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Sample records for finger reactive compounds

  1. Characterization of Junín virus particles inactivated by a zinc finger-reactive compound.

    PubMed

    García, Cybele C; Ellenberg, Paula C; Artuso, María C; Scolaro, Luis A; Damonte, Elsa B

    2009-07-01

    Our previous studies reported the inhibitory action against arenaviruses of antiretroviral zinc finger-reactive compounds provided by the National Cancer Institute (USA). These compounds were able to inactivate virions as well as to reduce virus yields from infected cells. Here, the inactivation of the arenavirus Junín (JUNV), agent of Argentine hemorrhagic fever, by the aromatic disulfide NSC20625 was analyzed. The treatment of purified JUNV with this compound eliminated infectivity apparently through irreversible modifications in the matrix Z protein detected by: (a) alterations in the electrophoretic migration profile of Z under non-reducing conditions; (b) an electrodense labeling in the internal layer beneath the envelope and around the matrix Z protein, in negatively stained preparations; (c) changes in the subcellular localization of Z in cells transfected with a recombinant fusion protein JUNVZ-eGFP. The infection of Vero cells with JUNV inactivated particles was blocked at the uncoating of viral nucleocapsid from endosomes, providing new evidence for a functional role of Z in this stage of arenavirus cycle. Furthermore, the inactivated JUNV particles retained the immunoreactivity of the surface glycoprotein GP1 suggesting that this disulfide may be useful in the pursuit of an inactivating agent to obtain a vaccine antigen or diagnostic tool. PMID:19463727

  2. Arenavirus Z protein as an antiviral target: virus inactivation and protein oligomerization by zinc finger-reactive compounds

    PubMed Central

    García, Cybele C.; Djavani, Mahmoud; Topisirovic, Ivan; Borden, Katherine L. B.; Salvato, María S.; Damonte, Elsa B.

    2008-01-01

    Several disulfide-based and azoic compounds have shown antiviral and virucidal properties against arenaviruses in virus yield-inhibition and inactivation assays, respectively. The most effective virucidal agent, the aromatic disulfide NSC20625, was able to inactivate two strains of the prototype arenavirus species Lymphocytic choriomeningitis virus (LCMV). Inactivated viral particles retained the biological functions of the virion envelope glycoproteins in virus binding and uptake, but were unable to perform viral RNA replication. Furthermore, in inactivated virions, the electrophoretic profile of the Z protein was altered when analysed under non-reducing conditions, whereas the patterns of the proteins NP and GP1 remained unaffected. Treatment of a recombinant LCMV Z protein with the virucidal agents induced unfolding and oligomerization of Z to high-molecular-mass aggregates, probably due to metal-ion ejection and the formation of intermolecular disulfide bonds through the cysteine residues of the Z RING finger. NSC20625 also exhibited antiviral properties in LCMV-infected cells without affecting other cellular RING-motif proteins, such as the promyelocytic leukaemia protein PML. Altogether, the investigations described here illustrate the potential of the Z protein as a promising target for therapy and the prospects of the Z-reactive compounds to prevent arenavirus dissemination. PMID:16603524

  3. Chalcogen bonding interactions between reducible sulfur and selenium compounds and models of zinc finger proteins.

    PubMed

    Lutz, Patricia B; Bayse, Craig A

    2016-04-01

    Reducible sulfur and selenium (r-S/Se) compounds, defined as sulfur and selenium compounds not in the lowest -2 oxidation state (e.g., -1 to +6), release Zn(2+) from zinc-sulfur proteins such as zinc fingers (ZFs) and metallothionein. A series of density functional theory calculations was performed on donor-acceptor complexes between r-S/Se compounds and models of the Cys2His2, Cys3His and Cys4 ZF sites. These S⋯S/Se chalcogen bonding interactions consist of the donation of electron density from a S lone pair on the ZF model to a S/Se-X antibonding molecular orbital of the r-S/Se compound. The strength of the interaction was shown to be dependent upon the Lewis basicity of the ZF model (Cys4>Cys3His>Cys2His2) and the Lewis acidity of the r-S/Se compound as measured by the energy of the S/Se-X antibonding orbital. Interactions with the softer r-Se compounds were stronger than the r-S compounds, consistent with the greater reactivity of the former with ZF proteins. PMID:26877152

  4. Reactive spreading: Adsorption, ridging and compound formation

    SciTech Connect

    Saiz, E.; Cannon, R.M.; Tomsia, A.P.

    2000-09-11

    Reactive spreading, in which a chemically active element is added to promote wetting of noble metals on nonmetallic materials, is evaluated. Theories for the energetics and kinetics of the necessary steps involved in spreading are outlined and compared to the steps in compound formation that typically accompany reactive wetting. These include: fluid flow, active metal adsorption, including nonequilibrium effects, and triple line ridging. All of these can be faster than compound nucleation under certain conditions. Analysis and assessment of recently reported experiments on metal/ceramic systems lead to a focus on those conditions under which spreading proceeds ahead of the actual formation of a new phase at the interface. This scenario may be more typical than believed, and perhaps the most effective situation leading to enhanced spreading. A rationale for the pervasive variability and hysteresis observed during high temperature wetting also emerges.

  5. Recent changes in anthropogenic reactive nitrogen compounds

    NASA Astrophysics Data System (ADS)

    Andronache, Constantin

    2014-05-01

    Significant anthropogenic perturbations of the nitrogen cycle are the result of rapid population growth, with mounting need for food and energy production. The increase of reactive nitrogen compounds (such as NOx, HNO3, NH3, and N2O) has a significant impact on human health, environment, and climate. NOx emissions contribute to O3 chemistry, aerosol formation and acidic precipitation. Ammonia is a notable atmospheric pollutant that may deteriorate ecosystems and contribute to respiratory problems. It reacts with acidic gases to form aerosols or is deposited back to ecosystems. The application of fertilizers accounts for most of the N2O production, adding to greenhouse gas emissions. We analyze the change of some reactive nitrogen compounds based on observations, in eastern United States. Results show that the control of NOx and SO2 emissions over the last decades caused a significant decrease of acidic deposition. The nitrate deposition is highest in eastern US, while the ammonium ion concentration is highest in central US regions. Overall, the inorganic nitrogen wet deposition from nitrate and ammonium is enhanced in central, and eastern US. Research shows that sensitive ecosystems in northeastern regions exhibit a slow recovery from the accumulated effects of acidic deposition. Given the growing demand for nitrogen in agriculture and industry, we discuss possible pathways to reduce the impact of excess reactive nitrogen on the environment.

  6. Oxime-induced reactivation of carboxylesterase inhibited by organophosphorus compounds

    SciTech Connect

    Maxwell, D.M.; Lieske, C.N.; Brecht, K.M.

    1993-05-13

    A structure-activity analysis of the ability of oximes to reactivate rat plasma carboxylesterase (CaE) that was inhibited by organophosphorus (OP) compounds revealed that uncharged oximes, such as diacetylmonoxime or monoisonitrosoacetone, were better reactivators than cationic oximes. Cationic oximes that are excellent reactivators of OP-inhibited acetylcholinesteraser such as pyridinium-2-aldoxime or the bis-pyridinium oximes, HI-6 and TMB-4, produced poor reactivation of OP-inhibited CaE. The best uncharged reactivator was diacetylmonoxime which produced complete reactivation at 0.3 mM in 2 hr of CaE that was inhibited by organophosphinates, alkoxy-containing phosphates, and alkoxy-containing phosphonates. Complete reactivation of CaE could be achieved even after inhibition by phosphonates with highly branched alkoxy groups, such as sarin and soman, that undergo rapid aging with acetylcholinesterase. CaE that was inhibited by phosphonates or phosphates that contained aryloxy groups were reactivated to a lower extent. The cause of this decreased reactivation appears to be an oxime-induced aging reaction that competes with the reactivation reaction. This oxime-induced aging reaction is accelerated by electron-withdrawing substituents on the aryloxy groups of phosphonates and by the presence of multiple aryloxy groups on phosphates. Thus, reactivation and aging of OP-inhibited CaE differ from the same processes for OP-inhibited acetylcholinesterase in both their oxime specificity and inhibitor specificity and, presumably, in their underlying mechanisms.

  7. Guanidino compounds generate reactive oxygen species.

    PubMed

    Mori, A; Kohno, M; Masumizu, T; Noda, Y; Packer, L

    1996-09-01

    Methylguanidine, guanidinoacetic acid and guanidinosuccinic acid are endogenous substances in body tissues. Extremely high levels of these substances are known to be related to the pathogenesis of epilepsy and renal failure such as uremia. In this study it was demonstrated that methylguanidine, guanidinoacetic acid and guanidinosuccinic acid, and arginine generate hydroxyl radicals in aqueous solution. These findings suggest that a high level of guanidino compounds accumulating near or within cells such as neurons (in an epileptogenic focus) or nephrons (in uremic patients) may cause free radical damage leading to these clinical disorders. Arginine may have a similar role in the pathogenesis of hyperarginemia. PMID:8886279

  8. Oxime-induced reactivation of carboxylesterase inhibited by organophosphorus compounds

    SciTech Connect

    Maxwell, D.M.; Lieske, C.N.; Brecht, K.M.

    1994-06-01

    A structure-activity analysis of the ability of oximes to reactivate rat plasma carboxylesterase (CaE) that was inhibited by organophosphorus (OP) compounds revealed that uncharged oximes, such as 2,3-butanedione monoxime (diacetylmonoxime) or monoisonitrosoacetone, were better reactivators than cationic oximes. Cationic oximes that are excellent reactivators of OP-inhibited acetylcholinesterase, such as pyridine-2-aldoxime or the bis-pyridine aldoximes, HI-6 and TMB. 4, produced poor reactivation of OP-inhibited CaE. The best uncharged reactivator was 2,3. butanedione monoxime, which produced complete reactivation at 0.3 mM in 2 h of CaE that was inhibited by phosphinates, alkoxy-containing phosphates, and alkoxy-containing phosphonates. Complete reactivation of CaE could be achieved even after inhibition by phosphonates with highly branched alkoxy groups, such as sarin and soman, that undergo rapid aging with acetylcholinesterase. CaE that was inhibited by phosphonates or phosphates that contained aryloxy groups were reactivated to a lesser extent. The cause of this decreased reactivation appears to be an oxime-induced aging reaction that competes with the reactivation reaction. This oxime-induced aging reaction is accelerated by electron-withdrawing substituents on the aryloxy groups of phosphonates and by the presence of multiple aryloxy groups on phosphates. Thus, reactivation and aging of OP-inhibited CaE differ from the same processes for OP- inhibited acetylcholinesterase in both their oxime specificity and inhibitor specificity and, presumably, in their underlying mechanisms.

  9. Hydrodesulfurization reactivities of various sulfur compounds in vacuum gas oil

    SciTech Connect

    Ma, X.; Sakanishi, K.; Mochida, I.

    1996-08-01

    The hydrodesulfurization (HDS) of a vacuum gas oil (VGO) was performed at 360 C (6.9 MPa) over a commercial NiMo catalyst to examine the HDS reactivities of various sulfur compounds which exist in the VGO by means of quantitative pseudo-first-order kinetic analysis. Four representative types of aromatic-skeleton sulfur compounds were observed in the VGO: alkylbenzothiophenes (BTs), alkyldibenzothiophenes (DBTs), alkylphenanthro[4,5-b,c,d]thiophenes (PTs), and alkylbenzonaphthothiophenes (BNTs). Among these, alkyl-BTs exhibited the highest HDS reactivity, whereas alkyl-DBTs with alkyl substituents at the 4 and/or 6 positions appeared to have the least reactivity even though their aromatic-skeleton is smaller than those of both alkyl-PTs and -BNTs. Steric hindrance of alkyl groups at specific positions appears to be a major reason for the low reactivity. Quantum chemical calculations on representative sulfur compounds were carried out to compare molecular parameters with their different HDS reactivities.

  10. Exposure Profiling of Reactive Compounds in Complex Mixtures

    PubMed Central

    Georgieva, Nadia I.; Boysen, Gunnar

    2016-01-01

    Humans are constantly exposed to mixtures, such as tobacco smoke, exhaust from diesel, gasoline or new bio-fuels, containing several thousand compounds, including many known human carcinogens. Covalent binding of reactive compounds or their metabolites to DNA and formation of stable adducts is believed to be the causal link between exposure and carcinogenesis. DNA and protein adducts are well established biomarkers for the internal dose of reactive compounds or their metabolites and are an integral part of science-based risk assessment. However, technical limitations have prevented comprehensive detection of a broad spectrum of adducts simultaneously. Therefore, most studies have focused on measurement of abundant individual adducts. These studies have produced valuable insight into the metabolism of individual carcinogens, but they are insufficient for risk assessment of exposure to complex mixtures. To overcome this limitation, we present herein proof-of-principle for comprehensive exposure assessment, using N-terminal valine adduct profiles as a biomarker. The reported method is based on our previously established immunoaffinity liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with modification to enrich all N-terminal valine alkylated peptides. The method was evaluated using alkylated peptide standards and globin reacted in vitro with alkylating agents (1,2-epoxy-3-butene, 1,2:3,4-diepoxybutane, propylene oxide, styrene oxide, N-ethyl-N-nitrosourea and methyl methanesulfonate), known to form N-terminal valine adducts. To demonstrate proof-of-principle, the method was successfully applied to globin from mice treated with four model compounds. The results suggest that this novel approach might be suitable for in vivo biomonitoring. PMID:23219592

  11. Quantum chemical modelling of reactivity and selectivity of 1,2-dithiolanes towards retroviral and cellular zinc fingers

    NASA Astrophysics Data System (ADS)

    Topol, Igor A.; Nemukhin, Alexander V.; Burt, Stanley K.

    Interactions of 1,2-dithiolane species with zinc-containing sites, which mimic the zinc finger domains of retroviral and the cellular zinc finger proteins, have been investigated by quantum chemistry tools. According to the calculations, the immediate domains of zinc binding sites in the cellular and retroviral zinc fingers interact differently with such agents of the disulphide family. Thus, when approaching the model cellular-type domains, the molecules of 1,2-dithiolanes experience considerable potential barriers along the reaction path. However, these species react practically barrier-less with the model retroviral-type domains at the correlated DFT level. The results of the quantum chemical modelling provide firm support to the selectivity of 1,2-dithiolanes towards retroviral and cellular zinc fingers. This can be of great practical importance for the design of therapeutics that accomplish functional inactivation of the zinc fingers of the human immunodeficiency virus (HIV-1) retroviral type nucleocapsid protein NCp7.

  12. Governing processes for reactive nitrogen compounds in the European atmosphere

    NASA Astrophysics Data System (ADS)

    Hertel, O.; Skjøth, C. A.; Reis, S.; Bleeker, A.; Harrison, R. M.; Cape, J. N.; Fowler, D.; Skiba, U.; Simpson, D.; Jickells, T.; Kulmala, M.; Gyldenkærne, S.; Sørensen, L. L.; Erisman, J. W.; Sutton, M. A.

    2012-12-01

    Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in the governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account the differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions generally have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3-). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3- contribute significantly to background PM2.5 and PM10 (mass of aerosols with an aerodynamic diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms. Further studies are needed to characterise the sources, air chemistry and

  13. Reactivity of monocyclic aromatic compounds under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    McCollom, T. M.; Seewald, J. S.; Simoneit, B. R. T.

    2001-02-01

    Monocyclic aromatic compounds (MAC) represent a significant fraction of the total organic carbon in many geologic environments such as hydrothermal systems and petroleum reservoirs, yet the factors that control their abundance in these environments remain highly uncertain. In order to evaluate whether aqueous reactions involving MAC have a significant impact on their occurrence, laboratory experiments were conducted to observe the reactivity of several simple MAC under hydrothermal conditions that included the presence of mineral redox buffers. Aqueous solutions of individual MAC were heated at 300 to 330°C and 350 bar in flexible gold reaction vessels with titanium fittings. Toluene in aqueous solution was found to gradually decompose during heating to form primarily benzene plus CO 2, indicating the decomposition proceeded by an oxidative decarboxylation pathway. The rate of this reaction was enhanced by the presence of dissolved sulfur compounds and relatively oxidizing conditions, suggesting that intermediate oxidation state sulfur compounds (such as thiosulfate or polythionates) could play a role in promoting the reaction by facilitating the transfer of electrons among reactants. Benzoic acid decomposed rapidly to benzene plus CO 2, suggesting that formation of benzoic acid is the rate-limiting step in the overall conversion of toluene to benzene. Both benzene and phenol were found to be essentially unreactive. An assessment of the reaction products was performed to evaluate whether reactions among MAC attained metastable thermodynamic equilibrium. The results of this assessment, however, were equivocal, with some observations suggesting approach to thermodynamic equilibrium while other data indicate that criteria to demonstrate equilibrium were not met. The laboratory results demonstrate that aqueous reactions can play a role in controlling the abundance of aromatic compounds in geologic environments.

  14. Electronic property and reactivity of (hydroperoxo)metal compounds.

    PubMed

    Nishida, Y; Nishino, S

    2001-01-01

    DFT calculations were done for the (hydroperoxo)metal complexes with eta1-coordination mode, where metal ions are Fe(III), Al(III), Cu(II) and Zn(II). Results shows that 1) the electron density at the two oxygen atoms of the hydroperoxide ion is highly dependent on the angle O-O-H in M-OOH species and the difference in electron density between the two oxygen atoms reaches a maximum at the angle O-O-H = 180 degrees, 2) total electron density at the two oxygen atoms of the peroxide ion increases by approach of methane to the (hydroperoxo)metal species in the cases of Fe(III) and Cu(II); on the other hand, significant decrease of the electron density on peroxide oxygen atoms was observed for the cases of Al(III) and Zn(II) compounds. These findings suggest that the (hydroperoxo)metal species acts as an electrophile in the former cases (M = Fe(III), Cu(II)) and as a nucleophile for the latter two compounds (M = Zn(II), Al(III)). The electrophilicity observed for the Fe(III) and Cu(II) complexes is attributed to the presence of unoccupied- or half-filled d-orbitals interacting with the hydroperoxide ion. 3) Two oxygen atoms of the (hydroperoxo)-compounds of Fe(III) and Cu(II) complexes exhibit quite different reactivity toward the substrate, such as methane. When methane approaches the oxygen atom which is coordinated to a metal ion, a strong decrease of electron density at the methane carbon atom occurs with concomitant increase of electron density at the peroxide oxygen atoms inducing its heterolytic O-O cleavage. When methane approaches the terminal oxygen atom, an oxidative coupling reaction occurs between peroxide ion and methane; at first a nucleophilic attack by the terminal electron-rich oxygen atom occurs at the carbon atom to induce C-O bond formation, and a subsequent oxidative electron transfer proceeds from substrate to the metal-peroxide species yielding CH3-OOH, CH3OH, or other oxidized products. These results clearly demonstrate that the (hydroperoxo

  15. Reactive Nitrogen Compounds in the Troposphere: Observations, Transport, and Photochemistry

    NASA Astrophysics Data System (ADS)

    Luke, Winston Thomas

    Oxides of nitrogen critically control the photochemical production of ozone and account for approximately 1/3 of the total acid deposition in North America. This dissertation presents the results of three studies designed to enhance our knowledge of the distribution, transport, and photochemistry of reactive (or odd) nitrogen compounds in the troposphere. Concentrations of odd nitrogen were measured in both urban and rural air advected from the polluted east coast of North America to the western Atlantic ocean as part of the 1986 Western ATlantic Ocean eXperiment. On January 9, 1986, median (NOy) rose from 0.28 ppbv in the free troposphere (FT) to 1.38 ppbv in the marine boundary layer (MBL), and ratios of peroxyacetyl nitrate (PAN) to NOy were similar to those observed at a non-urban site in Colorado during autumn. The maximum gross flux of nitrogen through the FT and MBL between 31.5-44.1^ circN was estimated to be 25.6 kg N s ^{-1}. Reactive nitrogen compounds, carbon monoxide, and ozone were measured over the central United States in 1985 and 1986 from a twin-jet aircraft. Vertical profiles of reactive nitrogen compounds show dramatic perturbations due to the effects of violent convective activity. Measurements made in stable air dominated by high pressure contrast with those made near organized, isolated convective cells, which efficiently transport odd nitrogen to the upper troposphere. The layered lifting associated with episodes of cold frontal passage efficiently mixes both the upper and middle troposphere, however. Rapid injection of boundary layer air into the upper troposphere, where colder temperatures and higher wind velocities combine to extend both the lifetimes and range of influence of a variety of primary and secondary pollutants, will increase the rate of photochemical ozone production aloft and may thus exacerbate the greenhouse effect. Finally, the photolysis rate coefficients (j) of several alkyl nitrates (RONO_2) to NO_2 and the alkoxy

  16. Exploratory study of reactivity in organic compounds subjected to shock loading. [Diphenylhexadiyne

    SciTech Connect

    Dodson, B.W.

    1981-01-01

    An exploratory study of chemical reactions occurring in organic compounds under shock loading has been carried out. Early results on shock reactivity of the organic compounds acrylamide, adamantane, hexamethylenetetramine, naphthalene, and 1,6-diphenyl-2,4-hexadiyne have established two points: (1) organic reactions occur under shock loading; and (2) chemical structure strongly influences shock reactivity.

  17. Novel Scaffold FingerPrint (SFP): applications in scaffold hopping and scaffold-based selection of diverse compounds.

    PubMed

    Rabal, Obdulia; Amr, Fares Ibrahim; Oyarzabal, Julen

    2015-01-26

    A novel 2D Scaffold FingerPrint (SFP) for mining ring fragments is presented. The rings are described not only by their topology, shape, and pharmacophoric features (hydrogen-bond acceptors and donors, their relative locations, sp3 carbons, and chirality) but also by the position and nature of their growing vectors because they play a critical role from the drug discovery perspective. SFP can be used (i) to identify alternative chemotypes to a reference ring either in a visual mode or by running quantitative similarity searches and (ii) in chemotype-based diversity selections. Two retrospective case studies focused on melanin concentrating hormone 1-receptor antagonists (MCH-R1) and phosphodiesterase-5 inhibitors (PDE5) demonstrate the capability of this method for identifying novel structurally different and synthetically accessible chemotypes. Good enrichment factor (155 and 219) and recall values (46% and 73%) are found within the first 100 ranked hits (0.3% of screened database). Our 2D SFP descriptor outperforms well-validated current gold-standard 2D fingerprints (ECFP_6) and 3D approaches based on shape and electrostatic similarity. Scaffold-based selection of diverse compounds has a critical impact on corporate library design and compound acquisitions; thus, a novel strategy is introduced that uses diverse scaffold selections using this SFP descriptor combined with R-group selection at the different substitution sites. Both approaches are available as part of an interactive web-based application that requires minimal input and no computational knowledge by medicinal chemists. PMID:25558803

  18. Finger pain

    MedlinePlus

    Pain - finger ... Nearly everyone has had finger pain at some time. You may have: Tenderness Burning Stiffness Numbness Tingling Coldness Swelling Change in skin color Redness Many conditions, such ...

  19. Gas chromatograph-mass spectrometer (GC/MS) system for quantitative analysis of reactive chemical compounds

    DOEpatents

    Grindstaff, Quirinus G.

    1992-01-01

    Described is a new gas chromatograph-mass spectrometer (GC/MS) system and method for quantitative analysis of reactive chemical compounds. All components of such a GC/MS system external to the oven of the gas chromatograph are programmably temperature controlled to operate at a volatilization temperature specific to the compound(s) sought to be separated and measured.

  20. Reactive codoping of GaAlInP compound semiconductors

    DOEpatents

    Hanna, Mark Cooper; Reedy, Robert

    2008-02-12

    A GaAlInP compound semiconductor and a method of producing a GaAlInP compound semiconductor are provided. The apparatus and method comprises a GaAs crystal substrate in a metal organic vapor deposition reactor. Al, Ga, In vapors are prepared by thermally decomposing organometallic compounds. P vapors are prepared by thermally decomposing phospine gas, group II vapors are prepared by thermally decomposing an organometallic group IIA or IIB compound. Group VIB vapors are prepared by thermally decomposing a gaseous compound of group VIB. The Al, Ga, In, P, group II, and group VIB vapors grow a GaAlInP crystal doped with group IIA or IIB and group VIB elements on the substrate wherein the group IIA or IIB and a group VIB vapors produced a codoped GaAlInP compound semiconductor with a group IIA or IIB element serving as a p-type dopant having low group II atomic diffusion.

  1. ESTIMATION OF PHYSICAL PROPERTIES AND CHEMICAL REACTIVITY PARAMETERS OF ORGANIC COMPOUNDS

    EPA Science Inventory

    The computer program SPARC (Sparc Performs Automated Reasoning in Chemistry)has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms ...

  2. PREDICTION OF CHEMICAL REACTIVITY PARAMETERS AND PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS FROM MOLECULAR STRUCTURE USING SPARC

    EPA Science Inventory

    The computer program SPARC (SPARC Performs Automated Reasoning in Chemistry) has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms...

  3. From carbanions to organometallic compounds: quantification of metal ion effects on nucleophilic reactivities.

    PubMed

    Corral-Bautista, Francisco; Klier, Lydia; Knochel, Paul; Mayr, Herbert

    2015-10-12

    The influence of the metal on the nucleophilic reactivities of indenyl metal compounds was quantitatively determined by kinetic investigations of their reactions with benzhydrylium ions (Ar2 CH(+) ) and structurally related quinone methides. With the correlation equation log k2 =sN (N+E), it can be derived that the ionic indenyl alkali compounds are 10(18) to 10(24) times more reactive (depending on the reference electrophile) than the corresponding indenyltrimethylsilane. PMID:25951612

  4. Estimating sources, sinks and fluxes of reactive atmospheric compounds within a forest canopy

    EPA Science Inventory

    While few dispute the significance of within-canopy sources or sinks of reactive gaseous and particulate compounds, their estimation continues to be the subject of active research and debate. Reactive species undergo turbulent dispersion within an inhomogeneous flow field, and ma...

  5. Characterization of the reactivities of volatile organic compounds using a master chemical mechanism.

    PubMed

    Derwent, R G; Jenkin, M E; Saunders, S M; Pilling, M J

    2001-05-01

    A comprehensive description of the ozone-forming potentials of 101 organic compounds has been constructed under North American urban "averaged conditions" using a detailed master chemical mechanism and a simple air parcel trajectory model. This chemical mechanism describes the reactions of 3603 chemical species taking part in more than 10,500 chemical reactions. An index value has been calculated for each organic compound, which describes the increment in ozone concentrations found downwind of an urban area following the emission of a fixed increment in the mass emission of each organic compound. These indices, termed photochemical ozone creation potentials (POCPs), have been expressed on a scale relative to ethylene (ethene) = 100, and, a reactivity scale has been generated for alkanes, alkenes, and oxygenated and halogenated organic compounds. A high degree of correlation (R2 = 0.9) was found between these POCP values and the most widely accepted urban reactivity scale. While the reactivities of most of the 86 organic compounds compared fell within a consistent range, significant discrepancies were found for only 5 compounds. Single-day or multiday conditions appear to be important in establishing quantitative reactivity scales for the less reactive organic compounds. PMID:11355457

  6. Diverse reactivity of borenium cations with >N-H compounds.

    PubMed

    Devillard, Marc; Mallet-Ladeira, Sonia; Bouhadir, Ghenwa; Bourissou, Didier

    2016-07-01

    The Ph2P-stabilized borenium reacts cleanly with PhNH2, NH3 and HNTf2 to give a variety of boron compounds, namely the amino-substituted borenium (substitution reaction at B), the neutral phosphine-borane , the mixed P/N-stabilized boronium and the dicationic boron species . Remote modulation of the Lewis acidity at boron has been studied by preparing the related iPr2P-stabilized borenium and reacting it with dihydrogen. PMID:27352236

  7. Reactivity of Various Compound Classes Towards the Folin-Ciocalteu Reagent

    NASA Astrophysics Data System (ADS)

    Walker, Richard B.; Everette, Jace D.; Bryant, Quinton M.; Green, Ashlee M.; Abbey, Yvonne A.; Wangila, Grant W.

    2010-04-01

    The Folin-Ciocalteu assay has been used for over 80 years for the detection and quantitation of phenols. A modification of it, called the Lowry assay, is used for the quantitation of proteins. It has been commonly reported that the Folin-Ciocalteu reagent, which is a complex mixture containing sodium molybdate and sodium tungstate, is reactive towards other antioxidants besides phenols. However, until now, no one has done experiments to test this hypothesis. In our study, we tested the reactivity of the reagent towards over 70 compounds. Compound classes included phenols, thiols, vitamins, amino acids, proteins, nucleotide bases, unsaturated fatty acids, carbohydrates, organic acids, inorganic ions, aldehydes and ketones. All phenols, proteins and thiols tested were reactive towards the reagent. Other compounds which showed reactivity included guanine, glyceraldehyde, dihydroxyacetone, tyrosine, tryptophan, cysteine, ascorbic acid, Trolox, retinoic acid, pyridoxine, Fe+2, Mn+2, I- and SO3-2. In summary, our study showed that the Folin-Ciocalteu reagent is significantly reactive towards other compounds besides phenols. Therefore, it should be seen as a measure of total antioxidant capacity rather than phenolic content. It would be useful as a general antioxidant assay for measuring antioxidant capacities of compounds of biomedical interest.

  8. Palmate-like pentafoliata1 encodes a novel Cys(2)His(2) zinc finger transcription factor essential for compound leaf morphogenesis in Medicago truncatula

    PubMed Central

    2010-01-01

    As the primary site for photosynthetic carbon fixation and the interface between plants and the environment, plant leaves play a key role in plant growth, biomass production and survival, and global carbon and oxygen cycles. Leaves can be simple with a single blade or compound with multiple units of blades known as leaflets. In a palmate-type compound leaf, leaflets are clustered at the tip of the leaf. In a pinnate-type compound leaf, on the other hand, leaflets are placed on a rachis in distance from each other. Higher orders of complexities such as bipinnate compound leaves of the “sensitive” plant, Mimosa pudica, also occur in nature. However, how different leaf morphologies are determined is still poorly understood. Medicago truncatula is a model legume closely related to alfalfa and soybean with trifoliate compound leaves. Recently, we have shown that Palmate-like Pentafoliata1 (PALM1) encodes a putative Cys(2) His(2) zinc finger transcription factor essential for compound leaf morphogenesis in M. truncatula. Here, we present our phylogenetic relationship analysis of PALM1 homologs from different species and demonstrate that PALM1 has transcriptional activity in the transactivation assay in yeast. PMID:20724826

  9. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  10. Predicting the Reactivity of Nitrile-Carrying Compounds with Cysteine: A Combined Computational and Experimental Study

    PubMed Central

    2014-01-01

    Here, we report on a mechanistic investigation based on DFT calculations and kinetic measures aimed at determining the energetics related to the cysteine nucleophilic attack on nitrile-carrying compounds. Activation energies were found to correlate well with experimental kinetic measures of reactivity with cysteine in phosphate buffer. The agreement between computations and experiments points to this DFT-based approach as a tool for predicting both nitrile reactivity toward cysteines and the toxicity of nitriles as electrophile agents. PMID:24900869

  11. Mallet finger - aftercare

    MedlinePlus

    Baseball finger - aftercare; Drop finger - aftercare; Avulsion fracture - mallet finger - aftercare ... Mallet finger occurs when you cannot straighten your finger: when you try to straighten it, the tip of your ...

  12. An Arabidopsis Zinc Finger Protein Increases Abiotic Stress Tolerance by Regulating Sodium and Potassium Homeostasis, Reactive Oxygen Species Scavenging and Osmotic Potential.

    PubMed

    Zang, Dandan; Li, Hongyan; Xu, Hongyun; Zhang, Wenhui; Zhang, Yiming; Shi, Xinxin; Wang, Yucheng

    2016-01-01

    Plant zinc finger proteins (ZFPs) comprise a large protein family and they are mainly involved in abiotic stress tolerance. Although Arabidopsis RING/FYVE/PHD ZFP At5g62460 (AtRZFP) is found to bind to zinc, whether it is involved in abiotic stress tolerance is still unknown. In the present study, we characterized the roles of AtRZFP in response to abiotic stresses. The expression of AtRZFP was induced significantly by salt and osmotic stress. AtRZFP positively mediates tolerance to salt and osmotic stress. Additionally, compared with wild-type Arabidopsis plants, plants overexpressing AtRZFP showed reduced reactive oxygen species (ROSs) accumulation, enhanced superoxide dismutase and peroxidase activity, increased soluble sugars and proline contents, reduced K(+) loss, decreased Na(+) accumulation, stomatal aperture and the water loss rate. Conversely, AtRZFP knockout plants displayed the opposite physiological changes when exposed to salt or osmotic stress conditions. These data suggested that AtRZFP enhances salt and osmotic tolerance through a series of physiological processes, including enhanced ROSs scavenging, maintaining Na(+) and K(+) homeostasis, controlling the stomatal aperture to reduce the water loss rate, and accumulating soluble sugars and proline to adjust the osmotic potential. PMID:27605931

  13. An Arabidopsis Zinc Finger Protein Increases Abiotic Stress Tolerance by Regulating Sodium and Potassium Homeostasis, Reactive Oxygen Species Scavenging and Osmotic Potential

    PubMed Central

    Zang, Dandan; Li, Hongyan; Xu, Hongyun; Zhang, Wenhui; Zhang, Yiming; Shi, Xinxin; Wang, Yucheng

    2016-01-01

    Plant zinc finger proteins (ZFPs) comprise a large protein family and they are mainly involved in abiotic stress tolerance. Although Arabidopsis RING/FYVE/PHD ZFP At5g62460 (AtRZFP) is found to bind to zinc, whether it is involved in abiotic stress tolerance is still unknown. In the present study, we characterized the roles of AtRZFP in response to abiotic stresses. The expression of AtRZFP was induced significantly by salt and osmotic stress. AtRZFP positively mediates tolerance to salt and osmotic stress. Additionally, compared with wild-type Arabidopsis plants, plants overexpressing AtRZFP showed reduced reactive oxygen species (ROSs) accumulation, enhanced superoxide dismutase and peroxidase activity, increased soluble sugars and proline contents, reduced K+ loss, decreased Na+ accumulation, stomatal aperture and the water loss rate. Conversely, AtRZFP knockout plants displayed the opposite physiological changes when exposed to salt or osmotic stress conditions. These data suggested that AtRZFP enhances salt and osmotic tolerance through a series of physiological processes, including enhanced ROSs scavenging, maintaining Na+ and K+ homeostasis, controlling the stomatal aperture to reduce the water loss rate, and accumulating soluble sugars and proline to adjust the osmotic potential. PMID:27605931

  14. Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

    SciTech Connect

    Spink, D.

    1990-09-21

    Hexanuclear molybdenum clusters with mixed chloride and sulfide bridging ligands were prepared by reacting {alpha}-MoCl{sub 2} with sodium hydrosulfide in the presence of sodium butoxide. The resulting species, Mo{sub 6}Cl{sub (8-x)}S{sub x}{center dot}npy(x {congruent} 3.6, n {congruent} 4, py = pyridine), was pyrophoric and insoluble. The mixed sulfide chloride cluster species Mo{sub 6}S{sub 4}Cl{sub 4}{center dot}6OPEt{sub 3} and Mo{sub 6}S{sub {approximately}5}Cl{sub {approximately}3}{center dot}6PEt{sub 3} and Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} were isolated and characterized. Phosphorus-31 nuclear magnetic resonance, electron paramagnetic resonance, and UV/visible spectra were obtained for each fraction. The completely sulfided cluster, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3}, was prepared similarly and used in various experiments as a possible precursor to Chevrel phase materials of the type Mo{sub 6}S{sub 8}or M{sub n}Mo{sub 6}S{sub 8}. With the goal of removing all of the triethylphosphine ligands, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} was reacted with the transition metal carbonyls molybdenum hexacarbonyl and dicobalt octacarbonyl. Reaction on the molecular sulfide cluster with copper(I) chloride in toluene gave a completely insoluble product. The reaction of Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} with propylene sulfide gave a product whose infrared spectra showed only very weak peaks associated with coordinated triethylphosphine. The elemental analysis of this product fit the formula Mo{sub 6}S{sub 8}{center dot}5SPEt{sub 3}. Reactivity of the outer ligands of the Mo{sub 6}S{sub 8}{center dot}npy and Mo{sub 6}S{sub 8}{center dot}(6{minus}x)PrNH{sub x} clusters were investigated. Crystalline Mo{sub 6}S{sub 8}{center dot}6THT was recovered from the reaction of the n-propylamine derivative with THT. A crystal structure determination was done. 87 refs., 12 fig., 15 tabs.

  15. Finger Stiffness.

    PubMed

    Oosterhoff, Thijs C H; Nota, Sjoerd P F T; Ring, David

    2015-06-01

    Background Finger stiffness varies substantially in patients with hand and upper extremity illness and can be notably more than expected for a given pathophysiology. In prior studies, pain intensity and magnitude of disability consistently correlate with coping strategies such as catastrophic thinking and kinesiophobia, which can be characterized as overprotectiveness. In this retrospective study we address the primary research question whether patients with finger stiffness are more often overprotective when the primary pathology is outside the hand (e.g. distal radius fracture) than when it is located within the hand. Methods In an orthopaedic hand surgery department 160 patients diagnosed with more finger stiffness than expected for a given pathophysiology or time point of recovery between December 2006 and September 2012 were analyzed to compare the proportion of patients characterized as overprotective for differences by site of pathology: (1) inside the hand, (2) outside the hand, and (3) psychiatric etiology (e.g. clenched fist). Results Among 160 subjects with more finger stiffness than expected, 132 (82 %) were characterized as overprotective including 88 of 108 (81 %) with pathology in the hand, 39 of 44 (89 %) with pathology outside the hand, and 5 of 8 (63 %) with psychiatric etiology. These differences were not significant. Conclusions Overprotectiveness is common in patients with more finger stiffness than expected regardless the site and type of primary pathology. It seems worthwhile to recognize and treat maladaptive coping strategies early during recovery to limit impairment, symptoms, and disability. PMID:26078497

  16. CRISPR-Cas9-based target validation for p53-reactivating model compounds

    PubMed Central

    Wanzel, Michael; Vischedyk, Jonas B; Gittler, Miriam P; Gremke, Niklas; Seiz, Julia R; Hefter, Mirjam; Noack, Magdalena; Savai, Rajkumar; Mernberger, Marco; Charles, Joël P; Schneikert, Jean; Bretz, Anne Catherine; Nist, Andrea; Stiewe, Thorsten

    2015-01-01

    Inactivation of the p53 tumor suppressor by Mdm2 is one of the most frequent events in cancer, so compounds targeting the p53-Mdm2 interaction are promising for cancer therapy. Mechanisms conferring resistance to p53-reactivating compounds are largely unknown. Here we show using CRISPR-Cas9–based target validation in lung and colorectal cancer that the activity of nutlin, which blocks the p53-binding pocket of Mdm2, strictly depends on functional p53. In contrast, sensitivity to the drug RITA, which binds the Mdm2-interacting N terminus of p53, correlates with induction of DNA damage. Cells with primary or acquired RITA resistance display cross-resistance to DNA crosslinking compounds such as cisplatin and show increased DNA cross-link repair. Inhibition of FancD2 by RNA interference or pharmacological mTOR inhibitors restores RITA sensitivity. The therapeutic response to p53-reactivating compounds is therefore limited by compound-specific resistance mechanisms that can be resolved by CRISPR-Cas9-based target validation and should be considered when allocating patients to p53-reactivating treatments. PMID:26595461

  17. Estimating sources, sinks and fluxes of reactive atmospheric compounds within a forest canopy

    NASA Astrophysics Data System (ADS)

    Ghannam, K.; Duman, T.; Walker, J. T.; Bash, J. O.; Huang, C. W.; Khlystov, A.; Katul, G. G.

    2015-12-01

    While few dispute the significance of within-canopy sources or sinks of reactive gaseous and particulate compounds, their estimation continues to be the subject of active research and debate. Reactive species undergo turbulent dispersion within an inhomogeneous flow field, and may be subjected to chemical, biological and/or physical deposition, emissions or transformations on leaves, woody elements, and the forest floor. This system involves chemical reactions and biological processes with multiple time scales and represents the terrestrial ecosystem's exposure to nutrient and acid deposition and atmospheric oxidants. The quantification of these processes is a first step in better understanding the ecological impact of air pollution and feedback to atmospheric composition. Hence, it follows that direct measurements of sources or sinks is difficult to conduct in the presence of all these processes. However, mean scalar concentration profiles measured within the canopy can be used to infer the profile distribution of effective sinks and sources if the flow field is known. This is commonly referred to as the 'inverse problem'. In-canopy and above-canopy multi-level concentration measurements of reactive nitrogen compounds (ammonia, nitric acid, nitrous acid), as well as other compounds that are highly reactive to ammonia and its secondary products (hydrochloric acid and sulfur dioxide), are presented within a deciduous second-growth 180 year old oak-hickory forest situated within the Southeastern U.S. Two different approaches are used to solve for the source-sink distribution from the measured mean scalar concentration profiles: (1) an Eulerian high-order closure model that solves the scalar flux budget equation and (2) a new Lagrangian stochastic model that estimates the dispersion matrix. As each of these methods is subject to different assumptions, the combination of the two can be used to constrain the solution to the inverse problem and permit inference on the

  18. Finger Multiplication

    ERIC Educational Resources Information Center

    Holmes, Bill

    2010-01-01

    The author has been prompted to write this article about finger multiplication for a number of reasons. Firstly there are a number of related articles in past issues of "Mathematics Teaching" ("MT") which have connections to this algorithm. Secondly, very few of his primary teaching students and professional colleagues appear to be aware of the…

  19. Porous desulfurization sorbent pellets containing a reactive metal oxide and an inert zirconium compound

    SciTech Connect

    Gardner, Todd H.; Gasper-Galvin, Lee D.

    1996-12-01

    Sorbent pellets for removing hydrogen sulfide from coal gas are prepared by combining a reactive oxide, in particular zinc oxide, with a zirconium compound such as an oxide, silicate, or aluminate of zirconium, and an inorganic binder and pelletizing and calcining the mixture. Alternately, the zinc oxide may be replaced by copper oxide or a combination of copper, molybdenum, and manganese oxides. The pellet components may be mixed in dry form, moistened to produce a paste, and converted to pellets by forming an aqueous slurry of the components and spray drying the slurry, or the reactive oxide may be formed on existing zirconium-containing catalyst-carrier pellets by infusing a solution of a salt of the active metal onto the existing pellets and firing at a high temperature to produce the oxide. Pellets made according to this invention show a high reactivity with hydrogen sulfide and durability such as to be useful over repeated cycles of sorption and regeneration.

  20. The synthesis, structure and reactivity of an imine-stabilized carboranylphosphorus(i) compound.

    PubMed

    Chan, Tek Long; Xie, Zuowei

    2016-06-01

    A new imine-stabilized carboranyl-phosphinidene has been synthesized and structurally characterized. DFT studies suggest that the imine moiety provides an electron pair to stabilize carboranyl-phosphinidene. On the other hand, the sterically demanding carboranyl ligand can prevent the dimerization, facilitating the formation of monomeric phosphinidene. These observations are supported by the reactivity studies. Such a monovalent phosphorous(i) compound can undergo reactions with Cu(OAc)2, S, Se, (TMS)CHN2 and HCl to give various phosphorus(iii) species. All compounds are fully characterized by NMR spectroscopy, elemental analyses as well as single-crystal X-ray analyses. PMID:27180610

  1. Reactive DESI-MS imaging of biological tissues with dicationic ion-pairing compounds.

    PubMed

    Lostun, Dragos; Perez, Consuelo J; Licence, Peter; Barrett, David A; Ifa, Demian R

    2015-03-17

    This work illustrates reactive desorption electrospray ionization mass spectrometry (DESI-MS) with a stable dication on biological tissues. Rat brain and zebra fish tissues were investigated with reactive DESI-MS in which the dictation forms a stable bond with biological tissue fatty acids and lipids. Tandem mass spectrometry (MS/MS) was used to characterize the dication (DC9) and to identify linked lipid-dication compounds formed. The fragment m/z 85 common to both DC9 fragmentation and DC9-lipid fragmentation was used to confirm that DC9 is indeed bonded with the lipids. Lipid signals in the range of m/z 250-350 and phosphoethanolamines (PE) m/z 700-800 observed in negative ion mode were also detected in positive ion mode with reactive DESI-MS with enhanced signal intensity. Reactive DESI-MS imaging in positive ion mode of rat brain and zebra fish tissues allowed enhanced detection of compounds commonly observed in the negative ion mode. PMID:25710577

  2. Reactivity of recently deposited organic matter: Degradation of lipid compounds near the sediment-water interface

    NASA Astrophysics Data System (ADS)

    Canuel, Elizabeth A.; Martens, Christopher S.

    1996-05-01

    The usefulness of biomarker compounds buried in marine sediments depends upon a quantita tive understanding of the effects of early diagenesis on their distribution. To address this, a new experimental approach was utilized to determine rates of degradation in a coastal sediment. Rates of degradation for solvent-extractable lipid components were quantified in four sediment horizons composed of newly accumulated organic matter (31-144 days since deposition). Sediment accumulation rate data derived from changes in the inventory of Be-7 ( t 1/2 = 53.3 days) were combined with concentration data for lipid biomarker compounds, enabling us to evaluate the reactivity of organic matter in the upper 8 cm of the rapidly accumulating sediments of Cape Lookout Bight, North Carolina, USA (CLB). Net rates of loss and rate constants were calculated for individual compounds belonging to three classes of lipids: fatty acids, sterols, and n-alkanes. Individual components showed a range in reactivity, in some cases (fatty acids), attributable to differences in their biological sources. Rates and rate constants were consistently highest in the surficial sediments (0-2.5 cm), indicating that the reactivity of a given molecule(s) decreases over time, and beginning soon after deposition. Comparison with apparent rate constants ( k') calculated over longer timescales (one and ten years) shows that steady-state diagenetic models underestimate rates of degradation at or near the sediment-water interface by an order of magnitude.

  3. Lignin model compounds as bio-based reactive diluents for liquid molding resins.

    PubMed

    Stanzione, Joseph F; Sadler, Joshua M; La Scala, John J; Wool, Richard P

    2012-07-01

    Lignin is a copious paper and pulping waste product that has the potential to yield valuable, low molecular weight, single aromatic chemicals when strategically depolymerized. The single aromatic lignin model compounds, vanillin, guaiacol, and eugenol, were methacrylated by esterification with methacrylic anhydride and a catalytic amount of 4-dimethylaminopyridine. Methacrylated guaiacol (MG) and methacrylated eugenol (ME) exhibited low viscosities at room temperature (MG: 17 cP and ME: 28 cP). When used as reactive diluents in vinyl ester resins, they produced resin viscosities higher than that of vinyl ester-styrene blends. The relative volatilities of MG (1.05 wt% loss in 18 h) and ME (0.96 wt% loss in 18 h) measured by means of thermogravimetric analysis (TGA) were considerably lower than that of styrene (93.7 wt% loss in 3 h) indicating the potential of these chemicals to be environmentally friendly reactive diluents. Bulk polymerization of MG and ME generated homopolymers with glass transition temperatures (T(g)s) of 92 and 103 °C, respectively. Blends of a standard vinyl ester resin with MG and ME (50 wt % reactive diluent) produced thermosets with T(g)s of 127 and 153 °C, respectively, which are comparable to vinyl ester-styrene resins, thus demonstrating the ability of MG and ME to completely replace styrene as reactive diluents in liquid molding resins without sacrificing cured-resin thermal performance. PMID:22517580

  4. Protection of neuronal cells against reactive oxygen species by carnosine and related compounds.

    PubMed

    Boldyrev, Alexander; Bulygina, Elena; Leinsoo, Toomas; Petrushanko, Irina; Tsubone, Shiori; Abe, Hiroki

    2004-01-01

    Carnosine and related compounds were compared in terms of their abilities to decrease the levels of reactive oxygen species (ROS) in suspensions of isolated neurons activated by N-methyl-D-aspartic acid (NMDA) using both stationary fluorescence measurements and flow cytometry. Carnosine was found to suppress the fluorescent signal induced by ROS production and decreased the proportion of highly fluorescent neurons, while histidine showed opposite effects. N-Acetylated derivatives of both carnosine and histidine demonstrated weak (statistically indistinguishable) suppressive effects on the ROS signal. N-Methylated derivatives of carnosine suppressed intracellular ROS generation to the same extent as carnosine. This rank of effectiveness is distinct from that previously obtained for the anti-radical ability of CRCs (anserine>carnosine>ophidine). These differences suggest that the similar ability of carnosine and its N-methylated derivatives to protect neuronal cells against the excitotoxic effect of NMDA is not solely related to the antioxidant properties of these compounds. PMID:14698913

  5. Finger Injuries and Disorders

    MedlinePlus

    You use your fingers and thumbs to do everything from grasping objects to playing musical instruments to typing. When there is something wrong ... the skin of your palm. It causes the fingers to stiffen and bend. Trigger finger - an irritation ...

  6. OH reactivity and concentrations of Biogenic Volatile Organic Compounds in a Mediterranean forest of downy oak trees

    NASA Astrophysics Data System (ADS)

    Zannoni, N.; Gros, V.; Lanza, M.; Sarda, R.; Bonsang, B.; Kalogridis, C.; Preunkert, S.; Legrand, M.; Jambert, C.; Boissard, C.; Lathiere, J.

    2015-08-01

    Understanding the processes between the biosphere and the atmosphere is challenged by the difficulty to determine with enough accuracy the composition of the atmosphere. Total OH reactivity, which is defined as the total loss of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify indirectly the important reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites. Such results demonstrated the importance of OH reactivity for characterizing two of the major unknowns currently present associated to forests: the set of primary emissions from the canopy to the atmosphere and biogenic compounds oxidation pathways. Previous studies also highlighted the need to quantify OH reactivity and missing OH reactivity at more forested sites. Our study presents results of a field experiment conducted during late spring 2014 at the forest site at the Observatoire de Haute Provence, OHP, France. The forest is mainly composed of downy oak trees, a deciduous tree species characteristic of the Mediterranean region. We deployed the Comparative Reactivity Method and a set of state-of-the-art techniques such as Proton Transfer Reaction-Mass Spectrometry and Gas Chromatography to measure the total OH reactivity, the concentration of volatile organic compounds and main atmospheric constituents at the site. We sampled the air masses at two heights: 2 m, i.e. inside the canopy, and 10 m, i.e. above the canopy, where the mean canopy height is 5 m. We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long lived atmospheric compounds (up to 26 % during daytime). We determined that the daytime total measured reactivity equaled the calculated reactivity obtained from the concentrations of the compounds measured at the site. Hence, no

  7. Nucleophilic reactivity and electrocatalytic reduction of halogenated organic compounds by nickel o-phenylenedioxamidate complexes.

    PubMed

    Das, Siva Prasad; Ganguly, Rakesh; Li, Yongxin; Soo, Han Sen

    2016-09-14

    A growing number of halogenated organic compounds have been identified as hazardous pollutants. Although numerous advanced oxidative processes have been developed to degrade organohalide compounds, reductive and nucleophilic molecular approaches to dehalogenate organic compounds have rarely been reported. In this manuscript, we employ nickel(ii)-ate complexes bearing the o-phenylenebis(N-methyloxamide) (Me2opba) tetraanionic ligand as nucleophilic reagents that can react with alkyl halides (methyl up to the bulky isobutyl) by O-alkylation to give their respective imidate products. Four new nickel(ii) complexes have been characterized by X-ray crystallography, and the salient structural parameters and FT-IR vibrational bands (∼1655 cm(-1)) concur with their assignment as the imidate tautomeric form. To the best of our knowledge, this is the first report on the nucleophilic reactivity of Ni(II)(Me2opba) with halogenated organic compounds. The parent nickel(ii) Me2opba complex exhibits reversible electrochemical oxidation and reduction behavior. As a proof of concept, Ni(II)(Me2opba) and its alkylated congeners were utilized for the electrocatalytic reduction of chloroform, as a representative, simple polyhalogenated organic molecule that could arise from the oxidative treatment of organic compounds by chlorination. Modest turnover numbers of up to 6 were recorded, with dichloromethane identified as one of the possible products. Future efforts are directed towards bulkier -ate complexes that possess metal-centered instead of ligand-centered nucleophilic activity to create more effective electrocatalysts for the reduction of halogenated organic compounds. PMID:27506275

  8. Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China

    NASA Astrophysics Data System (ADS)

    He, Qiusheng; Yan, Yulong; Li, Hongyan; Zhang, Yiqiang; Chen, Laiguo; Wang, Yuhang

    2015-08-01

    Volatile organic compounds (VOCs) were sampled from non-coal emission sources including fuel refueling, solvent use, industrial and commercial activities in China, and 62 target species were determined by gas chromatography-mass selective detector (GC-MSD). Based on the results, source profiles were developed and discussed from the aspects of composition characteristics, potential tracers, BTEX (benzene, toluene, ethylbenzene and xylene) diagnostic ratios and chemical reactivity. Compared with vehicle exhausts and liquid fuels, the major components in refueling emissions of liquefied petroleum gas (LPG), gasoline and diesel were alkenes and alkanes. Oppositely, aromatics were the most abundant group in emissions from auto-painting, book binding and plastic producing. Three groups contributed nearly equally in printing and commercial cooking emissions. Acetone in medical producing, chloroform and tetrachloroethylene in wet- and dry-cleaning, as well as TEX in plastic producing etc. were good tracers for the respective sources. BTEX ratios showed that some but not all VOCs sources could be distinguished by B/T, B/E and B/X ratios, while T/E, T/X and E/X ratios were not suitable as diagnostic indicators of different sources. The following reactivity analysis indicated that emissions from gasoline refueling, commercial cooking, auto painting and plastic producing had high atmospheric reactivity, and should be controlled emphatically to prevent ozone pollution, especially when there were large amounts of emissions for them.

  9. Emission of reactive terpene compounds from orange orchards and their removal by within-canopy processes

    NASA Astrophysics Data System (ADS)

    Ciccioli, Paolo; Brancaleoni, Enzo; Frattoni, Massimiliano; di Palo, Vincenzo; Valentini, Riccardo; Tirone, Giampiero; Seufert, Guenther; Bertin, Nadia; Hansen, Ute; Csiky, Olav; Lenz, Roman; Sharma, Meeta

    1999-04-01

    VOC emission from orange orchards was determined in the framework of two field campaigns aimed at assessing the contribution of vegetation emissions to tropospheric ozone formation in the Valencia Citrus belt. Branch emission from different varieties of Citrus sinensis and Citrus Clementi was dominated by β-caryophyllene during the summer period and by linalool during the blossoming season (April-May). Large emission of D-limonene from soil was also measured. Data collected with the enclosure technique were upscaled to determine canopy emission rates of terpene compounds. Values obtained were compared with fluxes measured by relaxed eddy accumulation. Substantial removal of β-caryophyllene and linalool was detected during transport from the canopy into the atmospheric boundary layer. While within-canopy removal of the sesquiterpene component was fully consistent with laboratory studies indicating the high reactivity of this compound with ozone, linalool losses were more difficult to explain. Although high canopy fluxes of acetone and acetaldehyde suggested linalool decomposition by gas-phase reactivity, removal by heterogeneous chemistry seems the more likely explanation for the observed losses.

  10. [Source profile and chemical reactivity of volatile organic compounds from vehicle exhaust].

    PubMed

    Qiao, Yue-Zhen; Wang, Hong-Li; Huang, Cheng; Chen, Chang-Hong; Su, Lei-Yan; Zhou, Min; Xu, Hua; Zhang, Gang-Feng; Chen, Yi-Ran; Li, Li; Chen, Ming-Hua; Huang, Hai-Ying

    2012-04-01

    Light-duty gasoline taxis (LDGT) and passenger cars (LDGV), heavy-duty diesel buses (HDDB) and trucks (HDDT), gasoline motorcycles (MC) and LPG scooters (LPGS), were selected for tailpipe volatile organic compounds (VOCs) samplings by using transient dynamometer and on road test combined with SUMMA canisters technology. The samples were tested by GC-MS to analyze the concentration and species composition of VOCs. The results indicate that light-duty gasoline automobiles have higher fractions of aromatic hydrocarbons, which account for 43.38%-44.45% of the total VOCs, the main aromatic hydrocarbons are toluene and xylenes. Heavy-duty diesel vehicles have higher fractions of alkanes, which constitute 46.86%-48.57% of the total VOCs, the main alkanes are propane, n-dodecane and n-undecane. In addition, oxy-organics account for 13.28%-15.01% of the VOCs, the main oxy-organics is acetone. The major compound from MC and LPGS exhaust is acetylene, it accounts for 39.75% and 76.67% of the total VOCs, respectively. VOCs exhaust from gasoline motorcycles and light-duty gasoline automobiles has a significantly higher chemical reactivity than those from heavy-duty diesel vehicles, which contribute 55% and 44% to the atmospheric chemical reactivity in Shanghai. The gasoline motorcycles and light-duty gasoline automobiles are the key pollution sources affecting city and region ambient oxidation, and the key active species of toluene, xylenes, propylene, and styrene make the greatest contribution. PMID:22720548

  11. Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

    SciTech Connect

    Hartwig, J.F.

    1990-12-01

    The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.

  12. Synthesis and Reactivity of Oxo-Peroxo-Vanadium(V) Bipyridine Compounds

    PubMed Central

    Waidmann, Christopher R.; DiPasquale, Antonio G.

    2010-01-01

    The vanadium(IV) compound [VIVO(OH)(tBu2bpy)2]BF4 (VIVO(OH)) (tBu2bpy = 4,4′-di-tert-butylbipyridine) is slowly oxidized by O2 in ethereal solvents to give the oxo-peroxo compound [VVO(O2)(tBu2bpy)2]BF4 (VVO(O2)) in excellent yield. This and related compounds were fully characterized by NMR, IR, and optical spectroscopies, mass spectrometry, elemental analyses, and an X-ray crystal structure of the 4,4′-dimethylbipyridine analog, [VVO(O2)(Me2bpy)2]BF4. Monitoring the reaction of VIVO(OH) with O2 in THF/acetonitrile mixtures by 1H NMR and optical spectroscopies surprisingly shows that the initial product is the cis-dioxo compound [VV(O)2(tBu2bpy)2]BF4 (VVO2), which then converts to VVO(O2). Reaction of VIVO(OH) with 18O2 gives ca. 60% triply 18O labeled VVO(O2). The mechanism of formation of VVO(O2) is complex and may occur via initial reduction of O2 at vanadium(IV) to give a superoxo-vanadium(V) intermediate, autoxidation of the THF solvent, or both. That VVO2 is generated first appears to be due to the ability of VIVO(OH) to act as a hydrogen atom donor. For instance, VIVO(OH) reacts with VVO(O2) give VVO2. VVO(O2) is also slowly reduced to VIVO(OH) by the organic hydrogen atom donors hydroquinone and TEMPOH (2,2,6,6-tetramethylpiperidin-1-ol) as well as by triphenylphosphine. Notably, the peroxo complex VVO(O2) is much less reactive with these substrates than the analogous dioxo compound VVO2. PMID:20108930

  13. Noncontacting Finger Seal

    NASA Technical Reports Server (NTRS)

    Proctor, Margaret P. (Inventor); Steinetz, Bruce M. (Inventor)

    2004-01-01

    An annular finger seal is adapted to be interposed between a high pressure upstream region and a lower pressure downstream region to provide noncontact sealing along a rotatable member. The finger seal comprises axially juxtaposed downstream and upstream finger elements, each having integrally spaced fingers. The downstream fingers each have a lift pad, whereas the upstream fingers lack a pad. Each pad extends in a downstream direction. Each upstream finger is spaced from the rotating member a greater distance than each pad. Upon sufficient rotational speed of the rotating member, each pad is operative to lift and ride on a thin film of fluid intermediate the rotating member and the Pad.

  14. Exploring the Reactivity of Flavonoid Compounds with Metal-Associated Amyloid-β Species

    PubMed Central

    He, Xiaoming; Park, Hyun Min; Hyung, Suk-Joon; DeToma, Alaina S.; Kim, Cheal; Ruotolo, Brandon T.; Lim, Mi Hee

    2016-01-01

    Metal ions associated with amyloid-β (Aβ) peptides have been suggested to be involved in the development of Alzheimer’s disease (AD), but this remains unclear and controversial. Some attempts to rationally design or select small molecules with structural moieties for metal chelation and Aβ interaction (i.e., bifunctionality) have been made to gain a better understanding of the hypothesis. In order to contribute to these efforts, four synthetic flavonoid derivatives FL1 – FL4 were rationally selected according to the principles of bifunctionality and their abilities to chelate metal ions, interact with Aβ, inhibit metal-induced Aβ aggregation, scavenge radicals, and regulate the formation of reactive oxygen species (ROS) were studied using physical methods and biological assays. The compounds FL1 – FL3 were able to chelate metal ions, but showed limited solubility in aqueous buffered solutions. In the case of FL4, which was most compatible with aqueous conditions, its binding affinities for Cu2+ and Zn2+ (nM and μM, respectively) were obtained through solution speciation studies. The direct interaction between FL4 and Aβ monomer was weak, which was monitored by NMR spectroscopy and mass spectrometry. Employing FL1 – FL4, no noticeable inhibitory effect on metal-mediated Aβ aggregation was observed. Among FL1 – FL4, FL3, having 3-OH, 4-oxo, and 4′-N(CH3)2 groups, exhibited similar antioxidant activity to the vitamin E analogue, Trolox, and ca. 60% reduction in the amount of hydrogen peroxide (H2O2) generated by Cu2+-Aβ in the presence of dioxygen (O2) and a reducing agent. Overall, the studies here suggest that although four flavonoid molecules were selected based on expected bifunctionality, their properties and metal-Aβ reactivity were varied depending on the structure differences, demonstrating that bifunctionality must be well tuned to afford desirable reactivity. PMID:22437427

  15. Senescing grass crops as regional sources of reactive volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Karl, T.; Harren, F.; Warneke, C.; de Gouw, J.; Grayless, C.; Fall, R.

    2005-08-01

    Grass crop species, rice and sorghum, that are widely grown in the southeastern Texas region were analyzed for release of biogenic volatile organic compounds (VOCs) in simulated leaf-drying/senescence experiments. VOC release was measured by both online proton transfer reaction mass spectrometry (PTR-MS) and proton transfer ion trap mass spectrometry (PIT-MS) methods, and it was demonstrated that these two grass crops release a large variety of oxygenated VOCs upon drying under laboratory conditions primarily from leaves and not from stems. VOC release from paddy rice varieties was much greater than from sorghum, and major VOCs identified by gas chromatography PTR-MS included methanol, acetaldehyde, acetone, n-pentanal, methyl propanal, hexenol, hexanal, cis-3-hexenal, and trans-2-hexenal. The latter four VOCs, all C6 compounds known to be formed in wounded leaves, were the major volatiles released from drying rice leaves; smaller but substantial amounts of acetaldehyde were observed in all drying experiments. Online detection of VOCs using PIT-MS gave results comparable to those obtained with PTR-MS, and use of PIT-MS with collision-induced dissociation of trapped ions allowed unambiguous determination of the ratios of cis- and trans-hexenals during different phases of drying. As rice is one of the largest harvested crops on a global scale, it is conceivable that during rice senescence releases of biogenic VOCs, especially the reactive C6 wound VOCs, may contribute to an imbalance in regional atmospheric oxidant formation during peak summer/fall ozone formation periods. A county-by-county estimate of the integrated emissions of reactive biogenic VOCs from sorghum and rice production in Texas suggests that these releases are orders of magnitude lower than anthropogenic VOCs in urban areas but also that VOC emissions from rice in southeastern coastal Texas may need to be included in regional air quality assessments during periods of extensive harvesting.

  16. Fingering dynamics driven by a precipitation reaction: Nonlinear simulations

    NASA Astrophysics Data System (ADS)

    Shukla, Priyanka; De Wit, A.

    2016-02-01

    A fingering instability can develop at the interface between two fluids when the more mobile fluid is injected into the less-mobile one. For example, viscous fingering appears when a less viscous (i.e., more mobile) fluid displaces a more viscous (and hence less mobile) one in a porous medium. Fingering can also be due to a local change in mobility arising when a precipitation reaction locally decreases the permeability. We numerically analyze the properties of the related precipitation fingering patterns occurring when an A +B →C chemical reaction takes place, where A and B are reactants in solution and C is a solid product. We show that, similarly to reactive viscous fingering patterns, the precipitation fingering structures differ depending on whether A invades B or vice versa. This asymmetry can be related to underlying asymmetric concentration profiles developing when diffusion coefficients or initial concentrations of the reactants differ. In contrast to reactive viscous fingering, however, precipitation fingering patterns appear at shorter time scales than viscous fingers because the solid product C has a diffusivity tending to zero which destabilizes the displacement. Moreover, contrary to reactive viscous fingering, the system is more unstable with regard to precipitation fingering when the high-concentrated solution is injected into the low-concentrated one or when the faster diffusing reactant displaces the slower diffusing one.

  17. OH reactivity and concentrations of biogenic volatile organic compounds in a Mediterranean forest of downy oak trees

    NASA Astrophysics Data System (ADS)

    Zannoni, N.; Gros, V.; Lanza, M.; Sarda, R.; Bonsang, B.; Kalogridis, C.; Preunkert, S.; Legrand, M.; Jambert, C.; Boissard, C.; Lathiere, J.

    2016-02-01

    Total OH reactivity, defined as the total loss frequency of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify the total loading of reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites.Our study presents atmospheric mixing ratios of biogenic compounds and total OH reactivity measured during late spring 2014 at the forest of downy oak trees of the Observatoire de Haute Provence (OHP), France. Air masses were sampled at two heights: 2 m, i.e., inside the canopy, and 10 m, i.e., above the canopy, where the mean canopy height is 5 m.We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long-lived atmospheric compounds (up to 26 % during daytime). During daytime, no significant missing OH reactivity was reported at the site, either inside or above the canopy. However, during two nights we determined a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. We confirmed that no significant oxidation of the primary species occurred within the canopy; primary compounds emitted by the forest were fast transported to the atmosphere. Finally, the OH reactivity at this site was maximum 69 s-1, which is a high value for a forest characterized by a temperate climate. Observations in various and diverse forests in the Mediterranean region are therefore needed to better constrain the impact of reactive gases over this area.

  18. Reactive and recoverable sorbents for halogenated organic compound remediation in sediments

    NASA Astrophysics Data System (ADS)

    Werner, David; Taggalou, Villy; Kordulis, Christos; Dolfing, Jan; Karapanagioti, Hrissi K.

    2013-04-01

    Activated carbon (AC) has been proposed as a sediment amendment for aquatic systems polluted with hydrophobic organic compounds. AC acts as a strong binding agent that lowers the pollutant concentration and thus, its toxicity. A draw back of this in-situ remediation method is that although the pollutant will remain non-bioavailable for many years being sorbed into AC, it actually stays in the system. A reactive sorbent, a sorbent that would, at the same time, facilitate the degradation of the pollutant, would be better accepted by the public or the regulators than AC amendment. So far, catalysts supported on AC with zero valent iron and a reactive metal have been proposed for the dechlorination of chlorinated organic compounds. These reactive metals are usually expensive or toxic and thus, their addition to the environment is not desirable. In the present study, activated carbon modified with reduced iron(AC/Fe) is tested in batch systems in the presence of sediment and DDT sorbed on polyethylene sheets. The batch systems are equilibrated for different contact times. Then, the DDT remaining in the polyethylene sheets is quantified along with DDD produced due to the dechlorination of DDT. A small percentage of DDT is degraded to DDD in the systems containing the AC/Fe material. No degradation of DDT is observed in the control systems containing the pollutant and the sediment or the pollutant, the sediment and AC. Thus, the addition of AC/Fe to the sediment with the DDT is enough to cause the dechlorination of DDT. At the end of the experiments, a magnet rod is used to recover the AC/Fe material from the batches with the sediment. An average recovery of 83% is achieved. This is a high percentage suggesting that the material can be easily recovered. Some drawbacks of the material preparation method are identified after the composite material characterization. For example, the AC/Fe surface area is decreased with the material preparation compared to the initial surface

  19. Synthesis and reactivity of oxo-peroxo-vanadium(V) bipyridine compounds.

    PubMed

    Waidmann, Christopher R; DiPasquale, Antonio G; Mayer, James M

    2010-03-01

    The vanadium(IV) compound [V(IV)O(OH)((t)Bu(2)bpy)(2)]BF(4) (V(IV)O(OH)) ((t)Bu(2)bpy = 4,4'-di-tert-butylbipyridine) is slowly oxidized by O(2) in ethereal solvents to give the oxo-peroxo compound [V(V)O(O(2))((t)Bu(2)bpy)(2)]BF(4) (V(V)O(O(2))) in excellent yield. This and related compounds were fully characterized by NMR, IR, and optical spectroscopies; mass spectrometry; elemental analyses; and an X-ray crystal structure of the 4,4'-dimethylbipyridine analog, [V(V)O(O(2))(Me(2)bpy)(2)]BF(4). Monitoring the reaction of V(IV)O(OH) with O(2) in THF/acetonitrile mixtures by (1)H NMR and optical spectroscopies surprisingly shows that the initial product is the cis-dioxo compound [V(V)(O)(2)((t)Bu(2)bpy)(2)]BF(4) (V(V)O(2)), which then converts to V(V)O(O(2)). Reaction of V(IV)O(OH) with (18)O(2) gives ca. 60% triply (18)O labeled V(V)O(O(2)). The mechanism of formation of V(V)O(O(2)) is complex and may occur via initial reduction of O(2) at vanadium(IV) to give a superoxo-vanadium(V) intermediate, autoxidation of the THF solvent, or both. That V(V)O(2) is generated first appears to be due to the ability of V(IV)O(OH) to act as a hydrogen atom donor. For instance, V(IV)O(OH) reacts with V(V)O(O(2)) to give V(V)O(2). V(V)O(O(2)) is also slowly reduced to V(IV)O(OH) by the organic hydrogen atom donors hydroquinone and TEMPOH (2,2,6,6-tetramethylpiperidin-1-ol) as well as by triphenylphosphine. Notably, the peroxo complex V(V)O(O(2)) is much less reactive with these substrates than the analogous dioxo compound V(V)O(2). PMID:20108930

  20. New insight into the photophysics and reactivity of trigonal and tetrahedral arylboron compounds.

    PubMed

    Santos, Willy G; Pina, João; Burrows, Douglas H; Forbes, Malcolm D E; Cardoso, Daniel R

    The photophysics and reactivity of two tetraphenylborate salts and triphenylborane have been studied using ultrafast transient absorption, steady-state fluorescence, electron paramagnetic resonance with spin trapping, and DFT calculations. The singlet excited state of tetraarylborates exhibit extended π-orbital coupling between two adjacent aryl groups. The maximum fluorescence band, as well as the transient absorption bands centered at 560 nm (τ = 1.05 ns) and 680 nm (τ = 4.35 ns) are influenced by solvent viscosity and polarity, indicative of a twisted intramolecular charge transfer (TICT) state. Orbital contour plots of the HOMO and LUMO orbitals of the tetraarylboron compounds support the existence of electron delocalization between two aryl groups in the LUMO. This TICT-state and aryl-aryl electron extension is not observed for the trigonal arylboron compound, in which excited π-orbital coupling only occurs between the boron atom and one aryl group, which restricts the twist motion of the aryl-boron bond. The excited triplet state is deactivated primarily through aryl-boron bond cleavage, yielding aryl and diphenylboryl radicals. In the presence of oxygen, this photochemistry results in phenoxyl and diphenylboroxyl radicals, as confirmed by EPR spectroscopy of spin trapped radical adducts. The TICT transition and radical generation is not expected for BoDIPY molecules where the rotational vibration of the B-aryl bond is rigid, restricting changes in the geometric structure. In this sense, this work contributes to the development of new BoDIPY derivatives where the TICT transition may be observed for aryl ligands with free rotational vibrations in the BoDIPY structure. PMID:27529675

  1. Flux measurements of reactive nitrogen compounds using a chemiluminescence analyser with different converter types

    NASA Astrophysics Data System (ADS)

    Ammann, Christof; Wolff, Veronika

    2015-04-01

    The availability of reactive nitrogen (Nr) is a key limiting factors for the productivity and the competition success of individual species. On the other hand, certain nitrogenous compounds can also be emitted from natural or managed ecosystems. Thus the quantification of the Nr exchange can be essential for the interpretation of ecosystem behavior. For the observation of Nr dry deposition and emission the eddy covariance (EC) method is preferable since it does not modify the environmental conditions of the ecosystem, is less prone to wall effects than chamber methods, and is less affected by gas phase chemical reactions than gradient methods. Since the various Nr compounds can undergo fast chemical reactions and have differing chemical and physical characteristics, a variety of detection techniques is usually necessary that often cannot meet the fast response requirements of the EC technique. Here we show applications of a fast response 2-channel NO analyzer suitable for EC measurements. In combination with different inlet converters (photolytic converter, gold catalyst converter, and high-temperature steel converter), the system could alternatively be used for flux measurements of NO2, NOy, and total Nr. The quantification of By combining the 2-channel analyzer with the NOy and total Nr converter simultaneously, the NH3 flux could be determined from the difference between the two channels. Concentration and flux measurements of the system were verified by inter-comparison with other methods. Potential problems include the damping of high-frequency fluctuations in the inlet system. It is therefore important to place the converter close to the sampling inlet and to quantify and correct the damping effects. Moreover, like most other flux measurement techniques, the system is susceptible to non-stationary trace gas concentrations that often occur near pollution sources.

  2. Hand and Finger Exercises

    MedlinePlus

    Hand and Finger Exercises  Place your palm flat on a table. Raise and lower your fingers one ... times for ____ seconds.  Pick up objects with your hand. Start out with larger objects. Repeat ____ times for ____ ...

  3. Induction of caspase 8 and reactive oxygen species by ruthenium-derived anticancer compounds with improved water solubility and cytotoxicity.

    PubMed

    Vidimar, Vania; Meng, Xiangjun; Klajner, Marcelina; Licona, Cynthia; Fetzer, Ludivine; Harlepp, Sébastien; Hébraud, Pascal; Sidhoum, Marjorie; Sirlin, Claude; Loeffler, Jean-Philippe; Mellitzer, Georg; Sava, Gianni; Pfeffer, Michel; Gaiddon, Christian

    2012-12-01

    Organometallic compounds which contain metals, such as ruthenium or gold, have been investigated as a replacement for platinum-derived anticancer drugs. They often show good antitumor effects, but the identification of their precise mode of action or their pharmacological optimization is still challenging. We have previously described a class of ruthenium(II) compounds with interesting anticancer properties. In comparison to cisplatin, these molecules have lower side effects, a reduced ability to interact with DNA, and they induce cell death in absence of p53 through CHOP/DDIT3. We have now optimized these molecules by improving their cytotoxicity and their water solubility. In this article, we demonstrate that by changing the ligands around the ruthenium we modify the ability of the compounds to interact with DNA. We show that these optimized molecules reduce tumor growth in different mouse models and retain their ability to induce CHOP/DDIT3. However, they are more potent inducers of cancer cell death and trigger the production of reactive oxygen species and the activation of caspase 8. More importantly, we show that blocking reactive oxygen species production or caspase 8 activity reduces significantly the activity of the compounds. Altogether our data suggest that water-soluble ruthenium(II)-derived compounds represent an interesting class of molecules that, depending on their structures, can target several pro-apoptotic signaling pathways leading to reactive oxygen species production and caspase 8 activation. PMID:22964219

  4. Estimation of Physical Properties and Chemical Reactivity Parameters of Organic Compounds for Environmental Modeling by SPARC

    EPA Science Inventory

    Mathematical models for predicting the transport and fate of pollutants in the environment require reactivity parameter values that is value of the physical and chemical constants that govern reactivity. Although empirical structure activity relationships have been developed th...

  5. Lung function and bronchial reactivity in asthmatics during exposure to volatile organic compounds

    SciTech Connect

    Harving, H.; Dahl, R.; Molhave, L. )

    1991-04-01

    The purpose of the present study was to investigate whether vapors of organic solvents at low concentrations could exert an adverse effect in the lower airways. Under controlled conditions in a climate chamber, 11 persons with bronchial hyperreactivity to histamine and bronchial asthma were exposed for 90 min to a mixture of organic solvents at levels of zero, 2.5, and 25 mg/m3. During exposure to 25 mg/m3 a decrease in FEV1 to 90.7% of baseline value was measured. This was significantly different from the initial value (p less than 0.05), but not significantly different from the value found after sham exposure (FEV1, 97.4% of initial value). The decline in FEV1 during exposure to 25 mg/m3 was most pronounced in persons with high bronchial sensitivity. No changes were found in histamine reactivity after exposure, and no late reactions were registered. Ratings of discomfort showed different individual patterns ranging from no response to reactions towards both of the concentrations. The ratings indicated development of tolerance during exposure. Volatile organic compounds in concentrations found in both the work and the home environments may influence lung function and are probably of importance as bronchial irritants.

  6. Effect of reactive core mat application on bioavailability of hydrophobic organic compounds

    PubMed Central

    Meric, Dogus; Barbuto, Sara M.; Alshawabkeh, Akram N.; Shine, James P.; Sheahan, Thomas C.

    2014-01-01

    Sediment remediation techniques to limit the bioavailability of contaminants are of special interest due to related acute or chronic toxicities associated with sediment contaminants. Bioavailability in aquatic sediments can be particularly problematic due to their accessibility to food chain biota, and interactions with surface and ground water. The effect of a reactive core mat (RCM) containing organoclay on the bioavailability of hydrophobic organic compounds (HOCs) (i.e., PCBs and naphthalene) was studied using oligochaete worms (Lumbriculus variegatus). Sediment sampled from the Neponset River (Milton, MA) with 10 ppm background PCB contamination was used in the experimental study. The objective of this study is to investigate the difference in HOC concentration of worms exposed to: a) a grab sample of contaminated sediment (10.4% total organic carbon); and b) an initially clean mixture of sand and organic matter (the so-called biouptake layer), placed on top of the RCM-capped sediment during consolidation coupled solute transport experiments. In addition to the experimental data, the U.S. Army Corps of Engineers (USACE) biota-sediment accumulation factor (BSAF) database was validated and used to model biouptake of contaminants for certain cases. Results indicate that RCM capping reduced the average bioavailability of both PCBs and naphthalene by a factor of about 50. In fact, worms exposed to the RCM-protected biouptake layer show virtually the same HOC concentrations as those measured in the control worm samples. PMID:22386995

  7. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation.

    PubMed

    Kato, Yoji

    2016-03-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  8. Anthropogenic Emissions of Highly Reactive Volatile Organic Compounds (HRVOCs) Inferred from Oversampling of OMI HCHO Columns

    NASA Technical Reports Server (NTRS)

    Zhu, Lei; Jacob, Daniel; Mickley, Loretta; Marais, Eloise; Zhang, Aoxing; Cohan, Daniel; Yoshida, Yasuko; Duncan, Bryan; Abad, Gonzalo Gonzalez; Chance, Kelly; DeSmedt, Isabelle

    2014-01-01

    Satellite observations of formaldehyde (HCHO) columns provide top-down constraints on emissions of highly reactive volatile organic compounds (HRVOCs). This approach has been used previously to constrain emissions of isoprene from vegetation, but application to US anthropogenic emissions has been stymied by lack of a discernable HCHO signal. Here we show that oversampling of HCHO data from the Ozone Monitoring Instrument (OMI) for 2005 - 2008 enables quantitative detection of urban and industrial plumes in eastern Texas including Houston, Port Arthur, and Dallas-Fort Worth. By spatially integrating the individual urban-industrial HCHO plumes observed by OMI we can constrain the corresponding HCHO-weighted HRVOC emissions. Application to the Houston plume indicates a HCHO source of 260 plus or minus 110 kmol h-1 and implies a factor of 5.5 plus or minus 2.4 underestimate of anthropogenic HRVOC emissions in the US Environmental Protection Agency inventory. With this approach we are able to monitor the trend in HRVOC emissions over the US, in particular from the oil-gas industry, over the past decade.

  9. Anthropogenic emissions of highly reactive volatile organic compounds inferred from oversampling of OMI HCHO columns

    NASA Astrophysics Data System (ADS)

    Zhu, L.; Jacob, D. J.; Mickley, L. J.; Marais, E. A.; Cohan, D. S.; Yoshida, Y.; Duncan, B. N.; Gonzalez Abad, G.; Chance, K.

    2014-12-01

    Satellite observations of formaldehyde (HCHO) columns provide top-down constraints on emissions of highly reactive volatile organic compounds (HRVOCs). This approach has been used previously to constrain emissions of isoprene from vegetation, but application to US anthropogenic emissions has been stymied by lack of a discernable HCHO signal. Here we show that oversampling of HCHO data from the Ozone Monitoring Instrument (OMI) for 2005-2008 enables quantitative detection of urban and industrial plumes in eastern Texas including Houston, Port Arthur, and Dallas/Fort Worth. By spatially integrating the individual urban/industrial HCHO plumes observed by OMI we can constrain the corresponding HCHO-weighted HRVOC emissions. Application to the Houston plume indicates a HCHO source of 260±110 kmol h-1 and implies a factor of 5.5±2.4 underestimate of anthropogenic HRVOC emissions in the US Environmental Protection Agency inventory. This approach allows us to monitor trends in HRVOC emissions over the US, in particular from the urban areas and oil/gas industry.

  10. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation

    PubMed Central

    Kato, Yoji

    2016-01-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  11. Reactivity of bis(organoamino)phosphanes with magnesium(II) compounds.

    PubMed

    Vrána, Jan; Jambor, Roman; Růžička, Aleš; Alonso, Mercedes; De Proft, Frank; Lyčka, Antonín; Dostál, Libor

    2015-03-14

    The reactivity of three phosphanes (PhP(NHR)2 [R = t-Bu (1), Ph (2)] and PhP(NEt2)(NHDip) (3) (where Dip = 2,6-i-Pr2C6H3)) with n-Bu2Mg and MeMgBr is presented. In the case of 1, the reaction with n-Bu2Mg gave [PhP(NHt-Bu)(Nt-Bu)]Mg(n-Bu) (4) or [PhP(NHt-Bu)(Nt-Bu)]2Mg (5) depending on the stoichiometry. The treatment of 1 with MeMgBr led to the phosphinate [Ph(H)P(Nt-Bu)2]2Mg (7) as a result of both the NH→PH tautomeric transformation and elimination of MgBr2 from the non-isolable intermediate [PhP(NHt-Bu)(Nt-Bu)]MgBr(THF) (6). Phosphane 2 reacted with n-Bu2Mg in a 1:1 molar ratio resulting in the formation of {[PhP(NPh)2]2Mg(THF)2}2 (8), but the analogous reaction in a 2:1 molar ratio yielded phosphinate [Ph(H)P(NPh)2]2Mg(THF) (9). The heteroleptic compound [Ph(H)P(NPh)2]MgBr(THF)2 (10) was obtained by the reaction of 2 with MeMgBr. Finally, the reaction of 3 with n-Bu2Mg and MeMgBr produced compounds [PhP(NEt2)(NDip)]2Mg (11) and {[PhP(NEt2)(NDip)2]Mg(μ-Br)(THF)}2 (12), respectively. All products were characterized using (1)H, (13)C{(1)H} and (31)P NMR spectroscopy and, except for compounds 4 and 6, their molecular structures were determined using single-crystal X-ray diffraction analysis. In addition, a theoretical study on plausible isomers of 10 was performed to provide additional evidence for the presence of a syn- and anti-isomer in dynamic equilibrium in a solution of 10. PMID:25652308

  12. Phase I Metabolic Stability and Electrophilic Reactivity of 2-Phenylaminophenylacetic Acid Derived Compounds.

    PubMed

    Pang, Yi Yun; Tan, Yee Min; Chan, Eric Chun Yong; Ho, Han Kiat

    2016-07-18

    Diclofenac and lumiracoxib are two highly analogous 2-phenylaminophenylacetic acid anti-inflammatory drugs exhibiting occasional dose-limiting hepatotoxicities. Prior data indicate that bioactivation and reactive metabolite formation play roles in the observed toxicity, but the exact chemical influence of the substituents remains elusive. In order to elucidate the role of chemical influence on metabolism related toxicity, metabolic stability and electrophilic reactivity were investigated for a series of structurally related analogues and their resulting metabolites. The resulting analogues embody progressive physiochemical changes through varying halogeno- and aliphatic substituents at two positions and were subjected to in vitro human liver microsomal metabolic stability and cell-based GSH depletion assays (to measure electrophilic reactivity). LC-MS/MS analysis of the GSH trapped reactive intermediates derived from the analogues was then used to identify the putative structures of reactive metabolites. We found that chemical modifications of the structural backbone led to noticeable perturbations of metabolic stability, electrophilic reactivity, and structures and composition of reactive metabolites. With the acquired data, the relationships between stability, reactivity, and toxicity were investigated in an attempt to correlate between Phase I metabolism and in vitro toxicity. A positive correlation was identified between reactivity and in vitro toxicity, indicating that electrophilic reactivity can be an indicator for in vitro toxicity. All in all, the effect of substituents on the structures and reactivity of the metabolites, however subtle the changes, should be taken into consideration during future drug design involving similar chemical features. PMID:27245204

  13. On the reactive adsorption of ammonia on activated carbons modified by impregnation with inorganic compounds.

    PubMed

    Bandosz, Teresa J; Petit, Camille

    2009-10-15

    Ammonia adsorption was studied under dynamic conditions, at room temperature, on activated carbons of different origins (coal-based, wood-based and coconut-shell-based carbons) before and after their impregnation with various inorganic compounds including metal chlorides, metal oxides and polycations. The role of humidity was evaluated by running tests in both dry and moist conditions. Adsorbents were analyzed before and after exposure to ammonia by thermal analyses, sorption of nitrogen, potentiometric titration, X-ray diffraction and FTIR spectroscopy. Results of breakthrough tests show significant differences in terms of adsorption capacity depending on the parent carbon, the impregnates and the experimental conditions. It is found that surface chemistry governs ammonia adsorption on the impregnated carbons. More precisely, it was demonstrated that a proper combination of the surface pH, the strength, type and amount of functional groups present on the adsorbents' surface is a key point in ammonia uptake. Water can have either positive or negative effects on the performance of adsorbents. It can enhance NH(3) adsorption capacity since it favors ammonia dissolution and thus enables reaction between ammonium ions and carboxylic groups from the carbons' surface. On the other hand, water can also reduce the performance from the strength of adsorption standpoint. It promotes dissolution of ammonia and that ammonia is first removed from the system when the adsorbent bed is purged with air. Ammonia, besides adsorption by van der Waals forces and dissolution in water, is also retained on the surface via reactive mechanisms such as acid-base reactions (Brønsted and Lewis) or complexation. Depending on the materials used and the experimental conditions, 6-47% ammonia adsorbed is strongly retained on the surface even when the bed is purged with air. PMID:19615690

  14. On the reactive adsorption of ammonia on activated carbons modified by impregnation with inorganic compounds

    SciTech Connect

    Bandosz, T.J.; Petit, C.

    2009-10-15

    Ammonia adsorption was studied under dynamic conditions, at room temperature, on activated carbons of different origins (coal-based, wood-based and coconut-shell-based carbons) before and after their impregnation with various inorganic compounds including metal chlorides, metal oxides and polycations. The role of humidity was evaluated by running tests in both dry and moist conditions. Adsorbents were analyzed before and after exposure to ammonia by thermal analyses, sorption of nitrogen, potentiometric titration, X-ray diffraction and FTIR spectroscopy. Results of breakthrough tests show significant differences in terms of adsorption capacity depending on the parent carbon, the impregnates and the experimental conditions. It is found that surface chemistry governs ammonia adsorption on the impregnated carbons. More precisely, it was demonstrated that a proper combination of the surface pH, the strength, type and amount of functional groups present on the adsorbents' surface is a key point in ammonia uptake. Water can have either positive or negative effects on the performance of adsorbents. It can enhance NH{sub 3} adsorption capacity since it favors ammonia dissolution and thus enables reaction between ammonium ions and carboxylic groups from the carbons' surface. On the other hand, water can also reduce the performance from the strength of adsorption standpoint. It promotes dissolution of ammonia and that ammonia is first removed from the system when the adsorbent bed is purged with air. Ammonia, besides adsorption by van der Waals forces and dissolution in water, is also retained on the surface via reactive mechanisms such as acid-base reactions (Bronsted and Lewis) or complexation. Depending on the materials used and the experimental conditions, 6-47% ammonia adsorbed is strongly retained on the surface even when the bed is purged with air.

  15. Antagonism between lipid-derived reactive carbonyls and phenolic compounds in the Strecker degradation of amino acids.

    PubMed

    Delgado, Rosa M; Hidalgo, Francisco J; Zamora, Rosario

    2016-03-01

    The Strecker-type degradation of phenylalanine in the presence of 2-pentanal and phenolic compounds was studied to investigate possible interactions that either promote or inhibit the formation of Strecker aldehydes in food products. Phenylacetaldehyde formation was promoted by 2-pentenal and also by o- and p-diphenols, but not by m-diphenols. This is consequence of the ability of phenolic compounds to be converted into reactive carbonyls and produce the Strecker degradation of the amino acid. When 2-pentenal and phenolic compounds were simultaneously present, an antagonism among them was observed. This antagonism is suggested to be a consequence of the ability of phenolic compounds to either react with both 2-pentenal and phenylacetaldehyde, or compete with other carbonyl compounds for the amino acids, a function that is determined by their structure. All these results suggest that carbonyl-phenol reactions may be used to modulate flavor formation produced in food products by lipid-derived reactive carbonyls. PMID:26471665

  16. Scale up tools in reactive extrusion and compounding processes. Could 1D-computer modeling be helpful?

    NASA Astrophysics Data System (ADS)

    Pradel, J.-L.; David, C.; Quinebèche, S.; Blondel, P.

    2014-05-01

    Industrial scale-up (or scale down) in Compounding and Reactive Extrusion processes is one of the most critical R&D challenges. Indeed, most of High Performances Polymers are obtained within a reactive compounding involving chemistry: free radical grafting, in situ compatibilization, rheology control... but also side reactions: oxidation, branching, chain scission... As described by basic Arrhenius and kinetics laws, the competition between all chemical reactions depends on residence time distribution and temperature. Then, to ensure the best possible scale up methodology, we need tools to match thermal history of the formulation along the screws from a lab scale twin screw extruder to an industrial one. This paper proposes a comparison between standard scale-up laws and the use of Computer modeling Software such as Ludovic® applied and compared to experimental data. Scaling data from a compounding line to another one, applying general rules (for example at constant specific mechanical energy), shows differences between experimental and computed data, and error depends on the screw speed range. For more accurate prediction, 1D-Computer Modeling could be used to optimize the process conditions to ensure the best scale-up product, especially in temperature sensitive reactive extrusion processes. When the product temperature along the screws is the key, Ludovic® software could help to compute the temperature profile along the screws and extrapolate conditions, even screw profile, on industrial extruders.

  17. Finger snapping during seizures.

    PubMed

    Overdijk, M J; Zijlmans, M; Gosselaar, P H; Olivier, A; Leijten, F S S; Dubeau, F

    2014-01-01

    We describe two patients who showed snapping of the right hand fingers during invasive intracranial EEG evaluation for epilepsy surgery. We correlated the EEG changes with the finger-snapping movements in both patients to determine the underlying pathophysiology of this phenomenon. At the time of finger snapping, EEG spread from the supplementary motor area towards the temporal region was seen, suggesting involvement of these sites. PMID:25667884

  18. Modulation of growth performance in disease: reactive nitrogen compounds and their impact on cell proteins.

    PubMed

    Elsasser, T H; Kahl, S; Rumsey, T S; Blum, J W

    2000-08-01

    During life, all animals encounter situations that challenge their capability for optimal growth. In reacting to immune challenges in the form of disease, homeostatic mechanisms attempt to overcome disharmony of the body's internal environment, or simply put, stress. The overall impact of stress revolves around a dynamic relationship between the level of challenge imparted on physiological systems and the degree of host response that is mounted in the process of detecting and reacting to the stress. In growing animals, the majority of milder stress encounters are manifest in terms of energetic inefficiencies and periods of reduced anabolism. In contrast, severe stress is often characterized by frank catabolism and tissue wasting. In some instances a level of stress (that might be termed a "stress breakpoint") is reached at which time the host response itself contributes to the cascade of negative effectors that further cause illness. These "breakpoint" responses are characterized by more intense acute responses to stress or a much more protracted duration of the response than would be expected given the nature of the stress. Key to understanding how growth in the young animal responds to infectious stresses is the recognition that (a) when immune responses that normally maintain health go awry, the reporters and effectors of the immune system (cytokines and the nitric oxide cascade) can contribute to stress disease processes and (b) reactive nitrogen compounds derived from the nitric oxide, as well as super oxide anion can modify intracellular proteins and block otherwise normal biochemical processes that regulate cell function. A key example of this is the loss of regulation of IGF-I by GH. As animals react more severely to disease stress, IGF-I concentrations in plasma decline progressively. Recent data derived from (LPS) challenges performed on young calves suggest that the prolonged decline in IGF-I is associated with the development of hepatic cytotoxicity

  19. Species profiles and normalized reactivity of volatile organic compounds from gasoline evaporation in China

    NASA Astrophysics Data System (ADS)

    Zhang, Yanli; Wang, Xinming; Zhang, Zhou; Lü, Sujun; Shao, Min; Lee, Frank S. C.; Yu, Jianzhen

    2013-11-01

    In China, fast increase in passenger cars and gasoline consumption with yet quite limited vapor recovery during gasoline distribution has procured growing concern about gasoline evaporation as an important emission source of volatile organic compounds (VOCs), particularly in megacities hard-hit by air quality problems. This study presents VOC species profiles related to major pathways of gasoline evaporative loss in China, including headspace displacement, refueling operations and spillage/leakage. Apart from liquid gasoline and headspace vapors, gasoline vapors emitted when refueling cars in service stations or tank trucks in oil marketing depots were also sampled in situ with vapor recovery units (VRUs) turning on/off. Alkanes, alkenes and aromatic hydrocarbons accounted for 55-66, 21-35 and 4-8% in refueling vapors, 59-72, 18-28 and 4-10% in headspace vapors and 33-51, 8-15 and 38-48% in liquid gasoline samples, respectively. During refueling with VRUs turning on, total VOCs in vapors were less than one fifth of that with VRUs turning off, and aromatic hydrocarbons had higher weight percentages of about 8% in contrast with that of about 4% during refueling with VRUs turning off. Refueling vapors, especially for that with VRUs turning off, showed a larger fraction of light hydrocarbons including C3-C5 light alkenes when compared to headspace vapors, probably due to splashing and disturbance during filling operation. In refueling or headspace vapors the ratios of i-pentane/benzene, i-pentane/toluene, and MTBE (methyl tert-butyl ether)/benzene ranged 8.7-57, 2.7-4.8, and 1.9-6.6, respectively; and they are distinctively much higher than those previously reported in vehicle exhausts. Calculated normalized reactivity or ozone formation potential of the gasoline vapors in China ranged 3.3-4.4 g O3 g-1 VOC, about twice that of gasoline headspace vapors reported in USA as a result of larger fractions of alkenes in China's gasoline vapors. The results suggested that

  20. Fingers that change color

    MedlinePlus

    ... conditions can cause fingers or toes to change color: Buerger disease Chilblains. Painful inflammation of small blood vessels. Cryoglobulinemia Frostbite Necrotizing vasculitis Peripheral artery disease ...

  1. Phenotypic assays to identify agents that induce reactive gliosis: a counter-screen to prioritize compounds for preclinical animal studies.

    PubMed

    Beckerman, Samuel R; Jimenez, Joaquin E; Shi, Yan; Al-Ali, Hassan; Bixby, John L; Lemmon, Vance P

    2015-09-01

    Astrocyte phenotypes change in a process called reactive gliosis after traumatic central nervous system (CNS) injury. Astrogliosis is characterized by expansion of the glial fibrillary acidic protein (GFAP) cytoskeleton, adoption of stellate morphologies, and differential expression of some extracellular matrix molecules. The astrocytic response immediately after injury is beneficial, but in the chronic injury phase, reactive astrocytes produce inhibitory factors (i.e., chondroitin sulfate proteoglycans [CSPGs]) that limit the regrowth of injured axons. There are no drugs that promote axon regeneration or functional recovery after CNS trauma in humans. To develop novel therapeutics for the injured CNS, we screened various libraries in a phenotypic assay to identify compounds that promote neurite outgrowth. However, the effects these compounds have on astrocytes are unknown. Specifically, we were interested in whether compounds could alter astrocytes in a manner that mimics the glial reaction to injury. To test this hypothesis, we developed cell-based phenotypic bioassays to measure changes in (1) GFAP morphology/localization and (2) CSPG expression/immunoreactivity from primary astrocyte cultures. These assays were optimized for six-point dose-response experiments in 96-well plates. The GFAP morphology assay is suitable for counter-screening with a Z-factor of 0.44±0.03 (mean±standard error of the mean; N=3 biological replicates). The CSPG assay is reproducible and informative, but does not satisfy common metrics for a "screenable" assay. As proof of principle, we tested a small set of hit compounds from our neurite outgrowth bioassay and identified one that can enhance axon growth without exacerbating the deleterious characteristics of reactive gliosis. PMID:26230074

  2. OH Reactivity and Potential SOA Yields from Volatile Organic Compounds and Other Trace Gases Measured in Controlled Laboratory Biomass Burns

    NASA Astrophysics Data System (ADS)

    Gilman, J. B.; Warneke, C.; Kuster, W. C.; Goldan, P. D.; Veres, P. R.; Roberts, J. M.; de Gouw, J. A.; Burling, I. R.; Yokelson, R. J.

    2010-12-01

    A comprehensive suite of instruments were used to characterize volatile organic compounds (VOCs) and other trace gases (e.g., CO, CH4, NO2, etc.) emitted from controlled burns of various fuel types common to the Southeastern and Southwestern United States. These laboratory-based measurements were conducted in February 2009 at the U.S. Department of Agriculture’s Fire Sciences Laboratory in Missoula, Montana. An on-line GC-MS provided highly speciated VOC measurements of alkenes, alkanes, oxygenates, aromatics, biogenics, and nitrogen-containing compounds during the flaming or smoldering phases of replicate burns. The speciated GC-MS “grab” samples were integrated with fast-response gas-phase measurements (e.g., PTR-MS, PTR-IT-MS, NI-PT-CIMS, and FTIR) in order to determine VOC emission ratios and the fraction of identified vs. unidentifiable mass detected by PTR-MS. Emission ratios were used to calculate OH reactivity, which is a measure of potential ozone formation, as well as potential secondary organic aerosol (SOA) yields from the various fuel types. Small oxygenated VOCs had the highest emission ratios of the compounds observed. Alkenes dominated the VOC OH reactivity, which occasionally exceeded 1000 s-1. Calculated SOA yields from known precursors were dominated by aromatic VOCs, such as toluene, naphthalene (C10H8), and 1,3-benzenediol (C6H6O2, resorcinol). The contribution of several compounds not typically reported in ambient air measurements, such as substituted furans (C4H4O), pyrroles (C4H5N), and unsaturated C9 aromatics (C9H10), on OH reactivity and SOA yields will be discussed.

  3. Ozone reactivity of biogenic volatile organic compound (BVOC) emissions during the Southeast Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Park, J.; Guenther, A. B.; Helmig, D.

    2013-12-01

    Recent studies on atmospheric chemistry in the forest environment showed that the total reactivity by biogenic volatile organic compound (BVOC) emission is still not well understood. During summer 2013, an intensive field campaign (Southeast Oxidant and Aerosol Study - SOAS) took place in Alabama, U.S.A. In this study, an ozone reactivity measurement system (ORMS) was deployed for the direct determination of the reactivity of foliage emissions. The ORMS is a newly developed measurement approach, in which a known amount of ozone is added to the ozone-free air sample stream, with the ORMS measuring ozone concentration difference between before and after a glass flask flow tube reaction vessel (2-3 minutes of residence time). Emissions were also collected onto adsorbent cartridges to investigate the discrepancy between total ozone reactivity observation and reactivity calculated from identified BVOC. Leaf and canopy level experiments were conducted by deploying branch enclosures on the three dominant tree species at the site (i.e. liquidambar, white oak, loblolly pine) and by sampling ambient air above the forest canopy. For the branch enclosure experiments, BVOC emissions were sampled from a 70 L Teflon bag enclosure, purged with air scrubbed for ozone, nitrogen oxides. Each branch experiment was performed for 3-5 days to collect at least two full diurnal cycle data. In addition, BVOCs were sampled using glass tube cartridges for 2 hours during daytime and 3 - 4 hours at night. During the last week of campaign, the inlet for the ORMS was installed on the top of scaffolding tower (~30m height). The ozone loss in the reactor showed distinct diurnal cycle for all three tree species investigated, and ozone reactivity followed patterns of temperature and light intensity.

  4. Rolling friction robot fingers

    NASA Technical Reports Server (NTRS)

    Vranish, John M. (Inventor)

    1992-01-01

    A low friction, object guidance, and gripping finger device for a robotic end effector on a robotic arm is disclosed, having a pair of robotic fingers each having a finger shaft slideably located on a gripper housing attached to the end effector. Each of the robotic fingers has a roller housing attached to the finger shaft. The roller housing has a ball bearing mounted centering roller located at the center, and a pair of ball bearing mounted clamping rollers located on either side of the centering roller. The object has a recess to engage the centering roller and a number of seating ramps for engaging the clamping rollers. The centering roller acts to position and hold the object symmetrically about the centering roller with respect to the X axis and the clamping rollers act to position and hold the object with respect to the Y and Z axis.

  5. Reactivity of polycyclic aromatic compounds (PAHs, NPAHs and OPAHs) adsorbed on natural aerosol particles exposed to atmospheric oxidants

    NASA Astrophysics Data System (ADS)

    Ringuet, Johany; Albinet, Alexandre; Leoz-Garziandia, Eva; Budzinski, Hélène; Villenave, Eric

    2012-12-01

    Reactivity of polycyclic aromatic compounds (PACs) adsorbed on natural aerosol particles exposed to different atmospheric oxidants (O3, OH and NO2/O3 mixture) was studied. Decay of polycyclic aromatic hydrocarbons (PAHs) and formation/decay of oxygenated PAHs (OPAHs) and nitrated PAHs (NPAHs) were monitored. Overall, benzo[a]pyrene appeared to be the most reactive PAH (degradation of 50%). Only its nitrated derivative, 6-nitrobenzo[a]pyrene, was significantly formed explaining just 0.4% of reacted benzo[a]pyrene. No other nitrated or oxygenated benzo[a]pyrene derivatives were detected. Interestingly, B[e]P and In[1,2,3,c,d]P, which are usually considered as quite stable PAHs, also underwent decay in all experiments. In presence of O3, ketones were significantly formed but their amount was not totally explained by decay of parent PAH. These results suggest that PAH derivatives could be formed from the reaction of other compounds than their direct parent PAHs and raise the question to know if the oxidation of methyl-PAHs, identified in vehicle-exhausts, could constitute this missing source of OPAHs. NPAHs were significantly formed in presence of O3/NO2 and OH. Surprisingly, NPAH formation was clearly observed during O3 experiments. Nitrated species, already associated with aerosol particles (NO3-, NO2-) or formed by ozonation of particulate nitrogen organic matter, could react with PAHs to form NPAHs. Heterogeneous formation of 2-nitropyrene from pyrene oxidation was for the first time observed, questioning its use as an indicator of NPAH formation in gaseous phase. Equally, formation of 2-nitrofluoranthene by heterogeneous reaction of fluoranthene with O3/NO2 was clearly shown, while only its formation by homogeneous processes (gaseous phase) is reported in the literature. Finally, results obtained highlighted the dependence of heterogeneous PAH reactivity with the substrate nature and the importance to focus reactivity studies on natural particles, whatever the

  6. Multiple Fingers - One Gestalt.

    PubMed

    Lezkan, Alexandra; Manuel, Steven G; Colgate, J Edward; Klatzky, Roberta L; Peshkin, Michael A; Drewing, Knut

    2016-01-01

    The Gestalt theory of perception offered principles by which distributed visual sensations are combined into a structured experience ("Gestalt"). We demonstrate conditions whereby haptic sensations at two fingertips are integrated in the perception of a single object. When virtual bumps were presented simultaneously to the right hand's thumb and index finger during lateral arm movements, participants reported perceiving a single bump. A discrimination task measured the bump's perceived location and perceptual reliability (assessed by differential thresholds) for four finger configurations, which varied in their adherence to the Gestalt principles of proximity (small versus large finger separation) and synchrony (virtual spring to link movements of the two fingers versus no spring). According to models of integration, reliability should increase with the degree to which multi-finger cues integrate into a unified percept. Differential thresholds were smaller in the virtual-spring condition (synchrony) than when fingers were unlinked. Additionally, in the condition with reduced synchrony, greater proximity led to lower differential thresholds. Thus, with greater adherence to Gestalt principles, thresholds approached values predicted for optimal integration. We conclude that the Gestalt principles of synchrony and proximity apply to haptic perception of surface properties and that these principles can interact to promote multi-finger integration. PMID:26863671

  7. Finger and toenail onycholysis.

    PubMed

    Zaias, N; Escovar, S X; Zaiac, M N

    2015-05-01

    Onycholysis - the separation of the nail plate from the nail bed occurs in fingers and toenails. It is diagnosed by the whitish appearance of the separated nail plate from the nail bed. In fingers, the majority is caused by trauma, manicuring, occupational or self-induced behavior. The most common disease producing fingernail onycholysis is psoriasis and pustular psoriasis. Phototoxic dermatitis, due to drugs can also produce finger onycholysis. Once the separation occurs, the environmental flora sets up temporary colonization in the available space. Finger onycholysis is most common in women. Candida albicans is often recovered from the onycholytic space. Many reports, want to associate the yeast as cause and effect, but the data are lacking and the treatment of the candida does not improve finger onycholysis. A reasonable explanation for the frequent isolation of Candida and Pseudomonas in fingernail onycholysis in women, is the close proximity the fingers have to the vaginal and gastrointestinal tract. Fifty per cent of humans harbour C. albicans in the GI tract and it is frequently carried to the vagina during hygienic practices. Finger onycholysis is best treated by drying the nail 'lytic' area with a hair blower, since all colonizing biota are moisture loving and perish in a dry environment. Toenail onycholysis has a very different etiology. It is mechanical, the result of pressure on the toes from the closed shoes, while walking, because of the ubiquitous uneven flat feet producing an asymmetric gait with more pressure on the foot with the flatter sole. PMID:25512134

  8. The pKa of Brønsted acids controls their reactivity with diazo compounds.

    PubMed

    Fei, Na; Sauter, Basilius; Gillingham, Dennis

    2016-06-14

    We study the O-alkylation of phosphate groups by alkyl diazo compounds in a range of small molecules and biopolymers. We show that the relatively high pKa of phosphate in comparison to the other naturally occurring Brønsted acids can be exploited to control alkylation selectivity. We provide a simple protocol for chemical modification of some of the most important instances of phosphates in natural compounds including in small molecule metabolites, nucleic acids, and peptides. PMID:27212133

  9. Governing processes for reactive nitrogen compounds in the atmosphere in relation to ecosystem, climatic and human health impacts

    NASA Astrophysics Data System (ADS)

    Hertel, O.; Skjøth, C. A.; Reis, S.; Bleeker, A.; Harrison, R.; Cape, J. N.; Fowler, D.; Skiba, U.; Simpson, D.; Jickells, T.; Kulmala, M.; Gyldenkærne, S.; Sørensen, L. L.; Erisman, J. W.; Sutton, M. A.

    2012-07-01

    Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account these differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3-). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3- contribute significantly to background PM2.5 and PM10 (mass of aerosols with a diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms in the atmosphere. Further studies are needed to characterize the sources, air chemistry and removal rates of organic N

  10. Evaluation of a horizontal permeable reactive barrier for preventing upward diffusion of volatile organic compounds through the unsaturated zone.

    PubMed

    Mahmoodlu, Mojtaba G; Hassanizadeh, S Majid; Hartog, Niels; Raoof, Amir; van Genuchten, Martinus Th

    2015-11-01

    Permeable reactive barriers are commonly used to treat contaminant plumes in the saturated zone. However, no known applications of horizontal permeable reactive barriers (HPRBs) exist for oxidizing volatile organic compounds (VOCs) in the unsaturated zone. In this study, laboratory column experiments were carried out to investigate the ability of a HPRB containing solid potassium permanganate, to oxidize the vapors of trichloroethylene (TCE), toluene, and ethanol migrating upward from a contaminated saturated zone. Results revealed that an increase in initial water saturation and HPRB thickness strongly affected the removal efficiency of the HPRB. Installing the HPRB relatively close to the water table was more effective due to the high background water content and enhanced diffusion of protons and/or hydroxides away from the HPRB. Inserting the HPRB far above the water table caused rapid changes in pH within the HPRB, leading to lower oxidation rates. The pH effects were included in a reactive transport model, which successfully simulated the TCE and toluene experimental observations. Simulations for ethanol were not affected by pH due to condensation of water during ethanol oxidation, which caused some dilution in the HRPB. PMID:26321530

  11. Growth behavior of intermetallic compounds during reactive diffusion between aluminum alloy 1060 and magnesium at 573-673 K

    NASA Astrophysics Data System (ADS)

    Xiao, Lin; Wang, Ning

    2015-01-01

    A potential new research reactor fuel design proposes to use U-Mo fuel in a Mg matrix clad with Al. Interdiffusion between the Mg containing fuel core and Al cladding can result in the formation of intermetallic compounds that can be detrimental to fuel element performance. The kinetics of the reactive diffusion in the binary Al-Mg system was experimentally studied. Layers of the intermetallic compounds, β (Al3Mg2) and γ (Al12Mg17) phases, were formed between the Al alloy 1060 and Mg during annealing. The β layer was observed to grow faster than the γ phase. The thickness of each layer can be expressed by a power function of the annealing time with the exponent n close to 0.5 for the β phase and less than 0.5 for the γ phase. The results suggest that the growth of β phase is controlled by lattice diffusion and that of the γ phase by grain boundary and lattice diffusion. Metallographic examination showed the grain boundary diffusion in the form of columnar growth of γ phase during annealing. Based on the reactive diffusion equation developed in this work, in the absence of irradiation effects, it will take more than 110 h to consume a half thickness of 400 μm of the cladding.

  12. Flux estimates and OH reaction potential of reactive biogenic volatile organic compounds (BVOCs) from a mixed northern hardwood forest

    NASA Astrophysics Data System (ADS)

    Ortega, John; Helmig, Detlev; Guenther, Alex; Harley, Peter; Pressley, Shelley; Vogel, Christoph

    Diurnal branch-level emission rates of biogenic volatile organic compounds (BVOC) including isoprene, monoterpenes (MT), and sesquiterpenes (SQT) were determined at the University of Michigan Biological Station for the tree species red maple ( Acer rubrum), red oak ( Quercus rubra), paper birch ( Betula papyrifera), white pine ( Pinus strobus), and big tooth aspen ( Populus grandidentata). These emission rates were combined with detailed biomass distribution and meteorological data and incorporated into the canopy model, model of emissions of gasses and aerosols from nature (MEGAN), for estimating whole-canopy fluxes of isoprene. The modeled half-hour fluxes (mgCm-2h-1) and cumulative seasonal fluxes (mgCm-2) compared favorably with results from direct, canopy-level eddy covariance (EC) isoprene measurements; modeled cumulative seasonal flux deviated less than 30% from the EC results. Significant MT emissions were found from four of the five tree species. MT emissions from three of these were both light- and temperature-dependent and were approximately one order of magnitude greater than light-independent MT emissions. SQT emissions were identified from three of the five tree species. The model was modified to incorporate SQT and both light-dependent and light-independent MT emissions for determining fluxes. Isoprene comprised >95% of the total terpenoid flux with MT and SQT comprising 4% and 0.3%, respectively. The average cumulative fluxes (in mgCm-2) from June through September were 2490 for isoprene, 105 for MT, and 7 for SQT. A simple box model analysis was used to estimate the contribution of the isoprene, MT, and SQT emissions to the total OH reactivity. These results confirm that isoprene dominates OH reactions especially during daytime hours. Emissions of reactive MT and SQT increase the BVOC+OH reactivity, but are still lower than estimates of BVOC fluxes at this site necessary for affecting OH reactivity to the significant degree suggested by recent

  13. Correlations between chemical reactivity and mutagenic activity against S. typhimurium TA100 for alpha-dicarbonyl compounds as a proof of the mutagenic mechanism.

    PubMed

    Rodríguez Mellado, J M; Ruiz Montoya, M

    1994-01-16

    The mutagenic activities in the Ames test against S. typhimurium TA100 for a series of alpha-dicarbonyl compounds are examined together with the formation constants of the adducts formed between such compounds and guanine and guanosine. Correlations between the equilibrium constants, the apparent reaction enthalpies, and the mutagenic activity are presented. These correlations imply that the mutagenic activity is related to the chemical reactivity of the dicarbonyl compounds with the puric bases. PMID:7506369

  14. Fingering in Confined Elastic Layers

    NASA Astrophysics Data System (ADS)

    Biggins, John; Mahadevan, L.; Wei, Z.; Saintyves, Baudouin; Bouchaud, Elizabeth

    2015-03-01

    Fingering has recently been observed in soft highly elastic layers that are confined between and bonded to two rigid bodies. In one case an injected fluid invades the layer in finger-like protrusions at the layer's perimeter, a solid analogue of Saffman-Taylor viscous fingering. In a second case, separation of the rigid bodies (with maintained adhesion to the layer) leads air to the formation of similar fingers at the layer's perimeter. In both cases the finger formation is reversible: if the fluid is removed or the separation reduced, the fingers vanish. In this talk I will discuss a theoretical model for such elastic fingers that shows that the origin of the fingers is large-strain geometric non-linearity in the elasticity of soft solids. Our simplified elastic model unifies the two types of fingering and accurately estimates the thresholds and wavelengths of the fingers.

  15. Tendon Driven Finger Actuation System

    NASA Technical Reports Server (NTRS)

    Ihrke, Chris A. (Inventor); Reich, David M. (Inventor); Bridgwater, Lyndon (Inventor); Linn, Douglas Martin (Inventor); Askew, Scott R. (Inventor); Diftler, Myron A. (Inventor); Platt, Robert (Inventor); Hargrave, Brian (Inventor); Valvo, Michael C. (Inventor); Abdallah, Muhammad E. (Inventor); Permenter, Frank Noble (Inventor); Mehling, Joshua S. (Inventor)

    2013-01-01

    A humanoid robot includes a robotic hand having at least one finger. An actuation system for the robotic finger includes an actuator assembly which is supported by the robot and is spaced apart from the finger. A tendon extends from the actuator assembly to the at least one finger and ends in a tendon terminator. The actuator assembly is operable to actuate the tendon to move the tendon terminator and, thus, the finger.

  16. Interactions between volatile organic compounds and reactive halogen in the tropical marine atmosphere using WRF-Chem

    NASA Astrophysics Data System (ADS)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; von Glasow, Roland

    2016-04-01

    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens cause ozone (O3) destruction, change the HOx and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. There are indications that the chemistry of reactive halogens and oxygenated VOCs (OVOCs) in the tropics are inter-related. Moreover, the presence of aldehydes, such as glyoxal (CHOCHO), has a potential impact on radical cycling and secondary organic aerosol (SOA) formation in the MBL and free troposphere (FT). Model calculations suggest aldehydes to be an important sink for bromine atoms and hence competition for their reaction with O3 forming BrO and so illustrating a link between the cycles of halogens and OVOCs in the marine atmosphere. The main objective of this contribution is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens and OVOCs and their links using the latest version of the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. WRF-Chem is a highly flexible community model for atmospheric research where aerosol-radiation-cloud feedback processes are taken into account. Our current reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. The MOZART mechanism includes detailed gas-phase chemistry of CHOCHO formation as well as state-of-the-science pathways to form SOA. Oceanic emissions of aldehydes, including CHOCHO, and of organic halogens based on measurements from the TORERO campaign have been added into the model. Sea

  17. Development of a QSAR for worst case estimates of acute toxicity of chemically reactive compounds.

    PubMed

    Freidig, A P; Dekkers, S; Verwei, M; Zvinavashe, E; Bessems, J G M; van de Sandt, J J M

    2007-05-15

    Future EU legislations enforce a fast hazard and risk assessment of thousands of existing chemicals. If conducted by means of present data requirements, this assessment will use a huge number of test animals and will be neither cost nor time effective. The purpose of the current research was to develop methods to increase the acceptability of in vitro data for classification and labelling regarding acute toxicity. For this purpose, a large existing database containing in vitro and in vivo data was analysed. For more than 300 compounds in the database, relations between in vitro cytotoxicity and rat or mouse intravenous and oral in vivo LD50 values were re-evaluated and the possibilities for definition of mechanism based chemical subclasses were investigated. A high in vitro-in vivo correlation was found for chemicals classified as irritants. This can be explained by a shared unspecific cytotoxicity of these compounds which will act as the predominant mode of action for both endpoints, irritation and acute toxicity. For this subclass, which covered almost 40% of all compounds in the database, the LD50 values after intravenous dosing could be predicted with high accuracy. A somewhat lower accuracy was found for the prediction of oral LD50 values based on in vitro cytotoxicity data. Based on this successful correlation, a classification and labelling scheme was developed, that includes a hazard based definition of the applicability domain (irritants) and a prediction of the labelling of compounds for their acute iv and oral toxicity. The scheme was tested by an external validation. PMID:17462838

  18. Marine and terrestrial sources of reactive volatile organic compounds and their impact on the tropospheric ozone chemistry of the earth

    NASA Astrophysics Data System (ADS)

    Riemer, Daniel David

    Two areas integral to the global cycle of tropospheric ozone were studied. The first segment of this investigation involved the study of marine ecosystems to define the sources of nonmethane hydrocarbons (NMHCs) in the surface ocean. This included laboratory and field investigations conducted to determine the function and importance of dissolved organic matter (DOM) in the abiotic photochemical production of nonmethane hydrocarbons (NMHCs) in surface seawater. Concurrently, phytoplankton were investigated as a biogenic source of NMHCs in the surface ocean. Low molecular weight alkenes, compounds observed in the greatest quantities in the surface ocean, are formed almost exclusively as a result of DOM-mediated photochemistry. Isoprene was found to be produced by all phytoplankton species investigated. The primary sink for NMHCs found in surface seawater was gas exchange. The second segment of this study focused on the prevalence of NMHCs and oxygenated volatile organic compounds (OVOCs) in the rural southeastern United States. To characterize the importance of NMHCs and OVOCs to the process of atmospheric reactivity and tropospheric ozone chemistry, mixing ratios for a number of NMHCs and OVOCs were determined. Isoprene and its primary oxidation products, methacrolein and methyl vinyl ketone, were observed to be the dominant hydroxyl radical (OH) sink in the rural atmosphere. Certain OVOCs, namely methanol, acetone and acetaldehyde-although not as important on a reactivity basis-were the most prevalent in terms of mass. Methanol was the dominant OVOC measured in the rural atmosphere and serves as an important source of formaldehyde in the rural atmosphere. On the basis of the mixing ratio patterns exhibited by many of the OVOCs present in the rural atmosphere, considerable biogenic sources are likely.

  19. Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Zhenfa; Docherty, Kenneth S.; Zhang, Haofei; Budisulistiorini, Sri Hapsari; Rubitschun, Caitlin L.; Shaw, Stephanie L.; Knipping, Eladio M.; Edgerton, Eric S.; Kleindienst, Tadeusz E.; Gold, Avram; Surratt, Jason D.

    2011-01-01

    Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NOx conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (> 99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7–6.4% for β-IEPOX and 3.4–5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C5-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NOx, isoprene-dominated regions influenced by the presence of acidic aerosols. PMID:22103348

  20. 2-Hydrazinoquinoline: a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry to detect gaseous carbonyl compounds.

    PubMed

    Shigeri, Yasushi; Kamimura, Takuya; Ando, Masanori; Uegaki, Koichi; Sato, Hiroaki; Tani, Fumito; Arakawa, Ryuichi; Kinumi, Tomoya

    2016-01-01

    The sensitivity, range of applications, and reaction mechanism of 2-hydrazinoquinoline as a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were examined. Using a reaction chamber (125L) equipped with a stirring fan and a window for moving the MALDI-MS plate and volatile samples in and out, the sensitivities of 2-hydrazinoquinoline to gaseous aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and n-butyraldehyde) and ketones (acetone, methyl ethyl ketone, and methyl isobutyl ketone) were determined to be at least parts per million (ppm) levels. On the other hand, carboxylic acids (formic acid, acetic acid, propionic acid, and butyric acid) and esters (ethyl acetate, pentyl acetate, isoamyl acetate, and methyl salicylate) could not be detected by 2-hydrazinoquinoline in MALDI-MS. In addition to 2,4-dinitrophenylhydrazine, a common derivatization reagent for analyzing carbonyl compounds quantitatively in gas chromatography and liquid chromatography, the dissolution of 2-hydrazinoquinoline in an acidic solution, such as trifluoroacetic acid, was essential for its function as a reactive matrix for MALDI- MS. PMID:27419901

  1. Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface.

    PubMed

    Fu, Hongbo; Ciuraru, Raluca; Dupart, Yoan; Passananti, Monica; Tinel, Liselotte; Rossignol, Stéphanie; Perrier, Sebastien; Donaldson, D James; Chen, Jianmin; George, Christian

    2015-07-01

    We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment. PMID:26068588

  2. Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface

    PubMed Central

    2015-01-01

    We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment. PMID:26068588

  3. Temporal distribution, behaviour and reactivities of BTEX compounds in a suburban Atlantic area during a year.

    PubMed

    Pérez-Rial, Débora; López-Mahía, Purificación; Muniategui-Lorenzo, Soledad; Prada-Rodríguez, Darío

    2009-06-01

    The temporal distribution of BTEX compounds (benzene, toluene, ethylbenzene and xylene isomers) in ambient air was studied in a suburban Atlantic area in the northwest of Spain. These compounds mean serious risks for public and occupational health and for biological and physical environments. A total of 1200 samples were analysed during a year, and in most of the samples toluene was the most abundant VOC followed by benzene or m+p-xylene. The average concentrations were 1.62, 2.15, 0.60, 0.94 and 0.47 microg m(-3) for benzene, toluene, ethylbenzene, m+p-xylenes and o-xylene respectively, although they reached values as high as 50.53, 28.57, 21.33, 46.13 and 22.74 microg m(-3) for the compounds in the same order. An exhaustive study was carried out to establish how both emission sources and the climatic conditions affected the BTEX levels measured in the outskirts of a small city. Wind directions and speeds, daily and seasonal BTEX profiles, ratios among the concentrations measured in the sampling site, in the city centre and in the fuels commonly used by the cars in the city were studied. The pollution roses revealed the presence of diffuse BTEX sources affecting the sampling point, although all the compounds reached their highest levels when the wind blew from an industrial area in the SW of the city. The daily BTEX profiles were well-correlated with the traffic pattern in the accesses to the city and the seasonal profile showed that the highest concentrations were reported in summertime. The ratios T/B, m+p-X/B and o-X/B were 1.32, 0.58 and 0.29 respectively; these values were lower than the ones reported in previous studies carried out in the centre of the same city. This could be caused by the major distance from the sampling point to the city centre and by the changes in the fuels and in the kind of vehicles used in the city. The correlation coefficients among the TEX fraction were always higher than 0.72 but benzene only showed a good correlation with these

  4. Osseointegrated finger prostheses.

    PubMed

    Doppen, P; Solomons, M; Kritzinger, S

    2009-02-01

    Amputation of a digit can lead to functional and psychological problems and patients can benefit from digital prostheses. Unfortunately, standard prostheses are often unstable, particularly when fitted over short amputation stumps. Prosthesis fixation by osseointegration is widely used in oral and extraoral applications and may help avoid the problem of instability. This paper reports the results of four patients with five finger amputations who were treated with osseointegrated implants to attach finger prostheses. One implant failed to osseointegrate and the procedure was abandoned. Three patients were successfully treated to completion of three finger prostheses and are extremely satisfied with their outcomes, both cosmetically and functionally, with osseoperception reported by all three patients. PMID:19091736

  5. Oxidation of sulfur compounds in petroleum residues: reactivity-structural relationships

    SciTech Connect

    Petersen, J.C.; Dorrence, S.M.; Nazir, M.; Plancher, H.; Barbour, F.A.

    1981-09-01

    Studies have been made on the reactivity of sulfur entities in oxidized asphalts and oxidized petroleum distillation residues during air oxidation. Asphalts are referred to as residues. The oxidation of these materials includes the rapid formation of an unsymmetrical ir band at ca 1030/cm. Sulfoxides are not normally found in unoxidized petroleum residues, but develop rapidly during air aging. Their presence in these residues has been inferred from their specific bands in ir spectra. Confirmation of sulfoxides was obtained from deoxygenation with chlorocarbenes and decomposition with bromine and peracetic acid. Hydroperoxides in amounts that might interfere with sulfoxide determination were not found in oxidated residues. The concentration of sulfoxides formed during air oxidation was found to rapidly reach a maximum value and to remain constant on further oxidation of the residue. Model studies indicate that hydroperoxides play a role in sulfoxide formation. The data show that both alkyl and aryl sulfides were present in aliphatic residues, that predominantly alkyl types were oxidized during oxidative aging in air and that concentrations of the alkyl and aryl types vary with crude source. Peracetic acid oxidation of the residues indicated that most of the sulfur present was in the form of sulfides. 2 figures, 6 tables.

  6. Multi-fingered robotic hand

    NASA Technical Reports Server (NTRS)

    Ruoff, Carl F. (Inventor); Salisbury, Kenneth, Jr. (Inventor)

    1990-01-01

    A robotic hand is presented having a plurality of fingers, each having a plurality of joints pivotally connected one to the other. Actuators are connected at one end to an actuating and control mechanism mounted remotely from the hand and at the other end to the joints of the fingers for manipulating the fingers and passing externally of the robot manipulating arm in between the hand and the actuating and control mechanism. The fingers include pulleys to route the actuators within the fingers. Cable tension sensing structure mounted on a portion of the hand are disclosed, as is covering of the tip of each finger with a resilient and pliable friction enhancing surface.

  7. Basalt Reactivity in the Presence of H2O-Saturated Supercritical CO2 Containing Gaseous Sulfur Compounds

    NASA Astrophysics Data System (ADS)

    Schaef, H. T.; McGrail, P.; Owen, A. T.

    2009-12-01

    Future impacts of climate change may be minimized by capture of emissions, primarily CO2 from fossil-fueled electric generating stations and subsequent sequestration in deep geologic formations. Injection of dry liquid CO2 into porous geologic reservoirs for long term storage is expected to eventually form a buoyant water-saturated bubble of supercritical fluid. Depending on purification processes and underground injection control regulations, the injected CO2 also could contain trace compounds associated with flue gas streams (SO2, N2, and O2). Once injected, the scCO2 will absorb water (1500 to 3000 ppmw) until becoming immobilized by reservoir trapping mechanisms. Reactivity of the water-bearing scCO2 with silicate minerals is relatively unknown and could have impacts on long term reservoir seal integrity and trapping by mineralization. To examine the reactivity of H2O-saturated scCO2, basalt experiments were conducted at pressures and temperatures relevant to geologic sequestration. Reaction products differed considerably depending on the gas mixtures used and type of basalt. In the presence of H2O-saturated CO2, the Newark Basin basalt reacted to produce secondary mineralization with needle-like morphologies and chemistries similar to aragonite. Exposing the same basalt to a CO2-H2S mixture (H2O saturated) produced two types of reaction products: carbonates in the form of small discrete nodules or needles and metallic-like circular areas similar in chemistry to pyrite and marcarsite. Tests conducted in the presence of CO2-SO2 produced the most extensive surface reaction products observed during the experiments. Some basalts were completely coated in white precipitate identified as a mixture of gypsum, sulfate bearing minerals (rozenite and melanterite), and a magnesium sulfate compound (MgSO4 ●5H2O). Hawaiian flow top basalts contained extensive reaction products including magnesium sulfate (MgSO4●6H2O), which formed on the large olivine crystals present

  8. Reactivity of tracheal smooth muscles in albino rats with experimental diabetes mellitus treated with a new complex compound of oxovanadium (IV) and isonicotinic acid hydrazide.

    PubMed

    Khafiz'yanova, R Kh; Minnebaev, M M; Gallyamov, R M; Latypov, R S; Gosmanov, A R; Aleeva, G N

    2003-06-01

    We studied functional properties of tracheal smooth muscle cells in rats with diabetes mellitus. Reactivity of tracheal smooth muscles increased in rats with experimental alloxan-induced diabetes mellitus. A new complex compound of oxovanadium (IV) and isonicotinic acid hydrazide affected reactivity of tracheal smooth muscles in albino rats with experimental type I diabetes mellitus. This new organic vanadium-containing compound reduced contractility of tracheal smooth muscles in rats and potentiated relaxation of smooth muscle cells in the trachea in response to exogenous nitric oxide. PMID:12937677

  9. Influence of coffee genotype on bioactive compounds and the in vitro capacity to scavenge reactive oxygen and nitrogen species.

    PubMed

    Rodrigues, Naira Poerner; Salva, Terezinha de Jesus Garcia; Bragagnolo, Neura

    2015-05-20

    The influence of green coffee genotype on the bioactive compounds and the in vitro antioxidant capacity against the principal reactive oxygen (ROO(•), H2O2, HO(•), and HOCl) and nitrogen (NO(•) and ONOO(-)) species of biological relevance was investigated. This is the first report on the capacity of green coffee to scavenge H2O2, HOCl, and NO(•). Variations in the contents of total chlorogenic acids (22.9-37.9 g/100 g), cinnamoyl-amino acid conjugates (0.03-1.12 g/100 g), trigonelline (3.1-6.7 g/100 g), and caffeine (3.9-11.8 g/100 g) were found. Hydrophilic extracts of Coffea canephora and Coffea kapakata were the most potent scavengers of ROO(•), H2O2, HO(•), NO(•), and ONOO(-) due to their chlorogenic acid contents, which were, on average, 30% higher than those found in Coffea arabica and Coffea racemosa. The results showed that genotype is a determinant characteristic in the bioactive compound contents and consequently in the antioxidant capacity of green coffee. PMID:25910038

  10. Near-Roadway Emission of Reactive Nitrogen Compounds and Other Non-Criteria Pollutants at a Southern California Freeway Site

    NASA Astrophysics Data System (ADS)

    Moss, J. A.; Baum, M.; Castonguay, A. E.; Aguirre, V., Jr.; Pesta, A.; Fanter, R. K.; Anderson, M.

    2015-12-01

    Emission control systems in light-duty motor vehicles (LDMVs) have played an important role in improving regional air quality by dramatically reducing the concentration of criteria pollutants (carbon monoxide, hydrocarbons, and nitrogen oxides) in exhaust emissions. Unintended side-reactions occurring on the surface of three-way catalysts may lead to emission of a number of non-criteria pollutants whose identity and emission rates are poorly understood. A series of near-roadway field studies conducted between 2009-2015 has investigated LDMV emissions of these pollutants with unprecedented depth of coverage, including reactive nitrogen compounds (NH3, amines, HCN, HONO, and HNO3), organic peroxides, and carbonyl compounds (aldehydes, ketones, and carboxylic acids). Methods to collect these pollutants using mist chambers, annular denuders, impingers, and solid-phase cartridges and quantify their concentration using GC-MS, LC-MS/MS, IC, and colorimetry were developed and validated in the laboratory and field. These methods were subsequently used in near-roadway field studies where the concentrations of the target compounds integrated over 1-4 hour blocks were measured at the edge of a freeway and at a background site 140 m from the roadway. Concentrations followed a steep decreasing gradient from the freeway to the background site. Emission factors (pollutant mass emitted per mass fuel consumed) were calculated by carbon mass balance using the difference in concentration measured between the freeway and background sites for the emitted pollutant and CO2 as a measure of carbon mass in the vehicle exhaust. The significance of these results will be discussed in terms of emissions inventories in the South Coast Air Basin of California, emission trends at this site over the period of 2009-2015, and for NH3, emission measurements conducted by our group and others over the period 2000-2015.

  11. Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

    PubMed

    Armendáriz-Vidales, Georgina; Frontana, Carlos

    2014-09-01

    An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)⁰ values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation. Analysis of the variation of the dimensionless cathodic peak potential values (ξ(p)) as a function of the scan rate (v) functions and complementary experiments in benzonitrile suggested that this process follows a dissociative electron transfer, in which the rate of heterogeneous electron transfer is slow (~0.2 cm s(-1)), and the rate constant of the chemical process is at least 10(5) larger. PMID:25007856

  12. Reactivity of thiosemicarbazides with redox active metal ions: controlled formation of coordination complexes versus heterocyclic compounds.

    PubMed

    López-Torres, Elena; Dilworth, Jonathan R

    2009-01-01

    The reactions of 1,1-dimethyl-4-phenylthiosemicarbazide (LH) with Cu(II) and Sn(IV) have been investigated. If THF or methanol is used as solvent with Cu(II), oxidative cyclisation and coupling are observed, yielding a 1,2,4-thiadiazole or a 1,3,4-thiadiazolium salt. SnI(4) is also able to induce oxidative coupling of two thiosemicarbazide ligands, yielding 1,2,4-thiadiazolium or 1,2,4-triazolium salts, with I(3)(-) as the counterion, depending on the reaction conditions. By contrast, reaction of LH with SnI(4) in acetone yields a 1,3-thiazolium salt, with I(-) as counterion. Reaction with Cu(II) salts or SnI(4) in basic media leads to the formation of metal complexes containing two deprotonated thiosemicarbazide ligands. In the reaction of CuCl(2) in water in the presence of acid a complex containing two neutral ligands is obtained. Reactions with SnCl(4) are not able to induce ligand cyclisation, although a coordination compound with two neutral ligands was isolated from methanol. PMID:19180593

  13. Three-Fingered Robot Hand

    NASA Technical Reports Server (NTRS)

    Ruoff, C. F.; Salisbury, J. K.

    1984-01-01

    Mechanical joints and tendons resemble human hand. Robot hand has three "human-like" fingers. "Thumb" at top. Rounded tips of fingers covered with resilient material provides high friction for griping. Hand potential as prosthesis for humans.

  14. Repair of webbed fingers - slideshow

    MedlinePlus

    ... gov/ency/presentations/100096.htm Repair of webbed fingers - series—Normal anatomy To use the sharing features ... Health Solutions, Ebix, Inc. Related MedlinePlus Health Topics Finger Injuries and Disorders A.D.A.M., Inc. ...

  15. Spiral viscous fingering.

    NASA Astrophysics Data System (ADS)

    Nagatsu, Yuichiro; Hayashi, Atsushi; Kato, Yoshihito; Tada, Yutaka

    2006-11-01

    When a less-viscous fluid displaces a more-viscous fluid in a radial Hele-Shaw cell, viscous fingering pattern is believed to develop in a radial direction. We performed experiments on viscous fingering in a radial Hele-Shaw cell when a polymer solution, a sodium polyacrylate (SPA) solution is used as the more-viscous fluid and the trivalent iron (Fe^3+) solution is as the less-viscous fluid. The experiment was done by varying the concentration of Fe^3+, cFe3+. We have found that viscous fingering pattern develops spirally when cFe3+ is larger than a threshold value, while the pattern develops in a radial direction for small cFe3+. We confirmed from different experiments that an instantaneous chemical reaction takes place between SPA solution and Fe^3+ solution. The chemical reaction produces precipitation and significantly reduces the viscosity of the SPA solution. The quantity of the precipitation is increased with cFe3+. We will make a discussion on the relationship between the formation of spiral viscous fingering and the chemical reaction taking place between the two fluids.

  16. Contributions of individual reactive biogenic volatile organic compounds to organic nitrates above a mixed forest

    NASA Astrophysics Data System (ADS)

    Pratt, K. A.; Mielke, L. H.; Shepson, P. B.; Bryan, A. M.; Steiner, A. L.; Ortega, J.; Daly, R.; Helmig, D.; Vogel, C. S.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Alaghmand, M.

    2012-11-01

    Biogenic volatile organic compounds (BVOCs) can react in the atmosphere to form organic nitrates, which serve as NOx (NO + NO2) reservoirs, impacting ozone and secondary organic aerosol production, the oxidative capacity of the atmosphere, and nitrogen availability to ecosystems. To examine the contributions of biogenic emissions and the formation and fate of organic nitrates in a forest environment, we simulated the oxidation of 57 individual BVOCs emitted from a rural mixed forest in northern Michigan. Key BVOC-oxidant reactions were identified for future laboratory and field investigations into reaction rate constants, yields, and speciation of oxidation products. Of the total simulated organic nitrates, monoterpenes contributed ~70% in the early morning at ~12 m above the forest canopy when isoprene emissions were low. In the afternoon, when vertical mixing and isoprene nitrate production were highest, the simulated contribution of isoprene-derived organic nitrates was greater than 90% at all altitudes, with the concentration of secondary isoprene nitrates increasing with altitude. Notably, reaction of isoprene with NO3 leading to isoprene nitrate formation was found to be significant (~8% of primary organic nitrate production) during the daytime, and monoterpene reactions with NO3 were simulated to comprise up to ~83% of primary organic nitrate production at night. Lastly, forest succession, wherein aspen trees are being replaced by pine and maple trees, was predicted to lead to increased afternoon concentrations of monoterpene-derived organic nitrates. This further underscores the need to understand the formation and fate of these species, which have different chemical pathways and oxidation products compared to isoprene-derived organic nitrates and can lead to secondary organic aerosol formation.

  17. Effects of a combined Diesel particle filter-DeNOx system (DPN) on reactive nitrogen compounds emissions: a parameter study.

    PubMed

    Heeb, Norbert V; Haag, Regula; Seiler, Cornelia; Schmid, Peter; Zennegg, Markus; Wichser, Adrian; Ulrich, Andrea; Honegger, Peter; Zeyer, Kerstin; Emmenegger, Lukas; Zimmerli, Yan; Czerwinski, Jan; Kasper, Markus; Mayer, Andreas

    2012-12-18

    The impact of a combined diesel particle filter-deNO(x) system (DPN) on emissions of reactive nitrogen compounds (RNCs) was studied varying the urea feed factor (α), temperature, and residence time, which are key parameters of the deNO(x) process. The DPN consisted of a platinum-coated cordierite filter and a vanadia-based deNO(x) catalyst supporting selective catalytic reduction (SCR) chemistry. Ammonia (NH₃) is produced in situ from thermolysis of urea and hydrolysis of isocyanic acid (HNCO). HNCO and NH₃ are both toxic and highly reactive intermediates. The deNO(x) system was only part-time active in the ISO8178/4 C1cycle. Urea injection was stopped and restarted twice. Mean NO and NO₂ conversion efficiencies were 80%, 95%, 97% and 43%, 87%, 99%, respectively, for α = 0.8, 1.0, and 1.2. HNCO emissions increased from 0.028 g/h engine-out to 0.18, 0.25, and 0.26 g/h at α = 0.8, 1.0, and 1.2, whereas NH₃ emissions increased from <0.045 to 0.12, 1.82, and 12.8 g/h with maxima at highest temperatures and shortest residence times. Most HNCO is released at intermediate residence times (0.2-0.3 s) and temperatures (300-400 °C). Total RNC efficiencies are highest at α = 1.0, when comparable amounts of reduced and oxidized compounds are released. The DPN represents the most advanced system studied so far under the VERT protocol achieving high conversion efficiencies for particles, NO, NO₂, CO, and hydrocarbons. However, we observed a trade-off between deNO(x) efficiency and secondary emissions. Therefore, it is important to adopt such DPN technology to specific application conditions to take advantage of reduced NO(x) and particle emissions while avoiding NH₃ and HNCO slip. PMID:23214996

  18. Safe Finger Tourniquet--Ideas.

    PubMed

    Wei, Lin-Gwei; Chen, Chieh-Feng; Hwang, Chun-Yuan; Chang, Chiung-Wen; Chiu, Wen-Kuan; Li, Chun-Chang; Wang, Hsian-Jenn

    2016-03-01

    Tourniquets are often needed for optimized phalangeal surgeries. However, few surgeons forget to remove them and caused ischemic injuries. We have a modified method to create a safe finger tourniquet for short duration finger surgeries, which can avoid such tragedy. It is done by donning a glove, cutting the tip of the glove over the finger of interest, and rolling the glove finger to the base. From 2010 to 2013, approximately 54 patients underwent digital surgical procedures with our safe finger tourniquet. Because the glove cannot be forgotten to be removed, the tourniquet must be released and removed. This is a simple and efficient way to apply a safe finger tourniquet by using hand rubber glove for a short-term bloodless finger surgery and can achieve an excellent surgical result. PMID:26855166

  19. Newly synthesized bis-benzimidazole compound 8 induces apoptosis, autophagy and reactive oxygen species generation in HeLa cells.

    PubMed

    Chu, Naying; Yao, Guodong; Liu, Yuan; Cheng, Maosheng; Ikejima, Takashi

    2016-09-01

    Compound 8 (C8) is a newly synthesized bis-benzimidazole derivative and exerts significant anti-tumor activity in vitro. Previous studies demonstrated that C8 induced apoptosis and autophagy in human promyelocytic leukemia HL60 cells. However, cytotoxicity study on human peripheral blood mononuclear cells (hPBMC) showed that C8 exhibited less toxicity in normal cells. In this study, the molecular mechanism of C8 on human cervical carcinoma HeLa cells was investigated. The results showed that C8 inhibited the growth of HeLa cells and triggered both apoptotic and autophagic cell death. Subsequent experiment also indicated that reactive oxygen species (ROS) generation was induced in C8-treated HeLa cells. Since ROS scavenger decreased the ratio of apoptotic and autophagic cells, ROS generation contributed to C8-induced apoptosis and autophagy. Furthermore, inhibitors of apoptosis and autophagy also reduced ROS generation, respectively. Autophagy inhibition increased cell growth compared to C8-treated group and attenuated apoptotic cell death, indicating that C8-induced autophagy promoted apoptosis for cell death. However, the percentage of autophagic cells was enhanced when limiting apoptosis process. Taken together, C8 induced ROS-mediated apoptosis and autophagy in HeLa cells, autophagy promoted apoptosis but the former was antagonized by the latter. The data also gave us a new perspective on the anti-tumor effect of C8. PMID:27497983

  20. New Class of Hydrido Iron(II) Compounds with cis-Reactive Sites: Combination of Iron and Diphosphinodithio Ligand.

    PubMed

    Liu, Jianguo; Zhang, Fanjun; Zhang, Ailing; Tong, Qingxiao; Tung, Chen-Ho; Wang, Wenguang

    2016-08-19

    The cationic complex [Fe(P2 S2 )(NCMe)2 ](2+) (P2 S2 =(Ph2 PC6 H4 CH2 S)2 (C2 H4 ) ([1(NCMe)2 ](2+) )), with two MeCN ligands in a cis orientation, was synthesized and characterized. The MeCN ligand in [1(NCMe)2 ](2+) undergoes further substitution by a hydride ligand or CO to give iron(II) hydrides [H1(NCMe)](+) , [H1H](0) , and [H1(CO)](+) . The order of reactivity of the hydrides was [H1H](0) >[H1(NCMe)](+) >[H1(CO)](+) , and was illustrated by their reactions toward protic acids, the organic cation of 10-methylacridinium (MeAcr(+) ) as a hydride acceptor, and intermolecular hydride transfer reactions among these ferrous compounds. For example, MeAcr(+) was reduced initially by a one-electron transfer process from [H1H](0) , resulting in competing reactions of MeAcr(.) dimerization, hydrogen atom transfer from [H1H](+) to MeAcr(.) , and decomposition of [H1H](+) . MeAcrH was produced in excellent yields through a single-step H(-) transfer from [H1(NCMe)](+) to MeAcr(+) , but [H1(CO)](+) was inactive toward MeAcr(+) . PMID:27362661

  1. An automated analyzer to measure surface-atmosphere exchange fluxes of water soluble inorganic aerosol compounds and reactive trace gases.

    PubMed

    Thomas, Rick M; Trebs, Ivonne; Otjes, René; Jongejan, Piet A C; Ten Brink, Harry; Phillips, Gavin; Kortner, Michael; Meixner, Franz X; Nemitz, Eiko

    2009-03-01

    Here, we present a new automated instrument for semicontinuous gradient measurements of water-soluble reactive trace gas species (NH3, HNO3, HONO, HCl, and SO2) and their related aerosol compounds (NH4+, NO3-, Cl-, SO4(2-)). Gas and aerosol samples are collected simultaneously at two heights using rotating wet-annular denuders and steam-jet aerosol collectors, respectively. Online (real-time) analysis using ion chromatography (IC) for anions and flow injection analysis (FIA) for NH4+ and NH3 provide a half-hourly averaged gas and aerosol gradients within each hour. Through the use of syringe pumps, IC preconcentration columns, and high-quality purified water, the system achieves detection limits (3sigma-definition) under field conditions of typically: 136/207,135/114, 29/ 22,119/92, and 189/159 ng m(-3) for NH3/NH4+, HNO3/NO3-, HONO/ NO2-, HCl/Cl- and SO2/SO4(2-), respectively. The instrument demonstrates very good linearity and accuracy for liquid and selected gas phase calibrations over typical ambient concentration ranges. As shown by examples from field experiments, the instrument provides sufficient precision (3-9%), even at low ambient concentrations, to resolve vertical gradients and calculate surface-atmosphere exchange fluxes undertypical meteorological conditions of the atmospheric surface layer using the aerodynamic gradient technique. PMID:19350912

  2. Viscous fingering with chemical reaction: effect of in-situ production of surfactants

    NASA Astrophysics Data System (ADS)

    Fernandez, Juan; Homsy, G. M.

    2003-04-01

    Viscous fingering experiments are performed in a radial Hele-Shaw cell for a liquid liquid system in the presence of a well-characterized interfacial reaction capable of changing the surface tension on the time scale of the experiments. The reaction is a neutralization of a fatty acid by an alkaline material to form a surfactant, which exhibits first-order kinetics for the surface tension as a function of time. The experiments are carried out for capillary numbers, Ca, high enough for the fingering to always be in the fractal regime, and for a wide range of Damköhler numbers, Da. The fingers are typically wider in the presence of the chemical reaction than the non-reactive case. We observe two different-behaviours of the reactive fingering patterns. For intermediate values of Da, 0.5 < Da < 4, the fractal dimension d_{f} is higher than the classical value measured for the non-reactive fingering patterns and reaches a maximum of about 1.9. For both small (Da < 0.5) and high Da (Da > 4), the reactive fingering patterns are similar to the fingers with no reaction: the fractal dimension is found to be the same for both systems. These effects are consistent with the hypothesis that Marangoni stresses are present and produce wider fingers.

  3. Reactive nitrogen compounds (RNCs) in exhaust of advanced PM-NO x abatement technologies for future diesel applications

    NASA Astrophysics Data System (ADS)

    Heeb, Norbert V.; Zimmerli, Yan; Czerwinski, Jan; Schmid, Peter; Zennegg, Markus; Haag, Regula; Seiler, Cornelia; Wichser, Adrian; Ulrich, Andrea; Honegger, Peter; Zeyer, Kerstin; Emmenegger, Lukas; Mosimann, Thomas; Kasper, Markus; Mayer, Andreas

    2011-06-01

    Long-term exposure to increased levels of reactive nitrogen compounds (RNCs) and particulate matter (PM) affect human health. Many cities are currently not able to fulfill European air quality standards for these critical pollutants. Meanwhile, promising new abatement technologies such as diesel particle filters (DPFs) and selective catalytic reduction (SCR) catalysts are developed to reduce PM and RNC emissions. Herein, effects of a urea-based SCR system on RNC emissions are discussed and we quantified the highly reactive intermediates isocyanic acid (HNCO) and ammonia (NH 3), both potential secondary pollutants of the urea-based SCR chemistry. A diesel engine (3.0 L, 100 kW), operated in the ISO 8178/4 C1, cycle was used as test platform. A V 2O 5-based SCR catalyst was either applied as such or down-stream of a high oxidation potential-DPF (hox-DPF). With active SCR, nitric oxide (NO) and nitrogen dioxide (NO 2) conversion efficiencies of 0.86-0.94 and 0.86-0.99 were obtained. On the other hand, mean HNCO and NH 3 emissions increased to 240-280 and 1800-1900 mg h -1. On a molar basis, HNCO accounted for 0.8-1.4% and NH 3 for 14-25% of the emitted RNCs. On roads, SCR systems will partly be inactive when exhaust temperatures drop below 220 °C. The system was active only during 75% of the test cycle, and urea dosing was stopped and restarted several times. Consequently, NO conversion stopped but interestingly, NO 2 was still converted. Such light-off and shutdown events are frequent in urban driving, compromising the overall deNO x efficiency. Another important effect of the SCR technology is illustrated by the NH 3/NO 2 ratio, which was >1 with active SCR, indicating that exhaust is basic rather than acidic after the SCR catalyst. Under these conditions, isocyanic acid is stable. The widespread use of various converter technologies already affected RNC release. Diesel oxidation catalysts (DOCs) and hox-DPFs increased NO 2 emissions, three-way catalysts (TWCs

  4. Reactivity of selenium-containing compounds with myeloperoxidase-derived chlorinating oxidants: Second-order rate constants and implications for biological damage.

    PubMed

    Carroll, Luke; Pattison, David I; Fu, Shanlin; Schiesser, Carl H; Davies, Michael J; Hawkins, Clare L

    2015-07-01

    Hypochlorous acid (HOCl) and N-chloramines are produced by myeloperoxidase (MPO) as part of the immune response to destroy invading pathogens. However, MPO also plays a detrimental role in inflammatory pathologies, including atherosclerosis, as inappropriate production of oxidants, including HOCl and N-chloramines, causes damage to host tissue. Low molecular mass thiol compounds, including glutathione (GSH) and methionine (Met), have demonstrated efficacy in scavenging MPO-derived oxidants, which prevents oxidative damage in vitro and ex vivo. Selenium species typically have greater reactivity toward oxidants compared to the analogous sulfur compounds, and are known to be efficient scavengers of HOCl and other hypohalous acids produced by MPO. In this study, we examined the efficacy of a number of sulfur and selenium compounds to scavenge a range of biologically relevant N-chloramines and oxidants produced by both isolated MPO and activated neutrophils and characterized the resulting selenium-derived oxidation products in each case. A dose-dependent decrease in the concentration of each N-chloramine was observed on addition of the sulfur compounds (cysteine, methionine) and selenium compounds (selenomethionine, methylselenocysteine, 1,4-anhydro-4-seleno-L-talitol, 1,5-anhydro-5-selenogulitol) studied. In general, selenomethionine was the most reactive with N-chloramines (k2 0.8-3.4×10(3)M(-1) s(-1)) with 1,5-anhydro-5-selenogulitol and 1,4-anhydro-4-seleno-L-talitol (k2 1.1-6.8×10(2)M(-1) s(-1)) showing lower reactivity. This resulted in the formation of the respective selenoxides as the primary oxidation products. The selenium compounds demonstrated greater ability to remove protein N-chloramines compared to the analogous sulfur compounds. These reactions may have implications for preventing cellular damage in vivo, particularly under chronic inflammatory conditions. PMID:25841785

  5. Cross-reactivity of antibodies with phenolic compounds in pistachios during quantification of ochratoxin A by commercial enzyme-linked immunosorbent assay kits.

    PubMed

    Lee, Hyun Jung; Meldrum, Alexander D; Rivera, Nicholas; Ryu, Dojin

    2014-10-01

    Ochratoxin A (OTA), a nephrotoxic mycotoxin, naturally occurs in wide range of agricultural commodities. Typical screening of OTA involves various enzyme-linked immunosorbent assay (ELISA) methods. Pistachio (Pistacia vera L.) is a rich source of phenolic compounds that may result in a false positive due to structural similarities to OTA. The present study investigated the cross-reactivity profiles of phenolic compounds using two commercial ELISA test kits. High-performance liquid chromatography was used to confirm the concentration of OTA in the pistachio samples and compared with the results obtained from ELISA. When the degree of interaction and 50 % inhibitory concentration of phenolic compounds were determined, the cross-reactivity showed a pattern similar to that observed with the commercial ELSIA kits, although quantitatively different. In addition, the degree of interaction increased with the increasing concentration of phenolic compounds. The ELISA value had stronger correlations with the content of total phenolic compound, gallic acid, and catechin (R(2) = 0.757, 0.732, and 0.729, respectively) compared with epicatechin (R(2) = 0.590). These results suggest that phenolic compounds in pistachio skins may cross-react with the OTA antibody and lead to a false positive or to an overestimation of OTA concentration in ELISA-based tests. PMID:25285493

  6. Finger Forces in Clarinet Playing

    PubMed Central

    Hofmann, Alex; Goebl, Werner

    2016-01-01

    Clarinettists close and open multiple tone holes to alter the pitch of the tones. Their fingering technique must be fast, precise, and coordinated with the tongue articulation. In this empirical study, finger force profiles and tongue techniques of clarinet students (N = 17) and professional clarinettists (N = 6) were investigated under controlled performance conditions. First, in an expressive-performance task, eight selected excerpts from the first Weber Concerto were performed. These excerpts were chosen to fit in a 2 × 2 × 2 design (register: low–high; tempo: slow–fast, dynamics: soft–loud). There was an additional condition controlled by the experimenter, which determined the expression levels (low–high) of the performers. Second, a technical-exercise task, an isochronous 23-tone melody was designed that required different effectors to produce the sequence (finger-only, tongue-only, combined tongue-finger actions). The melody was performed in three tempo conditions (slow, medium, fast) in a synchronization-continuation paradigm. Participants played on a sensor-equipped Viennese clarinet, which tracked finger forces and reed oscillations simultaneously. From the data, average finger force (Fmean) and peak force (Fmax) were calculated. The overall finger forces were low (Fmean = 1.17 N, Fmax = 3.05 N) compared to those on other musical instruments (e.g., guitar). Participants applied the largest finger forces during the high expression level performance conditions (Fmean = 1.21 N). For the technical exercise task, timing and articulation information were extracted from the reed signal. Here, the timing precision of the fingers deteriorated the timing precision of the tongue for combined tongue-finger actions, especially for faster tempi. Although individual finger force profiles were overlapping, the group of professional players applied less finger force overall (Fmean = 0.54 N). Such sensor instruments provide useful insights into player

  7. Robotic Finger Assembly

    NASA Technical Reports Server (NTRS)

    Ihrke, Chris A. (Inventor); Bridgwater, Lyndon (Inventor); Diftler, Myron A. (Inventor); Linn, Douglas M. (Inventor); Platt, Robert (Inventor); Hargrave, Brian (Inventor); Askew, Scott R. (Inventor); Valvo, Michael C. (Inventor)

    2013-01-01

    A robotic hand includes a finger with first, second, and third phalanges. A first joint rotatably connects the first phalange to a base structure. A second joint rotatably connects the first phalange to the second phalange. A third joint rotatably connects the third phalange to the second phalange. The second joint and the third joint are kinematically linked such that the position of the third phalange with respect to the second phalange is determined by the position of the second phalange with respect to the first phalange.

  8. Robotic Finger Assembly

    NASA Technical Reports Server (NTRS)

    Ihrke, Chris A. (Inventor); Bridgwater, Lyndon (Inventor); Diftler, Myron A. (Inventor); Linn, Douglas Martin (Inventor); Platt, Robert J., Jr. (Inventor); Hargrave, Brian (Inventor); Askew, Scott R. (Inventor); Valvo, Michael C. (Inventor)

    2014-01-01

    A robotic hand includes a finger with first, second, and third phalanges. A first joint rotatably connects the first phalange to a base structure. A second joint rotatably connects the first phalange to the second phalange. A third joint rotatably connects the third phalange to the second phalange. The second joint and the third joint are kinematically linked such that the position of the third phalange with respect to the second phalange is determined by the position of the second phalange with respect to the first phalange.

  9. Gert Finger Becomes Emeritus Physicist

    NASA Astrophysics Data System (ADS)

    de Zeeuw, T.; Lucuix, C.; Péron, M.

    2016-03-01

    Gert Finger has retired after almost 33 years service and he has been made the first Emeritus Physicist at ESO. An appreciation of some of his many achievements in the development of infrared instrumentation and detector controllers is given. A retirement party for Gert Finger was held in February 2016.

  10. Prototype Systems Containing Human Cytochrome P450 for High-Throughput Real-Time Detection of DNA Damage by Compounds That Form DNA-Reactive Metabolites.

    PubMed

    Brito Palma, Bernardo; Fisher, Charles W; Rueff, José; Kranendonk, Michel

    2016-05-16

    The formation of reactive metabolites through biotransformation is the suspected cause of many adverse drug reactions. Testing for the propensity of a drug to form reactive metabolites has increasingly become an integral part of lead-optimization strategy in drug discovery. DNA reactivity is one undesirable facet of a drug or its metabolites and can lead to increased risk of cancer and reproductive toxicity. Many drugs are metabolized by cytochromes P450 in the liver and other tissues, and these reactions can generate hard electrophiles. These hard electrophilic reactive metabolites may react with DNA and may be detected in standard in vitro genotoxicity assays; however, the majority of these assays fall short due to the use of animal-derived organ extracts that inadequately represent human metabolism. The current study describes the development of bacterial systems that efficiently detect DNA-damaging electrophilic reactive metabolites generated by human P450 biotransformation. These assays use a GFP reporter system that detects DNA damage through induction of the SOS response and a GFP reporter to control for cytotoxicity. Two human CYP1A2-competent prototypes presented here have appropriate characteristics for the detection of DNA-damaging reactive metabolites in a high-throughput manner. The advantages of this approach include a short assay time (120-180 min) with real-time measurement, sensitivity to small amounts of compound, and adaptability to a microplate format. These systems are suitable for high-throughput assays and can serve as prototypes for the development of future enhanced versions. PMID:27031942

  11. Comparing the potency of chemicals with multiple modes of action in aquatic toxicology: Acute toxicity due to narcosis versus reactive toxicity of acrylic compounds

    SciTech Connect

    Freidig, A.P.; Verhaar, H.J.M.; Hermens, J.L.M.

    1999-09-01

    A series of acrylates and methacrylates was used to illustrate a strategy to compare the importance of two modes of action (MOA) and thereby identify the predominant cause of acute fish toxicity. Acrylic compounds are known to be Michael acceptors and may therefore react with glutathione (GSH), causing GSH-depletion in vivo (reactive mechanism). On the other hand, acrylates may also act by a nonspecific mechanism (narcosis). The following two, physiologically meaningful parameters were calculated in order to estimate the contribution of these two mechanisms to the overall acute toxicity: (i) a lipid normalized body burden for narcosis and (ii) the potential degree of GSH depletion by chemical reactivity. The degree of GSH depletion was found to be related to the product of the reactivity toward GSH and the exposure concentration. This model was validated with four model compounds and an in vivo study. For both MOA, toxic ratios were calculated and compared for all chemicals in the series. The approach enables the comparison of the contribution to toxicity of chemicals with more than on MOA.

  12. Ozone reactivity of biogenic volatile organic compounds emitted from the four dominant tree species at PROPHET - CABINEX

    NASA Astrophysics Data System (ADS)

    Helmig, D.; Daly, R.; Bertman, S. B.

    2010-12-01

    A number of recent studies on biogenic volatile organic emissions (BVOC) released in the forest atmosphere have pointed out that identified emissions can not account for the entire chemical reactivity seen in the forest atmosphere. During the 2009 and 2010 Community Atmosphere-Biosphere Interactions Experiment (CABINEX) at the University of Michigan Biological Station (UMBS) PROPHET site BVOC emissions and their reactivity with ozone were studied with a newly developed ozone reactivity instrument. Experiments were conducted on the tree species red oak, white pine, quaking aspen, and red maple, representing ~ 87% of the canopy leaf area index at this site. BVOC emissions were sampled from a branch bag enclosure, mixed with ozone-enriched air, and directed through a series of reaction vessels. A differential ozone monitor was used to determine the reaction rate with ozone while emissions were being purged through the reaction vessel. BVOC in the outflow of the bag enclosure were also determined with a field gas chromatography-mass spectrometry instrument, and by collection on adsorbent cartridges with subsequent analysis in our Boulder laboratory. Experiments were performed over several days to capture emission changes under varying ambient temperature and light conditions. The ozone reactivity showed distinct diurnal cycles and a tight correlation with leaf temperature, typically maximizing during mid day to afternoon. Furthermore, the four tree species investigated displayed a distinctly different behavior, with emissions from the one coniferous tree species (white pine) exhibiting the overall highest ozone reactivity signal.

  13. Finger-Circumference-Measuring Device

    NASA Technical Reports Server (NTRS)

    Le, Suy

    1995-01-01

    Easy-to-use device quickly measures circumference of finger (including thumb) on human hand. Includes polytetrafluoroethylene band 1/8 in. wide, bent into loop and attached to tab that slides on scale graduated in millimeters. Sliding tab preloaded with constant-force tension spring, which pulls tab toward closure of loop. Designed to facilitate measurements at various points along fingers to obtain data for studies of volumetric changes of fingers in microgravity. Also used in normal Earth gravity studies of growth and in assessment of diseases like arthritis.

  14. Fingering Instabilities in Dewetting Nanofluids

    NASA Astrophysics Data System (ADS)

    Pauliac-Vaujour, E.; Stannard, A.; Martin, C. P.; Blunt, M. O.; Notingher, I.; Moriarty, P. J.; Vancea, I.; Thiele, U.

    2008-05-01

    The growth of fingering patterns in dewetting nanofluids (colloidal solutions of thiol-passivated gold nanoparticles) has been followed in real time using contrast-enhanced video microscopy. The fingering instability on which we focus here arises from evaporatively driven nucleation and growth in a nanoscopically thin precursor solvent film behind the macroscopic contact line. We find that well-developed isotropic fingering structures only form for a narrow range of experimental parameters. Numerical simulations, based on a modification of the Monte Carlo approach introduced by Rabani et al. [Nature (London)NATUAS0028-0836 426, 271 (2003)10.1038/nature02087], reproduce the patterns we observe experimentally.

  15. Fingering instabilities in dewetting nanofluids.

    PubMed

    Pauliac-Vaujour, E; Stannard, A; Martin, C P; Blunt, M O; Notingher, I; Moriarty, P J; Vancea, I; Thiele, U

    2008-05-01

    The growth of fingering patterns in dewetting nanofluids (colloidal solutions of thiol-passivated gold nanoparticles) has been followed in real time using contrast-enhanced video microscopy. The fingering instability on which we focus here arises from evaporatively driven nucleation and growth in a nanoscopically thin precursor solvent film behind the macroscopic contact line. We find that well-developed isotropic fingering structures only form for a narrow range of experimental parameters. Numerical simulations, based on a modification of the Monte Carlo approach introduced by Rabani et al. [Nature (London) 426, 271 (2003)10.1038/nature02087], reproduce the patterns we observe experimentally. PMID:18518311

  16. Finger Forces in Clarinet Playing.

    PubMed

    Hofmann, Alex; Goebl, Werner

    2016-01-01

    Clarinettists close and open multiple tone holes to alter the pitch of the tones. Their fingering technique must be fast, precise, and coordinated with the tongue articulation. In this empirical study, finger force profiles and tongue techniques of clarinet students (N = 17) and professional clarinettists (N = 6) were investigated under controlled performance conditions. First, in an expressive-performance task, eight selected excerpts from the first Weber Concerto were performed. These excerpts were chosen to fit in a 2 × 2 × 2 design (register: low-high; tempo: slow-fast, dynamics: soft-loud). There was an additional condition controlled by the experimenter, which determined the expression levels (low-high) of the performers. Second, a technical-exercise task, an isochronous 23-tone melody was designed that required different effectors to produce the sequence (finger-only, tongue-only, combined tongue-finger actions). The melody was performed in three tempo conditions (slow, medium, fast) in a synchronization-continuation paradigm. Participants played on a sensor-equipped Viennese clarinet, which tracked finger forces and reed oscillations simultaneously. From the data, average finger force (F mean ) and peak force (F max ) were calculated. The overall finger forces were low (F mean = 1.17 N, F max = 3.05 N) compared to those on other musical instruments (e.g., guitar). Participants applied the largest finger forces during the high expression level performance conditions (F mean = 1.21 N). For the technical exercise task, timing and articulation information were extracted from the reed signal. Here, the timing precision of the fingers deteriorated the timing precision of the tongue for combined tongue-finger actions, especially for faster tempi. Although individual finger force profiles were overlapping, the group of professional players applied less finger force overall (F mean = 0.54 N). Such sensor instruments provide useful insights into player

  17. Effects of crystal orientation and ferroelastic domain structure on the photochemical reactivity of BiVO4 and related compounds

    NASA Astrophysics Data System (ADS)

    Munprom, Ratiporn

    Bismuth vanadate, BiVO4, has been recognized for its high efficiency as a photoanode for water splitting. However, its performance is limited by photogenerated electron--hole recombination. Thus, researchers have attempted to modify BiVO4 to improve its performance. One strategy to improve charge separation is to utilize an internal field arising from surface termination differences. Previous studies concentrated on polygonal single crystals of BiVO4, providing limited information about the orientation-reactivity relationship. The current research focuses on polycrystalline BiVO4, which makes it possible to study the photochemical reactivity of all possible orientations and determine the complete orientation dependence of the photochemical reactivity of BiVO4. (Abstract shortened by UMI.).

  18. Rapid Diminution in the Level and Activity of DNA-Dependent Protein Kinase in Cancer Cells by a Reactive Nitro-Benzoxadiazole Compound

    PubMed Central

    Silva, Viviane A. O.; Lafont, Florian; Benhelli-Mokrani, Houda; Breton, Magali Le; Hulin, Philippe; Chabot, Thomas; Paris, François; Sakanyan, Vehary; Fleury, Fabrice

    2016-01-01

    The expression and activity of DNA-dependent protein kinase (DNA-PK) is related to DNA repair status in the response of cells to exogenous and endogenous factors. Recent studies indicate that Epidermal Growth Factor Receptor (EGFR) is involved in modulating DNA-PK. It has been shown that a compound 4-nitro-7-[(1-oxidopyridin-2-yl)sulfanyl]-2,1,3-benzoxadiazole (NSC), bearing a nitro-benzoxadiazole (NBD) scaffold, enhances tyrosine phosphorylation of EGFR and triggers downstream signaling pathways. Here, we studied the behavior of DNA-PK and other DNA repair proteins in prostate cancer cells exposed to compound NSC. We showed that both the expression and activity of DNA-PKcs (catalytic subunit of DNA-PK) rapidly decreased upon exposure of cells to the compound. The decline in DNA-PKcs was associated with enhanced protein ubiquitination, indicating the activation of cellular proteasome. However, pretreatment of cells with thioglycerol abolished the action of compound NSC and restored the level of DNA-PKcs. Moreover, the decreased level of DNA-PKcs was associated with the production of intracellular hydrogen peroxide by stable dimeric forms of Cu/Zn SOD1 induced by NSC. Our findings indicate that reactive oxygen species and electrophilic intermediates, generated and accumulated during the redox transformation of NBD compounds, are primarily responsible for the rapid modulation of DNA-PKcs functions in cancer cells. PMID:27187356

  19. Neural correlates of finger gnosis.

    PubMed

    Rusconi, Elena; Tamè, Luigi; Furlan, Michele; Haggard, Patrick; Demarchi, Gianpaolo; Adriani, Michela; Ferrari, Paolo; Braun, Christoph; Schwarzbach, Jens

    2014-07-01

    Neuropsychological studies have described patients with a selective impairment of finger identification in association with posterior parietal lesions. However, evidence of the role of these areas in finger gnosis from studies of the healthy human brain is still scarce. Here we used functional magnetic resonance imaging to identify the brain network engaged in a novel finger gnosis task, the intermanual in-between task (IIBT), in healthy participants. Several brain regions exhibited a stronger blood oxygenation level-dependent (BOLD) response in IIBT than in a control task that did not explicitly rely on finger gnosis but used identical stimuli and motor responses as the IIBT. The IIBT involved stronger signal in the left inferior parietal lobule (IPL), bilateral precuneus (PCN), bilateral premotor cortex, and left inferior frontal gyrus. In all regions, stimulation of nonhomologous fingers of the two hands elicited higher BOLD signal than stimulation of homologous fingers. Only in the left anteromedial IPL (a-mIPL) and left PCN did signal strength decrease parametrically from nonhomology, through partial homology, to total homology with stimulation delivered synchronously to the two hands. With asynchronous stimulation, the signal was stronger in the left a-mIPL than in any other region, possibly indicating retention of task-relevant information. We suggest that the left PCN may contribute a supporting visuospatial representation via its functional connection to the right PCN. The a-mIPL may instead provide the core substrate of an explicit bilateral body structure representation for the fingers that when disrupted can produce the typical symptoms of finger agnosia. PMID:24990921

  20. Reactivity of target compounds for chemical coal desulfurization. Technical report, 1 December 1993--28 February 1994

    SciTech Connect

    Buchanan, D.H.; Amin, M.; Cunningham, R.; Galyen, J.

    1994-06-01

    This project seeks to identify representative organosulfur compounds which are removed by coal desulfurization reactions. Demineralized coals from the Illinois Basin Coal Sample Program are solvent extracted and the extracts fractionated to separate and concentrate organosulfur compounds for analysis by Gas Chromatography/Mass Spectroscopy. After sulfur compounds are characterized, the parent extracts will be subjected to reactions previously shown to reduce the organic sulfur content of Illinois coals, fractionated and again analyzed for organosulfur content to determine which compounds reacted during the chemical treatment. The original coal will be subjected to chemical desulfurization, extraction, fractionation and analysis in order to correlate changes in organic sulfur content of the coal with reactions of specific sulfur compounds. These compounds can thus be reliably considered as target molecules for the next generation of desulfurization processes. During this quarter, work continued on developing efficient methods to isolate and analyze sulfur-rich coal extract fractions by GC/MS. Since only relatively non-polar compounds can be analyzed, pyridine extracts must be fractionated. Direct extraction of several coals with toluene is quicker but did not give as much toluene soluble material as fractionation of pyridine extracts and is thus not suitable for preparation of representative analytical samples. The authors observe that most IBC sample program coals contain elemental sulfur due to oxidation of pyrite. There is less elemental sulfur in IBC-101 than in other Herrin coals. This coal was washed in a preparation plant to reduce pyrite concentration. Since elemental sulfur slowly reacts to produce organosulfur compounds in coal during storage or handling, this suggests that early removal of pyrite can reduce formation of these hard to remove compounds.

  1. LGIT In Vitro Latency Model in Primary and T Cell Lines to Test HIV-1 Reactivation Compounds.

    PubMed

    Jung, Ulrike; Takahashi, Mayumi; Rossi, John J; Burnett, John C

    2016-01-01

    Persistent latent HIV-1 reservoirs pose a major barrier for combinatorial antiretroviral therapy (cART) to achieve eradication of the virus. A variety of mechanisms likely contribute to HIV-1 persistence, including establishment of post-integration latency in resting CD4+ T-lymphocytes, the proliferation of these latently infected cells, and the induced or spontaneous reactivation of latent virus. To elucidate the mechanisms of latency and to investigate therapeutic strategies for reactivating and purging the latent reservoir, investigators have developed in vitro models of HIV-1 latency using primary CD4+ T-lymphocytes and CD4+ T-cell lines. Several types of in vitro latency models range from replication-competent to single-round, replication-deficient viruses exhibiting different degrees of viral genomic deletion. Working under the hypothesis that HIV-1 post-integration latency is directly linked to HIV-1 promoter activity, which can be obscured by additional proteins expressed during replication, we focus here on the creation of latently infected primary human T-cells and cell lines through the single-round, replication deficient HIV-1 LGIT model. In this model the long terminal repeat (LTR) of the HIV-1 virus drives a cassette of GFP-IRES-Tat that allows testing of reactivating components and initiates a positive feedback loop through Tat expression. PMID:26714717

  2. Multi-finger interaction during involuntary and voluntary single finger force changes

    PubMed Central

    Martin, J.R.; Zatsiorsky, V.M.; Latash, M.L.

    2011-01-01

    Two types of finger interaction are characterized by positive co-variation (enslaving) or negative co-variation (error compensation) of finger forces. Enslaving reflects mechanical and neural connections among fingers, while error compensation results from synergic control of fingers to stabilize their net output. Involuntary and voluntary force changes by a finger were used to explore these patterns. We hypothesized that synergic mechanisms will dominate during involuntary force changes, while enslaving will dominate during voluntary finger force changes. Subjects pressed with all four fingers to match a target force that was 10% of their maximum voluntary contraction (MVC). One of the fingers was unexpectedly raised 5.0 mm at a speed of 30.0 mm/s. During finger raising the subject was instructed “not to intervene voluntarily”. After the finger was passively lifted and a new steady-state achieved, subjects pressed down with the lifted finger, producing a pulse of force voluntarily. The data were analyzed in terms of finger forces and finger modes (hypothetical commands to fingers reflecting their intended involvement). The target finger showed an increase in force during both phases. In the involuntary phase, the target finger force changes ranged between 10.71 ± 1.89% MVC (I-finger) and 16.60 ± 2.26% MVC (L-finger). Generally, non-target fingers displayed a force decrease with a maximum amplitude of −1.49 ± 0.43% MVC (L-finger). Thus, during the involuntary phase, error compensation was observed – non-lifted fingers showed a decrease in force (as well as in mode magnitude). During the voluntary phase, enslaving was observed – non-target fingers showed an increase in force and only minor changes in mode magnitude. The average change in force of non-target fingers ranged from 21.83 ± 4.47% MVC for R-finger (M-finger task) to 0.71 ± 1.10 % MVC for L-finger (I-finger task). The average change in mode of non-target fingers was between −7.34 ± 19

  3. Clay for Little Fingers.

    ERIC Educational Resources Information Center

    Koster, Joan Bouza

    1999-01-01

    Discusses the renewed interest in clay as a modeling compound in early childhood programs; describes the nature of clay and presents a working vocabulary. Suggests methods of working with clay, including introducing clay to children, discovering its uses, clean up, firing clay, and finishing baked clay. Includes activity suggestions and…

  4. Stability, Reactivity, and Constituent Interaction in TiSe2-Based Metastable Misfit Layer Compounds Synthesized from Designed Amorphous Precursors

    NASA Astrophysics Data System (ADS)

    Merrill, Devin R.

    A series of intergrowth compounds with the basic formula [(MSe) 1+delta]m(TiSe2)n are reported. The compounds are prepared from modulated elemental reactants and display interesting structural and electronic behavior. Section 1 of this dissertation outlines initial attempts to characterize constituent interaction. The first member of the SnSe based subclass is reported and displays the highest Seebeck coefficient of any m = n = 1 compound reported to date, and a surprising amount of order is observed, compared to previously reported compounds. With properly established deposition parameters, the synthesis was extended to included the m = 2-4 compounds. These compounds display interesting electronic behavior that suggests the band structure shifts considerably as the SnSe block is expanded, affecting the interaction between the constituent layers. The first compound based on BiSe is then reported, suggesting that the Bi structure donates more conduction electrons to the band structure. Targeted substitution through kinetic control is the focus of Section 2, and a family of (PbxSn1-xSe)1+deltaTiSe 2 is reported over the entire range of x, even though a miscibility gap exists in the bulk PbxSn1-xSe system. The resulting alloyed intergrowth compounds also display equal or higher mobility than the end members, suggesting modulation doping could be used to affect transport properties. As a proof of principle, the analogous system based on a Bi xSn1-xSe constituent was prepared to attempt to systematically affect carrier concentration. It was found that while carrier concentration can be controlled, the evolving structure affects the doping efficiency of the Bi atoms and mobility in the structure. Section 3 outlines attempts to form higher order TiSe2-based heterostructures and the important chemical considerations observed during the preparation of these materials. The 3 component systems in the Pb-Sn-Ti-Se system can be formed at low temperature, with SnSe2 rather than

  5. Experimental Evaluation of Gas-Phase Transport and Reactivity of Two Organophosphate Compounds in Unsaturated Porous Media

    NASA Astrophysics Data System (ADS)

    Rockhold, M.; Johnson, T.; Szecsody, J.; McKinley, J.; Blake, T.; Wietsma, T.; Covert, M.; Oostrom, M.

    2008-12-01

    An experimental study was undertaken to evaluate the feasibility of using organophosphate compounds that can be transported in the gas phase as a source of phosphorus for mineral formation (e.g. apatite) and contaminant sequestration in deep unsaturated zones. Previous work by others with gaseous phosphate compounds utilized triethyl phosphate (TEP) for bioremediation. In the current study we used both TEP and another chemically similar compound, dimethyl methylphosphonate (DMMP) that has a higher saturation vapor pressure. Batch abiotic degradation experiments in aqueous solutions with and without sediment (in both oxic and reducing conditions) indicate that both TEP and DMMP are very recalcitrant. Slow conversion from organic-to inorganic-P forms occurred (<5% in 3 months) under high temperature (80° C) and highly alkaline pH conditions. TEP and DMMP biodegradation to PO4 was found to be minimal over a similar time period using concentrated solutions of in situ microbes with no other growth substrates present. Gas transport studies using FTIR spectroscopy show that these compounds also adsorb very strongly to unsaturated sediments from the Hanford Site, to the extent that no breakthrough was observed even after >1000 pore volumes of gas exchange and complete dessication of the sediments. Methanol production was observed during the gas transport experiments, indicating that the lack of observed breakthrough of the original organophosphate compounds was attributable to both adsorption and reaction processes. FTIR reflection spectroscopy and microprobe analyses were performed to identify and quantify adsorbed species and possible mineral formation.

  6. Evaluation of nutraceutical and antinutritional properties in barnyard and finger millet varieties grown in Himalayan region.

    PubMed

    Panwar, Priyankar; Dubey, Ashutosh; Verma, A K

    2016-06-01

    Five elite varieties of barnyard (Echinochloa frumentacea) and finger (Eleusine coracana) growing at northwestern Himalaya were investigated for nutraceutical and antinutritional properties. Barnyard millet contained higher amount of crude fiber, total dietary fiber, tryptophan content, total carotenoids, α-tocopherol compared to the finger millet whereas the finger millet contains higher amount of methionine and ascorbic acid as compared to the barnyard millet. The secondary metabolites of biological functions were analyzed and found that barnyard millet contained the higher amount of polyphenols, tannins and ortho-dihydroxy phenol content compared to finger millet. Among antinutitional compounds barnyard millet contained lower phytic acid content compare to finger millet whereas no significant difference in trypsin inhibition activity of barnyard millet and finger millet varieties were found. Barnyard millet contained higher acid phosphatase, α-galactosidase and α-amylase inhibitor activity compared to finger millet. Finger millet seeds contained about 10-13 folds higher calcium content and double amount of manganese content in comparison to barnyard millet seeds. Present study suggests that barnyard millet varieties studied under present investigation were found nutritionally superior compared to finger millet varieties. PMID:27478234

  7. 6-Methyl 3-chromonyl 2,4-thiazolidinedione/2,4-imidazolidinedione/2-thioxo-imidazolidine-4-one compounds: novel scavengers of reactive oxygen species.

    PubMed

    Berczyński, Paweł; Duchnik, Ewa; Kruk, Irena; Piechowska, Teresa; Aboul-Enein, Hassan Y; Bozdağ-Dündar, Oya; Ceylan-Unlusoy, Meltem

    2014-06-01

    The benefits of antioxidants on human health are usually ascribed to their potential ability to remove reactive oxygen species providing protection against oxidative stress. In this paper the free radicals scavenging activities of nine 6-methyl 3-chromonyl derivatives (CMs) were evaluated for the first time by the chemiluminescence, electron paramagnetic resonance, spin trapping and 2,2-diphenyl-1-picrylhydrazyl (DPPH(•)) methods. The total antioxidant capacity was also measured using a ferric-ferrozine reagent. Compounds having a hydrogen atom at the N3-position of the β-ring were effective in quenching CL resulted from the KO2 /18-crown-6-ether system (a source of superoxide anion radical, O2•¯) in a dose-dependent manner over the range of 0.05-1 mmol/L [IC50 ranged from 0.353 (0.04) to 0.668 (0.05) mmol/L]. The examined compounds exhibited a significant scavenging effect towards hydroxyl radicals (HO(•) HO(•)), produced by the Fenton reaction, and this ranged from 24.0% to 61.0%, at the concentration of 2.5 mmol/L. Furthermore, the compounds examined were also found to inhibit DPPH(•) and this ranged from 51.9% to 97.4% at the same concentration. In addition, the use of the total antioxidant capacity assay confirmed that CM compounds are able to act as reductants. According to the present study, CM compounds showed effective in vitro free radical scavenging activity and may be considered as potential therapeutics to control diseases of oxidative stress-related etiology. PMID:23843284

  8. Disruption of focal adhesion kinase and p53 interaction with small molecule compound R2 reactivated p53 and blocked tumor growth

    PubMed Central

    2013-01-01

    Background Focal Adhesion Kinase (FAK) is a 125 kDa non-receptor kinase that plays a major role in cancer cell survival and metastasis. Methods We performed computer modeling of the p53 peptide containing the site of interaction with FAK, predicted the peptide structure and docked it into the three-dimensional structure of the N-terminal domain of FAK involved in the complex with p53. We screened small molecule compounds that targeted the site of the FAK-p53 interaction and identified compounds (called Roslins, or R compounds) docked in silico to this site. Results By different assays in isogenic HCT116p53+/+ and HCT116 p53-/- cells we identified a small molecule compound called Roslin 2 (R2) that bound FAK, disrupted the binding of FAK and p53 and decreased cancer cell viability and clonogenicity in a p53-dependent manner. In addition, dual-luciferase assays demonstrated that the R2 compound increased p53 transcriptional activity that was inhibited by FAK using p21, Mdm-2, and Bax-promoter targets. R2 also caused increased expression of p53 targets: p21, Mdm-2 and Bax proteins. Furthermore, R2 significantly decreased tumor growth, disrupted the complex of FAK and p53, and up-regulated p21 in HCT116 p53+/+ but not in HCT116 p53-/- xenografts in vivo. In addition, R2 sensitized HCT116p53+/+ cells to doxorubicin and 5-fluorouracil. Conclusions Thus, disruption of the FAK and p53 interaction with a novel small molecule reactivated p53 in cancer cells in vitro and in vivo and can be effectively used for development of FAK-p53 targeted cancer therapy approaches. PMID:23841915

  9. Fluid mixing from viscous fingering.

    PubMed

    Jha, Birendra; Cueto-Felgueroso, Luis; Juanes, Ruben

    2011-05-13

    Mixing efficiency at low Reynolds numbers can be enhanced by exploiting hydrodynamic instabilities that induce heterogeneity and disorder in the flow. The unstable displacement of fluids with different viscosities, or viscous fingering, provides a powerful mechanism to increase fluid-fluid interfacial area and enhance mixing. Here we describe the dissipative structure of miscible viscous fingering, and propose a two-equation model for the scalar variance and its dissipation rate. Our analysis predicts the optimum range of viscosity contrasts that, for a given Péclet number, maximizes interfacial area and minimizes mixing time. In the spirit of turbulence modeling, the proposed two-equation model permits upscaling dissipation due to fingering at unresolved scales. PMID:21668165

  10. Mesofluidic controlled robotic or prosthetic finger

    SciTech Connect

    Lind, Randall F; Jansen, John F; Love, Lonnie J

    2013-11-19

    A mesofluidic powered robotic and/or prosthetic finger joint includes a first finger section having at least one mesofluidic actuator in fluid communication with a first actuator, a second mesofluidic actuator in fluid communication with a second actuator and a second prosthetic finger section pivotally connected to the first finger section by a joint pivot, wherein the first actuator pivotally cooperates with the second finger to provide a first mechanical advantage relative to the joint point and wherein the second actuator pivotally cooperates with the second finger section to provide a second mechanical advantage relative to the joint point.

  11. Finger flexion does not contribute to ball speed in overarm throws.

    PubMed

    Hore, J; Watts, S; Martin, J

    1996-08-01

    The aim of this study was to determine whether, in overarm throws made by recreational ball players, the fingers undergo flexion movement before ball release and thereby contribute to the generation of ball speed. To obtain the high resolution needed to answer this question, the magnetic-field search-coil technique was used and the data were sampled at 1000 Hz. The subjects, who were either seated or were standing, threw tennis balls at different speeds at a target 3 m away. Angular positions in three dimensions were simultaneously recorded of the distal phalanx of the middle finger and hand and, in additional experiments to determine the mechanism of ball release in more detail, three middle finger phalanges and the hand. Different phases of ball release were determined by pressure-sensitive microswitches on the proximal and distal phalanges of the middle finger. Irrespective of whether the subjects were seated or were standing, for all throws at all speeds, finger flexion did not occur before ball release. That is, up until final release of the ball, the fingers only underwent extension associated with hand opening. For fast throws, at the instant of final ball release the fingers began to flex, presumably as a result of reactive forces associated with release of the ball. Thus, in overarm throws made by recreational ball players, finger flexion movement does not appear to contribute to the generation of ball speed. PMID:8887213

  12. Anthropogenic emissions of highly reactive volatile organic compounds in eastern Texas inferred from oversampling of satellite (OMI) measurements of HCHO columns

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Jacob, Daniel J.; Mickley, Loretta J.; Marais, Eloïse A.; Cohan, Daniel S.; Yoshida, Yasuko; Duncan, Bryan N.; González Abad, Gonzalo; Chance, Kelly V.

    2014-11-01

    Satellite observations of formaldehyde (HCHO) columns provide top-down constraints on emissions of highly reactive volatile organic compounds (HRVOCs). This approach has been used previously in the US to estimate isoprene emissions from vegetation, but application to anthropogenic emissions has been stymied by lack of a discernable HCHO signal. Here we show that temporal oversampling of HCHO data from the Ozone Monitoring Instrument (OMI) for 2005-2008 enables detection of urban and industrial plumes in eastern Texas including Houston, Port Arthur, and Dallas/Fort Worth. By spatially integrating the HCHO enhancement in the Houston plume observed by OMI we estimate an anthropogenic HCHO source of 250 ± 140 kmol h-1. This implies that anthropogenic HRVOC emissions in Houston are 4.8 ± 2.7 times higher than reported by the US Environmental Protection Agency inventory, and is consistent with field studies identifying large ethene and propene emissions from petrochemical industrial sources.

  13. Thiobarbituric acid reactive substances and volatile compounds in chicken breast meat infused with plant extracts and subjected to electron beam irradiation.

    PubMed

    Rababah, T; Hettiarachchy, N S; Horax, R; Cho, M J; Davis, B; Dickson, J

    2006-06-01

    The effect of irradiation on thiobarbituric acid reactive substances (TBARS) and volatile compounds in raw and cooked nonirradiated and irradiated chicken breast meat infused with green tea and grape seed extracts was investigated. Chicken breast meat was vacuum infused with green tea extract (3,000 ppm), grape seed extract (3,000 ppm), or their combination (at a total of 6,000 ppm), irradiated with an electron beam, and stored at 5 degrees C for 12 d. The targeted irradiation dosage was 3.0 kGy and the average absorbed dosage was 3.12 kGy. Values of TBARS and volatile compound contents of raw and cooked chicken meat were determined during the 12-d storage period. Thiobarbituric acid reactive substances values ranged from 15.5 to 71.4 mg of malondialdehyde/kg for nonirradiated raw chicken and 17.3 to 80.1 mg of malondialdehyde/kg for irradiated raw chicken. Values for cooked chicken ranged from 31.4 to 386.2 and 38.4 to 504.1 mg of malondialdehyde/kg for nonirradiated and irradiated chicken, respectively. Irradiation increased TBARS and hexanal values of controls and meat infused with plant extracts. Hexanal had the highest intensity of volatiles followed by pentanal and other volatiles. Cooking the samples significantly (P < 0.05) increased the amounts of TBARS and volatiles. Addition of plant extracts decreased the amount of TBARS as well as hexanal and pentanal values. Although irradiation increases lipid oxidation, infusion of chicken meat with plant extracts could reduce lipid oxidation caused by irradiation. PMID:16776483

  14. Aerobic biodegradation of chlorinated ethenes in a fractured bedrock aquifer: quantitative assessment by compound-specific isotope analysis (CSIA) and reactive transport modeling.

    PubMed

    Pooley, Kathryn E; Blessing, Michaela; Schmidt, Torsten C; Haderlein, Stefan B; Macquarrie, Kerry T B; Prommer, Henning

    2009-10-01

    A model-based analysis of concentration and isotope data was carried out to assess natural attenuation of chlorinated ethenes in an aerobic fractured bedrock aquifer. Tetrachloroethene (PCE) concentrations decreased downgradient of the source, but constant delta13C signatures indicated the absence of PCE degradation. In contrast, geochemical and isotopic data demonstrated degradation of trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) under the prevailing oxic conditions. Numerical modeling was employed to simulate isotopic enrichment of chlorinated ethenes and to evaluate alternative degradation pathway scenarios. Existing field information on groundwater flow, solute transport, geochemistry, and delta13C signatures of the chlorinated ethenes was integrated via reactive transport simulations. The results provided strong evidence for the occurrence of aerobic TCE and DCE degradation. The chlorinated ethene concentrations together with stable carbon isotope data allowed us to reliably constrain the assessment of the extent of biodegradation at the site and plume simulations quantitatively linked aerobic biodegradation with isotope signatures in the field. Our investigation provides the first quantitative assessment of aerobic biodegradation of chlorinated ethenes in a fractured rock aquifer based on compound specific stable isotope measurements and reactive transport modeling. PMID:19848161

  15. Recent advances in high performance poly(lactide): From ``green'' plasticization to super-tough materials via (reactive) compounding

    NASA Astrophysics Data System (ADS)

    Kfoury, Georgio; Raquez, Jean-Marie; Hassouna, Fatima; Odent, Jérémy; Toniazzo, Valérie; Ruch, David; Dubois, Philippe

    2013-12-01

    Due to its origin from renewable resources, its biodegradability, and recently, its industrial implementation at low costs, poly(lactide) (PLA) is considered as one of the most promising ecological, bio-sourced and biodegradable plastic materials to potentially and increasingly replace traditional petroleum derived polymers in many commodity and engineering applications. Beside its relatively high rigidity (high tensile strength and modulus compared with many common thermoplastics such as poly(ethylene terephthalate) (PET), high impact poly(styrene) (HIPS) and poly(propylene) (PP)), PLA suffers from an inherent brittleness, which can limit its applications especially where mechanical toughness such as plastic deformation at high impact rates or elongation is required. Therefore, the curve plotting stiffness vs. impact resistance and ductility must be shifted to higher values for PLA-based materials, while being preferably fully bio-based and biodegradable upon the application. This review aims to establish a state of the art focused on the recent progresses and preferably economically viable strategies developed in the literature for significantly improve the mechanical performances of PLA. A particular attention is given to plasticization as well as to impact resistance modification of PLA in the case of (reactive) blending PLA-based systems.

  16. Long-finger pollicization for macrodactyly of the thumb and index finger.

    PubMed

    Donohue, Kenneth W; Zlotolow, Dan A; Kozin, Scott H

    2014-01-01

    Pollicization of the long finger is rarely performed, and previously described for treating traumatic thumb and index finger loss. Because the long finger lacks the independence of motion and muscular attachments of the index finger, pollicization of the long finger requires modifications of the technique. We present the case of a 3-year-old girl with progressive macrodactyly of the thumb and index finger associated with a lipofibromatous hamartoma of the median nerve. The involved digits were severely enlarged, stiff, and nonfunctional. The child was treated with first and second ray resection followed by long-finger pollicization. Surgical pearls and pitfalls are discussed. PMID:24919138

  17. Evidence of the impact of deep convection on reactive Volatile Organic Compounds in the upper tropical troposphere during the AMMA experiment in West Africa

    NASA Astrophysics Data System (ADS)

    Bechara, J.; Borbon, A.; Jambert, C.; Colomb, A.; Perros, P. E.

    2010-11-01

    A large dataset of reactive trace gases was collected for the first time over West Africa during the African Monsoon Multidisciplinary Analysis (AMMA) field experiment in August 2006. Volatile Organic Compounds (VOC from C5-C9) were measured onboard the two French aircrafts the ATR-42 and the Falcon-20 by a new instrument AMOVOC (Airborne Measurement Of Volatile Organic Compounds). The goal of this study is (i) to characterize VOC distribution in the tropical region of West Africa (ii) to determine the impact of deep convection on VOC distribution and chemistry in the tropical upper troposphere (UT) and (iii) to characterize its spatial and temporal extensions. Experimental strategy consisted in sampling at altitudes between 0 and 12 km downwind of Mesoscale Convective Systems (MCS) and at cloud base. Biogenic and anthropogenic VOC distribution in West Africa is clearly affected by North to South emission gradient. Isoprene, the most abundant VOC, is at maximum level over the forest (1.26 ppb) while benzene reaches its maximum over the urban areas (0.11 ppb). First, a multiple physical and chemical tracers approach using CO, O3 and relative humidity was implemented to distinguish between convective and non-convective air masses. Then, additional tools based on VOC observations (tracer ratios, proxy of emissions and photochemical clocks) were adapted to characterize deep convection on a chemical, spatial and temporal basis. VOC vertical profiles show a "C-shaped" trend indicating that VOC-rich air masses are transported from the surface to the UT by deep convective systems. VOC mixing ratios in convective outflow are up to two times higher than background levels even for reactive and short-lived VOC (e.g. isoprene up to 0.19 ppb at 12 km-altitude) and are dependent on surface emission type. As a consequence, UT air mass reactivity increases from 0.52 s-1 in non-convective conditions to 0.95 s-1 in convective conditions. Fractions of boundary layer air contained in

  18. Combined experimental and theoretical study on the reactivity of compounds I and II in horseradish peroxidase biomimetics.

    PubMed

    Ji, Li; Franke, Alicja; Brindell, Małgorzata; Oszajca, Maria; Zahl, Achim; van Eldik, Rudi

    2014-10-27

    For the exploration of the intrinsic reactivity of two key active species in the catalytic cycle of horseradish peroxidase (HRP), Compound I (HRP-I) and Compound II (HRP-II), we generated in situ [Fe(IV) O(TMP(+.) )(2-MeIm)](+) and [Fe(IV) O(TMP)(2-MeIm)](0) (TMP=5,10,15,20-tetramesitylporphyrin; 2-MeIm=2-methylimidazole) as biomimetics for HRP-I and HRP-II, respectively. Their catalytic activities in epoxidation, hydrogen abstraction, and heteroatom oxidation reactions were studied in acetonitrile at -15 °C by utilizing rapid-scan UV/Vis spectroscopy. Comparison of the second-order rate constants measured for the direct reactions of the HRP-I and HRP-II mimics with the selected substrates clearly confirmed the outstanding oxidizing capability of the HRP-I mimic, which is significantly higher than that of HRP-II. The experimental study was supported by computational modeling (DFT calculations) of the oxidation mechanism of the selected substrates with the involvement of quartet and doublet HRP-I mimics ((2,4) Cpd I) and the closed-shell triplet spin HRP-II model ((3) Cpd II) as oxidizing species. The significantly lower activation barriers calculated for the oxidation systems involving (2,4) Cpd I than those found for (3) Cpd II are in line with the much higher oxidizing efficiency of the HRP-I mimic proven in the experimental part of the study. In addition, the DFT calculations show that all three reaction types catalyzed by HRP-I occur on the doublet spin surface in an effectively concerted manner, whereas these reactions may proceed in a stepwise mechanism with the HRP-II mimic as oxidant. However, the high desaturation or oxygen rebound barriers during CH bond activation processes by the HRP-II mimic predict a sufficient lifetime for the substrate radical formed through hydrogen abstraction. Thus, the theoretical calculations suggest that the dissociation of the substrate radical may be a more favorable pathway than desaturation or

  19. Quinoline-Based Compound BPIQ Exerts Anti-Proliferative Effects on Human Retinoblastoma Cells via Modulating Intracellular Reactive Oxygen Species.

    PubMed

    Cheng, Kai-Chun; Hung, Chun-Tzu; Chen, Kuo-Jen; Wu, Wen-Chuan; Suen, Jau-Ling; Chang, Cheng-Hsien; Lu, Chi-Yu; Tseng, Chih-Hua; Chen, Yeh-Long; Chiu, Chien-Chih

    2016-04-01

    Retinoblastoma (Rb) is the most common primary intraocular malignant tumor of childhood. It is important to develop the strategy for Rb treatment. We have tested a quinolone derivative 2,9-bis[2-(pyrrolidin-1-yl)ethoxy]-6-{4-[2-(pyrrolidin-1-yl)ethoxy]phenyl}-11H-indeno[1,2-c]quinolin-11-one (BPIQ) for its anti-cancer effects against Rb via cultured human Rb cell line Y79. Our results showed that BPIQ significantly inhibits cell growth of Y79. Furthermore, the flow cytometer-based assays and Western blotting showed that BPIQ induces the apoptosis of Y79 via increasing the level of reactive oxygen species (ROS). Besides, the activation of γH2AX, a DNA damage sensor in human Y79 cells was also observed, indicating the potential of BPIQ for causing DNA damage of Rb cells. On the contrary, BPIQ-induced apoptosis of Y79 cells was attenuated significantly by N-acetyl-L-cysteine (NAC), an ROS scavenger. The results of Western blot showed that BPIQ down-regulates the levels of anti-apoptotic proteins Bcl-2, survivin and XIAP while up-regulates the pro-apoptotic proteins Bad, Bax and Bid. Our present study demonstrated the anti-proliferative effect of BPIQ in human Y79 cells. The inhibitory effect of BPIQ on the proliferation of Y79 cells is, at least, partly mediated by the regulation of ROS and DNA damage pathway. In conclusion, BPIQ may provide an alternative option in the chemotherapeutics or chemoprevention on the Rb therapy in the future. PMID:26564153

  20. Quantification of reactive carbonyl compounds in icodextrin-based peritoneal dialysis fluids by combined UHPLC-DAD and -MS/MS detection.

    PubMed

    Gensberger-Reigl, Sabrina; Huppert, Jochen; Pischetsrieder, Monika

    2016-01-25

    During heat sterilization of peritoneal dialysis (PD) fluids, the glucose component is partially degraded. The formed glucose degradation products impair biocompatibility and limit the long-term application of PD fluids. As an alternative to glucose, icodextrin, a polyglucose, is used as osmotic agent in PD fluids. After targeted screening for reactive carbonyl compounds, NMR- and MS-analyses very recently revealed 4-deoxyglucosone (4-DG), 3-deoxyglucosone (3-DG), 3-deoxygalactosone (3-DGal), 3,4-dideoxypentosone (3,4-DDPS), and 5-hydroxymethylfurfural (5-HMF) as main polyglucose degradation products (pGDPs) in icodextrin-based PD fluids. Now, the present study established and validated a UHPLC method with DAD as well as a UHPLC-MS/MS method for the first-time quantification of those five major pGDPs in commercial icodextrin PD fluids after derivatization with o-phenylenediamine. Thus, 4-DG was identified to be the main degradation product (in concentrations up to 20 μM). In contrast to the values measured in glucose-based products, the concentration of 3-DGal (≤ 16 μM) was higher than the concentration of 3-DG (≤ 7 μM) indicating different reaction pathways starting from polyglucose compared to glucose. The compounds 3,4-DDPS and 5-HMF were present in minor quantities (≤ 0.3 μM each). PMID:26540628

  1. From viscous fingering to bulk elastic fingering in soft materials

    NASA Astrophysics Data System (ADS)

    Saintyves, Baudouin; Biggins, John; Wei, Zhiyan; Mora, Serge; Dauchot, Olivier; Mahadevan, L.; Bouchaud, Elisabeth

    2014-03-01

    Systematic experiments have been performed in purely elastic polyacrylamide gels in Hele-Shaw cells. We have shown that a bulk fingering instability arises in the highly deformable confined elastomers. It shares some similarities with the famous Saffman-Taylor instability, but a systematic study shows that surface tension is not relevant. This instability is sub-critical, with a clear hysteretic behavior. Our experimental observations have been compared very favorably to theoretical and finite element simulations results. In particular, the instability wavelength and the critical front advance have been shown to be proportional to the distance between the two glass plates constituting the cell. We have also shown that in Maxwell viscoelastic fluids, one crosses over continuously from a viscous to an elastic fingering instability.

  2. Mechanical model of a single tendon finger

    NASA Astrophysics Data System (ADS)

    Rossi, Cesare; Savino, Sergio

    2013-10-01

    The mechanical model of a single tendon three phalanxes finger is presented. By means of the model both kinematic and dynamical behavior of the finger itself can be studied. This finger is a part of a more complex mechanical system that consists in a four finger grasping device for robots or in a five finger human hand prosthesis. A first prototype has been realized in our department in order to verify the real behavior of the model. Some results of both kinematic and dynamical behavior are presented.

  3. Characteristics, source apportionment and reactivity of ambient volatile organic compounds at Dinghu Mountain in Guangdong Province, China.

    PubMed

    Wu, Fangkun; Yu, Ye; Sun, Jie; Zhang, Junke; Wang, Jian; Tang, Guiqian; Wang, Yuesi

    2016-04-01

    Volatile organic compounds (VOCs) play a very important role in the formation of ozone and secondary organic aerosols. The concentrations, compositions, and variability of VOCs were measured from 2005 to 2008 at Dinghu Mountain Forest Ecosystem Research Station, a remote station in Southeast China. Weekly samples were collected in the Dinghu Mountain area and were analysed via gas chromatography-mass spectrometry. The results revealed that the total VOC concentrations decreased continuously and that the dominant VOC components were alkanes (43%) and aromatics (33%), followed by halo-hydrocarbons (12%) and alkenes (12%). The general trend of seasonal variation indicated higher concentrations in spring and lower concentrations in summer. The positive matrix factorization model was used to identify the sources of the VOCs. Seven sources were resolved by the PMF model: (1) vehicular emissions, which contributed 25% of the total VOC concentration; (2) industrial sources and regional transportation, contributing 17%; (3) paint solvent use, contributing 17%; (4) fuel evaporation, contributing 13%; (5) stationary combustion sources, contributing 12%; (6) biogenic emissions, contributing 10%; and aged VOCs, contributing only 6%. The HYSPLIT model was used to analyse the effect of pollutant transport, and the results indicated that the transport of pollutants from cities cannot be ignored. Finally, the OH radical loss rates and ozone formation potentials (OFPs) were calculated, and the results indicated isoprene to have the highest OH radical loss rate and toluene to be the largest contributor to the OFP at the Dinghu Mountain site. PMID:26803733

  4. Impact of Finger Type in Fingerprint Authentication

    NASA Astrophysics Data System (ADS)

    Gafurov, Davrondzhon; Bours, Patrick; Yang, Bian; Busch, Christoph

    Nowadays fingerprint verification system is the most widespread and accepted biometric technology that explores various features of the human fingers for this purpose. In general, every normal person has 10 fingers with different size. Although it is claimed that recognition performance with little fingers can be less accurate compared to other finger types, to our best knowledge, this has not been investigated yet. This paper presents our study on the topic of influence of the finger type into fingerprint recognition performance. For analysis we employ two fingerprint verification software packages (one public and one commercial). We conduct test on GUC100 multi sensor fingerprint database which contains fingerprint images of all 10 fingers from 100 subjects. Our analysis indeed confirms that performance with small fingers is less accurate than performance with the others fingers of the hand. It also appears that best performance is being obtained with thumb or index fingers. For example, performance deterioration from the best finger (i.e. index or thumb) to the worst fingers (i.e. small ones) can be in the range of 184%-1352%.

  5. Does finger sense predict addition performance?

    PubMed

    Newman, Sharlene D

    2016-05-01

    The impact of fingers on numerical and mathematical cognition has received a great deal of attention recently. However, the precise role that fingers play in numerical cognition is unknown. The current study explores the relationship between finger sense, arithmetic and general cognitive ability. Seventy-six children between the ages of 5 and 12 participated in the study. The results of stepwise multiple regression analyses demonstrated that while general cognitive ability including language processing was a predictor of addition performance, finger sense was not. The impact of age on the relationship between finger sense, and addition was further examined. The participants were separated into two groups based on age. The results showed that finger gnosia score impacted addition performance in the older group but not the younger group. These results appear to support the hypothesis that fingers provide a scaffold for calculation and that if that scaffold is not properly built, it has continued differential consequences to mathematical cognition. PMID:26993292

  6. Environmental chamber studies of atmospheric reactivities of volatile organic compounds: Effects of varying chamber and light source

    SciTech Connect

    Carter, W.; Luo, D.; Malkina, I.; Pierce, J.

    1995-05-01

    Photochemical oxidant models are essential tools for assessing effects of emissions changes on ground-level ozone formation. Such models are needed for predicting the ozone impacts of increased alternative fuel use. The gas-phase photochemical mechanism is an important component of these models because ozone is not emitted directly, but is formed from the gas-phase photochemical reactions of the emitted volatile organic compounds (VOCs) and oxides of nitrogen (NO{sub x}) in air. The chemistry of ground level ozone formation is complex; hundreds of types of VOCs being emitted into the atmosphere, and most of their atmospheric reactions are not completely understood. Because of this, no chemical model can be relied upon to give even approximately accurate predictions unless it has been evaluated by comparing its predictions with experimental data. Therefore an experimental and modeling study was conducted to assess how chemical mechanism evaluations using environmental chamber data are affected by the light source and other chamber characteristics. Xenon arc lights appear to give the best artificial representation of sunlight currently available, and experiments were conducted in a new Teflon chamber constructed using such a light source. Experiments were also conducted in an outdoor Teflon Chamber using new procedures to improve the light characterization, and in Teflon chambers using blacklights. These results, and results of previous runs other chambers, were compared with model predictions using an updated detailed chemical mechanism. The magnitude of the chamber radical source assumed when modeling the previous runs were found to be too high; this has implications in previous mechanism evaluations. Temperature dependencies of chamber effects can explain temperature dependencies in chamber experiments when Ta-300{degree}K, but not at temperatures below that.

  7. Prooxidant action of furanone compounds: implication of reactive oxygen species in the metal-dependent strand breaks and the formation of 8-hydroxy-2'-deoxyguanosine in DNA.

    PubMed

    Murakami, K; Haneda, M; Makino, T; Yoshino, M

    2007-07-01

    Prooxidant properties of furanone compounds including 2,5-furanone (furaneol, 4-hydroxy-2,5-dimethyl-furan-3-one), 4,5-furanone (4,5-dimethyl-3-hydroxy-2(5H)-furanone) (sotolone) and cyclotene (2-hydroxy-3-methyl-2-cyclopenten-1-one) were analyzed in relation to the metal-reducing activity. Only 2.5-furanone known as a "strawberry or pineapple furanone" inactivated aconitase the most sensitive enzyme to active oxygen in the presence of ferrous sulfate, suggesting the furaneol/iron-mediated generation of reactive oxygen species. 2,5-Furanone caused strand scission of pBR322 DNA in the presence of copper. Treatment of calf thymus DNA with 2,5-furanone plus copper produced 8-hydroxy-2'-deoxyguanosine in DNA. 2,5-Furanone showed a potent copper-reducing activity, and thus, DNA strand breaks and the formation of 8-hydroxy-2'-deoxyguanosine by 2,5-furanone can be initiated by the production of superoxide radical through the reduction of cupric ion to cuprous ion, resulting in the conversion to hydrogen peroxide and hydroxyl radical. However, an isomer and analog of 2,5-furanone, 4,5-furanone and cyclotene, respectively, did not show an inactivation of aconitase, DNA injuries including strand breakage and the formation of 8-hydroxy-2'-deoxyguanosine, and copper-reducing activity. Cytotoxic effect of 2,5-furanone with hydroxyketone structure can be explained by its prooxidant properties: furaneol/transition metal complex generates reactive oxygen species causing the inactivation of aconitase and the formation of DNA base damage by hydroxyl radical. PMID:17316945

  8. Concentrations and Fluxes of Water-Soluble Reactive Nitrogen Gases and Aerosol Compounds Above a Forest Canopy

    NASA Astrophysics Data System (ADS)

    Wolff, V.; Trebs, I.; Moravek, A.; Zhu, Z.; Meixner, F. X.

    2008-12-01

    HNO3 gradients are indicating net deposition. These gradients may be biased by micrometeorology and chemistry. For example, gradients in NH3 and HNO3 may be product of a phase change in the thermodynamic equilibrium between NH3, HNO3 and particulate NH4NO3, induced by a temperature and/or humidity gradient above the forest canopy. The equilibrium will be investigated for the pure NH3- HNO3- NH4NO3 triad as well as for more complex inorganic aerosol mixtures and chemical timescales will be compared to turbulent timescales, to estimate the potential of chemical interferences affecting the gradient. If compounds react sufficiently slow and may therefore be treated as passive tracers, prerequisites for the application of micrometeorological methods to derive fluxes from gradients will be investigated.

  9. Regional biogenic emissions of reactive volatile organic compounds (BVOC) from forests: First results on process studies, modelling and validation experiments (BEWA2000)

    NASA Astrophysics Data System (ADS)

    Rappenglück, B.; Bewa2000 Team

    2003-04-01

    The overall objective of the research consortia is to develop for a forest canopy a prognostic, validated emission model for primary and secondary volatile organic compounds (VOC) to be used for estimating regional biogenic emissions with a higher spatial and temporal resolution than present. To achieve this objective requires a better description of biosynthetic processes as well as chemical degradation mechanisms for reactive biogenic VOC in combination with a process-based model and latest vegetation specific land use information. Up to now several highlights were achieved within the different key activities. In the section model development a process-based isoprenoid emission model was supplemented with new differential equations especially taking into account the influence of transport-resistances for leaf gas-exchange. In biochemical process-studies related to the formation of isoprene in leaves it turned out that during daytime about 20-70% of the total carbon delivered to poplar leaves (photosynthesis + other sources) was derived from xylem-transported sugars. This finding indicates that xylem-delivered carbon may indeed act as a significant alternative carbon source for isoprenoid biosynthesis. First chemical process studies on the reaction of limonene with NO3 radicals (observed in the night and under low light conditions) in the EUPHORE (European Photoreactor) demonstrated a secondary particle formation. At the field site Waldstein (Fichtelgebirge) this reaction may result in maximum pinonealdhyde concentrations in the air and on particles observed in night periods. A first analysis of particle size distributions over the Norway spruce canopy showed the appearance of small particles (< 10nm) during early daytime. The first results demonstrate that the proposed approach of combining interdisciplinary field, laboratory and modelling exercises to address the complexity of the biosphere/atmosphere exchange of reactive trace gases will contribute

  10. Evidence of the impact of deep convection on reactive volatile organic compounds in the upper tropical troposphere during the AMMA experiment in West Africa

    NASA Astrophysics Data System (ADS)

    Bechara, J.; Borbon, A.; Jambert, C.; Colomb, A.; Perros, P. E.

    2009-09-01

    A large dataset of reactive trace gases was collected for the first time over West Africa during the African Monsoon Multidisciplinary Analysis (AMMA) field experiment in August 2006. Volatile Organic Compounds (VOC from C5-C9) were measured onboard the two French aircrafts the ATR-42 and the Falcon-20 by a new instrument AMOVOC. The goal of this study is (i) to characterize VOC distribution in the tropical region of West Africa (ii) to determine the impact of deep convection on VOC distribution and chemistry in the tropical upper troposphere (UT) and (iii) to characterize its spatial and temporal extensions. Experimental strategy consisted in sampling at altitudes between 0 and 12 km downwind of Mesoscale Convective Systems (MCS) and at cloud base. Biogenic and anthropogenic VOC distribution in West Africa is clearly affected by North to South emission gradient. Isoprene, the most abundant VOC, is at maximum level over the forest (1.26 ppb) while benzene reaches its maximum over the urban areas (0.11 ppb). First, a multiple physical and chemical tracers approach using CO, O3 and relative humidity was implemented to distinguish between convective and non-convective air masses. Then, additional tools based on VOC observations (tracer ratios, proxy of emissions and photochemical clocks) were adapted to characterize deep convection on a chemical, spatial and temporal basis. VOC vertical profiles show a "C-shaped" trend indicating that VOC-rich air masses are transported from the surface to the UT by deep convective systems. VOC mixing ratios in convective outflow are up to two times higher than background levels even for reactive and short-lived VOC (e.g. isoprene up to 0.19 ppb at 12 km-altitude) and are dependent on surface emission type. As a consequence, UT air mass reactivity increases from 0.52 s-1 in non-convective conditions to 0.95 s-1 in convective conditions. Fractions of boundary layer air contained in convective outflow are estimated to be 40±15

  11. 1-Boraadamantane: reactivity towards di(1-alkynyl)silicon and -tin compounds: first access to 7-metalla-2,5-diboranorbornane derivatives.

    PubMed

    Wrackmeyer, B; Milius, W; Klimkina, E V; Bubnov, Y N

    2001-01-01

    1-Boraadamantane (1) reacts with di(1-alkynyl)silicon and -tin compounds 2 (Me2M(C...CR)2: M=Si; R=Me (a), tBu (b), SiMe3 (c); M=Sn, R=SiMe3 (e)) in a 1:1 ratio by intermolecular 1,1-alkylboration, followed by intramolecular 1,1-vinylboration, to give siloles 5a-c and the stannole 5e, respectively, in which the tricyclic 1-boraadamantane system is enlarged by two carbon atoms. Owing to the high reactivity of 1, a second fast intermolecular 1,1-alkylboration competes with the intramolecular 1,1-vinylboration as the second major step in the reaction if the substituent R at the C...C bond is small (2a) and/or if the M-C... bond is also highly reactive, as in 2d (M=Sn, R= Me) and 2e (M=Sn, R=SiMe3). This leads finally to the novel octacyclic 7-metalla-2,5-diboranorbornane derivatives 8a, 8d, and 8e, of which 8e was characterized by X-ray analysis in the solid state. 1,1,2,2-Tetramethyldi(1-propynyl)disilane, MeC...C-SiMe2SiMe2-C...CMe (3), reacts with 1 to give mainly a 1,2-dihydro-1,2,5-disilaborepine derivative 9 and the octacyclic compound 11, which is analogous to 8a but with an Me4Si2 bridge. All new products were characterized in solution by 1H, 11B, 13C, 29Si, and 119Sn NMR spectroscopy. For 8 and 11, highly resolved 29Si and 119Sn NMR spectra revealed the first two-bond isotope-induced chemical shifts, 2delta10/11B(29Si) and 2delta10/11B(119Sn) respectively, to be reported. PMID:11288867

  12. Removal of ammonium-nitrogen from groundwater using a fully passive permeable reactive barrier with oxygen-releasing compound and clinoptilolite.

    PubMed

    Huang, Guoxin; Liu, Fei; Yang, Yingzhao; Deng, Wei; Li, Shengpin; Huang, Yuanying; Kong, Xiangke

    2015-05-01

    A novel fully passive permeable reactive barrier (PRB) with oxygen-releasing compound (ORC) and clinoptilolite was proposed for the removal of ammonium-nitrogen from groundwater. The PRB involves a combination of oxygen release, biological nitrification, ion exchange, and bioregeneration. A pilot-scale performance comparison experiment was carried out employing three parallel columns to assess the proposed PRB. The results showed that the PRB achieved nearly complete [Formula: see text] depletion (>99%). [Formula: see text] of 5.23-10.88 mg/L was removed, and [Formula: see text] of <1.93 mg/L and [Formula: see text] of 2.03-19.67 mg/L were generated. Ion exchange and biological nitrification both contributed to [Formula: see text] removal, and the latter played a dominant role under the condition of sufficient oxygen. Biological nitrification favored a delay in sorption saturation and a release of exchange sites. The ORC could sufficiently, efficiently supply oxygen for approximately 120 pore volumes. The clinoptilolite ensured a robust [Formula: see text] removal in case of temporary insufficient biological activities. No external alkalinity sources had to be supplied and no inhibition of aerobic metabolism occurred. The ceramicite had a negligible effect on the biomass growth. Based on the research findings, a full-scale continuous wall PRB was installed in Shenyang, China in 2012. PMID:25700350

  13. Current status of ultrasonography of the finger

    PubMed Central

    2016-01-01

    The recent development of advanced high-resolution transducers has enabled the fast, easy, and dynamic ultrasonographic evaluation of small, superficial structures such as the finger. In order to best exploit these advances, it is important to understand the normal anatomy and the basic pathologies of the finger, as exemplified by the following conditions involving the dorsal, volar, and lateral sections of the finger: sagittal band injuries, mallet finger, and Boutonnière deformity (dorsal aspect); flexor tendon tears, trigger finger, and volar plate injuries (volar aspect); gamekeeper’s thumb (Stener lesions) and other collateral ligament tears (lateral aspect); and other lesions. This review provides a basis for understanding the ultrasonography of the finger and will therefore be useful for radiologists. PMID:26753604

  14. On the fly finger knuckle print authentication

    NASA Astrophysics Data System (ADS)

    Abe, Narishige; Shinzaki, Takashi

    2014-05-01

    Finger knuckle print authentication has been researched not only as a supplemental authentication modality to fingerprint recognition but also as a method for logging into a PC or entering a building. However, in previous works, some specific devices were necessary to capture a finger knuckle print and users had to keep their fingers perfectly still to capture their finger knuckle. In this paper, we propose a new on the fly finger knuckle print authentication system using a general web camera. In our proposed authentication system, users can input their finger knuckle prints without needing their hand to remain motionless during image capture. We also evaluate the authentication accuracy of the proposed system, achieving an 7% EER under best conditions.

  15. Prosthetic Hand With Two Gripping Fingers

    NASA Technical Reports Server (NTRS)

    Norton, William E.; Belcher, Jewell B.; Vest, Thomas W.; Carden, James R.

    1993-01-01

    Prosthetic hand developed for amputee who retains significant portion of forearm. Outer end of device is end effector including two fingers, one moved by rotating remaining part of forearm about its longitudinal axis. Main body of end effector is end member supporting fingers, roller bearing assembly, and rack-and-pinion mechanism. Advantage of rack-and-pinion mechanism enables user to open or close gap between fingers with precision and force.

  16. Piezoelectric Actuators On A Cold Finger

    NASA Technical Reports Server (NTRS)

    Kuo, Chin-Po; Garba, John A.; Glaser, Robert J.

    1995-01-01

    Developmental system for active suppression of vibrations of cold finger includes three piezoelectric actuators bonded to outer surface. Actuators used to suppress longitudinal and lateral vibrations of upper end of cold finger by applying opposing vibrations. Cold finger in question is part of a cryogenic system associated with an infrared imaging detector. When fully developed, system would be feedback sensor/control/actuator system automatically adapting to changing vibrational environment and suppresses pressure-induced vibrations by imposing compensatory vibrations via actuators.

  17. An endophytic fungus isolated from finger millet (Eleusine coracana) produces anti-fungal natural products

    PubMed Central

    Mousa, Walaa K.; Schwan, Adrian; Davidson, Jeffrey; Strange, Philip; Liu, Huaizhi; Zhou, Ting; Auzanneau, France-Isabelle; Raizada, Manish N.

    2015-01-01

    Finger millet is an ancient African cereal crop, domesticated 7000 years ago in Ethiopia, reaching India at 3000 BC. Finger millet is reported to be resistant to various fungal pathogens including Fusarium sp. We hypothesized that finger millet may host beneficial endophytes (plant-colonizing microbes) that contribute to the antifungal activity. Here we report the first isolation of endophyte(s) from finger millet. Five distinct fungal species were isolated from roots and predicted taxonomically based on 18S rDNA sequencing. Extracts from three putative endophytes inhibited growth of F. graminearum and three other pathogenic Fusarium species. The most potent anti-Fusarium strain (WF4, predicted to be a Phoma sp.) was confirmed to behave as an endophyte using pathogenicity and confocal microscopy experiments. Bioassay-guided fractionation of the WF4 extract identified four anti-fungal compounds, viridicatol, tenuazonic acid, alternariol, and alternariol monomethyl ether. All the purified compounds caused dramatic breakage of F. graminearum hyphae in vitro. These compounds have not previously been reported to have anti-Fusarium activity. None of the compounds, except for tenuazonic acid, have previously been reported to be produced by Phoma. We conclude that the ancient, disease-tolerant crop, finger millet, is a novel source of endophytic anti-fungal natural products. This paper suggests the value of the crops grown by subsistence farmers as sources of endophytes and their natural products. Application of these natural chemicals to solve real world problems will require further validation. PMID:26539183

  18. An endophytic fungus isolated from finger millet (Eleusine coracana) produces anti-fungal natural products.

    PubMed

    Mousa, Walaa K; Schwan, Adrian; Davidson, Jeffrey; Strange, Philip; Liu, Huaizhi; Zhou, Ting; Auzanneau, France-Isabelle; Raizada, Manish N

    2015-01-01

    Finger millet is an ancient African cereal crop, domesticated 7000 years ago in Ethiopia, reaching India at 3000 BC. Finger millet is reported to be resistant to various fungal pathogens including Fusarium sp. We hypothesized that finger millet may host beneficial endophytes (plant-colonizing microbes) that contribute to the antifungal activity. Here we report the first isolation of endophyte(s) from finger millet. Five distinct fungal species were isolated from roots and predicted taxonomically based on 18S rDNA sequencing. Extracts from three putative endophytes inhibited growth of F. graminearum and three other pathogenic Fusarium species. The most potent anti-Fusarium strain (WF4, predicted to be a Phoma sp.) was confirmed to behave as an endophyte using pathogenicity and confocal microscopy experiments. Bioassay-guided fractionation of the WF4 extract identified four anti-fungal compounds, viridicatol, tenuazonic acid, alternariol, and alternariol monomethyl ether. All the purified compounds caused dramatic breakage of F. graminearum hyphae in vitro. These compounds have not previously been reported to have anti-Fusarium activity. None of the compounds, except for tenuazonic acid, have previously been reported to be produced by Phoma. We conclude that the ancient, disease-tolerant crop, finger millet, is a novel source of endophytic anti-fungal natural products. This paper suggests the value of the crops grown by subsistence farmers as sources of endophytes and their natural products. Application of these natural chemicals to solve real world problems will require further validation. PMID:26539183

  19. Bonding of silicon scanning mirror having vertical comb fingers

    NASA Astrophysics Data System (ADS)

    Lee, Jin-Ho; Ko, Young-Chul; Choi, Byoung-So; Kim, Jong-Min; Jeon, Duk Young

    2002-09-01

    A 1500 μm × 1200 μm silicon scanning mirror has been fabricated by using anodic bonding and flip chip bonding. This scanning mirror is mainly composed of two structures having vertical comb fingers. By anodic bonding between the silicon wafer and the Pyrex glass substrate, and following deep inductively coupled plasma reactive ion etching (ICPRIE), isolated comb electrodes were fabricated at the lower structure. However, gold signal lines for electrical connection to the electrodes, which were inserted between silicon and Pyrex glass, were damaged during anodic bonding. This problem was solved by using the proposed processes and signal lines were successfully fabricated with the contact resistance below several tens of ohms. By flip chip bonding, the upper and lower structures having vertical comb fingers were assembled. Vertical comb fingers of two structures were aligned with a microscope and the frames of two structures were bonded at 300 °C for 20 s using the eutectic bonding material - electroplated AuSn. Finally, the scanning mirror was successfully fabricated and could be used for laser display as a galvanometric vertical scanner.

  20. Error compensation during finger force production after one- and four-finger voluntarily fatiguing exercise.

    PubMed

    Kruger, Eric S; Hoopes, Josh A; Cordial, Rory J; Li, Sheng

    2007-08-01

    The effect of muscle fatigue on error compensation strategies during multi-finger ramp force production tasks was investigated. Thirteen young, healthy subjects were instructed to produce a total force with four fingers of the right hand to accurately match a visually displayed template. The template consisted of a 3-s waiting period, a 3-s ramp force production [from 0 to 30% maximal voluntary contraction (MVC)], and a 3-s constant force production. A series of 12 ramp trials was performed before and after fatigue. Fatigue was induced by a 60-s maximal isometric force production with either the index-finger only or with all four fingers during two separate testing sessions. The average percent of drop was 38.2% in the MVC of the index finger after index-finger fatiguing exercise and 38.3% in the MVC of all fingers after four-finger fatiguing exercise. The ability of individual fingers to compensate for each other's errors in order for the total force to match the preset template was quantified as the error compensation index (ECI), i.e., the ratio of the sum of variances of individual finger forces and the variance of the total force. By comparing pre- and post-fatigue performance during four-finger ramp force production, we observed that the variance of the total force was not significantly changed after one- or four-finger fatiguing exercise. The ECI significantly decreased after four-finger fatiguing exercise, especially during the last second of the ramp; while the ECI remained unchanged after index finger single-finger fatiguing exercise. These results suggest that the central nervous system is able to utilize the abundant degrees of freedom to compensate for partial impairment of the motor apparatus induced by muscle fatigue to maintain the desired performance. However, this ability is significantly decreased when all elements of the motor apparatus are impaired. PMID:17443316

  1. Invariantly propagating dissolution fingers in finite-width systems

    NASA Astrophysics Data System (ADS)

    Dutka, Filip; Szymczak, Piotr

    2016-04-01

    Dissolution fingers are formed in porous medium due to positive feedback between transport of reactant and chemical reactions [1-4]. We investigate two-dimensional semi-infinite systems, with constant width W in one direction. In numerical simulations we solve the Darcy flow problem combined with advection-dispersion-reaction equation for the solute transport to track the evolving shapes of the fingers and concentration of reactant in the system. We find the stationary, invariantly propagating finger shapes for different widths of the system, flow and reaction rates. Shape of the reaction front, turns out to be controlled by two dimensionless numbers - the (width-based) Péclet number PeW = vW/Dφ0 and Damköhler number DaW = ksW/v, where k is the reaction rate, s - specific reactive surface area, v - characteristic flow rate, D - diffusion coefficient of the solute, and φ0 - initial porosity of the rock matrix. Depending on PeW and DaW stationary shapes can be divided into seperate classes, e.g. parabolic-like and needle-like structures, which can be inferred from theoretical predictions. In addition we determine velocity of propagating fingers in time and concentration of reagent in the system. Our simulations are compared with natural forms (solution pipes). P. Ortoleva, J. Chadam, E. Merino, and A. Sen, Geochemical self-organization II: the reactive-infiltration instability, Am. J. Sci, 287, 1008-1040 (1987). M. L. Hoefner, and H. S. Fogler. Pore evolution and channel formation during flow and reaction in porous media, AIChE Journal 34, 45-54 (1988). C. E. Cohen, D. Ding, M. Quintard, and B. Bazin, From pore scale to wellbore scale: impact of geometry on wormhole growth in carbonate acidization, Chemical Engineering Science 63, 3088-3099 (2008). P. Szymczak and A. J. C. Ladd, Reactive-infiltration nstabilities in rocks. Part II: Dissolution of a porous matrix, J. Fluid Mech. 738, 591-630 (2014).

  2. Ammonium-nitrogen-contaminated groundwater remediation by a sequential three-zone permeable reactive barrier (multibarrier) with oxygen-releasing compound (ORC)/clinoptilolite/spongy iron: column studies.

    PubMed

    Huang, Guoxin; Liu, Fei; Yang, Yingzhao; Kong, Xiangke; Li, Shengpin; Zhang, Ying; Cao, Dejun

    2015-03-01

    A novel sequential permeable reactive barrier (multibarrier), composed of oxygen-releasing compound (ORC)/clinoptilolite/spongy iron zones in series, was proposed for ammonium-nitrogen-contaminated groundwater remediation. Column experiments were performed to: (1) evaluate the overall NH4(+)-N removal performance of the proposed multibarrier, (2) investigate nitrogen transformation in the three zones, (3) determine the reaction front progress, and (4) explore cleanup mechanisms for inorganic nitrogens. The results showed that NH4 (+)-N percent removal by the multibarrier increased up to 90.43 % after 21 pore volumes (PVs) at the influent dissolved oxygen of 0.68∼2.45 mg/L and pH of 6.76∼7.42. NH4(+)-N of 4.06∼10.49 mg/L was depleted and NOx(-)-N (i.e., NO3 (-)-N + NO2(-)-N) of 4.26∼9.63 mg/L was formed before 98 PVs in the ORC zone. NH4(+)-N of ≤4.76 mg/L was eliminated in the clinoptilolite zone. NOx(-)-N of 10.44∼12.80 mg/L was lost before 21 PVs in the spongy iron zone. The clinoptilolite zone length should be reduced to 30 cm. Microbial nitrification played a dominant role in NH4(+)-N removal in the ORC zone. Ion exchange was majorly responsible for NH4(+)-N elimination in the clinoptilolite zone. Chemical reduction and hydrogenotrophic denitrification both contributed to NOx(-)-N transformation, but the chemical reduction capacity decreased after 21 PVs in the spongy iron. PMID:25256584

  3. Atmospheric reactivity of hydroxyl radicals with guaiacol (2-methoxyphenol), a biomass burning emitted compound: Secondary organic aerosol formation and gas-phase oxidation products

    NASA Astrophysics Data System (ADS)

    Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Deboudt, Karine; Fourmentin, Marc; Choël, Marie

    2014-04-01

    Methoxyphenols are low molecular weight semi-volatile polar aromatic compounds produced from the pyrolysis of wood lignin. The reaction of guaiacol (2-methoxyphenol) with hydroxyl radicals has been studied in the LPCA simulation chamber at (294 ± 2) K, atmospheric pressure, low relative humidity (RH < 1%) and under high-NOx conditions using CH3ONO as OH source. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer); the SOA yields were in the range from 0.003 to 0.87 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. Transmission (TEM) and Scanning (SEM) Electron Microscopy observations were performed to characterize the physical state of SOA produced from the OH reaction with guaiacol; they display both liquid and solid particles (in an amorphous state). GC-FID (Gas Chromatography - Flame Ionization Detection) and GC-MS (Gas Chromatography - Mass Spectrometry) analysis show the formation of nitroguaiacol isomers as main oxidation products in the gas- and aerosol-phases. In the gas-phase, the formation yields were (10 ± 2) % for 4-nitroguaiacol (1-hydroxy-2-methoxy-4-nitrobenzene; 4-NG) and (6 ± 2) % for 3- or 6-nitroguaiacol (1-hydroxy-2-methoxy-3-nitrobenzene or 1-hydroxy-2-methoxy-6-nitrobenzene; 3/6-NG; the standards are not commercially available so both isomers cannot be distinguished) whereas in SOA their yield were much lower (≤0.1%). To our knowledge, this work represents the first identification of nitroguaiacols as gaseous oxidation products of the OH reaction with guaiacol. As the reactivity of nitroguaiacols with atmospheric oxidants is probably low, we suggest using them as biomass burning emission gas tracers. The atmospheric implications of the guaiacol + OH reaction are also discussed.

  4. Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns

    NASA Astrophysics Data System (ADS)

    Velasco, E.; Lamb, B.; Westberg, H.; Allwine, E.; Sosa, G.; Arriaga-Colina, J. L.; Jobson, B. T.; Alexander, M. L.; Prazeller, P.; Knighton, W. B.; Rogers, T. M.; Grutter, M.; Herndon, S. C.; Kolb, C. E.; Zavala, M.; de Foy, B.; Volkamer, R.; Molina, L. T.; Molina, M. J.

    2007-01-01

    A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air

  5. Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 and 2003 field campaigns

    NASA Astrophysics Data System (ADS)

    Velasco, E.; Lamb, B.; Westberg, H.; Allwine, E.; Sosa, G.; Arriaga-Colina, J. L.; Jobson, B. T.; Alexander, M.; Prazeller, P.; Knighton, W. B.; Rogers, T. M.; Grutter, M.; Herndon, S. C.; Kolb, C. E.; Zavala, M.; de Foy, B.; Volkamer, R.; Molina, L. T.; Molina, M. J.

    2006-08-01

    A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that

  6. Creating Number Semantics through Finger Movement Perception

    ERIC Educational Resources Information Center

    Badets, Arnaud; Pesenti, Mauro

    2010-01-01

    Communication, language and conceptual knowledge related to concrete objects may rely on the sensory-motor systems from which they emerge. How abstract concepts can emerge from these systems is however still unknown. Here we report a functional interaction between a specific meaningful finger movement, such as a finger grip closing, and a concept…

  7. Feasibility of novel (H3C)nX(SiH3)3-n compounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations.

    PubMed

    Dos Santos, Renato B; Rivelino, R; Mota, F de Brito; Kakanakova-Georgieva, A; Gueorguiev, G K

    2015-02-21

    We employ ab initio calculations to predict the equilibrium structure, stability, reactivity, and Raman scattering properties of sixteen different (H3C)nX(SiH3)3-n compounds (X = B, Al, Ga, In) with n = 0-3. Among this methylsilylmetal family, only the (H3C)3X members, i.e., trimethylboron (TMB), trimethylaluminum (TMA), trimethylgallium (TMG), and trimethylindium (TMI), are currently well-studied. The remaining twelve compounds proposed here open up a two-dimensional array of new possibilities for precursors in various deposition processes, and evoke potential applications in the chemical synthesis of other compounds. We infer that within the (H3C)nX(SiH3)3-n family, the compounds with fewer silyl groups (and consequently with more methyl groups) are less reactive and more stable. This trend is verified from the calculated cohesive energy, Gibbs free energy of formation, bond strength, and global chemical indices. Furthermore, we propose sequential reaction routes for the synthesis of (H3C)nX(SiH3)3-n by substitution of methyl by silyl groups, where the silicon source is the silane gas. The corresponding reaction barriers for these chemical transformations lie in the usual energy range typical for MOCVD processes. We also report the Raman spectra and light scattering properties of the newly proposed (H3C)nX(SiH3)3-n compounds, in comparison with available data of known members of this family. Thus, our computational experiment provides useful information for a systematic understanding of the stability/reactivity and for the identification of these compounds. PMID:25599815

  8. Analysis and treatment of finger sucking.

    PubMed Central

    Ellingson, S A; Miltenberger, R G; Stricker, J M; Garlinghouse, M A; Roberts, J; Galensky, T L; Rapp, J T

    2000-01-01

    We analyzed and treated the finger sucking of 2 developmentally typical children aged 7 and 10 years. The functional analysis revealed that the finger sucking of both children was exhibited primarily during alone conditions, suggesting that the behavior was maintained by automatic reinforcement. An extended analysis provided support for this hypothesis and demonstrated that attenuation of stimulation produced by the finger sucking resulted in behavior reductions for both children. Treatment consisted of having each child wear a glove on the relevant hand during periods when he or she was alone. Use of the glove produced zero levels of finger sucking for 1 participant, whereas only moderate reductions were obtained for the other. Subsequently, an awareness enhancement device was used that produced an immediate reduction in finger sucking. PMID:10738951

  9. Fingering in Stochastic Growth Models

    PubMed Central

    Aristotelous, Andreas C.; Durrett, Richard

    2015-01-01

    Motivated by the widespread use of hybrid-discrete cellular automata in modeling cancer, two simple growth models are studied on the two dimensional lattice that incorporate a nutrient, assumed to be oxygen. In the first model the oxygen concentration u(x, t) is computed based on the geometry of the growing blob, while in the second one u(x, t) satisfies a reaction-diffusion equation. A threshold θ value exists such that cells give birth at rate β(u(x, t) − θ)+ and die at rate δ(θ − u(x, t)+. In the first model, a phase transition was found between growth as a solid blob and “fingering” at a threshold θc = 0.5, while in the second case fingering always occurs, i.e., θc = 0. PMID:26430353

  10. Differing Dynamics of Intrapersonal and Interpersonal Coordination: Two-finger and Four-Finger Tapping Experiments

    PubMed Central

    Kodama, Kentaro; Furuyama, Nobuhiro; Inamura, Tetsunari

    2015-01-01

    Finger-tapping experiments were conducted to examine whether the dynamics of intrapersonal and interpersonal coordination systems can be described equally by the Haken—Kelso—Bunz model, which describes inter-limb coordination dynamics. This article reports the results of finger-tapping experiments conducted in both systems. Two within-subject factors were investigated: the phase mode and the number of fingers. In the intrapersonal experiment (Experiment 1), the participants were asked to tap, paced by a gradually hastening auditory metronome, looking at their fingers moving, using the index finger in the two finger condition, or the index and middle finger in the four-finger condition. In the interpersonal experiment (Experiment 2), pairs of participants performed the task while each participant used the outside hand, tapping with the index finger in the two finger condition, or the index and middle finger in the four-finger condition. Some results did not agree with the HKB model predictions. First, from Experiment 1, no significant difference was observed in the movement stability between the in-phase and anti-phase modes in the two finger condition. Second, from Experiment 2, no significant difference was found in the movement stability between the in-phase and anti-phase mode in the four-finger condition. From these findings, different coordination dynamics were inferred between intrapersonal and interpersonal coordination systems against prediction from the previous studies. Results were discussed according to differences between intrapersonal and interpersonal coordination systems in the availability of perceptual information and the complexity in the interaction between limbs derived from a nested structure. PMID:26070119

  11. Finger wear detection for production line battery tester

    DOEpatents

    Depiante, Eduardo V.

    1997-01-01

    A method for detecting wear in a battery tester probe. The method includes providing a battery tester unit having at least one tester finger, generating a tester signal using the tester fingers and battery tester unit with the signal characteristic of the electrochemical condition of the battery and the tester finger, applying wavelet transformation to the tester signal including computing a mother wavelet to produce finger wear indicator signals, analyzing the signals to create a finger wear index, comparing the wear index for the tester finger with the index for a new tester finger and generating a tester finger signal change signal to indicate achieving a threshold wear change.

  12. Finger wear detection for production line battery tester

    DOEpatents

    Depiante, E.V.

    1997-11-18

    A method is described for detecting wear in a battery tester probe. The method includes providing a battery tester unit having at least one tester finger, generating a tester signal using the tester fingers and battery tester unit with the signal characteristic of the electrochemical condition of the battery and the tester finger, applying wavelet transformation to the tester signal including computing a mother wavelet to produce finger wear indicator signals, analyzing the signals to create a finger wear index, comparing the wear index for the tester finger with the index for a new tester finger and generating a tester finger signal change signal to indicate achieving a threshold wear change. 9 figs.

  13. Trigger finger, tendinosis, and intratendinous gene expression.

    PubMed

    Lundin, A-C; Aspenberg, P; Eliasson, P

    2014-04-01

    The pathogenesis of trigger finger has generally been ascribed to primary changes in the first annular ligament. In contrast, we recently found histological changes in the tendons, similar to the findings in Achilles tendinosis or tendinopathy. We therefore hypothesized that trigger finger tendons would show differences in gene expression in comparison to normal tendons in a pattern similar to what is published for Achilles tendinosis. We performed quantitative real-time polymerase chain reaction on biopsies from finger flexor tendons, 13 trigger fingers and 13 apparently healthy control tendons, to assess the expression of 10 genes which have been described to be differently expressed in tendinosis (collagen type 1a1, collagen 3a1, MMP-2, MMP-3, ADAMTS-5, TIMP-3, aggrecan, biglycan, decorin, and versican). In trigger finger tendons, collagen types 1a1 and 3a1, aggrecan and biglycan were all up-regulated, and MMP-3and TIMP-3 were down-regulated. These changes were statistically significant and have been previously described for Achilles tendinosis. The remaining four genes were not significantly altered. The changes in gene expression support the hypothesis that trigger finger is a form of tendinosis. Because trigger finger is a common condition, often treated surgically, it could provide opportunities for clinical research on tendinosis. PMID:22882155

  14. Fingered core structure of nematic boojums

    NASA Astrophysics Data System (ADS)

    Kralj, Samo; Rosso, Riccardo; Virga, Epifanio G.

    2008-09-01

    Using the Landau-de Gennes phenomenological approach, we study the fine biaxial core structure of a boojum residing on the surface of a nematic liquid crystal phase. The core is formed by a negatively uniaxial finger, surrounded by a shell with maximal biaxiality. The characteristic finger’s length and the shell’s width are comparable to the biaxial correlation length. The finger tip is melted for topological reasons. Upon decreasing the surface anchoring strength below a critical value, the finger gradually leaves the bulk and it is expelled through the surface.

  15. Aesthetic finger prosthesis with silicone biomaterial

    PubMed Central

    Raghu, K M; Gururaju, C R; Sundaresh, K J; Mallikarjuna, Rachappa

    2013-01-01

    The fabrication of finger prosthesis is as much an art as it is science. The ideally constructed prosthesis must duplicate the missing structures so precisely that patients can appear in public without fear of attracting unwanted attraction. A 65-years-old patient reported with loss of his right index finger up to the second phalanx and wanted to get it replaced. An impression of the amputated finger and donor were made. A wax pattern of the prosthesis was fabricated using the donor impression; a trial was performed and flasked. Medical grade silicone was intrinsically stained to match the skin tone, following which it was packed, processed and finished. This clinical report describes a method of attaining retention by selective scoring of the master cast of partially amputated finger to enhance the vacuum effect at par with the proportional distribution of the positive forces on the tissues exerted by the prosthesis. PMID:23975917

  16. Finger Cooling During Cold Air Exposure.

    NASA Astrophysics Data System (ADS)

    Tikuisis, Peter

    2004-05-01

    This paper presents a method for predicting the onset of finger freezing. It is an extension of a tissue-cooling model originally developed to predict the onset of cheek freezing. The extension to the finger is presented as a more conservative warning of wind chill. Indeed, guidance on the risk of finger freezing is important not only to safeguard the finger, but also because it pertains more closely to susceptible facial features, such as the nose, than if only the risk of cheek freezing was provided. The importance of blood flow to the finger and the modeling of vaso-constriction are demonstrated through cooling predictions that agree reasonably well with several reported observations. Differences in the prediction between the present physiologic-based model and the engineering model used to develop the wind chill index are also discussed. New wind chill charts are presented that tabulate the mean cooling rates and corresponding onset times to freezing of the finger for various combinations of air temperature and wind speed. Results indicate that the surface of the finger cools to its freezing point in approximately one-eighth of the time predicted for the cheek. For combinations that result in the same wind chill temperature (WCT), the rate of finger cooling is faster at the higher wind speed. This asymmetry was previously disclosed through the application of the model to cheek cooling, and it reiterates the ambiguity associated with the reporting of WCT. It is further emphasized that the reporting of onset times to freezing, or safe exposure limits, is a more logical and meaningful alternative to the WCT.

  17. New Finger Biometric Method Using Near Infrared Imaging

    PubMed Central

    Lee, Eui Chul; Jung, Hyunwoo; Kim, Daeyeoul

    2011-01-01

    In this paper, we propose a new finger biometric method. Infrared finger images are first captured, and then feature extraction is performed using a modified Gaussian high-pass filter through binarization, local binary pattern (LBP), and local derivative pattern (LDP) methods. Infrared finger images include the multimodal features of finger veins and finger geometries. Instead of extracting each feature using different methods, the modified Gaussian high-pass filter is fully convolved. Therefore, the extracted binary patterns of finger images include the multimodal features of veins and finger geometries. Experimental results show that the proposed method has an error rate of 0.13%. PMID:22163741

  18. Finger multibiometric cryptosystems: fusion strategy and template security

    NASA Astrophysics Data System (ADS)

    Peng, Jialiang; Li, Qiong; Abd El-Latif, Ahmed A.; Niu, Xiamu

    2014-03-01

    We address two critical issues in the design of a finger multibiometric system, i.e., fusion strategy and template security. First, three fusion strategies (feature-level, score-level, and decision-level fusions) with the corresponding template protection technique are proposed as the finger multibiometric cryptosystems to protect multiple finger biometric templates of fingerprint, finger vein, finger knuckle print, and finger shape modalities. Second, we theoretically analyze different fusion strategies for finger multibiometric cryptosystems with respect to their impact on security and recognition accuracy. Finally, the performance of finger multibiometric cryptosystems at different fusion levels is investigated on a merged finger multimodal biometric database. The comparative results suggest that the proposed finger multibiometric cryptosystem at feature-level fusion outperforms other approaches in terms of verification performance and template security.

  19. Scattering Removal for Finger-Vein Image Restoration

    PubMed Central

    Yang, Jinfeng; Zhang, Ben; Shi, Yihua

    2012-01-01

    Finger-vein recognition has received increased attention recently. However, the finger-vein images are always captured in poor quality. This certainly makes finger-vein feature representation unreliable, and further impairs the accuracy of finger-vein recognition. In this paper, we first give an analysis of the intrinsic factors causing finger-vein image degradation, and then propose a simple but effective image restoration method based on scattering removal. To give a proper description of finger-vein image degradation, a biological optical model (BOM) specific to finger-vein imaging is proposed according to the principle of light propagation in biological tissues. Based on BOM, the light scattering component is sensibly estimated and properly removed for finger-vein image restoration. Finally, experimental results demonstrate that the proposed method is powerful in enhancing the finger-vein image contrast and in improving the finger-vein image matching accuracy. PMID:22737028

  20. Scattering removal for finger-vein image restoration.

    PubMed

    Yang, Jinfeng; Zhang, Ben; Shi, Yihua

    2012-01-01

    Finger-vein recognition has received increased attention recently. However, the finger-vein images are always captured in poor quality. This certainly makes finger-vein feature representation unreliable, and further impairs the accuracy of finger-vein recognition. In this paper, we first give an analysis of the intrinsic factors causing finger-vein image degradation, and then propose a simple but effective image restoration method based on scattering removal. To give a proper description of finger-vein image degradation, a biological optical model (BOM) specific to finger-vein imaging is proposed according to the principle of light propagation in biological tissues. Based on BOM, the light scattering component is sensibly estimated and properly removed for finger-vein image restoration. Finally, experimental results demonstrate that the proposed method is powerful in enhancing the finger-vein image contrast and in improving the finger-vein image matching accuracy. PMID:22737028

  1. Characterization of Antifungal Natural Products Isolated from Endophytic Fungi of Finger Millet (Eleusine coracana).

    PubMed

    Mousa, Walaa Kamel; Schwan, Adrian L; Raizada, Manish N

    2016-01-01

    Finger millet is an ancient African-Indian crop that is resistant to many pathogens including the fungus, Fusarium graminearum. We previously reported the first isolation of putative fungal endophytes from finger millet and showed that the crude extracts of four strains had anti-Fusarium activity. However, active compounds were isolated from only one strain. The objectives of this study were to confirm the endophytic lifestyle of the three remaining anti-Fusarium isolates, to identify the major underlying antifungal compounds, and to initially characterize the mode(s) of action of each compound. Results of confocal microscopy and a plant disease assay were consistent with the three fungal strains behaving as endophytes. Using bio-assay guided fractionation and spectroscopic structural elucidation, three anti-Fusarium secondary metabolites were purified and characterized. These molecules were not previously reported to derive from fungi nor have antifungal activity. The purified antifungal compounds were: 5-hydroxy 2(3H)-benzofuranone, dehydrocostus lactone (guaianolide sesquiterpene lactone), and harpagoside (an iridoide glycoside). Light microscopy and vitality staining were used to visualize the in vitro interactions between each compound and Fusarium; the results suggested a mixed fungicidal/fungistatic mode of action. We conclude that finger millet possesses fungal endophytes that can synthesize anti-fungal compounds not previously reported as bio-fungicides against F. graminearum. PMID:27598120

  2. Anthropomorphic finger antagonistically actuated by SMA plates.

    PubMed

    Engeberg, Erik D; Dilibal, Savas; Vatani, Morteza; Choi, Jae-Won; Lavery, John

    2015-10-01

    Most robotic applications that contain shape memory alloy (SMA) actuators use the SMA in a linear or spring shape. In contrast, a novel robotic finger was designed in this paper using SMA plates that were thermomechanically trained to take the shape of a flexed human finger when Joule heated. This flexor actuator was placed in parallel with an extensor actuator that was designed to straighten when Joule heated. Thus, alternately heating and cooling the flexor and extensor actuators caused the finger to flex and extend. Three different NiTi based SMA plates were evaluated for their ability to apply forces to a rigid and compliant object. The best of these three SMAs was able to apply a maximum fingertip force of 9.01N on average. A 3D CAD model of a human finger was used to create a solid model for the mold of the finger covering skin. Using a 3D printer, inner and outer molds were fabricated to house the actuators and a position sensor, which were assembled using a multi-stage casting process. Next, a nonlinear antagonistic controller was developed using an outer position control loop with two inner MOSFET current control loops. Sine and square wave tracking experiments demonstrated minimal errors within the operational bounds of the finger. The ability of the finger to recover from unexpected disturbances was also shown along with the frequency response up to 7 rad s(-1). The closed loop bandwidth of the system was 6.4 rad s(-1) when operated intermittently and 1.8 rad s(-1) when operated continuously. PMID:26292164

  3. Design and preliminary evaluation of the FINGER rehabilitation robot: controlling challenge and quantifying finger individuation during musical computer game play

    PubMed Central

    2014-01-01

    Background This paper describes the design and preliminary testing of FINGER (Finger Individuating Grasp Exercise Robot), a device for assisting in finger rehabilitation after neurologic injury. We developed FINGER to assist stroke patients in moving their fingers individually in a naturalistic curling motion while playing a game similar to Guitar Hero®a. The goal was to make FINGER capable of assisting with motions where precise timing is important. Methods FINGER consists of a pair of stacked single degree-of-freedom 8-bar mechanisms, one for the index and one for the middle finger. Each 8-bar mechanism was designed to control the angle and position of the proximal phalanx and the position of the middle phalanx. Target positions for the mechanism optimization were determined from trajectory data collected from 7 healthy subjects using color-based motion capture. The resulting robotic device was built to accommodate multiple finger sizes and finger-to-finger widths. For initial evaluation, we asked individuals with a stroke (n = 16) and without impairment (n = 4) to play a game similar to Guitar Hero® while connected to FINGER. Results Precision design, low friction bearings, and separate high speed linear actuators allowed FINGER to individually actuate the fingers with a high bandwidth of control (−3 dB at approximately 8 Hz). During the tests, we were able to modulate the subject’s success rate at the game by automatically adjusting the controller gains of FINGER. We also used FINGER to measure subjects’ effort and finger individuation while playing the game. Conclusions Test results demonstrate the ability of FINGER to motivate subjects with an engaging game environment that challenges individuated control of the fingers, automatically control assistance levels, and quantify finger individuation after stroke. PMID:24495432

  4. Ultrafast High-Resolution Mass Spectrometric Finger Pore Imaging in Latent Finger Prints

    PubMed Central

    Elsner, Christian; Abel, Bernd

    2014-01-01

    Latent finger prints (LFPs) are deposits of sweat components in ridge and groove patterns, left after human fingers contact with a surface. Being important targets in biometry and forensic investigations they contain more information than topological patterns. With laser desorption mass spectrometry imaging (LD-MSI) we record ‘three-dimensional' finger prints with additional chemical information as the third dimension. Here we show the potential of fast finger pore imaging (FPI) in latent finger prints employing LD-MSI without a classical matrix in a high- spatial resolution mode. Thin films of gold rapidly sputtered on top of the sample are used for desorption. FPI employing an optical image for rapid spatial orientation and guiding of the desorption laser enables the rapid analysis of individual finger pores, and the chemical composition of their excretions. With this approach we rapidly detect metabolites, drugs, and characteristic excretions from the inside of the human organism by a minimally-invasive strategy, and distinguish them from chemicals in contact with fingers without any labeling. The fast finger pore imaging, analysis, and screening approach opens the door for a vast number of novel applications in such different fields as forensics, doping and medication control, therapy, as well as rapid profiling of individuals. PMID:25366032

  5. Ultrafast high-resolution mass spectrometric finger pore imaging in latent finger prints.

    PubMed

    Elsner, Christian; Abel, Bernd

    2014-01-01

    Latent finger prints (LFPs) are deposits of sweat components in ridge and groove patterns, left after human fingers contact with a surface. Being important targets in biometry and forensic investigations they contain more information than topological patterns. With laser desorption mass spectrometry imaging (LD-MSI) we record 'three-dimensional' finger prints with additional chemical information as the third dimension. Here we show the potential of fast finger pore imaging (FPI) in latent finger prints employing LD-MSI without a classical matrix in a high- spatial resolution mode. Thin films of gold rapidly sputtered on top of the sample are used for desorption. FPI employing an optical image for rapid spatial orientation and guiding of the desorption laser enables the rapid analysis of individual finger pores, and the chemical composition of their excretions. With this approach we rapidly detect metabolites, drugs, and characteristic excretions from the inside of the human organism by a minimally-invasive strategy, and distinguish them from chemicals in contact with fingers without any labeling. The fast finger pore imaging, analysis, and screening approach opens the door for a vast number of novel applications in such different fields as forensics, doping and medication control, therapy, as well as rapid profiling of individuals. PMID:25366032

  6. Ultrafast High-Resolution Mass Spectrometric Finger Pore Imaging in Latent Finger Prints

    NASA Astrophysics Data System (ADS)

    Elsner, Christian; Abel, Bernd

    2014-11-01

    Latent finger prints (LFPs) are deposits of sweat components in ridge and groove patterns, left after human fingers contact with a surface. Being important targets in biometry and forensic investigations they contain more information than topological patterns. With laser desorption mass spectrometry imaging (LD-MSI) we record `three-dimensional' finger prints with additional chemical information as the third dimension. Here we show the potential of fast finger pore imaging (FPI) in latent finger prints employing LD-MSI without a classical matrix in a high- spatial resolution mode. Thin films of gold rapidly sputtered on top of the sample are used for desorption. FPI employing an optical image for rapid spatial orientation and guiding of the desorption laser enables the rapid analysis of individual finger pores, and the chemical composition of their excretions. With this approach we rapidly detect metabolites, drugs, and characteristic excretions from the inside of the human organism by a minimally-invasive strategy, and distinguish them from chemicals in contact with fingers without any labeling. The fast finger pore imaging, analysis, and screening approach opens the door for a vast number of novel applications in such different fields as forensics, doping and medication control, therapy, as well as rapid profiling of individuals.

  7. Miscible viscous fingering involving production of gel by chemical reactions

    NASA Astrophysics Data System (ADS)

    Nagatsu, Yuichiro; Hoshino, Kenichi

    2015-11-01

    We have experimentally investigated miscible viscous fingering with chemical reactions producing gel. Here, two systems were employed. In one system, sodium polyacrylate (SPA) solution and aluminum ion (Al3 +) solution were used as the more and less viscous liquids, respectively. In another system, SPA solution and ferric ion (Fe3 +) solution were used as the more and less viscous liquids, respectively. In the case of Al3 +, displacement efficiency was smaller than that in the non-reactive case, whereas in the case of Fe3 +, the displacement efficiency was larger. We consider that the difference in change of the patterns in the two systems will be caused by the difference in the properties of the gels. Therefore, we have measured the rheological properties of the gels by means of a rheometer. We discuss relationship between the VF patterns and the rheological measurement.

  8. Reconstruction of Extensive Volar Finger Defects with Double Cross-Finger Flaps

    PubMed Central

    Buehrer, Gregor; Arkudas, Andreas; Ludolph, Ingo; Horch, Raymund E.

    2016-01-01

    Summary: Cross-finger flaps still represent a viable option to reconstruct small- to medium-sized full-thickness finger defects but they are not commonly used if larger areas have to be covered. We present 2 cases showing a simple and pragmatic approach with homodigital double cross-finger flaps to reconstruct extensive volar finger soft-tissue defects. We observed very low donor-site morbidity and excellent functional and aesthetic outcomes. Furthermore, there is no need for microsurgical techniques or equipment when using this method. Although this case report only addresses volar defects, one might also think of applying this concept to dorsal defects using reversed double cross-finger flaps. PMID:27200255

  9. Solid-state Forensic Finger sensor for integrated sampling and detection of gunshot residue and explosives: towards 'Lab-on-a-finger'.

    PubMed

    Bandodkar, Amay J; O'Mahony, Aoife M; Ramírez, Julian; Samek, Izabela A; Anderson, Sean M; Windmiller, Joshua R; Wang, Joseph

    2013-09-21

    Increasing security needs require field-deployable, on-the-spot detection tools for the rapid and reliable identification of gunshot residue (GSR) and nitroaromatic explosive compounds. This manuscript presents a simple, all-solid-state, wearable fingertip sensor for the rapid on-site voltammetric screening of GSR and explosive surface residues. To fabricate the new Forensic Fingers, we screen-print a three-electrode setup onto a nitrile finger cot, and coat another finger cot with an ionogel electrolyte layer. The new integrated sampling/detection methodology relies on 'voltammetry of microparticles' (VMP) and involves an initial mechanical transfer of trace amounts of surface-confined analytes directly onto the fingertip-based electrode contingent. Voltammetric measurements of the sample residues are carried out upon bringing the working electrode (printed on the index finger cot) in direct contact with a second finger cot coated with an ionogel electrolyte (worn on the thumb), thus completing the solid-state electrochemical cell. Sampling and screening are performed in less than four minutes and generate distinct voltammetric fingerprints which are specific to both GSR and explosives. The use of the solid, flexible ionogel electrolyte eliminates any liquid handling which can resolve problems associated with leakage, portability and contamination. A detailed study reveals that the fingertip detection system can rapidly identify residues of GSR and nitroaromatic compounds with high specificity, without compromising its attractive behavior even after undergoing repeated mechanical stress. This new integrated sampling/detection fingertip strategy holds considerable promise as a rapid, effective and low-cost approach for on-site crime scene investigations in various forensic scenarios. PMID:23865089

  10. Perceiving fingers in single-digit arithmetic problems.

    PubMed

    Berteletti, Ilaria; Booth, James R

    2015-01-01

    In this study, we investigate in children the neural underpinnings of finger representation and finger movement involved in single-digit arithmetic problems. Evidence suggests that finger representation and finger-based strategies play an important role in learning and understanding arithmetic. Because different operations rely on different networks, we compared activation for subtraction and multiplication problems in independently localized finger somatosensory and motor areas and tested whether activation was related to skill. Brain activations from children between 8 and 13 years of age revealed that only subtraction problems significantly activated finger motor areas, suggesting reliance on finger-based strategies. In addition, larger subtraction problems yielded greater somatosensory activation than smaller problems, suggesting a greater reliance on finger representation for larger numerical values. Interestingly, better performance in subtraction problems was associated with lower activation in the finger somatosensory area. Our results support the importance of fine-grained finger representation in arithmetical skill and are the first neurological evidence for a functional role of the somatosensory finger area in proficient arithmetical problem solving, in particular for those problems requiring quantity manipulation. From an educational perspective, these results encourage investigating whether different finger-based strategies facilitate arithmetical understanding and encourage educational practices aiming at integrating finger representation and finger-based strategies as a tool for instilling stronger numerical sense. PMID:25852582

  11. Tide-induced fingering flow during submarine groundwater discharge

    NASA Astrophysics Data System (ADS)

    Greskowiak, Janek

    2013-04-01

    range of 2 m initiates fingering flow. Flatter beach slope, higher hydraulic conductivity and increasing tidal range support this behavior. In the cases of fingering flow, freshwater is squeezed upward and pinches out within the inter-tidal zone. Once pinched out, the discharge point slowly moves along at the beach surface towards the low-tide mark. Overall, the fingering process further complicates the flow pattern and the mixing of salt and freshwater in the inter-tidal zone compared to the cases where the saline recirculation cell remains stable. This may have an important implication for the hydrogeochemical processes in this zone and thus the mass flux of reactive chemicals from the land to the ocean. Boufadel, M. C. (2000). A mechanistic study of nonlinear solute transport in a groundwater-surface water system under steady state and transient hydraulic conditions, Water Resour. Res., 36(9), 2549 2565. Bratton, J.F. (2010). The Three Scales of Submarine Groundwater Flow and Discharge across Passive Continental Margins, The Journal of Geology, 2010, 118, 565-575. Kuan, W. K., G. Jin, P. Xin, C. Robinson, B. Gibbes, and L. Li (2012). Tidal influence on seawater intrusion in unconfined coastal aquifers, Water Resour. Res., 48, W02502, doi:10.1029/2011WR010678. Langevin, C.D., D.T. Thorne, Jr., A.M. Dausman, M.C. Sukop, and G. Weixing (2007). Seawat version 4: a computer program for simulation of multi-species solute and heat transport, Technical Report, U.S. Geological Survey Techniques and Methods Book 6, Chapter A22, 39 pp. Robinson, C., L. Li, and H. Prommer (2007). Tide-induced recirculation across the aquifer-ocean interface, Water Resour. Res., 43, W07428, doi:10.1029/2006WR005679. Moore, W.S. (2010). The Effect of Submarine Groundwater Discharge on the Ocean, Annu. Rev. Mar. Sci., 2, 59-88.

  12. Finger millet [Eleusine coracana (L.) Gaertn].

    PubMed

    Ceasar, Stanislaus Antony; Ignacimuthu, Savarimuthu

    2015-01-01

    Millets are the primary food source for millions of people in tropical regions of the world supplying mineral nutrition and protein. In this chapter, we describe an optimized protocol for the Agrobacterium-mediated transformation of finger millet variety GPU 45. Agrobacterium strain LBA4404 harboring plasmid pCAMBIA1301 which contains hygromycin phosphotransferase (hph) as selectable marker gene and β-glucuronidase (GUS) as reporter gene has been used. This protocol utilizes the shoot apex explants for the somatic embryogenesis and regeneration of finger millet after the transformation by Agrobacterium. Desiccation of explants during cocultivation helps for the better recovery of transgenic plants. This protocol is very useful for the efficient production of transgenic plants in finger millet through Agrobacterium-mediated transformation. PMID:25300836

  13. Axon reflexes in human cold exposed fingers.

    PubMed

    Daanen, H A; Ducharme, M B

    2000-02-01

    Exposure of fingers to severe cold induces cold induced vasodilatation (CIVD). The mechanism of CIVD is still debated. The original theory states that an axon reflex causes CIVD. To test this hypothesis, axon reflexes were evoked by electrical stimulation of the middle fingers of hands immersed in water at either 5 degrees C or 35 degrees C. Axon reflexes were pronounced in the middle finger of the hand in warm water, but absent from the hand in cold water, even though the stimulation was rated as "rather painful" to "painful". These results showed that axon reflexes do not occur in a cold-exposed hand and thus are unlikely to explain the CIVD phenomenon. PMID:10638384

  14. Reactive Leidenfrost droplets

    NASA Astrophysics Data System (ADS)

    Raufaste, C.; Bouret, Y.; Celestini, F.

    2016-05-01

    We experimentally investigate the reactivity of Leidenfrost droplets with their supporting substrates. Several organic liquids are put into contact with a copper substrate heated above their Leidenfrost temperature. As the liquid evaporates, the gaseous flow cleans the superficial copper oxide formed at the substrate surface and the reaction maintains a native copper spot below the evaporating droplet. The copper spot can reach several times the droplet size for the most reactive organic compounds. This study shows an interesting coupling between the physics of the Leidenfrost effect and the mechanics of reactive flows. Different applications are proposed such as drop motion tracking and vapor flow monitoring.

  15. Sensitivity-Based VOC Reactivity Calculation

    EPA Science Inventory

    Volatile Organic Compound (VOC) reactivity scales are used to compare the ozone-forming potentials of various compounds. The comparison allows for substitution of compounds to lessen formation of ozone from paints, solvents, and other products. Current reactivity scales for VOC c...

  16. A reverse flow cross finger pedicle skin flap from hemidorsum of finger.

    PubMed

    Mishra, Satyanarayan; Manisundaram, S

    2010-04-01

    A reverse-flow cross-finger pedicle skin flap raised from the hemidorsum has been used, which is a modification of the distally based dorsal cross-finger flap. The flap is raised from the hemidorsum at a plane above the paratenon, the distal-most location of the base being at the level of the distal interphalangeal joint. Thirty-two flaps were used from as many fingers of as many patients. Of these, 31 (97%) flaps survived fully; there was stiffness of finger in one (3%) patient and the two-point discrimination was 4-8mm (n=14). Follow-up period was 2 months to 3 years, the median being 1 year and 3 months. The advantages of this flap are that there is less disruption of veins and less visible disfigurement of the dorsum of the finger when compared to other pedicled cross-finger skin flaps. The disadvantage of this flap is its restricted width. It is recommended as the cross-finger pedicle skin flap of choice when the defect is not wide. PMID:19386561

  17. Thermoregulatory control of finger blood flow

    NASA Technical Reports Server (NTRS)

    Wenger, C. B.; Roberts, M. F.; Nadel, E. R.; Stolwijk, J. A. J.

    1975-01-01

    In the present experiment, exercise was used to vary internal temperature and ambient air heat control was used to vary skin temperature. Finger temperature was fixed at about 35.7 C. Esophageal temperature was measured with a thermocouple at the level of the left atrium, and mean skin temperature was calculated from a weighted mean of thermocouple temperatures at different skin sites. Finger blood flow was measured by electrocapacitance plethysmography. An equation in these quantities is given which accounts for the data garnered.

  18. Interaction of finger enslaving and error compensation in multiple finger force production

    PubMed Central

    Martin, Joel R.; Latash, Mark L.; Zatsiorsky, Vladimir M.

    2009-01-01

    Previous studies have documented two patterns of finger interaction during multi-finger pressing tasks, enslaving and error compensation, which do not agree with each other. Enslaving is characterized by positive correlation between instructed (master) and non-instructed (slave) finger(s) while error compensation can be described as a pattern of negative correlation between master and slave fingers. We hypothesize that pattern of finger interaction, enslaving or compensation, depends on the initial force level and the magnitude of the targeted force change. Subjects were instructed to press with four fingers (I - index, M - middle, R - ring, and L - little) from a specified initial force to a target forces following a ramp target line. Force-force relations between master and each of three slave fingers were analyzed during the ramp phase of trials by calculating correlation coefficients within each master-slave pair and then 2-factor ANOVA was performed to determine effect of initial force and force increase on the correlation coefficients. It was found that, as initial force increased, the value of the correlation coefficient decreased and in some cases became negative, i.e. the enslaving transformed into error compensation. Force increase magnitude had a smaller effect on the correlation coefficients. The observations support the hypothesis that the pattern of inter-finger interaction—enslaving or compensation—depends on the initial force level and, to a smaller degree, on the targeted magnitude of the force increase. They suggest that the controller views tasks with higher steady-state forces and smaller force changes as implying a requirement to avoid large changes in the total force. PMID:18985331

  19. Compilation and evaluation of gas-phase diffusion coefficients of reactive trace gases in the atmosphere: volume 2. Organic compounds and Knudsen numbers for gas uptake calculations

    NASA Astrophysics Data System (ADS)

    Tang, M. J.; Shiraiwa, M.; Pöschl, U.; Cox, R. A.; Kalberer, M.

    2015-02-01

    Diffusion of organic vapours to the surface of aerosol or cloud particles is an important step for the formation and transformation of atmospheric particles. So far, however, a database of gas phase diffusion coefficients for organic compounds of atmospheric interest has not been available. In this work we have compiled and evaluated gas phase diffusivities (pressure-independent diffusion coefficients) of organic compounds reported by previous experimental studies, and we compare the measurement data to estimates obtained with Fuller's semi-empirical method. The difference between measured and estimated diffusivities are mostly < 10%. With regard to gas-particle interactions, different gas molecules, including both organic and inorganic compounds, exhibit similar Knudsen numbers (Kn) although their gas phase diffusivities may vary over a wide range. Knudsen numbers of gases with unknown diffusivity can be approximated by a simple function of particle diameter and pressure and can be used to characterize the influence of diffusion on gas uptake by aerosol or cloud particles. We use a kinetic multi-layer model of gas-particle interaction to illustrate the effects of gas phase diffusion on the condensation of organic compounds with different volatilities. The results show that gas-phase diffusion can play a major role in determining the growth of secondary organic aerosol particles by condensation of low-volatility organic vapours.

  20. Probing the Reactivity of Dimethylsulfoxonium Methylide with Conjugated and Nonconjugated Carbonyl Compounds: An Undergraduate Experiment Combining Synthesis, Spectral Analysis, and Mechanistic Discovery

    ERIC Educational Resources Information Center

    Ciaccio, James A.; Guevara, Elena L.; Alam, Rabeka; D'agrosa, Christina D.

    2010-01-01

    We introduce students to dimethylsulfoxonium methylide (DMSY) epoxidation of aryl and nonconjugated aliphatic aldehydes and ketones without revealing that DMSY cyclopropanates enones by Michael-initiated ring closure (MIRC). Each student performs the reaction of DMSY with one of nine carbonyl compounds, including four enones, and then analyzes the…

  1. Sticky fingers: Adhesive properties of human fingertips.

    PubMed

    Spinner, Marlene; Wiechert, Anke B; Gorb, Stanislav N

    2016-02-29

    Fingertip friction is a rather well studied subject. Although the phenomenon of finger stickiness is known as well, the pull-off force and the adhesive strength of human finger tips have never been previously quantified. For the first time, we provided here characterization of adhesive properties of human fingers under natural conditions. Human fingers can generate a maximum adhesive force of 15mN on a smooth surface of epoxy resin. A weak correlation of the adhesive force and the normal force was found on all test surfaces. Up to 300mN load, an increase of the normal force leads to an increase of the adhesive force. On rough surfaces, the adhesive strength is significantly reduced. Our data collected from untreated hands give also an impression of an enormous scattering of digital adhesion depending on a large set of inter-subject variability and time-dependent individual factors (skin texture, moisture level, perspiration). The wide inter- and intra-individual range of digital adhesion should be considered in developing of technical and medical products. PMID:26892897

  2. Fingerspell: Let Your Fingers Do the Talking

    ERIC Educational Resources Information Center

    Scarlatos, Tony; Nesterenko, Dmitri

    2004-01-01

    In this article we discuss an application that translates hand gestures of the American Sign Language (ASL) alphabet and converts them to text. The FingerSpell application addresses the communication barrier of the deaf and the hearing-impaired by eliminating the need for a third party with knowledge of the American Sign Language, allowing a user…

  3. Fingers Make a Comeback in Math

    ERIC Educational Resources Information Center

    Brooks, Andree

    1978-01-01

    Describes a new idea in finger-counting developed by 31 year old Hang Young Pai, a Korean teacher living in New York. It is called Chisanbop and it comes from a more advanced hand-calculation system used in the Orient in conjunction with the abacus. It is applicable for both elementary students and for more advanced mathematical applications, such…

  4. Finger arterial pressure measurement with Finapres.

    PubMed

    Wesseling, K H

    1996-01-01

    Finger arterial pressure measurement with Finapres has been available since a decade. Its availability has promoted at least 300 methodological and research papers over these years, outlining the usefulness and the limitations of the method and the device. Finapres is based on the volume clamp method of Peñáz and the Physiocal criteria of Wesseling. Tracking of intraarterial pressure is usually satisfactory even under conditions of strongly changing hemodynamics and high and very low blood pressures. Finapres accuracy is similar to that of other non-invasive methods. Systolic pressure levels scatter more than mean and diastolic levels. One source of error is physiologic and determined by the peripheral measurement site of the finger, causing pulse waveform distortion and a pressure gradient. The Finapres waveform can be filtered, however, to obtain a brachial pressure wave. This decreases systolic scatter under vaso-constrictive drug infusion and dynamic exercise to exhaustion, conditions where precision of systolic tracking has been criticized in the literature. Recently, level correction techniques were found which shift finger pressure up or down based on a regression equation with finger systolic and diastolic pressures. This procedure requires no additional measurements yet improves systolic, diastolic and mean level accuracy and precision remarkably. Finally, we show how to judge the quality of a Finapres recording from the behavior of Physiocal. PMID:8896298

  5. Viscous fingering with partial miscible fluids

    NASA Astrophysics Data System (ADS)

    Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

    2015-11-01

    When a less viscous fluid displaces a more viscous fluid, the contrast in viscosity destabilizes the interface between the two fluids, leading to the formation of fingers. Studies of viscous fingering have focused on fluids that are either fully miscible or perfectly immiscible. In practice, however, the miscibility of two fluids can change appreciably with temperature and pressure, and often falls into the case of partial miscibility, where two fluids have limited solubility in each other. Following our recent work for miscible (Jha et al., PRL 2011, 2013) and immiscible systems (Cueto-Felgueroso and Juanes, PRL 2012, JFM 2014), here we propose a phase-field model for fluid-fluid displacements in a Hele-Shaw cell, when the two fluids have limited (but nonzero) solubility in one another. Partial miscibility is characterized through the design of thermodynamic free energy of the two-fluid system. We elucidate the key dimensionless groups that control the behavior of the system. We present high-resolution numerical simulations of the model applied to the viscous fingering problem. On one hand, we demonstrate the effect of partial miscibility on the hydrodynamic instability. On the other, we elucidate the role of the degree of fingering on the rate of mutual fluid dissolution.

  6. Fjord geometry observed in viscous fingering*

    NASA Astrophysics Data System (ADS)

    Thrasher, Matt; Ristroph, Leif; Swinney, Harry L.; Mineev-Weinstein, Mark

    2004-11-01

    Injecting a less viscous fluid (air) into a more viscous fluid (oil) produces an unstable finger of air penetrating into the oil. For sufficiently large forcing, the tip of a finger splits. The region of oil left between adjacent fingers is called a fjord. We characterize the width, widening, and bending of fjords in experiments in a rectangular Hele-Shaw cell. The channel confines air and 50 cS silicone oil between two glass plates, which are 2500 mm long and 250 mm wide with a separation of 0.5 mm. The width of the base of a fjord is found to be approximately one-half of the capillary length scale. From this base, the fjords open with a distribution of angles having a mean of about 9 ^rc, which contradicts theoretical predictions of an opening angle of 0 ^rc (parallel sides). Finally, the centerline of a fjord bends. Lajeunesse and Couder [1] account for the bending of a fjord on a single, one-half width finger. We test the validity of their idea on the tip-splitting of more complicated interfaces and on the widening of fjords. *Supported by ONR [1] E. Lajeunesse and Y. Couder, J. Fluid. Mech. 419, 125 (2000).

  7. Fingering phenomena during grain-grain displacement

    NASA Astrophysics Data System (ADS)

    Mello, Nathália M. P.; Paiva, Humberto A.; Combe, G.; Atman, A. P. F.

    2016-05-01

    Spontaneous formation of fingered patterns during the displacement of dense granular assemblies was experimentally reported few years ago, in a radial Hele-Shaw cell. Here, by means of discrete element simulations, we have recovered the experimental findings and extended the original study to explore the control parameters space. In particular, using assemblies of grains with different geometries (monodisperse, bidisperse, or polydisperse), we measured the macroscopic stress tensor in the samples in order to confirm some conjectures proposed in analogy with Saffman-Taylor viscous fingering phenomena for immiscible fluids. Considering an axial setup which allows to control the discharge of grains and to follow the trajectory and the pressure gradient along the displacing interface, we have applied the Darcy law for laminar flow in fluids in order to measure an "effective viscosity" for each assembly combination, in an attempt to mimic variation of the viscosity ratio between the injected/displaced fluids in the Saffman-Taylor experiment. The results corroborate the analogy with the viscous fluids displacement, with the bidisperse assembly corresponding to the less viscous geometry. But, differently to fluid case, granular fingers only develop for a specific combination of displaced/injected geometries, and we have demonstrated that it is always related with the formation of a force chain network along the finger direction.

  8. Compact Tactile Sensors for Robot Fingers

    NASA Technical Reports Server (NTRS)

    Martin, Toby B.; Lussy, David; Gaudiano, Frank; Hulse, Aaron; Diftler, Myron A.; Rodriguez, Dagoberto; Bielski, Paul; Butzer, Melisa

    2004-01-01

    Compact transducer arrays that measure spatial distributions of force or pressure have been demonstrated as prototypes of tactile sensors to be mounted on fingers and palms of dexterous robot hands. The pressure- or force-distribution feedback provided by these sensors is essential for the further development and implementation of robot-control capabilities for humanlike grasping and manipulation.

  9. Finger force perception during ipsilateral and contralateral force matching tasks

    PubMed Central

    Park, Woo-Hyung; Leonard, Charles T.; Li, Sheng

    2010-01-01

    The aims of the present study were to compare matching performance between ipsilateral and contralateral finger force matching tasks and to examine the effect of handedness on finger force perception. Eleven subjects were instructed to produce reference forces by an instructed finger (index – I or little – L finger) and to reproduce the same amount force by the same or a different finger within the hand (i.e., ipsilateral matching task), or by a finger of the other hand (i.e., contralateral matching task). The results of the ipsilateral and contralateral tasks in the present study commonly showed that 1) the reference and matching forces were matched closely when the two forces were produced by the same or homologous finger(s) such as I/I task; 2) the weaker little finger underestimated the magnitude of reference force of the index finger (I/L task), even with the higher level of effort (relative force), but the two forces were matched when considering total finger forces; 3) the stronger index finger closely matched the reference force of the little finger with the lower level of relative force (i.e., L/I task); 4) when considering the constant errors, I/L tasks showed an underestimation and L/I tasks showed an overestimation compared to I/I tasks. There was no handedness effect during ipsilateral tasks. During the contralateral task, the dominant hand overestimated the force of the non-dominant hand, while the non-dominant hand attempted to match the absolute force of the dominant hand. The overall results support the notion that the absolute, rather than relative, finger force is perceived and reproduced during ipsilateral and contralateral finger force matching tasks, indicating the uniqueness of finger force perception. PMID:18488212

  10. Effect of olive mill wastewater phenol compounds on reactive carbonyl species and Maillard reaction end-products in ultrahigh-temperature-treated milk.

    PubMed

    Troise, Antonio Dario; Fiore, Alberto; Colantuono, Antonio; Kokkinidou, Smaro; Peterson, Devin G; Fogliano, Vincenzo

    2014-10-15

    Thermal processing and Maillard reaction (MR) affect the nutritional and sensorial qualities of milk. In this paper an olive mill wastewater phenolic powder (OMW) was tested as a functional ingredient for inhibiting MR development in ultrahigh-temperature (UHT)-treated milk. OMW was added to milk at 0.1 and 0.05% w/v before UHT treatment, and the concentration of MR products was monitored to verify the effect of OMW phenols in controlling the MR. Results revealed that OMW is able to trap the reactive carbonyl species such as hydroxycarbonyls and dicarbonyls, which in turn led to the increase of Maillard-derived off-flavor development. The effect of OMW on the formation of Amadori products and N-ε-(carboxymethyl)-lysine (CML) showed that oxidative cleavage, C2-C6 cyclization, and the consequent reactive carbonyl species formation were also inhibited by OMW. Data indicated that OMW is a functional ingredient able to control the MR and to improve the nutritional and sensorial attributes of milk. PMID:25280240

  11. Setting tool with retractable torque fingers

    SciTech Connect

    Nevels, D.L.; Baugh, J.L.

    1986-07-08

    A method is described of setting a liner in a well bore using a setting tool of the type adapted to be made up in a pipe string for releasably engaging a setting sleeve in a well bore, comprising the steps of: connecting a mandrel in the pipe string which has a setting nut with external connecting threads for engaging mating connecting threads located on the interior of a setting sleeve disposed about the mandrel, the mandrel being slidably disposed within the setting nut when the setting nut is engaging the setting sleeve, the mandrel being slidable between an extended, running-in position and a weight set-down position; mounting a torque collar on the mandrel exterior, the torque collar having at least one torque finger mounted thereon which is axially slidable on an external surface of the torque collar in a plane which is parallel to the longitudinal axis of the tool, the setting sleeve having at least one end notch adapted to receive the axially slidable torque finger; initially latching the mandrel to the setting sleeve with each torque finger received within its respective end notch; setting weight down on the pipe string from the well surface to release the latch and allow relative movement between the connecting threads of the setting nut and setting sleeve; applying right hand torque to the pipe string to release the connecting threads of the setting nut from the setting sleeve; temporarily lifting the pipe string and setting tool to test the disengagement of the setting nut; again resting the setting tool on the setting sleeve; rotating the pipe string to realign the torque finger and the setting sleeve end notch and reengage the torque finger with the end notch; and continuing to rotate to the right to rotate the setting sleeve during subsequent well bore operations.

  12. A dowel exercise tool to improve finger range of motion.

    PubMed

    Zavala, Paul

    2014-01-01

    A new clinical and home dowel exercise tool to reduce joint stiffness of the fingers is introduced, along with the fabrication and the exercises that are used with it. Patients may utilize it to improve their finger joint range of motion, and facilitate tendon glide by isolating the targeted stiff joints of the fingers. PMID:24044953

  13. Robot-assisted Guitar Hero for finger rehabilitation after stroke.

    PubMed

    Taheri, Hossein; Rowe, Justin B; Gardner, David; Chan, Vicky; Reinkensmeyer, David J; Wolbrecht, Eric T

    2012-01-01

    This paper describes the design and testing of a robotic device for finger therapy after stroke: FINGER (Finger Individuating Grasp Exercise Robot). FINGER makes use of stacked single degree-of-freedom mechanisms to assist subjects in moving individual fingers in a naturalistic grasping pattern through much of their full range of motion. The device has a high bandwidth of control (-3dB at approximately 8 Hz) and is backdriveable. These characteristics make it capable of assisting in grasping tasks that require precise timing. We therefore used FINGER to assist individuals with a stroke (n= 8) and without impairment (n= 4) in playing a game similar to Guitar Hero©. The subjects attempted to move their fingers to target positions at times specified by notes that were graphically streamed to popular music. We show here that by automatically adjusting the robot gains, it is possible to use FINGER to modulate the subject's success rate at the game, across a range of impairment levels. Modulating success rates did not alter the stroke subject's effort, although the unimpaired subjects exerted more force when they were made less successful. We also present a novel measure of finger individuation that can be assessed as individuals play Guitar Hero with FINGER. The results demonstrate the ability of FINGER to provide controlled levels of assistance during an engaging computer game, and to quantify finger individuation after stroke. PMID:23366783

  14. 21 CFR 888.3230 - Finger joint polymer constrained prosthesis.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Finger joint polymer constrained prosthesis. 888... SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3230 Finger joint polymer constrained prosthesis. (a) Identification. A finger joint polymer constrained prosthesis is a device...

  15. 21 CFR 888.3230 - Finger joint polymer constrained prosthesis.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Finger joint polymer constrained prosthesis. 888... SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3230 Finger joint polymer constrained prosthesis. (a) Identification. A finger joint polymer constrained prosthesis is a device...

  16. 21 CFR 888.3230 - Finger joint polymer constrained prosthesis.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Finger joint polymer constrained prosthesis. 888... SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3230 Finger joint polymer constrained prosthesis. (a) Identification. A finger joint polymer constrained prosthesis is a device...

  17. 21 CFR 888.3230 - Finger joint polymer constrained prosthesis.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Finger joint polymer constrained prosthesis. 888... SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3230 Finger joint polymer constrained prosthesis. (a) Identification. A finger joint polymer constrained prosthesis is a device...

  18. Pressure Balanced, Low Hysteresis Finger Seal Test Results

    NASA Technical Reports Server (NTRS)

    Arora, Gul K.; Proctor, Margaret; Steinetz, Bruce M.; Delgado, Irebert R.

    2000-01-01

    The purpose of this presentation is to demonstrate: low cost photoetching fabrication technique; pressure balanced finger seal design; and finger seal operation. The tests and analyses includes: finger seal air leakage analysis; rotor-run out and endurance tests; and extensive analytical work and rig testing.

  19. Left hand finger force in violin playing: tempo, loudness, and finger differences.

    PubMed

    Kinoshita, Hiroshi; Obata, Satoshi

    2009-07-01

    A three-dimensional force transducer was installed in the neck of a violin under the A string at the D5 position in order to study the force with which the violinist clamps the string against the fingerboard under normal playing conditions. Violinists performed repetitive sequences of open A- and fingered D-tones using the ring finger at tempi of 1, 2, 4, 8, and 16 notes/s at mezzo-forte. At selected tempi, the effects of dynamic level and the use of different fingers were investigated as well. The force profiles were clearly dependent on tempo and dynamic level. At slow tempi, the force profiles were characterized by an initial pulse followed by a level force to the end of the finger contact period. At tempi higher than 2 Hz, only pulsed profiles were observed. The peak force exceeded 4.5 N at 1 and 2 Hz and decreased to 1.7 N at 16 Hz. All force and impulse values were lower at softer dynamic levels, and when using the ring or little finger compared to the index finger. PMID:19603895

  20. The influence of radiation-induced vacancy on the formation of thin-film of compound layer during a reactive diffusion process

    NASA Astrophysics Data System (ADS)

    Akintunde, S. O.; Selyshchev, P. A.

    2016-05-01

    A theoretical approach is developed that describes the formation of a thin-film of AB-compound layer under the influence of radiation-induced vacancy. The AB-compound layer is formed as a result of a chemical reaction between the atomic species of A and B immiscible layers. The two layers are irradiated with a beam of energetic particles and this process leads to several vacant lattice sites creation in both layers due to the displacement of lattice atoms by irradiating particles. A- and B-atoms diffuse via these lattice sites by means of a vacancy mechanism in considerable amount to reaction interfaces A/AB and AB/B. The reaction interfaces increase in thickness as a result of chemical transformation between the diffusing species and surface atoms (near both layers). The compound layer formation occurs in two stages. The first stage begins as an interfacial reaction controlled process, and the second as a diffusion controlled process. The critical thickness and time are determined at a transition point between the two stages. The influence of radiation-induced vacancy on layer thickness, speed of growth, and reaction rate is investigated under irradiation within the framework of the model presented here. The result obtained shows that the layer thickness, speed of growth, and reaction rate increase strongly as the defect generation rate rises in the irradiated layers. It also shows the feasibility of producing a compound layer (especially in near-noble metal silicide considered in this study) at a temperature below their normal formation temperature under the influence of radiation.

  1. Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands

    SciTech Connect

    Wang, Xiaoping; Richmond, Michael G.; Hunt, Sean W

    2009-01-01

    Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). Compounds 2 C4 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2 C4 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been established by MO calculations at the extended H ckel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives.

  2. Determination of direct photolysis rate constants and OH radical reactivity of representative odour compounds in brewery broth using a continuous flow-stirred photoreactor

    NASA Astrophysics Data System (ADS)

    Jürgens, Marion; Jacob, Fritz; Ekici, Perihan; Friess, Albrecht; Parlar, Harun

    A method based on photolysis was developed for the appropriate treatment of organic pollutants in air exhausting from breweries upon wort decoction, and thereby causing smell nuisance. A continuous flow stirred photoreactor was built-up exclusively, allowing OH radicals to react with selected odorous compounds contained in exhaust vapours, such as: 2-methylpropanal, 3-methylbutanal, 2-methylbutanal, 3-methyl-1-butanol, n-hexanal, 2-methylbutyl isobutyrate, 2-undecanone, phenyl acetaldehyde, myrcene, limonene, linalool, humulene, dimethylsulphide, and dimethyltrisulphide. These substances were quantified in brewery broth before and after UV irradiation using high-resolution gas chromatography-mass spectrometry (HRGC-MS). For odour analysis, high-resolution gas chromatography-flame ionisation detection (HRGC-FID) coupled with sensory methods was used. Determined quantum yields of about 10 -3 for phenyl acetaldehyde, myrcene, and humulene pointed out that direct photolysis contributed to their decay. Quantum yields of below 10 -4 for the other substances indicated that UV irradiation did not contribute significantly to their degradation processes. Hydroxyl radical reaction rate constants and Henry constants of organic compounds were also measured. Substances accompanied with low Henry constants converted rapidly, whereas those with higher ones, relatively slowly. Determined aroma values concluded that after UV-H 2O 2 treatment, only dimethylsulphide and myrcene remained as important odorous compounds, but in significantly reduced concentrations. The UV-H 2O 2 treatment of brewery broth has been proved effective to reduce smell-irritating substances formed upon wort decoction.

  3. Involvement of 5f-orbitals in the bonding and reactivity of organoactinide compounds: thorium(IV) and uranium(IV) bis (hydrazonato) complexes

    SciTech Connect

    Cantat, Thibault; Graves, Christopher R; Morris, David E; Kiplinger, Jaqueline L

    2008-01-01

    Migratory insertion of diphenyldiazomethane into both metal-carbon bonds of the bis(alkyl) and bis(aryl) complexes (C5Me5)2AnR2 yields the first f-element bis(hydrazonato) complexes (C5Me5)2An[2-(N,N')-R-N-NCPh2]2 [An = Th, R = CH3 (18), PhCH2 (15), Ph (16); An = U, R = CH3 (17), PhCH2 (14)], which have been characterized by a combination of spectroscopy, electrochemistry, and X-ray crystallography. The two hydrazonato ligands adopt an 2-coordination mode leading to 20-electron (for Th) and 22-electron (for U) complexes that have no transition-metal analogues. In fact, reaction of (C5H5)2Zr(CH3)2 or (C5Me5)2Hf(CH3)2 with diphenyldiazomethane is limited to the formation of the corresponding mono(hydrazonato) complex (C5R5)2M[2-(N,N')-CH3-N-NCPh2](CH3) (M = Zr, R = H or M = Hf, R = CH3). The difference in the reactivities of the group 4 metal complexes and the actinides was used as a unique platform for investigating in depth the role of 5f orbitals on the reactivity and bonding in actinide organometallic complexes. The electronic structure of the (C5H5)2M[2-(N,N')-CH3-N-NCH2]2 (M = Zr, Th, U) model complexes was studied using density functional theory (DFT) calculations and compared to experimental structural, electrochemical, and spectroscopic results. Whereas transition-metal bis(cyclopentadienyl) complexes are known to stabilize three ligands in the metallocene girdle to form saturated (C5H5)2ML3 species, in a bis(hydrazonato) system, a fourth ligand is coordinated to the metal center to give (C5H5)2ML4. DFT calculations have shown that 5f orbitals in the actinide complexes play a crucial role in stabilizing this fourth ligand by stabilizing both the s and p electrons of the two 2-coordinated hydrazonato ligands. In contrast, the stabilization of the hydrazonato ligands was found to be significantly less effective for the putative bis(hydrazonato) zirconium(IV) complex, yielding a higher energy structure. However, the difference in the reactivities of the group 4

  4. Chicken Fetal Liver DNA Damage and Adduct Formation by Activation-Dependent DNA-Reactive Carcinogens and Related Compounds of Several Structural Classes

    PubMed Central

    Williams, Gary M.; Duan, Jian-Dong; Brunnemann, Klaus D.; Iatropoulos, Michael J.; Vock, Esther; Deschl, Ulrich

    2014-01-01

    The chicken egg genotoxicity assay (CEGA), which utilizes the liver of an intact and aseptic embryo-fetal test organism, was evaluated using four activation-dependent DNA-reactive carcinogens and four structurally related less potent carcinogens or non-carcinogens. In the assay, three daily doses of test substances were administered to eggs containing 9–11-day-old fetuses and the fetal livers were assessed for two endpoints, DNA breaks using the alkaline single cell gel electrophoresis (comet) assay and DNA adducts using the 32P-nucleotide postlabeling (NPL) assay. The effects of four carcinogens of different structures requiring distinct pathways of bioactivation, i.e., 2-acetylaminofluorene (AAF), aflatoxin B1 (AFB1), benzo[a]pyrene (B[a]P), and diethylnitrosamine (DEN), were compared with structurally related non-carcinogens fluorene (FLU) and benzo[e]pyrene (B[e]P) or weak carcinogens, aflatoxin B2 (AFB2) and N-nitrosodiethanolamine (NDELA). The four carcinogens all produced DNA breaks at microgram or low milligram total doses, whereas less potent carcinogens and non-carcinogens yielded borderline or negative results, respectively, at higher doses. AAF and B[a]P produced DNA adducts, whereas none was found with the related comparators FLU or B[e]P, consistent with comet results. DEN and NDELA were also negative for adducts, as expected in the case of DEN for an alkylating agent in the standard NPL assay. Also, AFB1 and AFB2 were negative in NPL, as expected, due to the nature of ring opened aflatoxin adducts, which are resistant to enzymatic digestion. Thus, the CEGA, using comet and NPL, is capable of detection of the genotoxicity of diverse DNA-reactive carcinogens, while not yielding false positives for non-carcinogens. PMID:24973097

  5. Assessment of the roles of reactive oxygen species in the UV and visible light photocatalytic degradation of cyanotoxins and water taste and odor compounds using C-TiO2.

    PubMed

    Fotiou, Theodora; Triantis, Theodoros M; Kaloudis, Triantafyllos; O'Shea, Kevin E; Dionysiou, Dionysios D; Hiskia, Anastasia

    2016-03-01

    Visible light (VIS) photocatalysis has large potential as a sustainable water treatment process, however the reaction pathways and degradation processes of organic pollutants are not yet clearly defined. The presence of cyanobacteria cause water quality problems since several genera can produce potent cyanotoxins, harmful to human health. In addition, cyanobacteria produce taste and odor compounds, which pose serious aesthetic problems in drinking water. Although photocatalytic degradation of cyanotoxins and taste and odor compounds have been reported under UV-A light in the presence of TiO2, limited studies have been reported on their degradation pathways by VIS photocatalysis of these problematic compounds. The main objectives of this work were to study the VIS photocatalytic degradation process, define the reactive oxygen species (ROS) involved and elucidate the reaction mechanisms. We report carbon doped TiO2 (C-TiO2) under VIS leads to the slow degradation of cyanotoxins, microcystin-LR (MC-LR) and cylindrospermopsin (CYN), while taste and odor compounds, geosmin and 2-methylisoborneol, were not appreciably degraded. Further studies were carried-out employing several specific radical scavengers (potassium bromide, isopropyl alcohol, sodium azide, superoxide dismutase and catalase) and probes (coumarin) to assess the role of different ROS (hydroxyl radical OH, singlet oxygen (1)O2, superoxide radical anion [Formula: see text] ) in the degradation processes. Reaction pathways of MC-LR and CYN were defined through identification and monitoring of intermediates using liquid chromatography tandem mass spectrometry (LC-MS/MS) for VIS in comparison with UV-A photocatalytic treatment. The effects of scavengers and probes on the degradation process under VIS, as well as the differences in product distributions under VIS and UV-A, suggested that the main species in VIS photocatalysis is [Formula: see text] , with OH and (1)O2 playing minor roles in the degradation. PMID

  6. The Shape of a Gravity Finger

    SciTech Connect

    Zhan, Lang; Yortsos, Yanis

    2000-09-11

    A new gravity finger model was proposed in this report in the absence of interfacial tension but in the presence of gravities. This model considered differences in density and viscosity of the two fluids. Thus, it was able to represent both stable and unstable displacements, and the finger development along either the upper or the bottom walls of a channel. This solution recovers the Saffman - Taylar solution if gravity is neglected. The results of the solution are very similar to the solutions proposed by Brener et al. for the gravity number up to 10. The solution provided in this work only has one free parameter while the solution of Brener et al. has three.

  7. Nylon-muscle-actuated robotic finger

    NASA Astrophysics Data System (ADS)

    Wu, Lianjun; Jung de Andrade, Monica; Rome, Richard S.; Haines, Carter; Lima, Marcio D.; Baughman, Ray H.; Tadesse, Yonas

    2015-04-01

    This paper describes the design and experimental analysis of novel artificial muscles, made of twisted and coiled nylon fibers, for powering a biomimetic robotic hand. The design is based on circulating hot and cold water to actuate the artificial muscles and obtain fast finger movements. The actuation system consists of a spring and a coiled muscle within a compliant silicone tube. The silicone tube provides a watertight, expansible compartment within which the coiled muscle contracts when heated and expands when cooled. The fabrication and characterization of the actuating system are discussed in detail. The performance of the coiled muscle fiber in embedded conditions and the related characteristics of the actuated robotic finger are described.

  8. Articular synovial chondromatosis of the finger.

    PubMed

    Sano, Kazufumi; Hashimoto, Tomohisa; Kimura, Kazumasa; Ozeki, Satoru

    2014-10-01

    A 40-year-old woman presented with a six-month history of synovial chondromatosis of the metacarpophalangeal joint of the right ring finger, which was resected through both dorsal and volar incisions. To our knowledge there have been only 17 reported cases of articular synovial chondromatosis of the digital joint so far. We present a case affecting the metacarpophalangeal joint with a review of scattered information found in other 17 reports. PMID:23596991

  9. Low-Friction Joint for Robot Fingers

    NASA Technical Reports Server (NTRS)

    Ruoff, C. F.

    1985-01-01

    Mechanical linkage allows adjacent parts to move relative to each other with low friction and with no chatter, slipping, or backlash. Low-friction joint of two surfaces in rolling contact, held in alinement by taut flexible bands. No sliding friction or "stick-slip" motion: Only rolling-contact and bending friction within bands. Proposed linkage intended for finger joints in mechanical hands for robots and manipulators.

  10. Recent advances in high performance poly(lactide): from “green” plasticization to super-tough materials via (reactive) compounding

    PubMed Central

    Kfoury, Georgio; Raquez, Jean-Marie; Hassouna, Fatima; Odent, Jérémy; Toniazzo, Valérie; Ruch, David; Dubois, Philippe

    2013-01-01

    Due to its origin from renewable resources, its biodegradability, and recently, its industrial implementation at low costs, poly(lactide) (PLA) is considered as one of the most promising ecological, bio-sourced and biodegradable plastic materials to potentially and increasingly replace traditional petroleum derived polymers in many commodity and engineering applications. Beside its relatively high rigidity [high tensile strength and modulus compared with many common thermoplastics such as poly(ethylene terephthalate) (PET), high impact poly(styrene) (HIPS) and poly(propylene) (PP)], PLA suffers from an inherent brittleness, which can limit its applications especially where mechanical toughness such as plastic deformation at high impact rates or elongation is required. Therefore, the curve plotting stiffness vs. impact resistance and ductility must be shifted to higher values for PLA-based materials, while being preferably fully bio-based and biodegradable upon the application. This review aims to establish a state of the art focused on the recent progresses and preferably economically viable strategies developed in the literature for significantly improve the mechanical performances of PLA. A particular attention is given to plasticization as well as to impact resistance modification of PLA in the case of (reactive) blending PLA-based systems. PMID:24790960