition or under a dry N2 atmosphere. Different chemical oxidation states and concentrations of atoms and atom types in the fresh and exposed films were found. We further found that the chemistry resulting from exposure in air and N2 is strikingly different, clearly illustrating the influence of film-gas interactions on the (photo)chemical processes that eventually determine the photoresist. Finally, a mechanistic hypothesis for the basic DUV photoreactions in molecular tin-oxo cages is proposed.

Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China

NASA Astrophysics Data System (ADS)

Shao, Ping; An, Junlin; Xin, Jinyuan; Wu, Fangkun; Wang, Junxiu; Ji, Dongsheng; Wang, Yuesi

2016-07-01

Volatile organic compounds (VOCs) were continuously observated in a northern suburb of Nanjing, a typical industrial area in the Yangtze River Delta, in a summer observation period from 15th May to 31st August 2013. The average concentration of total VOCs was (34.40 ± 25.20) ppbv, including alkanes (14.98 ± 12.72) ppbv, alkenes (7.35 ± 5.93) ppbv, aromatics (9.06 ± 6.64) ppbv and alkynes (3.02 ± 2.01) ppbv, respectively. Source apportionment via Positive Matrix Factorization was conducted, and six major sources of VOCs were identified. The industry-related sources, including industrial emissions and industrial solvent usage, occupied the highest proportion, accounting for about 51.26% of the VOCs. Vehicular emissions occupied the second highest proportion, accounting for about 34.08%. The rest accounted for about 14.66%, including vegetation emission and liquefied petroleum gas/natural gas usage. Contributions of VOCs to photochemical O3 formation were evaluated by the application of a detailed chemical mechanism model (NCAR MM). Alkenes were the dominant contributors to the O3 photochemical production, followed by aromatics and alkanes. Alkynes had a very small impact on photochemical O3 formation. Based on the outcomes of the source apportionment, a sensitivity analysis of relative O3 reduction efficiency (RORE), under different source removal regimes such as using the reduction of VOCs from 10% to 100% as input, was conducted. The RORE was the highest (~ 20%-40%) when the VOCs from solvent-related sources decreased by 40%. The highest RORE values for vegetation emissions, industrial emissions, vehicle exhaust, and LPG/NG usage were presented in the scenarios of 50%, 80%, 40% and 40%, respectively.

Unconventional Transport Routes of Soluble and Membrane Proteins and Their Role in Developmental Biology

PubMed Central

Pompa, Andrea; De Marchis, Francesca; Pallotta, Maria Teresa; Benitez-Alfonso, Yoselin; Jones, Alexandra; Schipper, Kerstin; Moreau, Kevin; Žárský, Viktor; Di Sansebastiano, Gian Pietro; Bellucci, Michele

2017-01-01

Many proteins and cargoes in eukaryotic cells are secreted through the conventional secretory pathway that brings proteins and membranes from the endoplasmic reticulum to the plasma membrane, passing through various cell compartments, and then the extracellular space. The recent identification of an increasing number of leaderless secreted proteins bypassing the Golgi apparatus unveiled the existence of alternative protein secretion pathways. Moreover, other unconventional routes for secretion of soluble or transmembrane proteins with initial endoplasmic reticulum localization were identified. Furthermore, other proteins normally functioning in conventional membrane traffic or in the biogenesis of unique plant/fungi organelles or in plasmodesmata transport seem to be involved in unconventional secretory pathways. These alternative pathways are functionally related to biotic stress and development, and are becoming more and more important in cell biology studies in yeast, mammalian cells and in plants. The city of Lecce hosted specialists working on mammals, plants and microorganisms for the inaugural meeting on “Unconventional Protein and Membrane Traffic” (UPMT) during 4–7 October 2016. The main aim of the meeting was to include the highest number of topics, summarized in this report, related to the unconventional transport routes of protein and membranes. PMID:28346345

A Simple Parallel Photochemical Reactor for Photodecomposition Studies

ERIC Educational Resources Information Center

Xiaobo Chen; Halasz, Sarah M.; Giles, Eric C.; Mankus, Jessica V.; Johnson, Joseph C.; Burda, Clemens

2006-01-01

A simple and useful parallel photochemical reactor intended to study the photodecomposition of dyes using semiconductor photocatalysis is presented. The photochemical reactions are followed through time-dependent changes in the ground-state absorption spectra of the dyes.

EMERGING TECHNOLOGY PROJECT BULLETIN: LASER INDUCED PHOTOCHEMICAL OXIDATIVE DESTRUCTION

EPA Science Inventory

The process developed by Energy and Environmental Engineering, Incorporated, is designed to photochemically oxidize organic compounds in wastewater by applying ultraviolet radiation using an Excimer laser. The photochemical reactor can destroy low to moderate concentrations...

Impact of Unconventional Gas Technology in the Annual Energy Outlook 2000

EIA Publications

2000-01-01

This paper describes the methodology used in the National Energy Modeling System (NEMS) to represent unconventional gas technologies and their impacts on projections in the Annual Energy Outlook 2000 (AEO2000).

Influence of Hot Plastic Deformation in γ and (γ + α) Area on the Structure and Mechanical Properties of High-Strength Low-Alloy (HSLA) Steel.

PubMed

Sas, Jan; Kvačkaj, Tibor; Milkovič, Ondrej; Zemko, Michal

2016-11-30

The main goal of this study was to develop a new processing technology for a high-strength low-alloy (HSLA) steel in order to maximize the mechanical properties attainable at its low alloy levels. Samples of the steel were processed using thermal deformation schedules carried out in single-phase (γ) and dual-phase (γ + α) regions. The samples were rolled at unconventional finishing temperatures, their final mechanical properties were measured, and their strength and plasticity behavior was analyzed. The resulting microstructures were observed using optical and transmission electron microscopy (TEM). They consisted of martensite, ferrite and (NbV)CN precipitates. The study also explored the process of ferrite formation and its influence on the mechanical properties of the material.

Seasonal Photochemical Transformations of Nitrogen Species in a Forest Stream and Lake

PubMed Central

Porcal, Petr; Kopáček, Jiří; Tomková, Iva

2014-01-01

The photochemical release of inorganic nitrogen from dissolved organic matter is an important source of bio-available nitrogen (N) in N-limited aquatic ecosystems. We conducted photochemical experiments and used mathematical models based on pseudo-first-order reaction kinetics to quantify the photochemical transformations of individual N species and their seasonal effects on N cycling in a mountain forest stream and lake (Plešné Lake, Czech Republic). Results from laboratory experiments on photochemical changes in N speciation were compared to measured lake N budgets. Concentrations of organic nitrogen (Norg; 40–58 µmol L−1) decreased from 3 to 26% during 48-hour laboratory irradiation (an equivalent of 4–5 days of natural solar insolation) due to photochemical mineralization to ammonium (NH4 +) and other N forms (Nx; possibly N oxides and N2). In addition to Norg mineralization, Nx also originated from photochemical nitrate (NO3 −) reduction. Laboratory exposure of a first-order forest stream water samples showed a high amount of seasonality, with the maximum rates of Norg mineralization and NH4 + production in winter and spring, and the maximum NO3 − reduction occurring in summer. These photochemical changes could have an ecologically significant effect on NH4 + concentrations in streams (doubling their terrestrial fluxes from soils) and on concentrations of dissolved Norg in the lake. In contrast, photochemical reactions reduced NO3 − fluxes by a negligible (<1%) amount and had a negligible effect on the aquatic cycle of this N form. PMID:25551441

Silicon solar cell process development, fabrication and analysis

NASA Technical Reports Server (NTRS)

Minahan, J. A.

1981-01-01

The fabrication of solar cells from several unconventional silicon materials is described, and cell performance measured and analyzed. Unconventional materials evaluated are edge defined film fed grown (EFG), heat exchanger method (HEM), dendritic web grown, and continuous CZ silicons. Resistivity, current voltage, and spectral sensitivity of the cells were measured. Current voltage was measured under AM0 and AM1 conditions. Maximum conversion efficiencies of cells fabricated from these and other unconventional silicons were compared and test results analyzed. The HEM and continuous CZ silicon were found to be superior to silicon materials considered previously.

Radon in unconventional natural gas from gulf coast geopressured-geothermal reservoirs

USGS Publications Warehouse

Kraemer, T.F.

1986-01-01

Radon-222 has been measured in natural gas produced from experimental geopressured-geothermal test wells. Comparison with published data suggests that while radon activity of this unconventional natural gas resource is higher than conventional gas produced in the gulf coast, it is within the range found for conventional gas produced throughout the U.S. A method of predicting the likely radon activity of this unconventional gas is described on the basis of the data presented, methane solubility, and known or assumed reservoir conditions of temperature, fluid pressure, and formation water salinity.

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati interstate...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati interstate...

Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

NASA Astrophysics Data System (ADS)

Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

2017-12-01

As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

Just fracking: a distributive environmental justice analysis of unconventional gas development in Pennsylvania, USA

NASA Astrophysics Data System (ADS)

Clough, Emily; Bell, Derek

2016-02-01

This letter presents a distributive environmental justice analysis of unconventional gas development in the area of Pennsylvania lying over the Marcellus Shale, the largest shale gas formation in play in the United States. The extraction of shale gas using unconventional wells, which are hydraulically fractured (fracking), has increased dramatically since 2005. As the number of wells has grown, so have concerns about the potential public health effects on nearby communities. These concerns make shale gas development an environmental justice issue. This letter examines whether the hazards associated with proximity to wells and the economic benefits of shale gas production are fairly distributed. We distinguish two types of distributive environmental justice: traditional and benefit sharing. We ask the traditional question: are there a disproportionate number of minority or low-income residents in areas near to unconventional wells in Pennsylvania? However, we extend this analysis in two ways: we examine income distribution and level of education; and we compare before and after shale gas development. This contributes to discussions of benefit sharing by showing how the income distribution of the population has changed. We use a binary dasymetric technique to remap the data from the 2000 US Census and the 2009-2013 American Communities Survey and combine that data with a buffer containment analysis of unconventional wells to compare the characteristics of the population living nearer to unconventional wells with those further away before and after shale gas development. Our analysis indicates that there is no evidence of traditional distributive environmental injustice: there is not a disproportionate number of minority or low-income residents in areas near to unconventional wells. However, our analysis is consistent with the claim that there is benefit sharing distributive environmental injustice: the income distribution of the population nearer to shale gas wells has not been transformed since shale gas development.

Fatty acid profile of unconventional oilseeds.

PubMed

Sabikhi, Latha; Sathish Kumar, M H

2012-01-01

The continued increase in human population has resulted in the rise in the demand as well as the price of edible oils, leading to the search for alternative unconventional sources of oils, particularly in the developing countries. There are hundreds of un- or underexplored plant seeds rich in oil suitable for edible or industrial purposes. Many of them are rich in polyunsaturated essential fatty acids, which establish their utility as "healthy oils." Some agrowaste products such as rice bran have gained importance as a potential source of edible oil. Genetic modification has paved the way for increasing the oil yields and improving the fatty acid profiles of traditional as well as unconventional oilseeds. Single cell oils are also novel sources of edible oil. Some of these unconventional oils may have excellent potential for medicinal and therapeutic uses, even if their low oil contents do not promote commercial production as edible oils. Copyright © 2012 Elsevier Inc. All rights reserved.

A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

NASA Astrophysics Data System (ADS)

Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H.

2004-09-01

A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.

Probing the unconventional superconducting state of LiFeAs by quasiparticle interference.

PubMed

Hänke, Torben; Sykora, Steffen; Schlegel, Ronny; Baumann, Danny; Harnagea, Luminita; Wurmehl, Sabine; Daghofer, Maria; Büchner, Bernd; van den Brink, Jeroen; Hess, Christian

2012-03-23

A crucial step in revealing the nature of unconventional superconductivity is to investigate the symmetry of the superconducting order parameter. Scanning tunneling spectroscopy has proven a powerful technique to probe this symmetry by measuring the quasiparticle interference (QPI) which sensitively depends on the superconducting pairing mechanism. A particularly well-suited material to apply this technique is the stoichiometric superconductor LiFeAs as it features clean, charge neutral cleaved surfaces without surface states and a relatively high T(c)∼18  K. Our data reveal that in LiFeAs the quasiparticle scattering is governed by a van Hove singularity at the center of the Brillouin zone which is in stark contrast to other pnictide superconductors where nesting is crucial for both scattering and s(±) superconductivity. Indeed, within a minimal model and using the most elementary order parameters, calculations of the QPI suggest a dominating role of the holelike bands for the quasiparticle scattering. Our theoretical findings do not support the elementary singlet pairing symmetries s(++), s(±), and d wave. This brings to mind that the superconducting pairing mechanism in LiFeAs is based on an unusual pairing symmetry such as an elementary p wave (which provides optimal agreement between the experimental data and QPI simulations) or a more complex order parameter (e.g., s+id wave symmetry).

Classification of gravity-flow deposits and their significance for unconventional petroleum exploration, with a case study from the Triassic Yanchang Formation (southern Ordos Basin, China)

NASA Astrophysics Data System (ADS)

Fan, Aiping; Yang, Renchao; (Tom) van Loon, A. J.; Yin, Wei; Han, Zuozhen; Zavala, Carlos

2018-08-01

The ongoing exploration for shale oil and gas has focused sedimentological research on the transport and deposition mechanisms of fine-grained sediments, and more specifically on fine-grained mass-flow deposits. It appears, however, that no easily applicable classification scheme for gravity-flow deposits exists, and that such classifications almost exclusively deal with sandy and coarser sediments. Since the lack of a good classification system for fine-grained gravity flow deposits hampers scientific communication and understanding, we propose a classification scheme on the basis of the mud content in combination with the presumed transport mechanism. This results in twelve types of gravity-flow deposits. In order to show the practical applicability of this classification system, we apply it to the Triassic lacustrine Yanchang Formation in the southern Ordos Basin (China), which contains numerous slumps, debris-flows deposits, turbidites and hyperpycnites. The slumps and debrites occur mostly close to a delta front, and the turbidites and hyperpycnites extend over large areas from the delta slopes into the basin plain. The case study shows that (1) mud cannot only be transported but also deposited under active hydrodynamic conditions; (2) fine-grained gravity-flow constitute a significant part of the lacustrine mudstones and shales; (3) muddy gravity flows are important for the transport and deposition of clastic particles, clay minerals and organic matter, and thus are important mechanisms involved in the generation of hydrocarbons, also largely determining the reservoir capability for unconventional petroleum.

Innate T cell responses in human gut.

PubMed

Meresse, Bertrand; Cerf-Bensussan, Nadine

2009-06-01

One arm of the gut-associated immune system is represented by a vast collection of T lymphocytes which participate in the subtle interplay between innate and adaptive immune mechanisms and maintain homeostasis at the main body external surface. Mounting data are providing exciting new insight into the innate-like mechanisms which enable intestinal T cells to rapidly sense local conditions and which broaden the spectrum of their functions and regulation at this strategic location. Herein we discuss how innate-like T cell recognition by unconventional T cell subsets and expression of innate NK receptors might modulate immune T cell responses in the human normal or diseased intestine.

Low-Energy Theory of Disordered Graphene

NASA Astrophysics Data System (ADS)

Altland, Alexander

2006-12-01

At low values of external doping, graphene displays a wealth of unconventional transport properties. Perhaps most strikingly, it supports a robust “metallic” regime, with universal conductance of the order of the conductance quantum. We here apply a combination of mean-field and bosonization methods to explore the large scale transport properties of the system. We find that, irrespective of the doping level, disordered graphene is subject to the common mechanisms of Anderson localization. However, at low doping a number of renormalization mechanisms conspire to protect the conductivity of the system, to an extend that strong localization may not be seen even at temperatures much smaller than those underlying present experimental work.

Light-induced changes in bottled white wine and underlying photochemical mechanisms.

PubMed

Grant-Preece, Paris; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

2017-03-04

Bottled white wine may be exposed to UV-visible light for considerable periods of time before it is consumed. Light exposure may induce an off-flavor known as "sunlight" flavor, bleach the color of the wine, and/or increase browning and deplete sulfur dioxide. The changes that occur in bottled white wine exposed to light depend on the wine composition, the irradiation conditions, and the light exposure time. The light-induced changes in the aroma, volatile composition, color, and concentrations of oxygen and sulfur dioxide in bottled white wine are reviewed. In addition, the photochemical reactions thought to have a role in these changes are described. These include the riboflavin-sensitized oxidation of methionine, resulting in the formation of methanethiol and dimethyl disulfide, and the photodegradation of iron(III) tartrate, which gives rise to glyoxylic acid, an aldehyde known to react with flavan-3-ols to form yellow xanthylium cation pigments.

Optical radiation in modern medicine

PubMed Central

Sowa, Paweł; Rutkowska-Talipska, Joanna; Rutkowski, Krzysztof; Kosztyła-Hojna, Bożena

2013-01-01

Optical radiation extends between microwaves and X-rays of the electromagnetic radiation and includes ultraviolet (UV), visible light (VL) and infrared (IR) components. The dose of radiation that reaches the skin is influenced by the ozone layer, position of the Sun, latitude, altitude, cloud cover and ground reflections. The photobiological effects of UV, VL and IR bands depend on their wavelength, frequency and mechanism of action. They are modified by the thickness, structure, vasculature and pigmentation of skin's stratum corneum, epidermis and dermis. Following absorption, IR affects the body mainly through transfer of thermal energy to tissues. Visible light and skin interact either thermally or photochemically, whereas UV acts mainly photochemically. Optical radiation in the form of sunlight therapy had been used already in ancient times. Nowadays IR, VL and UV are widely applied in the therapy of allergic, dermatological, cardiovascular, respiratory, rheumatic, neonatal, pediatric and psychiatric disorders. PMID:24278082

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

PubMed

Gómez-Gallego, Mar; Pellico, Daniel; Ramírez-López, Pedro; Mancheño, María J; Romano, Santiago; de la Torre, María C; Sierra, Miguel A

2005-10-07

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

Urban airshed modeling of air quality impacts of alternative transportation fuel use in Los Angeles and Atlanta

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

NONE

1997-12-01

The main objective of NREL in supporting this study is to determine the relative air quality impact of the use of compressed natural gas (CNG) as an alternative transportation fuel when compared to low Reid vapor pressure (RVP) gasoline and reformulated gasoline (RFG). A table lists the criteria, air toxic, and greenhouse gas pollutants for which emissions were estimated for the alternative fuel scenarios. Air quality impacts were then estimated by performing photochemical modeling of the alternative fuel scenarios using the Urban Airshed Model Version 6.21 and the Carbon Bond Mechanism Version IV (CBM-IV) (Geary et al., 1988) Using thismore » model, the authors examined the formation and transport of ozone under alternative fuel strategies for motor vehicle transportation sources for the year 2007. Photochemical modeling was performed for modeling domains in Los Angeles, California, and Atlanta, Georgia.« less

VALIDATION TESTING OF NEW MECHANISMS WITH OUTDOOR CHAMBER DATA, VOLUME 3: CALCULATION OF PHOTOCHEMICAL REACTION PHOTOLYSIS RATES IN THE UNC OUTDOOR CHAMBER

EPA Science Inventory

A new model is described for computing in-chamber actinic flux using site specific conditions that include time of day, air pressure, total column ozone, total column water vapor, relative humidity, aerosol type, aerosol optical density at 500 nm, and the spectral albedo of the g...

Excited-State Charge Separation in the Photochemical Mechanism of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase**

PubMed Central

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-01

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond–microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called “reactive” intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. PMID:25488797

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

NASA Technical Reports Server (NTRS)

Toon, Owen B.; Tolbert, Margaret A.

1995-01-01

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanism thought to be responsible for ozone depletion in the Antarctic and Arctic. Reactions of PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type 1 PSCs obtained in Antarctica in September 1987, using recently measured optical constants of the various compounds that might be present in PSCs. We find these PSCs were not composed of nitric acid trihydrate but instead had a more complex compositon, perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSCs to remove NOx permanently through sedimentation, The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism.

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

DOE PAGES

Ford, Peter C.

2001-01-01

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

Excited-state charge separation in the photochemical mechanism of the light-driven enzyme protochlorophyllide oxidoreductase.

PubMed

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-26

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond-microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called "reactive" intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unconventional Treatments for Vitiligo: Are They (Un) Satisfactory?

PubMed

Gianfaldoni, Serena; Tchernev, Georgi; Lotti, Jacopo; Wollina, Uwe; Satolli, Francesca; Rovesti, Miriam; França, Katlein; Lotti, Torello

2018-01-25

The authors show a brief overview of the vitiligo's unconventional therapies. A part for well-documented effectiveness of L-phenylalanine, PGE2 and antioxidant agents in the treatment of vitiligo, for the other therapeutical approaches more investigations are needed.

Unconventional Synthesis of γ-Fe2O3: Excellent Low-Concentration Ethanol Sensing Performance

NASA Astrophysics Data System (ADS)

Naskar, Atanu; Narjinary, Mousumi; Kundu, Susmita

2017-01-01

This study reports on a simple unconventional procedure for synthesis of γ-Fe2O3 nanopowder and its fabrication as a resistive ethanol sensor. γ-Fe2O3 powder having an average particle size of ˜15 nm was prepared by thermal decomposition of iron(III) acetylacetonate. Platinum incorporation (0.5-1.5 wt.%) was also carried out for enhancing sensing performance. The powders were characterized using an x-ray diffractometer, x-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area, field area scanning electron microscopy, transmission electron microscopy along with energy dispersion x-ray analyses. Sensor fabricated from pure γ-Fe2O3 exhibited excellent ethanol sensing performance at concentrations down to 1 ppm, having a great demand in medical diagnosis and food-processing industries. The response observed for pure γ-Fe2O3 (˜75% for 1 ppm ethanol) was enhanced ˜10% after 1 wt.% Pt impregnation. Sensors were quite stable and selective towards ethanol vapour detection. A possible mechanism for high sensing performance has been discussed.

URI Regulates KAP1 Phosphorylation and Transcriptional Repression via PP2A Phosphatase in Prostate Cancer Cells*

PubMed Central

Mita, Paolo; Savas, Jeffrey N.; Briggs, Erica M.; Ha, Susan; Gnanakkan, Veena; Yates, John R.; Robins, Diane M.; David, Gregory; Boeke, Jef D.; Garabedian, Michael J.; Logan, Susan K.

2016-01-01

URI (unconventional prefoldin RPB5 interactor protein) is an unconventional prefoldin, RNA polymerase II interactor that functions as a transcriptional repressor and is part of a larger nuclear protein complex. The components of this complex and the mechanism of transcriptional repression have not been characterized. Here we show that KAP1 (KRAB-associated protein 1) and the protein phosphatase PP2A interact with URI. Mechanistically, we show that KAP1 phosphorylation is decreased following recruitment of PP2A by URI. We functionally characterize the novel URI-KAP1-PP2A complex, demonstrating a role of URI in retrotransposon repression, a key function previously demonstrated for the KAP1-SETDB1 complex. Microarray analysis of annotated transposons revealed a selective increase in the transcription of LINE-1 and L1PA2 retroelements upon knockdown of URI. These data unveil a new nuclear function of URI and identify a novel post-transcriptional regulation of KAP1 protein that may have important implications in reactivation of transposable elements in prostate cancer cells. PMID:27780869

Superconductivity on the brink of spin-charge order in doped honeycomb bilayer

NASA Astrophysics Data System (ADS)

Vafek, Oskar; Murray, James; Cvetkovic, Vladimir

2014-03-01

Using a controlled weak-coupling renormalization group approach, we establish the mechanism of unconventional superconductivity in the vicinity of spin or charge ordered excitonic states for the case of electrons on the Bernal stacked bilayer honeycomb lattice. With one electron per site this system exhibits nearly parabolically touching conduction and valence bands. Such a state is unstable towards a spontaneous symmetry breaking, and repulsive interactions favor excitonic order, such as a charge nematic and/or a layer antiferromagnet. We find that upon adding charge carriers to the system, the excitonic order is suppressed, and unconventional superconductivity appears in its place, before it is replaced by a Fermi liquid. We focus on firmly establishing this phenomenon using the RG formalism within an idealized model with parabolic touching. This work was supported by the NSF CAREER award under Grant No. DMR-0955561 (OV), NSF Cooperative Agreement No. DMR-0654118, and the State of Florida (OV,JM,CV), as well as by ICAM-I2CAM (NSF grant DMR-0844115) and by DoE Award DE-FG02-08ER46544 (JM).

The molecular mechanism of excitation in visual transduction and bacteriorhodopsin

PubMed Central

Lewis, Aaron

1978-01-01

An electronic theory of excitation is proposed and described in terms of a three-dimensional excited/ground-state energy surface which elucidates the photochemical and excited-state dynamics of rhodopsins. In this theory the primary action of light is to produce significant electron redistribution in the retinal, thereby generating new interactions that vibrationally excite and perturb the ground-state protein conformation. Thus, light energy causes charge redistribution in the retinal and induces transient charge-density assisted bond rearrangements (such as proton translocation) in the protein structure which is stabilized by subsequent retinal structural alteration. In this theory the isoprenoid chain of the retinal is considered a structurally pliable molecular entity that can generate charge redistributions and can be subsequently achieve intermediate conformations or various isomeric states to minimize the energy of the new protein structure generated by light. Thus, the 11-cis to all trans isomerization of the retinylidene chromophore is not considered a primary mechanism of excitation. An alternate biological role for this molecular process (which is eventually completed in all photoreceptors but not in bacterial rhodopsins) is to provide the irreversibility needed for effective quantum detection on the time scale of a neural response. Finally, it will be demonstrated that this mechanism, which readily accounts for the photophysical and photochemical data, can also be restated in terms of the Monod, Wyman, and Changeux terminology suggesting that aggregates of these pigments may function allosterically. PMID:273216

Photophysical and Photochemical Properties of 3-methylpterin as a New and More Stable Pterin-type Photosensitizer.

PubMed

Estébanez, Sandra; Lorente, Carolina; Kaufman, Teodoro S; Larghi, Enrique L; Thomas, Andrés H; Serrano, Mariana P

2018-05-04

Pterin derivatives are heterocyclic compounds which are present in different biological systems. Neutral aqueous solutions of pterins presents acid-base and keto-enol equilibria. These compounds under UV-A radiation fluoresce, undergo photooxidation, generate reactive oxygen species, and photoinduce the oxidation of biological substrates. As photosensitizers, they may act through different mechanisms; mainly through an electron-transfer initiated process (type I mechanism), but they also produce singlet molecular oxygen ( 1 O 2 ) upon irradiation (type II mechanism). In general, upon UV-A excitation two triplet states, corresponding to the lactim and lactam tautomers, are formed, but only the last one is the responsible for the photosensitized reactions of biomolecules. We present a study of the photochemical properties of 3-methylpterin (3-Mep) which, in contrast to most pterin derivatives, exists only in the lactam form. Also an improvement in the synthesis of 3-Mep is reported. The spectroscopic properties 3-Mep in aqueous solution were similar to those of the unsubstituted pterin derivative (Ptr) in its acid form, such as absorption, fluorescent and phosphorescent emission spectra. Experiments using 2'-deoxyguanosine 5'-monophosphate (dGMP) as oxidizable target, demonstrated that methylation at C-3 position of the pterin moiety does not affect significantly the efficiency of photosensitization, but results in a more photostable sensitizer. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

An integrated computer system for analysis, selection, and evaluation of unconventional intersections.

DOT National Transportation Integrated Search

2011-03-01

The emergence of unconventional intersections in the traffic community has been motivated by the notion : of improving service quality with innovative control strategies, such as rerouting the turning movements : or flipping the paths of two traffic ...

Unconventional microfluidics: expanding the discipline.

PubMed

Nawaz, Ahmad Ahsan; Mao, Xiaole; Stratton, Zackary S; Huang, Tony Jun

2013-04-21

Since its inception, the discipline of microfluidics has been harnessed for innovations in the biomedicine/chemistry fields-and to great effect. This success has had the natural side-effect of stereotyping microfluidics as a platform for medical diagnostics and miniaturized lab processes. But microfluidics has more to offer. And very recently, some researchers have successfully applied microfluidics to fields outside its traditional domains. In this Focus article, we highlight notable examples of such "unconventional" microfluidics applications (e.g., robotics, electronics). It is our hope that these early successes in unconventional microfluidics prompt further creativity, and inspire readers to expand the microfluidics discipline.

Water Issues Related to Transitioning from Conventional to Unconventional Oil Production in the Permian Basin.

PubMed

Scanlon, Bridget R; Reedy, Robert C; Male, Frank; Walsh, Mark

2017-09-19

The Permian Basin is being transformed by the "shale revolution" from a major conventional play to the world's largest unconventional play, but water management is critical in this semiarid region. Here we explore evolving issues associated with produced water (PW) management and hydraulic fracturing water demands based on detailed well-by-well analyses. Our results show that although conventional wells produce ∼13 times more water than oil (PW to oil ratio, PWOR = 13), this produced water has been mostly injected back into pressure-depleted oil-producing reservoirs for enhanced oil recovery. Unconventional horizontal wells use large volumes of water for hydraulic fracturing that increased by a factor of ∼10-16 per well and ∼7-10 if normalized by lateral well length (2008-2015). Although unconventional wells have a much lower PWOR of 3 versus 13 from conventional wells, this PW cannot be reinjected into the shale reservoirs but is disposed into nonproducing geologic intervals that could result in overpressuring and induced seismicity. The potential for PW reuse from unconventional wells is high because PW volumes can support hydraulic fracturing water demand based on 2014 data. Reuse of PW with minimal treatment (clean brine) can partially mitigate PW injection concerns while reducing water demand for hydraulic fracturing.

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

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

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

DOE PAGES

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.; ...

2018-05-10

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Solar Irradiation of Bilirubin: An Experiment in Photochemical Oxidation

ERIC Educational Resources Information Center

Pillay A. E.; Salih, F. M.

2006-01-01

An experiment in photochemical oxidation, which deals with bilirubin, a well-known light-sensitive biological compound that is pedagogically ideal for photochemical experiments at tertiary institutes, is presented. The experiment would benefit students in chemistry who eventually branch out into the health sciences or biochemistry.

Mass Dependent and Mass Independent Fractionation of Hg Isotopes and Estimation of Photochemical Loss of Hg in Aquatic Systems

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Blum, J. D.

2007-12-01

Mercury is a globally distributed and highly toxic pollutant, the mobility and bioaccumulation of which is dependent on its redox cycling. Hg isotope analysis is an important new tool for identifying Hg sources and tracking Hg transformations in the environment. Most natural samples analyzed for Hg isotopes display mass-dependent isotope fractionation (MDF), but a small body of data suggests that some natural samples also display mass- independent isotope fractionation (MIF) of the odd Hg isotopes. Here we document MIF of Hg isotopes during an important natural process, constrain the potential mechanism of isotope fractionation, and apply the MIF observed in natural samples to quantify the photochemical reduction of Hg species in the environment. Reduction of Hg species to Hg0 vapor is an important pathway for removal of Hg from aqueous systems into the atmosphere and occurs by abiotic and biotic mechanisms. In laboratory experiments, we find that photochemical reduction Hg species by natural sunlight leads to large MIF of the odd isotopes. Also, the relationship between MIF for the two odd isotopes of Hg is significantly different for different photo-reduction pathways. In contrast, both biological reduction (Kritee et al., 2006) and dark abiotic organically-mediated reduction follow MDF. Natural samples from aquatic ecosystems preserve both MDF and MIF. In fish, MDF increases with the size and Hg concentration of fish suggesting MDF may be useful in understanding Hg bioaccumulation. Fish also display a large range in MIF (4‰), and the relationship between the MIF of the two odd isotopes in fish has a similar slope to the slope found for photo-reduction of CH3Hg+. Since fish bioaccumulate CH3Hg+, fish may be recording the extent to which CH3Hg+ is lost via photochemical reduction in an aquatic ecosystem. Fish populations from different locations have different MIF values, but mostly display similar MIF within a given locale. This suggests that MIF is preserved in the food web and could be used to quantify photo-reduction of CH3Hg+ in ecosystems. Both MDF and MIF of Hg isotopes will be useful for quantifying and understanding Hg biogeochemical cycling in the environment.

Stratospheric Ozone Loss Over the US in Summer: Recent Advances in Observations of Temperatures, Convective Injection of Condensed Phase Water, and Analyses of Volcanic Injections That are Used to Inform Model Calculations of Catalytic Mechanisms that Control the Response of O3.

NASA Astrophysics Data System (ADS)

Anderson, J. G.

2016-12-01

In the context of changes to the structure of the Earth's climate, consequences to stratospheric ozone over the US in summer are considered. Key advances in observations directly related to the catalytic loss of ozone in the lower stratosphere include: Analysis of high resolution temperature observations over the central US in July and August from both SEAC4RS in situ observations and radio occultation (RO) observations, Inclusion of gravity wave observations from both SEAC4RS and RO measurements, Climatology of NEXRAD weather radar mapping of the 3D convective injection of condensed phase water over the central US in summer, Analysis of the impact on ozone in the lower stratosphere over the US in summer using the AER 2D model calculations of the key rate limiting radicals and rate limiting catalytic loss rates as a function of water vapor, temperature and sulfate loading in the lower stratosphere, Analysis of the impact on ozone in summer over the US under conditions of volcanic injection, overt sulfate addition for solar radiation management, and/or convective injection of water vapor, Emphasis in the analysis is placed specifically on the geographic region over the Great Plains of the US in summer because of the confluence of temperatures and water vapor concentrations that initiate the heterogeneous catalytic conversion of inorganic chlorine, primarily HCl and ClONO2, to free radical form, ClO. The ClO radical in turn engages gas phase catalytic cycles that remove ozone via the photochemical reaction mechanisms virtually identical to the catalytic photochemical processes that remove ozone over the Arctic each year in late spring. In situ observations, in the lower stratosphere of the Arctic, of the principal reaction networks that establish the relationship between observed ozone loss and the threshold in temperature, water vapor and sulfate loading is used to establish the photochemical coordinate system required to analyze ozone loss in the lower stratosphere globally. Analysis is also presented of observed ozone loss resulting from the eruption of Mt. Pinatubo that tests the photochemical structure of large ozone loss at mid-latitude for the range in sulfate loading that accompanies a volcanic eruption.

Photochemical mechanisms of biological action of low-intensity laser irradiation

NASA Astrophysics Data System (ADS)

Klebanov, Gennady I.; Poltanov, Evgeny A.

2004-08-01

Low-intensity laser irradiation (LILI) is effectively used in clinical practice but the mechanisms of its stimulating action are still far from being understood completely and considered in the scientific literature only hypothetically. The main effects of LILI proved both in clinics and in experiments are bactericidal effect, vasodilatation, improved microcirculation, formation and growth of new microvessels, acceleration of wound healing, relieving of pain syndrome. We put forward a free radical conception underlying these effects. In this paper the experimental evidences of this conception is considered.

Assessment of unconventional tight-gas resources of the Magallanes Basin Province, Chile, 2015

USGS Publications Warehouse

Schenk, Christopher J.; Charpentier, Ronald R.; Pitman, Janet K.; Tennyson, Marilyn E.; Brownfield, Michael E.; Gaswirth, Stephanie B.; Le, Phuong A.; Leathers-Miller, Heidi M.; Marra, Kristen R.

2016-01-20

Using a geology-based assessment methodology, the U.S. Geological Survey assessed a technically recoverable mean resource of 8.3 trillion cubic feet of unconventional tight gas in the Zona Glauconitica of the Magallanes Basin Province, Chile.

Unconventional eating practices and their health implications.

PubMed

Hanning, R M; Zlotkin, S H

1985-04-01

The authors discuss a number of unconventional or faddist foods and eating practices and their health implications. Among the topics included are vegetarianism, Zen macrobiotic diets, fast foods, junk foods, megavitamins and their toxicity, health foods, fad diets in infancy, and elimination diets.

76 FR 72919 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-28

... Science Assessment for Ozone and Related Photochemical Oxidants AGENCY: Environmental Protection Agency... Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' (EPA/600/R-10/076B... national ambient air quality standards (NAAQS) for ozone. DATES: The public comment period began on...

76 FR 60820 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-30

... Science Assessment for Ozone and Related Photochemical Oxidants AGENCY: Environmental Protection Agency... Review Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' (EPA/600/R-10... standards (NAAQS) for ozone. EPA is releasing this draft document to seek review by the Clean Air Scientific...

76 FR 17121 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-28

... Science Assessment for Ozone and Related Photochemical Oxidants AGENCY: Environmental Protection Agency... Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' (EPA/600/R-10/076A... ambient air quality standards (NAAQS) for ozone. DATES: The public comment period began on February 28...

Photochemical Dimerization of Dibenzylideneacetone: A Convenient Exercise in [2+2] Cycloaddition Using Chemical Ionization Mass Spectrometry

ERIC Educational Resources Information Center

Rao, G. Nageswara; Janardhana, Chelli; Ramanathan, V.; Rajesh, T.; Kumar, P. Harish

2006-01-01

Chemical reactions induced by light have been utilized for synthesizing highly strained, thermodynamically unstable compounds, which are inaccessible through non-photochemical methods. Photochemical cycloaddition reactions, especially those leading to the formation of four-membered rings, constitute a convenient route to compounds that are…

INTERACTIONS BETWEEN PHOTOCHEMICAL AND MICROBIAL DECOMPOSITION IN MODIFYING THE BIOLOGICAL AVAILABILITY AND OPTICAL PROPERTIES OF ESTUARINE DISSOLVED ORGANIC MATTER

EPA Science Inventory

Direct photodecomposition and photochemically-mediated bacterial degradation (via photochemical modification of otherwise refractory DOM into biologically labile forms) provide
important pathways for the loss of dissolved organic matter in coastal waters. Here we report
lab...

Air Quality Criteria for Ozone and Other Photochemical Oxidants. External Review Draft No 1. Volume III

EPA Science Inventory

This review of the effects of photochemical oxidants on vegetation and the responses of vegetation to photochemical oxidants first discusses the general methodologies used in studies of air pollution effects to provide a basis for understanding the methods, approaches, and experi...

Photochemical Effects of Sunlight

PubMed Central

Daniels, Farrington

1972-01-01

The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields. PMID:5037333

Photochemical effects of sunlight.

PubMed

Daniels, F

1972-07-01

The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields.

Axi-symmetrical flow reactor for .sup.196 Hg photochemical enrichment

DOEpatents

Grossman, Mark W.

1991-01-01

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, .sup.196 Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired .sup.196 Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith.

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

PubMed

Hoffmann, Norbert

2012-11-01

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

Effective Control of Chronic γ-Herpesvirus Infection by Unconventional MHC Class Ia–Independent CD8 T Cells

PubMed Central

Tibbetts, Scott A; McClellan, Kelly B

2006-01-01

Control of virus infection is mediated in part by major histocompatibility complex (MHC) Class Ia presentation of viral peptides to conventional CD8 T cells. Although important, the absolute requirement for MHC Class Ia–dependent CD8 T cells for control of chronic virus infection has not been formally demonstrated. We show here that mice lacking MHC Class Ia molecules (Kb−/−xDb−/− mice) effectively control chronic γ-herpesvirus 68 (γHV68) infection via a robust expansion of β2-microglobulin (β2-m)-dependent, but CD1d-independent, unconventional CD8 T cells. These unconventional CD8 T cells expressed: (1) CD8αβ and CD3, (2) cell surface molecules associated with conventional effector/memory CD8 T cells, (3) TCRαβ with a significant Vβ4, Vβ3, and Vβ10 bias, and (4) the key effector cytokine interferon-γ (IFNγ). Unconventional CD8 T cells utilized a diverse TCR repertoire, and CDR3 analysis suggests that some of that repertoire may be utilized even in the presence of conventional CD8 T cells. This is the first demonstration to our knowledge that β2-m–dependent, but Class Ia–independent, unconventional CD8 T cells can efficiently control chronic virus infection, implicating a role for β2-n–dependent non-classical MHC molecules in control of chronic viral infection. We speculate that similar unconventional CD8 T cells may be able to control of other chronic viral infections, especially when viruses evade immunity by inhibiting generation of Class Ia–restricted T cells. PMID:16733540

Assessment of Methane Emissions – Impact of Using Natural Gas Engines in Unconventional Resource Development

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

Nix, Andrew; Johnson, Derek; Heltzel, Robert

Researchers at the Center for Alternative Fuels, Engines, and Emissions (CAFEE) completed a multi-year program under DE-FE0013689 entitled, “Assessing Fugitive Methane Emissions Impact Using Natural Gas Engines in Unconventional Resource Development.” When drilling activity was high and industry sought to lower operating costs and reduce emissions they began investing in dual fuel and dedicated natural gas engines to power unconventional well equipment. From a review of literature we determined that the prime-movers (or major fuel consumers) of unconventional well development were the service trucks (trucking), horizontal drilling rig (drilling) engines, and hydraulic stimulation pump (fracturing) engines. Based on early findingsmore » from on-road studies we assessed that conversion of prime movers to operate on natural gas could contribute to methane emissions associated with unconventional wells. As such, we collected significant in-use activity data from service trucks and in-use activity, fuel consumption, and gaseous emissions data from drilling and fracturing engines. Our findings confirmed that conversion of the prime movers to operate as dual fuel or dedicated natural gas – created an additional source of methane emissions. While some gaseous emissions were decreased from implementation of these technologies – methane and CO 2 equivalent emissions tended to increase, especially for non-road engines. The increases were highest for dual fuel engines due to methane slip from the exhaust and engine crankcase. Dedicated natural gas engines tended to have lower exhaust methane emissions but higher CO 2 emissions due to lower efficiency. Therefore, investing in currently available natural gas technologies for prime movers will increase the greenhouse gas footprint of the unconventional well development industry.« less

Photochemical reactions of cyanoacetylene and dicyanoacetylene: Possible processes in Titan's atmosphere

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Guillemin, J. C.

1991-01-01

Titan has an atmosphere which is subject to dramatic chemical evolution due mainly to the dramatic effect of the UV flux from the Sun. The energetic solar photons and other particles are converting the methane-nitrogen atmosphere into the unsaturated carbon compounds observed by the Voyager probes. These same solar photons are also converting some of these unsaturated reaction products into the aerosols observed in the atmosphere which obscure the view of the surface of Titan. In particular, the photochemical reactions of cyanoacetylene, dicyanoacetylene, acetylene and ethylene may result in the formation of the higher hydrocarbons and polymers which result in the aerosols observed in Titan's atmosphere. Polymers are the principal reaction products formed by irradiation of cyanoacetylene and dicyanoacetylene. Irradiation of cyanoacetylene with 185 nm of light also yields 1,3,5-tricyanobenzene while irradiation at 254 nm yields 1,2,4-tricyanobenzene and tetracyano cyclooctatetraenes. Photolyses of mixtures of cyanoacetylene and acetylene yields mono- and di- cyanobenzenes. The 1-Cyanocyclobutene is formed from the photochemical addition of cyanoacetylene with ethylene. The photolysis of dicyanoacetylene with acetylene yields 2,3-dicyano-1,3-butadiene and 1,2-dicyanobenzene. Tetracyano cyclooctatetraene products were also observed in the photolysis of mixtures of dicyanoacetylene and acetylene with 254 nm light. The 1,2-Dicyano cyclobutene is obtained from the photolysis dicyanoacetylene and ethylene. Reaction mechanisms will be proposed to explain the observed photoproducts.

Sunlight-Induced photochemical synthesis of Au nanodots on α-Fe2O3@Reduced graphene oxide nanocomposite and their enhanced heterogeneous catalytic properties.

PubMed

Bharath, G; Anwer, Shoaib; Mangalaraja, R V; Alhseinat, Emad; Banat, Fawzi; Ponpandian, N

2018-04-09

In this present study, we report the synthesis of Au nanodots on α-Fe 2 O 3 @reduced graphene oxide (RGO) based hetero-photocatalytic nanohybrids through a chlorophyll mediated photochemical synthesis. In this process, chlorophyll induces a rapid reduction (30 min) of Au 3+ ions to Au° metallic nanodots on α-Fe 2 O 3 @RGO surface under sunlight irradiation. The nucleation growth process, photo-induced electron-transfer mechanism and physico-chemical properties of the Au@α-Fe 2 O 3 @RGO ternary nanocomposites were systematically studied with various analytical techniques. This novel photochemical synthesis process is a cost-effective, convenient, surfactant-less, and scalable method. Moreover, the prepared ternary nanocomposites enhanced catalytic activity as compared to pure α-Fe 2 O 3 and α-Fe 2 O 3 @RGO. The advantages and synergistic effect of Au@α-Fe 2 O 3 @RGO exhibit, (i) a broader range of visible-light absorption due to visible light band gap of α-Fe 2 O 3 , (ii) lower recombination possibility of photo-generated electrons and holes due to effect of Au and (iii) faster electron transfer due to higher conductivity of RGO. Therefore, the prepared Au@α-Fe 2 O 3 @RGO hetero-photocatalytic nanohybrids exhibited a remarkable photocatalytic activity, thus enabling potential active hetero-photocatalyst for industrial and environmental applications.

Unconventional oil and gas: The role of politics and proximity

NASA Astrophysics Data System (ADS)

Schelly, Chelsea

2016-10-01

Political divisions are important in understanding public perceptions of unconventional oil and natural gas development, but so is proximity to drilling activities. New research highlights that, as geographical distance from development areas increases, political ideology becomes more influential in explaining diverging perceptions.

Energy-Water Modeling and Analysis | Energy Analysis | NREL

Science.gov Websites

future electricity scenarios under cases of limited water availability and electricity sector impacts of Manufacturing Water Use The Water Intensity and Resource Impacts of Unconventional Hydrocarbon Development Impacts of Unconventional Hydrocarbon Development Life Cycle Harmonization Project (Water) Sample

Target-cancer cell specific activatable fluorescence imaging Probes: Rational Design and in vivo Applications

PubMed Central

Kobayashi, Hisataka; Choyke, Peter L.

2010-01-01

CONSPECTUS Conventional imaging methods, such as angiography, computed tomography, magnetic resonance imaging and radionuclide imaging, rely on contrast agents (iodine, gadolinium, radioisotopes) that are “always on”. While these agents have proven clinically useful, they are not sufficiently sensitive because of the inadequate target to background ratio. A unique aspect of optical imaging is that fluorescence probes can be designed to be activatable, i.e. only “turned on” under certain conditions. These probes can be designed to emit signal only after binding a target tissue, greatly increasing sensitivity and specificity in the detection of disease. There are two basic types of activatable fluorescence probes; 1) conventional enzymatically activatable probes, which exist in the quenched state until activated by enzymatic cleavage mostly outside of the cells, and 2) newly designed target-cell specific activatable probes, which are quenched until activated in targeted cells by endolysosomal processing that results when the probe binds specific cell-surface receptors and is subsequently internalized. Herein, we present a review of the rational design and in vivo applications of target-cell specific activatable probes. Designing these probes based on their photo-chemical (e.g. activation strategy), pharmacological (e.g. biodistribution), and biological (e.g. target specificity) properties has recently allowed the rational design and synthesis of target-cell specific activatable fluorescence imaging probes, which can be conjugated to a wide variety of targeting molecules. Several different photo-chemical mechanisms have been utilized, each of which offers a unique capability for probe design. These include: self-quenching, homo- and hetero-fluorescence resonance energy transfer (FRET), H-dimer formation and photon-induced electron transfer (PeT). In addition, the repertoire is further expanded by the option for reversibility or irreversibility of the signal emitted using the aforementioned mechanisms. Given the wide range of photochemical mechanisms and properties, target-cell specific activatable probes possess considerable flexibility and can be adapted to specific diagnostic needs. Herein, we summarize the chemical, pharmacological, and biological basis of target-cell specific activatable imaging probes and discuss methods to successfully design such target-cell specific activatable probes for in vivo cancer imaging. PMID:21062101

Induced unconventional superconductivity on the surface states of Bi2Te3 topological insulator.

PubMed

Charpentier, Sophie; Galletti, Luca; Kunakova, Gunta; Arpaia, Riccardo; Song, Yuxin; Baghdadi, Reza; Wang, Shu Min; Kalaboukhov, Alexei; Olsson, Eva; Tafuri, Francesco; Golubev, Dmitry; Linder, Jacob; Bauch, Thilo; Lombardi, Floriana

2017-12-08

Topological superconductivity is central to a variety of novel phenomena involving the interplay between topologically ordered phases and broken-symmetry states. The key ingredient is an unconventional order parameter, with an orbital component containing a chiral p x  + ip y wave term. Here we present phase-sensitive measurements, based on the quantum interference in nanoscale Josephson junctions, realized by using Bi 2 Te 3 topological insulator. We demonstrate that the induced superconductivity is unconventional and consistent with a sign-changing order parameter, such as a chiral p x  + ip y component. The magnetic field pattern of the junctions shows a dip at zero externally applied magnetic field, which is an incontrovertible signature of the simultaneous existence of 0 and π coupling within the junction, inherent to a non trivial order parameter phase. The nano-textured morphology of the Bi 2 Te 3 flakes, and the dramatic role played by thermal strain are the surprising key factors for the display of an unconventional induced order parameter.

Material requirements for the adoption of unconventional silicon crystal and wafer growth techniques for high-efficiency solar cells

DOE PAGES

Hofstetter, Jasmin; del Cañizo, Carlos; Wagner, Hannes; ...

2015-10-15

Silicon wafers comprise approximately 40% of crystalline silicon module cost and represent an area of great technological innovation potential. Paradoxically, unconventional wafer-growth techniques have thus far failed to displace multicrystalline and Czochralski silicon, despite four decades of innovation. One of the shortcomings of most unconventional materials has been a persistent carrier lifetime deficit in comparison to established wafer technologies, which limits the device efficiency potential. In this perspective article, we review a defect-management framework that has proven successful in enabling millisecond lifetimes in kerfless and cast materials. Control of dislocations and slowly diffusing metal point defects during growth, coupled tomore » effective control of fast-diffusing species during cell processing, is critical to enable high cell efficiencies. As a result, to accelerate the pace of novel wafer development, we discuss approaches to rapidly evaluate the device efficiency potential of unconventional wafers from injection-dependent lifetime measurements.« less

Unconventional Consumption Methods and Enjoying Things Consumed: Recapturing the "First-Time" Experience.

PubMed

O'Brien, Ed; Smith, Robert W

2018-06-01

People commonly lament the inability to re-experience familiar things as they were first experienced. Four experiments suggest that consuming familiar things in new ways can disrupt adaptation and revitalize enjoyment. Participants better enjoyed the same familiar food (Experiment 1), drink (Experiment 2), and video (Experiments 3a-3b) simply when re-experiencing the entity via unusual means (e.g., eating popcorn using chopsticks vs. hands). This occurs because unconventional methods invite an immersive "first-time" perspective on the consumption object: boosts in enjoyment were mediated by revitalized immersion into the consumption experience and were moderated by time such that they were strongest when using unconventional methods for the first time (Experiments 1-2); likewise, unconventional methods that actively disrupted immersion did not elicit the boost, despite being novel (Experiments 3a-3b). Before abandoning once-enjoyable entities, knowing to consume old things in new ways (vs. attaining new things altogether) might temporarily restore enjoyment and postpone wasteful replacement.

Enhanced recovery of unconventional gas. Volume II. The program. [Tight gas basins; Devonian shale; coal seams; geopressured aquifers

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

Kuuskraa, V.A.; Brashear, J.P.; Doscher, T.M.

1978-10-01

This study was conducted to assist public decision-makers in selecting among many choices to obtain new gas supplies by addressing 2 questions: 1) how severe is the need for additional future supplies of natural gas, and what is the economic potential of providing part of future supply through enhanced recovery from unconventional natural gas resources. The study also serves to assist the DOE in designing a cost-effective R and D program to stimulate industry to recover this unconventional gas and to produce it sooner. Tight gas basins, Devonian shale, methane from coal seams, and methane from geopressured aquifers are considered.more » It is concluded that unconventional sources, already providing about 1 Tcf per year, could provide from 3 to 4 Tcf in 1985 and from 6 to 8 Tcf in 1990 (at $1.75 and $3.00 per Mcf, respectively). However, even with these additions to supply, gas supply is projected to remain below 1977 usage levels. (DLC)« less

Material requirements for the adoption of unconventional silicon crystal and wafer growth techniques for high-efficiency solar cells

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

Hofstetter, Jasmin; del Cañizo, Carlos; Wagner, Hannes

Silicon wafers comprise approximately 40% of crystalline silicon module cost and represent an area of great technological innovation potential. Paradoxically, unconventional wafer-growth techniques have thus far failed to displace multicrystalline and Czochralski silicon, despite four decades of innovation. One of the shortcomings of most unconventional materials has been a persistent carrier lifetime deficit in comparison to established wafer technologies, which limits the device efficiency potential. In this perspective article, we review a defect-management framework that has proven successful in enabling millisecond lifetimes in kerfless and cast materials. Control of dislocations and slowly diffusing metal point defects during growth, coupled tomore » effective control of fast-diffusing species during cell processing, is critical to enable high cell efficiencies. As a result, to accelerate the pace of novel wafer development, we discuss approaches to rapidly evaluate the device efficiency potential of unconventional wafers from injection-dependent lifetime measurements.« less

Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

PubMed Central

Hentschel, Carsten; Fontein, Florian; Stegemann, Linda; Hoeppener, Christiane; Fuchs, Harald; Hoeppener, Stefanie

2014-01-01

Summary A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM) of (3-aminopropyl)triethoxysilane (APTES) is explored with three different processes: 1) a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2) a chemical process induced by oxygen plasma etching as well as 3) a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL), which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern. PMID:25247126

Pore Characterization of Shale Rock and Shale Interaction with Fluids at Reservoir Pressure-Temperature Conditions Using Small-Angle Neutron Scattering

NASA Astrophysics Data System (ADS)

Ding, M.; Hjelm, R.; Watkins, E.; Xu, H.; Pawar, R.

2015-12-01

Oil/gas produced from unconventional reservoirs has become strategically important for the US domestic energy independence. In unconventional realm, hydrocarbons are generated and stored in nanopores media ranging from a few to hundreds of nanometers. Fundamental knowledge of coupled thermo-hydro-mechanical-chemical (THMC) processes that control fluid flow and propagation within nano-pore confinement is critical for maximizing unconventional oil/gas production. The size and confinement of the nanometer pores creates many complex rock-fluid interface interactions. It is imperative to promote innovative experimental studies to decipher physical and chemical processes at the nanopore scale that govern hydrocarbon generation and mass transport of hydrocarbon mixtures in tight shale and other low permeability formations at reservoir pressure-temperature conditions. We have carried out laboratory investigations exploring quantitative relationship between pore characteristics of the Wolfcamp shale from Western Texas and the shale interaction with fluids at reservoir P-T conditions using small-angle neutron scattering (SANS). We have performed SANS measurements of the shale rock in single fluid (e.g., H2O and D2O) and multifluid (CH4/(30% H2O+70% D2O)) systems at various pressures up to 20000 psi and temperature up to 150 oF. Figure 1 shows our SANS data at different pressures with H2O as the pressure medium. Our data analysis using IRENA software suggests that the principal changes of pore volume in the shale occurred on smaller than 50 nm pores and pressure at 5000 psi (Figure 2). Our results also suggest that with increasing P, more water flows into pores; with decreasing P, water is retained in the pores.

Creating unconventional geometric beams with large depth of field using double freeform-surface optics.

PubMed

Feng, Zexin; Froese, Brittany D; Huang, Chih-Yu; Ma, Donglin; Liang, Rongguang

2015-07-10

We consider here creation of an unconventional flattop beam with a large depth of field by employing double freeform optical surfaces. The output beam is designed with continuous variations from the flattop to almost zero near the edges to resist the influence of diffraction on its propagation. We solve this challenging problem by naturally incorporating an optimal transport map computation scheme for unconventional boundary conditions with a simultaneous point-by-point double surface construction procedure. We demonstrate experimentally the generation of a long-range propagated triangular beam through a plano-freeform lens pair fabricated by a diamond-tuning machine.

Unconventional cancer remedies.

PubMed Central

Danielson, K J; Stewart, D E; Lippert, G P

1988-01-01

Unproven and disproven remedies continue to abound for illnesses for which conventional treatment is only partially effective. This is particularly true with cancer, for which up to 50% of patients may be receiving unorthodox therapy. This article examines unconventional cancer remedies, their adverse effects, their common factors and the basis for their appeal, as well as what motivates and characterizes patients who choose these treatments. Also discussed is an approach that may be used by the conventional physician for patients who are likely to seek unorthodox treatment. This approach will help patients make the best decision about their treatment and protect them from the hazards of unconventional remedies. PMID:3285984

Non-equilibrium mechanisms of light in the microwave region

NASA Astrophysics Data System (ADS)

Mortenson, Juliana H. J.

2011-09-01

Quantum mechanics and quantum chemistry have taught for more than 100 years that "photons" associated with microwaves cannot exert photochemical effects because their "photon energies" are smaller than chemical bond energies. Those quantum theories have been strongly contradicted within the last few decades by physical experiments demonstrating non-equilibrium, photochemical and photomaterial activity by microwaves. Reactions among scientists to these real physical models and proofs have varied from disbelief and denial, to acceptance of the real physical phenomena and demands for revisions to quantum theory. At the previous "Nature of Light" meeting, an advance in the foundations of quantum mechanics was presented. Those discoveries have revealed the source of these conflicts between quantum theory and microwave experiments. Critical variables and constants were missing from quantum theory due to a minor mathematical inadvertence in Planck's original quantum work. As a result, erroneous concepts were formed nearly a century ago regarding the energetics and mechanisms of lower frequency light, such as in the microwave region. The new discoveries have revealed that the traditional concept of "photons" mistakenly attributed elementary particle status to what is actually an arbitrarily time-based collection of sub-photonic, elementary particles. In a mathematical dimensional sense, those time-based energy measurements cannot be mathematically equivalent to bond energies as historically believed. Only an "isolated quantity of energy", as De Broglie referred to it, can be equivalent to bond energy. With the aid of the new variables and constants, the non-equilibrium mechanisms of light in the microwave region can now be described. They include resonant absorption, splitting frequency stimulation leading to electronic excitation, and resonant acoustic transduction. Numerous practical engineering applications can be envisioned for non-equilibrium microwaves.

A renewable amine for photochemical reduction of CO(2).

PubMed

Richardson, Robert D; Holland, Edward J; Carpenter, Barry K

2011-04-01

Photochemical reduction of CO₂ (to produce formic acid) can be seen both as a method to produce a transportable hydrogen-based fuel and also to reduce levels of CO₂ in the atmosphere. However, an often overlooked necessity for photochemical CO₂ reduction is the need for a sacrificial electron donor, usually a tertiary amine. Here, we describe a new strategy for coupling the photochemical reduction of CO₂ to photochemical water splitting, and illustrate this with a prototype example. Instead of seeking to eliminate the use of an external reducing agent altogether, our alternative strategy makes the reducing agent recyclable. This has two potential advantages over the direct coupling of CO₂ reduction and water oxidation. First, it allows the two redox reactions to be carried out with existing chemistry, and second, it permits these reactions to be conducted under mutually incompatible conditions.

Axi-symmetrical flow reactor for [sup 196]Hg photochemical enrichment

DOEpatents

Grossman, M.W.

1991-04-30

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, [sup 196]Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired [sup 196]Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith. 10 figures.

Electrical signals as mechanism of photosynthesis regulation in plants.

PubMed

Sukhov, Vladimir

2016-12-01

This review summarizes current works concerning the effects of electrical signals (ESs) on photosynthesis, the mechanisms of the effects, and its physiological role in plants. Local irritations of plants induce various photosynthetic responses in intact leaves, including fast and long-term inactivation of photosynthesis, and its activation. Irritation-induced ESs, including action potential, variation potential, and system potential, probably causes the photosynthetic responses in intact leaves. Probable mechanisms of induction of fast inactivation of photosynthesis are associated with Ca 2+ - and (or) H + -influxes during ESs generation; long-term inactivation of photosynthesis might be caused by Ca 2+ - and (or) H + -influxes, production of abscisic and jasmonic acids, and inactivation of phloem H + -sucrose symporters. It is probable that subsequent development of inactivation of photosynthesis is mainly associated with decreased CO 2 influx and inactivation of the photosynthetic dark reactions, which induces decreased photochemical quantum yields of photosystems I and II and increased non-photochemical quenching of photosystem II fluorescence and cyclic electron flow around photosystem I. However, other pathways of the ESs influence on the photosynthetic light reactions are also possible. One of them might be associated with ES-connected acidification of chloroplast stroma inducing ferredoxin-NADP + reductase accumulation at the thylakoids in Tic62 and TROL complexes. Mechanisms of ES-induced activation of photosynthesis require further investigation. The probable ultimate effect of ES-induced photosynthetic responses in plant life is the increased photosynthetic machinery resistance to stressors, including high and low temperatures, and enhanced whole-plant resistance to environmental factors at least during 1 h after irritation.

A New Numerical Simulation technology of Multistage Fracturing in Horizontal Well

NASA Astrophysics Data System (ADS)

Cheng, Ning; Kang, Kaifeng; Li, Jianming; Liu, Tao; Ding, Kun

2017-11-01

Horizontal multi-stage fracturing is recognized the effective development technology of unconventional oil resources. Geological mechanics in the numerical simulation of hydraulic fracturing technology occupies very important position, compared with the conventional numerical simulation technology, because of considering the influence of geological mechanics. New numerical simulation of hydraulic fracturing can more effectively optimize the design of fracturing and evaluate the production after fracturing. This paper studies is based on the three-dimensional stress and rock physics parameters model, using the latest fluid-solid coupling numerical simulation technology to engrave the extension process of fracture and describes the change of stress field in fracturing process, finally predict the production situation.

On the operation of machines powered by quantum non-thermal baths

DOE PAGES

Niedenzu, Wolfgang; Gelbwaser-Klimovsky, David; Kofman, Abraham G.; ...

2016-08-02

Diverse models of engines energised by quantum-coherent, hence non-thermal, baths allow the engine efficiency to transgress the standard thermodynamic Carnot bound. These transgressions call for an elucidation of the underlying mechanisms. Here we show that non-thermal baths may impart not only heat, but also mechanical work to a machine. The Carnot bound is inapplicable to such a hybrid machine. Intriguingly, it may exhibit dual action, concurrently as engine and refrigerator, with up to 100% efficiency. Here, we conclude that even though a machine powered by a quantum bath may exhibit an unconventional performance, it still abides by the traditional principlesmore » of thermodynamics.« less

Simulation of photoreactive transients and of photochemical transformation of organic pollutants in sunlit boreal lakes across 14 degrees of latitude: A photochemical mapping of Sweden.

PubMed

Koehler, Birgit; Barsotti, Francesco; Minella, Marco; Landelius, Tomas; Minero, Claudio; Tranvik, Lars J; Vione, Davide

2018-02-01

Lake water constituents, such as chromophoric dissolved organic matter (CDOM) and nitrate, absorb sunlight which induces an array of photochemical reactions. Although these reactions are a substantial driver of pollutant degradation in lakes they are insufficiently understood, in particular on large scales. Here, we provide for the first time comprehensive photochemical maps covering a large geographic region. Using photochemical kinetics modeling for 1048 lakes across Sweden we simulated the steady-state concentrations of four photoreactive transient species, which are continuously produced and consumed in sunlit lake waters. We then simulated the transient-induced photochemical transformation of organic pollutants, to gain insight into the relevance of the different photoreaction pathways. We found that boreal lakes were often unfavorable environments for photoreactions mediated by hydroxyl radicals (OH) and carbonate radical anions (CO 3 - ), while photoreactions mediated by CDOM triplet states ( 3 CDOM*) and, to a lesser extent, singlet oxygen ( 1 O 2 ) were the most prevalent. These conditions promote the photodegradation of phenols, which are used as plastic, medical drug and herbicide precursors. When CDOM concentrations increase, as is currently commonly the case in boreal areas such as Sweden, 3 CDOM* will also increase, promoting its importance in photochemical pathways even more. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of photochemical pollution in summer and winter using a photochemical box model in the center of Tokyo, Japan.

PubMed

Huang, H; Akustu, Y; Arai, M; Tamura, M

2001-07-01

In order to give an effective and rapid analysis of the photochemical pollution and information for emission control strategies, a photochemical box model (PBM) was applied to one moderate summer episode, 11 July 1996, and one typical winter episode, 3 December 1996, in the center of Tokyo, Japan. The box model gave a good prediction of the photochemical pollution with minimal investment. As expected, the peak ozone in summer is higher than in winter. The NOx concentrations in winter are higher than those in summer. In summer, NO and NO2 have one peak in the morning. In winter, NO and NO2 show two peaks during the day. Three model runs including no reactions, a zero ozone boundary condition and dark reactions were conducted to understand the photochemical processes. The effects of emission reduction on the formation of the photochemical pollution in the center of Tokyo have been studied. The results show that the reduction of NMHC emission can decrease the ozone, however, the reduction of NOx emission can increase the ozone. It can be concluded that if the NOx emission are reduced, the reduction of NMHC should be more emphasized in order to decrease the ozone concentration in the center of Tokyo, Japan, especially the reduction of the NMHC from stationary source emission.

Adapting Unconventional Warfare Doctrine to Cyberspace Operations: An Examination of Hacktivist Based Insurgencies

DTIC Science & Technology

2015-06-12

Unconventional Warfare, Cyberspace Operations, Cyber Warfare , Hacktivism, China, Russia, Georgia, Estonia, Umbrella Revolution, UW, Cyber, Guerilla, Hacktivist...6 Cyber Warfare ............................................................................................................. 7...Internet, and cyber warfare , the nature of the human element in cyberspace exhibits only a scientific advancement in the evolution of warfare, not a

Assessment of potential unconventional Carboniferous-Permian gas resources of the Liaohe Basin eastern uplift, Liaoning Province, China, 2011

USGS Publications Warehouse

Pollastro, Richard M.; Potter, Christopher J.; Schenk, Christopher J.; Charpentier, Ronald R.; Cook, Troy A.; Klett, Timothy R.; Kirschbaum, Mark A.

2012-01-01

The U.S. Geological Survey estimated a mean of 448 billion cubic feet of potential technically recoverable unconventional natural gas in Carboniferous and Permian coal-bearing strata in the eastern uplift of the Liaohe Basin, Liaoning Province, China.

Conquest from Within: A Comparative Analysis between Soviet Active Measures and United States Unconventional Warfare Doctrine

DTIC Science & Technology

2015-05-27

irregular threats. Unconventional Warfare (UW), traditionally a Special Operations Forces core activity, has served U.S. strategic interests in a variety...Special Operations Forces core activity, has served U.S. strategic interests in a variety of operational environments. Throughout the Cold War, the

Retrospective Case Study in Wise County, Texas, Study of the Potential Impacts of Hydraulic Fracturing on Drinking Water Resources

EPA Science Inventory

This report describes the retrospective case study in north central Texas, conducted at three locations in Wise County where both conventional and unconventional gas production occurred in the past. Currently unconventional gas production occurs from the Mississippian-aged Barne...

Adolescents' Response to Unconventional War Threat Prior to the Gulf War.

ERIC Educational Resources Information Center

Klingman, Avigdor; Goldstein, Zehava

1994-01-01

Examined Israeli adolescents' responses to impending unconventional warfare by administering Nuclear Threat Index to 269 junior high school students 2 months prior to Persian Gulf War. Younger adolescents and females reported more activity, pessimistic thoughts, and concerns than older adolescents and males, respectively; and "internal"…

Ironing Out the Unconventional Mechanisms of Iron Acquisition and Gene Regulation in Chlamydia

PubMed Central

Pokorzynski, Nick D.; Thompson, Christopher C.; Carabeo, Rey A.

2017-01-01

The obligate intracellular pathogen Chlamydia trachomatis, along with its close species relatives, is known to be strictly dependent upon the availability of iron. Deprivation of iron in vitro induces an aberrant morphological phenotype termed “persistence.” This persistent phenotype develops in response to various immunological and nutritional insults and may contribute to the development of sub-acute Chlamydia-associated chronic diseases in susceptible populations. Given the importance of iron to Chlamydia, relatively little is understood about its acquisition and its role in gene regulation in comparison to other iron-dependent bacteria. Analysis of the genome sequences of a variety of chlamydial species hinted at the involvement of unconventional mechanisms, being that Chlamydia lack many conventional systems of iron homeostasis that are highly conserved in other bacteria. Herein we detail past and current research regarding chlamydial iron biology in an attempt to provide context to the rapid progress of the field in recent years. We aim to highlight recent discoveries and innovations that illuminate the strategies involved in chlamydial iron homeostasis, including the vesicular mode of acquiring iron from the intracellular environment, and the identification of a putative iron-dependent transcriptional regulator that is synthesized as a fusion with a ABC-type transporter subunit. These recent findings, along with the noted absence of iron-related homologs, indicate that Chlamydia have evolved atypical approaches to the problem of iron homeostasis, reinvigorating research into the iron biology of this pathogen. PMID:28951853

Photochemically Switching Diamidocarbene Spin States Leads to Reversible Büchner Ring Expansions.

PubMed

Perera, Tharushi A; Reinheimer, Eric W; Hudnall, Todd W

2017-10-18

The discovery of thermal and photochemical control by Woodward and Hoffmann revolutionized how we understand chemical reactivity. Similarly, we now describe the first example of a carbene that exhibits differing thermal and photochemical reactivity. When a singlet ground-state N,N'-diamidocarbene 1 was photolyzed at 380 nm, excitation to a triplet state was observed. The triplet-state electronic structure was characteristic of the expected biradical σ 1 p π 1 spin configuration according to a combination of spectroscopic and computational methods. Surprisingly, the triplet state of 1 was found to engage a series of arenes in thermally reversible Büchner ring expansion reactions, marking the first examples where both cyclopropanation and ring expansion of arenes were rendered reversible. Not only are these photochemical reactions different from the known thermal chemistry of 1, but the reversibility enabled us to perform the first examples of photochemically induced arene exchange/expansion reactions at a single carbon center.

Method of making gold thiolate and photochemically functionalized microcantilevers

DOEpatents

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

2009-08-25

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

Investigation of the photochemical changes of chlorogenic acids induced by ultraviolet light in model systems and in agricultural practice with Stevia rebaudiana cultivation as an example.

PubMed

Karaköse, Hande; Jaiswal, Rakesh; Deshpande, Sagar; Kuhnert, Nikolai

2015-04-08

Mono- and diacyl chlorogenic acids undergo photochemical trans-cis isomerization under ultraviolet (UV) irradiation. The photochemical equilibrium composition was established for eight selected derivatives. In contrast to all other dicaffeoylquinic acid derivatives, cynarin (1,3-dicaffeoylquinic acid) undergoes a [2 + 2] photochemical cycloaddition reaction, constituting a first example of Schmidt's law in a natural product family. The relevance of photochemical isomerization in agricultural practice was investigated using 120 samples of Stevia rebaudiana leave samples grown under defined cultivation conditions. Ratios of cis to trans chlorogenic acids were determined in leaf samples and correlated with climatic and harvesting conditions. The data indicate a clear correlation between the formation of cis-caffeoyl derivatives and sunshine hours prior to harvesting and illustrate the relevance of UV exposure to plant material affecting its phytochemical composition.

Impact of synoptic controls and boundary layer processes on ground-level ozone evolution at an urban site

NASA Astrophysics Data System (ADS)

Haman, Christine Lanier

Houston, Texas frequently exceeds the standard for ground-level ozone during the spring and fall. The large commuting population and vast number of industrial sources provide the necessary ingredients for photochemical ozone production in the presence of favorable meteorological conditions. The lack of continuous boundary layer (BL) observations prevents a comprehensive understanding of its role in ozone evolution. In this study, almost two years of BL observations are utilized to investigate the impacts of synoptic and micrometeorological-scale forcings on ozone. Aerosol gradients derived from ceilometer backscatter retrievals are used to identify the BL and residual layers (RL). Overall agreement is found between ceilometer and sonde estimates of the RL and BL heights (BLH), but difficulty detecting the layers occurs during cloud periods or immediately following precipitation. Large monthly variability is present in the peak afternoon BLH (e.g. mean August and December peaks are ˜2000 and 1100 m, respectively). Monthly nocturnal BLHs display much smaller differences. The majority of ozone exceedances occur during large-scale subsidence and weak winds in a postfrontal environment. These conditions result in turbulent kinetic energy, mechanical mixing, and ventilation processes that are 2--3 times weaker on exceedance days, which inhibit morning BL growth by an average of ˜100 m·hr-1 compared to low ozone days. The spring has higher nocturnal ozone levels, which is likely attributable to longer day lengths (˜78 minutes), stronger winds (˜0.78 m·s -1), and higher background ozone (˜5 ppbv) compared to the fall. Boundary layer entrainment plays an important role in ozone evolution. Exceedance days show a characteristic early morning rapid rise of ozone. Vertical ozone profiles indicate the RL ozone peak is ˜60 ppbv on exceedance days, which is ˜25 ppbv (+/- 10 ppbv) greater than low ozone days. The Integrated Profile Mixing (IPM) and Photochemical Budget (PB) methods are used to quantify ozone transport and photochemical production. On low ozone days, both the IPM and PB methods indicate ozone entrainment is ˜3--4 ppbv·hr-1 in this low photochemical environment of ˜1--4 ppbv·hr-1. During the rapid early morning ozone rise on exceedance days, RL entrainment and photochemical ozone production rates are 5--10 and 10--15 ppbv·hr -1, respectively.

A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

NASA Astrophysics Data System (ADS)

Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H.

2003-09-01

A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.

Mechanism of UV-Induced Damage to Mammalian Collagen

DTIC Science & Technology

2014-12-12

enough to use under physiological conditions. We carried out UV photolysis with a UVG – 11 short wavelength hand lamp that emits primarily254 nm. We have...photochemical interaction between UV and mammalian collagen as functions of excitation wavelengths, temperature, fluorescence spectral distribution, and...but has little fluorescence at 325/400 nm (dityrosine). The 325/400 band INCREASES with UV - 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND SUBTITLE 13

Development of Device Quality Nonlinear Optical Materials and Definition of Mechanisms of Optical Nonlinearity

DTIC Science & Technology

1994-09-01

Methods. We arbitrarily divide sequential synthesis methods into the following four categories: (1) traditional Langmuir - Blodgett methods, (2) techniques... Langmuir - Blodgett methods. Films from small amphiphilic molecules, fabricated by Langmuir - Blodgett methods, have been extensively investigated.", 48 -54,67...fabrication of Langmuir - Blodgett films. We shall see in the next section that photochemical reactions can be used to define buried channel waveguides

Variations in protein/flavin hydrogen bonding in a LOV domain produce non-Arrhenius kinetics of adduct decay†

PubMed Central

Zoltowski, Brian D.; Nash, Abigail I.; Gardner, Kevin H.

2011-01-01

Light Oxygen Voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue-light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark state cleavage of the photochemically-generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2 and ribityl hydroxyls with the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. PMID:21923139

The photochemical reflectance index provides an optical indicator of spring photosynthetic activation in evergreen conifers.

PubMed

Wong, Christopher Y S; Gamon, John A

2015-04-01

In evergreens, the seasonal down-regulation and reactivation of photosynthesis is largely invisible and difficult to assess with remote sensing. This invisible phenology may be changing as a result of climate change. To better understand the mechanism and timing of these hidden physiological transitions, we explored several assays and optical indicators of spring photosynthetic activation in conifers exposed to a boreal climate. The photochemical reflectance index (PRI), chlorophyll fluorescence, and leaf pigments for evergreen conifer seedlings were monitored over 1 yr of a boreal climate with the addition of gas exchange during the spring. PRI, electron transport rate, pigment levels, light-use efficiency and photosynthesis all exhibited striking seasonal changes, with varying kinetics and strengths of correlation, which were used to evaluate the mechanisms and timing of spring activation. PRI and pigment pools were closely timed with photosynthetic reactivation measured by gas exchange. The PRI provided a clear optical indicator of spring photosynthetic activation that was detectable at leaf and stand scales in conifers. We propose that PRI might provide a useful metric of effective growing season length amenable to remote sensing and could improve remote-sensing-driven models of carbon uptake in evergreen ecosystems. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Variations in protein-flavin hydrogen bonding in a light, oxygen, voltage domain produce non-Arrhenius kinetics of adduct decay.

PubMed

Zoltowski, Brian D; Nash, Abigail I; Gardner, Kevin H

2011-10-18

Light, oxygen, voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine-tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark-state cleavage of the photochemically generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2, and ribityl hydroxyls and the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility, and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. © 2011 American Chemical Society

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

NASA Technical Reports Server (NTRS)

Toon, Owen B.; Tolbert, Margaret A.

1995-01-01

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanisms thought to be responsible for ozone depletion in the Antarctic and the Arctic. Reactions on PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type I PCS's obtained in Antarctica in September 1987, using recently measured optical constraints of the various compounds that might be present in PSC's. We find that these PSC's were not composed of nitric acid trihydrate but instead had a more complex composition perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSC's to remove NOx permanently through sedimentation. The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Experimental study of heterogeneous organic chemistry induced by far ultraviolet light: Implications for growth of organic aerosols by CH3 addition in the atmospheres of Titan and early Earth

NASA Astrophysics Data System (ADS)

Hong, Peng; Sekine, Yasuhito; Sasamori, Tsutoni; Sugita, Seiji

2018-06-01

Formation of organic aerosols driven by photochemical reactions has been observed and suggested in CH4-containing atmospheres, including Titan and early Earth. However, the detailed production and growth mechanisms of organic aerosols driven by solar far ultraviolet (FUV) light remain poorly constrained. We conducted laboratory experiments simulating photochemical reactions in a CH4sbnd CO2 atmosphere driven by the FUV radiations dominated by the Lyman-α line. In the experiments, we analyzed time variations in thickness and infrared spectra of solid organic film formed on an optical window in a reaction cell. Gas species formed by FUV irradiation were also analyzed and compared with photochemical model calculations. Our experimental results show that the growth rate of the organic film decreases as the CH4/CO2 ratio of reactant gas mixture decreases, and that the decrease becomes very steep for CH4/CO2 < 1. Comparison with photochemical model calculations suggests that polymerizations of gas-phase hydrocarbons, such as polyynes and aromatics, cannot account for the growth rate of the organic film but that the addition reaction of CH3 radicals onto the organic film with the reaction probability around 10-2 can explain the growth rate. At CH4/CO2 < 1, etching by O atom formed by CO2 photolysis would reduce or inhibit the growth of the organic film. Our results suggest that organic aerosols would grow through CH3 addition onto the surface during the precipitation of aerosol particles in the middle atmosphere of Titan and early Earth. On Titan, effective CH3 addition would reduce C2H6 production in the atmosphere. On early Earth, growth of aerosol particles would be less efficient than those on Titan, possibly resulting in small-sized monomers and influencing UV shielding.

Symbiont shuffling linked to differential photochemical dynamics of Symbiodinium in three Caribbean reef corals

NASA Astrophysics Data System (ADS)

Cunning, Ross; Silverstein, Rachel N.; Baker, Andrew C.

2018-03-01

Dynamic symbioses with functionally diverse dinoflagellate algae in the genus Symbiodinium may allow some reef corals to alter their phenotypes through `symbiont shuffling', or changes in symbiont community composition. In particular, corals may become more bleaching resistant by increasing the relative abundance of thermally tolerant Symbiodinium in clade D after bleaching. Despite the immediate relevance of this phenomenon to corals living in warming oceans—and to interventions aimed at boosting coral resilience—the mechanisms governing how, why, and when symbiont shuffling occurs are still poorly understood. Here, we performed controlled thermal bleaching and recovery experiments on three species of Caribbean corals hosting mixtures of D1a ( S. trenchii) and other symbionts in clades B or C. We show that the degree of symbiont shuffling is related to (1) the duration of stress exposure and (2) the difference in photochemical efficiency ( F v /F m) of co-occurring symbionts under stress (i.e., the `photochemical advantage' of one symbiont over the other). The advantage of D1a under stress was greatest in Montastraea cavernosa, intermediate in Siderastrea siderea, and lowest in Orbicella faveolata and correlated positively with the magnitude of shuffling toward D1a. In holobionts where D1a had less of an advantage over co-occurring symbionts (i.e., only slightly higher F v /F m under stress), a longer stress duration was required to elicit commensurate increases in D1a abundance. In fact, across these three coral species, 92.9% of variation in the degree of symbiont shuffling could be explained by the time-integrated photochemical advantage of D1a under heat stress. Although F v /F m is governed by numerous factors that this study is unable to resolve mechanistically, its strong empirical relationship with symbiont shuffling helps elucidate general features that govern this process in reef corals, which will help refine predictions of coral responses to environmental change and inform interventions to manipulate symbiont communities to enhance coral resilience.

Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

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

Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon

This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn 2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO 2) nanosheets.

Changes of Photochemical Properties of Dissolved Organic Matter During a Hydrological Year

NASA Astrophysics Data System (ADS)

Porcal, P.; Dillon, P. J.

2009-05-01

The fate of dissolved organic matter (DOM) in lakes and streams is significantly affected by photochemical transformation of DOM. A series of laboratory photochemical experiments has been conducted to describe long term changes in photochemical properties of DOM. The stream samples used in this study originated from three different watersheds in Dorset area (Ontario, Canada), the first watershed has predominantly coniferous cove, the second one is dominated by maple and birch, and a large wetland dominates to the third one. The first order kinetic constant rate was used as a suitable characteristic of photochemical properties of DOM. The higher rates were observed in samples from watershed dominated by coniferous forest while the lower rates were determined in deciduous forest. Kinetic rates from all three watersheds showed sinusoidal pattern during the hydrological year. The rates increased steadily during autumn and winter and decreased during spring and summer. The highest values were observed during the spring melt events when the fresh DOM was flushed out from terrestrial sources. The minimum rate constants were in summer when the discharge was lower. The photochemical properties of DOM changes during the hydrological year and correspond to the seasonal cycles of terrestrial organic matter.

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

PubMed Central

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

2017-01-01

Melatonin plays an important role in tolerance to multiple stresses in plants. Recent studies have shown that melatonin relieves photoinhibition in plants under cold stress; however, the mechanisms are not fully understood. Non-photochemical quenching (NPQ) is a key process thermally dissipating excess light energy that plants employ as a protective mechanism to prevent the over reduction of photosystem II. Here, we report the effects of exogenous melatonin on NPQ and mitigation of photoinhibition in tomato seedlings exposed to moderate light during chilling. In response to moderate light during chilling, the maximum quantum yield (Fv/Fm) and the effective photochemical efficiency (F′v/F′m) of PSII were both substantially reduced, showing severe photoinhibition in tomato seedlings, whereas exogenous application of melatonin effectively alleviated the photoinhibition. Further experiment showed that melatonin accelerated the induction of NPQ in response to moderate light and maintained higher level of NPQ upon longer exposure to light during chilling. Consistent with the increased NPQ was the elevated de-epoxidation state of xanthophyll pigments in melatonin-pretreated seedlings exposed to light during chilling. Enzyme activity assay showed that violaxanthin de-epoxidase (VDE), which catalyzes the de-epoxidation reaction in the xanthophyll cycle, was activated by light and the activity was further enhanced by application of melatonin. Further analysis revealed that melatonin induced the expression of VDE gene in tomato seedlings under moderate light and chilling conditions. Ascorbic acid is an essential cofactor of VDE and the level of it was found to be increased in melatonin-pretreated seedlings. Feeding tomato seedlings with dithiothreitol, an inhibitor of VDE, blocked the effects of melatonin on the de-epoxidation state of xanthophyll pigments and the induction of NPQ. Collectively, these results suggest that exogenous melatonin mitigates photoinhibition by accelerating NPQ through the stimulation of VDE activity and the enhancement of de-epoxidation state of xanthophyll pigments. PMID:28265283

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

PubMed

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

2017-01-01

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

Heat Transfer and Fluid Mechanics Institute, 24th, Oregon State University, Corvallis, Ore., June 12-14, 1974, Proceedings

NASA Technical Reports Server (NTRS)

Davis, L. R. (Editor); Wilson, R. E.

1974-01-01

Recent theoretical and experimental studies in heat transfer and fluid mechanics, including some environmental protection investigations, are presented in a number of papers. Some of the topics covered include condensation heat transfer, a model of turbulent momentum and heat transfer at points of separation and reattachment, an explicit scheme for calculations of confined turbulent flows with heat transfer, heat transfer effects on a delta wing in subsonic flow, fluid mechanics of ocean outfalls, thermal plumes from industrial cooling water, a photochemical air pollution model for the Los Angeles air basin, and a turbulence model of diurnal variations in the planetary boundary layer. Individual items are announced in this issue.

Compaction bands in high temperature/pressure diagenetically altered unconventional shale gas reservoirs

NASA Astrophysics Data System (ADS)

Regenauer-Lieb, K.; Veveakis, M.; Poulet, T.

2014-12-01

Unconventional energy and mineral resources are typically trapped in a low porosity/permeability environment and are difficult to produce. An extreme end-member is the shale gas reservoir in the Cooper Basin (Australia) that is located at 3500-4000 m depth and ambient temperature conditions around 200oC. Shales of lacustrine origin (with high clay content) are diagenetically altered. Diagenesis involves fluid release mineral reactions of the general type Asolid ↔ Bsolid +Cfluid and switches on suddenly in the diagenetic window between 100-200oC. Diagenetic reactions can involve concentrations of smectite, aqueous silica compound, illite, potassium ions, aqueous silica, quartz, feldspar, kerogen, water and gas . In classical petroleum engineering such interlayer water/gas release reactions are considered to cause cementation and significantly reduce porosity and permeability. Yet in contradiction to the expected permeability reduction gas is successfully being produced. We propose that the success is based on the ductile equivalent of classical compaction bands in solid mechanics. The difference being that that the rate of the volumetric compaction is controlled by the diagenetic reactions. Ductile compaction bands are forming high porosity fluid channels rather than low porosity crushed grains in the solid mechanical equivalent. We show that this new type of volumetric instability appears in rate-dependent heterogenous materials as Cnoidal waves. These are nonlinear and exact periodic stationary waves, well known in the shallow water theory of fluid mechanics. Their distance is a direct function of the hydromechanical diffusivities. These instabilities only emerge in low permeability environment where the fluid diffusivity is about an order of magnitude lower than the mechanical loading. The instabilities are expected to be of the type as shown in the image below. The image shows a CT-scan of a laboratory experiment kindly provided by Papamichos (pers.comm.). Periodic compaction bands are clearly detected by the CT analysis of a shale sample compressed under high confining pressure.

Carbon Disulfide (CS2) Mechanisms in Formation of Atmospheric Carbon Dioxide (CO2) Formation from Unconventional Shale Gas Extraction and Processing Operations and Global Climate Change.

PubMed

Rich, Alisa L; Patel, Jay T

2015-01-01

Carbon disulfide (CS2) has been historically associated with the production of rayon, cellophane, and carbon tetrachloride. This study identifies multiple mechanisms by which CS2 contributes to the formation of CO2 in the atmosphere. CS2 and other associated sulfide compounds were found by this study to be present in emissions from unconventional shale gas extraction and processing (E&P) operations. The breakdown products of CS2; carbonyl sulfide (COS), carbon monoxide (CO), and sulfur dioxide (SO2) are indirect greenhouse gases (GHGs) that contribute to CO2 levels in the atmosphere. The heat-trapping nature of CO2 has been found to increase the surface temperature, resulting in regional and global climate change. The purpose of this study is to identify five mechanisms by which CS2 and the breakdown products of CS2 contribute to atmospheric concentrations of CO2. The five mechanisms of CO2 formation are as follows: Chemical Interaction of CS2 and hydrogen sulfide (H2S) present in natural gas at high temperatures, resulting in CO2 formation;Combustion of CS2 in the presence of oxygen producing SO2 and CO2;Photolysis of CS2 leading to the formation of COS, CO, and SO2, which are indirect contributors to CO2 formation;One-step hydrolysis of CS2, producing reactive intermediates and ultimately forming H2S and CO2;Two-step hydrolysis of CS2 forming the reactive COS intermediate that reacts with an additional water molecule, ultimately forming H2S and CO2. CS2 and COS additionally are implicated in the formation of SO2 in the stratosphere and/or troposphere. SO2 is an indirect contributor to CO2 formation and is implicated in global climate change.

78 FR 15377 - Agency Information Collection Activities; Submission for OMB Review; Comment Request; Requests To...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-11

... for OMB Review; Comment Request; Requests To Approve Conformed Wage Classifications and Unconventional... Classifications and Unconventional Fringe Benefit Plans Under the Davis-Bacon and Related Acts and Contract Work... collection consist of: (A) Reports of conformed classifications and wage rates and (B) requests for approval...

Assessment of undiscovered oil and gas resources of the Paris Basin, France, 2015

USGS Publications Warehouse

Schenk, Christopher J.; Charpentier, Ronald R.; Klett, Timothy R.; Tennyson, Marilyn E.; Mercier, Tracey J.; Le, Phoung A.; Brownfield, Michael E.; Pitman, Janet K.; Gaswirth, Stephanie B.; Marra, Kristen R.; Leathers, Heidi M.

2015-01-01

Using a geology-based assessment methodology, the U.S. Geological Survey estimated means of 222 million barrels of unconventional oil; 2,092 billion cubic feet of unconventional gas; 18 million barrels of conventional oil; and 47 billion cubic feet of conventional gas resources in the Paris Basin of France.

Aspects of a Neoteric Approach to Advance Students' Ability to Conjecture, Prove, or Disprove

ERIC Educational Resources Information Center

McLoughlin, M. Padraig M. M.

2010-01-01

The author of this paper suggests several neoteric, unconventional, idiosyncratic, or unique approaches to beginning Set Theory that he found seems to work well in building students' introductory understanding of the Foundations of Mathematics. This paper offers some ideas on how the author uses certain "unconventional" definitions and…

Non-hydroxyl radical mediated photochemical processes for dye degradation.

PubMed

Liu, Xitong; Song, Xiaojie; Zhang, Shujuan; Wang, Mengshu; Pan, Bingcai

2014-04-28

Using solar energy for the decontamination of wastewater is a promising solution to the water-energy nexus. Current advanced oxidation processes have an unsatisfactory efficiency in the treatment of dye wastewater due to the non-selectivity of hydroxyl radicals. More efficient photochemical approaches for dye degradation are highly needed. Three diketones, biacetyl, acetylacetone, and acetonylacetone, were proven to be potent activators for the photodecoloration of azo, triarylmethane and anthraquinone dyes. The photodegradation kinetics of Acid Orange 7 in the UV/diketone processes was much faster than that in the UV/H2O2 system. Photo-induced energy and electron transfer were possible mechanisms for dye degradation in the diketone systems. Adducts of dye and acetylacetone were identified, indicating a unique dye degradation route through adduct formation and decomposition. Unlike acting only as the target substrate of ˙OH in advanced oxidation processes, the dyes played vital roles in the UV/diketone processes. The findings here provide new insights for designing more efficient technologies for environmental remediation, based on diketone photochemistry.

Approaches to efficient molecular catalyst systems for photochemical H2 production using [FeFe]-hydrogenase active site mimics.

PubMed

Wang, Mei; Chen, Lin; Li, Xueqiang; Sun, Licheng

2011-12-28

The research on structural and functional biomimics of the active site of [FeFe]-hydrogenases is in an attempt to elucidate the mechanisms of H(2)-evolution and uptake at the [FeFe]-hydrogenase active site, and to learn from Nature how to create highly efficient H(2)-production catalyst systems. Undoubtedly, it is a challenging, arduous, and long-term work. In this perspective, the progresses in approaches to photochemical H(2) production using mimics of the [FeFe]-hydrogenase active site as catalysts in the last three years are reviewed, with emphasis on adjustment of the redox potentials and hydrophilicity of the [FeFe]-hydrogenase active site mimics to make them efficient catalysts for H(2) production. With gradually increasing understanding of the chemistry of the [FeFe]-hydrogenases and their mimics, more bio-inspired proton reduction catalysts with significantly improved efficiency of H(2) production will be realized in the future. This journal is © The Royal Society of Chemistry 2011

Chemical Evolution and the Origin of Life: Bibliography 1975

NASA Technical Reports Server (NTRS)

West, Martha W. (Compiler); Koch, Rowena A. (Compiler); Chang, Sherwood (Compiler)

1977-01-01

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon-carbon bond fragmentation reactions of tetrameric lignin model compounds.

PubMed

Cho, Dae Won; Latham, John A; Park, Hea Jung; Yoon, Ung Chan; Langan, Paul; Dunaway-Mariano, Debra; Mariano, Patrick S

2011-04-15

New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.

Organic photochemical storage of solar energy. Progress report, July 1, 1977--Feburary 28, 1978

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

Jones, G. II

1978-03-01

The prospects for driving endoergic reactions of simple, relatively abundant organic chemicals by photochemical means have been examined. Strategies for utilization of light of varying wavelength involve sensitization mechanisms which depend on the redox properties of energy storing substrates and photosensitizers. Of principal interest is valence isomerization which can be induced by electron donor-acceptor interaction between substrate and sensitizer in an excited complex or exciplex. Photophysical studies show that potentially isomerizable substrates efficiently intercept redox photosensitizers. The quenching of emission of electron acceptor sensitizers by non conjugated hydrocarbon dienes is indeed a function of the reduction potential of the acceptorsmore » (a series of aromatics with varying absorption characteristics) and the oxidation potentials of the substrates. Electron deficient dienes have been shown alternatively to be efficient quenchers of excited donor sensitizers. That exciplexes are formed between isomerizable substrates and donor or acceptor sensitizers has been confirmed by emission spectroscopy. The rearrangement of hexamethyldewarbenzene, a model exciplex isomerization has been examined in some detail.« less

Relationships Between Dissolved Organic Matter Composition and Photochemistry in Lakes of Diverse Trophic Status.

PubMed

Maizel, Andrew C; Li, Jing; Remucal, Christina K

2017-09-05

The North Temperate Lakes Long-Term Ecological Research site includes seven lakes in northern Wisconsin that vary in hydrology, trophic status, and landscape position. We examine the molecular composition of dissolved organic matter (DOM) within these lakes using Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) and quantify DOM photochemical activity using probe compounds. Correlations between the relative intensity of individual molecular formulas and reactive species production demonstrate the influence of DOM composition on photochemistry. For example, highly aromatic, tannin-like formulas correlate positively with triplet formation rates, but negatively with triplet quantum yields, as waters enriched in highly aromatic formulas exhibit much higher rates of light absorption, but only slightly higher rates of triplet production. While commonly utilized optical properties also correlate with DOM composition, the ability of FT-ICR MS to characterize DOM subpopulations provides unique insight into the mechanisms through which DOM source and environmental processing determine composition and photochemical activity.

Economic photoprotection in photosystem II that retains a complete light-harvesting system with slow energy traps

NASA Astrophysics Data System (ADS)

Belgio, Erica; Kapitonova, Ekaterina; Chmeliov, Jevgenij; Duffy, Christopher D. P.; Ungerer, Petra; Valkunas, Leonas; Ruban, Alexander V.

2014-07-01

The light-harvesting antenna of higher plant photosystem II has an intrinsic capability for self-defence against intense sunlight. The thermal dissipation of excess energy can be measured as the non-photochemical quenching of chlorophyll fluorescence. It has recently been proposed that the transition between the light-harvesting and self-defensive modes is associated with a reorganization of light-harvesting complexes. Here we show that despite structural changes, the photosystem II cross-section does not decrease. Our study reveals that the efficiency of energy trapping by the non-photochemical quencher(s) is lower than the efficiency of energy capture by the reaction centres. Consequently, the photoprotective mechanism works effectively for closed rather than open centres. This type of defence preserves the exceptional efficiency of electron transport in a broad range of light intensities, simultaneously ensuring high photosynthetic productivity and, under hazardous light conditions, sufficient photoprotection for both the reaction centre and the light-harvesting pigments of the antenna.

Photochemical oxidants: state of the science.

PubMed

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

1999-01-01

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

Introductory study of the chemical behavior of jet emissions in photochemical smog. [computerized simulation

NASA Technical Reports Server (NTRS)

Whitten, G. Z.; Hogo, H.

1976-01-01

Jet aircraft emissions data from the literature were used as initial conditions for a series of computer simulations of photochemical smog formation in static air. The chemical kinetics mechanism used in these simulations was an updated version which contains certain parameters designed to account for hydrocarbon reactivity. These parameters were varied to simulate the reaction rate constants and average carbon numbers associated with the jet emissions. The roles of surface effects, variable light sources, NO/NO2 ratio, continuous emissions, and untested mechanistic parameters were also assessed. The results of these calculations indicate that the present jet emissions are capable of producing oxidant by themselves. The hydrocarbon/nitrous oxides ratio of present jet aircraft emissions is much higher than that of automobiles. These two ratios appear to bracket the hydrocarbon/nitrous oxides ratio that maximizes ozone production. Hence an enhanced effect is seen in the simulation when jet exhaust emissions are mixed with automobile emissions.

Degradation of artificial sweeteners via direct and indirect photochemical reactions.

PubMed

Perkola, Noora; Vaalgamaa, Sanna; Jernberg, Joonas; Vähätalo, Anssi V

2016-07-01

We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment.

Unconventional topological Hall effect in skyrmion crystals caused by the topology of the lattice

NASA Astrophysics Data System (ADS)

Göbel, Börge; Mook, Alexander; Henk, Jürgen; Mertig, Ingrid

2017-03-01

The hallmark of a skyrmion crystal (SkX) is the topological Hall effect (THE). In this article we predict and explain an unconventional behavior of the topological Hall conductivity in SkXs. In simple terms, the spin texture of the skyrmions causes an inhomogeneous emergent magnetic field whose associated Lorentz force acts on the electrons. By making the emergent field homogeneous, the THE is mapped onto the quantum Hall effect (QHE). Consequently, each electronic band of the SkX is assigned to a Landau level. This correspondence of THE and QHE allows us to explain the unconventional behavior of the THE of electrons in SkXs. For example, a skyrmion crystal on a triangular lattice exhibits a quantized topological Hall conductivity with steps of 2 .e2/h below and with steps of 1 .e2/h above the van Hove singularity. On top of this, the conductivity shows a prominent sign change at the van Hove singularity. These unconventional features are deeply connected to the topology of the structural lattice.

Associations Between Positive Body Image, Sexual Liberalism, and Unconventional Sexual Practices in U.S. Adults.

PubMed

Swami, Viren; Weis, Laura; Barron, David; Furnham, Adrian

2017-11-01

While studies have documented robust relationships between body image and sexual health outcomes, few studies have looked beyond sexual functioning in women. Here, we hypothesized that more positive body image would be associated with greater sexual liberalism and more positive attitudes toward unconventional sexual practices. An online sample of 151 women and 164 men from the U.S. completed measures of sexual liberalism, attitudes toward unconventional sexual practices, and indices of positive body image (i.e., body appreciation, body acceptance by others, body image flexibility, and body pride), and provided their demographic details. Regression analyses indicated that, once the effects of sexual orientation, relationship status, age, and body mass index had been accounted for, higher body appreciation was significantly associated with greater sexual liberalism in women and men. Furthermore, higher body appreciation and body image flexibility were significantly associated with more positive attitudes toward unconventional sexual practices in women and men. These results may have implications for scholars working from a sex-positive perspective, particularly in terms of understanding the role body image plays in sexual attitudes and behaviors.

URI Regulates KAP1 Phosphorylation and Transcriptional Repression via PP2A Phosphatase in Prostate Cancer Cells.

PubMed

Mita, Paolo; Savas, Jeffrey N; Briggs, Erica M; Ha, Susan; Gnanakkan, Veena; Yates, John R; Robins, Diane M; David, Gregory; Boeke, Jef D; Garabedian, Michael J; Logan, Susan K

2016-12-02

URI (unconventional prefoldin RPB5 interactor protein) is an unconventional prefoldin, RNA polymerase II interactor that functions as a transcriptional repressor and is part of a larger nuclear protein complex. The components of this complex and the mechanism of transcriptional repression have not been characterized. Here we show that KAP1 (KRAB-associated protein 1) and the protein phosphatase PP2A interact with URI. Mechanistically, we show that KAP1 phosphorylation is decreased following recruitment of PP2A by URI. We functionally characterize the novel URI-KAP1-PP2A complex, demonstrating a role of URI in retrotransposon repression, a key function previously demonstrated for the KAP1-SETDB1 complex. Microarray analysis of annotated transposons revealed a selective increase in the transcription of LINE-1 and L1PA2 retroelements upon knockdown of URI. These data unveil a new nuclear function of URI and identify a novel post-transcriptional regulation of KAP1 protein that may have important implications in reactivation of transposable elements in prostate cancer cells. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Recycling of Rare Earth Elements

NASA Astrophysics Data System (ADS)

Lorenz, Tom; Bertau, Martin

2017-01-01

Any development of an effective process for rare earth (RE) recycling has become more and more challenging, especially in recent years. Since 2011, when commodity prices of REs had met their all-time maximum, prices have dropped rapidly by more than 90 %. An economic process able to offset these fluctuations has to take unconventional methods into account beside well-known strategies like acid/basic leaching or solvent extraction. The solid-state chlorination provides such an unconventional method for mobilizing RE elements from waste streams. Instead of hydrochloric acid this kind of chlorination decomposes NH4Cl thermally to release up to 400 °C hot HCl gas. After cooling the resulting solid metal chlorides may be easily dissolved in pH-adjusted water. Without producing strongly acidic wastes and with NH4Cl as cheap source for hydrogen chloride, solid-state chlorination provides various advantages in terms of costs and disposal. In the course of the SepSELSA project this method was examined, adjusted and optimized for RE recycling from fluorescent lamp scraps as well as Fe14Nd2B magnets. Thereby many surprising influences and trends required various analytic methods to examine the reasons and special mechanisms behind them.

Reusable High Aspect Ratio 3-D Nickel Shadow Mask

PubMed Central

Shandhi, M.M.H.; Leber, M.; Hogan, A.; Warren, D.J.; Bhandari, R.; Negi, S.

2017-01-01

Shadow Mask technology has been used over the years for resistless patterning and to pattern on unconventional surfaces, fragile substrate and biomaterial. In this work, we are presenting a novel method to fabricate high aspect ratio (15:1) three-dimensional (3D) Nickel (Ni) shadow mask with vertical pattern length and width of 1.2 mm and 40 μm respectively. The Ni shadow mask is 1.5 mm tall and 100 μm wide at the base. The aspect ratio of the shadow mask is 15. Ni shadow mask is mechanically robust and hence easy to handle. It is also reusable and used to pattern the sidewalls of unconventional and complex 3D geometries such as microneedles or neural electrodes (such as the Utah array). The standard Utah array has 100 active sites at the tip of the shaft. Using the proposed high aspect ratio Ni shadow mask, the Utah array can accommodate 300 active sites, 200 of which will be along and around the shaft. The robust Ni shadow mask is fabricated using laser patterning and electroplating techniques. The use of Ni 3D shadow mask will lower the fabrication cost, complexity and time for patterning out-of-plane structures. PMID:29056835

Physics and chemistry of complex oxide etching and redeposition control

NASA Astrophysics Data System (ADS)

Margot, Joëlle

2012-10-01

Since its introduction in the 1970s, plasma etching has become the universal method for fine-line pattern transfer onto thin films and is anticipated to remain so in foreseeable future. Despite many success stories, plasma etching processes fail to meet the needs for several of the newest materials involved in advanced devices for photonic, electronic and RF applications like ferroelectrics, electro-optic materials, high-k dielectrics, giant magnetoresistance materials and unconventional conductors. In this context, the work achieved over the last decade on the etching of multicomponent oxides thin films such as barium strontium titanate (BST), strontium titanate (STO) and niobate of calcium and barium (CBN) will be reviewed. These materials present a low reactivity with usual etching gases such as fluorinated and chlorinated gases, their etching is mainly governed by ion sputtering and reactive gases sometimes interact with surface materials to form compounds that inhibit etching. The etching of platinum will also be presented as an example of unconventional conductor materials for which severe redeposition limits the achievable etching quality. Finally, it will be shown how simulation can help to understand the etching mechanisms and to define avenues for higher quality patterning.

Modeling the Relative GHG Emissions of Conventional and Shale Gas Production

PubMed Central

2011-01-01

Recent reports show growing reserves of unconventional gas are available and that there is an appetite from policy makers, industry, and others to better understand the GHG impact of exploiting reserves such as shale gas. There is little publicly available data comparing unconventional and conventional gas production. Existing studies rely on national inventories, but it is not generally possible to separate emissions from unconventional and conventional sources within these totals. Even if unconventional and conventional sites had been listed separately, it would not be possible to eliminate site-specific factors to compare gas production methods on an equal footing. To address this difficulty, the emissions of gas production have instead been modeled. In this way, parameters common to both methods of production can be held constant, while allowing those parameters which differentiate unconventional gas and conventional gas production to vary. The results are placed into the context of power generation, to give a ″well-to-wire″ (WtW) intensity. It was estimated that shale gas typically has a WtW emissions intensity about 1.8–2.4% higher than conventional gas, arising mainly from higher methane releases in well completion. Even using extreme assumptions, it was found that WtW emissions from shale gas need be no more than 15% higher than conventional gas if flaring or recovery measures are used. In all cases considered, the WtW emissions of shale gas powergen are significantly lower than those of coal. PMID:22085088

Modeling the relative GHG emissions of conventional and shale gas production.

PubMed

Stephenson, Trevor; Valle, Jose Eduardo; Riera-Palou, Xavier

2011-12-15

Recent reports show growing reserves of unconventional gas are available and that there is an appetite from policy makers, industry, and others to better understand the GHG impact of exploiting reserves such as shale gas. There is little publicly available data comparing unconventional and conventional gas production. Existing studies rely on national inventories, but it is not generally possible to separate emissions from unconventional and conventional sources within these totals. Even if unconventional and conventional sites had been listed separately, it would not be possible to eliminate site-specific factors to compare gas production methods on an equal footing. To address this difficulty, the emissions of gas production have instead been modeled. In this way, parameters common to both methods of production can be held constant, while allowing those parameters which differentiate unconventional gas and conventional gas production to vary. The results are placed into the context of power generation, to give a ″well-to-wire″ (WtW) intensity. It was estimated that shale gas typically has a WtW emissions intensity about 1.8-2.4% higher than conventional gas, arising mainly from higher methane releases in well completion. Even using extreme assumptions, it was found that WtW emissions from shale gas need be no more than 15% higher than conventional gas if flaring or recovery measures are used. In all cases considered, the WtW emissions of shale gas powergen are significantly lower than those of coal.

Heavy fermions, quantum criticality, and unconventional superconductivity in filled skutterudites and related materials

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

Andraka, Bohdan

2015-05-14

The main goal of this program was to explore the possibility of novel states and behaviors in Pr-based system exhibiting quantum critical behavior, PrOs₄Sb₁₂. Upon small changes of external parameter, such as magnetic field, physical properties of PrOs₄Sb₁₂ are drastically altered from those corresponding to a superconductor, to heavy fermion, to field-induced ordered phase with primary quadrupolar order parameter. All these states are highly unconventional and not understood in terms of current theories thus offer an opportunity to expand our knowledge and understanding of condensed matter. At the same time, these novel states and behaviors are subjects to intense internationalmore » controversies. In particular, two superconducting phases with different transition temperatures were observed in some samples and not observed in others leading to speculations that sample defects might be partially responsible for these exotic behaviors. This work clearly established that crystal disorder is important consideration, but contrary to current consensus this disorder suppresses exotic behavior. Superconducting properties imply unconventional inhomogeneous state that emerges from unconventional homogeneous normal state. Comprehensive structural investigations demonstrated that upper superconducting transition is intrinsic, bulk, and unconventional. The high quality of in-house synthesized single crystals was indirectly confirmed by de Haas-van Alphen quantum oscillation measurements. These measurements, for the first time ever reported, spanned several different phases, offering unprecedented possibility of studying quantum oscillations across phase boundaries.« less

Unconventional therapies for cancer: 1. Essiac

PubMed Central

Kaegi, E

1998-01-01

Physicians and patients have been frustrated by the lack of reliable information on unconventional therapies. To help fill this gap in the area of breast cancer therapy, the Canadian Breast Cancer Research Initiative formed a task force to advise it on how best to promote research into unconventional therapies. As part of the work of the task force, a review of the available literature was carried out for each of the following products: Essiac, green tea, Iscador, hydrazine sulfate, vitamins A, C and E, and 714-X. The first article in this series on unconventional therapies for cancer describes the methodology used to obtain and evaluate the information and provides a summary of the findings on Essiac. Subsequent articles will cover the other products. For most of the products reviewed, there has been some indication of possible benefit but no definitive evidence. Innovative and collaborative research needed to meet the information needs of growing numbers of patients and their physicians is now being sponsored by the Canadian Breast Cancer Research Initiative. Open communication between patients and physicians is also necessary for the maintenance of an appropriate therapeutic partnership and for the identification and control of side effects. The Ontario Division of the Canadian Cancer Society, a partner in the Canadian Breast Cancer Research Initiative, supported the preparation of a patient-information piece on unconventional therapies to accompany the series. This item will assist patients who are considering such therapies and will promote open communication between patients and their physicians. PMID:9559016

Unconventional oil and gas spills: Materials, volumes, and risks to surface waters in four states of the U.S.

PubMed

Maloney, Kelly O; Baruch-Mordo, Sharon; Patterson, Lauren A; Nicot, Jean-Philippe; Entrekin, Sally A; Fargione, Joseph E; Kiesecker, Joseph M; Konschnik, Kate E; Ryan, Joseph N; Trainor, Anne M; Saiers, James E; Wiseman, Hannah J

2017-03-01

Extraction of oil and gas from unconventional sources, such as shale, has dramatically increased over the past ten years, raising the potential for spills or releases of chemicals, waste materials, and oil and gas. We analyzed spill data associated with unconventional wells from Colorado, New Mexico, North Dakota and Pennsylvania from 2005 to 2014, where we defined unconventional wells as horizontally drilled into an unconventional formation. We identified materials spilled by state and for each material we summarized frequency, volumes and spill rates. We evaluated the environmental risk of spills by calculating distance to the nearest stream and compared these distances to existing setback regulations. Finally, we summarized relative importance to drinking water in watersheds where spills occurred. Across all four states, we identified 21,300 unconventional wells and 6622 reported spills. The number of horizontal well bores increased sharply beginning in the late 2000s; spill rates also increased for all states except PA where the rate initially increased, reached a maximum in 2009 and then decreased. Wastewater, crude oil, drilling waste, and hydraulic fracturing fluid were the materials most often spilled; spilled volumes of these materials largely ranged from 100 to 10,000L. Across all states, the average distance of spills to a stream was highest in New Mexico (1379m), followed by Colorado (747m), North Dakota (598m) and then Pennsylvania (268m), and 7.0, 13.3, and 20.4% of spills occurred within existing surface water setback regulations of 30.5, 61.0, and 91.4m, respectively. Pennsylvania spills occurred in watersheds with a higher relative importance to drinking water than the other three states. Results from this study can inform risk assessments by providing improved input parameters on volume and rates of materials spilled, and guide regulations and the management policy of spills. Published by Elsevier B.V.

Unconventional oil and gas spills: Materials, volumes, and risks to surface waters in four states of the U.S.

USGS Publications Warehouse

Maloney, Kelly O.; Baruch-Mordo, Sharon; Patterson, Lauren A.; Nicot, Jean-Philippe; Entrekin, Sally; Fargione, Joe E.; Kiesecker, Joseph M.; Konschnik, Kate E.; Ryan, Joseph N.; Trainor, Anne M.; Saiers, James E.; Wiseman, Hannah J.

2017-01-01

Extraction of oil and gas from unconventional sources, such as shale, has dramatically increased over the past ten years, raising the potential for spills or releases of chemicals, waste materials, and oil and gas. We analyzed spill data associated with unconventional wells from Colorado, New Mexico, North Dakota and Pennsylvania from 2005 to 2014, where we defined unconventional wells as horizontally drilled into an unconventional formation. We identified materials spilled by state and for each material we summarized frequency, volumes and spill rates. We evaluated the environmental risk of spills by calculating distance to the nearest stream and compared these distances to existing setback regulations. Finally, we summarized relative importance to drinking water in watersheds where spills occurred. Across all four states, we identified 21,300 unconventional wells and 6622 reported spills. The number of horizontal well bores increased sharply beginning in the late 2000s; spill rates also increased for all states except PA where the rate initially increased, reached a maximum in 2009 and then decreased. Wastewater, crude oil, drilling waste, and hydraulic fracturing fluid were the materials most often spilled; spilled volumes of these materials largely ranged from 100 to 10,000 L. Across all states, the average distance of spills to a stream was highest in New Mexico (1379 m), followed by Colorado (747 m), North Dakota (598 m) and then Pennsylvania (268 m), and 7.0, 13.3, and 20.4% of spills occurred within existing surface water setback regulations of 30.5, 61.0, and 91.4 m, respectively. Pennsylvania spills occurred in watersheds with a higher relative importance to drinking water than the other three states. Results from this study can inform risk assessments by providing improved input parameters on volume and rates of materials spilled, and guide regulations and the management policy of spills.

JPRS Report, Science & Technology, USSR: Chemistry

DTIC Science & Technology

1990-11-08

desorption cycle. The photochemical activity of the oxides was determined by irradiating them with UV light at 353 K during the oxidation reactions of...No 1, Jan 90] 8 Acid-Base Properties Photochemically Active Titanium Oxide Surfaces [N D. Konovalova, V. I. Stepanenko, etal; UKRAINSKIY...Figures 4; references 13: 10 Russian, 3 Western. UDC 541.183 Acid-Base Properties Photochemically Active Titanium Oxide Surfaces 907M0149B Kiev

The photochemical formation and gas-particle partitioning of oxidation products of decamethyl cyclopentasiloxane and decamethyl tetrasiloxane in the atmosphere

NASA Astrophysics Data System (ADS)

Chandramouli, Bharadwaj; Kamens, Richard M.

Decamethyl cyclopentasiloxane (D 5) and decamethyl tetrasiloxane (MD 2M) were injected into a smog chamber containing fine Arizona road dust particles (95% surface area <2.6 μM) and an urban smog atmosphere in the daytime. A photochemical reaction - gas-particle partitioning reaction scheme, was implemented to simulate the formation and gas-particle partitioning of hydroxyl oxidation products of D 5 and MD 2M. This scheme incorporated the reactions of D 5 and MD 2M into an existing urban smog chemical mechanism carbon bond IV and partitioned the products between gas and particle phase by treating gas-particle partitioning as a kinetic process and specifying an uptake and off-gassing rate. A photochemical model PKSS was used to simulate this set of reactions. A Langmuirian partitioning model was used to convert the measured and estimated mass-based partitioning coefficients ( KP) to a molar or volume-based form. The model simulations indicated that >99% of all product silanol formed in the gas-phase partition immediately to particle phase and the experimental data agreed with model predictions. One product, D 4TOH was observed and confirmed for the D 5 reaction and this system was modeled successfully. Experimental data was inadequate for MD 2M reaction products and it is likely that more than one product formed. The model set up a framework into which more reaction and partitioning steps can be easily added.

Gold nanorods for in-drop colorimetric determination of thiomersal after photochemical decomposition.

PubMed

Martín-Alonso, Manuel; Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

2018-03-13

This work reports on the implementation of gold nanorods (AuNRs) in headspace solvent microextraction for colorimetric determination of volatile analyte derivatives in a single drop. The exposure of AuNRs to both H 2 Se and elemental mercury (Hg 0 ) results in a shift of the longitudinal plasmonic band, unlike a number of volatiles. Accordingly, a method is reported for the determination of Hg 0 with potential applicability to the determination of thiomersal (sodium ethylmercurithiosalicylate). It is based on the photochemical decomposition of thiomersal into Hg(II) and subsequent exposure of AuNRs-containing microdrop to in situ generated Hg 0 . Colorimetric analysis of the enriched drop was carried out without dilution by means of a cuvetteless microvolume UV-vis spectrometer. Under optimal conditions, the limit of detection was 0.5 ng mL -1 (as Hg). The repeatability, expressed as relative standard deviation, was 8.4% (for n = 10). AuNRs exposed to increasing concentrations of the analyte were characterized by means of transmission electron microscopy and UV-vis spectrophotometry to ascertain the mechanism of detection. The method was finally applied to the determination of thiomersal in various pharmaceutical samples and showed quantitative recoveries. Graphical abstract Schematic illustration of a miniaturized colorimetric method based on the use of a microdrop of gold nanorods (AuNRs) for thiomersal determination in pharmaceuticals. It is based on the photochemical decomposition of thiomersal and subsequent Hg 0 generation with in-drop amalgamation.

Unconventional plasticity of HIV-1 reverse transcriptase: how inhibitors could open a connection "gate" between allosteric and catalytic sites.

PubMed

Bellucci, Luca; Angeli, Lucilla; Tafi, Andrea; Radi, Marco; Botta, Maurizio

2013-12-23

Targeted molecular dynamics (TMD) simulations allowed for identifying the chemical/structural features of the nucleotide-competitive HIV-1 inhibitor DAVP-1, which is responsible for the disruption of the T-shape motif between Try183 and Trp229 of the reverse transcriptase (RT). DAVP-1 promoted the opening of a connection "gate" between allosteric and catalytic sites of HIV-1 RT, thus explaining its peculiar mechanism of action and providing useful insights to develop novel nucleotide-competitive RT inhibitors.

Ultrafast magnetic vortex core switching driven by the topological inverse Faraday effect.

PubMed

Taguchi, Katsuhisa; Ohe, Jun-ichiro; Tatara, Gen

2012-09-21

We present a theoretical discovery of an unconventional mechanism of inverse Faraday effect which acts selectively on topological magnetic structures. The effect, topological inverse Faraday effect, is induced by the spin Berry's phase of the magnetic structure when a circularly polarized light is applied. Thus a spin-orbit interaction is not necessary unlike that in the conventional inverse Faraday effect. We demonstrate by numerical simulation that topological inverse Faraday effect realizes ultrafast switching of a magnetic vortex within a switching time of 150 ps without magnetic field.

1,2-diketones promoted degradation of poly(epsilon-caprolactone)

NASA Astrophysics Data System (ADS)

Danko, Martin; Borska, Katarina; Ragab, Sherif Shaban; Janigova, Ivica; Mosnacek, Jaroslav

2012-07-01

Photochemical reactions of Benzil and Camphorquinone were used for modification of poly(ɛ-caprolactone) polymer films. Photochemistry of dopants was followed by infrared spectroscopy, changes on polymer chains of matrix were followed by gel permeation chromatography. Benzoyl peroxide was efficiently photochemically generated from benzyl in solid polymer matrix in the presence of air. Following decomposition of benzoyl peroxide led to degradation of matrix. Photochemical transformation of benzil in vacuum led to hydrogen abstraction from the polymer chains in higher extent, which resulted to chains recombination and formation of gel. Photochemical transformation of camphorquinone to corresponding camphoric peroxide was not observed. Only decrease of molecular weight of polymer matrix doped with camphorquinone was observed during the irradiation.

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

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

Kim, S.; Kim, S. -Y.; Lee, M.

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NO x, SO 2,more » ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HO x (OH, HO 2, and RO 2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO 2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.« less

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

DOE PAGES

Kim, S.; Kim, S. -Y.; Lee, M.; ...

2015-04-29

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NO x, SO 2,more » ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HO x (OH, HO 2, and RO 2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO 2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.« less

Photochemical coatings for the prevention of bacterial colonization.

PubMed

Dunkirk, S G; Gregg, S L; Duran, L W; Monfils, J D; Haapala, J E; Marcy, J A; Clapper, D L; Amos, R A; Guire, P E

1991-10-01

Biomaterials are being used with increasing frequency for tissue substitution. Implantable, prosthetic devices are instrumental in the saving of patients' lives and enhancing the quality of life for many others. However, the greatest barrier to expanding the use of biomedical devices is the high probability of bacterial adherence and proliferation, causing very difficult and often untreatable medical-device centered infections. The difficulty in treating such infections results in great danger to the patient, and usually retrieval of the device with considerable pain and suffering. Clearly, development of processes that make biomedical devices resistant to bacterial adherence and colonization would have widespread application in the field of biomedical technology. A photochemical surface modification process is being investigated as a generic means of applying antimicrobial coatings to biomedical devices. The photochemical process results in covalent immobilization of coatings to all classes of medical device polymers. A discussion of the photochemical surface modification process and preliminary results demonstrating the success of photochemical coatings in formulating microbial-resistant surfaces are presented in this paper.

Photochemical oxidation: A solution for the mixed waste dilemma

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

Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A.

1995-12-31

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

Electronic-carrier-controlled photochemical etching process in semiconductor device fabrication

DOEpatents

Ashby, C.I.H.; Myers, D.R.; Vook, F.L.

1988-06-16

An electronic-carrier-controlled photochemical etching process for carrying out patterning and selective removing of material in semiconductor device fabrication includes the steps of selective ion implanting, photochemical dry etching, and thermal annealing, in that order. In the selective ion implanting step, regions of the semiconductor material in a desired pattern are damaged and the remainder of the regions of the material not implanted are left undamaged. The rate of recombination of electrons and holes is increased in the damaged regions of the pattern compared to undamaged regions. In the photochemical dry etching step which follows ion implanting step, the material in the undamaged regions of the semiconductor are removed substantially faster than in the damaged regions representing the pattern, leaving the ion-implanted, damaged regions as raised surface structures on the semiconductor material. After completion of photochemical dry etching step, the thermal annealing step is used to restore the electrical conductivity of the damaged regions of the semiconductor material.

Electronic-carrier-controlled photochemical etching process in semiconductor device fabrication

DOEpatents

Ashby, Carol I. H.; Myers, David R.; Vook, Frederick L.

1989-01-01

An electronic-carrier-controlled photochemical etching process for carrying out patterning and selective removing of material in semiconductor device fabrication includes the steps of selective ion implanting, photochemical dry etching, and thermal annealing, in that order. In the selective ion implanting step, regions of the semiconductor material in a desired pattern are damaged and the remainder of the regions of the material not implanted are left undamaged. The rate of recombination of electrons and holes is increased in the damaged regions of the pattern compared to undamaged regions. In the photochemical dry etching step which follows ion implanting step, the material in the undamaged regions of the semiconductor are removed substantially faster than in the damaged regions representing the pattern, leaving the ion-implanted, damaged regions as raised surface structures on the semiconductor material. After completion of photochemical dry etching step, the thermal annealing step is used to restore the electrical conductivity of the damaged regions of the semiconductor material.

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

PubMed

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

2014-08-18

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

"Total Physical Response": Un apprentissage non conventionnel ("Total Physical Response": An Unconventional Way to Learn).

ERIC Educational Resources Information Center

Lafayette, R. C.

1991-01-01

A discussion of the Total Physical Response method of second language instruction places the concept within the context of other unconventional language learning methods, reviews the rationale behind the approach, and outlines the classroom procedures used. A sampling of useful commands for classroom use is included. (19 references) (MSE)

An unconventional approach to ecosystem unit classification in western North Carolina, USA

Treesearch

W. Henry McNab; Sara A. Browning; Steven A. Simon; Penelope E. Fouts

1999-01-01

The authors used an unconventional combination of data transformation and multivariate analyses to reduce subjectivity in identification of ecosystem units in a mountainous region of western North Carolina, USA. Vegetative cover and environmental variables were measured on 79 stratified, randomly located, 0.1 ha sample plots in a 4000 ha watershed. Binary...

Introduction

USGS Publications Warehouse

Warwick, Peter D.

2011-01-01

The Energy Minerals Division (EMD) of the American Association of Petroleum Geologists (AAPG) is a membership-based, technical interest group having the primary goal of advancing the science of geology, especially as it relates to exploration, discovery, and production of unconventional energy resources. Current research on unconventional energy resources is rapidly changing and exploration and development efforts for these resources are constantly expanding. Nine summaries derived from 2011 committee reports presented at the EMD Annual Meeting in Houston, Texas in April, 2011, are contained in this review. The complete set of committee reports is available to AAPG members at http://emd.aapg.org/members_only/ annual2011/index.cfm. This report updates the 2006 and 2009 EMD unconventional energy review published in this journal (American Association of Petroleum Geologists, Energy Minerals Division 2007, 2009).

Unconventional aspects of electronic transport in delafossite oxides

NASA Astrophysics Data System (ADS)

Daou, Ramzy; Frésard, Raymond; Eyert, Volker; Hébert, Sylvie; Maignan, Antoine

2017-12-01

The electronic transport properties of the delafossite oxides ? are usually understood in terms of two well-separated entities, namely the triangular ? and (? layers. Here, we review several cases among this extensive family of materials where the transport depends on the interlayer coupling and displays unconventional properties. We review the doped thermoelectrics based on ? and ?, which show a high-temperature recovery of Fermi-liquid transport exponents, as well as the highly anisotropic metals ?, ?, and ?, where the sheer simplicity of the Fermi surface leads to unconventional transport. We present some of the theoretical tools that have been used to investigate these transport properties and review what can and cannot be learned from the extensive set of electronic structure calculations that have been performed.

Surface Raman Spectroscopy for Evaluation of Conformal Wafer Level Union Architectures

DTIC Science & Technology

1990-05-01

require that it be returned. Final Report for Expert Science-Task-A-9-1911 Order #18 by J. Chaiken One goal was to produce ultrafine particles which could...that we have synthesized thin films of nonstoichiometric tungsten oxides by a unique photochemical/physical mechanism involving ultrafine particles /clusters...appropriate data base is underway. In this Final Report we first present a section dealing with the fabrication of the metal-metal oxide ultrafine

Improving Joint Function Using Photochemical Hydrogels for Articular Surface Repair

DTIC Science & Technology

2017-02-01

dilution groups , tdeg increased with increasing concentration of EDC/NHS. Mechanical testing Values for storage modulus in spontaneous control gels (25.86...red) in 48-well nontreated tissue culture plates. As a positive control , a subset group of gels without tethered growth factor was exposed to 0.3 nM...in a cartilage ring and capped with fibrin and collagen gel. A control group consisted of chondrocytes encapsulated in fibrin gel. Constructs were

Method for mercury refinement

DOEpatents

Grossman, M.W.; Speer, R.; George, W.A.

1991-04-09

The effluent from mercury collected during the photochemical separation of the [sup 196]Hg isotope is often contaminated with particulate mercurous chloride, Hg[sub 2]Cl[sub 2]. The use of mechanical filtering via thin glass tubes, ultrasonic rinsing with acetone (dimethyl ketone) and a specially designed cold trap have been found effective in removing the particulate (i.e., solid) Hg[sub 2]Cl[sub 2] contaminant. The present invention is particularly directed to such filtering. 5 figures.

Apparatus for mercury refinement

DOEpatents

Grossman, M.W.; Speer, R.; George, W.A.

1991-07-16

The effluent from mercury collected during the photochemical separation of the [sup 196]Hg isotope is often contaminated with particulate mercurous chloride, Hg[sub 2]Cl[sub 2]. The use of mechanical filtering via thin glass tubes, ultrasonic rinsing with acetone (dimethyl ketone) and a specially designed cold trap have been found effective in removing the particulate (i.e., solid) Hg[sub 2]Cl[sub 2] contaminant. The present invention is particularly directed to such filtering. 5 figures.

Apparatus for mercury refinement

DOEpatents

Grossman, Mark W.; Speer, Richard; George, William A.

1991-01-01

The effluent from mercury collected during the photochemical separation of the .sup.196 Hg isotope is often contaminated with particulate mercurous chloride, Hg.sub.2 Cl.sub.2. The use of mechanical filtering via thin glass tubes, ultrasonic rinsing with acetone (dimethyl ketone) and a specially designed cold trap have been found effective in removing the particulate (i.e., solid) Hg.sub.2 Cl.sub.2 contaminant. The present invention is particularly directed to such filtering.

Method for mercury refinement

DOEpatents

Grossman, Mark W.; Speer, Richard; George, William A.

1991-01-01

The effluent from mercury collected during the photochemical separation of the .sup.196 Hg isotope is often contaminated with particulate mercurous chloride, Hg.sub.2 Cl.sub.2. The use of mechanical filtering via thin glass tubes, ultrasonic rinsing with acetone (dimethyl ketone) and a specially designed cold trap have been found effective in removing the particulate (i.e., solid) Hg.sub.2 Cl.sub.2 contaminant. The present invention is particularly directed to such filtering.

Thermal analysis of microlens formation on a sensitized gelatin layer

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

Muric, Branka; Pantelic, Dejan; Vasiljevic, Darko

2009-07-01

We analyze a mechanism of direct laser writing of microlenses. We find that thermal effects and photochemical reactions are responsible for microlens formation on a sensitized gelatin layer. An infrared camera was used to assess the temperature distribution during the microlens formation, while the diffraction pattern produced by the microlens itself was used to estimate optical properties. The study of thermal processes enabled us to establish the correlation between thermal and optical parameters.

Photochemical mineralization of europium, titanium, and iron oxyhydroxide nanoparticles in the ferritin protein cage.

PubMed

Klem, Michael T; Mosolf, Jesse; Young, Mark; Douglas, Trevor

2008-04-07

The Fe storage protein ferritin was used as a size-constrained reaction vessel for the photoreduction and reoxidation of complexed Eu, Fe, and Ti precursors for the formation of oxyhydroxide nanoparticles. The resultant materials were characterized by dynamic light scattering, gel electrophoresis, UV-vis spectroscopy, and transmission electron microscopy. The photoreduction and reoxidation process is inspired by biological sequestration mechanisms observed in some marine siderophore systems.

Ladderenes: The mechanochemistry and the photochemistry of an exciting class of substances

NASA Astrophysics Data System (ADS)

Frank, Irmgard

2018-06-01

Recently, Chen et al. presented a fascinating paper about the synthesis and mechanochemical transformation of ladderenes. These compounds are sufficiently stable to undergo controlled transformation to polyacetylene if exposed to mechanical load caused, for example, by ultrasound. The present paper adds a closer analysis of the behaviour of the electronic structure under these conditions as well as a study of the photochemical behaviour. The influence of potential side reactions is discussed.

Improving Joint Function Using Photochemical Hydrogels for Articular Surface Repair

DTIC Science & Technology

2013-10-01

riboflavin and blue light in hypoxic conditions. Control gels were not photochemically crosslinked . New cartilage matrix was formed in vivo in mice after 4...Sections were probed with AlexaFluor 568- conjugated secondary antibodies and counterstained with DAPI for cell nuclei. All samples were processed at...calcium deposits demonstrated with von Kossa stains; 2) A degradable form of photochemically crosslinked PEG norbomene gel was formulated and growth

Photochemical and thermal bergman cyclization of a pyrimidine enediynol and enediynone.

PubMed

Choy, N; Blanco, B; Wen, J; Krishan, A; Russell, K C

2000-11-30

[reaction: see text] Novel 10-membered pyrimidine enediynes (3 and 4) were synthesized in seven and eight steps, respectively. These compounds were compared for their abilities to undergo Bergman cyclization both thermally and photochemically. Alcohol 3 readily cyclized both thermally and photochemically in (i)PrOH, while ketone 4 only showed efficient thermal cyclization. Both compounds were also shown to cleave dsDNA under the appropriate conditions.

A model approach to assess the long-term trends of indirect photochemistry in lake water. The case of Lake Maggiore (NW Italy).

PubMed

Minella, Marco; Rogora, Michela; Vione, Davide; Maurino, Valter; Minero, Claudio

2011-08-15

A model-based approach is here developed and applied to predict the long-term trends of indirect photochemical processes in the surface layer (5m water depth) of Lake Maggiore, NW Italy. For this lake, time series of the main parameters of photochemical importance that cover almost two decades are available. As a way to assess the relevant photochemical reactions, the modelled steady-state concentrations of important photogenerated transients ((•)OH, ³CDOM* and CO₃(-•)) were taken into account. A multivariate analysis approach was adopted to have an overview of the system, to emphasise relationships among chemical, photochemical and seasonal variables, and to highlight annual and long-term trends. Over the considered time period, because of the decrease of the dissolved organic carbon (DOC) content of water and of the increase of alkalinity, a significant increase is predicted for the steady-state concentrations of the radicals (•)OH and CO₃(-•). Therefore, the photochemical degradation processes that involve the two radical species would be enhanced. Another issue of potential photochemical importance is related to the winter maxima of nitrate (a photochemical (•)OH source) and the summer maxima of DOC ((•)OH sink and ³CDOM* source) in the lake water under consideration. From the combination of sunlight irradiance and chemical composition data, one predicts that the processes involving (•)OH and CO₃(-•) would be most important in spring, while the reactions involving ³CDOM* would be most important in summer. Copyright © 2011 Elsevier B.V. All rights reserved.

[Effects of optical radiation in ocular structures].

PubMed

Pascu, Ruxandra Angela

2007-01-01

The eye and the skin are organs that are particularly vulnerable to external aggression, such as electromagnetic radiation- meaning ultraviolet radiation, visible radiation (especially blue light) and infrared radiation. The three mechanisms involved are: the photo-thermic mechanism, the photochemical mechanism and the photomechanical mechanism. The effects of such exposures can be either temporary or permanent, if inadequate protection occurs. Today, there are enough data so that special protection measures can be taken concerning the potential damage of optical radiation. Among those, we mention artificial implants or sun glasses containing UV filters or surgical gestures that can be taken to protect the eye against the surgical light. Ultimately, the effects of optical radiation upon the eye are related to being well informed about the risks of uncontrolled exposure and the protection measures against it.

Combination of dynamic transformation and dynamic recrystallization for realizing ultrafine-grained steels with superior mechanical properties

PubMed Central

Zhao, Lijia; Park, Nokeun; Tian, Yanzhong; Shibata, Akinobu; Tsuji, Nobuhiro

2016-01-01

Dynamic recrystallization (DRX) is an important grain refinement mechanism to fabricate steels with high strength and high ductility (toughness). The conventional DRX mechanism has reached the limitation of refining grains to several microns even though employing high-strain deformation. Here we show a DRX phenomenon occurring in the dynamically transformed (DT) ferrite, by which the required strain for the operation of DRX and the formation of ultrafine grains is significantly reduced. The DRX of DT ferrite shows an unconventional temperature dependence, which suggests an optimal condition for grain refinement. We further show that new strategies for ultra grain refinement can be evoked by combining DT and DRX mechanisms, based on which fully ultrafine microstructures having a mean grain size down to 0.35 microns can be obtained without high-strain deformation and exhibit superior mechanical properties. This study will open the door to achieving optimal grain refinement to nanoscale in a variety of steels requiring no high-strain deformation in practical industrial application. PMID:27966603

Glyphosate resistance: state of knowledge

PubMed Central

Sammons, Robert Douglas; Gaines, Todd A

2014-01-01

Studies of mechanisms of resistance to glyphosate have increased current understanding of herbicide resistance mechanisms. Thus far, single-codon non-synonymous mutations of EPSPS (5-enolypyruvylshikimate-3-phosphate synthase) have been rare and, relative to other herbicide mode of action target-site mutations, unconventionally weak in magnitude for resistance to glyphosate. However, it is possible that weeds will emerge with non-synonymous mutations of two codons of EPSPS to produce an enzyme endowing greater resistance to glyphosate. Today, target-gene duplication is a common glyphosate resistance mechanism and could become a fundamental process for developing any resistance trait. Based on competition and substrate selectivity studies in several species, rapid vacuole sequestration of glyphosate occurs via a transporter mechanism. Conversely, as the chloroplast requires transporters for uptake of important metabolites, transporters associated with the two plastid membranes may separately, or together, successfully block glyphosate delivery. A model based on finite glyphosate dose and limiting time required for chloroplast loading sets the stage for understanding how uniquely different mechanisms can contribute to overall glyphosate resistance. PMID:25180399

Optimizing Water Management for Collocated Conventional and Unconventional Reservoirs

NASA Astrophysics Data System (ADS)

Reedy, R. C.; Scanlon, B. R.; Walsh, M.

2016-12-01

With the U.S. producing much more water than oil from oil and gas reservoirs, managing produced water is becoming a critical issue. Here we quantify water production from collocated conventional and unconventional reservoirs using well by well analysis and evaluate various water management strategies using the U.S. Permian Basin as a case study. Water production during the past 15 years in the Permian Basin totaled 55×109 barrels (bbl), 95% from wells in conventional reservoirs resulting in an average water to oil ratio of 12 compared to ratios of 2-3 in wells in unconventional reservoirs. Some of this water ( 25%) is returned to the reservoir for secondary oil recovery (water flooding) while the remaining water is injected into an average of 18,000 salt water disposal wells. Total water production over the past 15 yr (2000 - 2015) exceeds water used for hydraulic fracturing by almost 40 times. Analyzing water injection into salt water disposal wells relative to water requirements for hydraulic fracturing at a 5 square mile grid scale based on 2014 data indicates that water disposal exceeds water requirements for hydraulic fracturing throughout most of the play. Reusing/recycling of produced water for hydraulic fracturing would reduce sourcing and disposal issues related to hydraulic fracturing. Because shales (unconventional reservoirs) provide the source rocks for many conventional reservoirs, coordinating water management from both conventional and unconventional reservoirs can help resolve issues related to sourcing of water for hydraulic fracturing and disposing of produced water. Reusing/recycling produced water can also help reduce water scarcity concerns in some regions.

Can Unconventional Exercise be Helpful in the Treatment, Management and Prevention of Osteosarcopenic Obesity?

PubMed

Kelly, Owen J; Gilman, Jennifer C

2017-01-01

Body composition changes occur with aging; bone and muscle mass decrease while fat mass increases. The collective term for these changes is osteosarcopenic obesity. It is known that conventional resistance exercise programs build/maintain lean mass and reduce fat mass. However, unconventional (to Western society/medicine) forms of exercise may be viable for the treatment/prevention of osteosarcopenic obesity. The purpose of this review is to assess relatively unconventional exercises for their efficacy in maintaining/improving bone and muscle mass and reducing fat mass. A literature search for unconventional exercise showed Tai Chi, yoga, Pilates, whole body vibration, electrical stimulation of muscle, and the Alexander Technique were considered alternative/ unconventional. A PubMed and Medline search for human data using combinations and synonyms of osteoporosis, sarcopenia and obesity, and each exercise was then conducted. Tai Chi, yoga, and Pilates, in addition to whole body vibration, electrical stimulation of muscle, and the Alexander Technique are all considered low impact. Tai Chi, yoga, and Pilates not only physically support the body, but also increase balance and quality of life. The devices showed promise in reducing or preventing muscle atrophy in older people that are unable to perform conventional exercises. Any exercise, conventional or otherwise, especially in sedentary older people, at risk of, or diagnosed with osteosarcopenic obesity may be better than none. Exercise prescriptions should suit the patient and the desired outcomes; the patient should not be forced to fit an exercise prescription, so all potential forms of exercise should be considered. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

The Dynamics of the Photofragmentation of Ketene 3-Cyclopentenone, 3,5-Cycloheptadienone, and Tropone.

DTIC Science & Technology

1985-01-01

suggested that the concerted reaction should be allowed photochemically and the conrotatory mode should be favored. The data were in accord with this...crossing), or (4) reaction to form products, e.g., isomers or fragments, directly from the excited state. Further radiative, non-radiative, and photochemical ...processes can occur from intermediate excited states. Typical photochemical reactions observed in simple ketones in the gas phase are: (1) Norrish

Composition and Photochemical Reactivity of Turbine Engine Exhaust

DTIC Science & Technology

1984-09-01

ESL-TR-84-28 Composition and Photochemical Reactivity of Turbine Engine Exhaust In IL) C.W. SPICER. M.W. HOLDREN, T.F. LYON. and R.M. RIGGIN...NUMBER 2. GOVT ACCIESION NO RECIPIENT’S CATALOG NUMmE" 4. TITLE (aid Sub•ttlC) S. TYPE OF REPORT & PERIOD COvERE0 Composition and Photochemical...involved detailed exhaust organic composition studies with two -. full-scale turbine engines utilizing three fuels. Tiask 4 investigated the

1,2-diketones promoted degradation of poly(epsilon-caprolactone)

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

Danko, Martin; Borska, Katarina; Ragab, Sherif Shaban

2012-07-11

Photochemical reactions of Benzil and Camphorquinone were used for modification of poly({epsilon}-caprolactone) polymer films. Photochemistry of dopants was followed by infrared spectroscopy, changes on polymer chains of matrix were followed by gel permeation chromatography. Benzoyl peroxide was efficiently photochemically generated from benzyl in solid polymer matrix in the presence of air. Following decomposition of benzoyl peroxide led to degradation of matrix. Photochemical transformation of benzil in vacuum led to hydrogen abstraction from the polymer chains in higher extent, which resulted to chains recombination and formation of gel. Photochemical transformation of camphorquinone to corresponding camphoric peroxide was not observed. Only decreasemore » of molecular weight of polymer matrix doped with camphorquinone was observed during the irradiation.« less

Novel gradient-diameter magnetic nanowire arrays with unconventional magnetic anisotropy behaviors.

PubMed

Wang, Jing; Zuo, Zhili; Huang, Liang; Warsi, Muhammad Asif; Xiao, John Q; Hu, Jun

2018-06-21

Fe-Co-Ni gradient-diameter magnetic nanowire arrays were fabricated via direct-current electrodeposition into a tapered anodic aluminium oxide template. In contrast to the magnetic behaviors of uniform-diameter nanowire arrays, these arrays exhibited tailorable magnetic anisotropy that can be used to switch magnetic nanowires easily and unconventional temperature-dependent coercivity with much better thermal stability.

Crustal wavespeed structure of North Texas and Oklahoma based on ambient noise cross-correlation functions and adjoint tomography

NASA Astrophysics Data System (ADS)

Zhu, Hejun

2018-04-01

Recently, seismologists observed increasing seismicity in North Texas and Oklahoma. Based on seismic observations and other geophysical measurements, numerous studies suggested links between the increasing seismicity and wastewater injection during unconventional oil and gas exploration. To better monitor seismic events and investigate their triggering mechanisms, we need an accurate 3D crustal wavespeed model for the study region. Considering the uneven distribution of earthquakes in this area, seismic tomography with local earthquake records have difficulties achieving even illumination. To overcome this limitation, in this study, ambient noise cross-correlation functions are used to constrain subsurface variations in wavespeeds. I use adjoint tomography to iteratively fit frequency-dependent phase differences between observed and predicted band-limited Green's functions. The spectral-element method is used to numerically calculate the band-limited Green's functions and the adjoint method is used to calculate misfit gradients with respect to wavespeeds. Twenty five preconditioned conjugate gradient iterations are used to update model parameters and minimize data misfits. Features in the new crustal model TO25 correlates well with geological provinces in the study region, including the Llano uplift, the Anadarko basin and the Ouachita orogenic front, etc. In addition, there are relatively good correlations between seismic results with gravity and magnetic observations. This new crustal model can be used to better constrain earthquake source parameters in North Texas and Oklahoma, such as epicenter location as well as moment tensor solutions, which are important for investigating triggering mechanisms between these induced earthquakes and unconventional oil and gas exploration activities.

Si Thermoelectric Power Generator with an Unconventional Structure

NASA Astrophysics Data System (ADS)

Sakamoto, Tatsuya; Iida, Tsutomu; Ohno, Yota; Ishikawa, Masashi; Kogo, Yasuo; Hirayama, Naomi; Arai, Koya; Nakamura, Takashi; Nishio, Keishi; Takanashi, Yoshifumi

2014-06-01

We examine the mechanical stability of an unconventional Mg2Si thermoelectric generator (TEG) structure. In this structure, the angle θ between the thermoelectric (TE) chips and the heat sink is less than 90°. We examined the tolerance to an external force of various Mg2Si TEG structures using a finite-element method (FEM) with the ANSYS code. The output power of the TEGs was also measured. First, for the FEM analysis, the mechanical properties of sintered Mg2Si TE chips, such as the bending strength and Young's modulus, were measured. Then, two-dimensional (2D) TEG models with various values of θ (90°, 75°, 60°, 45°, 30°, 15°, and 0°) were constructed in ANSYS. The x and y axes were defined as being in the horizontal and vertical directions of the substrate, respectively. In the analysis, the maximum tensile stress in the chip when a constant load was applied to the TEG model in the x direction was determined. Based on the analytical results, an appropriate structure was selected and a module fabricated. For the TEG fabrication, eight TE chips, each with dimensions of 3 mm × 3 mm × 10 mm and consisting of Sb-doped n-Mg2Si prepared by a plasma-activated sintering process, were assembled such that two chips were connected in parallel, and four pairs of these were connected in series on a footprint of 46 mm × 12 mm. The measured power generation characteristics and temperature distribution with temperature differences between 873 K and 373 K are discussed.

Differential Expression of Unconventional Myosins in Apoptotic and Regenerating Chick Hair Cells Confirms Two Regeneration Mechanisms

PubMed Central

DUNCAN, LUKE J.; MANGIARDI, DOMINIC A.; MATSUI, JONATHAN I.; ANDERSON, JULIA K.; McLAUGHLIN-WILLIAMSON, KATE; COTANCHE, DOUGLAS A.

2008-01-01

Hair cells of the inner ear are damaged by intense noise, aging, and aminoglycoside antibiotics. Gentamicin causes oxidative damage to hair cells, inducing apoptosis. In mammals, hair cell loss results in a permanent deficit in hearing and balance. In contrast, avians can regenerate lost hair cells to restore auditory and vestibular function. This study examined the changes of myosin VI and myosin VIIa, two unconventional myosins that are critical for normal hair cell formation and function, during hair cell death and regeneration. During the late stages of apoptosis, damaged hair cells are ejected from the sensory epithelium. There was a 4–5-fold increase in the labeling intensity of both myosins and a redistribution of myosin VI into the stereocilia bundle, concurrent with ejection. Two separate mechanisms were observed during hair cell regeneration. Proliferating supporting cells began DNA synthesis 60 hours after gentamicin treatment and peaked at 72 hours postgentamicin treatment. Some of these mitotically produced cells began to differentiate into hair cells at 108 hours after gentamicin (36 hours after bromodeoxyuridine (BrdU) administration), as demonstrated by the colabeling of myosin VI and BrdU. Myosin VIIa was not expressed in the new hair cells until 120 hours after gentamicin. Moreover, a population of supporting cells expressed myosin VI at 78 hours after gentamicin treatment and myosin VIIa at 90 hours. These cells did not label for BrdU and differentiated far too early to be of mitotic origin, suggesting they arose by direct transdifferentiation of supporting cells into hair cells. PMID:17048225

Unconventional Dentistry in India – An Insight into the Traditional Methods

PubMed Central

Boloor, Vinita Ashutosh; Hosadurga, Rajesh; Rao, Anupama; Jenifer, Haziel; Pratap, Sruthy

2014-01-01

Unconventional medicine (UM) has been known and practised since the recorded history of civilization. Some unconventional practices may be viewed as “the continuity of traditions, religious beliefs, and even quackery that non-specialists practice.” These practices have been associated with religious beliefs and the spiritual domain as well as with the physical domain. In ancient Old World civilizations, UM was performed by skilled experts or wise men; in today's Western civilization, practitioners may or may not be licensed, and some are charlatans. Dentistry, like medicine, is a traditional, science-based, highly regulated healthcare profession that serves increasingly sophisticated and demanding clients. Today, traditional dental practice is dealing with an array of challenges to the established professional system; these challenges are generally termed “alternative” (or complementary, unconventional, or integrative). Genuine alternatives are comparable methods of equal value that have met scientific and regulatory criteria for safety and effectiveness. Because “alternative care” has become politicized and is often a misnomer – referring to practices that are not alternative to, complementary to, or integrating with conventional health care – the more accurate term “unconventional” is used. PMID:25161919

Monitoring radionuclides in subsurface drinking water sources near unconventional drilling operations: a pilot study.

PubMed

Nelson, Andrew W; Knight, Andrew W; Eitrheim, Eric S; Schultz, Michael K

2015-04-01

Unconventional drilling (the combination of hydraulic fracturing and horizontal drilling) to extract oil and natural gas is expanding rapidly around the world. The rate of expansion challenges scientists and regulators to assess the risks of the new technologies on drinking water resources. One concern is the potential for subsurface drinking water resource contamination by naturally occurring radioactive materials co-extracted during unconventional drilling activities. Given the rate of expansion, opportunities to test drinking water resources in the pre- and post-fracturing setting are rare. This pilot study investigated the levels of natural uranium, lead-210, and polonium-210 in private drinking wells within 2000 m of a large-volume hydraulic fracturing operation--before and approximately one-year following the fracturing activities. Observed radionuclide concentrations in well waters tested did not exceed maximum contaminant levels recommended by state and federal agencies. No statistically-significant differences in radionuclide concentrations were observed in well-water samples collected before and after the hydraulic fracturing activities. Expanded monitoring of private drinking wells before and after hydraulic fracturing activities is needed to develop understanding of the potential for drinking water resource contamination from unconventional drilling and gas extraction activities. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of nitric oxide on photochemical ozone formation in mixtures of air with molecular chlorine and with trichlorofluoromethane

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Wong, E. L.

1978-01-01

Ozone formation in a reaction chamber at room temperature and atmospheric pressure were studied for the photolysis of mixtures of NO with either Cl2 or CFCl3 in air. Both Cl2 + NO and CFCl3 + NO in air strongly inhibited O3 formation during the entire 3 to 4 hour reaction. A chemical mechanism that explains the results was presented. An important part of this mechanism was the formation and destruction of chlorine nitrate. Computations were performed with this same mechanism for CFCl3-NO-air mixtures at stratospheric temperatures, pressures, and concentrations. Results showed large reductions in steady-state O3 concentrations in these mixtures as compared with pure air.

Asymmetric photoredox transition-metal catalysis activated by visible light.

PubMed

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-06

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the 'green' synthesis of non-racemic chiral molecules.

Asymmetric photoredox transition-metal catalysis activated by visible light

NASA Astrophysics Data System (ADS)

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-01

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

Approach and potentiality of low level laser therapy in veterinary medicine

NASA Astrophysics Data System (ADS)

Paterniani, Valentina; Grolli, Stefano

2018-04-01

The Low Level Laser Therapy (LLLT) is an innovative and increasing therapeutic technique in Veterinary Medicine. As in Human Medicine, the low power red/near-infrared laser light could be used to reduce inflammatory conditions, induce analgesia and promote damaged tissues repair, both in conventional animals like horses, dogs and cats and in unconventional ones, including reptiles, birds and exotic mammals. Since A.Eistein (1917) and E.Mester (1968) built its physical and biochemical fundamentals, a growing number of researches, over the years, have expanded the knowledge of the molecular process considered today at the basis of the macroscopic therapeutic effects. Producing a photochemical tissue interaction, laser light is absorbed by the mitochondrial respiratory chain stimulating the generation of ATP, ROS and NO; this determines a modulation in gene expression of proteins playing key roles in cellular processes as tissue repair, inflammatory response and pain control. Different animal pathological conditions could significantly benefit from this therapy, such as acute/chronic muscle-skeletal disorders, dental afflictions, dermatitis, otitis, stomatitis and different kind of skin lesions, as traumatic or post-operative ones. Furthermore, other significant applications are developing scientifically: the treatment of internal organ diseases, the regenerative effects on nervous tissue and the possibility of a beneficial cell-specific cytotoxicity, relevant for oncological cases, are some of these. A high-quality research is therefore crucial for this quickly expanding field of Veterinary Medicine, in order to find the most effective protocols and the ideal doses for each pathological conditions, aiming to always ensure the best and up-todate animal care.

Retinal light toxicity

PubMed Central

Youssef, P N; Sheibani, N; Albert, D M

2011-01-01

The ability of light to enact damage on the neurosensory retina and underlying structures has been well understood for hundreds of years. While the eye has adapted several mechanisms to protect itself from such damage, certain exposures to light can still result in temporal or permanent damage. Both clinical observations and laboratory studies have enabled us to understand the various ways by which the eye can protect itself from such damage. Light or electromagnetic radiation can result in damage through photothermal, photomechanical, and photochemical mechanisms. The following review seeks to describe these various processes of injury and many of the variables, which can mitigate these modes of injury. PMID:21178995

Resistance mechanisms and their difference between the root and leaf of Microsorum pteropus - A novel potential aquatic cadmium hyperaccumulator.

PubMed

Lan, Xin-Yu; Yang, Bin; Yan, Yun-Yun; Li, Xin-Yuan; Xu, Fu-Liu

2018-03-01

Microsorum pteropus (M. pteropus), an aquatic Polypodiaceae fern, was identified as a novel potential cadmium (Cd) hyperaccumulator in our previous study. This study reveals the Cd-resistance mechanisms and their difference between the root and leaf of M. pteropus based on analyses of photosynthesis, antioxidant systems and gene expression. A high level of Cd at 500μM was used to treat the samples to test the effects of this compound. Superoxide dismutase (SOD), peroxidase (POD), malondialdehyde (MDA) and flavonoids were used as indicators for antioxidant system changes. Five chlorophyll fluorescent parameters including the maximal photochemical efficiency of photosystem II (F v /F m ), effective quantum yield of photosystem II (Y(II)), photochemical quenching (qP), nonphotochemical quenching (qN) and electron transport rate (ETR) were measured to determine the photosynthetic changes. RNA-sequencing analysis was used to study the changes in gene expression. The results showed that after exposure to high levels of Cd, the concentrations of enzymatic oxidants (SOD and POD) were significantly increased, while the MDA levels were significantly decreased. There were no significant changes for the chlorophyll fluorescent parameters during Cd stress, which indicates that M. pteropus is highly effective at protecting itself. Certain functional genes, including photosystem genes and secondary metabolites, had significantly altered levels of expression. Different Cd-resistance mechanisms were found between the root and leaf tissues of M. pteropus. The root tissues of M. pteropus resist Cd damage using antioxidants, while its leaf tissues mainly protect themselves using photosystem self-protection. Copyright © 2017 Elsevier B.V. All rights reserved.

Zeaxanthin-independent energy quenching and alternative electron sinks cause a decoupling of the relationship between the photochemical reflectance index (PRI) and photosynthesis in an evergreen conifer during spring

PubMed Central

Fréchette, Emmanuelle; Wong, Christopher Y. S.; Junker, Laura Verena; Chang, Christine Yao-Yun; Ensminger, Ingo

2015-01-01

In evergreen conifers, the winter down-regulation of photosynthesis and its recovery during spring are the result of a reorganization of the chloroplast and adjustments of energy-quenching mechanisms. These phenological changes may remain undetected by remote sensing, as conifers retain green foliage during periods of photosynthetic down-regulation. The aim was to assess if the timing of the spring recovery of photosynthesis and energy-quenching characteristics are accurately monitored by the photochemical reflectance index (PRI) in the evergreen conifer Pinus strobus. The recovery of photosynthesis was studied using chlorophyll fluorescence, leaf gas exchange, leaf spectral reflectance, and photosynthetic pigment measurements. To assess if climate change might affect the recovery of photosynthesis, seedlings were exposed to cold spring conditions or warm spring conditions with elevated temperature. An early spring decoupling of the relationship between photosynthesis and PRI in both treatments was observed. This was caused by differences between the timing of the recovery of photosynthesis and the timing of carotenoid and chlorophyll pool size adjustments which are the main factors controlling PRI during spring. It was also demonstrated that zeaxanthin-independent NPQ mechanisms undetected by PRI further contributed to the early spring decoupling of the PRI–LUE relationship. An important mechanism undetected by PRI seems to involve increased electron transport around photosystem I, which was a significant energy sink during the entire spring transition, particularly in needles exposed to a combination of high light and cold temperatures. PMID:26386258

Temperature-controlled in vivo ocular exposure to 1090-nm radiation suggests that near-infrared radiation cataract is thermally induced

NASA Astrophysics Data System (ADS)

Yu, Zhaohua; Schulmeister, Karl; Talebizadeh, Nooshin; Kronschläger, Martin; Söderberg, Per

2015-01-01

The damage mechanism for near-infrared radiation (IRR) induced cataract is unclear. Both a photochemical and a thermal mechanism were suggested. The current paper aims to elucidate a photochemical effect based on investigation of irradiance-exposure time reciprocity. Groups of 20 rats were unilaterally exposed to 96-W/cm2 IRR at 1090 nm within the dilated pupil accumulating 57, 103, 198, and 344 kJ/cm2, respectively. Temperature was recorded at the limbus of the exposed eye. Seven days after exposure, the lenses were macroscopically imaged and light scattering was quantitatively measured. The average maximum temperature increases for exposure times of 10, 18, 33, and 60 min were expressed as 7.0±1.1, 6.8±1.1, 7.6±1.3, and 7.4±1.1°C [CI (0.95)] at the limbus of the exposed eye. The difference of light scattering in the lenses between exposed and contralateral not-exposed eyes was 0.00±0.02, 0.01±0.03, -0.01±0.02, and -0.01±0.03 transformed equivalent diazepam concentration (tEDC), respectively, and no apparent morphological changes in the lens were observed. An exposure to 96-W/cm2 1090-nm IRR projected on the cornea within the dilated pupil accumulating radiant exposures up to 344 kJ/cm2 does not induce cataract if the temperature rise at the limbus is <8°C. This is consistent with a thermal damage mechanism for IRR-induced cataract.

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

Holland, Steven C.; Artier, Juliana; Miller, Neil T.

Genetic engineering of photosynthetic organisms typically redirects native metabolism towards desirable products, which thereby represent new metabolic sinks. There is limited information on how these modifications impact the evolved mechanisms of photosynthetic energy metabolism and cellular growth. Two engineered strains of Synechocystis sp. PCC 6803 with altered carbon sink capacity were assayed for their photosynthetic and CO 2 concentrating mechanism properties in conditions of high and low inorganic carbon (Ci) availability. In the ΔglgC mutant, glycogen cannot be synthesized and a carbon sink pathway has been effectively removed. The JU547 strain has been engineered by integration of the Pseudomonas syringaemore » ethylene forming enzyme and provides a new sink. When cultured under high carbon conditions, ΔglgC displayed diminished photochemical efficiency, a more reduced NADPH pool, delayed initiation of the Calvin-Benson-Bassham cycle, and impairment of linear and cyclic electron flows. It also exhibited a large decrease in photochemical quenching indicative of the accumulation of Q A-, normally associated with a reduced PQ pool, but appears instead to be the result of an undefined dissipative mechanism to spill excess energy. In the case of carbon sink integration, JU547 displayed slightly more oxidized PQ and NADPH pools and increased rates of cyclic electron flow and an enhanced demand for inorganic carbon as suggested by increase in the expression of the bicarbonate transporter, SbtA. Overall, the results highlight the importance of the native regulatory network of autotrophic metabolism in governing photosynthetic performance and provide cogent examples of both predicable and difficult to predict phenotypic consequences upon installation of new pathways in autotrophs.« less

Anaerobiosis Induced State Transition: A Non Photochemical Reduction of PQ Pool Mediated by NDH in Arabidopsis thaliana

PubMed Central

Tirupathi, Malavath; Subramanyam, Rajagopal

2012-01-01

Background Non photochemical reduction of PQ pool and mobilization of LHCII between PSII and PSI are found to be linked under abiotic stress conditions. The interaction of non photochemical reduction of PQ pool and state transitions associated physiological changes are critically important under anaerobic condition in higher plants. Methodology/Findings The present study focused on the effect of anaerobiosis on non-photochemical reduction of PQ pool which trigger state II transition in Arabidopsis thaliana. Upon exposure to dark-anaerobic condition the shape of the OJIP transient rise is completely altered where as in aerobic treated leaves the rise is unaltered. Rise in F o and F J was due to the loss of oxidized PQ pool as the PQ pool becomes more reduced. The increase in Fo′ was due to the non photochemical reduction of PQ pool which activated STN7 kinase and induced LHCII phosphorylation under anaerobic condition. Further, it was observed that the phosphorylated LHCII is migrated and associated with PSI supercomplex increasing its absorption cross-section. Furthermore, evidences from crr2-2 (NDH mutant) and pgr5 mutants (deficient in non NDH pathway of cyclic electron transport) have indicated that NDH is responsible for non photochemical reduction of the PQ pool. We propose that dark anaerobic condition accelerates production of reducing equivalents (such as NADPH by various metabolic pathways) which reduce PQ pool and is mediated by NDH leading to state II transition. Conclusions/Significance Anaerobic condition triggers non photochemical reduction of PQ pool mediated by NDH complex. The reduced PQ pool activates STN7 kinase leading to state II transition in A. thaliana. PMID:23185453

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-01-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-07-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Investigation of the Photochemical Method for Uranium Isotope Separation

DOE R&D Accomplishments Database

Urey, H. C.

1943-07-10

To find a process for successful photochemical separation of isotopes several conditions have to be fulfilled. First, the different isotopes have to show some differences in the spectrum. Secondly, and equally important, this difference must be capable of being exploited in a photochemical process. Parts A and B outline the physical and chemical conditions, and the extent to which one might expect to find them fulfilled. Part C deals with the applicability of the process.

Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

PubMed

Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

2015-05-05

Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

Sulfur Chemistry in the Early and Present Atmosphere of Mars

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Summers, M. E.

2011-01-01

Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

Damage Thresholds for Exposure to NIR and Blue Lasers in an In Vitro RPE Cell System

DTIC Science & Technology

2006-07-01

damage , and to identify antioxidants capable of protecting these cells from laser-in- duced cell death. MATERIALS AND METHODS The human RPE cell...melanosomes in blue laser-induced damage in vitro, which confirms the view that melanin plays an important role in photochemical damage mechanisms in...community has only a validating role in the animal ED50 damage threshold data used by safety committees. Systems of in vitro analysis must be

Squaraine rotaxanes with boat conformation macrocycles.

PubMed

Fu, Na; Baumes, Jeffrey M; Arunkumar, Easwaran; Noll, Bruce C; Smith, Bradley D

2009-09-04

Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocycles with 1,4-phenylene sidewalls and 2,6-pyridine dicarboxamide bridging units are more likely to adopt boat conformations in the solid state than analogous squaraine rotaxane systems with isophthalamide-containing macrocycles. A truncated squaraine dye, with a secondary amine attached directly to the central C(4)O(2) core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is maintained in solution. Encapsulation as a rotaxane increases the dye's brightness by a factor of 6. The encapsulation process appears to constrain the dye and reduce deformation of the chromophore from planarity. This study shows how mechanical encapsulation as a rotaxane can be used as a rational design parameter to fine-tune the chemical and photochemical properties of squaraine dyes.

Squaraine Rotaxanes with Boat Conformation Macrocycles

PubMed Central

Fu, Na; Baumes, Jeffrey M.; Arunkumar, Easwaran; Noll, Bruce C.; Smith, Bradley D.

2010-01-01

Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocycles with 1,4-phenylene-sidewalls and 2,6-pyridine dicarboxamide bridging units are more likely to adopt boat conformations in the solid-state than analogous squaraine rotaxane systems with isophthalamide-containing macrocycles. A truncated squaraine dye, with a secondary amine attached directly to the central C4O2 core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is maintained in solution. Encapsulation as a rotaxane increases the dye’s brightness by a factor of six. The encapsulation process appears to constrain the dye and reduce deformation of the chromophore from planarity. This study shows how mechanical encapsulation as a rotaxane can be used as a rational design parameter to fine-tune the chemical and photochemical properties of squaraine dyes. PMID:19639940

Photosynthetic and cellular toxicity of cadmium in Chlorella vulgaris.

PubMed

Ou-Yang, Hui-Ling; Kong, Xiang-Zhen; Lavoie, Michel; He, Wei; Qin, Ning; He, Qi-Shuang; Yang, Bin; Wang, Rong; Xu, Fu-Liu

2013-12-01

The toxic effects of cadmium (Cd) on the green alga Chlorella vulgaris were investigated by following the response to Cd of various toxicity endpoints (cell growth, cell size, photochemical efficiency of PSII in the light or Φ(PSII), maximal photochemical efficiency or Fv/Fm, chlorophyll a fluorescence, esterase activity, and cell viability). These toxicity endpoints were studied in laboratory batch cultures of C. vulgaris over a long-term 96-h exposure to different Cd concentrations using flow cytometry and pulse amplitude modulated fluorometry. The sequence of sensitivity of these toxicity endpoints was: cell yield > Φ(PSII) ≈ esterase activity > Fv/Fm > chlorophyll a fluorescence ≈ cell viability. It is shown that cell apoptosis or cell death only accounted for a minor part of the reduction in cell yield even at very high algistatic free Cd²⁺ concentrations, and other mechanisms such as blocked cell divisions are major contributors to cell yield inhibition. Furthermore, cadmium may affect both the electron donors and acceptors of the electron transport chain at high free Cd²⁺ concentration. Finally, the resistance of cells to cell death was size-dependent; medium-sized cells had the highest toxicity threshold. The present study brings new insights into the toxicity mechanisms of Cd in C. vulgaris and provides a detailed comparison of the sensitivity of various Cd toxicity endpoints. © 2013 SETAC.

Spectroscopic and kinetic studies of photochemical reaction of magnesium tetraphenylporphyrin with oxygen.

PubMed

Zhang, Jianbin; Zhang, Pengyan; Zhang, Zhengfu; Wei, Xionghui

2009-05-07

Magnesium tetraphenylporphyrin (MgTPP) was synthesized from meso-tetraphenylporphyrin (H(2)TPP) in N,N-dimethylformamide (DMF). The photochemical properties of MgTPP in the presence of oxygen were investigated in dichloromethane (CH(2)Cl(2)) by conventional fluorescence, UV-vis, (1)H NMR, MALDI-TOF-MS, FTIR, and XPS spectroscopic techniques. Spectral analyses showed that under irradiation, MgTPP molecules reacted with O(2) molecules, and a stable 1:1 adduct was produced. During the photochemical reaction process, one oxygen molecule was bound to the pyrrolenine nitrogens in the MgTPP molecule, and the characteristic N-O bonds were identified using the FTIR and XPS techniques. The kinetics of the photochemical reaction of MgTPP with O(2) has been studied in an oxygen-saturated solution. Under irradiation conditions, the experimental rate follows a pseudo-first-order reaction for MgTPP, having a half-life from 40 to 130 min under various irradiation intensities. The kinetic rate constant of photochemical reaction of MgTPP with O(2) showed a linear dependence.

Unconventional Tough Double-Network Hydrogels with Rapid Mechanical Recovery, Self-Healing, and Self-Gluing Properties.

PubMed

Jia, Haiyan; Huang, Zhangjun; Fei, Zhaofu; Dyson, Paul J; Zheng, Zhen; Wang, Xinling

2016-11-16

Hydrogels are polymeric materials that have a relatively high capacity for holding water. Recently, a double network (DN) technique was developed to fabricate hydrogels with a toughness comparable to rubber. The mechanical properties of DN hydrogels may be attributed to the brittle sacrificial bonding network of one hydrogel, facilitating stress dispersion, combined with ductile polymer chains of a second hydrogel. Herein, we report a novel class of tunable DN hydrogels composed of a polyurethane hydrogel and a stronger, dipole-dipole and H-bonding interaction reinforced (DHIR) hydrogel. Compared to conventional DN hydrogels, these materials show remarkable improvements in mechanical recovery, modulus, and yielding, with excellent self-healing and self-gluing properties. In addition, the new DN hydrogels exhibit excellent tensile and compression strengths and possess shape-memory properties, which make them promising for applications in engineering, biomedicine, and other domains where load bearing is required.

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis.

PubMed

Kärkäs, Markus D; Porco, John A; Stephenson, Corey R J

2016-09-14

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis.

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

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Stewart, Richard W.

1991-01-01

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

Evaluation of Potential Damage to Unconventional Structures by Sonic Booms

DTIC Science & Technology

1990-05-01

plaster and gypsum board caused by sonic boom is broken...on wood lath 3.3 5.6 2. Plaster on gyplath 7.5 16 3. Plaster on expanded metal lath 16 16 4. Plaster on concrete block 16 16 5. Gypsum board (new) 16... wallboard (also called plasterboard or drywall), it is assumed that interior walls of unconventional historic wood frame buildings used plaster instead.

How to Survive and Prosper in the Real World after Graduation: An Unconventional Approach to Achieving Your Success.

ERIC Educational Resources Information Center

Connors, Shawn M.

Unconventional advice to help college graduates be successful is offered. Ways to find sources of money (i.e., jobs) are described, including: using services or products offered through the mail, making phone calls to build a network of contacts in a particular industry, attending seminars to further one's knowledge of a field, learning about…

Unconventional Cyber Warfare: Cyber Opportunities in Unconventional Warfare

DTIC Science & Technology

2014-06-01

thanks to Tunisia’s modern communications infrastructure , pervasive Internet, and mobile phone network.”151 Although the use of information and...and physical space. Tunisia had a well-developed mobile phone and Internet infrastructure with nearly nine out of 10 Tunisians owning a mobile phone...OF TABLES Table 1. Top 20 countries of mobile phones per 100 people .........................................60 Table 2. Top 20 countries by number

Unconventional signal detection techniques with Gaussian probability mixtures adaptation in non-AWGN channels: full resolution receiver

NASA Astrophysics Data System (ADS)

Chabdarov, Shamil M.; Nadeev, Adel F.; Chickrin, Dmitry E.; Faizullin, Rashid R.

2011-04-01

In this paper we discuss unconventional detection technique also known as «full resolution receiver». This receiver uses Gaussian probability mixtures for interference structure adaptation. Full resolution receiver is alternative to conventional matched filter receivers in the case of non-Gaussian interferences. For the DS-CDMA forward channel with presence of complex interferences sufficient performance increasing was shown.

Unconventional Warfare in the American Civil War

DTIC Science & Technology

2004-06-18

Miller Thesis Title: Unconventional Warfare in the American Civil War Approved by: , Thesis Committee Chair LTC ( R ) Gregory T. Beck...M.A. , Member LTC ( R ) Richard Barbuto, Ph.D. , Consulting Faculty LTC ( R ) James B. Martin, Ph.D. Accepted this 18th day of...troops and supplies to forward areas. In official correspondence dated 26 May 1864 from Captain A. V. Barringer , Chief Quartermaster, Department of West

On the Composition of Young, Directly Imaged Giant Planets

NASA Technical Reports Server (NTRS)

Moses, J. I.; Marley, M. S.; Zahnle, K.; Line, M. R.; Fortney, J. J.; Barman, T. S.; Visscher, C.; Lewis, N. K.; Wolff, M. J.

2016-01-01

The past decade has seen significant progress on the direct detection and characterization of young, self-luminous giant planets at wide orbital separations from their host stars. Some of these planets show evidence for disequilibrium processes like transport-induced quenching in their atmospheres; photochemistry may also be important, despite the typically large orbital distances. Disequilibrium chemical processes such as these can alter the expected composition, spectral behavior, thermal structure, and cooling history of the planets, and can potentially confuse determinations of bulk elemental ratios, which provide important insights into planet-formation mechanisms. Using a thermo/photochemical kinetics and transport model, we investigate the extent to which disequilibrium chemical processes affect the composition and spectra of directly imaged giant exoplanets. Results for specific "young Jupiters" such as HR 8799 b and c and 51 Eri b are presented, as are general trends as a function of planetary effective temperature, surface gravity, incident ultraviolet flux, and strength of deep atmospheric convection. We find that quenching is very important on young Jupiters, leading to CO/CH4 and N2/NH3 ratios much greater than; and H2O mixing ratios a factor of a few less than chemical equilibrium predictions. Photochemistry can also be important on such planets, with CO2 and HCN being key photochemical products. Carbon dioxide becomes a particularly major constituent when stratospheric temperatures are low and recycling of water following H2O photolysis becomes stifled. Young Jupiters with effective temperatures less than 700 degrees Kelvin are in a particularly interesting photochemical regime that differs from both transiting hot Jupiters and our own solar-system giant planets.

Photochemical Grafting of Organic Alkenes to Single-Crystal TiO2 Surfaces: A Mechanistic Study

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

Franking, Ryan A.; Kim, Heesuk; Chambers, Scott A.

2012-08-21

The UV-induced photochemical grafting of terminal alkenes has emerged as a versatile way to form molecular layers on semiconductor surfaces. Recent studies have shown that grafting reactions can be initiated by photoelectron emission into the reactant liquid as well as by excitation across the semiconductor bandgap, but the relative importance of these two processes is expected to depend on the nature of the semiconductor and the reactant alkene and the excitation wavelength. Here we report a study of the wavelength-dependent photochemical grafting of alkenes onto single-crystal TiO2 samples. Trifluoroacetamide-protected 10-aminododec-1-ene (TFAAD), 10-N-BOC-aminodec-1-ene (t-BOC) and 1-dodecene were used as model alkenes.more » On rutile(110), photons with energy above the bandgap but below the expected work function are not effective at inducing grafting, while photons with energy sufficient to induce electronic transitions from the TiO2 Fermi level to electronic acceptor states of the reactant molecules induce grafting. A comparison of rutile (110), rutile(001), anatase (001), and anatase(101) samples shows slightly enhanced grafting for rutile but no difference between crystal faces for a given crystal phase. Hydroxylation of the surface increases the reaction rate by lowering the work function and thereby facilitating photoelectron ejection into the adjacent alkene. These results demonstrate that photoelectron emission is the dominant mechanism responsible for grafting when using short-wavelength (~254 nm) light and suggest that photoemission events beginning on mid-gap states may play a crucial role.« less

Gender-related traits in the dioecious shrub Empetrum rubrum in two plant communities in the Magellanic steppe

NASA Astrophysics Data System (ADS)

Díaz-Barradas, Mari Cruz; Zunzunegui, María; Collantes, Marta; Álvarez-Cansino, Leonor; García Novo, Francisco

2014-10-01

Following the theory on costs of reproduction, sexually dimorphic plants may exhibit several trade-offs in energy and resources that can determine gender dimorphism in morphological or physiological traits, especially during the reproductive period. In this study we assess whether the sexes of the dioecious species Empetrum rubrum differ in morphological and ecophysiological traits related to water economy and photochemical efficiency and whether these differences change in nearby populations with contrasting plant communities. We conducted physiological, morphological, sex ratio, and cover measurements in E. rubrum plants in the Magellanic steppe, North-Eastern part of Tierra del Fuego (Argentina), from two types of heathlands with differing community composition. We found differences between sites in soil pH and wind speed at the canopy level. E. rubrum plants exhibited lower photosynthetic height and higher LAI (leaf area index), lower RWC (relative water content) and higher water-use efficiency (lower Δ13C) in the heathland with harsher environmental conditions. Gender dimorphism in the physiological response was patent for photochemical efficiency and water use (RWC and Δ13C discrimination), with males showing a more conservative strategy in relation to females. Accordingly, male-biased sex ratio in the stress-prone community suggested a better performance of male plants under stressful environmental conditions. The integrated analysis of all variables (photochemical efficiency, RWC, leaf dry matter content (LDMC), pigments, and Δ13C) indicated an interaction between gender and heathland community effects in the physiological response. We suggest that female plants may exhibit compensatory mechanisms to face their higher reproductive costs.

Upper atmosphere research: Reaction rate and optical measurements

NASA Technical Reports Server (NTRS)

Stief, L. J.; Allen, J. E., Jr.; Nava, D. F.; Payne, W. A., Jr.

1990-01-01

The objective is to provide photochemical, kinetic, and spectroscopic information necessary for photochemical models of the Earth's upper atmosphere and to examine reactions or reactants not presently in the models to either confirm the correctness of their exclusion or provide evidence to justify future inclusion in the models. New initiatives are being taken in technique development (many of them laser based) and in the application of established techniques to address gaps in the photochemical/kinetic data base, as well as to provide increasingly reliable information.

Application of Reservoir Flow Simulation Integrated with Geomechanics in Unconventional Tight Play

NASA Astrophysics Data System (ADS)

Lin, Menglu; Chen, Shengnan; Mbia, Ernest; Chen, Zhangxing

2018-01-01

Multistage hydraulic fracturing techniques, combined with horizontal drilling, have enabled commercial production from the vast reserves of unconventional tight formations. During hydraulic fracturing, fracturing fluid and proppants are pumped into the reservoir matrix to create the hydraulic fractures. Understanding the propagation mechanism of hydraulic fractures is essential to estimate their properties, such as half-length. In addition, natural fractures are often present in tight formations, which might be activated during the fracturing process and contribute to the post-stimulation well production rates. In this study, reservoir simulation is integrated with rock geomechanics to predict the well post-stimulation productivities. Firstly, a reservoir geological model is built based on the field data collected from the Montney formation in the Western Canadian Sedimentary Basin. The hydraulic fracturing process is then simulated through an integrated approach of fracturing fluid injection, rock geomechanics, and tensile failure criteria. In such a process, the reservoir pore pressure increases with a continuous injection of the fracturing fluid and proppants, decreasing the effective stress exerted on the rock matrix accordingly as the overburden pressure remains constant. Once the effective stress drops to a threshold value, tensile failure of the reservoir rock occurs, creating hydraulic fractures in the formation. The early production history of the stimulated well is history-matched to validate the predicted fracture geometries (e.g., half-length) generated from the fracturing simulation process. The effects of the natural fracture properties and well bottom-hole pressures on well productivity are also studied. It has been found that nearly 40% of hydraulic fractures propagate in the beginning stage (the pad step) of the fracturing schedule. In addition, well post-stimulation productivity will increase significantly if the natural fractures are propped or partially propped by the proppants. This paper provides insights on fracture propagation and can be a reference for fracturing treatments in unconventional tight reservoirs.

Unconventional gas development facilitates plant invasions.

PubMed

Barlow, Kathryn M; Mortensen, David A; Drohan, Patrick J; Averill, Kristine M

2017-11-01

Vegetation removal and soil disturbance from natural resource development, combined with invasive plant propagule pressure, can increase vulnerability to plant invasions. Unconventional oil and gas development produces surface disturbance by way of well pad, road, and pipeline construction, and increased traffic. Little is known about the resulting impacts on plant community assembly, including the spread of invasive plants. Our work was conducted in Pennsylvania forests that overlay the Marcellus and Utica shale formations to determine if invasive plants have spread to edge habitat created by unconventional gas development and to investigate factors associated with their presence. A piecewise structural equation model was used to determine the direct and indirect factors associated with invasive plant establishment on well pads. The model included the following measured or calculated variables: current propagule pressure on local access roads, the spatial extent of the pre-development road network (potential source of invasive propagules), the number of wells per pad (indicator of traffic density), and pad age. Sixty-one percent of the 127 well pads surveyed had at least one invasive plant species present. Invasive plant presence on well pads was positively correlated with local propagule pressure on access roads and indirectly with road density pre-development, the number of wells, and age of the well pad. The vast reserves of unconventional oil and gas are in the early stages of development in the US. Continued development of this underground resource must be paired with careful monitoring and management of surface ecological impacts, including the spread of invasive plants. Prioritizing invasive plant monitoring in unconventional oil and gas development areas with existing roads and multi-well pads could improve early detection and control of invasive plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Longitudinal pathways from unconventional personal attributes in the late 20s to cannabis use prior to sexual intercourse in the late 30s.

PubMed

Lee, Jung Yeon; Brook, Judith S; Pahl, Kerstin; Brook, David W

2017-11-01

A quarter of people living with human immunodeficiency virus (HIV) infection in the United States are women. Furthermore, African American and Hispanic/Latina women continue to be disproportionately affected by HIV, compared with women of other races/ethnicities. Cannabis use prior to intercourse may be associated with increased risky sexual behaviors which are highly related to HIV. The ultimate goal of this research is to better understand the relationships between unconventional personal attributes (e.g., risk-taking behaviors) in the late 20s, substance use (e.g., alcohol) in the mid 30s, and cannabis use prior to intercourse in the late 30s using a community sample; such an understanding may inform interventions. This study employing data from the Harlem Longitudinal Development Study includes 343 female participants (50% African Americans, 50% Puerto Ricans). Structural equation modeling indicated that unconventional personal attributes in the late 20s were associated with substance use in the mid 30s (β=0.32, p<0.001), which in turn, was associated with cannabis use prior to sexual intercourse in the late 30s (β=0.64, p<0.001). Unconventional personal attributes in the late 20s were also directly related to cannabis use prior to sexual intercourse in the late 30s (β=0.39, p<0.01). The findings of this study suggest that interventions focused on decreasing unconventional personal attributes as well as substance use may reduce sexual risk behaviors among urban African American and Puerto Rican women. Also, the implications of this study for health care providers and researchers working in HIV prevention are that these precursors may be useful as patient screening tools. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pig Feeding under the Potato-green Forage Base System with or without Addition of Herbs versus a Concentrate Based System: Effect on Post-slaughter Performance and Pork Characteristics

PubMed Central

Turyk, Zofia; Osek, Maria; Olkowski, Bogusław; Janocha, Alina

2014-01-01

This study examined carcass and meat quality parameters in growing/finishing pigs fed unconventionally versus the concentrate-based system. Ninety-six, 12 wk old pigs (34±SD 0.3 kg) were randomly divided into three groups, assigned to one of the three dietary treatments: standard complete concentrate mixture, conventional (C diet); unconventional, steamed potato-green forage-concentrate based diet (U diet), and unconventional basal diet+herbage mix (UH diet). Pigs fed U diet showed lower dressing percentage, meatiness, loin eye area, and weight of pork neck (p≤0.05), but their carcasses were significantly (p≤0.05) longer and had increased backfat depth (p≤0.05). There was no impact of the diet on the meat content of dry matter, crude ash, acidity, and colour parameters of m. longissimus. Unconventional feeding significantly (p≤0.05) elevated water the holding capacity of m. longissimus and slightly improved the sensory attributes analysis of meat. The addition of herbs resulted in increased loin eye area (p≤0.05), decreased fat content (p≤0.05) in m. longissimus, and tended to improve some sensory attributes of meat. There were significant gender differences in response to all diets. There were significant diet×sex interactions for some measured variables, but there were no clearly identifiable trends with regard to any specific carcass or meat parameters. Feeding unconventional diet to pigs may offer better culinary attributes of the meat, and improve some technologically important characteristics of pig carcass, but may negatively affect some carcass or meat parameters. PMID:25050003

Sarcomeric Myosin Expression in the Tongue Body of Humans, Macaques and Rats

PubMed Central

Rahnert, Jill A.; Sokoloff, Alan J.; Burkholder, Thomas J.

2010-01-01

Expression of developmental and unconventional myosin heavy chain (MHC) isoforms in some adult head and neck muscles is thought to reflect specific contractile demands of muscle fibers active during kinematically complex movements. Mammalian tongue muscles are active during oromotor behaviors that encompass a wide range of tongue movement speeds and tongue shape changes (e.g. respiration, oral transport, swallowing, rejection), but the extent to which tongue muscles express developmental and unconventional MHC is not known. Quantitative PCR was used to determine the mRNA content of conventional MHC-beta, MHC-2a, MHC-2b and MHC-2x, the developmental isoforms embryonic MHC and neonatal MHC and the unconventional isoforms atrial/cardiac-α MHC (MHC-alpha), extraocular MHC, masseter MHC and slow tonic MHC in tongue body muscles of the rat, macaque and human. In all species, conventional MHC isoforms predominate. MHC-2b and MHC-2x account for 98% of total MHC mRNA in the rat. MHC-2a, MHC-2x and MHC-beta account for 94% of total MHC mRNA in humans and 96% of total MHC mRNA in macaque. With the exception of MHC-alpha in humans (5%), developmental and unconventional MHC mRNA represents less than 0.3% of total MHC mRNA. We conclude that in these species, there is limited expression of developmental and unconventional MHC and that diversity of tongue body muscle fiber contractile properties is achieved primarily by MHC-beta, MHC-2a, MHC-2x and MHC-2b. Whether expression of MHC-alpha mRNA in tongue is unique to humans or present in other hominoids awaits further investigation. PMID:19907142

Water Issues Associated with Increasing Unconventional Oil Production in the Permian Basin

NASA Astrophysics Data System (ADS)

Reedy, R. C.; Scanlon, B. R.; Male, F.; Walsh, M.

2017-12-01

The Permian Basin is being transformed from a major conventional oil play to the world's largest unconventional play; however, managing water for this transition is critical in this semiarid region. The study included quantifying produced water volumes with oil and gas production along with water demands for hydraulic fracturing using a detailed well-by-well analysis. Our results show that oil wells in conventional reservoirs generate large volumes of produced water relative to oil production with produced water to oil ratios of 13 (i.e. 13 barrels [bbl] of water relative to a bbl of oil). However, produced water from conventional reservoirs has been mostly injected back into the pressure-depleted oil-producing reservoirs for enhanced oil recovery using water flooding. Unconventional horizontal wells use large volumes of water for hydraulic fracturing that has been markedly increasing by factors of 10 - 16 per well and by factors of 7-10 after dividing by lateral well length (2008-2015). Although unconventional wells generate less produced water relative to oil ( 3 bbl of water relative to oil) than conventional wells, the main difference is that this produced water cannot be reinjected into the low permeability shale reservoirs. Instead, the produced water is disposed into non-producing geologic zones that could result in overpressuring and induced seismicity. There is a high potential for reusing produced water from unconventional wells in the Permian Basin because the produced water volumes can support the hydraulic fracturing water demand based on 2014 data. Reusing produced water with minimal water treatment (clean brine) could partially mitigate produced water injection concerns while reducing water demand for hydraulic fracturing.

Kinetics and photochemistry Golden, D. M.

NASA Technical Reports Server (NTRS)

Demore, W. B.; Golden, R. F.; Howard, C. J.; Kurylo, M. J.; Margitan, J. J.; Molina, M. J.; Ravishankara, A. R.; Watson, R. T.; Hampson, R. F.

1985-01-01

The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.

MCAK and Stathmin Upregulation in Breast Cancer Cells: Etiology and Response to Pharmacologic Reagents

DTIC Science & Technology

2004-07-01

and the affinity for MTs are cells (Maney et al., 2001). Finally, the neck domain is not molecular refinements that adapt motile kinesins for specific...1,500 nM taxol-stabilized MTs in 80 p.I of BRB80 (80 mM molecular motor. Nature. 389:93-96. Pipes, pH 6.8, 1 mM EGTA, and 1 mM MgCI2), 12.5 p.M taxol, 1...summarizes the biological functions and examines the possible molecular the r egio immeiatel iete mt core mechanisms of Kin C and Kin I unconventional

SCDFT Study of High Tc Nitride Superconductors

NASA Astrophysics Data System (ADS)

Arita, R.

Based on the density functional theory for superconductors (SCDFT), we study the pairing mechanism of the layered nitride superconductors, β-LixMNCl (M=Zr, Hf). Recently, it has been shown that SCDFT reproduces experimental superconducting transition temperatures (Tc) of conventional superconductors very accurately. Here we use SCDFT as a "litmus paper" to determine whether the system is a conventional or unconventional superconductor. We show that Tc estimated by SCDFT is less than half of the experimental Tc and its doping dependence is opposite to that observed in the experiments. The present result suggests that β- LixMNCl is not a Migdal-Eliashberg type superconductor.

A measuring stand for a ducted fan aircraft propulsion unit

NASA Astrophysics Data System (ADS)

Hlaváček, David

2014-03-01

The UL-39 ultra-light aircraft which is being developed by the Department of Aerospace Engineering, Faculty of Mechanical Engineering, Czech Technical University in Prague, is equipped with an unconventional ducted fan propulsion unit. The unit consists of an axial fan driven by a piston engine and placed inside a duct ended with a nozzle. This article describes the arrangement of a modernised measuring stand for this highly specific propulsion unit which will be able to measure the fan pressure ratio and velocity field in front of and behind the fan and its characteristic curve.

Dimensionality-Driven Metal-Insulator Transition in Spin-Orbit-Coupled SrIrO3

NASA Astrophysics Data System (ADS)

Schütz, P.; Di Sante, D.; Dudy, L.; Gabel, J.; Stübinger, M.; Kamp, M.; Huang, Y.; Capone, M.; Husanu, M.-A.; Strocov, V. N.; Sangiovanni, G.; Sing, M.; Claessen, R.

2017-12-01

Upon reduction of the film thickness we observe a metal-insulator transition in epitaxially stabilized, spin-orbit-coupled SrIrO3 ultrathin films. By comparison of the experimental electronic dispersions with density functional theory at various levels of complexity we identify the leading microscopic mechanisms, i.e., a dimensionality-induced readjustment of octahedral rotations, magnetism, and electronic correlations. The astonishing resemblance of the band structure in the two-dimensional limit to that of bulk Sr2 IrO4 opens new avenues to unconventional superconductivity by "clean" electron doping through electric field gating.

Prelysosomal Compartments in the Unconventional Secretion of Amyloidogenic Seeds

PubMed Central

Borland, Helena; Vilhardt, Frederik

2017-01-01

A mechanistic link between neuron-to-neuron transmission of secreted amyloid and propagation of protein malconformation cytopathology and disease has recently been uncovered in animal models. An enormous interest in the unconventional secretion of amyloids from neurons has followed. Amphisomes and late endosomes are the penultimate maturation products of the autophagosomal and endosomal pathways, respectively, and normally fuse with lysosomes for degradation. However, under conditions of perturbed membrane trafficking and/or lysosomal deficiency, prelysosomal compartments may instead fuse with the plasma membrane to release any contained amyloid. After a brief introduction to the endosomal and autophagosomal pathways, we discuss the evidence for autophagosomal secretion (exophagy) of amyloids, with a comparative emphasis on Aβ1–42 and α-synuclein, as luminal and cytosolic amyloids, respectively. The ESCRT-mediated import of cytosolic amyloid into late endosomal exosomes, a known vehicle of transmission of macromolecules between cells, is also reviewed. Finally, mechanisms of lysosomal dysfunction, deficiency, and exocytosis are exemplified in the context of genetically identified risk factors, mainly for Parkinson’s disease. Exocytosis of prelysosomal or lysosomal organelles is a last resort for clearance of cytotoxic material and alleviates cytopathy. However, they also represent a vehicle for the concentration, posttranslational modification, and secretion of amyloid seeds. PMID:28124989

Stretchable and high-performance supercapacitors with crumpled graphene papers.

PubMed

Zang, Jianfeng; Cao, Changyong; Feng, Yaying; Liu, Jie; Zhao, Xuanhe

2014-10-01

Fabrication of unconventional energy storage devices with high stretchability and performance is challenging, but critical to practical operations of fully power-independent stretchable electronics. While supercapacitors represent a promising candidate for unconventional energy-storage devices, existing stretchable supercapacitors are limited by their low stretchability, complicated fabrication process, and high cost. Here, we report a simple and low-cost method to fabricate extremely stretchable and high-performance electrodes for supercapacitors based on new crumpled-graphene papers. Electrolyte-mediated-graphene paper bonded on a compliant substrate can be crumpled into self-organized patterns by harnessing mechanical instabilities in the graphene paper. As the substrate is stretched, the crumpled patterns unfold, maintaining high reliability of the graphene paper under multiple cycles of large deformation. Supercapacitor electrodes based on the crumpled graphene papers exhibit a unique combination of high stretchability (e.g., linear strain ~300%, areal strain ~800%), high electrochemical performance (e.g., specific capacitance ~196 F g(-1)), and high reliability (e.g., over 1000 stretch/relax cycles). An all-solid-state supercapacitor capable of large deformation is further fabricated to demonstrate practical applications of the crumpled-graphene-paper electrodes. Our method and design open a wide range of opportunities for manufacturing future energy-storage devices with desired deformability together with high performance.

Stretchable and High-Performance Supercapacitors with Crumpled Graphene Papers

NASA Astrophysics Data System (ADS)

Zang, Jianfeng; Cao, Changyong; Feng, Yaying; Liu, Jie; Zhao, Xuanhe

2014-10-01

Fabrication of unconventional energy storage devices with high stretchability and performance is challenging, but critical to practical operations of fully power-independent stretchable electronics. While supercapacitors represent a promising candidate for unconventional energy-storage devices, existing stretchable supercapacitors are limited by their low stretchability, complicated fabrication process, and high cost. Here, we report a simple and low-cost method to fabricate extremely stretchable and high-performance electrodes for supercapacitors based on new crumpled-graphene papers. Electrolyte-mediated-graphene paper bonded on a compliant substrate can be crumpled into self-organized patterns by harnessing mechanical instabilities in the graphene paper. As the substrate is stretched, the crumpled patterns unfold, maintaining high reliability of the graphene paper under multiple cycles of large deformation. Supercapacitor electrodes based on the crumpled graphene papers exhibit a unique combination of high stretchability (e.g., linear strain ~300%, areal strain ~800%), high electrochemical performance (e.g., specific capacitance ~196 F g-1), and high reliability (e.g., over 1000 stretch/relax cycles). An all-solid-state supercapacitor capable of large deformation is further fabricated to demonstrate practical applications of the crumpled-graphene-paper electrodes. Our method and design open a wide range of opportunities for manufacturing future energy-storage devices with desired deformability together with high performance.

Stretchable and High-Performance Supercapacitors with Crumpled Graphene Papers

PubMed Central

Zang, Jianfeng; Cao, Changyong; Feng, Yaying; Liu, Jie; Zhao, Xuanhe

2014-01-01

Fabrication of unconventional energy storage devices with high stretchability and performance is challenging, but critical to practical operations of fully power-independent stretchable electronics. While supercapacitors represent a promising candidate for unconventional energy-storage devices, existing stretchable supercapacitors are limited by their low stretchability, complicated fabrication process, and high cost. Here, we report a simple and low-cost method to fabricate extremely stretchable and high-performance electrodes for supercapacitors based on new crumpled-graphene papers. Electrolyte-mediated-graphene paper bonded on a compliant substrate can be crumpled into self-organized patterns by harnessing mechanical instabilities in the graphene paper. As the substrate is stretched, the crumpled patterns unfold, maintaining high reliability of the graphene paper under multiple cycles of large deformation. Supercapacitor electrodes based on the crumpled graphene papers exhibit a unique combination of high stretchability (e.g., linear strain ~300%, areal strain ~800%), high electrochemical performance (e.g., specific capacitance ~196 F g−1), and high reliability (e.g., over 1000 stretch/relax cycles). An all-solid-state supercapacitor capable of large deformation is further fabricated to demonstrate practical applications of the crumpled-graphene-paper electrodes. Our method and design open a wide range of opportunities for manufacturing future energy-storage devices with desired deformability together with high performance. PMID:25270673

In-ground operation of Geothermic Fuel Cells for unconventional oil and gas recovery

NASA Astrophysics Data System (ADS)

Sullivan, Neal; Anyenya, Gladys; Haun, Buddy; Daubenspeck, Mark; Bonadies, Joseph; Kerr, Rick; Fischer, Bernhard; Wright, Adam; Jones, Gerald; Li, Robert; Wall, Mark; Forbes, Alan; Savage, Marshall

2016-01-01

This paper presents operating and performance characteristics of a nine-stack solid-oxide fuel cell combined-heat-and-power system. Integrated with a natural-gas fuel processor, air compressor, reactant-gas preheater, and diagnostics and control equipment, the system is designed for use in unconventional oil-and-gas processing. Termed a ;Geothermic Fuel Cell; (GFC), the heat liberated by the fuel cell during electricity generation is harnessed to process oil shale into high-quality crude oil and natural gas. The 1.5-kWe SOFC stacks are packaged within three-stack GFC modules. Three GFC modules are mechanically and electrically coupled to a reactant-gas preheater and installed within the earth. During operation, significant heat is conducted from the Geothermic Fuel Cell to the surrounding geology. The complete system was continuously operated on hydrogen and natural-gas fuels for ∼600 h. A quasi-steady operating point was established to favor heat generation (29.1 kWth) over electricity production (4.4 kWe). Thermodynamic analysis reveals a combined-heat-and-power efficiency of 55% at this condition. Heat flux to the geology averaged 3.2 kW m-1 across the 9-m length of the Geothermic Fuel Cell-preheater assembly. System performance is reviewed; some suggestions for improvement are proposed.

Drosophila BRUCE inhibits apoptosis through non-lysine ubiquitination of the IAP-antagonist REAPER

PubMed Central

Domingues, C; Ryoo, H D

2012-01-01

Active caspases execute apoptosis to eliminate superfluous or harmful cells in animals. In Drosophila, living cells prevent uncontrolled caspase activation through an inhibitor of apoptosis protein (IAP) family member, dIAP1, and apoptosis is preceded by the expression of IAP-antagonists, such as Reaper, Hid and Grim. Strong genetic modifiers of this pathway include another IAP family gene encoding an E2 ubiquitin conjugating enzyme domain, dBruce. Although the genetic effects of dBruce mutants are well documented, molecular targets of its encoded protein have remained elusive. Here, we report that dBruce targets Reaper for ubiquitination through an unconventional mechanism. Specifically, we show that dBruce physically interacts with Reaper, dependent upon Reaper's IAP-binding (IBM) and GH3 motifs. Consistently, Reaper levels were elevated in a dBruce −/− background. Unexpectedly, we found that dBruce also affects the levels of a mutant form of Reaper without any internal lysine residues, which normally serve as conventional ubiquitin acceptor sites. Furthermore, we were able to biochemically detect ubiquitin conjugation on lysine-deficient Reaper proteins, and knockdown of dBruce significantly reduced the extent of this ubiquitination. Our results indicate that dBruce inhibits apoptosis by promoting IAP-antagonist ubiquitination on unconventional acceptor sites. PMID:21886178

Application of solidifiers for oil spill containment: A review.

PubMed

Motta, Fernanda L; Stoyanov, Stanislav R; Soares, João B P

2018-03-01

The need for new and/or improvement of existing oil spill remediation measures has increased substantially amidst growing public concern with the increased transportation of unconventional crudes, such as diluted bitumen products. Solidifiers may be a very good spill response measure to contain and mitigate the effects of oil discharge incidents, as these interact with the oil to limit hydrocarbon release into air and water, prevent it from adhering onto sediment and debris, and could allow for oil recovery and reuse. Solidifiers change the physical state of the spilled oil from liquid to a coherent mass by chemical interactions between the spilled oil and the solidifier. Currently, the use of solidifiers is limited to small spills near shorelines. To extend their use to large-scale spill containment operations, it is necessary to understand the mechanism of solidifier action and to establish consistent criteria for evaluation of their effectiveness. The research effort to date has been focused mainly on gelators and cross-linking agents, with particularly impressive advancements in the areas of phase-selective polymeric and small-molecule gelators. Substantial research efforts are needed to improve solidifier performance and integrate solidifiers as part of spill response procedures, particularly for acute oil spills involving unconventional petroleum products. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Controlled flight of a biologically inspired, insect-scale robot.

PubMed

Ma, Kevin Y; Chirarattananon, Pakpong; Fuller, Sawyer B; Wood, Robert J

2013-05-03

Flies are among the most agile flying creatures on Earth. To mimic this aerial prowess in a similarly sized robot requires tiny, high-efficiency mechanical components that pose miniaturization challenges governed by force-scaling laws, suggesting unconventional solutions for propulsion, actuation, and manufacturing. To this end, we developed high-power-density piezoelectric flight muscles and a manufacturing methodology capable of rapidly prototyping articulated, flexure-based sub-millimeter mechanisms. We built an 80-milligram, insect-scale, flapping-wing robot modeled loosely on the morphology of flies. Using a modular approach to flight control that relies on limited information about the robot's dynamics, we demonstrated tethered but unconstrained stable hovering and basic controlled flight maneuvers. The result validates a sufficient suite of innovations for achieving artificial, insect-like flight.

Embedding Quantum Mechanics Into a Broader Noncontextual Theory: A Conciliatory Result

NASA Astrophysics Data System (ADS)

Garola, Claudio; Sozzo, Sandro

2010-12-01

The extended semantic realism ( ESR) model embodies the mathematical formalism of standard (Hilbert space) quantum mechanics in a noncontextual framework, reinterpreting quantum probabilities as conditional instead of absolute. We provide here an improved version of this model and show that it predicts that, whenever idealized measurements are performed, a modified Bell-Clauser-Horne-Shimony-Holt ( BCHSH) inequality holds if one takes into account all individual systems that are prepared, standard quantum predictions hold if one considers only the individual systems that are detected, and a standard BCHSH inequality holds at a microscopic (purely theoretical) level. These results admit an intuitive explanation in terms of an unconventional kind of unfair sampling and constitute a first example of the unified perspective that can be attained by adopting the ESR model.

Modeling the Impact of Deformation on Unstable Miscible Displacements in Porous Media

NASA Astrophysics Data System (ADS)

Santillán, D.; Cueto-Felgueroso, L.

2014-12-01

Coupled flow and geomechanics is a critical research challenge in engineering and the geosciences. The simultaneous flow of two or more fluids with different densities or viscosities through deformable media is ubiquitous in environmental, industrial, and biological processes, including the removal of non-aqueous phase liquids from underground water bodies, the geological storage of CO2, and current challenges in energy technologies, such as enhanced geothermal systems, unconventional hydrocarbon resources or enhanced oil recovery techniques. Using numerical simulation, we study the interplay between viscous-driven flow instabilities (viscous fingering) and rock mechanics, and elucidate the structure of the displacement patterns as a function of viscosity contrast, injection rate and rock mechanical properties. Finally, we discuss the role of medium deformation on transport and mixing processes in porous media.

Modeling the Impact of Fracture Growth on Fluid Displacements in Deformable Porous Media

NASA Astrophysics Data System (ADS)

Santillán, D.; Cueto-Felgueroso, L.; Juanes, R.

2015-12-01

Coupled flow and geomechanics is a critical research challenge in engineering and the geosciences. The flow of a fluid through a deformable porous media is present in manyenvironmental, industrial, and biological processes,such as the removal of pollutants from underground water bodies, enhanced geothermal systems, unconventional hydrocarbon resources or enhanced oil recovery techniques. However, the injection of a fluid can generate or propagate fractures, which are preferential flow paths. Using numerical simulation, we study the interplay between injection and rock mechanics, and elucidate fracture propagation as a function of injection rate, initial crack topology and mechanical rock properties. Finally, we discuss the role of fracture growth on fluid displacements in porous media. Figure: An example of fracture (in red) propagated in a porous media (in blue)

Failure of cap-rock seals as determined from mechanical stratigraphy, stress history, and tensile-failure analysis of exhumed analogs

DOE PAGES

Petrie, E. S.; Evans, J. P.; Bauer, S. J.

2014-11-01

In this study, the sedimentologic and tectonic histories of clastic cap rocks and their inherent mechanical properties control the nature of permeable fractures within them. The migration of fluid through mm- to cm-scale fracture networks can result in focused fluid flow allowing hydrocarbon production from unconventional reservoirs or compromising the seal integrity of fluid traps. To understand the nature and distribution of subsurface fluid-flow pathways through fracture networks in cap-rock seals we examine four exhumed Paleozoic and Mesozoic seal analogs in Utah. We combine these outcrop analyses with subsidence analysis, paleoloading histories, and rock-strength testing data in modified Mohr–Coulomb–Griffith analysesmore » to evaluate the effects of differential stress and rock type on fracture mode.« less

Unconventional energy resources: 2007-2008 review

USGS Publications Warehouse

Warwick, Peter D.; ,

2009-01-01

This paper summarizes five 2007–2008 resource commodity committee reports prepared by the Energy Minerals Division (EMD) of the American Association of Petroleum Geologists. Current United States and global research and development activities related to gas hydrates, gas shales, geothermal resources, oil sands, and uranium resources are included in this review. These commodity reports were written to advise EMD leadership and membership of the current status of research and development of unconventional energy resources. Unconventional energy resources are defined as those resources other than conventional oil and natural gas that typically occur in sandstone and carbonate rocks. Gas hydrate resources are potentially enormous; however, production technologies are still under development. Gas shale, geothermal, oil sand, and uranium resources are now increasing targets of exploration and development, and are rapidly becoming important energy resources that will continue to be developed in the future.

Magnetic Field Enhanced Superconductivity in Epitaxial Thin Film WTe2.

PubMed

Asaba, Tomoya; Wang, Yongjie; Li, Gang; Xiang, Ziji; Tinsman, Colin; Chen, Lu; Zhou, Shangnan; Zhao, Songrui; Laleyan, David; Li, Yi; Mi, Zetian; Li, Lu

2018-04-25

In conventional superconductors an external magnetic field generally suppresses superconductivity. This results from a simple thermodynamic competition of the superconducting and magnetic free energies. In this study, we report the unconventional features in the superconducting epitaxial thin film tungsten telluride (WTe 2 ). Measuring the electrical transport properties of Molecular Beam Epitaxy (MBE) grown WTe 2 thin films with a high precision rotation stage, we map the upper critical field H c2 at different temperatures T. We observe the superconducting transition temperature T c is enhanced by in-plane magnetic fields. The upper critical field H c2 is observed to establish an unconventional non-monotonic dependence on temperature. We suggest that this unconventional feature is due to the lifting of inversion symmetry, which leads to the enhancement of H c2 in Ising superconductors.

Nucleophile sensitivity of Drosophila TRPA1 underlies light-induced feeding deterrence

PubMed Central

Du, Eun Jo; Ahn, Tae Jung; Wen, Xianlan; Seo, Dae-Won; Na, Duk L; Kwon, Jae Young; Choi, Myunghwan; Kim, Hyung-Wook; Cho, Hana; Kang, KyeongJin

2016-01-01

Solar irradiation including ultraviolet (UV) light causes tissue damage by generating reactive free radicals that can be electrophilic or nucleophilic due to unpaired electrons. Little is known about how free radicals induced by natural sunlight are rapidly detected and avoided by animals. We discover that Drosophila Transient Receptor Potential Ankyrin 1 (TRPA1), previously known only as an electrophile receptor, sensitively detects photochemically active sunlight through nucleophile sensitivity. Rapid light-dependent feeding deterrence in Drosophila was mediated only by the TRPA1(A) isoform, despite the TRPA1(A) and TRPA1(B) isoforms having similar electrophile sensitivities. Such isoform dependence re-emerges in the detection of structurally varied nucleophilic compounds and nucleophilicity-accompanying hydrogen peroxide (H2O2). Furthermore, these isoform-dependent mechanisms require a common set of TRPA1(A)-specific residues dispensable for electrophile detection. Collectively, TRPA1(A) rapidly responds to natural sunlight intensities through its nucleophile sensitivity as a receptor of photochemically generated radicals, leading to an acute light-induced behavioral shift in Drosophila. DOI: http://dx.doi.org/10.7554/eLife.18425.001 PMID:27656903