Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

USGS Publications Warehouse

Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

2015-01-01

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N–NO3, and δ18O–NO3 data show only about 5–10% denitrification of septic nitrate in most samples—although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

Limited denitrification in glacial deposit aquifers having thick unsaturated zones (Long Island, USA)

NASA Astrophysics Data System (ADS)

Young, Caitlin; Kroeger, Kevin D.; Hanson, Gilbert

2013-12-01

The goal of this study was to demonstrate how the extent of denitrification, which is indirectly related to dissolved organ carbon and directly related to oxygen concentrations, can also be linked to unsaturated-zone thickness, a mappable aquifer property. Groundwater from public supply and monitoring wells in Northport on Long Island, New York state (USA), were analyzed for denitrification reaction progress using dissolved N2/Ar concentrations by membrane inlet mass spectrometry. This technique allows for discernment of small amounts of excess N2, attributable to denitrification. Results show an average 15 % of total nitrogen in the system was denitrified, significantly lower than model predictions of 35 % denitrification. The minimal denitrification is due to low dissolved organic carbon (29.3-41.1 μmol L-1) and high dissolved oxygen concentrations (58-100 % oxygen saturation) in glacial sediments with minimal solid-phase electron donors to drive denitrification. A mechanism is proposed that combines two known processes for aquifer re-aeration in unconsolidated sands with thick (>10 m) unsaturated zones. First, advective flux provides 50 % freshening of pore space oxygen in the upper 2 m due to barometric pressure changes. Then, oxygen diffusion across the water-table boundary occurs due to high volumetric air content in the unsaturated-zone catchment area.

Two-Carbon Homologation of Ketones to 3-Methyl Unsaturated Aldehydes

USDA-ARS?s Scientific Manuscript database

The usual scheme of two-carbon homologation of ketones to 3-methyl unsaturated aldehydes by Horner-Wadsworth-Emmons condensations with phosphonate esters, such as triethyl-2-phosphonoacetate, involves three steps. The phosphonate condensation step results in extension of the carbon chain by two carb...

Reversed-phase high-performance liquid chromatography purification of methyl esters of C(16)-C(28) polyunsaturated fatty acids in microalgae, including octacosaoctaenoic acid [28:8(n-3)].

PubMed

Mansour, Maged P

2005-12-02

A preparative reversed-phase (RP; C(18)) high-performance liquid chromatography (HPLC) method with gradient elution using acetonitrile (MeCN)-chloroform (CHCl(3)) (or dichloromethane (DCM)) and evaporative light-scattering detection (ELSD) with automatic multiple injection and fraction collection was used to purify milligram quantities of microalgal polyunsaturated fatty acids (PUFA), separated as methyl esters (ME). PUFA-ME purified included methyl esters of docosahexaenoic acid (DHA; 22:6(n-3)), eicosapentaenoic acid (EPA; 20:5(n-3)) and the unusual very long-chain (C(28)) highly unsaturated fatty acid (VLC-HUFA), octacosaoctaenoic acid [28:8(n-3)(4, 7, 10, 13, 16, 19, 22, 25)] from the marine dinoflagellate Scrippsiella sp. CS-295/c. Other PUFA purified from various microalgae using this RP-HPLC method to greater than 95% purity included 16:3(n-4), 16:4(n-3), 16:4(n-1) and 18:5(n-3). The number of injections required was variable and depended on the abundance of the desired PUFA-ME, and resolution from closely eluting PUFA-ME, which determined the maximum loading. The purity of these fatty acids was determined by electron impact (EI) GC-MS and the chain length and location of double bonds was determined by EI GC-MS of 4,4-dimethyl oxazoline (DMOX) derivatives formed using a low temperature method. Advantages over silver-ion HPLC for purifying PUFA-ME is that separation occurs according to chain length as well as degree of unsaturation enabling separation of PUFA-ME with the same degree of unsaturation but different chain length (i.e. between 18:5(n-3) and 20:5(n-3)). In addition, PUFA-ME are not strongly adsorbed, but elute earlier than their more saturated corresponding FAME of the same chain length. This method is robust, simple, and requires only a short re-equilibration time. It is a useful tool for preparing milligram quantities of pure PUFA-ME for bioactive screening (as free fatty acids), although many multiple injections may be required for minor PUFA

Different stabilities of liposomes containing saturated and unsaturated lipids toward the addition of cyclodextrins.

PubMed

Ikeda, Atsushi; Funada, Rikushi; Sugikawa, Kouta

2016-06-14

Liposomes composed of unsaturated lipids were more stable than those containing saturated lipids toward DMe-β-CDx, DMe-α-CDx and DMe-β-CDx. The Hill coefficient values (n) indicated that the saturated lipid·DMe-CDx complexes had stoichiometric ratios in the range of 1 : 3-1 : 4, while the unsaturated lipid·DMe-CDx complexes had ratios in the range of 1 : 1.5-1 : 3. That is, a cis alkene group in the unsaturated lipids prevented complexation with a second DMe-CDx in the direction toward each acyl chain. Furthermore, the liposomes composed of the unsaturated lipids were much slower to form precipitates upon the addition of α-CDx than those of the saturated lipids. To the best of our knowledge, this is the first example showing that CDxs interact with unsaturated lipids.

Impact of Diverse Hydrologic Pathways, 3D Failure Geometries, and Unsaturated Soil Suctions on Shallow Landsliding

NASA Astrophysics Data System (ADS)

Reid, M. E.; Iverson, R. M.; Brien, D. L.; Iverson, N. R.; Lahusen, R. G.; Logan, M.

2016-12-01

Shallow landslides and ensuing debris flows can be triggered by diverse hydrologic phenomena such as groundwater inflow, prolonged moderate-intensity precipitation, or bursts of high-intensity precipitation. However, hazard assessments typically rely on simplistic hydrologic models that disregard this diversity. We used the USGS debris-flow flume to conduct controlled, field-scale slope failure experiments designed to investigate the effects of diverse hydrologic pathways, as well as the effects of 3D landslide geometries and suction stresses in unsaturated soil. Using overhead sprinklers or groundwater injectors on the flume bed, we induced failures in 6 m3 (0.65-m thick and 2-m wide) prisms of loamy sand on a 31º slope. We used 50 sensors to monitor soil deformation, variably saturated pore pressures, and moisture changes. We also determined shear strength, hydraulic conductivity, and unsaturated moisture retention characteristics from ancillary tests. The three hydrologic scenarios noted above led to different behaviors. Groundwater injection and prolonged infiltration created differing soil moisture patterns. Intense sprinkling bursts caused rapid failure without development of widespread positive pore pressures. We simulated these observed differences numerically by coupling 2D variably saturated groundwater flow modeling and 3D limit-equilibrium analysis. We also simulated the time evolution of changes in factors of safety, and quantified the mechanical effects of 3D geometry and unsaturated soil suction on stability. When much of the soil became relatively wet, effects of 3D geometry and soil suction produced slight increases ( 10-20%) in factors of safety. Suction effects were more pronounced with drier soils. Our results indicate that simplistic models cannot consistently predict the timing of slope failure, and that high frequency monitoring (with sampling periods < 60 s) is needed to measure and interpret the effects of rapid hydrologic triggers.

Limited denitrification in glacial deposit aquifers having thick unsaturated zones (Long Island, USA)

USGS Publications Warehouse

Young, Caitlin; Kroeger, Kevin D.; Hanson, Gilbert

2013-01-01

The goal of this study was to demonstrate how the extent of denitrification, which is indirectly related to dissolved organ carbon and directly related to oxygen concentrations, can also be linked to unsaturated-zone thickness, a mappable aquifer property. Groundwater from public supply and monitoring wells in Northport on Long Island, New York state (USA), were analyzed for denitrification reaction progress using dissolved N2/Ar concentrations by membrane inlet mass spectrometry. This technique allows for discernment of small amounts of excess N2, attributable to denitrification. Results show an average 15 % of total nitrogen in the system was denitrified, significantly lower than model predictions of 35 % denitrification. The minimal denitrification is due to low dissolved organic carbon (29.3–41.1 μmol L−1) and high dissolved oxygen concentrations (58–100 % oxygen saturation) in glacial sediments with minimal solid-phase electron donors to drive denitrification. A mechanism is proposed that combines two known processes for aquifer re-aeration in unconsolidated sands with thick (>10 m) unsaturated zones. First, advective flux provides 50 % freshening of pore space oxygen in the upper 2 m due to barometric pressure changes. Then, oxygen diffusion across the water-table boundary occurs due to high volumetric air content in the unsaturated-zone catchment area.

Fish oil increases mitochondrial phospholipid unsaturation, upregulating reactive oxygen species and apoptosis in rat colonocytes

NASA Technical Reports Server (NTRS)

Hong, Mee Young; Chapkin, Robert S.; Barhoumi, Rola; Burghardt, Robert C.; Turner, Nancy D.; Henderson, Cara E.; Sanders, Lisa M.; Fan, Yang-Yi; Davidson, Laurie A.; Murphy, Mary E.;

Lack of Effects of a Single High-Fat Meal Enriched with Vegetable n-3 or a Combination of Vegetable and Marine n-3 Fatty Acids on Intestinal Peptide Release and Adipokines in Healthy Female Subjects.

PubMed

Narverud, Ingunn; Myhrstad, Mari C W; Herzig, Karl-Heinz; Karhu, Toni; Dahl, Tuva B; Halvorsen, Bente; Ulven, Stine M; Holven, Kirsten B

2016-01-01

Peptides released from the small intestine and colon regulate short-term food intake by suppressing appetite and inducing satiety. Intake of marine omega-3 (n-3) fatty acids (FAs) from fish and fish oils is associated with beneficial health effects, whereas the relation between intake of the vegetable n-3 fatty acid α-linolenic acid and diseases is less clear. The aim of the present study was to investigate the postprandial effects of a single high-fat meal enriched with vegetable n-3 or a combination of vegetable and marine n-3 FAs with their different unsaturated fatty acid composition on intestinal peptide release and the adipose tissue. Fourteen healthy lean females consumed three test meals with different fat quality in a fixed order. The test meal consisted of three cakes enriched with coconut fat, linseed oil, and a combination of linseed and cod liver oil. The test days were separated by 2 weeks. Fasting and postprandial blood samples at 3 and 6 h after intake were analyzed. A significant postprandial effect was observed for cholecystokinin, peptide YY, glucose-dependent insulinotropic polypeptide, amylin and insulin, which increased, while leptin decreased postprandially independent of the fat composition in the high-fat meal. In conclusion, in healthy, young, lean females, an intake of a high-fat meal enriched with n-3 FAs from different origin stimulates intestinal peptide release without any difference between the different fat compositions.

Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel

NASA Astrophysics Data System (ADS)

Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

2007-03-01

With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

High-quality unsaturated zone hydraulic property data for hydrologic applications

USGS Publications Warehouse

Perkins, Kimberlie; Nimmo, John R.

2009-01-01

In hydrologic studies, especially those using dynamic unsaturated zone moisture modeling, calculations based on property transfer models informed by hydraulic property databases are often used in lieu of measured data from the site of interest. Reliance on database-informed predicted values has become increasingly common with the use of neural networks. High-quality data are needed for databases used in this way and for theoretical and property transfer model development and testing. Hydraulic properties predicted on the basis of existing databases may be adequate in some applications but not others. An obvious problem occurs when the available database has few or no data for samples that are closely related to the medium of interest. The data set presented in this paper includes saturated and unsaturated hydraulic conductivity, water retention, particle-size distributions, and bulk properties. All samples are minimally disturbed, all measurements were performed using the same state of the art techniques and the environments represented are diverse.

Nitrogen fluxes through unsaturated zones in five agricultural settings across the United States

USGS Publications Warehouse

Green, C.T.; Fisher, L.H.; Bekins, B.A.

2008-01-01

The main physical and chemical controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Indiana, Maryland, Nebraska, and Washington from 2004 to 2005. Sites included irrigated and nonirrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 1 to 22 m. Chemical analyses of water from lysimeters and shallow wells indicate that advective transport of nitrate is the dominant process affecting the flux of N below the root zone. Vertical profiles of (i) nitrogen species, (ii) stable isotopes of nitrogen and oxygen, and (iii) oxygen, N, and argon in unsaturated zone air and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. As a result, physical factors, such as N application rate, water inputs, and evapotranspiration, control the differences in concentrations among the sites. Concentrations of N in shallow lysimeters exhibit seasonal variation, whereas concentrations in lysimeters deeper than a few meters are relatively stable. Based on concentration and recharge estimates, fluxes of N through the deep unsaturated zone range from 7 to 99 kg ha-1 yr-1. Vertical fluxes of N in ground water are lower due to spatial and historical changes in N inputs. High N fluxes are associated with coarse sediments and high N application rates. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Variation of unsaturated fatty acids in soybean sprout of high oleic acid accessions.

PubMed

Dhakal, Krishna Hari; Jung, Ki-Hwal; Chae, Jong-Hyun; Shannon, J Grover; Lee, Jeong-Dong

2014-12-01

Oleic acid and oleic acid rich foods may have beneficial health effects in humans. Soybeans with high oleic acid (around 80% in seed oil) have been developed. Soybean sprouts are an important vegetable in Korea, Japan and China. The objective of this study was to investigate the variation of unsaturated fatty acids, oleic, linoleic and α-linolenic acids, in sprouts from soybeans with normal and high oleic acid concentration. Twelve soybean accessions with six high oleic acid lines, three parents of high oleic acid lines, and three checks with normal and high oleic acid concentration were used in this study. The unsaturated fatty acid concentration in sprouts from each genotype was similar to the concentration in the ungerminated seed. The oleic acid concentration in the sprouts of high oleic acid lines (up to 80%) was still high (>70%) compared to the ungerminated seed. Thus, high oleic soybean varieties developed for sprout production could add valuable health benefits to sprouts and the individuals who consume this vegetable. Copyright © 2014 Elsevier Ltd. All rights reserved.

Water movement through thick unsaturated zones overlying the central High Plains aquifer, southwestern Kansas, 2000-2001

USGS Publications Warehouse

McMahon, Peter B.; Dennehy, K.F.; Michel, R.L.; Sophocleous, M.A.; Ellett, K.M.; Hurlbut, D.B.

2003-01-01

The role of irrigation as a driving force for water and chemical movement to the central High Plains aquifer is uncertain because of the thick unsaturated zone overlying the aquifer. Water potentials and profiles of tritium, chloride, nitrate, and pesticide concentrations were used to evaluate water movement through thick unsaturated zones overlying the central High Plains aquifer at three sites in southwestern Kansas. One site was located in rangeland and two sites were located in areas dominated by irrigated agriculture. In 2000?2001, the depth to water at the rangeland site was 50 meters and the depth to water at the irrigated sites was about 45.4 meters. Irrigation at the study sites began in 1955?56. Measurements of matric potential and volumetric water content indicate wetter conditions existed in the deep unsaturated zone at the irrigated sites than at the rangeland site. Total water potentials in the unsaturated zone at the irrigated sites systematically decreased with depth to the water table, indicating a potential existed for downward water movement from the unsaturated zone to the water table at those sites. At the rangeland site, total water potentials in the deep unsaturated zone indicate small or no potential existed for downward water movement to the water table. Postbomb tritium was not detected below a depth of 1.9 meters in the unsaturated zone or in ground water at the rangeland site. In contrast, postbomb tritium was detected throughout most of the unsaturated zone and in ground water at both irrigated sites. These results indicate post-1953 water moved deeper in the unsaturated zone at the irrigated sites than at the rangeland site. The depth of the interface between prebomb and postbomb tritium and a tritium mass-balance method were used to estimate water fluxes in the unsaturated zone at each site. The average water fluxes at the rangeland site were 5.4 and 4.4 millimeters per year for the two methods, which are similar to the average water

Artificial recharge through a thick, heterogeneous unsaturated zone

USGS Publications Warehouse

Izbicki, J.A.; Flint, A.L.; Stamos, C.L.

2008-01-01

Thick, heterogeneous unsaturated zones away from large streams in desert areas have not previously been considered suitable for artificial recharge from ponds. To test the potential for recharge in these settings, 1.3 ?? 10 6 m3 of water was infiltrated through a 0.36-ha pond along Oro Grande Wash near Victorville, California, between October 2002 and January 2006. The pond overlies a regional pumping depression 117 m below land surface and is located where thickness and permeability of unsaturated deposits allowed infiltration and saturated alluvial deposits were sufficiently permeable to allow recovery of water. Because large changes in water levels caused by nearby pumping would obscure arrival of water at the water table, downward movement of water was measured using sensors in the unsaturated zone. The downward rate of water movement was initially as high as 6 m/d and decreased with depth to 0.07 m/d; the initial time to reach the water table was 3 years. After the unsaturated zone was wetted, water reached the water table in 1 year. Soluble salts and nitrate moved readily with the infiltrated water, whereas arsenic and chromium were less mobile. Numerical simulations done using the computer program TOUGH2 duplicated the downward rate of water movement, accumulation of water on perched zones, and its arrival at the water table. Assuming 10 ?? 10 6 m3 of recharge annually for 20 years, a regional ground water flow model predicted water level rises of 30 m beneath the ponds, and rises exceeding 3 m in most wells serving the nearby urban area.

The Basicity of Unsaturated Hydrocarbons as probed by H-Bond Acceptor Ability. Bifurcated N–H+⋯π Hydrogen Bonding

PubMed Central

Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A.

2009-01-01

The competitive substitution of the anion in contact ion pairs of the type [Oct3NH+]B(C6F5)4− by unsaturated hydrocarbons L in accordance with the equilibrium Oct3NH+⋯Anion− + nL ↔ [Oct3NH+⋯Ln]Anion− has been studied in CCl4 solution. On the basis of equilibrium constants K and shifts of νNH to low frequency, it is established that complexed Oct3NH+⋯Ln cations with n = 1 and 2 are formed, having unidentate and bifurcated N–H+⋯π hydrogen bonds, respectively. Bifurcated H-bonds to unsaturated hydrocarbons have not been observed previously. The unsaturated hydro-carbons studied include benzene and methylbenzenes, fused-ring aromatics, alkenes, conjugated dienes, and alkynes. From the magnitude of the red shifts in N-H stretching frequencies, ΔνNH, a new scale for ranking the π-basicity of unsaturated hydrocarbons is proposed: fused-ring aromatics ≤ benzene < toluene < xylene < mesitylene < durene < conjugated dienes ∼ 1-alkynes < pentamethylbenzene < hexamethyl-benzene < internal alkynes ∼ cyclo-alkenes < 1-methylcycloalkenes. This scale is relevant to the discussion of π complexes for incipient protonation reactions and to understanding N–H+⋯π hydrogen bonding in proteins and molecular crystals. PMID:18637650

Addition of CF3 across unsaturated moieties: a powerful functionalization tool

PubMed Central

2014-01-01

In the last few years, the efficient introduction of trifluoromethyl groups in organic molecules has become a major research focus. This review highlights the recent developments enabling the incorporation of CF3 groups across unsaturated moieties, preferentially alkenes, and the mechanistic scenarios governing these transformations. We have specially focused on methods involving the simultaneous formation of C–CF3 and C–C or C–heteroatom bonds by formal addition reactions across π-systems, as such difunctionalization processes hold valuable synthetic potential. PMID:24789472

Effect of artificial regulations of Artemia n-3 HUFA content on growth and survival of black seabream ( Sparus macrocephalus) larvae

NASA Astrophysics Data System (ADS)

Liu, Jing-Ke

1998-06-01

The requirement for dietary n-3 HUFA (highly unsaturated fatty acid) for growth and survival of black seabream ( Sparus macrocephalus) larvae was tested using Artemia with various levels of n-3 HUFA. Four treatments with Artemia differing in their n-3 HUFA were prepared by feeding them various oil emulsions. The results indicated that dietary n-3 HUFA significantly influences fish n-3 HUFA levels and are necessary for good growth and survival of black seabream larvae. The proper value of n-3 HUFA level and DHA, EPA level in Artemia should be 4.273% and 0.873% (wet weight) for good growth and survival in black seabream larvae respectively.

Predicting unsaturated zone nitrogen mass balances in agricultural settings of the United States

USGS Publications Warehouse

Nolan, Bernard T.; Puckett, Larry J.; Ma, Liwang; Green, Christopher T.; Bayless, E. Randall; Malone, Robert W.

2009-01-01

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond [Prunus dulcis (Mill.) D.A. Webb] orchard and cornfield (Zea mays L.) in the lower Merced River study basin, California; and corn–soybean [Glycine max (L.) Merr.] rotations in study basins at Maple Creek, Nebraska, and at Morgan Creek, Maryland. We used inverse modeling with a new version of the Root Zone Water Quality Model (RZWQM2) to estimate soil hydraulic and nitrogen transformation parameters throughout the unsaturated zone; previous versions were limited to 3-m depth and relied on manual calibration. The overall goal of the modeling was to derive unsaturated zone N mass balances for the four sites. RZWQM2 showed promise for deeper simulation profiles. Relative root mean square error (RRMSE) values for predicted and observed nitrate concentrations in lysimeters were 0.40 and 0.52 for California (6.5 m depth) and Nebraska (10 m), respectively, and index of agreement (d) values were 0.60 and 0.71 (d varies between 0 and 1, with higher values indicating better agreement). For the shallow simulation profile (1 m) in Maryland, RRMSE and d for nitrate were 0.22 and 0.86, respectively. Except for Nebraska, predictions of average nitrate concentration at the bottom of the simulation profile agreed reasonably well with measured concentrations in monitoring wells. The largest additions of N were predicted to come from inorganic fertilizer (153–195 kg N ha−1 yr−1 in California) and N fixation (99 and 131 kg N ha−1 yr−1 in Maryland and Nebraska, respectively). Predicted N losses occurred primarily through plant uptake (144–237 kg N ha−1 yr−1) and deep seepage out of the profile (56–102 kg N ha−1 yr−1). Large reservoirs of organic N (up to 17,500 kg N ha−1 m−1 at Nebraska) were predicted to reside in the unsaturated zone, which has implications for potential future transfer of nitrate to groundwater.

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

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

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

Synergies between Unsaturated Zn/Cu Doping Sites in Carbon Dots Provide New Pathways for Photocatalytic Oxidation

DOE PAGES

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin; ...

2017-12-07

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

P[N(i-Bu)CH(2)CH(2)](3)N: nonionic Lewis base for promoting the room-temperature synthesis of α,β-unsaturated esters, fluorides, ketones, and nitriles using Wadsworth-Emmons phosphonates.

PubMed

Chintareddy, Venkat Reddy; Ellern, Arkady; Verkade, John G

2010-11-05

The bicyclic triaminophosphine P(RNCH(2)CH(2))(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.

Climate variability controls on unsaturated water and chemical movement, High Plains aquifer, USA

USGS Publications Warehouse

Gurdak, J.J.; Hanson, R.T.; McMahon, P.B.; Bruce, B.W.; McCray, J.E.; Thyne, G.D.; Reedy, R.C.

2007-01-01

Responses in the vadose zone and groundwater to interannual, interdecadal, and multidecadal climate variability have important implications for groundwater resource sustainability, yet they are poorly documented and not well understood in most aquifers of the USA. This investigation systematically examines the role of interannual to multidecadal climate variability on groundwater levels, deep infiltration (3-23 m) events, and downward displacement (>1 m) of chloride and nitrate reservoirs in thick (15-50 m) vadose zones across the regionally extensive High Plains aquifer. Such vadose zone responses are unexpected across much of the aquifer given a priori that unsaturated total-potential profiles indicate upward water movement from the water table toward the root zone, mean annual potential evapotranspiration exceeds mean annual precipitation, and millennia-scale evapoconcentration results in substantial vadose zone chloride and nitrate reservoirs. Using singular spectrum analysis (SSA) to reconstruct precipitation and groundwater level time-series components, variability was identified in all time series as partially coincident with known climate cycles, such as the Pacific Decadal Oscillation (PDO) (10-25 yr) and the El Nin??o/Southern Oscillation (ENSO) (2-6 yr). Using these lag-correlated hydrologic time series, a new method is demonstrated to estimate climate-varying unsaturated water flux. The results suggest the importance of interannual to interdecadal climate variability on water-flux estimation in thick vadose zones and provide better understanding of the climate-induced transients responsible for the observed deep infiltration and chemical-mobilization events. Based on these results, we discuss implications for climate-related sustainability of the High Plains aquifer. ?? Soil Science Society of America.

Sophorolipid-derived unsaturated and epoxy fatty acid estolides as plasticizers for poly(3-hydroxybutyrate)

USDA-ARS?s Scientific Manuscript database

Unsaturated and epoxy fatty acid estolides were synthesized from the omega and omega-1 hydroxy fatty acids derived from sophorolipids (SLs) prepared by fermentation from glucose:soybean oil and glucose:oleic acid, respectively. These estolides were utilized as additives in solution-cast poly(3-hydro...

Regional variability of nitrate fluxes in the unsaturated zone and groundwater, Wisconsin, USA

USGS Publications Warehouse

Green, Christopher T.; Liao, Lixia; Nolan, Bernard T.; Juckem, Paul F.; Shope, Christopher L.; Tesoriero, Anthony J.; Jurgens, Bryant

2018-01-01

Process-based modeling of regional NO3− fluxes to groundwater is critical for understanding and managing water quality, but the complexity of NO3− reactive transport processes make implementation a challenge. This study introduces a regional vertical flux method (VFM) for efficient estimation of reactive transport of NO3− in the vadose zone and groundwater. The regional VFM was applied to 443 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3−, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and tritiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with estimates from previous studies. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams (2) since 1945 fractions of applied N leached to groundwater have increased for manure-N, possibly due to increased injection of liquid manure, and decreased for fertilizer-N, and (3) under current practices and conditions, approximately 60% of the shallow aquifer will eventually be affected by downward migration of NO3−, with denitrification protecting the remaining 40%. Recharge variability strongly affected the unsaturated zone lag times and the eventual depth of the NO3− front. Principal components regression demonstrated that VFM parameters and predictions were significantly correlated with hydrogeochemical landscape features. The diverse and sometimes conflicting aspects of N management (e.g. limiting N volatilization versus limiting N losses to groundwater) warrant continued development of large-scale holistic strategies to manage water quality and quantity.

Regional Variability of Nitrate Fluxes in the Unsaturated Zone and Groundwater, Wisconsin, USA

NASA Astrophysics Data System (ADS)

Green, Christopher T.; Liao, Lixia; Nolan, Bernard T.; Juckem, Paul F.; Shope, Christopher L.; Tesoriero, Anthony J.; Jurgens, Bryant C.

2018-01-01

Process-based modeling of regional NO3- fluxes to groundwater is critical for understanding and managing water quality, but the complexity of NO3- reactive transport processes makes implementation a challenge. This study introduces a regional vertical flux method (VFM) for efficient estimation of reactive transport of NO3- in the vadose zone and groundwater. The regional VFM was applied to 443 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3-, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and tritiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with estimates from previous studies. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams, (2) since 1945 fractions of applied N leached to groundwater have increased for manure-N, possibly due to increased injection of liquid manure, and decreased for fertilizer-N, and (3) under current practices and conditions, approximately 60% of the shallow aquifer will eventually be affected by downward migration of NO3-, with denitrification protecting the remaining 40%. Recharge variability strongly affected the unsaturated zone lag times and the eventual depth of the NO3- front. Principal components regression demonstrated that VFM parameters and predictions were significantly correlated with hydrogeochemical landscape features. The diverse and sometimes conflicting aspects of N management (e.g., limiting N volatilization versus limiting N losses to groundwater) warrant continued development of large-scale holistic strategies to manage water quality and quantity.

Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or alpha,beta-unsaturated enals or enones.

PubMed

Huang, Xian; Xie, Meihua

2002-12-13

beta-Phenylseleno-alpha-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or alpha,beta-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of alpha,beta-unsaturated enones, functionalized allylic alcohols or functionalized gamma,delta-unsaturated ketones were obtained, depending on the structures of the ketones.

New insights into hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds by rhenium(V)-dioxo complexes.

PubMed

Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan

2015-04-23

The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.

Highly versatile enantioselective conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters.

PubMed

Ruiz, Beatriz Maciá; Geurts, Koen; Fernández-Ibáñez, M Angeles; ter Horst, Bjorn; Minnaard, Adriaan J; Feringa, Ben L

2007-11-22

Herein, we report efficient catalysts for the asymmetric copper-catalyzed conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters. MeMgBr adds to aromatic alpha,beta-unsaturated thioesters with excellent enantioselectivities and moderate to good yields using Josiphos/CuBr and Tol-BINAP/CuI complexes. The use of bulky Grignard reagents leads to unprecedented enantioselectivities in the 1,4-addition to a broad range of aromatic and aliphatic alpha,beta-unsaturated thioesters using Tol-BINAP/CuI. The highest enantioselectivities reported so far for the addition of Grignard reagents to crowded beta-substituted aliphatic substrates are achieved with Tol-BINAP/CuI.

Kinetics of the gas-phase reaction between ozone and three unsaturated oxygenated compounds: Ethyl 3,3-dimethyl acrylate, 2-methyl-2-pentenal and 6-methyl-5-hepten-2-one at atmospheric pressure

NASA Astrophysics Data System (ADS)

Gaona Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

2015-05-01

Rate coefficients for the gas-phase reactions of O3 molecules with three unsaturated oxygenated compounds have been determined using the relative kinetic technique in an environmental chamber with FTIR detection of the reactants at (298 ± 2) K in 760 Torr total pressure of synthetic air. The following rate coefficients (in units of 10-17 cm3 molecule-1 s-1) were determined: ethyl 3,3-dimethyl acrylate (0.82 ± 0.19), 2-methyl-2-pentenal (0.71 ± 0.16) and 6-methyl-5-hepten-2-one (26 ± 7). The different reactivity of the unsaturated oxygenated compounds toward O3 is discussed in terms of their chemical structure. In addition, a correlation between the reactivity of structurally different unsaturated compounds (alkenes and unsaturated oxygenated VOCs, such as ethers, esters, aldehydes, ketones and alcohols) toward O3 molecules and the HOMO (Highest Occupied Molecular Orbital) of the compounds is presented. Using the kinetic parameters determined in this work, residence times of these unsaturated compounds in the atmosphere with respect to reaction with O3 have been calculated. In urban and rural areas the main sink of 6-methyl-5-hepten-2-one is reaction with O3 molecules with a residence time in the order of few minutes.

Photosensitized oxidation of unsaturated polymers

NASA Technical Reports Server (NTRS)

Golub, M. A.

1979-01-01

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

Coordinatively Unsaturated Metal-Organic Frameworks M3(btc)2 (M = Cr, Fe, Co, Ni, Cu, and Zn) Catalyzing the Oxidation of CO by N2O: Insight from DFT Calculations.

PubMed

Ketrat, Sombat; Maihom, Thana; Wannakao, Sippakorn; Probst, Michael; Nokbin, Somkiat; Limtrakul, Jumras

2017-11-20

The oxidation of CO by N 2 O over metal-organic framework (MOF) M 3 (btc) 2 (M = Fe, Cr, Co, Ni, Cu, and Zn) catalysts that contain coordinatively unsaturated sites has been investigated by means of density functional theory calculations. The reaction proceeds in two steps. First, the N-O bond of N 2 O is broken to form a metal oxo intermediate. Second, a CO molecule reacts with the oxygen atom of the metal oxo site, forming one C-O bond of CO 2 . The first step is a rate-determining step for both Cu 3 (btc) 2 and Fe 3 (btc) 2 , where it requires the highest activation energy (67.3 and 19.6 kcal/mol, respectively). The lower value for the iron compound compared to the copper one can be explained by the larger amount of electron density transferred from the catalytic site to the antibonding of N 2 O molecules. This, in turn, is due to the smaller gap between the highest occupied molecular orbital (HOMO) of the MOF and the lowest unoccupied molecular orbital (LUMO)  of N 2 O for Fe 3 (btc) 2 compared to Cu 3 (btc) 2 . The results indicate the important role of charge transfer for the N-O bond breaking in N 2 O. We computationally screened other MOF M 3 (btc) 2 (M = Cr, Fe, Co, Ni, Cu, and Zn) compounds in this respect and show some relationships between the activation energy and orbital properties like HOMO energies and the spin densities of the metals at the active sites of the MOFs.

Integrated assessment on groundwater nitrate by unsaturated zone probing and aquifer sampling with environmental tracers.

PubMed

Yuan, Lijuan; Pang, Zhonghe; Huang, Tianming

2012-12-01

By employing chemical and isotopic tracers ((15)N and (18)O in NO(3)(-)), we investigated the main processes controlling nitrate distribution in the unsaturated zone and aquifer. Soil water was extracted from two soil cores drilled in a typical agricultural cropping area of the North China Plain (NCP), where groundwater was also sampled. The results indicate that evaporation and denitrification are the two major causes of the distribution of nitrate in soil water extracts in the unsaturated zone. Evaporation from unsaturated zone is evidenced by a positive correlation between chloride and nitrate, and denitrification by a strong linear relationship between [Formula: see text] and ln(NO(3)(-)/Cl). The latter is estimated to account for up to 50% of the nitrate loss from soil drainage. In the saturated zone, nitrate is reduced at varying extents (100 mg/L and 10 mg/L at two sites, respectively), largely by dilution of the aquifer water. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Unsaturated magnetoconductance of epitaxial La0.7Sr0.3MnO3 thin films in pulsed magnetic fields up to 60 T

NASA Astrophysics Data System (ADS)

Niu, Wei; Wang, Xuefeng; Gao, Ming; Xia, Zhengcai; Du, Jun; Nie, Yuefeng; Song, Fengqi; Xu, Yongbing; Zhang, Rong

2017-05-01

We report on the temperature and field dependence of resistance of La0.7Sr0.3MnO3 thin films over a wide temperature range and in pulsed magnetic fields up to 60 T. The epitaxial La0.7Sr0.3MnO3 thin films were deposited by laser molecular beam epitaxy. High magnetic field magnetoresistance curves were fitted by the Brillouin function, which indicated the existence of magnetically polarized regions and the underlying hopping mechanism. The unsaturated magnetoconductance was the most striking finding observed in pulsed magnetic fields up to 60 T. These observations can deepen the fundamental understanding of the colossal magnetoresistance in manganites with strong correlation of transport properties and magnetic ordering.

Studies on unsaturated flow in dual-scale fiber fabrics

NASA Astrophysics Data System (ADS)

Yan, Fei; Yan, Shilin; Li, Yongjing

2018-03-01

Fiber fabrics in liquid composite molding (LCM) can be recognized as a dual-scale structure. As sink theory developed, this unsaturated flow behavior has already been simulated successfully; however, most of simulated results based on a unit cell under ideal status, thus making results were not agreement with experiment. In this study, an experimental method to establish sink function was proposed. After compared the simulation results by this sink function, it shows high accuracy with the experimental data. Subsequently, the key influencing factors for unsaturated flow have been further investigated; results show that the filling time for unsaturated flow was much longer than saturated flow. In addition, the injection pressure and permeability were the key factors lead to unsaturated flow.

Base flow recession from unsaturated-saturated porous media considering lateral unsaturated discharge and aquifer compressibility

NASA Astrophysics Data System (ADS)

Liang, Xiuyu; Zhan, Hongbin; Zhang, You-Kuan; Schilling, Keith

2017-09-01

Unsaturated flow is an important process in base flow recessions and its effect is rarely investigated. A mathematical model for a coupled unsaturated-saturated flow in a horizontally unconfined aquifer with time-dependent infiltrations is presented. The effects of the lateral discharge of the unsaturated zone and aquifer compressibility are specifically taken into consideration. Semianalytical solutions for hydraulic heads and discharges are derived using Laplace transform and Cosine transform. The solutions are compared with solutions of the linearized Boussinesq equation (LB solution) and the linearized Laplace equation (LL solution), respectively. A larger dimensionless constitutive exponent κD (a smaller retention capacity) of the unsaturated zone leads to a smaller discharge during the infiltration period and a larger discharge after the infiltration. The lateral discharge of the unsaturated zone is significant when κD≤1, and becomes negligible when κD≥100. The compressibility of the aquifer has a nonnegligible impact on the discharge at early times. For late times, the power index b of the recession curve -dQ/dt˜ aQb, is 1 and independent of κD, where Q is the base flow and a is a constant lumped aquifer parameter. For early times, b is approximately equal to 3 but it approaches infinity when t→0. The present solution is applied to synthetic and field cases. The present solution matched the synthetic data better than both the LL and LB solutions, with a minimum relative error of 16% for estimate of hydraulic conductivity. The present solution was applied to the observed streamflow discharge in Iowa, and the estimated values of the aquifer parameters were reasonable.

Microbial dispersal in unsaturated porous media: Characteristics of motile bacterial cell motions in unsaturated angular pore networks

NASA Astrophysics Data System (ADS)

Ebrahimi, Ali N.; Or, Dani

2014-09-01

The dispersal rates of self-propelled microorganisms affect their spatial interactions and the ecological functioning of microbial communities. Microbial dispersal rates affect risk of contamination of water resources by soil-borne pathogens, the inoculation of plant roots, or the rates of spoilage of food products. In contrast with the wealth of information on microbial dispersal in water replete systems, very little is known about their dispersal rates in unsaturated porous media. The fragmented aqueous phase occupying complex soil pore spaces suppress motility and limits dispersal ranges in unsaturated soil. The primary objective of this study was to systematically evaluate key factors that shape microbial dispersal in model unsaturated porous media to quantify effects of saturation, pore space geometry, and chemotaxis on characteristics of principles that govern motile microbial dispersion in unsaturated soil. We constructed a novel 3-D angular pore network model (PNM) to mimic aqueous pathways in soil for different hydration conditions; within the PNM, we employed an individual-based model that considers physiological and biophysical properties of motile and chemotactic bacteria. The effects of hydration conditions on first passage times in different pore networks were studied showing that fragmentation of aquatic habitats under dry conditions sharply suppresses nutrient transport and microbial dispersal rates in good agreement with limited experimental data. Chemotactically biased mean travel speed of microbial cells across 9 mm saturated PNM was ˜3 mm/h decreasing exponentially to 0.45 mm/h for the PNM at matric potential of -15 kPa (for -35 kPa, dispersal practically ceases and the mean travel time to traverse the 9 mm PNM exceeds 1 year). Results indicate that chemotaxis enhances dispersal rates by orders of magnitude relative to random (diffusive) motions. Model predictions considering microbial cell sizes relative to available liquid pathways sizes were

Nitrogen fluxes through unsaturated zones in five agricultural settings across the USA

NASA Astrophysics Data System (ADS)

Green, C. T.; Fisher, L. H.; Bekins, B. A.

2006-12-01

The main controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Washington, Nebraska, Indiana, and Maryland in 2004 and 2005. Sites included irrigated and non-irrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 0.5 to 20 m. Chemical analyses of water from lysimeters, shallow wells, and sediment cores indicate that advective transport of nitrate is the dominant process affecting the rate of N transport below the root zone. Vertical profiles of (1) N species, (2) stable N and O isotopes, and (3) oxygen gas in unsaturated zone air and shallow ground water, and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. Relatively stable concentrations at depths greater than a few meters allow calculation of nitrogen fluxes to the saturated zone. These fluxes are equivalent to 14 - 64% of the N application rates. At the same locations, median vertical fluxes of N in ground water are generally lower, ranging from 4 - 37% of N application rates. The lower nitrate fluxes in ground water reflect processes including lateral flow to tile drains and denitrification in the capillary fringe, as well as historical changes in N inputs.

Organocatalytic Enantioselective Michael/Cyclization Domino Reaction between 3-Amideoxindoles and α,β-Unsaturated Aldehydes: One-Pot Preparation of Chiral Spirocyclic Oxindole-γ-lactams.

PubMed

Yang, Peng; Wang, Xiao; Chen, Feng; Zhang, Zheng-Bing; Chen, Chao; Peng, Lin; Wang, Li-Xin

2017-04-07

The first organocatalytic enantioselective Michael/cyclization domino reaction between 3-amideoxindoles and α,β-unsaturated aldehydes is described. After sequential oxidation with pyridinium chlorochromate, a direct and one-pot preparation of highly sterically hindered spirocyclic oxindole-γ-lactams was achieved in 51-81% yields with 75-97% ee and ≤80/20 dr.

Unsaturation level decreased in bone marrow fat of postmenopausal women with low bone density using high resolution magic angle spinning (HRMAS) 1H NMR spectroscopy.

PubMed

Li, Xiaojuan; Shet, Keerthi; Xu, Kaipin; Rodríguez, Juan Pablo; Pino, Ana María; Kurhanewicz, John; Schwartz, Ann; Rosen, Clifford J

2017-12-01

There are increasing evidences suggesting bone marrow adiposity tissue (MAT) plays a critical role in affecting both bone quantity and quality. However, very limited studies that have investigated the association between the composition of MAT and bone mineral density (BMD). The goal of this study was to quantify MAT unsaturation profile of marrow samples from post-menopausal women using ex vivo high-resolution magic angle spinning (HRMAS) proton nuclear magnetic resonance ( 1 H NMR) spectroscopy, and to investigate the relationship between MAT composition and BMD. Bone marrow samples were obtained by iliac crest aspiration during surgical procedures from 24 postmenopausal women (65-89years) who had hip surgery due to bone fracture or arthroplasty. Marrow fat composition parameters, in particular, unsaturation level (UL), mono-unsaturation level (MUL) and saturation level (SL), were quantified using HRMAS 1 H NMR spectroscopy. The patients were classified into three groups based on the DXA BMD T-scores: controls, osteopenia and osteoporosis. Marrow fat composition was compared between these three groups as well as between subjects with and without factures using ANOCOVA, adjusted for age. Subjects with lower BMD (n=17) had significantly lower MUL (P=0.003) and UL (P=0.039), and significantly higher SL (P=0.039) compared to controls (n=7). When separating lower BMD into osteopenia (n=9) and osteoporosis (n=8) groups, subjects with osteopenia had significantly lower MUL (P=0.002) and UL (P=0.010), and significantly higher SL (P=0.010) compared to healthy controls. No significant difference was observed between subjects with osteopenia and osteoporosis. Using HRMAS 1 H NMR, significantly lower unsaturation and significantly higher saturation levels were observed in the marrow fat of subjects with lower BMD. HRMAS 1 H NMR was shown to be a powerful tool for identifying novel MR markers of marrow fat composition that are associated with bone quality and potentially

Development of an Unsaturated Region Below a Perennial River

NASA Astrophysics Data System (ADS)

Su, G. W.; Zhou, Q.; Constantz, J.; Hatch, C.

2004-12-01

Field observations at the Russian River Bank Filtration Facility in Sonoma County, California indicate that an unsaturated region exists below the streambed near two adjacent groundwater pumping wells located along the riverbank. Understanding the conditions that give rise to unsaturated flow below the streambed is critical for improving and optimizing riverbank well pumping operations. To investigate the development of an unsaturated region below a perennial river near pumping wells, a three-dimensional model was developed using the multi-phase subsurface flow model, TOUGH2. The model is based on the region around the two pumping wells in the Russian River Bank Filtration Facility. The pumping wells consist of 9 perforated pipes that are projected horizontally into the aquifer at a depth of approximately 20 m below the land surface. A grid was developed for the TOUGH2 model with finer resolution near the wells to represent individual pipes. The effect of varying the pumping operation and the streambed permeability on the extent of the unsaturated region was investigated with the TOUGH2 model. The formation remained saturated below the streambed when only one of the wells was pumped at a rate of 1600 m3/hr, but an unsaturated region developed below the streambed when the two wells each pumped at a rate of 1600 m3/hr. This unsaturated region was deeper when the permeability of the streambed was lower than the aquifer material compared to when the streambed and aquifer permeabilities were the same.

Nutritional quality of fish faeces is enhanced by highly unsaturated fatty acid-producing heterotrophic protozoa

NASA Astrophysics Data System (ADS)

Fujibayashi, Megumu; Tanaka, Nobuyuki; Hashido, Shun; Takasawa, Aya; Nishimura, Osamu

2018-05-01

Highly unsaturated fatty acids such as 20:5n3 (EPA) are both hormone precursors and cell membrane components, making them important nutrients for aquatic animals. Many animals must obtain EPA from their diets because they cannot synthesize enough EPA to meet their requirements, and algae are the main source of EPA in aquatic ecosystems. In a previous study, we detected EPA in the faeces of Danio rerio, a freshwater fish, even though the fish consumed a green algae diet that did not contain EPA. The objective of this study was to determine why EPA was detected in fish faeces. A significant positive relationship was detected between the number of heterotrophic protozoa and the concentration of EPA in the faeces, which suggests that this EPA was of protozoan origin. In addition, another experiment showed that protozoa adhered to faeces far more than the green algal diet remnants, which indicates that protozoa preferred to swarm on faeces. Furthermore, we cultured protozoa in an EPA-free medium and fed them a bacterial diet also lacking EPA, and found that Cyclidium sp. synthesized EPA de novo. The results demonstrate that protozoa produce essential fatty acids and enhance the nutritional quality of animal faeces in detritus-based food webs in freshwater ecosystems.

Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

USDA-ARS?s Scientific Manuscript database

A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

Stabilized unsaturated polyesters

NASA Technical Reports Server (NTRS)

Vogl, O.; Borsig, E. (Inventor)

1985-01-01

An unsaturated polyester, such as propylene glycolmaleic acid phthalic acid prepolymer dissolved in styrene is interpolymerized with an ultraviolet absorber and/or an antioxidant. The unsaturated chain may be filled with H or lower alkyl such as methyl and tertiary alkyl such as tertiary butyl. A polymer stable to exposure to the outdoors without degradation by ultraviolet radiation, thermal and/or photooxidation is formed.

Fate and Transport of CL-20 and RDX in Unsaturated Laboratory Columns

NASA Astrophysics Data System (ADS)

Lemond, L. A.; Gamerdinger, A. P.; Szecsody, J. E.

2005-05-01

This research examines the fate and transport of two explosive compounds, Hexanitrohexaazaisowurtzitane (CL-20) and Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in unsaturated laboratory columns. The transport and fate of these compounds were studied under saturated and unsaturated conditions in three natural soils: coarse sand, sandy loam, and a silt loam. Unsaturated column experiments were conducted using an ultra-centrifugation method. Sorption and degradation parameters were determined by moment analysis and hydrodynamic parameters were assessed with a two-region flow model. Differences in these parameters were evaluated as a function of water content. The fate and transport of CL-20 is highly dependent on 1) the soil type and 2) the compound's residence time in the soil and 3) water content of the media. Sorption of CL-20 was rate-limited. CL-20 degradation in saturated columns produced a half-life of as much as 22hr, but in unsaturated columns the degradation rate increased considerably, producing a half life of as little as 2hr. The fate and transport of RDX are also affected by the soil type, but sorption appeared to be instantaneous. Degradation of RDX was negligible. Our results suggest that at very low water content immobile water regions may become (at least in effect) isolated water regions and significantly alter the retardation of the tracer. In the sandy loam, there was as much as a 20-fold over-prediction of the retardation factor in the unsaturated saturated columns when predicted by Kd values derived from saturated columns. In the coarse sand, Kd values derived from saturated columns over-predicted retardation in the unsaturated columns by as much as 30%. In the silt loam, retardation factors were over-predicted by as much as 80%. At very low water contents, predictions of tracer behavior become very difficult because of changes in the flow regime that cannot be directly accounted for.

STRUCTURE TOXICITY IN RELATIONSHIPS FOR A,B-UNSATURATED ALCOHOLS IN FISH

EPA Science Inventory

Previous toxicity testing with fathead minnows (Pimephales promelas) indicated that some unsaturated acetylenic and allylic alcohols can be metabolically activated, via alcohol dehydrogenase, to highly toxic a,B-unsaturated aldehydes and ketones or allene derivatives. lthough sev...

Measurement and modeling of unsaturated hydraulic conductivity

USGS Publications Warehouse

Perkins, Kim S.; Elango, Lakshmanan

2011-01-01

The unsaturated zone plays an extremely important hydrologic role that influences water quality and quantity, ecosystem function and health, the connection between atmospheric and terrestrial processes, nutrient cycling, soil development, and natural hazards such as flooding and landslides. Unsaturated hydraulic conductivity is one of the main properties considered to govern flow; however it is very difficult to measure accurately. Knowledge of the highly nonlinear relationship between unsaturated hydraulic conductivity (K) and volumetric water content is required for widely-used models of water flow and solute transport processes in the unsaturated zone. Measurement of unsaturated hydraulic conductivity of sediments is costly and time consuming, therefore use of models that estimate this property from more easily measured bulk-physical properties is common. In hydrologic studies, calculations based on property-transfer models informed by hydraulic property databases are often used in lieu of measured data from the site of interest. Reliance on database-informed predicted values with the use of neural networks has become increasingly common. Hydraulic properties predicted using databases may be adequate in some applications, but not others. This chapter will discuss, by way of examples, various techniques used to measure and model hydraulic conductivity as a function of water content, K. The parameters that describe the K curve obtained by different methods are used directly in Richards’ equation-based numerical models, which have some degree of sensitivity to those parameters. This chapter will explore the complications of using laboratory measured or estimated properties for field scale investigations to shed light on how adequately the processes are represented. Additionally, some more recent concepts for representing unsaturated-zone flow processes will be discussed.

Process for the synthesis of unsaturated alcohols

DOEpatents

Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

2007-02-13

A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

Intravenous iron-dextran: studies on unsaturated iron-binding capacity

PubMed Central

Cox, J. S. G.; Moss, G. F.; Bremner, I.; Reason, Janet

1968-01-01

A method is described for measuring the plasma unsaturated iron-binding capacity in the presence of very high concentrations of iron as iron-dextran. The procedure utilizes 59Fe to label the apotransferrin with subsequent separation of ionic iron from transferrin-bound iron on an ion exchange or Sephadex G.25 column. The unsaturated iron-binding capacity has been measured in rabbits and dogs after intravenous injection of iron-dextran and in human subjects after total dose infusion of iron-dextran. No evidence of saturation of the unsaturated iron-binding capacity was found even when the plasma iron values were greater than 40,000 μg Fe/100 ml. PMID:5697365

Effects of Diets High in Unsaturated Fatty Acids on Socially Induced Stress Responses in Guinea Pigs

PubMed Central

Nemeth, Matthias; Millesi, Eva; Wagner, Karl-Heinz; Wallner, Bernard

2014-01-01

Unsaturated fatty acids (UFAs), such as omega-3 and omega-6 poly- and omega-9 monounsaturated fatty acids are important nutrients and major components of neuronal cell membranes. They play a major role in modulating brain functions and physiology and may therefore diminish behavioral and physiological stress reactions in corroboration with decreased cortisol concentrations. Functionally, cortisol itself can modulate several behaviors and also the fatty acid metabolism in the long term. But only little is known about the behavioral and physiological influences of dietary UFAs in a social group, where individuals are regularly exposed to stressful situations. Therefore, the aim of this study was to determine the effects of dietary UFAs on saliva cortisol concentrations and behavioral responses in socially confronted guinea pigs. Three groups of animals were additionally supplemented with 500 mg chia seeds (high in omega-3), walnuts (high in omega-6), or peanuts (high in omega-9) per kg bodyweight each day and compared to a control group. During social confrontation saliva cortisol concentrations significantly increased in all groups, which was accompanied by a loss in bodyweight. However, cortisol levels remained lower in the chia and walnut groups compared to controls. Additionally, the walnut group displayed significantly increased locomotion, while no differences between groups were detected in socio-positive, sexual, or aggressive behaviors. Total plasma omega-3, omega-6, and omega-9 fatty acids were significantly increased in the corresponding groups, due to the dietary supplementations. However, a significant decrease in plasma omega-3 and an increase in plasma n-6 fatty acids were detected in the chia group when comparing the measurements before and after social confrontation. We conclude that both omega-3 and omega-6 polyunsaturated fatty acids can diminish behavioral and physiological stress responses to the social environment, enabling individuals to cope

Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.

PubMed

Sammis, Glenn M; Danjo, Hiroshi; Jacobsen, Eric N

2004-08-18

Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.

Transport of citrate-coated silver nanoparticles in unsaturated sand

NASA Astrophysics Data System (ADS)

Kumahor, Samuel; Hron, Pavel; Metreveli, George; Schaumann, Gabriele; Vogel, Hans-Jörg

2015-04-01

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Unlike for saturated transport, studies on unsaturated transport as typical for soil are currently scarce. We investigated the mobility of citrate-coated Ag NPs in unsaturated sand (grain diameter: 0.1-0.3 mm). For three flux rates and a given pore-water ionic strength (1 mM KNO3), the citrate-coated Ag NPs were less mobile at pH = 5 compared to pH = 9. The classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory suggests unfavorable deposition conditions at both, the air-water interface and solid-water interface. Breakthrough curves measured under quasi-steady state unsaturated flow showed retardation of the citrate-coated Ag NPs compared to inert solute (KBr). After flushing with nanoparticle-free 1 mM KNO3 solution (pH-adjusted), retention was much lower in deeper depths compared to the surface where the particles entered the flow field. The results show a non-linear dependence of nanoparticle (NP) mobility on flux rate and water content. Especially the observed retardation similar to equilibrium sorption is in contrast to observations under saturated flow conditions. A convection-dispersion and reaction model that combines a reversible equilibrium process and a non-equilibrium interaction process reproduced the measured breakthrough curves reasonably well. From comparison between saturated and unsaturated experiments we conclude that the air-water interface is responsible for the reversible equilibrium process while the water-solid interface accounts for irreversible soption.

Percolation induced heat transfer in deep unsaturated zones

USGS Publications Warehouse

Lu, N.; LeCain, G.D.

2003-01-01

Subsurface temperature data from a borehole located in a desert wash were measured and used to delineate the conductive and advective heat transfer regimes, and to estimate the percolation quantity associated with the 1997-1998 El Ni??no precipitation. In an arid environment, conductive heat transfer dominates the variation of shallow subsurface temperature most of the time, except during sporadic precipitation periods. The subsurface time-varying temperature due to conductive heat transfer is highly correlated with the surface atmospheric temperature variation, whereas temperature variation due to advective heat transfer is strongly correlated with precipitation events. The advective heat transfer associated with precipitation and infiltration is the focus of this paper. Disruptions of the subsurface conductive temperature regime, associated with the 1997-1998 El Ni??no precipitation, were detected and used to quantify the percolation quantity. Modeling synthesis using a one-dimensional coupled heat and unsaturated flow model indicated that a percolation per unit area of 0.7 to 1.3 m height of water in two weeks during February 1998 was responsible for the observed temperature deviations down to a depth of 35.2 m. The reported study demonstrated quantitatively, for the first time, that the near surface temperature variation due to advective heat transfer can be significant at a depth greater than 10 m in unsaturated soils and can be used to infer the percolation amount in thick unsaturated soils.

Analysis of Rainfall Infiltration Law in Unsaturated Soil Slope

PubMed Central

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θ s - θ r), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process. PMID:24672332

Analysis of rainfall infiltration law in unsaturated soil slope.

PubMed

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θs - θr), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process.

Observations on preferential flow and horizontal transport of nitrogen fertilizer in the unsaturated zone

USGS Publications Warehouse

Wilkison, D.H.; Blevins, D.W.

1999-01-01

A study site underlain by a claypan soil was instrumented to examine the transport of fertilizer nitrogen (N) under corn (Zea mays L.) cultivation. The study was designed to examine N transport within the unsaturated zone and in interflow (the saturated flow of water on top of the claypan). A 15N- labeled fertilizer (labeled N), bromide (Br), and chloride (Cl) were used as field tracers. Rapid or prolonged infiltration events allowed water and dissolved solutes to perch on the claypan for brief periods. However, a well- developed network of preferential flow paths quickly diverted water and solutes through the claypan and into the underlying glacial till aquifer. Excess fertilizer N in the unsaturated zone supplied a continuous, but declining input of N to ground water for a period of 15 mo after a single fertilizer application. Calculated solute velocities through the claypan matrix (6.4 x 10-6 cm s-1) were similar to horizontal transport rates along the claypan (3.5 to 7.3 x 10-6 cm s-1) but much slower than infiltration rates determined for preferential flow paths (1.67 x 10-3 cm s-1). These flow paths accounted for 35% of the transport. A seasonally variable, dual mode of transport (matrix and preferential flow) prevented the claypan from being an effective barrier to vertical transport. Simulations of selected field observations, conducted using the variably saturated two- dimensional flow and transport model, VS2DT, confirmed the presence of a dual flow regime in the claypan.

Aquifer Recharge Estimation In Unsaturated Porous Rock Using Darcian And Geophysical Methods.

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; De Carlo, L.; Masciale, R.; Turturro, A. C.; Perkins, K. S.; Caputo, M. C.

2016-12-01

Within the unsaturated zone a constant downward gravity-driven flux of water commonly exists at depths ranging from a few meters to tens of meters depending on climate, medium, and vegetation. In this case a steady-state application of Darcy's law can provide recharge rate estimates.We have applied an integrated approach that combines field geophysical measurements with laboratory hydraulic property measurements on core samples to produce accurate estimates of steady-state aquifer recharge, or, in cases where episodic recharge also occurs, the steady component of recharge. The method requires (1) measurement of the water content existing in the deep unsaturated zone at the location of a core sample retrieved for lab measurements, and (2) measurement of the core sample's unsaturated hydraulic conductivity over a range of water content that includes the value measured in situ. Both types of measurements must be done with high accuracy. Darcy's law applied with the measured unsaturated hydraulic conductivity and gravitational driving force provides recharge estimates.Aquifer recharge was estimated using Darcian and geophysical methods at a deep porous rock (calcarenite) experimental site in Canosa, southern Italy. Electrical Resistivity Tomography (ERT) and Vertical Electrical Sounding (VES) profiles were collected from the land surface to water table to provide data for Darcian recharge estimation. Volumetric water content was estimated from resistivity profiles using a laboratory-derived calibration function based on Archie's law for rock samples from the experimental site, where electrical conductivity of the rock was related to the porosity and water saturation. Multiple-depth core samples were evaluated using the Quasi-Steady Centrifuge (QSC) method to obtain hydraulic conductivity (K), matric potential (ψ), and water content (θ) estimates within this profile. Laboratory-determined unsaturated hydraulic conductivity ranged from 3.90 x 10-9 to 1.02 x 10-5 m

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

PubMed

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

Early endothelial damage detected by circulating particles in baboons fed a diet high in simple carbohydrates in conjunction with saturated or unsaturated fat.

PubMed

Shi, Qiang; Hodara, Vida; Meng, Qinghe; Voruganti, V Saroja; Rice, Karen; Michalek, Joel E; Comuzzie, Anthony G; VandeBerg, John L

2014-01-01

Studies have shown that high-fat diets cause blood vessel damage, however, assessing pathological effects accurately and efficiently is difficult. In this study, we measured particle levels of static endothelium (CD31+ and CD105+) and activated endothelium (CD62E+, CD54+ and CD106+) in plasma. We determined individual responses to two dietary regimens in two groups of baboons. One group (n = 10), was fed a diet high in simple carbohydrates and saturated fats (the HSF diet) and the other (n = 8) received a diet high in simple carbohydrates and unsaturated fats (the HUF diet). Plasma samples were collected at 0, 3, and 7 weeks. The percentages of CD31+ and CD62E+ particles were elevated at 3 weeks in animals fed either diet, but these elevations were statistically significant only in animals fed the HUF diet. Surprisingly, both percentages and counts of CD31+ particles were significantly lower at week 7 compared to week 0 and 3 in the HSF group. The median absolute counts of CD105+ particles were progressively elevated over time in the HSF group with a significant increase from week 0 to 7; the pattern was somewhat different for the HUF group with significant increase from week 3 to 7. The counts of CD54+ particles exhibited wide variation in both groups during the dietary challenge, while the median counts of CD106+ particles were significantly lower at week 3 than at week 0 and week 7. Endothelial particles exhibited time-dependent changes, suggesting they were behaving as quantifiable surrogates for the early detection of vascular damage caused by dietary factors.

Pumping-Induced Unsaturated Regions Beneath a Perennial River

NASA Astrophysics Data System (ADS)

Su, G. W.; Jasperse, J.; Seymour, D.; Constantz, J.; Delaney, C.; Zhou, Q.

2006-12-01

The development of an unsaturated region beneath a streambed during groundwater pumping near streams reduces the capacity of the pumping system, changes flow paths, and alters the types of biological transformations in the streambed sediments. To investigate the formation of an unsaturated region beneath the streambed during near-stream groundwater pumping, a three-dimensional, multi-phase flow model was developed using TOUGH2 of the region near two horizontal collector wells operated by the Sonoma County Water Agency along the Russian River near Forestville, California. The simulations focus on the impact of streambed permeability on the development of an unsaturated region since streambed permeability controls the flux of river water entering and recharging the aquifer. The results indicate that as the streambed permeability decreases relative to the aquifer permeability, the size of the unsaturated region beneath the streambed increases. The simulations also demonstrate that the streambed permeabilities over which the aquifer beneath the streambed is unsaturated and able to extract water at the specified rate of 3200 m3/hr occurs over a relatively narrow range of values. Field measurements of streambed flow velocities, volumetric water content, and temperatures near the collector wells are also presented and compared with the simulation results. This work was supported by the Sonoma County Water Agency, through U.S. Department of Energy Contract No. DE-AC03-76SF00098.

UNSATURATED AMINO ACIDS V.

PubMed Central

Shapira, Jacob; Dittmer, Karl

1961-01-01

Shapira, Jacob (Department of Chemistry, Florida State University, Tallahassee) and Karl Dittmer. Unsaturated amino acids. V. Microbiological properties of some halogenated olefinic amino acids. J. Bacteriol. 82:640–647. 1961.—It has been shown previously that several amino acid analogues containing unsaturated linkages were inhibitors of the growth of Escherichia coli and Saccharomyces cerevisiae. This paper reports the results obtained when a series of unsaturated halogen-containing amino acids was examined. The cis isomer of ω-chloroallylglycine showed the greatest toxicity yet found in this series of unsaturated amino acids toward E. coli, whereas the trans-isomer was usually far less toxic. The major effect of cis-ω-chloroallylglycine in E. coli appeared to be to extend the lag phase before the normal rate of growth began. A wide variety of amino acids was capable of partially or completely preventing the toxicity of low levels of these compounds. At higher levels, relatively few amino acids (primarily valine, leucine, and glutamic acid) were effective. In E. coli, cis-ω-chloroallylglycine showed an unusual [Formula: see text] relationship with both glutamic acid and valine over a wide range in concentration. PMID:13911278

Rhodium-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds: large accelerating effects of bases and ligands.

PubMed

Itooka, Ryoh; Iguchi, Yuki; Miyaura, Norio

2003-07-25

The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)](2) exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 degrees C. A cationic rhodium(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF(4), catalyzed the reaction at 25-50 degrees C in the presence of Et(3)N with high enantioselectivities of up to 99% ee for alpha,beta-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.

PRZM-3, A MODEL FOR PREDICTING PESTICIDE AND NITROGEN FATE IN THE CROP ROOT AND UNSATURATED SOIL ZONES: USER'S MANUAL FOR RELEASE 3.12.2

EPA Science Inventory

This publication contains documentation for the PRZM-3 model. PRZM-3 is the most recent version of a modeling system that links two subordinate models, PRZM and VADOFT, in order to predict pesticide transport and transformation down through the crop root and unsaturated soil zone...

Metal-free catalytic enantioselective C-B bond formation: (pinacolato)boron conjugate additions to α,β-unsaturated ketones, esters, Weinreb amides, and aldehydes promoted by chiral N-heterocyclic carbenes.

PubMed

Wu, Hao; Radomkit, Suttipol; O'Brien, Jeannette M; Hoveyda, Amir H

2012-05-16

The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C-B bond forming reactions are promoted in the presence of 2.5-7.5 mol % of a readily accessible C(1)-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B(2)(pin)(2)], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides, and aldehydes, can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50-66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene, or aldehyde).

Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

PubMed Central

Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

2012-01-01

The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

Metamodeling and mapping of nitrate flux in the unsaturated zone and groundwater, Wisconsin, USA

NASA Astrophysics Data System (ADS)

Nolan, Bernard T.; Green, Christopher T.; Juckem, Paul F.; Liao, Lixia; Reddy, James E.

2018-04-01

Nitrate contamination of groundwater in agricultural areas poses a major challenge to the sustainability of water resources. Aquifer vulnerability models are useful tools that can help resource managers identify areas of concern, but quantifying nitrogen (N) inputs in such models is challenging, especially at large spatial scales. We sought to improve regional nitrate (NO3-) input functions by characterizing unsaturated zone NO3- transport to groundwater through use of surrogate, machine-learning metamodels of a process-based N flux model. The metamodels used boosted regression trees (BRTs) to relate mappable landscape variables to parameters and outputs of a previous "vertical flux method" (VFM) applied at sampled wells in the Fox, Wolf, and Peshtigo (FWP) river basins in northeastern Wisconsin. In this context, the metamodels upscaled the VFM results throughout the region, and the VFM parameters and outputs are the metamodel response variables. The study area encompassed the domain of a detailed numerical model that provided additional predictor variables, including groundwater recharge, to the metamodels. We used a statistical learning framework to test a range of model complexities to identify suitable hyperparameters of the six BRT metamodels corresponding to each response variable of interest: NO3- source concentration factor (which determines the local NO3- input concentration); unsaturated zone travel time; NO3- concentration at the water table in 1980, 2000, and 2020 (three separate metamodels); and NO3- "extinction depth", the eventual steady state depth of the NO3- front. The final metamodels were trained to 129 wells within the active numerical flow model area, and considered 58 mappable predictor variables compiled in a geographic information system (GIS). These metamodels had training and cross-validation testing R2 values of 0.52 - 0.86 and 0.22 - 0.38, respectively, and predictions were compiled as maps of the above response variables. Testing

Water Drainage from Unsaturated Soils in a Centrifuge Permeameter

NASA Astrophysics Data System (ADS)

Ornelas, G.; McCartney, J.; Zhang, M.

2013-12-01

This study involves an analysis of water drainage from an initially saturated silt layer in a centrifuge permeameter to evaluate the hydraulic properties of the soil layer in unsaturated conditions up to the point where the water phase becomes discontinuous. These properties include the soil water retention curve (SWRC) and the hydraulic conductivity function (HCF). The hydraulic properties of unsaturated silt are used in soil-atmosphere interaction models that take into account the role of infiltration and evaporation of water from soils due to atmospheric interaction. These models are often applied in slope stability analyses, landfill cover design, aquifer recharge analyses, and agricultural engineering. The hydraulic properties are also relevant to recent research concerning geothermal heating and cooling, as they can be used to assess the insulating effects of soil around underground heat exchangers. This study employs a high-speed geotechnical centrifuge to increase the self-weight of a compacted silt specimen atop a filter plate. Under a centrifuge acceleration of N times earth's gravity, the concept of geometric similitude indicates that the water flow process in a small-scale soil layer will be similar to those in a soil layer in the field that is N times thicker. The centrifuge acceleration also results in an increase in the hydraulic gradient across the silt specimen, which causes water to flow out of the pores following Darcy's law. The drainage test was performed until the rate of liquid water flow out of the soil layer slowed to a negligible level, which corresponds to the transition point at which further water flow can only occur due to water vapor diffusion following Fick's law. The data from the drainage test in the centrifuge were used to determine the SWRC and HCF at different depths in the silt specimen, which compared well with similar properties defined using other laboratory tests. The transition point at which liquid water flow stopped (and

Effect Of Air-Water Interface On Microorganism Transport Under Unsaturated Conditions

NASA Astrophysics Data System (ADS)

Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.

2005-12-01

Groundwater may become contaminated with pathogenic microorganisms from land application of treated wastewater, septic wells, and effluent from septic tanks, and leaking sewage pipes. The unsaturated zone is of special importance since it often represents the first line of natural defense against groundwater pollution. Moreover, many experimental studies have shown that contaminant removal is more significant under lower saturation levels. Interaction of microbial particles with the air-water interfaces (AWI) has been previously suggested to explain high removal of pathogenic microorganisms during transport through unsaturated soil. The objective of this research was to explore the effect of AWI on virus transport. The transport of bacteriophages MS2 and FiX174 in sand columns was studied under various conditions, such as different pH, and saturation levels. Fitting of a transport model to the breakthrough curves was performed to determine the adsorption parameters. FiX174 with isoelectric point of 6.7 exhibited high affinity to the air-water interface by decreasing pH from 7.5 to 6.2. MS2 with isoelectric point of 3.5 has lower affinity to air-water interfaces than FiX174, but has similar pH- dependence. These results show the importance of electrostatic interactions, instead of hydrophobic, between the AWI and viruses. Adsorption to AWI is strongly pH dependent, increasing as pH decreases. It was found that two-site kinetic model should be used for modeling of virus transport under unsaturated conditions Moreover, by draining the unsaturated column, we found out that the attached viruses to AWI are viable, which is in contrast with the literature where retained viruses to AWI are considered as inactivated.

Mineralization of isoproturon, mecoprop and acetochlor in a deep unsaturated limestone and sandy aquifer.

PubMed

Janniche, G S; Lindberg, E; Mouvet, C; Albrechtsen, H-J

2010-11-01

Isoproturon (N,N-dimethyl-N'-[4-(1-methylethyl)phenyl]urea), mecoprop (MCPP) (2-(4-chloro-2-methylphenoxy)propanoic acid) and acetochlor (2-chloro-N-(2-ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide) are agricultural pesticides that may leach through the vadose zone down to groundwater. Sediment samples were collected from intact sediment cores from 0 to 59 m below surface, including soil, unsaturated limestone and aquifer sand. In the unsaturated limestone, the initial pesticide concentrations (0.5-100 μg kg(-1)) did not systematically affect the proportion of mineralized pesticides or the kinetics. However, in the aquifer, mecoprop and to some degree isoproturon mineralization was found to increase with increasing initial concentration (0.5-100 μg L(-1) equivalent to 1-220 μg kg(-1)) demonstrating the importance of using environmentally relevant concentrations when predicting pesticide fate. The mineralization of isoproturon, mecoprop and acetochlor was studied in 40 samples at low concentrations (1-3 μg L(-1)) and specific pesticide-mineralizing bacteria were enumerated using 14C-MPN. Presence of the mineralizers documented a degradation potential of the pesticides within the catchment. The number of mineralizers varied from <0.18 to >16000 g(-1) and was not found to correlate with depth. Mecoprop, isoproturon and acetochlor were substantially mineralized in the soils (19-44% after 8months incubation at 1 μg kg(-1)), in sub-surface unsaturated limestone samples (≤2% for acetochlor, ≤21% for isoproturon and ≤31% for mecoprop) and in aquifer samples (4-28% for mecoprop, ≤4.7% for isoproturon and ≤5.6% for acetochlor). The finding of isoproturon and acetochlor mineralization in deep aquifers is novel and important for the evaluation of the fate of these pesticides, as even low mineralization rates can be important in aquifers exhibiting long residence times. Copyright © 2010 Elsevier Ltd. All rights reserved.

A series of new manganese thioarsenates(v) based on different unsaturated [Mn(amine)x](2+) complexes.

PubMed

Zhou, Jian; Tan, Xiao-Feng; Liu, Xing; Qing, Miao; Zhao, Rong-Qing; Tang, Qiuling

2015-10-07

A series of new manganese thioarsenates(V) [Mn(en)2Cu(AsVS4)]n (1, en = ethylenediamine), [Mn(dien)2][Mn(dien)(AsVS4)]2 (2, dien = diethylenetriamine), [Mn(teta)(AsVS4)]n (3, teta = triethylenetetramine), and {[Mn(dap)2][Mn(dap)(AsVS4)]2}n (4, dap = 1,2-diaminopropane) have been solvothermally synthesized and structurally characterized. 1 displays a neutral heterometallic [Mn(en)2Cu(AsVS4)]n chain built up from the linkages of [Mn(en)2]2+ complexes and infinite heterometallic [Cu(AsVS4)2−]n chains, and represents the only example of incorporation of an unsaturated [Mn(en)2]2+ complex into the 1-D [Cu(AsVS4)2−]n framework. 2 consists of a discrete {[Mn(dien)]2(AsVS4)2}2− cluster and a charge compensating complex cation [Mn(dien)2]2+. 3 shows a 1-D neutral [Mn(teta)(AsVS4)]n chain constructed by the combination of both complex [Mn(teta)]2+ ions and tetrahedral [AsVS4]3− anions. 4 exhibits a rare 2-D {[Mn(dap)2][Mn(dap)(AsVS4)]2}n layer based on the linkages of [AsVS4]3− anions and [Mn(dap)x]2+ (x = 1, 2) groups. These results show that different unsaturated [Mn(amine)x]2+ complexes are directly bonded to [AsVS4]3− anions to give different manganese thioarsenates(V), which have a significant structure directing effect on the structures of manganese thioarsenates(V) under similar solvothermal conditions. The present compounds exhibit wide-band-gap semiconducting properties with absorption band edges between 2.00 and 2.58 eV, and density functional theory calculations for compounds 1, 3 and 4 have also been performed.

Mechanical properties of three layer glass fibre reinforced unsaturated polyester filled with P84 Polyimide

NASA Astrophysics Data System (ADS)

Ibrahim, Nik Noor Idayu Nik; Mamauod, Siti Nur Liyana; Romli, Ahmad Zafir

2017-12-01

The glass fibre reinforced orthophthalic unsaturated polyester composite was widely used in the pipeline industry as a replacement to the corroded steel pipes. A filler which possesses high mechanical performance at high temperature; P84 Polyimide used as the particulate reinforcement in the unsaturated polyester matrix system to increase the mechanical performance of the glass fibre reinforced unsaturated polyester. The glass fibre composite laminates were prepared through a hand lay-up technique and fabricated into three layer laminate. Prior to be used as the matrix system in the lamination process, the unsaturated polyester resin was mixed with masterbatch P84 Polyimide at three loadings amount of 1, 3, and 5 wt%. The addition of P84 Polyimide at 1, 3, and 5 wt% increased the tensile properties and flexural properties especially at 1 wt% filler loading. As the filler loading increased, the tensile properties and flexural properties showed decreasing pattern. In the dynamic mechanical analysis, the values of storage modulus were taken at two points; 50 °C and 150 °C which were the storage modulus before and after the glass transition temperature. All storage modulus showed fluctuation trend for both before and after Tg. However, the storage modulus of the filled composite laminates after Tg showed higher values than unfilled composite laminates at all filler loading. Since the P84 Polyimide possesses high thermal stability, the presence of P84 Polyimide inside the composite system had assisted in delaying the Tg. In terms of the filler dispersion, the Cole-Cole plot showed an imperfect semi-circular shape which indicated good filler dispersion.

Metallophosphite-Catalyzed Asymmetric Acylation of α,β -Unsaturated Amides

PubMed Central

Nahm, Mary R.; Potnick, Justin R.; White, Peter S.; Johnson, Jeffrey S.

2007-01-01

The l-menthone-derived TADDOL phosphite 6b catalyzes highly enantioselective conjugate additions of acyl silanes to α,β-unsaturated amides. p-Methoxybenzoyl cyclohexyldimethylsilane adds to a variety of N,N-dimethyl acrylamide derivatives in the presence of the lithium salt of 6b. In many instances the α-silyl-γ-ketoamide product undergoes facile enantioenrichment (to 97–99% ee) upon recrystallization. Desilylation with HF·pyr affords the formal Stetter addition products. Baeyer–Villiger oxidation of the desilylated γ-ketoamides affords useful ester products. An X-ray diffraction study of 6b reveals that the isopropyl group of the menthone ketal influences the position of the syn-pseudoaxial phenyl group in the TADDOL structure. Through a crossover experiment, the silicon migration step in the reaction mechanism is shown to be strictly intramolecular. PMID:16492064

Asymmetric conjugate 1,4-addition of arylboronic acids to alpha, beta-unsaturated esters catalyzed by Rhodium(I)/(S)-binap

PubMed

Sakuma; Sakai; Itooka; Miyaura

2000-09-22

Arylboronic acids underwent the conjugate 1,4-addition to alpha, beta-unsaturated esters to give beta-aryl esters in high yields in the presence of a rhodium(I) catalyst. The addition of arylboronic acids to isopropyl crotonate resulted in high yields and high enantioselectivity exceeding 90% ee in the presence of 3 mol % of Rh(acac)(C(2)H(4))(2) and (S)-binap at 100 degrees C. The rhodium/(S)-binap complex provided (R)-3-phenylbutanoate in the addition of phenylboronic acid to benzyl crotonate. The effects on the enantioselectivity of chiral phosphine ligands, rhodium precursors, and substituents on alpha,beta-unsaturated esters are discussed, as well as the mechanistic aspect of the catalytic cycle.

Using ambient ozone for assignment of double bond position in unsaturated lipids.

PubMed

Ellis, Shane R; Hughes, Jessica R; Mitchell, Todd W; in het Panhuis, Marc; Blanksby, Stephen J

2012-03-07

Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.

Non-methylene-interrupted fatty acids with Δ5 unsaturation in Sargassum species.

PubMed

Kim, Gwang-Woo; Itabashi, Yutaka

2012-01-01

Detailed fatty acid compositions of five species of the brown algae Sargassum (S. fulvellum, S. horneri, S. boreale, S. thunbergii, and S. yezoense) were determined using silver ion solid phase extraction, gas chromatography (GC), and GC-mass spectrometry (GC-MS) techniques. In addition to a high number of typical saturated and unsaturated fatty acids, the GC-MS spectra of the 4,4-dimethyloxazoline derivatives of fatty acids revealed the occurrence of small amounts of unusual non-methylene-interrupted (NMI) fatty acids with Δ5 unsaturation, namely, 5,9-eicosadienoic (5,9-20:2), 5,11,14-eicosatrienoic (5,11,14-20:3), and 5,11,14,17-eicosatetraenoic (5,11,14,17-20:4) acids. Of these three NMI acids, the 5,9-20:2 acid was found to be the most abundant (0.4%-2.3% of the total fatty acids) and was detected for the first time in algae.

Metamodeling and mapping of nitrate flux in the unsaturated zone and groundwater, Wisconsin, USA

USGS Publications Warehouse

Nolan, Bernard T.; Green, Christopher T.; Juckem, Paul F.; Liao, Lixia; Reddy, James E.

2018-01-01

Nitrate contamination of groundwater in agricultural areas poses a major challenge to the sustainability of water resources. Aquifer vulnerability models are useful tools that can help resource managers identify areas of concern, but quantifying nitrogen (N) inputs in such models is challenging, especially at large spatial scales. We sought to improve regional nitrate (NO3−) input functions by characterizing unsaturated zone NO3− transport to groundwater through use of surrogate, machine-learning metamodels of a process-based N flux model. The metamodels used boosted regression trees (BRTs) to relate mappable landscape variables to parameters and outputs of a previous “vertical flux method” (VFM) applied at sampled wells in the Fox, Wolf, and Peshtigo (FWP) river basins in northeastern Wisconsin. In this context, the metamodels upscaled the VFM results throughout the region, and the VFM parameters and outputs are the metamodel response variables. The study area encompassed the domain of a detailed numerical model that provided additional predictor variables, including groundwater recharge, to the metamodels. We used a statistical learning framework to test a range of model complexities to identify suitable hyperparameters of the six BRT metamodels corresponding to each response variable of interest: NO3− source concentration factor (which determines the local NO3− input concentration); unsaturated zone travel time; NO3− concentration at the water table in 1980, 2000, and 2020 (three separate metamodels); and NO3− “extinction depth”, the eventual steady state depth of the NO3−front. The final metamodels were trained to 129 wells within the active numerical flow model area, and considered 58 mappable predictor variables compiled in a geographic information system (GIS). These metamodels had training and cross-validation testing R2 values of 0.52 – 0.86 and 0.22 – 0.38, respectively, and predictions were compiled as maps of the above

Nitrate transport and transformation processes in unsaturated porous media

USGS Publications Warehouse

Tindall, James A.; Petrusak, Robin L.; McMahon, Peter B.

1995-01-01

A series of experiments was conducted on two contrasting agricultural soils to observe the influence of soil texture, preferential flow, and plants on nitrate transport and denitrification under unsaturated conditions. Calcium nitrate fertilizer was applied to the surface of four large undisturbed soil cores (30 cm diameter by 40 cm height). Two of the cores were a structured clay obtained from central Missouri and two were an unstructured fine sand obtained from central Florida. The cores were irrigated daily and maintained at a matric potential of -20 kPa, representative of soil tension in the rooting zone of irrigated agricultural fields. Volumetric water content (θ), concentration of nitrate-N in the soil solution, and nitrous oxide flux at the surface, 10, 20, and 30 cm were monitored daily. Leaching loss of surface-applied N03− -N was significant in both the sand and the clay. In unplanted sand cores, almost all of the applied nitrate was leached below 30 cm within 10 days. Gaseous N loss owing to denitrification was no greater than 2% of the nitrate-N applied to the unplanted sand cores and, in general, was less than 1 %. Although leaching was somewhat retarded in the clay cores, about 60% of the applied nitrate-N was leached from the unplanted clay soil in 5–6 weeks. Under unsaturated conditions, the clay had little to no tendency to denitrify despite the greater moisture content of the clay and retarded leaching of nitrate in the clay. The planted sand cores had surprisingly large gaseous N loss owing to denitrification, as much as 17% of the nitrate-N. Results from both the clay and sand experiments show that the dynamics of nitrate transport and transformation in unsaturated soils are affected by small, localized variations in the soil moisture content profile, the gaseous diffusion coefficient of the soil, the rate at which the nitrate pulse passes through the soil, the solubility of N2O and N2 and the diffusion of the gasses through the soil

Effect of Selection for High Activity-Related Metabolism on Membrane Phospholipid Fatty Acid Composition in Bank Voles.

PubMed

Stawski, Clare; Valencak, Teresa G; Ruf, Thomas; Sadowska, Edyta T; Dheyongera, Geoffrey; Rudolf, Agata; Maiti, Uttaran; Koteja, Paweł

2015-01-01

Endothermy, high basal metabolic rates (BMRs), and high locomotor-related metabolism were important steps in the evolution of mammals. It has been proposed that the composition of membrane phospholipid fatty acids plays an important role in energy metabolism and exercise muscle physiology. In particular, the membrane pacemaker theory of metabolism suggests that an increase in cell membrane fatty acid unsaturation would result in an increase in BMR. We aimed to determine whether membrane phospholipid fatty acid composition of heart, liver, and gastrocnemius muscles differed between lines of bank voles selected for high swim-induced aerobic metabolism-which also evolved an increased BMR-and unselected control lines. Proportions of fatty acids significantly differed among the organs: liver was the least unsaturated, whereas the gastrocnemius muscles were most unsaturated. However, fatty acid proportions of the heart and liver did not differ significantly between selected and control lines. In gastrocnemius muscles, significant differences between selection directions were found: compared to control lines, membranes of selected voles were richer in saturated C18:0 and unsaturated C18:2n-6 and C18:3n-3, whereas the pattern was reversed for saturated C16:0 and unsaturated C20:4n-6. Neither unsaturation index nor other combined indexes of fatty acid proportions differed between lines. Thus, our results do not support the membrane pacemaker hypothesis. However, the differences between selected and control lines in gastrocnemius muscles reflect chain lengths rather than number of double bonds and are probably related to differences in locomotor activity per se rather than to differences in the basal or routine metabolic rate.

Exploration of a mechanism for the production of highly unsaturated fatty acids in Scenedesmus sp. at low temperature grown on oil crop residue based medium.

PubMed

Lu, Qian; Li, Jun; Wang, Jinghan; Li, Kun; Li, Jingjing; Han, Pei; Chen, Paul; Zhou, Wenguang

2017-11-01

The ability of algae to produce lipids comprising of unsaturated fatty acids varies with strains and culture conditions. This study investigates the effect of temperature on the production of unsaturated fatty acids in Scenedesmus sp. grown on oil crop residue based medium. At low temperature (10°C), synthesis of lipids compromising of high contents of unsaturated fatty acids took place primarily in the early stage while protein accumulation mainly occurred in the late stage. This stepwise lipid-protein synthesis process was found to be associated with the contents of acetyl-CoA and α-KG in the algal cells. A mechanism was proposed and tested through simulation experiments which quantified the carbon flux allocation in algal cells at different cultivation stages. It is concluded that low culture temperature such as 10°C is suitable for the production of lipids comprising of unsaturated fatty acids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Role of Lipid Peroxidation-Derived α, β-Unsaturated Aldehydes in Vascular Dysfunction

PubMed Central

Lee, Seung Eun; Park, Yong Seek

2013-01-01

Vascular diseases are the most prominent cause of death, and inflammation and vascular dysfunction are key initiators of the pathophysiology of vascular disease. Lipid peroxidation products, such as acrolein and other α, β-unsaturated aldehydes, have been implicated as mediators of inflammation and vascular dysfunction. α, β-Unsaturated aldehydes are toxic because of their high reactivity with nucleophiles and their ability to form protein and DNA adducts without prior metabolic activation. This strong reactivity leads to electrophilic stress that disrupts normal cellular function. Furthermore, α, β-unsaturated aldehydes are reported to cause endothelial dysfunction by induction of oxidative stress, redox-sensitive mechanisms, and inflammatory changes such as induction of cyclooxygenase-2 and cytokines. This review provides an overview of the effects of lipid peroxidation products, α, β-unsaturated aldehydes, on inflammation and vascular dysfunction. PMID:23819013

Focused Flow During Infiltration Into Ethanol-Contaminated Unsaturated Porous Media

NASA Astrophysics Data System (ADS)

Jazwiec, A.; Smith, J. E.

2017-12-01

The increasing commercial and industrial use of ethanol, e.g. in biofuels, has generated increased incidents of vadose zone contamination by way of ethanol spills and releases. This has increased the interest in better understanding behaviors of ethanol in unsaturated porous media and it's multiphase interactions in the vadose zone. This study uses highly controlled laboratory experiments in a 2-D (0.6mx0.6mx0.01m) flow cell to investigate water infiltration behaviors into ethanol-contaminated porous media. Ethanol and water were applied by either constant head or constant flux methods onto the surface of sands homogenously packed into the flow cell. The constant flux experiments at both low and high application rates were conducted using a rainulator with a row of hypodermic needles connected to a peristaltic pump. The constant head experiments were conducted using an 8cm diameter tension disk infiltrometer set to both low and high tensions. The presence of ethanol contamination generated solute-dependent capillarity induced focused flow (SCIFF) of water infiltration, which was primarily due to decreases in interfacial tensions at the air-liquid interfaces in the unsaturated sands as a function of ethanol concentration. SCIFF was clearly expressed as an unsaturated water flow phenomenon comprised of narrowly focused vertical flow fingers of water within the initially ethanol contaminated porous media. Using analyses of photos and video, comparisons were made between constant flux and constant head application methods. Further comparisons were made between low and high infiltration rates and the two sand textures used. A high degree of sensitivity to minor heterogeneity in relatively homogeneous sands was also observed. The results of this research have implications for rainfall infiltration into ethanol contaminated vadose zones expressing SCIFF, including implications for associated mass fluxes and the nature of flushing of ethanol from the unsaturated zone to

Assessment of groundwater quality by unsaturated zone study due to migration of leachate from Abloradjei waste disposal site, Ghana

NASA Astrophysics Data System (ADS)

Egbi, Courage Davidson; Akiti, Tetteh Thomas; Osae, Shiloh; Dampare, Samuel Boakye; Abass, Gibrilla; Adomako, Dickson

2017-05-01

Leachate generated by open solid waste disposal sites contains substances likely to contaminate groundwater. The impact of potential contaminants migrating from leachate on groundwater can be quantified by monitoring their concentration and soil properties at specific points in the unsaturated zone. In this study, physical and chemical analyses were carried out on leachate, soil and water samples within the vicinity of the municipal solid waste disposal site at Abloradjei, a suburb of Accra, Ghana. The area has seen a massive increase in population and the residents depend on groundwater as the main source of water supply. Results obtained indicate alkaline pH for leachate and acidic conditions for unsaturated zone water. High EC values were recorded for leachate and unsaturated zone water. Major ions (Ca2+, Na+, Mg2+, K+, NO3 -, SO4 2-, Cl-, PO4 3- were analysed in leachate, unsaturated zone water, soil solution and groundwater while trace metals (Al, Fe, Cu, Zn, Pb) were analysed in both soil and extracted soil solution. Concentrations of major ions were high in all samples indicating possible anthropogenic origin. Mean % gravel, % sand, % clay, bulk density, volumetric water content and porosity were 28.8, 63.93, 6.6, 1 g cm-3, 35 and 62.7 %, respectively. Distribution of trace elements showed Kd variation of Al > Cu > Fe > Pb > Zn in the order of sequential increasing solubility. It was observed that the quality of groundwater is not suitable for drinking.

n-3 fatty acids: role in neurogenesis and neuroplasticity.

PubMed

Crupi, R; Marino, A; Cuzzocrea, S

2013-01-01

Omega-3 polyunsaturated fatty acids (PUFA) are essential unsaturated fatty acids with a double bond (C=C) starting after the third carbon atom from the end of the carbon chain. They are important nutrients but, unfortunately, mammals cannot synthesize them, whereby they must be obtained from food sources or from supplements. Amongst nutritionally important polyunsaturated n-3 fatty acids, α-linolenic acid (ALA), eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are highly concentrated in the brain and have anti-oxidative stress, anti-inflammatory and antiapoptotic effects. They are involved in many bodily processes and may reportedly lead to neuron protection in neurological diseases. aged or damaged neurons and in Alzheimer's disease. Their effect in cognitive and behavioral functions and in several neurological and psychiatric disorders has been also proven. The dentate gyrus (DG), a sub-region of hippocampus, is implicated in cognition and mood regulation. The hippocampus represents one of the two areas in the mammalian brain in which adult neurogenesis occurs. This process is associated with beneficial effects on cognition, mood and chronic pharmacological treatment. The exposure to n-3 fatty acids enhances adult hippocampal neurogenesis associated with cognitive and behavioral processes, promotes synaptic plasticity by increasing long-term potentiation and modulates synaptic protein expression to stimulate the dendritic arborization and new spines formation. On this basis we review the effect of n-3 fatty acids on adult hippocampal neurogenesis and neuroplasticity. Moreover their possible use as a new therapeutic approach for neurodegenerative diseases is pointed out.

Water and solute permeability of rat lung caveolae: high permeabilities explained by acyl chain unsaturation.

PubMed

Hill, Warren G; Almasri, Eyad; Ruiz, W Giovanni; Apodaca, Gerard; Zeidel, Mark L

2005-07-01

Caveolae are invaginated membrane structures with high levels of cholesterol, sphingomyelin, and caveolin protein that are predicted to exist as liquid-ordered domains with low water permeability. We isolated a caveolae-enriched membrane fraction without detergents from rat lung and characterized its permeability properties to nonelectrolytes and protons. Membrane permeability to water was 2.85 +/- 0.41 x 10(-3) cm/s, a value 5-10 times higher than expected based on comparisons with other cholesterol and sphingolipid-enriched membranes. Permeabilities to urea, ammonia, and protons were measured and found to be moderately high for urea and ammonia at 8.85 +/- 2.40 x 10(-7)and 6.84 +/- 1.03 x 10(-2) respectively and high for protons at 8.84 +/- 3.06 x 10(-2) cm/s. To examine whether caveolin or other integral membrane proteins were responsible for high permeabilities, liposomes designed to mimic the lipids of the inner and outer leaflets of the caveolar membrane were made. Osmotic water permeability to both liposome compositions were determined and a combined inner/outer leaflet water permeability was calculated and found to be close to that of native caveolae at 1.58 +/- 1.1 x 10(-3) cm/s. In caveolae, activation energy for water flux was high (19.4 kcal/mol) and water permeability was not inhibited by HgCl2; however, aquaporin 1 was detectable by immunoblotting. Immunostaining of rat lung with AQP1 and caveolin antisera revealed very low levels of colocalization. We conclude that aquaporin water channels do not contribute significantly to the observed water flux and that caveolae have relatively high water and solute permeabilities due to the high degree of unsaturation in their fatty acyl chains.

Transport of environmental tracers through a karst system with a thick unsaturated zone

NASA Astrophysics Data System (ADS)

Geyer, Tobias; Sültenfuss, Jürgen; Eichinger, Florian; Sauter, Martin

2010-05-01

The transport of the environmental tracers tritium (3H), krypton-85 (85Kr) and helium (3He) in a karst system is investigated. Differences between mean tracer ages determined in spring water are explained by slow percolation of water through the thick unsaturated zone reflecting the importance of slow and diffuse unsaturated flow processes in these systems. Mean tracer ages on the Gallusquelle spring (Swabian Alb) were determined with lumped parameter modeling and decrease in the following order: 3H >> 85Kr > 3He. Since 3H is part of the water molecule it enters a karst system via precipitation, i.e. the mean 3H age is a measure of water flow through the whole karst system, including the unsaturated and saturated zone. The mean 85Kr age and 3H/3He age are measures of time since groundwater recharge arrived at the water table. Therefore our results indicate a long travel time of 3H through the unsaturated zone of the karst system. The interpretation is supported by a two-dimensional numerical simulation of flow and transport in a fissured matrix block that contains a thick unsaturated zone (ca. 100 m) and is drained by a conduit. Transport simulation is performed in the sense of backtracking, i.e. the flow field is reversed, and the boundary conditions are adapted accordingly. At any position in the model domain, the time required for a water molecule to reach the outlet is estimated corresponding to the "life expectancy" (Cornaton and Perrochet 2006), i.e. the life expectancy on the outlet is zero. The simulation of life expectancy of water in the matrix block shows (1) the importance of heterogeneities for interpretation of groundwater ages, (2) the location of stagnant zones in areas of low hydraulic permeability and/or low hydraulic gradient and (3) that flow through unsaturated fissured matrix blocks may cause a considerable travel time of water through a karst system. The travel time of water from the recharge area to the discharge point for the shown example

Asymmetric conjugate addition of Grignard reagents to 3-silyl unsaturated esters for the facile preparation of enantioenriched β-silylcarbonyl compounds and allylic silanes.

PubMed

Zhao, Kai; Loh, Teck-Peng

2014-12-08

A highly enantioselective conjugate addition of Grignard reagents to 3-silyl unsaturated esters to deliver synthetically useful chiral β-silylcarbonyl compounds was developed. The synthetic value of this methodology was further illustrated by the synthesis of enantioenriched β-hydroxyl esters and the facile access granted to various α-chiral allylic silanes. A plethora of diastereoselective transformations of β-silylenolates were also investigated and afforded manifold organosilanes that contained contiguous stereogenic centers with excellent enantioselectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-situ arsenic removal during groundwater recharge through unsaturated alluvium

USGS Publications Warehouse

O'Leary, David; Izbicki, John; T.J. Kim,; Clark Ajawani,; Suarez, Donald; Barnes, Thomas; Thomas Kulp,; Burgess, Matthew K.; Tseng, Iwen

2015-01-01

OBJECTIVES The purpose of this study was to determine the feasibility and sustainability of in-situ removal of arsenic from water infiltrated through unsaturated alluvium. BACKGROUND Arsenic is naturally present in aquifers throughout the southwestern United States and elsewhere. In January 2006, the U.S. Environmental Protection Agency (EPA) lowered the Maximum Contaminant Level (MCL) for arsenic from 50 to 10 micrograms per liter (g/L). This raised concerns about naturally-occurring arsenic in groundwater. Although commercially available systems using sorbent iron or aluminum oxide resins are available to treat high-arsenic water, these systems are expensive to build and operate, and may generate hazardous waste. Iron and aluminum oxides occur naturally on the surfaces of mineral grains that compose alluvial aquifers. In areas where alluvial deposits are unsaturated, these oxides may sorb arsenic in the same manner as commercial resins, potentially providing an effective low-cost alternative to commercially engineered treatment systems. APPROACH The Antelope Valley within the Mojave Desert of southern California contains a shallow water-table aquifer with arsenic concentrations of 5 g/L, and a deeper aquifer with arsenic concentrations of 30 g/L. Water was pumped from the deep aquifer into a pond and infiltrated through an 80 m-thick unsaturated zone as part of field-scale and laboratory experiments to treat high-arsenic groundwater and recharge the shallow water table aquifer at the site. The field-scale recharge experiment included the following steps: 1) construction of a recharge pond 2) test drilling for sample collection and instrument installation adjacent to the pond 3) monitoring downward migration of water infiltrated from the pond 4) monitoring changes in selected trace-element concentrations as water infiltrated through the unsaturated zone Data from instruments within the borehole adjacent to the pond were supplemented with borehole and

Predicting Unsaturated Zone Nitrogen Mass Balances in Agricultural Settings of the United States

USDA-ARS?s Scientific Manuscript database

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond orchard and cornfield in the lower Merced River study basin, California (CA); and corn-soybean rotations in study basins at Maple Creek, Nebraska (NE) and at Morgan Creek, ...

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

NASA Astrophysics Data System (ADS)

George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

2016-12-01

The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

Copper-Catalyzed Enantioselective Henry Reaction of β,γ-Unsaturated α-Ketoesters with Nitromethane in Water.

PubMed

Li, Yanan; Huang, Yekai; Gui, Yang; Sun, Jianan; Li, Jindong; Zha, Zhenggen; Wang, Zhiyong

2017-12-01

A highly enantioselective Henry reaction of β,γ-unsaturated α-ketoesters with nitromethane in water by virtue of chiral copper complexes has been developed. A series of unsaturated β-nitro-α-hydroxy esters bearing tetrasubstituted carbon stereocenters were obtained exclusively with high yields and excellent enantioselectivities. This method could avoid tedious anaerobic anhydrous manipulation and reduce the environmental pollution caused by organic solvents.

Highly Active GaN-Stabilized Ta3 N5 Thin-Film Photoanode for Solar Water Oxidation.

PubMed

Zhong, Miao; Hisatomi, Takashi; Sasaki, Yutaka; Suzuki, Sayaka; Teshima, Katsuya; Nakabayashi, Mamiko; Shibata, Naoya; Nishiyama, Hiroshi; Katayama, Masao; Yamada, Taro; Domen, Kazunari

2017-04-18

Ta 3 N 5 is a very promising photocatalyst for solar water splitting because of its wide spectrum solar energy utilization up to 600 nm and suitable energy band position straddling the water splitting redox reactions. However, its development has long been impeded by poor compatibility with electrolytes. Herein, we demonstrate a simple sputtering-nitridation process to fabricate high-performance Ta 3 N 5 film photoanodes owing to successful synthesis of the vital TaO δ precursors. An effective GaN coating strategy is developed to remarkably stabilize Ta 3 N 5 by forming a crystalline nitride-on-nitride structure with an improved nitride/electrolyte interface. A stable, high photocurrent density of 8 mA cm -2 was obtained with a CoPi/GaN/Ta 3 N 5 photoanode at 1.2 V RHE under simulated sunlight, with O 2 and H 2 generated at a Faraday efficiency of unity over 12 h. Our vapor-phase deposition method can be used to fabricate high-performance (oxy)nitrides for practical photoelectrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palmitic acid (16:0) competes with omega-6 linoleic and omega-3 ɑ-linolenic acids for FADS2 mediated Δ6-desaturation.

PubMed

Park, Hui Gyu; Kothapalli, Kumar S D; Park, Woo Jung; DeAllie, Christian; Liu, Lei; Liang, Allison; Lawrence, Peter; Brenna, J Thomas

2016-02-01

Sapienic acid, 16:1n-10 is the most abundant unsaturated fatty acid on human skin where its synthesis is mediated by FADS2 in the sebaceous glands. The FADS2 product introduces a double bond at the Δ6, Δ4 and Δ8 positions by acting on at least ten substrates, including 16:0, 18:2n-6, and 18:3n-3. Our aim was to characterize the competition for accessing FADS2 mediated Δ6 desaturation between 16:0 and the most abundant polyunsaturated fatty acids (PUFA) in the human diet, 18:2n-6 and 18:3n-3, to evaluate whether competition may be relevant in other tissues and thus linked to metabolic abnormalities associated with FADS2 or fatty acid levels. MCF7 cells stably transformed with FADS2 biosynthesize 16:1n-10 from exogenous 16:0 in preference to 16:1n-7, the immediate product of SCD highly expressed in cancer cell lines, and 16:1n-9 via partial β-oxidation of 18:1n-9. Increasing availability of 18:2n-6 or 18:3n-3 resulted in decreased bioconversion of 16:0 to 16:1n-10, simultaneously increasing the levels of highly unsaturated products. FADS2 cells accumulate the desaturation-elongation products 20:3n-6 and 20:4n-3 in preference to the immediate desaturation products 18:3n-6 and 18:4n-3 implying prompt/coupled elongation of the nascent desaturation products. MCF7 cells incorporate newly synthesized 16:1n-10 into phospholipids. These data suggest that excess 16:0 due to, for instance, de novo lipogenesis from high carbohydrate or alcohol consumption, inhibits synthesis of highly unsaturated fatty acids, and may in part explain why supplemental preformed EPA and DHA in some studies improves insulin resistance and other factors related to diabetes and metabolic syndrome aggravated by excess calorie consumption. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface oxidation under ambient air--not only a fast and economical method to identify double bond positions in unsaturated lipids but also a reminder of proper lipid processing.

PubMed

Zhou, Ying; Park, Hyejung; Kim, Philseok; Jiang, Yan; Costello, Catherine E

2014-06-17

A simple, fast approach elucidated carbon-carbon double bond positions in unsaturated lipids. Lipids were deposited onto various surfaces and the products from their oxidation in ambient air were observed by electrospray ionization (ESI) mass spectrometry (MS). The most common oxidative products, aldehydes, were detected as transformations at the cleaved double bond positions. Ozonides and carboxylic acids were generated in certain lipids. Investigations of the conditions controlling the appearance of these products indicated that the surface oxidation depends on light and ambient air. Since the lipid oxidation was slower in a high concentration of ozone, singlet oxygen appeared to be a parallel oxidant for unsaturated lipids. The 3-hydroxyl group in the sphingoid base of sulfatides offered some protection from oxidation for the Δ4,5-double bond, slowing its oxidation rate relative to that of the isolated double bond in the N-linked fatty acyl chain. Direct sampling by thin-layer chromatography (TLC)-ESI-MS provides a powerful approach to elucidate detailed structural information on biological samples. Co-localization of the starting lipids and their oxidation products after TLC separation allowed assignment of the native unsaturation sites. Phosphatidylserine and N,N-dimethyl phosphatidylethanolamine isomers in a bovine brain total lipid extract were distinguished on the basis of their oxidation products. Meanwhile, the findings reported herein reveal a potential pitfall in the assignment of structures to lipids extracted from TLC plates because of artifactual oxidation after the plate development.

3-D Distribution of Retained Colloids in Unsaturated Porous Media

NASA Astrophysics Data System (ADS)

Morales, V. L.; Perez-Reche, F. J.; Holzner, M.; Kinzelbach, W. K.; Otten, W.

2013-12-01

It is well accepted that colloid transport processes in porous media differ substantially between water saturated and unsaturated conditions. Differences are frequently ascribed to colloid immobilization by association with interfaces with the gas, as well as to restrictions of the liquid medium through which colloids are transported. Such factors depend on interfacial conditions provided by the water saturation of the porous medium. Yet, the current understanding of the importance of colloid retention at gas interfaces is based on observations of single pores or two-dimensional pore network representations, leaving open the question of their statistical significance when all pores in the medium are considered. In order to address this question, column experiments were performed using a model porous medium of glass beads through which colloidal silver particles were transported for conditions of varying water content. X-ray microtomography was subsequently employed as a non-destructive imaging technique to obtain pore-scale information of the entire column regarding: i) the presence and distribution of the four main locations where colloids can become retained (interfaces with the liquid-solid, gas-liquid and gas-solid, and the bulk liquid), ii) deposition profiles of colloids along the column classified by the available retention location, iii) morphological characteristics of the deposited colloidal aggregates, and iv) channel widths of 3-dimensional pore-water network representations. The results presented provide, for the first time, a direct statistical evaluation on the significance of colloid retention by attachment to the liquid-solid, gas-liquid, gas-solid interfaces, and by straining in the bulk liquid. Additionally, an effective-pore structure characteristic is proposed to improve predictions of mass removal by straining under various water saturations. A) Unsaturated conditions. B) Saturated conditions. Left: Tomograph slice illustrating with false

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

USGS Publications Warehouse

Hancock, T.C.; Sandstrom, M.W.; Vogel, J.R.; Webb, R.M.T.; Bayless, E.R.; Barbash, J.E.

2008-01-01

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to > 0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

Investigations of the unsaturated zone at two radioactive waste disposal sites in Lithuania.

PubMed

Skuratovič, Žana; Mažeika, Jonas; Petrošius, Rimantas; Martma, Tõnu

2016-01-01

The unsaturated zone is an important part of the water cycle, governed by many hydrological and hydrogeological factors and processes and provide water and nutrients to the terrestrial ecosystem. Besides, the soils of the unsaturated zone are regarded as the first natural barrier to a large extent and are able to limit the spread of contaminants depending on their properties. The unsaturated zone provides a linkage between atmospheric moisture, groundwater, and seepage of groundwater to streams, lakes, or other surface water bodies. The major difference between water flow in saturated and unsaturated soils is that the hydraulic conductivity, which is conventionally assumed to be a constant in saturated soils, is a function of the degree of saturation or matrix suction in the unsaturated soils. In Lithuania, low and intermediate level radioactive wastes generated from medicine, industry and research were accumulated at the Maisiagala radioactive waste repository. Short-lived low and intermediate levels radioactive waste, generated during the operation of the Ignalina Nuclear Power Plant (INPP) and arising after the INPP decommissioning will be disposed of in the near surface repository close to the INPP (Stabatiske site). Extensive data sets of the hydraulic properties and water content attributed to unsaturated zone soil profiles of the two radioactive waste disposal sites have been collected and summarized. Globally widespread radionuclide tritium ((3)H) and stable isotope ratio ((18)O/(16)O and (2)H/(1)H) distribution features were determined in precipitation, unsaturated zone soil moisture profiles and groundwater.

Thermodynamics of the clusterization process of cis isomers of unsaturated fatty acids at the air/water interface.

PubMed

Vysotsky, Yu B; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Aksenenko, E V; Miller, R

2009-04-02

In the framework of the semiempirical PM3 method, the thermodynamic parameters of cis isomers of unsaturated carboxylic acids at the air/water interface are studied. The model systems used are unsaturated cis fatty acid of the composition Delta = 12-15 and omega = 6-11, where Delta and omega refer to the number of carbon atoms between the functional group and double bond, and that between the double bond and methyl group, respectively. For dimers, trimers, and tetramers of the four acid series, the thermodynamic parameters of clusterization are calculated. It is shown that the position of the double bond does not significantly affect the values of thermodynamic parameters of formation and clusterization of carboxylic acids for equal chain lengths (n = Delta + omega). The calculated results show that for cis unsaturated fatty acid with odd Delta values the spontaneous clusterization threshold corresponds to n = 17-18 carbon atoms in the alkyl chain, while for monounsaturated acids with even Delta values this threshold corresponds to n = 18-19 carbon atoms in the alkyl chain. These differences in the clusterization threshold between the acids with even and odd Delta values are attributed to the formation of additional intermolecular hydrogen bonds between the ketonic oxygen atom of one monomer and the hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with odd Delta values or between the hydroxyl oxygen atom of one monomer and hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with even Delta values. The results obtained in the study agree satisfactorily with our experimental data for cis unsaturated nervonic (Delta15, omega9) and erucic acids (Delta13, omega9), and published data for some fatty acids, namely cis-16-heptadecenoic (Delta16, omega1), cis-9-hexadecenoic (Delta7, omega9), cis-11-eicosenoic (Delta11, omega9) and cis-9-octadecenoic acid (Delta9, omega9).

Camelina sativa cake improved unsaturated fatty acids in ewe's milk.

PubMed

Szumacher-Strabel, Malgorzata; Cieślak, Adam; Zmora, Pawel; Pers-Kamczyc, Emilia; Bielińska, Sylwia; Stanisz, Marek; Wójtowski, Jacek

2011-08-30

Camelina sativa cake (CSC), a rich source of unsaturated fatty acids, in the case of ruminants, may improve the energy value of a diet and also increase the unsaturated fatty acid content in milk. Effects of basal diet (control), basal diet plus 30 g kg(-1) of CSC in dietary dry matter (DM), basal diet plus 60 g kg(-1) of CSC in dietary dry matter on milk production and the fatty acid composition of ewe's milk with particular emphasis on the monoenes and conjugated isomers of linoleic acid content were examined. Elevated concentration of total monounsaturated fatty acids, the effect of an increase in monounsaturated fatty acids in the trans configuration, as well as the increased content of total polyunsaturated fatty acids, resulted from CSC supplementation. Total saturated fatty acid concentration was decreased. Milk from CSC-supplemented ewes was characterized by increased levels of beneficial nutritional factors, including mono- and n-3 polyunsaturated fatty acids, and was also by lower atherogenic and thrombogenic indices. Taking into consideration all the obtained results and recommended fat concentrations in a daily ruminant ration, we recommend supplementing a dairy ewe's diet with 30 g kg(-1) DM of CSC cake in practice. Copyright © 2011 Society of Chemical Industry.

3D printing of new biobased unsaturated polyesters by microstereo-thermallithography.

PubMed

Gonçalves, Filipa A M M; Costa, Cátia S M F; Fabela, Inês G P; Farinha, Dina; Faneca, Henrique; Simões, Pedro N; Serra, Arménio C; Bártolo, Paulo J; Coelho, Jorge F J

2014-09-01

New micro three-dimensional (3D) scaffolds using biobased unsaturated polyesters (UPs) were prepared by microstereo-thermal-lithography (μSTLG). This advanced processing technique offers indubitable advantages over traditional printing methods. The accuracy and roughness of the 3D structures were evaluated by scanning electron microscopy and infinite focus microscopy, revealing a suitable roughness for cell attachment. UPs were synthesized by bulk polycondensation between biobased aliphatic diacids (succinic, adipic and sebacic acid) and two different glycols (propylene glycol and diethylene glycol) using fumaric acid as the source of double bonds. The chemical structures of the new oligomers were confirmed by proton nuclear magnetic resonance spectra, attenuated total reflectance Fourier transform infrared spectroscopy and matrix assisted laser desorption/ionization-time of flight mass spectrometry. The thermal and mechanical properties of the UPs were evaluated to determine the influence of the diacid/glycol ratio and the type of diacid in the polyester's properties. In addition an extensive thermal characterization of the polyesters is reported. The data presented in this work opens the possibility for the use of biobased polyesters in additive manufacturing technologies as a route to prepare biodegradable tailor made scaffolds that have potential applications in a tissue engineering area.

Controls on shallow landslide initiation: Diverse hydrologic pathways, 3D failure geometries, and unsaturated soil suctions

NASA Astrophysics Data System (ADS)

Reid, Mark; Iverson, Richard; Brien, Dianne; Iverson, Neal; LaHusen, Richard; Logan, Matthew

2017-04-01

Shallow landslides and ensuing debris flows are a common hazard worldwide, yet forecasting their initiation at a specific site is challenging. These challenges arise, in part, from diverse near-surface hydrologic pathways under different wetting conditions, 3D failure geometries, and the effects of suction in partially saturated soils. Simplistic hydrologic models typically used for regional hazard assessment disregard these complexities. As an alterative to field studies where the effects of these governing factors can be difficult to isolate, we used the USGS debris-flow flume to conduct controlled, field-scale landslide initiation experiments. Using overhead sprinklers or groundwater injectors on the flume bed, we triggered failures using three different wetting conditions: groundwater inflow from below, prolonged moderate-intensity precipitation, and bursts of high-intensity precipitation. Failures occurred in 6 m3 (0.65-m thick and 2-m wide) prisms of loamy sand on a 31° slope; these field-scale failures enabled realistic incorporation of nonlinear scale-dependent effects such as soil suction. During the experiments, we monitored soil deformation, variably saturated pore pressures, and moisture changes using ˜50 sensors sampling at 20 Hz. From ancillary laboratory tests, we determined shear strength, saturated hydraulic conductivities, and unsaturated moisture retention characteristics. The three different wetting conditions noted above led to different hydrologic pathways and influenced instrumental responses and failure timing. During groundwater injection, pore-water pressures increased from the bed of the flume upwards into the sediment, whereas prolonged moderate infiltration wet the sediment from the ground surface downward. In both cases, pore pressures acting on the impending failure surface slowly rose until abrupt failure. In contrast, a burst of intense sprinkling caused rapid failure without precursory development of widespread positive pore

Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life

PubMed Central

Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

2016-01-01

All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts. PMID:27283227

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

PubMed

Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

2012-07-15

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result it's imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Atypical cleavage of protonated N-fatty acyl amino acids derived from aspartic acid evidenced by sequential MS3 experiments.

PubMed

Boukerche, Toufik Taalibi; Alves, Sandra; Le Faouder, Pauline; Warnet, Anna; Bertrand-Michel, Justine; Bouchekara, Mohamed; Belbachir, Mohammed; Tabet, Jean-Claude

2016-12-01

Lipidomics calls for information on detected lipids and conjugates whose structural elucidation by mass spectrometry requires to rationalization of their gas phase dissociations toward collision-induced dissociation (CID) processes. This study focused on activated dissociations of two lipoamino acid (LAA) systems composed of N-palmitoyl acyl coupled with aspartic and glutamic acid mono ethyl esters (as LAA (*D) and LAA (*E) ). Although in MS/MS, their CID spectra show similar trends, e.g., release of water and ethanol, the [(LAA (*D/*E) +H)-C 2 H 5 OH] + product ions dissociate via distinct pathways in sequential MS 3 experiments. The formation of all the product ions is rationalized by charge-promoted cleavages often involving stepwise processes with ion isomerization into ion-dipole prior to dissociation. The latter explains the maleic anhydride or ketene neutral losses from N-palmitoyl acyl aspartate and glutamate anhydride fragment ions, respectively. Consequently, protonated palmitoyl acid amide is generated from LAA (*D), whereas LAA (*E) leads to the [*E+H-H 2 O] + anhydride. The former releases ammonia to provide acylium, which gives the C n H (2n-1) and C n H (2n-3) carbenium series. This should offer structural information, e.g., to locate either unsaturation(s) or alkyl group branching present on the various fatty acyl moieties of lipo-aspartic acid in further studies based on MS n experiments.

New Hydrologic Insights to Advance Geophysical Investigation of the Unsaturated Zone

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; Perkins, K. S.

2015-12-01

Advances in hydrology require information from the unsaturated zone, especially for problems related to groundwater contamination, water-supply sustainability, and ecohydrology. Unsaturated-zone processes are notoriously difficult to quantify; soils and rocks are visually opaque, spatially variable in the extreme, and easily disturbed by instrument installation. Thus there is great value in noninvasive techniques that produce water-related data of high density in space and time. Methods based on resistivity and electromagnetic waves have already produced significant new understanding of percolation processes, root-zone water retention, influences of evapotranspiration on soil-water, and effects of preferential flow. Further developments are underway for such purposes as noninvasive application to greater depths, increased resolution, adaptation for lab-scale experiments, and calibration in heterogeneous media. Beyond these, however, there is need for a stronger marriage of hydrologic and geophysical knowledge and perspective. Possible means to greater and faster progress include: Apply the latest hydrologic understanding, both pore-scale and macroscopic, to the detection of preferential flow paths and their degree of activation. In the continuing advancement of hardware and techniques, draw creatively from developments in such fields as high-energy physics, medical imaging, astrogeology, high-tech semiconductors, and bioinstrumentation. Sidestep the imaging process where possible to measure essential properties and fluxes more directly. Pose questions that have a strong end-use character, like "how does storm intensity relate to aquifer recharge rate" rather than "what is the shape of the wetting front". The greatest advances in geophysical investigation of the unsaturated zone will come from methods informed by the latest understanding of unsaturated systems and processes, and aimed as directly as possible at the answers to important hydrologic questions.

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

NASA Astrophysics Data System (ADS)

Yue, Cheng-Yang; Lei, Xiao-Wu; Tian, Ya-Wei; Xu, Jing; Bai, Yi-Qun; Wang, Fei; Zhou, Peng-Fei; Liu, Xiao-Fan; Yi, Fei-Yan

2016-03-01

The incorporation of unsaturated [Mn(1,2-dap)]2+, [Mn(1,2-dap)2]2+, [Mn(2,2-bipy)]2+ (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [AsIIIS3]3- and [AsVS4]3- led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]2MnAs2S6 (1), [Mn(1,2-dap)2]{[Mn(1,2-dap)]2As2S8} (2) and (NH4)[Mn(2,2-bipy)2]AsS4 (3). In compound 1, the unsaturated [Mn(1,2-dap)]2+ complexes, [MnS4]6- tetrahedra and [AsIIIS3]3- trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]2MnAs2S6 chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]2+ and [Mn(1,2-dap)2]2+ complexes as well as [AsVS4]3- tetrahedral units. For compound 3, two [AsVS4]3- anions bridge two [Mn(2,2-bipy)]2+ complex cations into a butterfly like {[Mn(2,2-bipy)]2As2S8}2- anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2-3. The UV-vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation.

Gas breakthrough and emission through unsaturated compacted clay in landfill final cover

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

Ng, C.W.W.; Chen, Z.K.; Coo, J.L.

Highlights: • Explore feasibility of unsaturated clay as a gas barrier in landfill cover. • Gas breakthrough pressure increases with clay thickness and degree of saturation. • Gas emission rate decreases with clay thickness and degree of saturation. • A 0.6 m-thick clay layer may be sufficient to meet gas emission rate limit. - Abstract: Determination of gas transport parameters in compacted clay plays a vital role for evaluating the effectiveness of soil barriers. The gas breakthrough pressure has been widely studied for saturated swelling clay buffer commonly used in high-level radioactive waste disposal facility where the generated gas pressuremore » is very high (in the order of MPa). However, compacted clay in landfill cover is usually unsaturated and the generated landfill gas pressure is normally low (typically less than 10 kPa). Furthermore, effects of clay thickness and degree of saturation on gas breakthrough and emission rate in the context of unsaturated landfill cover has not been quantitatively investigated in previous studies. The feasibility of using unsaturated compacted clay as gas barrier in landfill covers is thus worthwhile to be explored over a wide range of landfill gas pressures under various degrees of saturation and clay thicknesses. In this study, to evaluate the effectiveness of unsaturated compacted clay to minimize gas emission, one-dimensional soil column tests were carried out on unsaturated compacted clay to determine gas breakthrough pressures at ultimate limit state (high pressure range) and gas emission rates at serviceability limit state (low pressure range). Various degrees of saturation and thicknesses of unsaturated clay sample were considered. Moreover, numerical simulations were carried out using a coupled gas–water flow finite element program (CODE-BRIGHT) to better understand the experimental results by extending the clay thickness and varying the degree of saturation to a broader range that is typical at

The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

PubMed

Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

2013-04-28

The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

Numerical model for thermodynamical behaviors of unsaturated soil

NASA Astrophysics Data System (ADS)

Miyamoto, Yuji; Yamada, Mitsuhide; Sako, Kazunari; Araki, Kohei; Kitamura, Ryosuke

Kitamura et al. have proposed the numerical models to establish the unsaturated soil mechanics aided by probability theory and statistics, and to apply the unsaturated soil mechanics to the geo-simulator, where the numerical model for the thermodynamical behaviors of unsaturated soil are essential. In this paper the thermodynamics is introduced to investigate the heat transfer through unsaturated soil and the evaporation of pore water in soil based on the first and second laws of thermodynamics, i.e., the conservation of energy, and increasing entropy. On the other hand the lysimeter equipment is used to obtain the data for the evaporation of pore water during fine days and seepage of rain water during rainy days. The numerical simulation is carried out by using the proposed numerical model and the results are compared with those obtained from the lysimeter test.

Dietary (n-3) fatty acids reduce plasma F2-isoprostanes but not prostaglandin F2alpha in healthy humans.

PubMed

Nälsén, Cecilia; Vessby, Bengt; Berglund, Lars; Uusitupa, Matti; Hermansen, Kjeld; Riccardi, Gabrielle; Rivellese, Angela; Storlien, Len; Erkkilä, Arja; Ylä-Herttuala, Seppo; Tapsell, Linda; Basu, Samar

2006-05-01

(n-3) Fatty acids are unsaturated and are therefore easily subject to oxidization; however, they have several beneficial health effects, which include protection against cardiovascular diseases. The aim of this study was to investigate whether (n-3) fatty acids, with a controlled fat quality in the background diet, affect nonenzymatic and enzymatic lipid peroxidation and antioxidant status in humans. A total of 162 men and women in a multicenter study (The KANWU study) were randomly assigned to a diet containing a high proportion of saturated fatty acids or monounsaturated fatty acids (MUFA) for 3 mo. Within each diet group, there was a second random assignment to supplementation with fish-oil capsules [3.6 g (n-3) fatty acids/d] or placebo. Biomarkers of nonenzymatic and enzymatic lipid peroxidation in vivo were determined by measuring 8-iso-prostaglandin F(2alpha) (8-iso-PGF(2alpha)) and prostaglandin F(2alpha) (PGF(2alpha)) concentrations in plasma at baseline and after 3 mo. Antioxidant status was determined by measuring plasma antioxidant capacity with an enhanced chemiluminescence assay. The plasma 8-iso-PGF(2alpha) concentration was significantly decreased after 3 mo of supplementation with (n-3) fatty acids (P = 0.015), whereas the PGF(2alpha) concentration was not affected. The antioxidant status was not affected by supplementation of (n-3) fatty acids, but was improved by the background diet with a high proportion of MUFA. We conclude that supplementation with (n-3) fatty acids decreases nonenzymatic free radical-catalyzed isoprostane formation, but does not affect cyclooxygenase-mediated prostaglandin formation.

Total fatty acid content of the plasma membrane of Saccharomyces cerevisiae is more responsible for ethanol tolerance than the degree of unsaturation.

PubMed

Kim, Hyun-Soo; Kim, Na-Rae; Choi, Wonja

2011-03-01

The effect of change in unsaturated fatty acid composition on ethanol tolerance in Saccharomyces cerevisiae overexpressing ScOLE1 (∆9 fatty acid desaturase gene of S. cerevisiae), CaFAD2 (∆12 fatty acid desaturase gene of Candida albicans), or CaFAD3 (ω3 fatty acid desaturase gene of C. albicans) was examined. ScOLE1 over-expression increased the total unsaturated fatty acid content and enhanced ethanol tolerance, compared with a control strain. In contrast, overexpression of CaFAD2 and CaFAD3, which led to production of linoleic acid (18:2) and α-linolenic acid (18:3), respectively, neither changed total unsaturated fatty acids nor enhanced ethanol tolerance. The total unsaturated fatty acid content rather than the degree of unsaturation is thus an important factor for ethanol tolerance.

Unsaturated flow characterization utilizing water content data collected within the capillary fringe

USGS Publications Warehouse

Baehr, Arthur; Reilly, Timothy J.

2014-01-01

An analysis is presented to determine unsaturated zone hydraulic parameters based on detailed water content profiles, which can be readily acquired during hydrological investigations. Core samples taken through the unsaturated zone allow for the acquisition of gravimetrically determined water content data as a function of elevation at 3 inch intervals. This dense spacing of data provides several measurements of the water content within the capillary fringe, which are utilized to determine capillary pressure function parameters via least-squares calibration. The water content data collected above the capillary fringe are used to calculate dimensionless flow as a function of elevation providing a snapshot characterization of flow through the unsaturated zone. The water content at a flow stagnation point provides an in situ estimate of specific yield. In situ determinations of capillary pressure function parameters utilizing this method, together with particle-size distributions, can provide a valuable supplement to data libraries of unsaturated zone hydraulic parameters. The method is illustrated using data collected from plots within an agricultural research facility in Wisconsin.

Seasonal variations and cycling of nitrous oxide using nitrogen isotopes and concentrations from an unsaturated zone of a floodplain

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.; Kolding, S.; Williams, K. H.; Tokunaga, T. K.

2014-12-01

Nitrous oxide (N2O) concentrations and isotope ratios of 15N to 14N of N2O in the vadose zone mainly depend on atmospheric deposition, symbiotic or non-symbiotic N2 fixation, and nitrification/denitrification processes in underlying groundwater. In an effort to quantify N2O seasonal variations, cycling and N budgets in an alluvial aquifer in western Colorado (Rifle, CO), the concentrations and nitrogen stable isotopes of N2O within the pore space of partially saturated sediments have been monitored over the 2013-2014 years. Vertically resolved profiles spanning from 0m to 3m depth were sampled at 0.5m increments at a periodicity of one month. At each of the profile locations, N2O concentrations decreased from 3m depth to the surface. The maximum concentrations were observed at the interface between the unsaturated zone and groundwater, with minimum values observed in the near surface samples. The d15N values tend to increase from the unsaturated zone/groundwater interface to the surface. Both variation of N2O concentrations and d15N values suggest that denitrification is the main contribution to N2O production and both parameters exhibited a strong seasonal variation. The maximum concentrations (~10ppmv) were observed at the beginning of summer, during the annual maximum in water table elevation. The minimum N2O concentrations were observed in the period from January to May and coincided with low water table elevations. Additionally, nitrogen concentrations and d15N values of the shallowest sediments within the vertical profiles do not show variation, suggesting that the main source of N2O is associated with groundwater denitrification, with the shallower, partially saturated sediments acting as a sink for N2O.

Global metabolomic profiling reveals an association of metal fume exposure and plasma unsaturated fatty acids.

PubMed

Wei, Yongyue; Wang, Zhaoxi; Chang, Chiung-yu; Fan, Tianteng; Su, Li; Chen, Feng; Christiani, David C

2013-01-01

Welding-associated air pollutants negatively affect the health of exposed workers; however, their molecular mechanisms in causing disease remain largely unclear. Few studies have systematically investigated the systemic toxic effects of welding fumes on humans. To explore the effects of welding fumes on the plasma metabolome, and to identify biomarkers for risk assessment of welding fume exposure. The two-stage, self-controlled exploratory study included 11 boilermakers from a 2011 discovery panel and 8 boilermakers from a 2012 validation panel. Plasma samples were collected pre- and post-welding fume exposure and analyzed by chromatography/mass spectrometry. Eicosapentaenoic or docosapentaenoic acid metabolic changes post-welding were significantly associated with particulate (PM2.5) exposure (p<0.05). The combined analysis by linear mixed-effects model showed that exposure was associated with a statistically significant decline in metabolite change of eicosapentaenoic acid [β(95% CI) = -0.013(-0.022 ≈ -0.004); p = 0.005], docosapentaenoic acid n3 [β(95% CI) = -0.010(-0.018 ≈ -0.002); p = 0.017], and docosapentaenoic acid n6 [β(95% CI) = -0.007(-0.013 ≈ -0.001); p = 0.021]. Pathway analysis identified an association of the unsaturated fatty acid pathway with exposure (p Study-2011 = 0.025; p Study-2012 = 0.021; p Combined = 0.009). The functional network built by these fatty acids and their interactive genes contained significant enrichment of genes associated with various diseases, including neoplasms, cardiovascular diseases, and lipid metabolism disorders. High-dose exposure of metal welding fumes decreases unsaturated fatty acids with an exposure-response relationship. This alteration in fatty acids is a potential biological mediator and biomarker for exposure-related health disorders.

Highly Corrosion Resistant and Sandwich-like Si3N4/Cr-CrNx/Si3N4 Coatings Used for Solar Selective Absorbing Applications.

PubMed

Zhang, Ke; Du, Miao; Haoa, Lei; Meng, Jianping; Wang, Jining; Mi, Jing; Liu, Xiaopeng

2016-12-14

Highly corrosion resistant, layer-by-layer nanostructured Si 3 N 4 /Cr-CrN x /Si 3 N 4 coatings were deposited on aluminum substrate by DC/RF magnetron sputtering. Corrosion resistance experiments were performed in 0.5, 1.0, 3.0, and 5.0 wt % NaCl salt spray at 35 °C for 168 h. Properties of the coatings were comprehensively investigated in terms of optical property, surface morphology, microstructure, elemental valence state, element distribution, and potentiodynamic polarization. UV-vis-near-IR spectrophotometer and FTIR measurements show that the change process in optical properties of Si 3 N 4 /Cr-CrN x /Si 3 N 4 /Al coatings can be divided into three stages: a rapid active degradation stage, a steady passivation stage, and a transpassivation degradation stage. With the increase in the concentration of NaCl salt spray, solar absorptance and thermal emittance experienced a slight degradation. SEM images reveal that there is an increase in surface defects, such as microcracks and holes and -cracks. XRD and TEM measurements indicate that the phase structure changed partially and the content of CrO x and Al 2 O 3 has increased. Auger electron spectroscopy shows that the elements of Cr, N, and O have undergone a minor diffusion. Electrochemical polarization curves show that the as-deposited Si 3 N 4 /Cr-CrN x /Si 3 N 4 /Al coatings have excellent corrosion resistance of 3633.858 kΩ, while after corroding in 5.0 wt % NaCl salt spray for 168 h the corrosion resistance dropped to 13.759 kΩ. However, these coatings still have an outstanding performance of high solar absorptance of 0.924 and low thermal emittance of 0.090 after corroding in 3.0 wt % NaCl salt spray for 120 h. Thus, the Si 3 N 4 /Cr-CrN x /Si 3 N 4 /Al coating is a good choice for solar absorber coatings applied in the high-saline environment.

Role of air-water interfaces on retention of viruses under unsaturated conditions

NASA Astrophysics Data System (ADS)

Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.; van den Berg, H. H. J. L.

2006-12-01

We investigated transport of viruses through saturated and unsaturated sand columns. Unsaturated experiments were conducted under conditions of uniform saturation and steady state water flow. The water saturation ranged from 1 to 0.5. Bacteriophages MS2 and ϕX174 were used as surrogates for pathogenic viruses in these studies. Phosphate-buffered solutions with different pH values (7.5, 6.2, 5.5, and 5) were utilized. Virus transport was modeled assuming first-order kinetic adsorption for interactions to the solid-water interface (SWI) and the air-water interface (AWI). Under saturated conditions, virus retention increased as pH decreased, and a one-site kinetic model produced a good fit to the breakthrough curves. Under unsaturated conditions a two-site kinetic model was needed to fit the breakthrough curves satisfactorily. The second site was attributed to the adsorption of phages to the AWI. According to our results, ϕX174 exhibits a high affinity to the AWI at pH values below 6.6 (the isoelectric point of ϕX174). Although it is believed that MS2 is more hydrophobic than ϕX174, MS2 had a lower affinity to the AWI than ϕX174, presumably because of the lower isoelectric point of MS2, which is equal to 3.9. Under unsaturated conditions, viruses captured within the column could be recovered in the column outflow by resaturating and immediately draining the column. Draining columns under saturated conditions, however, did not result in any recovery of viruses. Therefore the recovery can be attributed to the release of viruses adsorbed to the AWI. Our results suggest that electrostatic interactions of viruses with the AWI are much more important than hydrophobicity.

Survey Observations to Study Chemical Evolution from High-mass Starless Cores to High-mass Protostellar Objects. I. HC3N and HC5N

NASA Astrophysics Data System (ADS)

Taniguchi, Kotomi; Saito, Masao; Sridharan, T. K.; Minamidani, Tetsuhiro

2018-02-01

We carried out survey observations of HC3N and HC5N in the 42‑45 GHz band toward 17 high-mass starless cores (HMSCs) and 35 high-mass protostellar objects (HMPOs) with the Nobeyama 45 m radio telescope. We have detected HC3N from 15 HMSCs and 28 HMPOs, and HC5N from 5 HMSCs and 14 HMPOs, respectively. The average values of the column density of HC3N are found to be (5.7+/- 0.7) × {10}12 and (1.03+/- 0.12)×{10}13 cm‑2 in HMSCs and HMPOs, respectively. The average values of the fractional abundance of HC3N are derived to be (6.6+/- 0.8)× {10}-11 and (3.6+/- 0.5)× {10}-11 in HMSCs and HMPOs, respectively. We find that the fractional abundance of HC3N decreases from HMSCs to HMPOs using the Kolmogorov–Smirnov test. On the other hand, its average value of the column density slightly increases from HMSCs to HMPOs. This may imply that HC3N is newly formed in dense gas in HMPO regions. We also investigate the relationship between the column density of HC3N in HMPOs and the luminosity-to-mass ratio (L/M), a physical evolutional indicator. The column density of HC3N tends to decrease with the increase of the L/M ratio, which suggests that HC3N is destroyed by the stellar activities.

Hydrology of the unsaturated zone, Yucca Mountain, Nevada

USGS Publications Warehouse

Lecain, Gary D.; Stuckless, John S.

2012-01-01

The unsaturated zone at Yucca Mountain was investigated as a possible site for the nation's first high-level nuclear waste repository. Scientific investigations included infiltration studies, matrix properties testing, borehole testing and monitoring, underground excavation and testing, and the development of conceptual and numerical models of the hydrologic processes at Yucca Mountain. Infiltration estimates by empirical and geochemical methods range from 0.2 to 1.4 mm/yr and 0.2–6.0 mm/yr, respectively. Infiltration estimates from numerical models range from 4.5 mm/yr to 17.6 mm/yr. Rock matrix properties vary vertically and laterally as the result of depositional processes and subsequent postdepositional alteration. Laboratory tests indicate that the average matrix porosity and hydraulic conductivity values for the main level of the proposed repository (Topopah Spring Tuff middle nonlithophysal zone) are 0.08 and 4.7 × 10−12 m/s, respectively. In situ fracture hydraulic conductivity values are 3–6 orders of magnitude greater. The permeability of fault zones is approximately an order of magnitude greater than that of the surrounding rock unit. Water samples from the fault zones have tritium concentrations that indicate some component of postnuclear testing. Gas and water vapor movement through the unsaturated zone is driven by changes in barometric pressure, temperature-induced density differences, and wind effects. The subsurface pressure response to surface barometric changes is controlled by the distribution and interconnectedness of fractures, the presence of faults and their ability to conduct gas and vapor, and the moisture content and matrix permeability of the rock units. In situ water potential values are generally less than −0.2 MPa (−2 bar), and the water potential gradients in the Topopah Spring Tuff units are very small. Perched-water zones at Yucca Mountain are associated with the basal vitrophyre of the Topopah Spring Tuff or the Calico

Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

EPA Science Inventory

We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a...

Pumping Test Determination of Unsaturated Aquifer Properties

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2008-12-01

Tartakovsky and Neuman [2007] presented a new analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering the unsaturated zone. In their solution three-dimensional, axially symmetric unsaturated flow is described by a linearized version of Richards' equation in which both hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value, the latter defining the interface between the saturated and unsaturated zones. Both exponential functions are characterized by a common exponent k having the dimension of inverse length, or equivalently a dimensionless exponent kd=kb where b is initial saturated thickness. The authors used their solution to analyze drawdown data from a pumping test conducted by Moench et al. [2001] in a Glacial Outwash Deposit at Cape Cod, Massachusetts. Their analysis yielded estimates of horizontal and vertical saturated hydraulic conductivities, specific storage, specific yield and k . Recognizing that hydraulic conductivity and water content seldom vary identically with incremental capillary pressure head, as assumed by Tartakovsky and Neuman [2007], we note that k is at best an effective rather than a directly measurable soil parameter. We therefore ask to what extent does interpretation of a pumping test based on the Tartakovsky-Neuman solution allow estimating aquifer unsaturated parameters as described by more common constitutive water retention and relative hydraulic conductivity models such as those of Brooks and Corey [1964] or van Genuchten [1980] and Mualem [1976a]? We address this question by showing how may be used to estimate the capillary air entry pressure head k and the parameters of such constitutive models directly, without a need for inverse unsaturated numerical simulations of the kind described by Moench [2003]. To assess the validity of such direct estimates we use maximum

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

NASA Astrophysics Data System (ADS)

Nimmo, John R.; Creasey, Kaitlyn M.; Perkins, Kim S.; Mirus, Benjamin B.

2017-03-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

USGS Publications Warehouse

Nimmo, John R.; Creasey, Kaitlyn M; Perkins, Kimberlie; Mirus, Benjamin B.

2017-01-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

High-temperature deformation and microstructural analysis for Si3N4-Sc2O3

NASA Technical Reports Server (NTRS)

Cheong, Deock-Soo; Sanders, William A.

1990-01-01

It was indicated that Si3N4 doped with Sc2O3 may exhibit high temperature mechanical properties superior to Si3N4 systems with various other oxide sintered additives. High temperature deformation of samples was studied by characterizing the microstructures before and after deformation. It was found that elements of the additive, such as Sc and O, exist in small amounts at very thin grain boundary layers and most of them stay in secondary phases at triple and multiple grain boundary junctions. These secondary phases are devitrified as crystalline Sc2Si2O7. Deformation of the samples was dominated by cavitational processes rather than movements of dislocations. Thus the excellent deformation resistance of the samples at high temperature can be attributed to the very small thickness of the grain boundary layers and the crystalline secondary phase.

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, H.H.; Chaar, M.A.

1988-10-11

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, Harold H.; Chaar, Mohamed A.

1988-01-01

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

USGS Publications Warehouse

Whelan, J.F.; Neymark, L.A.; Moscati, R.J.; Marshall, B.D.; Roedder, E.

2008-01-01

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ???80 ??C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite ??18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ???35 to ???90 ??C. Calcite ??18O values range from ???0 to ???22??? (SMOW) but most fall between 12 and 20???. The highest Th and the lowest ??18O values are found in the older calcite. Calcite Th and ??18O values indicate that most calcite precipitated from water with ??18O values between -13 and -7???, similar to modern meteoric waters. Twenty-two 207Pb/235U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ???9.5 to 1.9 Ma. New and published 207Pb/235U and 230Th/Uages coupled with the Th values and estimates of temperature from calcite ??18O values indicate that maximum unsaturated zone temperatures probably predate ???10 Ma and that the unsaturated zone had cooled to near-present-day temperatures (24-26 ??C at a depth of 250 m) by 2-4 Ma. The evidence

Autoxidation of unsaturated lipids in food emulsion.

PubMed

Sun, Yue-E; Wang, Wei-Dong; Chen, Hong-Wei; Li, Chao

2011-05-01

Unsaturated lipids having various physiological roles are of significance in biochemistry, nutrition, medicine, and food. However, the susceptibility of lipids to oxidation is a major cause of quality deterioration in food emulsions. The reaction mechanism and factors that influence oxidation are appreciably different for emulsified lipids and bulk lipids. This article gives a brief overview of the current knowledge on autoxidation of oil-in-water food emulsions, especially those that contain unsaturated lipids, which are important in the food industry. Autoxidation of unsaturated lipids in oil-in-water emulsion is discussed, and so also their oxidation mechanism, the major factors influencing oxidation, determination measures, research status, and the problems encountered in recent years. Some effective strategies for controlling lipid oxidation in food emulsion have been presented in this review.

Enantioselective Diels-Alder reactions of unsaturated beta-ketoesters catalyzed by chiral ruthenium PNNP complexes.

PubMed

Schotes, Christoph; Mezzetti, Antonio

2011-01-01

We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

Organocatalysed asymmetric beta-amination and multicomponent syn-selective diamination of alpha,beta-unsaturated aldehydes.

PubMed

Jiang, Hao; Nielsen, Johanne B; Nielsen, Martin; Jørgensen, Karl Anker

2007-01-01

An easy and affordable route for obtaining chiral beta-aminated- and alpha,beta-diaminated aldehydes, 1,3-aminoalcohols, and related compounds by using organocatalysis is presented. The chiral secondary amine (S)-2-[bis(3,5-bistrifluoromethylphenyl)trimethylsilanyloxymethyl]pyrrolidine is used as the catalyst to activate alpha,beta-unsaturated aldehydes, which allows succinimide to add in a 1,4-regio- and stereoselective fashion thereby forming N-protected 1,3-aminoaldehydes in good yields and enantioselectivities. This is followed by two easy transformations giving rise to optically active 1,3-aminoalcohols, a common motif in many biologically active compounds, for example, fibrinogen receptor antagonists. Furthermore, optically active alpha,beta-syn-diaminated aldehydes were obtained by the addition of diethyl azodicarboxylate in a one-pot reaction.

Unsaturated macrocyclic dihydroxamic acid siderophores produced by Shewanella putrefaciens using precursor-directed biosynthesis.

PubMed

Soe, Cho Z; Codd, Rachel

2014-04-18

To acquire iron essential for growth, the bacterium Shewanella putrefaciens produces the macrocyclic dihydroxamic acid putrebactin (pbH2; [M + H(+)](+), m/zcalc 373.2) as its native siderophore. The assembly of pbH2 requires endogenous 1,4-diaminobutane (DB), which is produced from the ornithine decarboxylase (ODC)-catalyzed decarboxylation of l-ornithine. In this work, levels of endogenous DB were attenuated in S. putrefaciens cultures by augmenting the medium with the ODC inhibitor 1,4-diamino-2-butanone (DBO). The presence in the medium of DBO together with alternative exogenous non-native diamine substrates, (15)N2-1,4-diaminobutane ((15)N2-DB) or 1,4-diamino-2(E)-butene (E-DBE), resulted in the respective biosynthesis of (15)N-labeled pbH2 ((15)N4-pbH2; [M + H(+)](+), m/zcalc 377.2, m/zobs 377.2) or the unsaturated pbH2 variant, named here: E,E-putrebactene (E,E-pbeH2; [M + H(+)](+), m/zcalc 369.2, m/zobs 369.2). In the latter system, remaining endogenous DB resulted in the parallel biosynthesis of the monounsaturated DB-E-DBE hybrid, E-putrebactene (E-pbxH2; [M + H(+)](+), m/zcalc 371.2, m/zobs 371.2). These are the first identified unsaturated macrocyclic dihydroxamic acid siderophores. LC-MS measurements showed 1:1 complexes formed between Fe(III) and pbH2 ([Fe(pb)](+); [M](+), m/zcalc 426.1, m/zobs 426.2), (15)N4-pbH2 ([Fe((15)N4-pb)](+); [M](+), m/zcalc 430.1, m/zobs 430.1), E,E-pbeH2 ([Fe(E,E-pbe)](+); [M](+), m/zcalc 422.1, m/zobs 422.0), or E-pbxH2 ([Fe(E-pbx)](+); [M](+), m/zcalc 424.1, m/zobs 424.2). The order of the gain in siderophore-mediated Fe(III) solubility, as defined by the difference in retention time between the free ligand and the Fe(III)-loaded complex, was pbH2 (ΔtR = 8.77 min) > E-pbxH2 (ΔtR = 6.95 min) > E,E-pbeH2 (ΔtR = 6.16 min), which suggests one possible reason why nature has selected for saturated rather than unsaturated siderophores as Fe(III) solubilization agents. The potential to conduct multiple types of ex situ chemical

LNAPL Removal from Unsaturated Porous Media using Surfactant Infiltration

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

Zhong, Lirong; Oostrom, Martinus

A series of unsaturated column experiments was performed to evaluate light non-aqueous phase liquid (LNAPL) fate and removal during surfactant solution infiltration. Surfactant-LNAPL phase behavior tests were conducted to optimize the remedial solutions. Packed sand and site sediment columns were first processed to establish representative LNAPL smear zone under unsaturated conditions. Infiltration of low-concentration surfactant was then applied in a stepwise flush mode, with 0.3 column pore volume (PV) of solution in each flush. The influence of infiltrated surfactant solution volume and pH on LNAPL removal was assessed. A LNAPL bank was observed at the very front of the firstmore » surfactant infiltration in each column, indicating that a very low surfactant concentration is needed to reduce the LNAPL-water interfacial tension sufficiently enough to mobilize trapped LNAPL under unsaturated conditions. More LNAPL was recovered as additional steps of surfactant infiltration were applied. Up to 99% LNAPL was removed after six infiltration steps, with less than 2.0 PV of total surfactant solution application, suggesting surfactant infiltration may be an effective method for vadose zone LNAPL remediation. The influence of pH tested in this study (3.99~10.85) was insignificant because the buffering capacity of the sediment kept the pH in the column higher than the zero point charge, pHzpc, of the sediment and therefore the difference between surfactant sorption was negligible.« less

Acoustic waves in unsaturated soils

NASA Astrophysics Data System (ADS)

Lo, Wei-Cheng; Sposito, Garrison

2013-09-01

Seminal papers by Brutsaert (1964) and Brutsaert and Luthin (1964) provided the first rigorous theoretical framework for examining the poroelastic behavior of unsaturated soils, including an important application linking acoustic wave propagation to soil hydraulic properties. Theoretical developments during the 50 years that followed have led Lo et al., (2005) to a comprehensive model of these phenomena, but the relationship of its elasticity parameters to standard poroelasticity parameters measured in hydrogeology has not been established. In the present study, we develop this relationship for three key parameters, the Gassman modulus, Skempton coefficient, and Biot-Willis coefficient by generalizing them to an unsaturated porous medium. We demonstrate the remarkable result that well-known and widely applied relationships among these parameters for a porous medium saturated by a single fluid are also valid under very general conditions for unsaturated soils. We show further that measurement of the Biot-Willis coefficient along with three of the six elasticity coefficients in the model of Lo et al. (2005) is sufficient to characterize poroelastic behavior. The elasticity coefficients in the model of Lo et al. (2005) are sensitive to the dependence of capillary pressure on water saturation and its viscous-drag coefficients are functions of relative permeability, implying that hysteresis in the water retention curve and hydraulic conductivity function should affect acoustic wave behavior in unsaturated soils. To quantify these as-yet unknown effects, we performed numerical simulations for Dune sand at two representative wave excitation frequencies. Our results show that the acoustic wave investigated by Brutsaert and Luthin (1964) propagates at essentially the same speed during imbibition and drainage, but is attenuated more during drainage than imbibition. Overall, effects on acoustic wave behavior caused by hysteresis become more significant as the excitation

Numerical convergence improvements for porflow unsaturated flow simulations

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

Flach, Greg

2017-08-14

Section 3.6 of SRNL (2016) discusses various PORFLOW code improvements to increase modeling efficiency, in preparation for the next E-Area Performance Assessment (WSRC 2008) revision. This memorandum documents interaction with Analytic & Computational Research, Inc. (http://www.acricfd.com/default.htm) to improve numerical convergence efficiency using PORFLOW version 6.42 for unsaturated flow simulations.

Cryopreservation prevents iron-initiated highly unsaturated fatty acid loss during storage of human blood on chromatography paper at -20°C.

PubMed

Metherel, Adam H; Stark, Ken D

2015-03-01

Fingertip prick whole blood collection on chromatography paper is amenable to high-throughput fatty acid (FA) profiling for large clinical and field studies. However, sample storage is problematic because highly unsaturated FAs (HUFAs) in erythrocytes rapidly degrade in samples stored at -20°C. The aim of the current study was to determine the mechanism of HUFA degradation and to develop prevention protocols. Free fatty acid (FFA) standards and whole blood reference material from a single participant were used to examine sample storage at -20°C for up to 90 d in triplicate. Iron chelation with deferoxamine (0-5000 μg), antioxidant protection with butylated hydroxytoluene (50 μg), cryopreservation with glycerol, and blood drying were examined using whole blood on chromatography strips. Biological replicate blood samples from additional participants (n = 6) with a range of ω-3 (n-3) HUFA concentrations were similarly assessed. FFAs were relatively stable when stored on chromatography strips at -20°C. Glycerol treatment prevented HUFA degradation in whole blood reference material for 30 d (45 ± 0.4 to 46.8 ± 0.1, means ± SDs) compared to untreated saline controls (45.9 ± 1.0 to 6.8 ± 0.2). Pretreatment of paper for blood spots with deferoxamine and drying blood before storage slowed, but not entirely prevented, HUFA degradation over 30 d to 22% and 19% below baseline, respectively, compared to 86-92% in the controls. Protection against HUFA degradation with blood drying and glycerol treatment was confirmed in the biological replicate study and confirmed by prevention of cell lysis. HUFA degradation during storage at -20°C appears to be due to hemolysis and subsequent iron-initiated peroxidation. This degradation may be prevented by glycerol, iron chelation, and/or dried blood spotting. A more thorough understanding of methods to prevent degradation during storage is critical with increasing use of FA profiling in large clinical studies. © 2015 American

Preferential flow occurs in unsaturated conditions

USGS Publications Warehouse

Nimmo, John R.

2012-01-01

Because it commonly generates high-speed, high-volume flow with minimal exposure to solid earth materials, preferential flow in the unsaturated zone is a dominant influence in many problems of infiltration, recharge, contaminant transport, and ecohydrology. By definition, preferential flow occurs in a portion of a medium – that is, a preferred part, whether a pathway, pore, or macroscopic subvolume. There are many possible classification schemes, but usual consideration of preferential flow includes macropore or fracture flow, funneled flow determined by macroscale heterogeneities, and fingered flow determined by hydraulic instability rather than intrinsic heterogeneity. That preferential flow is spatially concentrated associates it with other characteristics that are typical, although not defining: it tends to be unusually fast, to transport high fluxes, and to occur with hydraulic disequilibrium within the medium. It also has a tendency to occur in association with large conduits and high water content, although these are less universal than is commonly assumed. Predictive unsaturated-zone flow models in common use employ several different criteria for when and where preferential flow occurs, almost always requiring a nearly saturated medium. A threshold to be exceeded may be specified in terms of the following (i) water content; (ii) matric potential, typically a value high enough to cause capillary filling in a macropore of minimum size; (iii) infiltration capacity or other indication of incipient surface ponding; or (iv) other conditions related to total filling of certain pores. Yet preferential flow does occur without meeting these criteria. My purpose in this commentary is to point out important exceptions and implications of ignoring them. Some of these pertain mainly to macropore flow, others to fingered or funneled flow, and others to combined or undifferentiated flow modes.

Alteration in levels of unsaturated fatty acids in mutants of Escherichia coli defective in DNA replication.

PubMed

Suzuki, E; Kondo, T; Makise, M; Mima, S; Sakamoto, K; Tsuchiya, T; Mizushima, T

1998-07-01

We previously reported that mutations in the dnaA gene which encodes the initiator of chromosomal DNA replication in Escherichia coli caused an alteration in the levels of unsaturated fatty acids of phospholipids in membranes. In this study, we examined fatty acid compositions in other mutants which are defective in DNA replication. As in the case of temperature-sensitive dnaA mutants, temperature-sensitive dnaC and dnaE mutants, which have defects in initiation and elongation, respectively, of DNA replication showed a lower level of unsaturation of fatty acids (ratio of unsaturated to saturated fatty acids) compared with the wild-type strain, especially at high temperatures. On the other hand, temperature-sensitive mutants defective in cellular processes other than DNA replication, such as RNA synthesis and cell division, did not show a lower level of unsaturation of fatty acids compared with the wild-type strain. These results suggest that the inhibition of DNA replication causes a lower level of unsaturation of fatty acids in Escherichia coli cells.

Global Metabolomic Profiling Reveals an Association of Metal Fume Exposure and Plasma Unsaturated Fatty Acids

PubMed Central

Chang, Chiung-yu; Fan, Tianteng; Su, Li; Chen, Feng; Christiani, David C.

2013-01-01

Background Welding-associated air pollutants negatively affect the health of exposed workers; however, their molecular mechanisms in causing disease remain largely unclear. Few studies have systematically investigated the systemic toxic effects of welding fumes on humans. Objectives To explore the effects of welding fumes on the plasma metabolome, and to identify biomarkers for risk assessment of welding fume exposure. Methods The two-stage, self-controlled exploratory study included 11 boilermakers from a 2011 discovery panel and 8 boilermakers from a 2012 validation panel. Plasma samples were collected pre- and post-welding fume exposure and analyzed by chromatography/mass spectrometry. Results Eicosapentaenoic or docosapentaenoic acid metabolic changes post-welding were significantly associated with particulate (PM2.5) exposure (p<0.05). The combined analysis by linear mixed-effects model showed that exposure was associated with a statistically significant decline in metabolite change of eicosapentaenoic acid [(95% CI) = −0.013(−0.022∼−0.004); p = 0.005], docosapentaenoic acid n3 [(95% CI) = −0.010(−0.018∼−0.002); p = 0.017], and docosapentaenoic acid n6 [(95% CI) = −0.007(−0.013∼−0.001); p = 0.021]. Pathway analysis identified an association of the unsaturated fatty acid pathway with exposure (p Study−2011 = 0.025; p Study−2012 = 0.021; p Combined = 0.009). The functional network built by these fatty acids and their interactive genes contained significant enrichment of genes associated with various diseases, including neoplasms, cardiovascular diseases, and lipid metabolism disorders. Conclusions High-dose exposure of metal welding fumes decreases unsaturated fatty acids with an exposure-response relationship. This alteration in fatty acids is a potential biological mediator and biomarker for exposure-related health disorders. PMID:24143234

Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

PubMed

Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

2012-11-16

An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

Unsaturated fatty acids prevent activation of NLRP3 inflammasome in human monocytes/macrophages[S

PubMed Central

L'homme, Laurent; Esser, Nathalie; Riva, Laura; Scheen, André; Paquot, Nicolas; Piette, Jacques; Legrand-Poels, Sylvie

2013-01-01

The NLRP3 inflammasome is involved in many obesity-associated diseases, such as type 2 diabetes, atherosclerosis, and gouty arthritis, through its ability to induce interleukin (IL)-1β release. The molecular link between obesity and inflammasome activation is still unclear, but free fatty acids have been proposed as one triggering event. Here we reported opposite effects of saturated fatty acids (SFAs) compared with unsaturated fatty acids (UFAs) on NLRP3 inflammasome in human monocytes/macrophages. Palmitate and stearate, both SFAs, triggered IL-1β secretion in a caspase-1/ASC/NLRP3-dependent pathway. Unlike SFAs, the UFAs oleate and linoleate did not lead to IL-1β secretion. In addition, they totally prevented the IL-1β release induced by SFAs and, with less efficiency, by a broad range of NLRP3 inducers, including nigericin, alum, and monosodium urate. UFAs did not affect the transcriptional effect of SFAs, suggesting a specific effect on the NLRP3 activation. These results provide a new anti-inflammatory mechanism of UFAs by preventing the activation of the NLRP3 inflammasome and, therefore, IL-1β processing. By this way, UFAs might play a protective role in NLRP3-associated diseases. PMID:24006511

Effects of saturated and unsaturated fats with vitamin E supplementation on the antioxidant status of broiler chicken tissues.

PubMed

Husvéth, F; Manilla, H A; Gaál, T; Vajdovich, P; Balogh, N; Wágner, L; Lóth, I; Németh, K

2000-01-01

The influence of fish oil (highly unsaturated) and beef tallow (highly saturated) with vitamin E (100 IU/kg) supplementation on the antioxidant status of broiler chicken cockerels was investigated. Chicks were fed a control diet with no added fat, 40 g/kg each of fish oil and beef tallow diets, respectively, from 11 to 42 days of age. Tocopherol concentration and the rate of lipid peroxidation, thiobarbituric acid reactive substance (TBARS) in liver, fatty acid composition of the liver lipids, blood serum total antioxidant status (TAS), and reduced glutathione (GSH) content were determined. Vitamin E supplementation of the diet increased liver alpha-tocopherol content in chicks regardless of the type of dietary fat. Fish oil diet resulted in higher liver TBARS value while beef tallow diet showed lower values compared to the control diet. Vitamin E supplementation reduced liver TBARS as well as serum GSH, and raised serum TAS for all diets. Serum GSH was the same for vitamin E supplemented diets regardless of the fat supplement. Fish oil diets resulted in a significant increase in hepatic lipid n-3 PUFA content. A significant positive correlation was found between liver TBARS and n-3 PUFA content. No relationships were established, however, between liver TBARS and n-6 PUFA or saturated fatty acids. The results suggest that feeding oils rich in n-3 PUFA increases tissue concentration of these fatty acids, consequently increasing tissue lipid peroxidation and reducing the antioxidative status of broiler chickens. Supplementing high levels of vitamin E with such oils may increase tissue oxidative stability. Serum TAS or GSH may be used as a measure of antioxidative status in chickens.

Quantifying Preferential Flow and Seasonal Storage in an Unsaturated Fracture-Facial Domain

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; Malek-Mohammadi, S.

2012-12-01

Preferential flow through deep unsaturated zones of fractured rock is hydrologically important to a variety of contaminant transport and water-resource issues. The unsaturated zone of the English Chalk Aquifer provides an important opportunity for a case study of unsaturated preferential flow in isolation from other flow modes. The chalk matrix has low hydraulic conductivity and stays saturated, owing to its fine uniform pores and the wet climate of the region. Therefore the substantial fluxes observed in the unsaturated chalk must be within fractures and interact minimally with matrix material. Price et al. [2000] showed that irregularities on fracture surfaces provide a significant storage capacity in the chalk unsaturated zone, likely accounting for volumes of water required to explain unexpected dry-season water-table stability during substantial continuing streamflow observed by Lewis et al. [1993] In this presentation we discuss and quantify the dynamics of replenishment and drainage of this unsaturated zone fracture-face storage domain using a modification of the source-responsive model of Nimmo [2010]. This model explains the processes in terms of two interacting flow regimes: a film or rivulet preferential flow regime on rough fracture faces, active on an individual-storm timescale, and a regime of adsorptive and surface-tension influences, resembling traditional diffuse formulations of unsaturated flow, effective mainly on a seasonal timescale. The modified model identifies hydraulic parameters for an unsaturated fracture-facial domain lining the fractures. Besides helping to quantify the unsaturated zone storage described by Price et al., these results highlight the importance of research on the topic of unsaturated-flow relations within a near-fracture-surface domain. This model can also facilitate understanding of mechanisms for reinitiation of preferential flow after temporary cessation, which is important in multi-year preferential flow through deep

Mobilization of aluminum by the acid percolates within unsaturated zone of sandstones.

PubMed

Navrátil, Tomáš; Vařilová, Zuzana; Rohovec, Jan

2013-09-01

The area of the Black Triangle has been exposed to extreme levels of acid deposition in the twentieth century. The chemical weathering of sandstones found within the Black Triangle became well-known phenomenon. Infiltration of acid rain solutions into the sandstone represents the main input of salt components into the sandstone. The infiltrated solutions--sandstone percolates--react with sandstone matrix and previously deposited materials such as salt efflorescence. Acidic sandstone percolates pH 3.2-4.8 found at ten sites within the National Park Bohemian Switzerland contained high Al-tot (0.8-10 mg L(-1)) concentrations and high concentrations of anions SO4 (5-66 mg L(-1)) and NO3 (2-42 mg L(-1)). A high proportion (50-98 %) of Al-tot concentration in acid percolates was represented by toxic reactive Al(n+). Chemical equilibrium modeling indicated as the most abundant Al species Al(3+), AlSO4 (+), and AlF(2+). The remaining 2-50 % of Al-tot concentration was present in the form of complexes with dissolved organic matter Al-org. Mobilization and transport of Al from the upper zones of sandstone causes chemical weathering and sandstone structure deterioration. The most acidic percolates contained the highest concentrations of dissolved organic material (estimated up to 42 mg L(-1)) suggesting the contribution of vegetation on sandstone weathering processes. Very low concentrations of Al-tot in springs at BSNP suggest that Al mobilized in unsaturated zone is transported deeper into the sandstone. This process of mobilization could represent a threat for the water quality small-perched aquifers.

Decomposing potassium peroxychromate produces hydroxyl radical (.OH) that can peroxidize the unsaturated fatty acids of phospholipid dispersions.

PubMed

Edwards, J C; Quinn, P J

1982-09-01

The unsaturated fatty acyl residues of egg yolk lecithin are selectively removed when bilayer dispersions of the lipid are exposed to decomposing peroxychromate at pH 7.6 or pH 9.0. Mannitol (50 mM or 100 mM)partially prevents the oxidation of the phospholipid due to decomposing peroxychromate at pH 7.6 and the amount of lipid lost is inversely proportional to the concentration of mannitol. N,N-Dimethyl-p-nitrosoaniline, mixed with the lipid in a molar ratio of 1.3:1, completely prevents the oxidation of lipid due to decomposing peroxychromate at pH 9.0, but some linoleic acid is lost if the incubation is done at pH 7.6. If the concentration of this quench reagent is reduced tenfold, oxidation of linoleic acid by decomposing peroxychromate at pH 9.0 is observed. Hydrogen peroxide is capable of oxidizing the unsaturated fatty acids of lecithin dispersions. Catalase or boiled catalase (2 mg/ml) protects the lipid from oxidation due to decomposing peroxychromate at pH 7.6 to approximately the same extent, but their protective effect is believed to be due to the non-specific removal of .OH. It is concluded that .OH is the species responsible for the lipid oxidation caused by decomposing peroxychromate. This is consistent with the observed bleaching of N,N-dimethyl-p-nitrosoanaline and the formation of a characteristic paramagnetic .OH adduct of the spin trap, 5,5-dimethylpyrroline-1-oxide.

The transport and behaviour of isoproturon in unsaturated chalk cores

NASA Astrophysics Data System (ADS)

Besien, T. J.; Williams, R. J.; Johnson, A. C.

2000-04-01

A batch sorption study, a microcosm degradation study, and two separate column leaching studies were used to investigate the transport and fate of isoproturon in unsaturated chalk. The column leaching studies used undisturbed core material obtained from the field by dry percussion drilling. Each column leaching study used 25 cm long, 10 cm wide unsaturated chalk cores through which a pulse of isoproturon and bromide was eluted. The cores were set-up to simulate conditions in the unsaturated zone of the UK Chalk aquifer by applying a suction of 1 kPa (0.1 m H 2O) to the base of each column, and eluting at a rate corresponding to an average recharge rate through the unsaturated Chalk. A dye tracer indicated that the flow was through the matrix under these conditions. The results from the first column study showed high recovery rates for both isoproturon (73-92%) and bromide (93-96%), and that isoproturon was retarded by a factor of about 1.23 relative to bromide. In the second column study, two of the four columns were eluted with non-sterile groundwater in place of the sterile groundwater used on all other columns, and this study showed high recovery rates for bromide (85-92%) and lower recovery rates for isoproturon (66-79% — sterile groundwater, 48-61% — non-sterile groundwater). The enhanced degradation in the columns eluted with non-sterile groundwater indicated that groundwater microorganisms had increased the degradation rate within these columns. Overall, the reduced isoproturon recovery in the second column study was attributed to increased microbial degradation as a result of the longer study duration (162 vs. 105 days). The breakthrough curves (BTCs) for bromide had a characteristic convection-dispersion shape and were accurately simulated with the minimum of calibration using a simple convection-dispersion model (LEACHP). However, the isoproturon BTCs had an unusual shape and could not be accurately simulated.

Development of Sintered Si3N4 for High Performance Thermomechanical Applications.

DTIC Science & Technology

1984-01-01

noted( 17) that final grain size of sintered Si3 N4 is quite sensitive to both temperature and time at temperature. The sintering of Si NI containing...Characterization of Ube-SN-E0 Si3 N4 Chemical Analysis Lot A-10 Lot A-18 N (alkali fusion) wt . % 38 38 0 (inert gas fusion) wt . % 1.2 1.4 C (inert gas fusion) wt ...temperature stutral applications except for the high creep rate, Which is of the ame order a NC-13. The sintering of -qfiN4ontaning 5 wt % LiAIq0 1and

Damping Effect of an Unsaturated-Saturated System on Tempospatial Variations of Pressure Head and Specific Flux

NASA Astrophysics Data System (ADS)

Yang, C.; Zhang, Y. K.; Liang, X.

2014-12-01

Damping effect of an unsaturated-saturated system on tempospatialvariations of pressurehead and specificflux was investigated. The variance and covariance of both pressure head and specific flux in such a system due to a white noise infiltration were obtained by solving the moment equations of water flow in the system and verified with Monte Carlo simulations. It was found that both the pressure head and specific flux in this case are temporally non-stationary. The variance is zero at early time due to a deterministic initial condition used, then increases with time, and approaches anasymptotic limit at late time.Both pressure head and specific flux arealso non-stationary in space since the variance decreases from source to sink. The unsaturated-saturated systembehavesasa noise filterand it damps both the pressure head and specific flux, i.e., reduces their variations and enhances their correlation. The effect is stronger in upper unsaturated zone than in lower unsaturated zone and saturated zone. As a noise filter, the unsaturated-saturated system is mainly a low pass filter, filtering out the high frequency components in the time series of hydrological variables. The damping effect is much stronger in the saturated zone than in the saturated zone.

Electrical characteristics of proton-irradiated Sc2O3 passivated AlGaN/GaN high electron mobility transistors

NASA Astrophysics Data System (ADS)

Luo, B.; Kim, Jihyun; Ren, F.; Gillespie, J. K.; Fitch, R. C.; Sewell, J.; Dettmer, R.; Via, G. D.; Crespo, A.; Jenkins, T. J.; Gila, B. P.; Onstine, A. H.; Allums, K. K.; Abernathy, C. R.; Pearton, S. J.; Dwivedi, R.; Fogarty, T. N.; Wilkins, R.

2003-03-01

Sc2O3-passivated AlGaN/GaN high electron mobility transistors (HEMTs) were irradiated with 40 MeV protons to a fluence corresponding to approximately 10 years in low-earth orbit (5×109 cm-2). Devices with an AlGaN cap layer showed less degradation in dc characteristics than comparable GaN-cap devices, consistent with differences in average band energy. The changes in device performance could be attributed completely to bulk trapping effects, demonstrating that the effectiveness of the Sc2O3 layers in passivating surface states in the drain-source region was undiminished by the proton irradiation. Sc2O3-passivated AlGaN/HEMTs appear to be attractive candidates for space and terrestrial applications where resistance to high fluxes of ionizing radiation is a criteria.

Effects of unsaturated zone on ground-water mounding

USGS Publications Warehouse

Sumner, D.M.; Rolston, D.E.; Marino, M.A.

1999-01-01

The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding-an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the dynamic nature of basin infiltration, the finite transmission time of the infiltration front to the water table, or the interception of the basin floor by the capillary fringe.The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding - an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the

Hydrogen sensors based on Sc2O3/AlGaN/GaN high electron mobility transistors

NASA Astrophysics Data System (ADS)

Kang, B. S.; Mehandru, R.; Kim, S.; Ren, F.; Fitch, R. C.; Gillespie, J. K.; Moser, N.; Jessen, G.; Jenkins, T.; Dettmer, R.; Via, D.; Crespo, A.; Baik, K. H.; Gila, B. P.; Abernathy, C. R.; Pearton, S. J.

2005-05-01

Pt contacted AlGaN/GaN high electron mobility transistors with Sc2O3 gate dielectrics show reversible changes in drain-source current upon exposure to H2-containing ambients, even at room temperature. The changes in current (as high as 3 mA for relatively low gate voltage and drain-source voltage at 25 °C for the HEMTs and a change in forward current of 40 μA at a bias of 2.5 V was obtained for the MOS-diodes in response to a change in ambient from pure N2 to 10% H2/90% N2. The current changes in the latter case are almost linearly proportional to the testing temperature and reach around 400 μA at 400 °C. These signals are approximately an order of magnitude larger than for Pt /GaN Schottky diodes and a factor of 5 larger than Sc2O3/AlGaN/GaN metal-oxide semiconductor (MOS) diodes exposed under the same conditions. This shows the advantage of using a transistor structure in which the gain produces larger current changes upon exposure to hydrogen-containing ambients. The increase in current is the result of a decrease in effective barrier height of the MOS gate of 30-50 mV at 25 °C for 10%H2/90%N₂ ambients relative to pure N₂ and is due to catalytic dissociation of the H₂ on the Pt contact, followed by diffusion to the Sc₂O₃/AlGaN interface.

Effects of Unsaturated Zones on Baseflow Recession: Analytical Solution and Application

NASA Astrophysics Data System (ADS)

Zhan, H.; Liang, X.; Zhang, Y. K.

2017-12-01

Unsaturated flow is an important process in baseflow recessions and its effect is rarely investigated. A mathematical model for a coupled unsaturated-saturated flow in a horizontally unconfined aquifer with time-dependent infiltrations is presented. Semi-analytical solutions for hydraulic heads and discharges are derived using Laplace transform and Cosine transform. The solutions are compared with solutions of the linearized Boussinesq equation (LB solution) and the linearized Laplace equation (LL solution), respectively. The result indicates that a larger dimensionless constitutive exponent κD of the unsaturated zone leads to a smaller discharge during the infiltration period and a larger discharge after the infiltration. The lateral discharge of the unsaturated zone is significant when κD≤1, and becomes negligible when κD≥100. For late times, the power index b of the recession curve-dQ/dt aQb, is 1 and independent of κD, where Q is the baseflow and a is a constant lumped aquifer parameter. For early times, b is approximately equal to 3 but it approaches infinity when t→1. The present solution is applied to synthetic and field cases. The present solution matched the synthetic data better than both the LL and LB solutions, with a minimum relative error of 16% for estimate of hydraulic conductivity. The present solution was applied to the observed streamflow discharge in Iowa, and the estimated values of the aquifer parameters were reasonable.

Modeling tritium transport through a deep unsaturated zone in an arid environment

USGS Publications Warehouse

Mayers, C.J.; Andraski, Brian J.; Cooper, C.A.; Wheatcraft, S.W.; Stonestrom, David A.; Michel, R.L.

2005-01-01

Understanding transport of tritium (3H) in unsaturated zones is critical to evaluating options for waste isolation. Tritium typically is a large component of low-level radioactive waste (LLRW). Studies at the U.S. Geological Survey's Amargosa Desert Research Site (ADRS) in Nevada investigate 3H transport from a closed LLRW facility. Two boreholes are 100 and 160 m from the nearest waste trench and extend to the water table at 110 m. Soil-water vapor samples from the deep boreholes show elevated levels of 3H at all depths. The objectives of this study were to (i) test source thermal and gas-advection mechanisms driving 3H transport and (ii) evaluate model sensitivity to these mechanisms and to selected physical and hydraulic properties including porosity, tortuosity, and anisotropy. A two-dimensional numerical model incorporated a non-isothermal, heterogeneous domain of the unsaturated zone and instantaneous isotopic equilibrium. The TOUGH2 code was used; however, it required modification to account for temperature dependence of both the Henry's law equilibrium constant and isotopic fractionation with respect to tritiated water. Increases in source temperature, pressure, and porosity enhanced 3H migration, but failed to match measured 3H distributions. All anisotropic simulations with a source pressure component resembled, in shape, the upper portion of the 3H distribution of the nearest borehole. Isotopic equilibrium limited migration of 3H, while effects of radioactive decay were negligible. A 500 Pa pressure increase above ambient pressure in conjunction with a high degree of anisotropy (1:100) was necessary for simulated 3H transport to reach the nearest borehole.

Consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates.

PubMed

Vero, S E; Ibrahim, T G; Creamer, R E; Grant, J; Healy, M G; Henry, T; Kramers, G; Richards, K G; Fenton, O

2014-12-01

The true efficacy of a programme of agricultural mitigation measures within a catchment to improve water quality can be determined only after a certain hydrologic time lag period (subsequent to implementation) has elapsed. As the biophysical response to policy is not synchronous, accurate estimates of total time lag (unsaturated and saturated) become critical to manage the expectations of policy makers. The estimation of the vertical unsaturated zone component of time lag is vital as it indicates early trends (initial breakthrough), bulk (centre of mass) and total (Exit) travel times. Typically, estimation of time lag through the unsaturated zone is poor, due to the lack of site specific soil physical data, or by assuming saturated conditions. Numerical models (e.g. Hydrus 1D) enable estimates of time lag with varied levels of input data. The current study examines the consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates using simulated and actual soil profiles. Results indicated that: greater temporal resolution (from daily to hourly) of meteorological data was more critical as the saturated hydraulic conductivity of the soil decreased; high clay content soils failed to converge reflecting prevalence of lateral component as a contaminant pathway; elucidation of soil hydraulic properties was influenced by the complexity of soil physical data employed (textural menu, ROSETTA, full and partial soil water characteristic curves), which consequently affected time lag ranges; as the importance of the unsaturated zone increases with respect to total travel times the requirements for high complexity/resolution input data become greater. The methodology presented herein demonstrates that decisions made regarding input data and landscape position will have consequences for the estimated range of vertical travel times. Insufficiencies or inaccuracies regarding such input data can therefore mislead policy makers regarding

Evaluation of probabilistic flow in two unsaturated soils

NASA Astrophysics Data System (ADS)

Boateng, Samuel

2001-11-01

A variably saturated flow model is coupled to a first-order reliability algorithm to simulate unsaturated flow in two soils. The unsaturated soil properties are considered as uncertain variables with means, standard deviations, and marginal probability distributions. Thus, each simulation constitutes an unsaturated probability flow event. Sensitivities of the uncertain variables are estimated for each event. The unsaturated hydraulic properties of a fine-textured soil and a coarse-textured soil are used. The properties are based on the van Genuchten model. The flow domain has a recharge surface, a seepage boundary along the bottom, and a no-flow boundary along the sides. The uncertain variables are saturated water content, residual water content, van Genuchten model parameters alpha (α) and n, and saturated hydraulic conductivity. The objective is to evaluate the significance of each uncertain variable to the probabilistic flow. Under wet conditions, saturated water content and residual water content are the most significant uncertain variables in the sand. For dry conditions in the sand, however, the van Genuchten model parameters α and n are the most significant. Model parameter n and saturated hydraulic conductivity are the most significant for the wet clay loam. Saturated water content is most significant for the dry clay loam. Résumé. Un modèle d'écoulement variable en milieu saturé est couplé à un algorithme d'exactitude de premier ordre pour simuler les écoulements en milieu non saturé dans deux sols. Les propriétés des sols non saturés sont considérés comme des variables incertaines avec des moyennes, des écarts-types et des distributions de probabilité marginale. Ainsi chaque simulation constitue un événement d'écoulement non saturé probable. La sensibilité des variables incertaines est estimée pour chaque événement. Les propriétés hydrauliques non saturées d'un sol à texture fine et d'un sol à texture grossière sont utilis

Kinetic study of the degradation of C5 and C6 unsaturated aldehydes and alcohols by ozone

NASA Astrophysics Data System (ADS)

Kalalian, Carmen; Roth, Estelle; Chakir, Abdelkhaleq

2017-04-01

Emissions of biogenic volatile organic compounds (VOCs) are higher than those from anthropogenic sources. They are therefore likely to have a great influence on atmospheric chemistry both locally and regionally, through their impact on the HOx balance (HOx = HO + HO2), ozone production and ability to form secondary organic aerosols (SOA). Among the volatile organic compounds of biogenic origin are the family of C5 and C6 unsaturated aldehydes and alcohols. Few information exist regarding the fate of these compounds in the atmosphere especially there reaction with ozone. In this work, we studied the kinetics of the reaction of three unsaturated aldehydes (trans-2-pentenal, trans-2-hexenal and 2-methyl-2-pentenal) and three unsaturated alcohols (1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol) with ozone O3 in a rigid atmospheric simulation chamber coupled to an FTIR spectrometer at four different temperatures (273, 298, 333 and 353 K) and at atmospheric pressure. The rate constants of the ozonolysis reaction of the unsaturated aldehydes and the unsaturated alcohols studied were determined and the following Arrhenius expression was obtained (cm3 molecule -1 s -1): k (Trans -2-pentenal)= (3.83 ± 3.71) x 10-16 exp (- (1706 ± 295) / T) k (Trans-2-hexenal)= (1.43 ± 0.67) x 10-16 exp (- (1369 ± 141) / T) k(2-Methyl-2-pentenal)= (3.62± 0.22) x 10-18 exp (- (121 ± 20) / T) k(1-penten-3-ol) = (1.42 ± 1.24) x 10-16 exp (- (642 ± 250) / T) k(Cis-2-penten-1-ol)= (3.14 ± 0.45) x 10-15 exp (- (1045 ± 40) / T) k(Trans-3-hexen-1-ol)= (6.38 ± 1.75) x 10-16 exp (- (686 ± 89) / T) The obtained data will be discussed in terms of structure-reactivity relationship and compared with the reported reactivity with OH radicals. The atmospheric implications derived from this study are discussed as well.

Biological variability of transferrin saturation and unsaturated iron binding capacity

PubMed Central

Adams, PC; Reboussin, DM; Press, RD; Barton, JC; Acton, RT; Moses, GC; Leiendecker-Foster, C; McLaren, GD; Dawkins, FW; Gordeuk, VR; Lovato, L; Eckfeldt, JH

2007-01-01

Background Transferrin saturation is widely considered the preferred screening test for hemochromatosis. Unsaturated iron binding capacity has similar performance at lower cost. However, the within-person biological variability of both these tests may limit their ability at commonly used cut points to detect HFE C282Y homozygous patients. Methods The Hemochromatosis and Iron Overload Screening (HEIRS) Study screened 101,168 primary care participants for iron overload using tansferrin saturation, unsaturated iron binding capacity, ferritin and HFE C282Y and H63D genotyping. Transferrin saturation and unsaturated iron binding capacity were performed at initial screening and again when selected participants and controls returned for a clinical examination several months later. A missed case was defined as a C282Y homozygote who had transferrin saturation below cut point (45 % women, 50 % men) or unsaturated iron binding capacity above cut point (150 μmol/L women, 125 μmol/L men) at either the initial screening or clinical examination, or both, regardless of serum ferritin. Results There were 209 C282Y previously undiagnosed homozygotes with transferrin saturation and unsaturated iron binding capacity testing done at initial screening and clinical examination. Sixty-eight C282Y homozygotes (33%) would have been missed at these transferrin saturation cut points (19 men, 49 women, median SF 170 μg/L, first and third quartiles 50 and 474 μg/L), and 58 homozygotes (28 %) would have been missed at the unsaturated iron binding capacity cut points (20 men, 38 women, median SF 168 μg/L, quartiles 38 and 454 μg/L). There was no advantage to using fasting samples. Conclusions The within-person biological variability of transferrin saturation and unsaturated iron binding capacity limit their usefulness as an initial screening test for expressing C282Y homozygotes. PMID:17976429

Investigating unsaturated fat, monensin, or bromoethanesulfonate in continuous cultures retaining ruminal protozoa. I. Fermentation, biohydrogenation, and microbial protein synthesis.

PubMed

Karnati, S K R; Sylvester, J T; Ribeiro, C V D M; Gilligan, L E; Firkins, J L

2009-08-01

Methane is an end product of ruminal fermentation that is energetically wasteful and contributes to global climate change. Bromoethanesulfonate, animal-vegetable fat, and monensin were compared with a control treatment to suppress different functional groups of ruminal prokaryotes in the presence or absence of protozoa to evaluate changes in fermentation, digestibility, and microbial N outflow. Four dual-flow continuous culture fermenter systems were used in 4 periods in a 4 x 4 Latin square design split into 2 subperiods. In subperiod 1, a multistage filter system (50-microm smallest pore size) retained most protozoa. At the start of subperiod 2, conventional filters (300-microm pore size) were substituted to efflux protozoa via filtrate pumps over 3 d; after a further 7 d of adaptation, the fermenters were sampled for 3 d. Treatments were retained during both subperiods. Flow of total N and digestibilities of NDF and OM were 18, 16, and 9% higher, respectively, for the defaunated subperiod but were not different among treatments. Ammonia concentration was 33% higher in the faunated fermenters but was not affected by treatment. Defaunation increased the flow of nonammonia N and bacterial N from the fermenters. Protozoal counts were not different among treatments, but bromoethanesulfonate increased the generation time from 43.2 to 55.6 h. Methanogenesis was unaffected by defaunation but tended to be increased by unsaturated fat. Defaunation did not affect total volatile fatty acid production but decreased the acetate:propionate ratio; monensin increased production of isovalerate and valerate. Biohydrogenation of unsaturated fatty acids was impaired in the defaunated fermenters because effluent flows of oleic, linoleic, and linolenic acids were 60, 77, and 69% higher, and the ratio of vaccenic acid:unsaturated FA ratio was decreased by 34% in the effluent. This ratio was increased in both subperiods with the added fat diet, indicating an accumulation of

Time-lapse gravity data for monitoring and modeling artificial recharge through a thick unsaturated zone

NASA Astrophysics Data System (ADS)

Kennedy, Jeffrey; Ferré, Ty P. A.; Creutzfeldt, Benjamin

2016-09-01

Groundwater-level measurements in monitoring wells or piezometers are the most common, and often the only, hydrologic measurements made at artificial recharge facilities. Measurements of gravity change over time provide an additional source of information about changes in groundwater storage, infiltration, and for model calibration. We demonstrate that for an artificial recharge facility with a deep groundwater table, gravity data are more sensitive to movement of water through the unsaturated zone than are groundwater levels. Groundwater levels have a delayed response to infiltration, change in a similar manner at many potential monitoring locations, and are heavily influenced by high-frequency noise induced by pumping; in contrast, gravity changes start immediately at the onset of infiltration and are sensitive to water in the unsaturated zone. Continuous gravity data can determine infiltration rate, and the estimate is only minimally affected by uncertainty in water-content change. Gravity data are also useful for constraining parameters in a coupled groundwater-unsaturated zone model (Modflow-NWT model with the Unsaturated Zone Flow (UZF) package).

Time-lapse gravity data for monitoring and modeling artificial recharge through a thick unsaturated zone

USGS Publications Warehouse

Kennedy, Jeffrey R.; Ferre, Ty P.A.; Creutzfeldt, Benjamin

2016-01-01

Groundwater-level measurements in monitoring wells or piezometers are the most common, and often the only, hydrologic measurements made at artificial recharge facilities. Measurements of gravity change over time provide an additional source of information about changes in groundwater storage, infiltration, and for model calibration. We demonstrate that for an artificial recharge facility with a deep groundwater table, gravity data are more sensitive to movement of water through the unsaturated zone than are groundwater levels. Groundwater levels have a delayed response to infiltration, change in a similar manner at many potential monitoring locations, and are heavily influenced by high-frequency noise induced by pumping; in contrast, gravity changes start immediately at the onset of infiltration and are sensitive to water in the unsaturated zone. Continuous gravity data can determine infiltration rate, and the estimate is only minimally affected by uncertainty in water-content change. Gravity data are also useful for constraining parameters in a coupled groundwater-unsaturated zone model (Modflow-NWT model with the Unsaturated Zone Flow (UZF) package).

Degree of fatty acyl chain unsaturation in biliary lecithin dictates cholesterol nucleation and crystal growth.

PubMed

Tazuma, S; Ochi, H; Teramen, K; Yamashita, Y; Horikawa, K; Miura, H; Hirano, N; Sasaki, M; Aihara, N; Hatsushika, S

1994-11-17

To clarify factors involved in the formation of cholesterol gallstones, we studied the relationship between the degree of fatty acyl chain unsaturation of biliary lecithin and bile metastability. We used supersaturated model bile solutions (molar taurocholate/lecithin/cholesterol ratio (73:19.5:7.5), total lipid concentration 9 g/dl) that contained equimolar egg yolk or soybean lecithins or a sn-1 palmitoyl, sn-2 linoleoyl phosphatidylcholine. Gel permeation chromatographic studies showed that the vesicular cholesterol distribution and dimension were inversely related to the degree of unsaturation of the lecithin species, estimated by reverse phase, high-performance liquid chromatography. Differential interference contrast microscopy and assay of cholesterol crystal growth showed that a higher degree of fatty acyl chain unsaturation of the lecithin species was associated with a faster nucleation time and rate of crystal growth. Our results suggest that vesicular lecithins containing more unsaturated fatty acyl chains bind less tightly to cholesterol than lecithins containing predominantly saturated fatty acids, and that the biliary lecithin species dictates, in part, the nucleation and growth of cholesterol crystals in bile.

Alteration in the contents of unsaturated fatty acids in dnaA mutants of Escherichia coli.

PubMed

Suzuki, E; Kondo, T; Makise, M; Mima, S; Sakamoto, K; Tsuchiya, T; Mizushima, T

1998-04-01

DnaA protein, the initiator of chromosomal DNA replication in Escherichia coli, has a high affinity for acidic phospholipids containing unsaturated fatty acids. We have examined here the fatty acid composition of phospholipids in dnaA mutants. A temperature-sensitive dnaA46 mutant showed a lower level of unsaturation of fatty acids (ratio of unsaturated to saturated fatty acids) at 42 degrees C (non-permissive temperature) and at 37 degrees C (semi-permissive temperature), but not at 28 degrees C (permissive temperature), compared with the wild-type strain. Plasmid complementation analysis revealed that the dnaA46 mutation is responsible for the phenotype. Other temperature-sensitive dnaA mutants showed similar results. On the other hand, a cold-sensitive dnaAcos mutant, in which over-initiation of DNA replication occurs at low temperature (28 degrees C), showed a higher level of unsaturation of fatty acids at 28 degrees C. Based on these observations, we discuss the role of phospholipids in the regulation of the activity of DnaA protein.

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

USGS Publications Warehouse

Reilly, T.J.; Fishman, N.S.; Baehr, A.L.

2009-01-01

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (???8-km2) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO3- and SO42-) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80-94% w/w), are coated with a very fine-grained (<20 ??m), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO42- were observed, indicative of anion sorption. Other mineral-chemical relations indicate that negatively charged surfaces and competition with SO 42- results in exclusion of NO3- from inner sphere exchange sites. The observed NO3- storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3- and SO42- in the unsaturated zone. ?? Soil Science Society of America. All rights reserved.

Multimodel analysis of anisotropic diffusive tracer-gas transport in a deep arid unsaturated zone

USGS Publications Warehouse

Green, Christopher T.; Walvoord, Michelle Ann; Andraski, Brian J.; Striegl, Robert G.; Stonestrom, David A.

2015-01-01

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Comparison of different filter methods for data assimilation in the unsaturated zone

NASA Astrophysics Data System (ADS)

Lange, Natascha; Berkhahn, Simon; Erdal, Daniel; Neuweiler, Insa

2016-04-01

The unsaturated zone is an important compartment, which plays a role for the division of terrestrial water fluxes into surface runoff, groundwater recharge and evapotranspiration. For data assimilation in coupled systems it is therefore important to have a good representation of the unsaturated zone in the model. Flow processes in the unsaturated zone have all the typical features of flow in porous media: Processes can have long memory and as observations are scarce, hydraulic model parameters cannot be determined easily. However, they are important for the quality of model predictions. On top of that, the established flow models are highly non-linear. For these reasons, the use of the popular Ensemble Kalman filter as a data assimilation method to estimate state and parameters in unsaturated zone models could be questioned. With respect to the long process memory in the subsurface, it has been suggested that iterative filters and smoothers may be more suitable for parameter estimation in unsaturated media. We test the performance of different iterative filters and smoothers for data assimilation with a focus on parameter updates in the unsaturated zone. In particular we compare the Iterative Ensemble Kalman Filter and Smoother as introduced by Bocquet and Sakov (2013) as well as the Confirming Ensemble Kalman Filter and the modified Restart Ensemble Kalman Filter proposed by Song et al. (2014) to the original Ensemble Kalman Filter (Evensen, 2009). This is done with simple test cases generated numerically. We consider also test examples with layering structure, as a layering structure is often found in natural soils. We assume that observations are water content, obtained from TDR probes or other observation methods sampling relatively small volumes. Particularly in larger data assimilation frameworks, a reasonable balance between computational effort and quality of results has to be found. Therefore, we compare computational costs of the different methods as well

Pore-water extraction from unsaturated tuff by triaxial and one-dimensional compression methods, Nevada Test Site, Nevada

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

Mower, T.E.; Higgins, J.D.; Yang, In C.

1994-07-01

The hydrologic system in the unsaturated tuff at Yucca Mountain, Nevada, is being evaluated for the US Department of Energy by the Yucca Mountain Project Branch of the US Geological Survey as a potential site for a high-level radioactive-waste repository. Part of this investigation includes a hydrochemical study that is being made to assess characteristics of the hydrologic system such as: traveltime, direction of flow, recharge and source relations, and types and magnitudes of chemical reactions in the unsaturated tuff. In addition, this hydrochemical information will be used in the study of the dispersive and corrosive effects of unsaturated-zone watermore » on the radioactive-waste storage canisters. This report describes the design and validation of laboratory experimental procedures for extracting representative samples of uncontaminated pore water from welded and nonwelded, unsaturated tuffs from the Nevada Test Site.« less

Unsaturated Fatty Acids Supplementation Reduces Blood Lead Level in Rats

PubMed Central

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: “super lecithin” (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

Unsaturated fatty acids supplementation reduces blood lead level in rats.

PubMed

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: "super lecithin" (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05).

The Soil-Water Characteristic Curve of Unsaturated Tropical Residual Soil

NASA Astrophysics Data System (ADS)

Yusof, M. F.; Setapa, A. S.; Tajudin, S. A. A.; Madun, A.; Abidin, M. H. Z.; Marto, A.

2016-07-01

This study was conducted to determine the SWCC of unsaturated tropical residual soil in Kuala Lumpur, Malaysia. Undisturbed soil samples at five locations of high-risk slopes area were taken at a depth of 0.5 m using block sampler. In the determination of the SWCC, the pressure plate extractor with the capacity of 1500 kN/m2 has been used. The index properties of the soil such as natural moisture content, Atterberg limits, specific gravity, and soil classification are performed according to BS 1377: Part 2: 1990. The results of index properties show that the natural moisture content of the soil is between 36% to 46%, the plasticity index is between 10% - 26%, the specific gravity is between 2.51 - 2.61 and the soils is classified as silty organic clay of low plasticity. The SWCC data from the pressure plate extractor have been fitted with the Fredlund and Xing equation. The results show that the air entry value and residual matric suction for residual soils are in the range of 17 kN/m2 to 24 kN/m2 and 145 kN/m2 to 225 kN/m2 respectively. From the fitting curve, it is found that the average value of the Fredlund and Xing parameters such as a, n and m are in the range of 0.24-0.299, 1.7-4.8 and 0.142-0.440 respectively.

Documentation of the Unsaturated-Zone Flow (UZF1) Package for modeling Unsaturated Flow Between the Land Surface and the Water Table with MODFLOW-2005

USGS Publications Warehouse

Niswonger, Richard G.; Prudic, David E.; Regan, R. Steven

2006-01-01

Percolation of precipitation through unsaturated zones is important for recharge of ground water. Rain and snowmelt at land surface are partitioned into different pathways including runoff, infiltration, evapotranspiration, unsaturated-zone storage, and recharge. A new package for MODFLOW-2005 called the Unsaturated-Zone Flow (UZF1) Package was developed to simulate water flow and storage in the unsaturated zone and to partition flow into evapotranspiration and recharge. The package also accounts for land surface runoff to streams and lakes. A kinematic wave approximation to Richards? equation is solved by the method of characteristics to simulate vertical unsaturated flow. The approach assumes that unsaturated flow occurs in response to gravity potential gradients only and ignores negative potential gradients; the approach further assumes uniform hydraulic properties in the unsaturated zone for each vertical column of model cells. The Brooks-Corey function is used to define the relation between unsaturated hydraulic conductivity and water content. Variables used by the UZF1 Package include initial and saturated water contents, saturated vertical hydraulic conductivity, and an exponent in the Brooks-Corey function. Residual water content is calculated internally by the UZF1 Package on the basis of the difference between saturated water content and specific yield. The UZF1 Package is a substitution for the Recharge and Evapotranspiration Packages of MODFLOW-2005. The UZF1 Package differs from the Recharge Package in that an infiltration rate is applied at land surface instead of a specified recharge rate directly to ground water. The applied infiltration rate is further limited by the saturated vertical hydraulic conductivity. The UZF1 Package differs from the Evapotranspiration Package in that evapotranspiration losses are first removed from the unsaturated zone above the evapotranspiration extinction depth, and if the demand is not met, water can be removed

Effect of Unsaturated Flow on Delayed Response of Unconfined Aquifiers to Pumping

NASA Astrophysics Data System (ADS)

Tartakovsky, G.; Neuman, S. P.

2005-12-01

A new analytical solution is presented for the delayed response process characterizing flow to a partially penetrating well in an unconfined aquifer. The new solution generalizes that of Neuman [1972, 1974] by accounting for unsaturated flow above the water table. Axially symmetric three-dimensional flow in the unsaturated zone is described by a linearized version of Richards' equation in which hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value (defining the interface between the saturated and unsaturated zones). Unsaturated soil properties are characterized by an exponent κ having the dimension of inverse length and a dimensionless exponent κD = κb where b is initial saturated thickness. Our treatment of the unsaturated zone is similar to that of Kroszynski and Dagan [1975] who however have ignored internal (artesian) aquifer storage. It has been suggested by Boulton [1954, 1963, 1970] and Neuman [1972, 1974], and is confirmed by our solution, that internal storage is required to reproduce the early increase in drawdown characterizing delayed response to pumping in typical aquifers. According to our new solution such aquifers are characterized by relatively large κ_ D values, typically 10 or larger; in the limit as κD tends to infinity (the soil unsaturated water retention capacity becomes insignificant and/or aquifer thickness become large), unsaturated flow becomes unimportant and our solution reduces to that of Neuman. In typical cases corresponding to κD larger than or equal to 10, unsaturated flow is found to have little impact on early and late dimensionless time behaviors of drawdown measured wholly or in part at some distance below the water table; unsaturated flow causes drawdown to increase slightly at intermediate dimensionless time values that represent transition from an early artesian dominated to a late water-table dominated flow regime. The increase in drawdown

Surface morphology of Al0.3Ga0.7N/Al2O3-high electron mobility transistor structure.

PubMed

Cörekçi, S; Usanmaz, D; Tekeli, Z; Cakmak, M; Ozçelik, S; Ozbay, E

2008-02-01

We present surface properties of buffer films (AIN and GaN) and Al0.3Gao.zN/Al2O3-High Electron Mobility Transistor (HEMT) structures with/without AIN interlayer grown on High Temperature (HT)-AIN buffer/Al2O3 substrate and Al2O3 substrate. We have found that the GaN surface morphology is step-flow in character and the density of dislocations was about 10(8)-10(9) cm(-2). The AFM measurements also exhibited that the presence of atomic steps with large lateral step dimension and the surface of samples was smooth. The lateral step sizes are in the range of 100-250 nm. The typical rms values of HEMT structures were found as 0.27, 0.30, and 0.70 nm. HT-AIN buffer layer can have a significant impact on the surface morphology of Al0.3Ga0.7N/Al2O3-HEMT structures.

Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.

DOEpatents

McDonald, William F.; Huang, Zhi Heng; Wright, Stacy C.; Danzig, Morris; Taylor, Andrew C.

2002-07-17

A polyamide and a process for preparing the polyamide are disclosed. The process comprises reacting in a reaction mixture a monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product in the reaction mixture, wherein the first amine is selected from RR.sub.1 NH, RNH.sub.2, RR.sub.1 NH.sub.2.sup.+, RNH.sub.3.sup.+ and mixtures thereof, wherein R and R.sub.1 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, and reacting the intermediate reaction product and a second amine to form a polyamide, wherein the second amine is selected from R.sub.2 R.sub.3 NH, R.sub.2 NH.sub.2, R.sub.2 R.sub.3 NH.sub.2.sup.+, R.sub.2 NH.sub.3.sup.+ and mixtures thereof wherein R.sub.2 and R.sub.3 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein multiple of the R, R.sub.1, R.sub.2, and R.sub.3 are in vertically aligned spaced relationship along a backbone formed by the polyamide. In one version of the invention, the monomer is selected from maleic anhydride, maleic acid esters, and mixtures thereof. In another version of the invention, the first amine is an alkylamine, such as tetradecylamine, and the second amine is a polyalkylene polyamine, such as pentaethylenehexamine. In yet another version of the invention, the first amine and the second amine are olefinic or acetylenic amines, such as the reaction products of an alkyldiamine and an acetylenic carboxylic acid. The first amine and the second amine may be the same or different depending on the desired polyamide polymer structure.

Preferential dealkylation reactions of s-triazine herbicides in the unsaturated zone

USGS Publications Warehouse

Mills, M.S.; Michael, Thurman E.

1994-01-01

The preferential dealkylation pathways of the s-triazine herbicides, atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), propazine [2-chloro-4,6-bis(isopropylamino)-s-triazine], and simazine [2-chloro-4,6-bis(ethylamino)-s-triazine], and two monodealkylated triazine metabolites, deisopropylatrazine (DIA: 2-amino-4-chloro-6-ethylamino-s-triazine) and deethylatrazine (DEA: 2-amino-4-chloro-6-isopropylamino-s-triazine) were investigated on two adjacent Eudora silt-loam plots growing corn (Zea mays L.). Results from the shallow unsaturated zone and surface-water runoff showed preferential removal of an ethyl side chain from atrazine, simazine, and DIA relative to an isopropyl side chain from atrazine, propazine, and DEA. It is hypothesized that deethylation reactions may proceed at 2-3 times the rate of deisopropylation reactions. It is concluded that small concentrations of DIA reportedly associated with the degradation of atrazine may be due to a rapid turnover rate of the metabolite in the unsaturated zone, not to small production levels. Because of continued dealkylation of both monodealkylated metabolites, a strong argument is advanced for the presence of a didealkylated metabolite in the unsaturated zone.

Structural Analysis of Unsaturated Glycosphingolipids Using Shotgun Ozone-Induced Dissociation Mass Spectrometry

NASA Astrophysics Data System (ADS)

Barrientos, Rodell C.; Vu, Ngoc; Zhang, Qibin

2017-08-01

Glycosphingolipids are essential biomolecules widely distributed across biological kingdoms yet remain relatively underexplored owing to both compositional and structural complexity. While the glycan head group has been the subject of most studies, there is paucity of reports on the lipid moiety, particularly the location of unsaturation. In this paper, ozone-induced dissociation mass spectrometry (OzID-MS) implemented in a traveling wave-based quadrupole time-of-flight (Q-ToF) mass spectrometer was applied to study unsaturated glycosphingolipids using shotgun approach. Resulting high resolution mass spectra facilitated the unambiguous identification of diagnostic OzID product ions. Using [M+Na]+ adducts of authentic standards, we observed that the long chain base and fatty acyl unsaturation had distinct reactivity with ozone. The reactivity of unsaturation in the fatty acyl chain was about 8-fold higher than that in the long chain base, which enables their straightforward differentiation. Influence of the head group, fatty acyl hydroxylation, and length of fatty acyl chain on the oxidative cleavage of double bonds was also observed. Application of this technique to bovine brain galactocerebrosides revealed co-isolated isobaric and regioisomeric species, which otherwise would be incompletely identified using contemporary collision-induced dissociation (CID) alone. These results highlight the potential of OzID-MS in glycosphingolipids research, which not only provides complementary structural information to existing CID technique but also facilitates de novo structural determination of these complex biomolecules. [Figure not available: see fulltext.

Oxygen transport and pyrite oxidation in unsaturated coal-mine spoil

USGS Publications Warehouse

Guo, Weixing; Cravotta, Charles A.

1996-01-01

An understanding of the mechanisms of oxygen (02) transport in unsaturated mine spoil is necessary to design and implement effective measures to exclude 02 from pyritic materials and to control the formation of acidic mine drainage. Partial pressure of oxygen (Po2) in pore gas, chemistry of pore water, and temperature were measured at different depths in unsaturated spoil at two reclaimed surface coal mines in Pennsylvania. At mine 1, where spoil was loose, blocky sandstone, Po2 changed little with depth, decreasing from 21 volume percent (vol%) at the ground surface to a minimum of about 18 vol% at 10 m depth. At mine 2, where spoil was compacted, friable shale, Po2 decreased to less than 2 vol% at depth of about 10 m. Although pore-water chemistry and temperature data indicate that acid-forming reactions were active at both mines, the pore-gas data indicate that mechanisms for 0 2 transport were different at each mine. A numerical model was developed to simulate 02 transport and pyrite oxidation in unsaturated mine spoil. The results of the numerical simulations indicate that differences in 02 transport at the two mines can be explained by differences in the air permeability of spoil. Po2 changes little with depth if advective transport of 02 dominates as at mine 1, but decreases greatly with depth if diffusive transport of 02 dominates, as in mine 2. Model results also indicate that advective transport becomes significant if the air permeability of spoil is greater than 10-9 m2, which is expected for blocky sandstone spoil. In the advective-dominant system, thermally-induced convective air flow, as a consequence of the exothermic oxidation of pyrite, supplies the 02 to maintain high Po2 within the deep unsaturated zone.

Biodegradation of vapor-phase toluene in unsaturated porous media: Column experiments.

PubMed

Khan, Ali M; Wick, Lukas Y; Harms, Hauke; Thullner, Martin

2016-04-01

Biodegradation of organic chemicals in the vapor phase of soils and vertical flow filters has gained attention as promising approach to clean up volatile organic compounds (VOC). The drivers of VOC biodegradation in unsaturated systems however still remain poorly understood. Here, we analyzed the processes controlling aerobic VOC biodegradation in a laboratory setup mimicking the unsaturated zone above a shallow aquifer. The setup allowed for diffusive vapor-phase transport and biodegradation of three VOC: non-deuterated and deuterated toluene as two compounds of highly differing biodegradability but (nearly) identical physical and chemical properties, and MTBE as (at the applied experimental conditions) non-biodegradable tracer and internal control. Our results showed for toluene an effective microbial degradation within centimeter VOC transport distances despite high gas-phase diffusivity. Degradation rates were controlled by the reactivity of the compounds while oxic conditions were found everywhere in the system. This confirms hypotheses that vadose zone biodegradation rates can be extremely high and are able to prevent the outgassing of VOC to the atmosphere within a centimeter range if compound properties and site conditions allow for sufficiently high degradation rates. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Influence of Soil Suction on the Shear Strength of Unsaturated Soil

DTIC Science & Technology

1990-09-01

the shear strength parameters c’ and 0’ for montmorillonitic and kaolinitic clays increased following the addition of divalent calcium hydroxide to...503-513. Sridharan, A., Rao, S.N., and Rao, G.V. (1971), "Shear Strength Char- acteristics of Saturated Montmorillonite and Kaolinite Clays," Soils...Summary of Shear Strengths of Unsaturated Specimens of Compacted Kaolinite and Compacted Red Earth (After Murthy, Sridharan and Nagaraj, 1987

Pathological hypertrophy and cardiac dysfunction are linked to aberrant endogenous unsaturated fatty acid metabolism

PubMed Central

Salomé Campos, Dijon Henrique; Grippa Sant’Ana, Paula; Okoshi, Katashi; Padovani, Carlos Roberto; Masahiro Murata, Gilson; Nguyen, Son; Kolwicz, Stephen C.; Cicogna, Antonio Carlos

2018-01-01

Pathological cardiac hypertrophy leads to derangements in lipid metabolism that may contribute to the development of cardiac dysfunction. Since previous studies, using high saturated fat diets, have yielded inconclusive results, we investigated whether provision of a high-unsaturated fatty acid (HUFA) diet was sufficient to restore impaired lipid metabolism and normalize diastolic dysfunction in the pathologically hypertrophied heart. Male, Wistar rats were subjected to supra-valvar aortic stenosis (SVAS) or sham surgery. After 6 weeks, diastolic dysfunction and pathological hypertrophy was confirmed and both sham and SVAS rats were treated with either normolipidic or HUFA diet. At 18 weeks post-surgery, the HUFA diet failed to normalize decreased E/A ratios or attenuate measures of cardiac hypertrophy in SVAS animals. Enzymatic activity assays and gene expression analysis showed that both normolipidic and HUFA-fed hypertrophied hearts had similar increases in glycolytic enzyme activity and down-regulation of fatty acid oxidation genes. Mass spectrometry analysis revealed depletion of unsaturated fatty acids, primarily linoleate and oleate, within the endogenous lipid pools of normolipidic SVAS hearts. The HUFA diet did not restore linoleate or oleate in the cardiac lipid pools, but did maintain body weight and adipose mass in SVAS animals. Overall, these results suggest that, in addition to decreased fatty acid oxidation, aberrant unsaturated fatty acid metabolism may be a maladaptive signature of the pathologically hypertrophied heart. The HUFA diet is insufficient to reverse metabolic remodeling, diastolic dysfunction, or pathologically hypertrophy, possibly do to preferentially partitioning of unsaturated fatty acids to adipose tissue. PMID:29494668

Biogenic Volatile Organic Compounds as Indicators of Change in a Deep Arid Unsaturated Zone, Amargosa Desert, USA

NASA Astrophysics Data System (ADS)

Green, C. T.; Baker, R. J.; Luo, W.; Andraski, B. J.; Haase, K.; Stonestrom, D. A.

2016-12-01

Biogenic volatile organic compounds (bVOCs) are important agents in atmospheric chemistry, climatic forcing, plant physiology, and ecologic signaling. Despite a marked increase in scientific attention to bVOCs since the 1990s, relatively little is known about bVOC dynamics in soils and virtually nothing is known about bVOCs in deep unsaturated zones. The goal of this study was to systematically explore subsurface bVOCs through characterization and analysis of deep unsaturated zone VOCs in an arid setting. A wide range of VOCs have been sampled from the unsaturated zone at the Amargosa Desert Research Site (ADRS) at least annually for over a decade in the vicinity of a hazardous waste repository in southwestern Nevada. Grid- and transect-based soil gas samples were collected at shallow (0.5-m and 1.5-m) depths, and vertical arrays of samples were collected from three unsaturated zone boreholes ( 10m intervals from 0 to 110 m below ground surface), one of which is in an undisturbed area 3000 m from the waste repository. The VOC data were analyzed to identify bVOCs and processes related to bVOC transport in the deep unsaturated zone. Locally generated bVOCs were identified on the basis of (1) frequency of detections at the remote borehole location, (2) patterns of distribution in shallow unsaturated zone samples around the waste repository, (3) comparisons with atmospheric concentrations, and (4) comparisons with travel blank samples. Several dozen compounds met the criteria to be characterized as bVOCs. The relatively abundant compound m,p-xylene was selected as a tracer for subsequent modeling analysis of vertical and horizontal transport processes in the unsaturated zone. Targeted processes comprised (1) changes in vertical bVOC profiles as a result of ecological shifts, and (2) predominantly horizontal transport of unsaturated-zone gases following installation of the low level nuclear waste repository at the ADRS. To the best of our knowledge the results document

Production of 8,11-dihydroxy and 8-hydroxy unsaturated fatty acids from unsaturated fatty acids by recombinant Escherichia coli expressing 8,11-linoleate diol synthase from Penicillium chrysogenum.

PubMed

Kim, Min-Ji; Seo, Min-Ju; Shin, Kyung-Chul; Oh, Deok-Kun

2017-03-01

Hydroxy unsaturated fatty acids can be used as antimicrobial surfactants. 8,11-Linoleate diol synthase (8,11-LDS) catalyzes the conversion of unsaturated fatty acid to 8-hydroperoxy unsaturated fatty acid, and it is subsequently isomerized to 8,11-dihydroxy unsaturated fatty acid by the enzyme. The optimal reaction conditions of recombinant Escherichia coli expressing Penicillium chrysogenum 8,11-LDS for the production of 8,11-dihydroxy-9,12(Z,Z)-octadecadienoic acid (8,11-DiHODE), 8,11-dihydroxy-9,12,15(Z,Z,Z)-octadecatrienoic acid (8,11-DiHOTrE), 8-hydroxy-9(Z)-hexadecenoic acid (8-HHME), and 8-hydroxy-9(Z)-octadecenoic acid (8-HOME) were pH 7.0, 25°C, 10 g/L linoleic acid, and 20 g/L cells; pH 6.0, 25°C, 6 g/L α-linolenic acid, and 60 g/L cells; pH 7.0, 25°C, 8 g/L palmitoleic acid, and 25 g/L cells; and pH 8.5, 30°C, 6 g/L oleic acid, and 25 g/L cells, respectively. Under these optimized conditions, the recombinant cells produced 6.0 g/L 8,11-DiHODE for 60 min, with a conversion of 60% (w/w) and a productivity of 6.0 g/L/h; 4.3 g/L 8,11-DiHOTrE for 60 min, with a conversion of 72% (w/w) and a productivity of 4.3 g/L/h; 4.3 g/L 8-HHME acid for 60 min, with a conversion of 54% (w/w) and a productivity of 4.3 g/L/h; and 0.9 g/L 8-HOME for 30 min, with a conversion of 15% (w/w) and a productivity of 1.8 g/L/h. To best of our knowledge, this is the first report on the biotechnological production of 8,11-DiHODE, 8,11-DiHOTrE, 8-HHME, and 8-HOME. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:390-396, 2017. © 2017 American Institute of Chemical Engineers.

Eco-friendly polyethylene glycol promoted Michael addition reactions of α,β-unsaturated carbonyl compounds

EPA Science Inventory

Abstract- Intra- and inter-nucleophilic addition reactions of different unsaturated compounds were found to be highly effective without any additives in PEG-400 as a recyclable reaction medium under neutral conditions.

Supplementation with bypass fat in silvopastoral systems diminishes the ratio of milk saturated/unsaturated fatty acids.

PubMed

Mahecha, L; Angulo, J; Salazar, B; Cerón, M; Gallo, J; Molina, C H; Molina, E J; Suárez, J F; Lopera, J J; Olivera, M

2008-04-01

This study was conducted to evaluate if supplementing bypass fat to cows under silvopastoral systems, increases the concentration of unsaturated fatty acids in milk, thus improving the saturated/ unsaturated ratio without a negative effect on total milk yield in fat or protein. Two concentrations of two different sources of bypass fat were evaluated for 40 days, each in a group of 24 multiparous Lucerna (Colombian breed) cows. A cross-over design of 8 Latin squares 3 x 3 was used. The variables submitted to analysis were body condition, daily milk production and milk composition. Body condition, milk yield and milk quality were not different but there was a significant decrease in the amount of saturated fatty acid in both experiments while the unsaturated fat increased significantly in experiment 1 and remained stable in experiment 2. Results, such as these have as far as we know, not been reported previously and they provide an approach for the improvement of milk as a "functional food".

Surface quality of unsaturated polyester resin processed via continuous multi-shot rotational molding

NASA Astrophysics Data System (ADS)

Ogila, K. O.; Yang, W.; Shao, M.; Tan, J.

2017-05-01

Unsaturated Polyester Resin is a versatile and cost efficient thermosetting plastic whose application in rotational molding is currently limited by its relatively high initial viscosity and heat of reaction. These material characteristics result in uneven material distribution, poor surface finish and imperfections in the moldings especially when large wall thicknesses are required. The current work attempts to remedy these shortcomings through the development of a continuous multi-shot system which adds predetermined loads of unsaturated polyester resin into a rotating mold at various intervals. As part of this system, a laboratory-scale uniaxial rotational molding machine was used to produce Unsaturated Polyester Resin moldings in single and double shots. Optimal processing conditions were determined through visual studies, three dimensional microscopic studies, thickness distribution analysis and Fourier Transform Infrared spectroscopy. Volume filling fractions of 0.049-0.065, second shot volumes of 0.5-0.75 from the first shot, rotational speeds of 15-20 rpm and temperatures of 30-50 °C resulted in moldings of suitable quality on both the inner and outer surfaces.

Hydraulic Properties of Unsaturated Soils

USDA-ARS?s Scientific Manuscript database

Many agrophysical applications require knowledge of the hydraulic properties of unsaturated soils. These properties reflect the ability of a soil to retain or transmit water and its dissolved constituents. The objective of this work was to develop an entry for the Encyclopedia of Agrophysics that w...

Evolution of the conceptual model of unsaturated zone hydrology at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Flint, Alan L.; Flint, Lorraine E.; Bodvarsson, Gudmundur S.; Kwicklis, Edward M.; Fabryka-Martin, June

2001-06-01

Yucca Mountain is an arid site proposed for consideration as the United States' first underground high-level radioactive waste repository. Low rainfall (approximately 170 mm/yr) and a thick unsaturated zone (500-1000 m) are important physical attributes of the site because the quantity of water likely to reach the waste and the paths and rates of movement of the water to the saturated zone under future climates would be major factors in controlling the concentrations and times of arrival of radionuclides at the surrounding accessible environment. The framework for understanding the hydrologic processes that occur at this site and that control how quickly water will penetrate through the unsaturated zone to the water table has evolved during the past 15 yr. Early conceptual models assumed that very small volumes of water infiltrated into the bedrock (0.5-4.5 mm/yr, or 2-3 percent of rainfall), that much of the infiltrated water flowed laterally within the upper nonwelded units because of capillary barrier effects, and that the remaining water flowed down faults with a small amount flowing through the matrix of the lower welded, fractured rocks. It was believed that the matrix had to be saturated for fractures to flow. However, accumulating evidence indicated that infiltration rates were higher than initially estimated, such as infiltration modeling based on neutron borehole data, bomb-pulse isotopes deep in the mountain, perched water analyses and thermal analyses. Mechanisms supporting lateral diversion did not apply at these higher fluxes, and the flux calculated in the lower welded unit exceeded the conductivity of the matrix, implying vertical flow of water in the high permeability fractures of the potential repository host rock, and disequilibrium between matrix and fracture water potentials. The development of numerical modeling methods and parameter values evolved concurrently with the conceptual model in order to account for the observed field data

Evolution of the conceptual model of unsaturated zone hydrology at Yucca Mountain, Nevada

USGS Publications Warehouse

Flint, Alan L.; Flint, Lorraine E.; Bodvarsson, Gudmundur S.; Kwicklis, Edward M.; Fabryka-Martin, June

2001-01-01

Yucca Mountain is an arid site proposed for consideration as the United States’ first underground high-level radioactive waste repository. Low rainfall (approximately 170 mm/yr) and a thick unsaturated zone (500–1000 m) are important physical attributes of the site because the quantity of water likely to reach the waste and the paths and rates of movement of the water to the saturated zone under future climates would be major factors in controlling the concentrations and times of arrival of radionuclides at the surrounding accessible environment. The framework for understanding the hydrologic processes that occur at this site and that control how quickly water will penetrate through the unsaturated zone to the water table has evolved during the past 15 yr. Early conceptual models assumed that very small volumes of water infiltrated into the bedrock (0.5–4.5 mm/yr, or 2–3 percent of rainfall), that much of the infiltrated water flowed laterally within the upper nonwelded units because of capillary barrier effects, and that the remaining water flowed down faults with a small amount flowing through the matrix of the lower welded, fractured rocks. It was believed that the matrix had to be saturated for fractures to flow. However, accumulating evidence indicated that infiltration rates were higher than initially estimated, such as infiltration modeling based on neutron borehole data, bomb-pulse isotopes deep in the mountain, perched water analyses and thermal analyses. Mechanisms supporting lateral diversion did not apply at these higher fluxes, and the flux calculated in the lower welded unit exceeded the conductivity of the matrix, implying vertical flow of water in the high permeability fractures of the potential repository host rock, and disequilibrium between matrix and fracture water potentials. The development of numerical modeling methods and parameter values evolved concurrently with the conceptual model in order to account for the observed field data

Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

PubMed Central

Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

1993-01-01

The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

EPA Science Inventory

This report describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soil...

A Preliminary Design of a Calibration Chamber for Evaluating the Stability of Unsaturated Soil Slope

NASA Astrophysics Data System (ADS)

Hsu, H.-H.

2012-04-01

The unsaturated soil slopes, which have ground water tables and are easily failure caused by heavy rainfalls, are widely distributed in the arid and semi-arid areas. For analyzing the stability of slope, in situ tests are the direct methods to obtain the test site characteristics. The cone penetration test (CPT) is a popular in situ test method. Some of the CPT empirical equations established from calibration chamber tests. The CPT performed in calibration chamber was commonly used clean quartz sand as testing material in the past. The silty sand is observed in many actual slopes. Because silty sand is relatively compressible than quartz sand, it is not suitable to apply the correlations between soil properties and CPT results built from quartz sand to silty sand. The experience on CPT calibration in silty sand has been limited. CPT calibration tests were mostly performed in dry or saturated soils. The condition around cone tip during penetration is assumed to be fully drained or fully undrained, yet it was observed to be partially drained for unsaturated soils. Because of the suction matrix has a great effect on the characteristics of unsaturated soils, they are much sensitive to the water content than saturated soils. The design of an unsaturated calibration chamber is in progress. The air pressure is supplied from the top plate and the pore water pressure is provided through the high air entry value ceramic disks located at the bottom plate of chamber cell. To boost and uniform distribute the unsaturated effect, four perforated burettes are installed onto the ceramic disks and stretch upwards to the midheight of specimen. This paper describes design concepts, illustrates this unsaturated calibration chamber, and presents the preliminary test results.

Estimating the Spatial Extent of Unsaturated Zones in Heterogeneous River-Aquifer Systems

NASA Astrophysics Data System (ADS)

Schilling, Oliver S.; Irvine, Dylan J.; Hendricks Franssen, Harrie-Jan; Brunner, Philip

2017-12-01

The presence of unsaturated zones at the river-aquifer interface has large implications on numerous hydraulic and chemical processes. However, the hydrological and geological controls that influence the development of unsaturated zones have so far only been analyzed with simplified conceptualizations of flow processes, or homogeneous conceptualizations of the hydraulic conductivity in either the aquifer or the riverbed. We systematically investigated the influence of heterogeneous structures in both the riverbed and the aquifer on the development of unsaturated zones. A stochastic 1-D criterion that takes both riverbed and aquifer heterogeneity into account was developed using a Monte Carlo sampling technique. The approach allows the reliable estimation of the upper bound of the spatial extent of unsaturated areas underneath a riverbed. Through systematic numerical modeling experiments, we furthermore show that horizontal capillary forces can reduce the spatial extent of unsaturated zones under clogged areas. This analysis shows how the spatial structure of clogging layers and aquifers influence the propensity for unsaturated zones to develop: In riverbeds where clogged areas are made up of many small, spatially disconnected patches with a diameter in the order of 1 m, unsaturated areas are less likely to develop compared to riverbeds where large clogged areas exist adjacent to unclogged areas. A combination of the stochastic 1-D criterion with an analysis of the spatial structure of the clogging layers and the potential for resaturation can help develop an appropriate conceptual model and inform the choice of a suitable numerical simulator for river-aquifer systems.

Importance of unsaturated zone flow for simulating recharge in a humid climate

USGS Publications Warehouse

Hunt, R.J.; Prudic, David E.; Walker, J.F.; Anderson, M.P.

2008-01-01

Transient recharge to the water table is often not well understood or quantified. Two approaches for simulating transient recharge in a ground water flow model were investigated using the Trout Lake watershed in north-central Wisconsin: (1) a traditional approach of adding recharge directly to the water table and (2) routing the same volume of water through an unsaturated zone column to the water table. Areas with thin (less than 1 m) unsaturated zones showed little difference in timing of recharge between the two approaches; when water was routed through the unsaturated zone, however, less recharge was delivered to the water table and more discharge occurred to the surface because recharge direction and magnitude changed when the water table rose to the land surface. Areas with a thick (15 to 26 m) unsaturated zone were characterized by multimonth lags between infiltration and recharge, and, in some cases, wetting fronts from precipitation events during the fall overtook and mixed with infiltration from the previous spring snowmelt. Thus, in thicker unsaturated zones, the volume of water infiltrated was properly simulated using the traditional approach, but the timing was different from simulations that included unsaturated zone flow. Routing of rejected recharge and ground water discharge at land surface to surface water features also provided a better simulation of the observed flow regime in a stream at the basin outlet. These results demonstrate that consideration of flow through the unsaturated zone may be important when simulating transient ground water flow in humid climates with shallow water tables.

The Role of Highly Unsaturated Fatty Acids in Aquatic Food Webs

NASA Astrophysics Data System (ADS)

Perhar, G.; Arhonditsis, G. B.

2009-05-01

Highly unsaturated fatty acids (HUFAs) are important molecules transferred across the plant-animal interface in aquatic food webs. Defined here as carbon chains of length 18 (carbons) or more, with a double bond in the third (Omega 3) or sixth (Omega 6) bond from the methyl end, HUFAs are formed in primary producers (phytoplankton). With limited abilities to synthesize de novo, consumers and higher trophic organisms are required to obtain their HUFAs primarily from diet. Bioconversion of HUFAs from one form to another is in theory possible, as is synthesis via elongation and the transformation of a saturated to highly saturated fatty acid, but the enzymes required for these processes are absent in most species. HUFAs are hypothesized to be somatic growth limiting compounds for herbivorous zooplankton and have been shown to be critical for juvenile fish growth and wellbeing. Zooplankton tend to vary their fatty acid concentrations, collection strategies and utilization methods based on taxonomy, and various mechanisms have been suggested to account for these differences i.e., seasonal and nervous system hypotheses. Considering also the facts that copepods overwinter in an active state while daphnids overwinter as resting eggs, and that copepods tend to accumulate Docosahexaenoic acid (DHA) through collection and bioconversion, while daphnids focus on Eicosapentaenoic acid (EPA), one can link high DHA concentrations to active overwintering; but both EPA and DHA have similar melting points, putting DHA's cold weather adaptation abilities into question. Another characteristic setting copepods apart from daphnids is nervous system complexity: copepod axons are coated in thick myelin sheaths, permitting rapid neural processing, such as rapid prey attack and intelligent predator avoidance; DHA may be required for the proper functioning of copepod neurons. Recent modeling results have suggested food webs with high quality primary producers (species high in HUFAs, i

Fabrication and characterization of Si3N4 ceramics without additives by high pressure hot pressing

NASA Technical Reports Server (NTRS)

Shimada, M.; Tanaka, A.; Yamada, T.; Koizumi, M.

1984-01-01

High pressure hot-pressing of Si3N4 without additives was performed using various kinds of Si3N4 powder as starting materials, and the relation between densification and alpha-beta phase transformation was studied. The temperature dependences of Vickers microhardness and fracture toughness were also examined. Densification of Si3N4 was divided into three stages, and it was found that densification and phase transformation of Si3N4 under pressure were closely associated. The results of the temperature dependence of Vickers microhardness indicated that the high-temperature hardness was strongly influenced not only by the density and microstructure of sintered body but also by the purity of starting powder. The fracture toughness values of Si3N4 bodies without additives were 3.29-4.39 MN/m to the 3/2 power and independent of temperature up to 1400 C.

Potential Approach of Microbial Conversion to Develop New Antifungal Products of Omega-3 Fatty Acids

USDA-ARS?s Scientific Manuscript database

Omega-3/('-3) or n-3 fatty acids are a family of unsaturated fatty acids that have in common a final carbon-carbon double bond in the n-3 position. n-3 Fatty acids which are important in human nutrition are: a-linolenic acid (18:3, n-3; ALA), eicosapentaenoic acid (20:5, n-3; EPA), and docosahexaen...

Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators

PubMed Central

2015-01-01

α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism. PMID:24512241

Impact of Microorganisms on Unsatured Flow within Fractures

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

Daphne L. Stoner; Robert D. Stedtfeld; Tina L. Tyler

An experiment is described in which a groundwater bacterium, Sphingomonas sp., influenced the dynamics of unsaturated flow at a fracture intersection. A washed cell suspension increased by three-fold the length of time that water pooled at the fracture intersection. On the other hand, the addition of growth substrates resulted in cell growth and the conversion from intermittent to continuous flow behavior at the fracture intersection. The results suggest that microbial properties and processes need to be included with other important variables for understanding unsaturated flow in fractured geomatrices.

Removing volatile contaminants from the unsaturated zone by inducing advective air-phase transport

USGS Publications Warehouse

Baehr, A.L.; Hoag, G.E.; Marley, M.C.

1989-01-01

Organic liquids inadvertently spilled and then distributed in the unsaturated zone can pose a long-term threat to ground water. Many of these substances have significant volatility, and thereby establish a premise for contaminant removal from the unsaturated zone by inducing advective air-phase transport with wells screened in the unsaturated zone. In order to focus attention on the rates of mass transfer from liquid to vapour phases, sand columns were partially saturated with gasoline and vented under steady air-flow conditions. The ability of an equilibrium-based transport model to predict the hydrocarbon vapor flux from the columns implies an efficient rate of local phase transfer for reasonably high air-phase velocities. Thus the success of venting remediations will depend primarily on the ability to induce an air-flow field in a heterogeneous unsaturated zone that will intersect the distributed contaminant. To analyze this aspect of the technique, a mathematical model was developed to predict radially symmetric air flow induced by venting from a single well. This model allows for in-situ determinations of air-phase permeability, which is the fundamental design parameter, and for the analysis of the limitations of a single well design. A successful application of the technique at a site once contaminated by gasoline supports the optimism derived from the experimental and modeliing phases of this study, and illustrates the well construction and field methods used to document the volatile contaminant recovery. ?? 1989.

Lewis acid tuned facial stereodivergent HDA reactions using beta-substituted N-vinyloxazolidinones.

PubMed

Gohier, Frédéric; Bouhadjera, Keltoum; Faye, Djibril; Gaulon, Catherine; Maisonneuve, Vincent; Dujardin, Gilles; Dhal, Robert

2007-01-18

The [4 + 2] acido-catalyzed heterocycloaddition between new beta-substituted N-vinyl-1,3-oxazolidin-2-ones (with R' = Me, Ar, CH2 Ar) and beta,gamma-unsaturated alpha-ketoesters (R = Ar) afforded heteroadducts with high levels of endo and facial selectivities. A complete reversal of facial differentiation was achieved by varying the Lewis acid, leading to the stereoselective formation of either endo-alpha or endo-beta adducts. [reaction: see text].

Geohydrology, water quality, and nitrogen geochemistry in the saturated and unsaturated zones beneath various land uses, Riverside and San Bernardino counties, California, 1991-93

USGS Publications Warehouse

Rees, Terry F.; Bright, Daniel J.; Fay, Ronald G.; Christensen, Allen H.; Anders, Robert; Baharie, Brian S.; Land, Michael T.

1995-01-01

The U.S. Geological Survey, in cooperation with the Eastern Municipal Water District, the Metropolitan Water District of Southern California, and the Orange County Water District, has completed a detailed study of the Hemet groundwater basin. The quantity of ground water stored in the basin in August 1992 is estimated to be 327,000 acre-feet. Dissolved-solids concentration ranged from 380 to 700 mg/L (milligrams per liter), except in small areas where the concentration exceeded 1,000 mg/L. Nitrate concentrations exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level (MCL) of 10 mg/L nitrate (as nitrogen) in the southeastern part of the basin, in the Domenigoni Valley area, and beneath a dairy in the Diamond Valley area. Seven sites representing selected land uses-- residential, turf grass irrigated with reclaimed water, citrus grove, irrigated farm, poultry farm, and dairy (two sites)--were selected for detailed study of nitrogen geochemistry in the unsaturated zone. For all land uses, nitrate was the dominant nitrogen species in the unsaturated zone.Although nitrate was seasonally present in the shallow unsaturated zone beneath the residential site, it was absent at moderate depths, suggesting negligible migration of nitrate from the surface at this time. Microbial denitrification probably is occurring in the shallow unsaturated zone. High nitrate concentrations in the deep unsaturated zone (greater than 100 ft) suggest either significantly higher nitrate loading at some time in the past, or lateral movement of nitrate at depth. Nitrate also is seasonally present in the shallow unsaturated zone beneath the reclaimed-water site, and (in contrast with the residential site), nitrate is perennially present in the deeper unsaturated zone. Microbial denitrification in the unsaturated zone and in the capillary fringe above the water table decreases the concentrations of nitrate in pore water to below the MCL before reaching the water table

Transport and time lag of chlorofluorocarbon gases in the unsaturated zone, Rabis Creek, Denmark

USGS Publications Warehouse

Engesgaard, Peter; Højberg, Anker L.; Hinsby, Klaus; Jensen, Karsten H.; Laier, Troels; Larsen, Flemming; Busenberg, Eurybiades; Plummer, Niel

2004-01-01

Transport of chlorofluorocarbon (CFC) gases through the unsaturated zone to the water table is affected by gas diffusion, air–water exchange (solubility), sorption to the soil matrix, advective–dispersive transport in the water phase, and, in some cases, anaerobic degradation. In deep unsaturated zones, this may lead to a time lag between entry of gases at the land surface and recharge to groundwater. Data from a Danish field site were used to investigate how time lag is affected by variations in water content and to explore the use of simple analytical solutions to calculate time lag. Numerical simulations demonstrate that either degradation or sorption of CFC-11 takes place, whereas CFC-12 and CFC-113 are nonreactive. Water flow did not appreciably affect transport. An analytical solution for the period with a linear increase in atmospheric CFC concentrations (approximately early 1970s to early 1990s) was used to calculate CFC profiles and time lags. We compared the analytical results with numerical simulations. The time lags in the 15-m-deep unsaturated zone increase from 4.2 to between 5.2 and 6.1 yr and from 3.4 to 3.9 yr for CFC-11 and CFC-12, respectively, when simulations change from use of an exponential to a linear increase in atmospheric concentrations. The CFC concentrations at the water table before the early 1990s can be estimated by displacing the atmospheric input function by these fixed time lags. A sensitivity study demonstrates conditions under which a time lag in the unsaturated zone becomes important. The most critical parameter is the tortuosity coefficient. The analytical approach is valid for the low range of tortuosity coefficients (τ = 0.1–0.4) and unsaturated zones greater than approximately 20 m in thickness. In these cases the CFC distribution may still be from either the exponential or linear phase. In other cases, the use of numerical models, as described in our work and elsewhere, is an option.

Saturated and unsaturated salt transport in peat from a constructed fen

NASA Astrophysics Data System (ADS)

Simhayov, Reuven B.; Weber, Tobias K. D.; Price, Jonathan S.

2018-02-01

The underlying processes governing solute transport in peat from an experimentally constructed fen peatland were analyzed by performing saturated and unsaturated solute breakthrough experiments using Na+ and Cl- as reactive and non-reactive solutes, respectively. We tested the performance of three solute transport models, including the classical equilibrium convection-dispersion equation (CDE), a chemical non-equilibrium one-site adsorption model (OSA) and a model to account for physical non-equilibrium, the mobile-immobile (MIM) phases. The selection was motivated by the fact that the applicability of the MIM in peat soils finds a wide consensus. However, results from inverse modeling and a robust statistical evaluation of this peat provide evidence that the measured breakthrough of the conservative tracer, Cl-, could be simulated well using the CDE. Furthermore, the very high Damköhler number (which approaches infinity) suggests instantaneous equilibration between the mobile and immobile phases underscoring the redundancy of the MIM approach for this particular peat. Scanning electron microscope images of the peat show the typical multi-pore size distribution structures have been homogenized sufficiently by decomposition, such that physical non-equilibrium solute transport no longer governs the transport process. This result is corroborated by the fact the soil hydraulic properties were adequately described using a unimodal van Genuchten-Mualem model between saturation and a pressure head of ˜ -1000 cm of water. Hence, MIM was not the most suitable choice, and the long tailing of the Na+ breakthrough curve was caused by chemical non-equilibrium. Successful description was possible using the OSA model. To test our results for the unsaturated case, we conducted an unsaturated steady-state evaporation experiment to drive Na+ and Cl- transport. Using the parameterized transport models from the saturated experiments, we could numerically simulate the unsaturated

The effects of poly-unsaturated fatty acids on the physiology of hibernation in a South American marsupial, Dromiciops gliroides.

PubMed

Contreras, Carolina; Franco, Marcela; Place, Ned J; Nespolo, Roberto F

2014-11-01

Many mammals hibernate, which is a profound lethargic state of several weeks or months during winter, that represents a transitory episode of hetherothermy. As with other cases of dormancy, the main benefit of hibernation seems to be energy saving. However, the depth and duration of torpor can be experimentally modified by the composition of food, especially by fattyacid composition. In eutherians, diets rich in unsaturated fatty acids (i.e., fatty acids with at least one double bond) lengthen torpor, reduce metabolism and permit hibernation at lower temperatures. Here we studied whether diets varying in fatty acid composition have an effect on the physiology of hibernation in a South American marsupial, Dromiciops gliroides. We designed a factorial experiment where thermal acclimation (two levels: natural versus constant temperature) was combined with diet acclimation: saturated (i.e., diets with high concentration of saturated fatty acids) versus unsaturated (i.e., diets with high concentration of unsaturated fatty acids). We measured energy metabolism in active and torpid individuals, as well as torpor duration, and a suite of 12 blood biochemical parameters. After a cafeteria test, we found that D. gliroides did not show any preference for a given diet. Also, we did not find effects of diet on body temperature during torpor, or its duration. However, saturated diets, combined with high temperatures provoked a disproportionate increase in fat utilization, leading to body mass reduction. Those animals were more active, and metabolized more fats than those fed with a high proportion of unsaturated fatty acids (="unsaturated diets"). These results contrast with previous studies, which showed a significant effect of fatty acid composition of diets on food preferences and torpor patterns in mammals. Copyright © 2014 Elsevier Inc. All rights reserved.

Pd-Catalyzed Carbonylative Conjugate Addition of Dialkylzinc Reagents to Unsaturated Carbonyls

PubMed Central

Custar, Daniel W.; Le, Hai; Morken, James P.

2010-01-01

The Pd-catalyzed addition of organozinc reagents to unsaturated carbonyls in the presence of carbon monoxide provides 1,4-diketones in good yield. The reaction was studied with a number of substituted cyclic and acyclic ketones as well as α,β-unsaturated aldehydes. PMID:20687574

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

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

Yue, Cheng-Yang; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Lei, Xiao-Wu, E-mail: xwlei_jnu@163.com

2016-03-15

The incorporation of unsaturated [Mn(1,2-dap)]{sup 2+}, [Mn(1,2-dap){sub 2}]{sup 2+}, [Mn(2,2-bipy)]{sup 2+} (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [As{sup III}S{sub 3}]{sup 3−} and [As{sup V}S{sub 4}]{sup 3−} led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} (1), [Mn(1,2-dap){sub 2}]{[Mn(1,2-dap)]_2As_2S_8} (2) and (NH{sub 4})[Mn(2,2-bipy){sub 2}]AsS{sub 4} (3). In compound 1, the unsaturated [Mn(1,2-dap)]{sup 2+} complexes, [MnS{sub 4}]{sup 6−} tetrahedra and [As{sup III}S{sub 3}]{sup 3−} trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]{sup 2+} and [Mn(1,2-dap){sub 2}]{sup 2+} complexes as well as [As{sup V}S{sub 4}]{sup 3−}more » tetrahedral units. For compound 3, two [As{sup V}S{sub 4}]{sup 3−} anions bridge two [Mn(2,2-bipy)]{sup 2+} complex cations into a butterfly like {[Mn(2,2-bipy)]_2As_2S_8}{sup 2−} anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2–3. The UV–vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation. - Highlights: Three new hybrid manganese thioarsenates have been prepared and structurally characterized. These hybrid phases feature interesting magnetic and visible light responding photocatalytic properties.« less

The acyl desaturase CER17 is involved in producing wax unsaturated primary alcohols and cutin monomers

USDA-ARS?s Scientific Manuscript database

We report here n-6 mono-unsaturated primary alcohols (the C26:1, C28:1, and C30:1 homologues) in the cuticular waxes of Arabidopsis inflorescence stem, a class of wax compound not previously reported in Arabidopsis. Further, we used mutation and transgenic complementation analyses to demonstrate tha...

High-Resolution Time-Lapse Monitoring of Unsaturated Flow using Automated GPR Data Collection

NASA Astrophysics Data System (ADS)

Mangel, A. R.; Moysey, S. M.; Lytle, B. A.; Bradford, J. H.

2015-12-01

High-resolution ground-penetrating radar (GPR) data provide the detailed information required to image subsurface structures. Recent advances in GPR monitoring now also make it possible to study transient hydrologic processes, but high-speed data acquisition is critical for this application. We therefore highlight the capabilities of our automated system to acquire time-lapse, high-resolution multifold GPR data during infiltration of water into soils. The system design allows for fast acquisition of constant-offset (COP) and common-midpoint profiles (CMP) to monitor unsaturated flow at multiple locations. Qualitative interpretation of the unprocessed COPs can provide substantial information regarding the hydrologic response of the system, such as the complexities of patterns associated with the wetting of the soil and geophysical evidence of non-uniform propagation of a wetting front. While we find that unprocessed images are informative, we show that the spatial variability of velocity introduced by infiltration events can complicate the images and that migration of the data is an effective tool to improve interpretability of the time-lapse images. The ability of the system to collect high density CMP data also introduces the potential for improving the velocity model along with the image via reflection tomography in the post-migrated domain. We show that for both simulated and empirical time-lapse GPR profiles we can resolve a propagating wetting front in the soil that is in good agreement with the response of in-situ soil moisture measurements. The data from these experiments illustrate the importance of high-speed, high-resolution GPR data acquisition for obtaining insight about the dynamics of hydrologic events. Continuing research is aimed at improving the quantitative analysis of surface-based GPR monitoring data for identifying preferential flow in soils.

Hydrogen-induced reversible changes in drain current in Sc2O3/AlGaN/GaN high electron mobility transistors

NASA Astrophysics Data System (ADS)

Kang, B. S.; Mehandru, R.; Kim, S.; Ren, F.; Fitch, R. C.; Gillespie, J. K.; Moser, N.; Jessen, G.; Jenkins, T.; Dettmer, R.; Via, D.; Crespo, A.; Gila, B. P.; Abernathy, C. R.; Pearton, S. J.

2004-06-01

Pt contacted AlGaN/GaN high electron mobility transistors with Sc2O3 gate dielectrics show reversible changes in drain-source current upon exposure to H2-containing ambients, even at room temperature. The changes in current (as high as 3 mA for relatively low gate voltage and drain-source voltage) are approximately an order of magnitude larger than for Pt/GaN Schottky diodes and a factor of 5 larger than Sc2O3/AlGaN/GaN metal-oxide-semiconductor (MOS) diodes exposed under the same conditions. This shows the advantage of using a transistor structure in which the gain produces larger current changes upon exposure to hydrogen-containing ambients. The increase in current is the result of a decrease in effective barrier height of the MOS gate of 30-50 mV at 25 °C for 10% H2/90% N2 ambients relative to pure N2 and is due to catalytic dissociation of the H2 on the Pt contact, followed by diffusion to the Sc2O3/AlGaN interface.

Bacterial uptake of antibiotics in model unsaturated systems

NASA Astrophysics Data System (ADS)

Zhang, W.; Chen, Z.; Zhang, Y.; Zhao, Z.; Wang, G.; Gao, Y.; Boyd, S. A.; Zhu, D.; Li, H.

2016-12-01

Anthropogenic antibiotics are ubiquitously present in the environment due to large uses in human medicine and animal agriculture, and are causing unintended consequence to human and ecosystem health. Bacterial uptake of antibiotics could exert selection pressure on antibiotic resistance development among bacteria population. Therefore, understanding environmental factors controlling bioavailability of antibiotics to bacteria is critical to better assessing exposure risks and developing mitigation strategies. Nonetheless, conventional bioavailability assays are often performed in water-saturated systems that do not represent unsaturated soils where most bacteria live, therefore neglecting soil water as a controlling factor in determining the extent of antibiotic bacterial uptake. Therefore, we propose to study bacterial uptake of antibiotics in model unsaturated systems using GFP-tagged Escherichia coli bioreporter for tetracyclines. Our preliminary studies demonstrated the important role of water content (or water matric potential) in determining the bioavailability of antibiotics, and complex interactions of water potential, tetracycline diffusion, and E. coli growth. Therefore, unsaturated processes are important for understanding antibiotic resistance development and developing mitigation strategies.

Unsaturated free fatty acids increase benzodiazepine receptor agonist binding depending on the subunit composition of the GABAA receptor complex.

PubMed

Witt, M R; Westh-Hansen, S E; Rasmussen, P B; Hastrup, S; Nielsen, M

1996-11-01

It has been shown previously that unsaturated free fatty acids (FFAs) strongly enhance the binding of agonist benzodiazepine receptor ligands and GABAA receptor ligands in the CNS in vitro. To investigate the selectivity of this effect, recombinant human GABAA/benzodiazepine receptor complexes formed by different subunit compositions (alpha x beta y gamma 2, x = 1, 2, 3, and 5; y = 1, 2, and 3) were expressed using the baculovirus-transfected Sf9 insect cell system. At 10(-4) M, unsaturated FFAs, particularly arachidonic (20:4) and docosahexaenoic (22:6) acids, strongly stimulated (> 200% of control values) the binding of [3H]flunitrazepam ([3H]FNM) to the alpha 3 beta 2 gamma 2 receptor combination in whole cell preparations. No effect or small increases in levels of unsaturated FFAs on [3H]FNM binding to alpha 1 beta x gamma 2 and alpha 2 beta x gamma 2 receptor combinations were observed, and weak effects (130% of control values) were detected using the alpha 5 beta 2 gamma 2 receptor combination. The saturated FFAs, stearic and palmitic acids, were without effect on [3H]FNM binding to any combination of receptor complexes. The hydroxylated unsaturated FFAs, ricinoleic and ricinelaidic acids, were shown to decrease the binding of [3H]FNM only if an alpha 1 beta 2 gamma 2 receptor combination was used. Given the heterogeneity of the GABAA/ benzodiazepine receptor subunit distribution in the CNS, the effects of FFAs on the benzodiazepine receptor can be assumed to vary at both cellular and regional levels.

High temperature compounds for turbine vanes. [of SiC, Si3N4, and Si composites

NASA Technical Reports Server (NTRS)

Rhodes, W. H.; Cannon, R. M., Jr.

1974-01-01

Fabrication and microstructure control studies were conducted on SiC, Si3N and composites based on Si3N. Charpy mode impact testing to 2400 F established that Si3N4/Mo composites have excellent potential. Attempts to fabricate composites of Si3N4 with superalloys, both by hot pressing and infiltration were largely unsuccessful in comparison to using Mo, Re, and Ta which are less reactive. Modest improvements in impact strength were realized for monolithic Si3N4; however, SiC strengths increased by a factor of six and now equal values achieved for Si3N4. Correlations of impact strength with material properties are discussed. Reduced MgO densification aid additions to Si3N4 were found to decrease densification kinetics, increase final porosity, decrease room temperature bend strength, increase high temperature bend strength, and decrease bend stress rupture properties. The decrease in bend strength at high temperature for fine grain size SiC suggested that a slightly larger grain size material with a nearly constant strength-temperature relation may prove desirable in the creep and stress rupture mode.

Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters.

PubMed

Gammack Yamagata, Adam D; Datta, Swarup; Jackson, Kelvin E; Stegbauer, Linus; Paton, Robert S; Dixon, Darren J

2015-04-13

A new catalytic asymmetric desymmetrization reaction for the synthesis of enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, has been developed. Employing a cyclohexanediamine-derived primary amine organocatalyst, a range of prochiral cyclohexanone derivatives possessing an α,β-unsaturated ester moiety linked to the 4-position afforded the bicyclic products, which possess three stereogenic centers, as single diastereoisomers in high enantioselectivity (83-99% ee) and in good yields (60-90%). Calculations revealed that stepwise C-C bond formation and proton transfer via a chair-shaped transition state dictate the exclusive endo selectivity and enabled the development of a highly enantioselective primary amine catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unsaturated soil moisture drying and wetting diffusion coefficient measurements in the laboratory.

DOT National Transportation Integrated Search

2009-09-01

ABSTRACTTransient moisture flow in an unsaturated soil in response to suction changes is controlled by the unsaturated moisture diffusion coefficient. The moisture diffusion coefficient can be determined by measuring suction profiles over time. The l...

Saturated-unsaturated flow in a compressible leaky-unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, Phoolendra K.; Vesselinov, Velimir V.; Kuhlman, Kristopher L.

2012-06-01

An analytical solution is developed for three-dimensional flow towards a partially penetrating large-diameter well in an unconfined aquifer bounded below by a leaky aquitard of finite or semi-infinite extent. The analytical solution is derived using Laplace and Hankel transforms, then inverted numerically. Existing solutions for flow in leaky unconfined aquifers neglect the unsaturated zone following an assumption of instantaneous drainage due to Neuman. We extend the theory of leakage in unconfined aquifers by (1) including water flow and storage in the unsaturated zone above the water table, and (2) allowing the finite-diameter pumping well to partially penetrate the aquifer. The investigation of model-predicted results shows that aquitard leakage leads to significant departure from the unconfined solution without leakage. The investigation of dimensionless time-drawdown relationships shows that the aquitard drawdown also depends on unsaturated zone properties and the pumping-well wellbore storage effects.

Photorechargeable High Voltage Redox Battery Enabled by Ta3 N5 and GaN/Si Dual-Photoelectrode.

PubMed

Cheng, Qingmei; Fan, Weiqiang; He, Yumin; Ma, Peiyan; Vanka, Srinivas; Fan, Shizhao; Mi, Zetian; Wang, Dunwei

2017-07-01

Solar rechargeable battery combines the advantages of photoelectrochemical devices and batteries and has emerged as an attractive alternative to artificial photosynthesis for large-scale solar energy harvesting and storage. Due to the low photovoltages by the photoelectrodes, however, most previous demonstrations of unassisted photocharge have been realized on systems with low open circuit potentials (<0.8 V). In response to this critical challenge, here it is shown that the combined photovoltages exceeding 1.4 V can be obtained using a Ta 3 N 5 nanotube photoanode and a GaN nanowire/Si photocathode with high photocurrents (>5 mA cm -2 ). The photoelectrode system makes it possible to operate a 1.2 V alkaline anthraquinone/ferrocyanide redox battery with a high ideal solar-to-chemical conversion efficiency of 3.0% without externally applied potentials. Importantly, the photocharged battery is successfully discharged with a high voltage output. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry and Biology of DNA Containing 1,N2-Deoxyguanosine Adducts of the α,β-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and 4-Hydroxynonenal

PubMed Central

2009-01-01

The α,β-unsaturated aldehydes (enals) acrolein, crotonaldehyde, and trans-4-hydroxynonenal (4-HNE) are products of endogenous lipid peroxidation, arising as a consequence of oxidative stress. The addition of enals to dG involves Michael addition of the N2-amine to give N2-(3-oxopropyl)-dG adducts, followed by reversible cyclization of N1 with the aldehyde, yielding 1,N2-dG exocyclic products. The 1,N2-dG exocyclic adducts from acrolein, crotonaldehyde, and 4-HNE exist in human and rodent DNA. The enal-induced 1,N2-dG lesions are repaired by the nucleotide excision repair pathway in both Escherichia coli and mammalian cells. Oligodeoxynucleotides containing structurally defined 1,N2-dG adducts of acrolein, crotonaldehyde, and 4-HNE were synthesized via a postsynthetic modification strategy. Site-specific mutagenesis of enal adducts has been carried out in E. coli and various mammalian cells. In all cases, the predominant mutations observed are G→T transversions, but these adducts are not strongly miscoding. When placed into duplex DNA opposite dC, the 1,N2-dG exocyclic lesions undergo ring opening to the corresponding N2-(3-oxopropyl)-dG derivatives. Significantly, this places a reactive aldehyde in the minor groove of DNA, and the adducted base possesses a modestly perturbed Watson−Crick face. Replication bypass studies in vitro indicate that DNA synthesis past the ring-opened lesions can be catalyzed by pol η, pol ι, and pol κ. It also can be accomplished by a combination of Rev1 and pol ζ acting sequentially. However, efficient nucleotide insertion opposite the 1,N2-dG ring-closed adducts can be carried out only by pol ι and Rev1, two DNA polymerases that do not rely on the Watson−Crick pairing to recognize the template base. The N2-(3-oxopropyl)-dG adducts can undergo further chemistry, forming interstrand DNA cross-links in the 5′-CpG-3′ sequence, intrastrand DNA cross-links, or DNA−protein conjugates. NMR and mass spectrometric analyses

An evaluation of the mobility of pathogen indicators, Escherichia coli and bacteriophage MS-2, in a highly weathered tropical soil under unsaturated conditions

USGS Publications Warehouse

Wong, T.-P.; Byappanahalli, M.; Yoneyama, B.; Ray, C.

2008-01-01

Laboratory column experiments were conducted to study the effects of anionic polyacrylamide (PAM) polymer and surfactant linear alkylbenzene sulfonate (LAS) on the movement of Escherichia coli and the FRNA phage MS-2. The study was designed to evaluate if PAM or PAM + LAS would enhance the mobility of human pathogens in tropical soils under unsaturated conditions. No breakthrough of phage was observed in a 10 cm column after passing 100 pore volumes of solution containing 1 ?? 108 plaque-forming units (PFU)/ml. In later experiments, after passing 10-20 pore volumes of influent containing 1 ?? 108/ml MS-2 or E. coli through 15 cm columns, the soil was sliced and the organisms eluted. Phage moved slightly deeper in the polymer-treated column than in the control column. There was no measurable difference in the movement of E. coli in either polymer-treated or control columns. The properties of the soil (high amounts of metal oxides, kaolinitic clay), unsaturated flow conditions, and relatively high ionic strengths of the leaching solution attributed to significant retention of these indicators. The impacts of PAM and LAS on the mobility of E. coli or MS-2 phage in the chosen soils were not significant. ?? IWA Publishing 2008.

Nuclear Hyperfine Structure in the Donor – Acceptor Complexes (CH3)3N-BF3 and (CH)33N-B(CH3)3

EPA Science Inventory

The donor-acceptor complexes (CH3)3N-BF3 and (CH3)3N-B(CH3)3 have been reinvestigated at high resolution by rotational spectroscopy in a supersonic jet. Nuclear hyperfine structure resulting from both nitrogen and boron has been resolved and quadrupole coupling constants have bee...

Gas transport in unsaturated porous media: the adequacy of Fick's law

USGS Publications Warehouse

Thorstenson, D.C.; Pollock, D.W.

1989-01-01

The increasing use of natural unsaturated zones as repositories for landfills and disposal sites for hazardous wastes (chemical and radioactive) requires a greater understanding of transport processes in the unsaturated zone. For volatile constituents an important potential transport mechanism is gaseous diffusion. Diffusion, however, cannot be treated as an independent isolated transport mechanism. A complete understanding of multicomponent gas transport in porous media (unsaturated zones) requires a knowledge of Knudsen transport, the molecular and nonequimolar components of diffusive flux, and viscous (pressure driven) flux. This review presents a brief discussion of the underlying principles and interrelationships among each of the above flux mechanisms. -from Authors

Suitability of parametric models to describe the hydraulic properties of an unsaturated coarse sand and gravel

USGS Publications Warehouse

Mace, Andy; Rudolph, David L.; Kachanoski , R. Gary

1998-01-01

The performance of parametric models used to describe soil water retention (SWR) properties and predict unsaturated hydraulic conductivity (K) as a function of volumetric water content (θ) is examined using SWR and K(θ) data for coarse sand and gravel sediments. Six 70 cm long, 10 cm diameter cores of glacial outwash were instrumented at eight depths with porous cup ten-siometers and time domain reflectometry probes to measure soil water pressure head (h) and θ, respectively, for seven unsaturated and one saturated steady-state flow conditions. Forty-two θ(h) and K(θ) relationships were measured from the infiltration tests on the cores. Of the four SWR models compared in the analysis, the van Genuchten (1980) equation with parameters m and n restricted according to the Mualem (m = 1 - 1/n) criterion is best suited to describe the θ(h) relationships. The accuracy of two models that predict K(θ) using parameter values derived from the SWR models was also evaluated. The model developed by van Genuchten (1980) based on the theoretical expression of Mualem (1976) predicted K(θ) more accurately than the van Genuchten (1980) model based on the theory of Burdine (1953). A sensitivity analysis shows that more accurate predictions of K(θ) are achieved using SWR model parameters derived with residual water content (θr) specified according to independent measurements of θ at values of h where θ/h ∼ 0 rather than model-fit θr values. The accuracy of the model K(θ) function improves markedly when at least one value of unsaturated K is used to scale the K(θ) function predicted using the saturated K. The results of this investigation indicate that the hydraulic properties of coarse-grained sediments can be accurately described using the parametric models. In addition, data collection efforts should focus on measuring at least one value of unsaturated hydraulic conductivity and as complete a set of SWR data as possible, particularly in the dry range.

Influences of rich in saturated and unsaturated fatty acids diets in rat myocardium.

PubMed

Pinotti, Matheus Fécchio; Silva, Maeli Dal-Pai; Sugizaki, Mário Mateus; Novelli, Yeda Santana Diniz; Sant'ana, Lea Sílvia; Aragon, Flávio Ferrari; Padovani, Carlos Roberto; Novelli, Ethel Lourenzi Barbosa; Cicogna, Antonio Carlos

2007-03-01

To study the influence of saturated (SFA) and unsaturated fatty acid (UFA) rich diets on mechanical function, morphology and oxidative stress in rat myocardium. Male, 60-day-old Wistar rats were fed a control (n=8), a SFA (n=8), or a UFA-rich diet (n=8) for sixty days. Mechanical function was studied in isolated left ventricle papillary muscle under isometric and isotonic contractions, in basal conditions (1.25 mM calcium chloride) and after 5.2 mM calcium chloride and beta-adrenergic stimuli with 1.0 microM isoproterenol. Left ventricle fragments were used to study oxidative stress and morphology under light and electron microscopy. SFA and UFA-rich diets did not change myocardium mechanical function. Both diets caused oxidative stress, with high lipid hydroperoxide and low superoxide-dismutase concentrations. UFA rich diet decreased catalase expression and SFA rich diet decreased the amount of myocardial glutathione-peroxidase. Both diets promoted light ultrastructural injuries such as lipid deposits and cell membrane injuries. Results suggest that SFA and UFA rich diets do not alter isolated muscle mechanical function, but promote light myocardial morphological injuries and oxidative stress.

Spin-glass behavior of Sn{sub 0.9}Fe{sub 3.1}N: An experimental and quantum-theoretical study

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

Scholz, Tanja; Dronskowski, Richard, E-mail: drons@HAL9000.ac.rwth-aachen.de

Based on comprehensive experimental and quantum-theoretical investigations, we identify Sn{sub 0.9}Fe{sub 3.1}N as a canonical spin glass and the first ternary iron nitride with a frustrated spin ground state. Sn{sub 0.9}Fe{sub 3.1}N is the end member of the solid solution Sn{sub x}Fe{sub 4−x}N (0 < x ≤ 0.9) derived from ferromagnetic γ′-Fe{sub 4}N. Within the solid solution, the gradual incorporation of tin is accompanied by a drastic weakening of the ferromagnetic interactions. To explore the dilution of the ferromagnetic coupling, the highly tin-substituted Sn{sub 0.9}Fe{sub 3.1}N has been magnetically reinvestigated. DC magnetometry reveals diverging susceptibilities for FC and ZFC measurementsmore » at low temperatures and an unsaturated hysteretic loop even at high magnetic fields. The temperature dependence of the real component of the AC susceptibility at different frequencies proves the spin-glass transition with the characteristic parameters T{sub g}  =  12.83(6) K, τ{sup *} = 10{sup −11.8(2)} s, zv = 5.6(1) and ΔT{sub m}/(T{sub m} ⋅ Δlgω) = 0.015. The time-dependent response of the magnetic spins to the external field has been studied by extracting the distribution function of relaxation times g(τ, T) up to T{sub g} from the complex plane of AC susceptibilities. The weakening of the ferromagnetic coupling by substituting tin into γ′-Fe{sub 4}N is explained by the Stoner criterion on the basis of electronic structure calculations and a quantum-theoretical bonding analysis.« less

Lewis base activation of Lewis acids. Vinylogous aldol addition reactions of conjugated N,O-silyl ketene acetals to aldehydes.

PubMed

Denmark, Scott E; Heemstra, John R

2006-02-01

N,O-Silyl dienyl ketene acetals derived from unsaturated morpholine amides have been developed as highly useful reagents for vinylogous aldol addition reactions. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-3, N,O-silyl dienyl ketene acetal 8 undergoes high-yielding and highly site-selective addition to a wide variety of aldehydes with excellent enantioselectivity. Of particular note is the high yields and selectivities obtained from aliphatic aldehydes. Low catalyst loadings (2-5 mol %) can be employed. The morpholine amide serves as a useful precursor for further synthetic manipulation.

Effect of adsorbants on in vitro biohydrogenation of 22:6n-3 by mixed cultures of rumen microorganisms.

PubMed

Escobar, M; Vlaeminck, B; Jeyanathan, J; Thanh, L P; Shingfield, K J; Wallace, R J; Fievez, V

2016-09-01

Studies on microbial biohydrogenation of fatty acids in the rumen are of importance as this process lowers the availability of nutritionally beneficial unsaturated fatty acids for incorporation into meat and milk but also might result in the accumulation of biologically active intermediates. The impact was studied of adsorption of 22:6n-3 (DHA) to particulate material on its disappearance during 24 h in vitro batch incubations with rumen inoculum. Four adsorbants were used in two doses (1 and 5 mg/ml of mucin, gum arabic, bentonite or silicic acid). In addition, the distribution of 22:6n-3 in the pellet and supernatant of diluted rumen fluid was measured. Bentonite and silicic acid did not alter the distribution of 22:6n-3 between pellet and supernatant nor increased the disappearance of 22:6n-3 during the incubation. Both mucin and gum arabic increased the recovery of 22:6n-3 in the supernatant, indicating that these compounds lowered the adsorption of the fatty acid to ruminal particles. This was associated with an increased disappearance of 22:6n-3, when initial 22:6n-3 was 0.06 or 0.10 mg/ml, and an increased formation of 22:0, when initial 22:6n-3 was 0.02 mg/ml, during the 24 h batch culture experiment. Addition of gum arabic to pure cultures of Butyrivibrio fibrisolvens or Butyrivibrio proteoclasticus did not negate the inhibitory effect of 22:6n-3 on growth. As both mucin and gum arabic provide fermentable substrate for ruminal bacteria, an additional experiment was performed in which mucin and gum arabic were replaced by equal amounts of starch, cellulose or xylan. No differences in disappearance of 22:6n-3 were observed, suggesting that the stimulatory effect of mucin and gum arabic on disappearance of 22:6n-3 most probably is not due to provision of an alternative site of adsorption but related to stimulation of bacterial growth. A relatively high proportion of 22:6n-3 can be reduced to 22:0 provided the initial concentration is low.

Biological hydrogen production by Clostridium acetobutylicum in an unsaturated flow reactor.

PubMed

Zhang, Husen; Bruns, Mary Ann; Logan, Bruce E

2006-02-01

A mesophilic unsaturated flow (trickle bed) reactor was designed and tested for H2 production via fermentation of glucose. The reactor consisted of a column packed with glass beads and inoculated with a pure culture (Clostridium acetobutylicum ATCC 824). A defined medium containing glucose was fed at a flow rate of 1.6 mL/min (0.096 L/h) into the capped reactor, producing a hydraulic retention time of 2.1 min. Gas-phase H2 concentrations were constant, averaging 74 +/- 3% for all conditions tested. H2 production rates increased from 89 to 220 mL/hL of reactor when influent glucose concentrations were varied from 1.0 to 10.5 g/L. Specific H2 production rate ranged from 680 to 1270 mL/g glucose per liter of reactor (total volume). The H2 yield was 15-27%, based on a theoretical limit by fermentation of 4 moles of H2 from 1 mole of glucose. The major fermentation by-products in the liquid effluent were acetate and butyrate. The reactor rapidly (within 60-72 h) became clogged with biomass, requiring manual cleaning of the system. In order to make long-term operation of the reactor feasible, biofilm accumulation in the reactor will need to be controlled through some process such as backwashing. These tests using an unsaturated flow reactor demonstrate the feasibility of the process to produce high H2 gas concentrations in a trickle-bed type of reactor. A likely application of this reactor technology could be H2 gas recovery from pre-treatment of high carbohydrate-containing wastewaters.

Et3B-mediated radical-polar crossover reaction for single-step coupling of O,Te-acetal, α,β-unsaturated ketones, and aldehydes/ketones.

PubMed

Kamimura, Daigo; Urabe, Daisuke; Nagatomo, Masanori; Inoue, Masayuki

2013-10-04

Et3B-mediated three-component coupling reactions between O,Te-acetal, α,β-unsaturated ketones, and aldehydes/ketones were developed. Et3B promoted the generation of the potently reactive bridgehead radical from the O,Te-acetal of the trioxaadamantane structure and converted the α-carbonyl radical of the resultant two-component adduct to the boron enolate, which then underwent a stereoselective aldol reaction with the aldehyde/ketone. This powerful, yet mild, radical-polar crossover reaction efficiently connected the hindered linkages between the three units and selectively introduced three new stereocenters.

Investigation of trap states in Al2O3 InAlN/GaN metal-oxide-semiconductor high-electron-mobility transistors

NASA Astrophysics Data System (ADS)

Zhang, Peng; Zhao, Sheng-Lei; Xue, Jun-Shuai; Zhu, Jie-Jie; Ma, Xiao-Hua; Zhang, Jin-Cheng; Hao, Yue

2015-12-01

In this paper the trapping effects in Al2O3/In0.17Al0.83N/GaN MOS-HEMT (here, HEMT stands for high electron mobility transistor) are investigated by frequency-dependent capacitance and conductance analysis. The trap states are found at both the Al2O3/InAlN and InAlN/GaN interface. Trap states in InAlN/GaN heterostructure are determined to have mixed de-trapping mechanisms, emission, and tunneling. Part of the electrons captured in the trap states are likely to tunnel into the two-dimensional electron gas (2DEG) channel under serious band bending and stronger electric field peak caused by high Al content in the InAlN barrier, which explains the opposite voltage dependence of time constant and relation between the time constant and energy of the trap states. Project supported by the Program for National Natural Science Foundation of China (Grant Nos. 61404100 and 61306017).

Stereoselective syntheses of four diastereomers of 3,9,12-trihydroxycalamenene via a benzobicyclo[3.3.1] intermediate.

PubMed

Sun, Yongquan; Yu, Binxun; Wang, Xiaolei; Tang, Shibing; She, Xuegong; Pan, Xinfu

2010-06-18

The highly stereoselective syntheses of four diastereomers of natural 3,9,12-trihydroxycalamenene are described. The syntheses highlight the utility of an unusual framework of benzobicyclo[3.3.1] lactones, which were accomplished via an intramolecular Friedel-Crafts-type Michael addition of alpha,beta-unsaturated lactones.

The Vertical Flux Method (VFM) for regional estimates of temporally and spatially varying nitrate fluxes in unsaturated zone and groundwater

NASA Astrophysics Data System (ADS)

Green, C. T.; Liao, L.; Nolan, B. T.; Juckem, P. F.; Ransom, K.; Harter, T.

2017-12-01

Process-based modeling of regional NO3- fluxes to groundwater is critical for understanding and managing water quality. Measurements of atmospheric tracers of groundwater age and dissolved-gas indicators of denitrification progress have potential to improve estimates of NO3- reactive transport processes. This presentation introduces a regionalized version of a vertical flux method (VFM) that uses simple mathematical estimates of advective-dispersive reactive transport with regularization procedures to calibrate estimated tracer concentrations to observed equivalents. The calibrated VFM provides estimates of chemical, hydrologic and reaction parameters (source concentration time series, recharge, effective porosity, dispersivity, reaction rate coefficients) and derived values (e.g. mean unsaturated zone travel time, eventual depth of the NO3- front) for individual wells. Statistical learning methods are used to extrapolate parameters and predictions from wells to continuous areas. The regional VFM was applied to 473 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3-, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and triogiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with independent estimates. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams (2) fractions of N leached to groundwater have changed over time, with increasing fractions from manure and decreasing fractions from fertilizer, and (3) under current practices and conditions, 60% of the shallow aquifer will eventually be affected by NO3- contamination. Based on GIS coverages of variables related to soils, land use and hydrology, the VFM results at individual wells were extrapolated regionally using boosted regression trees, a statistical learning approach, that related

An updated model of induced airflow in the unsaturated zone

USGS Publications Warehouse

Baehr, Arthur L.; Joss, Craig J.

1995-01-01

Simulation of induced movement of air in the unsaturated zone provides a method to determine permeability and to design vapor extraction remediation systems. A previously published solution to the airflow equation for the case in which the unsaturated zone is separated from the atmosphere by a layer of lower permeability (such as a clay layer) has been superseded. The new solution simulates airflow through the layer of lower permeability more rigorously by defining the leakage in terms of the upper boundary condition rather than by adding a leakage term to the governing airflow equation. This note presents the derivation of the new solution. Formulas for steady state pressure, specific discharge, and mass flow in the domain are obtained for the new model and for the case in which the unsaturated zone is in direct contact with the atmosphere.

Modeling water infiltration and pesticides transport in unsaturated zone of a sedimentary aquifer

NASA Astrophysics Data System (ADS)

Sidoli, Pauline; Angulo-Jaramillo, Rafael; Baran, Nicole; Lassabatère, Laurent

2015-04-01

Groundwater quality monitoring has become an important environmental, economic and community issue since increasing needs drinking water at the same time with high anthropic pressure on aquifers. Leaching of various contaminants as pesticide into the groundwater is closely bound to water infiltration in the unsaturated zone which whom solute transport can occur. Knowledge's about mechanisms involved in the transfer of pesticides in the deep unsaturated zone are lacking today. This study aims to evaluate and to model leaching of pesticides and metabolites in the unsaturated zone, very heterogeneous, of a fluvio-glacial aquifer, in the South-East of France, where contamination of groundwater resources by pesticides is frequently observed as a consequence of intensive agricultural activities. Water flow and pesticide transport were evaluated from column tests under unsaturated conditions and from adsorption batch experiments onto the predominant lithofacies collected, composed of a mixture of sand and gravel. A maize herbicide, S-metolachlor, applied on the study site and worldwide and its two major degradation products (metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were studied here. A conservative tracer, bromide ion, was used to determine water dispersive parameters of porous media. Elution curves were obtained from pesticide concentrations analyzed by an ultra-performance liquid chromatography system interfaced to a triple quadrupole mass spectrometer and from bromide concentrations measured by ionic chromatography system. Experimental data were implemented into Hydrus to model flow and solute transfer through a 1D profile in the vadose zone. Nonequilibrium solute transport model based on dual-porosity model with mobile and immobile water is fitting correctly elution curves. Water dispersive parameters show flow pattern realized in the mobile phase. Exchanges between mobile and immobile water are very limited. Because of low adsorptions onto

Lipid droplets induced by secreted phospholipase A2 and unsaturated fatty acids protect breast cancer cells from nutrient and lipotoxic stress.

PubMed

Jarc, Eva; Kump, Ana; Malavašič, Petra; Eichmann, Thomas O; Zimmermann, Robert; Petan, Toni

2018-03-01

Cancer cells driven by the Ras oncogene scavenge unsaturated fatty acids (FAs) from their environment to counter nutrient stress. The human group X secreted phospholipase A 2 (hGX sPLA 2 ) releases FAs from membrane phospholipids, stimulates lipid droplet (LD) biogenesis in Ras-driven triple-negative breast cancer (TNBC) cells and enables their survival during starvation. Here we examined the role of LDs, induced by hGX sPLA 2 and unsaturated FAs, in protection of TNBC cells against nutrient stress. We found that hGX sPLA 2 releases a mixture of unsaturated FAs, including ω-3 and ω-6 polyunsaturated FAs (PUFAs), from TNBC cells. Starvation-induced breakdown of LDs induced by low micromolar concentrations of unsaturated FAs, including PUFAs, was associated with protection from cell death. Interestingly, adipose triglyceride lipase (ATGL) contributed to LD breakdown during starvation, but it was not required for the pro-survival effects of hGX sPLA 2 and unsaturated FAs. High micromolar concentrations of PUFAs, but not OA, induced oxidative stress-dependent cell death in TNBC cells. Inhibition of triacylglycerol (TAG) synthesis suppressed LD biogenesis and potentiated PUFA-induced cell damage. On the contrary, stimulation of LD biogenesis by hGX sPLA 2 and suppression of LD breakdown by ATGL depletion reduced PUFA-induced oxidative stress and cell death. Finally, lipidomic analyses revealed that sequestration of PUFAs in LDs by sPLA 2 -induced TAG remodelling and retention of PUFAs in LDs by inhibition of ATGL-mediated TAG lipolysis protect from PUFA lipotoxicity. LDs are thus antioxidant and pro-survival organelles that guard TNBC cells against nutrient and lipotoxic stress and emerge as attractive targets for novel therapeutic interventions. Copyright © 2017 Elsevier B.V. All rights reserved.

Gold-catalyzed heterogeneous aerobic dehydrogenative amination of α,β-unsaturated aldehydes to enaminals.

PubMed

Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

2014-01-07

Although enaminals (β-enaminals) are very important compounds and have been utilized as useful synthons for various important compounds, they have been synthesized through non-green and/or limited procedures until now. Herein, we have successfully developed a green synthetic procedure using a heterogeneous catalyst. In the presence of gold nanoparticles supported on manganese-oxide-based octahedral molecular sieves OMS-2 (Au/OMS-2), dehydrogenative amination of α,β-unsaturated aldehydes with amines proceeded efficiently, with the corresponding enaminals isolated in moderate to high yields (50-97 %). The catalysis was truly heterogeneous, and Au/OMS-2 could be reused. Furthermore, the formal Wacker-type oxidation of α,β-unsaturated aldehydes to enaminones has been realized. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling a thick unsaturated zone at San Gorgonio Pass, California: lessons learned after five years of artificial recharge

USGS Publications Warehouse

Flint, Alan L.; Ellett, Kevin M.; Christensen, Allen H.; Martin, Peter

2012-01-01

The information flow among the tasks of framework assessment, numerical modeling, model forecasting and hind casting, and system-performance monitoring is illustrated. Results provide an understanding of artificial recharge in high-altitude desert settings where large vertical distances may separate application ponds from their target aquifers.Approximately 3.8 million cubic meters of surface water was applied to spreading ponds from 2003–2007 to artificially recharge the underlying aquifer through a 200-meter thick unsaturated zone in the San Gorgonio Pass area in southern California. A study was conducted between 1997 and 2003, and a numerical model was developed to help determine the suitability of the site for artificial recharge. Ongoing monitoring results indicated that the existing model needed to be modified and recalibrated to more accurately predict artificial recharge at the site. The objective of this work was to recalibrate the model by using observation of the application rates, the rise and fall of the water level above a perching layer, and the approximate arrival time to the water table during the 5-yr monitoring period following initiation of long-term artificial recharge. Continuous monitoring of soil-matric potential, temperature, and water levels beneath the site indicated that artificial recharge reached the underlying water table between 3.75 and 4.5 yr after the initial application of the recharge water. The model was modified to allow the simulation to more adequately match the perching layer dynamics and the time of arrival at the water table. The instrumentation also showed that the lag time between changes in application of water at the surface and the response at the perching layer decreased from about 4 mo to less than 1 mo due to the wet-up of the unsaturated zone and the increase in relative permeability. The results of this study demonstrate the importance of iteratively monitoring and modeling the unsaturated zone in layered

Structural requirements for the cytoprotective actions of mono-unsaturated fatty acids in the pancreatic β-cell line, BRIN-BD11

PubMed Central

Dhayal, S; Welters, H J; Morgan, N G

2008-01-01

Background and purpose: Exposure of pancreatic β-cells to long-chain free fatty acids leads to differential responses according to the chain length and degree of unsaturation. In particular, long-chain saturated molecules such as palmitate (C16:0) cause apoptosis, whereas equivalent mono-unsaturated species (for example, palmitoleate (C16:1)) are not overtly toxic. Moreover, mono-unsaturates exert a powerful cytoprotective response against a range of proapoptotic stimuli. However, the structural requirements that determine cytoprotection have not been determined and form the basis of the present study. Experimental approach: BRIN-BD11 and INS-1 β-cells were exposed either to the saturated fatty acid palmitate, or to serum withdrawal, to mediate cytotoxicity. The protective effects of a wide range of mono-unsaturated fatty acid derivatives were tested in cytotoxicity assays. Effector caspase activity was also measured and correlated with viability. Key results: The cytotoxic actions of palmitate were inhibited dose-dependently by long-chain mono-unsaturated fatty acids with a defined potency order C18:1>C16:1≫C14:1. The configuration of the double bond was also important with cis forms being more potent than trans forms. Alkylated mono-unsaturated fatty-acid derivates were also cytoprotective, although their efficacy declined as the alkyl chain length increased. Cytoprotection was achieved rapidly on addition of mono-unsaturates and correlated with a rapid and dramatic inhibition of caspase-3/7 activity in palmitate-treated cells. Conclusions and implications: The data reveal the structural requirements that dictate the cytoprotective actions of mono-unsaturated fatty acids in pancreatic β-cells. Metabolic activation is not required and the data point at the potential involvement of a fatty acid receptor in mediating cytoprotection. PMID:18297101

Transport of elemental mercury in the unsaturated zone from a waste disposal site in an arid region

USGS Publications Warehouse

Walvoord, Michelle Ann; Andraski, Brian J.; Krabbenhoft, D.P.; Striegl, Robert G.

2008-01-01

Mercury contained in buried landfill waste may be released via upward emission to the atmosphere or downward leaching to groundwater. Data from the US Geological Survey’s Amargosa Desert Research Site (ADRS) in arid southwestern Nevada reveal another potential pathway of Hg release: long-distance (102 m) lateral migration of elemental Hg (Hg0) through the unsaturated zone. Gas collected from multiple depths from two instrumented boreholes that sample the entire 110-m unsaturated zone thickness and are located 100 and 160 m away from the closest waste burial trench exhibit gaseous Hg concentrations of up to 33 and 11 ng m−3, respectively. The vertical distribution of gaseous Hg in the borehole closest to the disposal site shows distinct subsurface peaks in concentration at depths of 1.5 and 24 m that cannot be explained by radial diffusive transport through a heterogeneous layered unsaturated zone. The inability of current models to explain gaseous Hg distribution at the ADRS highlights the need to advance the understanding of gas-phase contaminant transport in unsaturated zones to attain a comprehensive model of landfill Hg release.

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

A practical and highly sensitive C3N4-TYR fluorescent probe for convenient detection of dopamine

NASA Astrophysics Data System (ADS)

Li, Hao; Yang, Manman; Liu, Juan; Zhang, Yalin; Yang, Yanmei; Huang, Hui; Liu, Yang; Kang, Zhenhui

2015-07-01

The C3N4-tyrosinase (TYR) hybrid is a highly accurate, sensitive and simple fluorescent probe for the detection of dopamine (DOPA). Under optimized conditions, the relative fluorescence intensity of C3N4-TYR is proportional to the DOPA concentration in the range from 1 × 10-3 to 3 × 10-8 mol L-1 with a correlation coefficient of 0.995. In the present system, the detection limit achieved is as low as 3 × 10-8 mol L-1. Notably, these quantitative detection results for clinical samples are comparable to those of high performance liquid chromatography. Moreover, the enzyme-encapsulated C3N4 sensing arrays on both glass slide and test paper were evaluated, which revealed sensitive detection and excellent stability. The results reported here provide a new approach for the design of a multifunctional nanosensor for the detection of bio-molecules.The C3N4-tyrosinase (TYR) hybrid is a highly accurate, sensitive and simple fluorescent probe for the detection of dopamine (DOPA). Under optimized conditions, the relative fluorescence intensity of C3N4-TYR is proportional to the DOPA concentration in the range from 1 × 10-3 to 3 × 10-8 mol L-1 with a correlation coefficient of 0.995. In the present system, the detection limit achieved is as low as 3 × 10-8 mol L-1. Notably, these quantitative detection results for clinical samples are comparable to those of high performance liquid chromatography. Moreover, the enzyme-encapsulated C3N4 sensing arrays on both glass slide and test paper were evaluated, which revealed sensitive detection and excellent stability. The results reported here provide a new approach for the design of a multifunctional nanosensor for the detection of bio-molecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03316k

Analysis of a mesoscale infiltration and water seepage test in unsaturated fractured rock: Spatial variabilities and discrete fracture patterns

USGS Publications Warehouse

Zhou, Q.; Salve, R.; Liu, H.-H.; Wang, J.S.Y.; Hudson, D.

2006-01-01

A mesoscale (21??m in flow distance) infiltration and seepage test was recently conducted in a deep, unsaturated fractured rock system at the crossover point of two underground tunnels. Water was released from a 3??m ?? 4??m infiltration plot on the floor of an alcove in the upper tunnel, and seepage was collected from the ceiling of a niche in the lower tunnel. Significant temporal and (particularly) spatial variabilities were observed in both measured infiltration and seepage rates. To analyze the test results, a three-dimensional unsaturated flow model was used. A column-based scheme was developed to capture heterogeneous hydraulic properties reflected by these spatial variabilities observed. Fracture permeability and van Genuchten ?? parameter [van Genuchten, M.T., 1980. A closed-form equation for predicting the hydraulic conductivity of unsaturated soils. Soil Sci. Soc. Am. J. 44, 892-898] were calibrated for each rock column in the upper and lower hydrogeologic units in the test bed. The calibrated fracture properties for the infiltration and seepage zone enabled a good match between simulated and measured (spatially varying) seepage rates. The numerical model was also able to capture the general trend of the highly transient seepage processes through a discrete fracture network. The calibrated properties and measured infiltration/seepage rates were further compared with mapped discrete fracture patterns at the top and bottom boundaries. The measured infiltration rates and calibrated fracture permeability of the upper unit were found to be partially controlled by the fracture patterns on the infiltration plot (as indicated by their positive correlations with fracture density). However, no correlation could be established between measured seepage rates and density of fractures mapped on the niche ceiling. This lack of correlation indicates the complexity of (preferential) unsaturated flow within the discrete fracture network. This also indicates that continuum

Effects of thermal vapor diffusion on seasonal dynamics of water in the unsaturated zone

USGS Publications Warehouse

Milly, Paul C.D.

1996-01-01

The response of water in the unsaturated zone to seasonal changes of temperature (T) is determined analytically using the theory of nonisothermal water transport in porous media, and the solutions are tested against field observations of moisture potential and bomb fallout isotopic (36Cl and 3H) concentrations. Seasonally varying land surface temperatures and the resulting subsurface temperature gradients induce thermal vapor diffusion. The annual mean vertical temperature gradient is close to zero; however, the annual mean thermal vapor flux is downward, because the temperature‐dependent vapor diffusion coefficient is larger, on average, during downward diffusion (occurring at high T) than during upward diffusion (low T). The annual mean thermal vapor flux is shown to decay exponentially with depth; the depth (about 1 m) at which it decays to e−1of its surface value is one half of the corresponding decay depth for the amplitude of seasonal temperature changes. This depth‐dependent annual mean flux is effectively a source of water, which must be balanced by a flux divergence associated with other transport processes. In a relatively humid environment the liquid fluxes greatly exceed the thermal vapor fluxes, so such a balance is readily achieved without measurable effect on the dynamics of water in the unsaturated zone. However, if the mean vertical water flux through the unsaturated zone is very small (<1 mm y−1), as it may be at many locations in a desert landscape, the thermal vapor flux must be balanced mostly by a matric‐potential‐induced upward flux of water. This return flux may include both vapor and liquid components. Below any near‐surface zone of weather‐related fluctuations of matric potential, maintenance of this upward flux requires an increase with depth in the annual mean matric potential; this theoretical prediction is supported by long‐term field measurements in the Chihuahuan Desert. The analysis also makes predictions

Comparison of the Distribution of Unsaturated Fatty Acids at the Sn-2 Position of Phospholipids and Triacylglycerols in Marine Fishes and Mammals.

PubMed

Beppu, Fumiaki; Yasuda, Keiko; Okada, Ayako; Hirosaki, Yoshitsugu; Okazaki, Masako; Gotoh, Naohiro

2017-11-01

Highly unsaturated fatty acid (HUFA) binding at the sn-2 position of phospholipids (PL) becomes a resource for prostaglandin, leukotriene, resolvin, and protectin synthesis. Both triacylglycerol (TAG) and PL synthesis pathways in vivo are via phosphatidic acid; therefore, the distribution of fatty acid species at the sn-2 position must theoretically be the same for TAG and PL if rearrangement does not occur. However, it is known that little HUFA is located at the sn-2 position of TAG in marine mammals. Therefore, distribution of fatty acid species at the sn-2 position of TAG and PL was compared between marine fishes and mammals in this study. The composition of fatty acids binding at the sn-2 or sn-1,3 position of PL and TAG was analyzed via hydrolysis with enzymes and GC-FID. The results showed that 20:4n-6, 20:5n-3, 22:5n-3, and 22:6n-3 were primarily located at the sn-1,3 positions of TAG in marine mammals. Comparison of the binding positions of HUFA and 16:0 in PL and TAG suggested the existence of Lands' cycle in marine fishes and mammals. In conclusion, both marine fishes and mammals condensed HUFA as a source of eicosanoid at the sn-2 position of PL. Furthermore, abundance ratios for 22:5n-3 or 22:6n-3 at the sn-2 position (sn-2 ratio) in TAG and PL (calculated by the equation: [abundance ratio at sn-2 position of TAG]/[abundance ratio at sn-2 position of PL]) was less than 0.35 in marine mammals; however, it was greater than 0.80 in marine fishes. These differences suggested that the HUFA consisted of 22 carbon atoms and had different roles in marine fishes and mammals.

Unsaturated Lipids Change in Olive Tree Drupe and Seed during Fruit Development and in Response to Cold-Stress and Acclimation

PubMed Central

D’Angeli, Simone; Altamura, Maria Maddalena

2016-01-01

The olive tree is a plant of economic value for the oil of its drupe. It is a cultigen complex composed of genotypes with differences in cold-hardiness. About 90% of the oil is stored in oil bodies (OBs) in the drupe during the oleogenic phase. Phenols and lipids contribute to oil quality, but the unsaturated fatty acid (FA) fraction is emerging as the most important for quality, because of the very high content in oleic acid, the presence of ω6-linoleic acid and ω3-linolenic acid, and the very low saturated FA content. Another 10% of oil is produced by the seed. Differences in unsaturated FA-enriched lipids exist among seed coat, endosperm, and embryo. Olive oil quality is also affected by the environmental conditions during fruit growth and genotype peculiarities. Production of linoleic and α-linolenic acids, fruit growth, fruit and leaf responses to low temperatures, including cuticle formation, and cold-acclimation are related processes. The levels of unsaturated FAs are changed by FA-desaturase (FAD) activities, involving the functioning of chloroplasts and endoplasmic reticulum. Cold induces lipid changes during drupe and seed development, affecting FADs, but its effect is related to the genotype capability to acclimate to the cold. PMID:27845749

The Structure-Activity Relationship of the 3-Oxy Site in the Anticonvulsant (R)-N-Benzyl 2-Acetamido-3-methoxypropionamide

PubMed Central

Morieux, Pierre; Salomé, Christophe; Park, Ki Duk; Stables, James P.; Kohn, Harold

2010-01-01

Lacosamide ((R)-N-benzyl 2-acetamido-3-methoxypropionamide, (R)-1) is a low molecular weight anticonvulsant recently introduced in the United States and Europe for adjuvant treatment of partial-onset seizures in adults. In this study, we define the structure-activity relationship (SAR) for the compound's 3-oxy site. Placement of small non-polar, non-bulky substituents at the 3-oxy site provided compounds with pronounced seizure protection in the maximal electroshock (MES) seizure test with activities similar to (R)-1. The anticonvulsant activity loss that accompanied introduction of larger moieties at the 3-oxy site in (R)-1 was offset, in part, by including unsaturated groups at this position. Our findings were similar to a recently reported SAR study of the 4′-benzylamide site in (R)-1 (J. Med. Chem.2010, 53, 1288–1305). Together, these results indicate that both the 3-oxy and 4′-benzylamide positions in (R)-1 can accommodate non-bulky, hydrophobic groups and still retain pronounced anticonvulsant activities in rodents in the MES seizure model. PMID:20614888

NO3 uptake in shallow, oligotrophic, mountain lakes: The influence of elevated NO3 concentrations

USGS Publications Warehouse

Nydick, K.R.; LaFrancois, B.M.; Baron, Jill S.

2004-01-01

Nutrient enrichment experiments were conducted in 1.2-m deep enclosures in 2 shallow, oligotrophic, mountain lakes. 15N-NO3 isotope tracer was used to compare the importance of phytoplankton and benthic compartments (epilithon, surface sediment [epipelon], and subsurface sediment) for NO3 uptake under high and low NO3 conditions. NO3 uptake approached saturation in the high-N lake, but not in the low-N lake. The capacity of phytoplankton and benthic compartments to take up NO3 differed among treatments and between lakes, and depended on water-column nutrient conditions and the history of NO3 availability. Phytoplankton productivity responded strongly to addition of limiting nutrients, and NO3 uptake was related to phytoplankton biomass and photosynthesis. However, more NO3 usually was taken up by benthic compartments (57–92% combined) than by phytoplankton, even though the response of benthic algal biomass to nutrient additions was less pronounced than that of phytoplankton and benthic NO3 uptake was unrelated to benthic algal biomass. In the low-N lake where NO3 uptake was unsaturated, C content or % was related to NO3 uptake in benthic substrates, suggesting that heterotrophic bacterial processes could be important in benthic NO3 uptake. These results suggest that phytoplankton are most sensitive to nutrient additions, but benthic processes are important for NO3 uptake in shallow, oligotrophic lakes.

l-2',3'-Didehydro-2',3'-dideoxy-3'-fluoronucleosides: synthesis, anti-HIV activity, chemical and enzymatic stability, and mechanism of resistance.

PubMed

Chong, Youhoon; Gumina, Giuseppe; Mathew, Judy S; Schinazi, Raymond F; Chu, Chung K

2003-07-17

As antiviral nucleosides containing a 2',3'-unsaturated sugar moiety with 2'-fluoro substitution are endowed with increased stabilization of the glycosyl bond, it was of interest to investigate the influence of the fluorine atom at the 3'-position. Various pyrimidine and purine L-3'-fluoro-2',3'-unsaturated nucleosides were synthesized from their precursors, L-3',3'-difluoro-2',3'-dideoxy nucleosides, by elimination of hydrogen fluoride. In the L-3',3'-difluoro-2',3'-dideoxy nucleoside series, cytidine 16 and 5-fluorocytidine 18 analogues showed modest antiviral activity (EC(50) 11.5 and 8.8 microM, respectively) when evaluated against HIV-1 in human peripheral blood mononuclear (PBM) cells. In the 2',3'-unsaturated series, L-3'-fluoro-2',3'-didehydro-2',3'-dideoxycytidine 24 and 5-fluorocytidine 26 showed highly potent antiviral activity (EC(50) 0.089 and 0.018 microM, respectively) without significant cytotoxicity. The guanosine analogue 48 showed only marginal anti-HIV activity with some cytotoxicity (EC(50) 38.5 microM, and IC(50) 17.4, 58.4, 36.5 microM in PBM, CEM, and Vero cells, respectively). The cytidine 24 and 5-fluorocytidine 26 analogues, however, showed significantly decreased antiviral activity against the clinically important lamivudine-resistant variants (HIV-1(M184V)). Molecular modeling studies demonstrated that the 3'-fluoro atom of the L-3'-fluoro-2',3'-unsaturated nucleoside is within the hydrogen bonding distance with the amide backbone of Asp185, which favors the binding of the nucleoside triphosphate to the wild-type RT. This favorable binding mode, however, cannot be maintained when the triphosphate of 3'-fluoro 2',3'-unsaturated nucleoside binds to the active site of M184V RT because the bulky side chain of Val184 occupies the space needed for the nucleotide. The biological results suggest that, in addition to the sugar conformation, the base moiety may also play a role in their interaction with the M184V RT.

Improved forward and inverse analyses of saturated-unsaturated flow toward a well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, Phoolendra Kumar; Neuman, Shlomo P.

2010-07-01

We present an analytical solution for flow to a partially penetrating well in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from drawdowns recorded in the saturated and/or unsaturated zone. We improve upon a previous such solution due to Tartakovsky and Neuman (2007) by (1) adopting a more flexible representation of unsaturated zone constitutive properties and (2) allowing the unsaturated zone to have finite thickness. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of unsaturated zone constitutive parameters and thickness on drawdowns in the saturated and unsaturated zones as functions of position and time; demonstrate the development of significant horizontal hydraulic gradients in the unsaturated zone in response to pumping; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten-Mualem constitutive model; use our solution to analyze drawdown data from a pumping test conducted by the U.S. Geological Survey at Cape Cod, Massachusetts; and compare our estimates of van Genuchten-Mualem parameters with laboratory values obtained for similar materials in the area.

Saturated and cis- and trans-unsaturated fatty acids intake in rural and urban Costa Rican adolescents.

PubMed

Monge-Rojas, Rafael; Campos, Hannia; Fernández Rojas, Xinia

2005-08-01

The purpose of this study is to determine whether intake of saturated fatty acids and cis- and trans-unsaturated fatty acids is associated with an urban compared to a rural lifestyle, and whether these associations are responsible for differences in plasma lipid concentrations. Two hundred seventy-five adolescents, aged 12 to 19 years, living in rural and urban areas of San José, Costa Rica, were included in the study. All participants completed three-day food records, provided a fasting blood sample, and carried out a modified Harvard Step Test. Compared to rural, urban adolescents reported higher intakes of energy-adjusted individual and total saturated fatty acids, total n-3, total n-6 (p < 0.05). Compared to rural, urban adolescents had higher intake of 18:1 (3.65 vs. 3.25, p = 0.0001) and 18:2 (0.62 vs. 0.80, p = 0.001) trans fatty acids, as well as lower intake of carbohydrate (p < 0.05). Palm shortening was the main source of saturated fat (32%), and partially hydrogenated soybean oil used for cooking was the main source of n-3 fatty acids (33%), n-6 fatty acids (33%) and trans fatty acids (34%). Compared to rural, urban adolescents had lower systolic and diastolic blood pressure and higher plasma HDL cholesterol concentration (44 vs. 40 mg/dL, p < 0.0001), but were more likely to be sedentary (68% vs. 57%, p < 0.0001). Among environmental factors, higher carbohydrate intake was a significant determinant of a lower HDL cholesterol (beta coeff = -1.45, p = 0.04), while lauric and myristic fatty acids correlated with increased LDL cholesterol (beta coeff = 3.6, 1.7, p < 0.05). A diet containing less carbohydrate and less saturated fatty acids contributes to a more beneficial lipid profile in Costa Rican adolescents, but a trend towards high trans fatty acids intake, particularly in the urban area, is worrisome given the well-known adverse effects of trans fatty acids.

g-C{sub 3}N{sub 4}/NaTaO{sub 3} organic–inorganic hybrid nanocomposite: High-performance and recyclable visible light driven photocatalyst

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

Kumar, Santosh; Kumar, Bharat; Surendar, T.

2014-01-01

Graphical abstract: High-performance and recyclable visible-light driven g-C{sub 3}N{sub 4}/NaTaO{sub 3} hybrid nanocomposite photocatalysts have been prepared by a facile ultrasonic dispersion method. The hybrid nanocomposite photocatalyst can be promising photocatalytic material for practical application in water splitting and environmental remediation. - Highlights: • Novel g-C{sub 3}N{sub 4}/NaTaO{sub 3} nanocomposites as a high performance and recyclable photocatalysts. • These catalysts exhibited significantly enhanced photocatalytic activity under UV–visible light irradiation. • More attractively, dramatic activity is generated under visible light irradiation due to the g-C{sub 3}N{sub 4} loaded. • Interestingly, the as-prepared hybrid nanocomposites possess high reusability. - Abstract: Novel g-C{submore » 3}N{sub 4}/NaTaO{sub 3} hybrid nanocomposites have been prepared by a facile ultrasonic dispersion method. Our results clearly show the formation of interface between NaTaO{sub 3} and g-C{sub 3}N{sub 4} and further loading of g-C{sub 3}N{sub 4} did not affect the crystal structure and morphology of NaTaO{sub 3}. The g-C{sub 3}N{sub 4}/NaTaO{sub 3} nanocomposites exhibited enhanced photocatalytic performance for the degradation of Rhodamine B under UV–visible and visible light irradiation compared to pure NaTaO{sub 3} and Degussa P25. Interestingly, the visible light photocatalytic activity is generated due to the loading of g-C{sub 3}N{sub 4}. A mechanism is proposed to discuss the enhanced photocatalytic activity based on trapping experiments of photoinduced radicals and holes. Under visible light irradiation, electron excited from the valance band (VB) to conduction band (CB) of g-C{sub 3}N{sub 4} could directly inject into the CB of NaTaO{sub 3}, making g-C{sub 3}N{sub 4}/NaTaO{sub 3} visible light driven photocatalyst. Since the as-prepared hybrid nanocomposites possess high reusability therefore it can be promising photocatalyst for

Groundwater recharge dynamics in unsaturated fractured chalk: a case study

NASA Astrophysics Data System (ADS)

Cherubini, Claudia; Pastore, Nicola; Giasi, Concetta I.; Allegretti, Nicolaetta M.

2016-04-01

The heterogeneity of the unsaturated zone controls its hydraulic response to rainfall and the extent to which pollutants are delayed or attenuated before reaching groundwater. It plays therefore a very important role in the recharge of aquifers and the transfer of pollutants because of the presence of temporary storage zones and preferential flows. A better knowledge of the physical processes in the unsaturated zone would allow an improved assessment of the natural recharge in a heterogeneous aquifer and of its vulnerability to surface-applied pollution. The case study regards the role of the thick unsaturated zone of the Cretaceous chalk aquifer in Picardy (North of France) that controls the hydraulic response to rainfall. In the North Paris Basin, much of the recharge must pass through a regional chalk bed that is composed of a porous matrix with embedded fractures. Different types of conceptual models have been formulated to explain infiltration and recharge processes in the unsaturated fractured rock. The present study analyses the episodic recharge in fractured Chalk aquifer using the kinematic diffusion theory to predict water table fluctuation in response to rainfall. From an analysis of the data, there is the evidence of 1) a seasonal behavior characterized by a constant increase in the water level during the winter/spring period and a recession period, 2) a series of episodic behaviors during the summer/autumn. Kinematic diffusion models are useful for predict preferential fluxes and dynamic conditions. The presented approach conceptualizes the unsaturated flow as a combination of 1) diffusive flow refers to the idealized portion of the pore space of the medium within the flow rate is driven essentially by local gradient of potential; 2) preferential flow by which water moves across macroscopic distances through conduits of macropore length.

Cardiovascular disease risk of dietary stearic acid compared with trans, other saturated, and unsaturated fatty acids: a systematic review.

PubMed

Hunter, J Edward; Zhang, Jun; Kris-Etherton, Penny M

2010-01-01

High stearic acid (STA) soybean oil is a trans-free, oxidatively stable, non-LDL-cholesterol-raising oil that can be used to replace trans fatty acids (TFAs) in solid fat applications. The objective was to assess the cardiovascular health effects of dietary STA compared with those of trans, other saturated, and unsaturated fatty acids. We reviewed epidemiologic and clinical studies that evaluated the relation between STA and cardiovascular disease (CVD) risk factors, including plasma lipids and lipoproteins, hemostatic variables, and inflammatory markers. In comparison with other saturated fatty acids, STA lowered LDL cholesterol, was neutral with respect to HDL cholesterol, and directionally lowered the ratio of total to HDL cholesterol. STA tended to raise LDL cholesterol, lower HDL cholesterol, and increase the ratio of total to HDL cholesterol in comparison with unsaturated fatty acids. In 2 of 4 studies, high-STA diets increased lipoprotein(a) in comparison with diets high in saturated fatty acids. Three studies showed increased plasma fibrinogen when dietary STA exceeded 9% of energy (the current 90th percentile of intake is 3.5%). Replacing industrial TFAs with STA might increase STA intake from 3.0% (current) to approximately 4% of energy and from 4% to 5% of energy at the 90th percentile. One-to-one substitution of STA for TFAs showed a decrease or no effect on LDL cholesterol, an increase or no effect on HDL cholesterol, and a decrease in the ratio of total to HDL cholesterol. TFA intake should be reduced as much as possible because of its adverse effects on lipids and lipoproteins. The replacement of TFA with STA compared with other saturated fatty acids in foods that require solid fats beneficially affects LDL cholesterol, the primary target for CVD risk reduction; unsaturated fats are preferred for liquid fat applications. Research is needed to evaluate the effects of STA on emerging CVD risk markers such as fibrinogen and to understand the responses

Molecular dynamics simulation of unsaturated lipid bilayers at low hydration: parameterization and comparison with diffraction studies.

PubMed Central

Feller, S E; Yin, D; Pastor, R W; MacKerell, A D

1997-01-01

A potential energy function for unsaturated hydrocarbons is proposed and is shown to agree well with experiment, using molecular dynamics simulations of a water/octene interface and a dioleoyl phosphatidylcholine (DOPC) bilayer. The simulation results verify most of the assumptions used in interpreting the DOPC experiments, but suggest a few that should be reconsidered. Comparisons with recent results of a simulation of a dipalmitoyl phosphatidylcholine (DPPC) lipid bilayer show that disorder is comparable, even though the temperature, hydration level, and surface area/lipid for DOPC are lower. These observations highlight the dramatic effects of unsaturation on bilayer structure. Images FIGURE 3 PMID:9370424

NH3 assisted photoreduction and N-doping of graphene oxide for high performance electrode materials in supercapacitors

NASA Astrophysics Data System (ADS)

Huang, Haifu; Luo, Guangsheng; Xu, Lianqiang; Lei, Chenglong; Tang, Yanmei; Tang, Shaolong; Du, Youwei

2015-01-01

Nitrogen-doped graphene was synthesized by simple photoreduction of graphene oxide (GO) deposited on nickel foam under NH3 atmosphere. The combination of photoreduction and NH3 not only reduces the GO in a shorter time but also induces nitrogen doping easily. The nitrogen doped content of N-rGO@NF reaches a high of 5.99 at% with 15 min of irradiation. The nitrogen-doped graphene deposited on Ni foam (N-rGO@NF) can be directly used as an electrode for supercapacitors, without any conductive agents and polymer binders. In the electrochemical measurement, N-rGO@NF displays remarkable electrochemical performance. In particular, the N-rGO@NF irradiated for 45 min at a high current density of 92.3 A g-1 retained about 77% (190.4 F g-1) of its initial specific capacitance (247.1 F g-1 at 0.31 A g-1). Furthermore, the stable voltage window could be extended to 2.0 and 1.5 V by using Li2SO4 and a mixed Li2SO4/KOH electrolyte, and the maximum energy density was high up to 32.6 and 21.2 Wh kg-1, respectively. The results show that compared to Li2SO4, a mixed electrolyte (Li2SO4/KOH) more efficiently balances the relationship between the high energy densities and high power densities.Nitrogen-doped graphene was synthesized by simple photoreduction of graphene oxide (GO) deposited on nickel foam under NH3 atmosphere. The combination of photoreduction and NH3 not only reduces the GO in a shorter time but also induces nitrogen doping easily. The nitrogen doped content of N-rGO@NF reaches a high of 5.99 at% with 15 min of irradiation. The nitrogen-doped graphene deposited on Ni foam (N-rGO@NF) can be directly used as an electrode for supercapacitors, without any conductive agents and polymer binders. In the electrochemical measurement, N-rGO@NF displays remarkable electrochemical performance. In particular, the N-rGO@NF irradiated for 45 min at a high current density of 92.3 A g-1 retained about 77% (190.4 F g-1) of its initial specific capacitance (247.1 F g-1 at 0.31 A g-1

Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

USGS Publications Warehouse

Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

1997-01-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

NASA Astrophysics Data System (ADS)

Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

1997-06-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

Liposomes composed of unsaturated lipids for membrane modification of human erythrocytes.

PubMed

Stoll, Christoph; Holovati, Jelena L; Acker, Jason P; Wolkers, Willem F

2011-01-01

Previous studies have shown that certain saturated lipids protect red blood cells (RBCs) during hypothermic storage but provide little protection during freezing or freeze-drying, whereas various unsaturated lipids destabilize RBCs during hypothermic storage but protect during freezing and freeze-drying. The protective effect of liposomes has been attributed to membrane modifications. We have previously shown that cholesterol exchange and lipid transfer between liposomes composed of saturated lipids and RBCs critically depends on the length of the lipid acyl chains. In this study the effect of unsaturated lipids with differences in their number of unsaturated bonds (18:0/18:1, 18:1/18:1, 18:2/18:2) on RBC membrane properties has been studied. RBCs were incubated in the presence of liposomes and both the liposomal and RBC fraction were analyzed by Fourier transform infrared spectroscopy (FTIR) after incubation. The liposomes caused an increase in RBC membrane conformational disorder at suprazero temperatures. The fluidizing effect of the liposomes on the RBC membranes, however, was found to be similar for the different lipids irrespective of their unsaturation level. The gel to liquid crystalline phase transition temperature of the liposomes increased after incubation with RBCs. RBC membrane fluidity increased linearly during the first 8 hours of incubation in the presence of liposomes. The increase in RBC membrane fluidity was found to be temperature dependent and displayed Arrhenius behaviour between 20 and 40°C, with an activation energy of 88 kJ mol⁻¹. Taken together, liposomes composed of unsaturated lipids increase RBC membrane conformational disorder, which could explain their cryoprotective action.

Highly pathogenic avian influenza A(H7N3) virus in poultry workers, Mexico, 2012.

PubMed

Lopez-Martinez, Irma; Balish, Amanda; Barrera-Badillo, Gisela; Jones, Joyce; Nuñez-García, Tatiana E; Jang, Yunho; Aparicio-Antonio, Rodrigo; Azziz-Baumgartner, Eduardo; Belser, Jessica A; Ramirez-Gonzalez, José E; Pedersen, Janice C; Ortiz-Alcantara, Joanna; Gonzalez-Duran, Elizabeth; Shu, Bo; Emery, Shannon L; Poh, Mee K; Reyes-Teran, Gustavo; Vazquez-Perez, Joel A; Avila-Rios, Santiago; Uyeki, Timothy; Lindstrom, Stephen; Villanueva, Julie; Tokars, Jerome; Ruiz-Matus, Cuitláhuac; Gonzalez-Roldan, Jesus F; Schmitt, Beverly; Klimov, Alexander; Cox, Nancy; Kuri-Morales, Pablo; Davis, C Todd; Diaz-Quiñonez, José Alberto

2013-01-01

We identified 2 poultry workers with conjunctivitis caused by highly pathogenic avian influenza A(H7N3) viruses in Jalisco, Mexico. Genomic and antigenic analyses of 1 isolate indicated relatedness to poultry and wild bird subtype H7N3 viruses from North America. This isolate had a multibasic cleavage site that might have been derived from recombination with host rRNA.

Project Summary. THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

EPA Science Inventory

This summary describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soi...

Process for making unsaturated hydrocarbons using microchannel process technology

DOEpatents

Tonkovich, Anna Lee [Dublin, OH; Yuschak, Thomas [Lewis Center, OH; LaPlante, Timothy J [Columbus, OH; Rankin, Scott [Columbus, OH; Perry, Steven T [Galloway, OH; Fitzgerald, Sean Patrick [Columbus, OH; Simmons, Wayne W [Dublin, OH; Mazanec, Terry Daymo, Eric

2011-04-12

The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200.degree. C. to about 1200.degree. C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

SUTRA: A model for 2D or 3D saturated-unsaturated, variable-density ground-water flow with solute or energy transport

USGS Publications Warehouse

Voss, Clifford I.; Provost, A.M.

2002-01-01

SUTRA (Saturated-Unsaturated Transport) is a computer program that simulates fluid movement and the transport of either energy or dissolved substances in a subsurface environment. This upgraded version of SUTRA adds the capability for three-dimensional simulation to the former code (Voss, 1984), which allowed only two-dimensional simulation. The code employs a two- or three-dimensional finite-element and finite-difference method to approximate the governing equations that describe the two interdependent processes that are simulated: 1) fluid density-dependent saturated or unsaturated ground-water flow; and 2) either (a) transport of a solute in the ground water, in which the solute may be subject to: equilibrium adsorption on the porous matrix, and both first-order and zero-order production or decay; or (b) transport of thermal energy in the ground water and solid matrix of the aquifer. SUTRA may also be used to simulate simpler subsets of the above processes. A flow-direction-dependent dispersion process for anisotropic media is also provided by the code and is introduced in this report. As the primary calculated result, SUTRA provides fluid pressures and either solute concentrations or temperatures, as they vary with time, everywhere in the simulated subsurface system. SUTRA flow simulation may be employed for two-dimensional (2D) areal, cross sectional and three-dimensional (3D) modeling of saturated ground-water flow systems, and for cross sectional and 3D modeling of unsaturated zone flow. Solute-transport simulation using SUTRA may be employed to model natural or man-induced chemical-species transport including processes of solute sorption, production, and decay. For example, it may be applied to analyze ground-water contaminant transport problems and aquifer restoration designs. In addition, solute-transport simulation with SUTRA may be used for modeling of variable-density leachate movement, and for cross sectional modeling of saltwater intrusion in

Experimental Study on Shear Strength of Unsaturated Loess Based on Different Water Content in Xining Area

NASA Astrophysics Data System (ADS)

guibo, Bao; hui, Li; yu, Zhang; wuyu, Zhang; ningshan, Jiang

2018-05-01

Today, the study of shear strength of unsaturated soils has become a hot topic in unsaturated soil mechanics research. There are any number of factors affecting the strength of unsaturated soils. Among these factors, the moisture content has the most significant effect on the shear strength. In this paper, unsaturated loess in Xining is taken as the research object, the triaxial test without consolidation and undrain is used to determine the shear strength and its parameters under the condition of different water content, then the relationship between unsaturated loess’ water content and shear strength parameters is explored, and curve fitting is performed. The relevantily approximate mathematics formulas are obtained. The study can provide strength parameter for slope stability and foundation pit support in Xining.

Improved predictions of saturated and unsaturated zone drawdowns in a heterogeneous unconfined aquifer via transient hydraulic tomography: Laboratory sandbox experiments

NASA Astrophysics Data System (ADS)

Berg, Steven J.; Illman, Walter A.

2012-11-01

SummaryInterpretation of pumping tests in unconfined aquifers has largely been based on analytical solutions that disregard aquifer heterogeneity. In this study, we investigate whether the prediction of drawdown responses in a heterogeneous unconfined aquifer and the unsaturated zone above it with a variably saturated groundwater flow model can be improved by including information on hydraulic conductivity (K) and specific storage (Ss) from transient hydraulic tomography (THT). We also investigate whether these predictions are affected by the use of unsaturated flow parameters estimated through laboratory hanging column experiments or calibration of in situ drainage curves. To investigate these issues, we designed and conducted laboratory sandbox experiments to characterize the saturated and unsaturated properties of a heterogeneous unconfined aquifer. Specifically, we conducted pumping tests under fully saturated conditions and interpreted the drawdown responses by treating the medium to be either homogeneous or heterogeneous. We then conducted another pumping test and allowed the water table to drop, similar to a pumping test in an unconfined aquifer. Simulations conducted using a variably saturated flow model revealed: (1) homogeneous parameters in the saturated and unsaturated zones have a difficult time predicting the responses of the heterogeneous unconfined aquifer; (2) heterogeneous saturated hydraulic parameter distributions obtained via THT yielded significantly improved drawdown predictions in the saturated zone of the unconfined aquifer; and (3) considering heterogeneity of unsaturated zone parameters produced a minor improvement in predictions in the unsaturated zone, but not the saturated zone. These results seem to support the finding by Mao et al. (2011) that spatial variability in the unsaturated zone plays a minor role in the formation of the S-shape drawdown-time curve observed during pumping in an unconfined aquifer.

Short communication: Estimates of heritabilities and genetic correlations among milk fatty acid unsaturation indices in Canadian Holsteins.

PubMed

Bilal, G; Cue, R I; Mustafa, A F; Hayes, J F

2012-12-01

The objectives of the present study were to estimate genetic parameters of milk fatty acid unsaturation indices in Canadian Holsteins. Data were available on milk fatty acid composition of 2,573 Canadian Holstein cows from 46 commercial herds enrolled in the Québec Dairy Production Centre of Expertise, Valacta (Sainte-Anne-de-Bellevue, Quebec, Canada). Individual fatty acid percentages (g/100 g of total fatty acids) were determined for each milk sample by gas chromatography. The unsaturation indices were calculated as the ratio of an unsaturated fatty acid to the sum of that unsaturated fatty acid and its corresponding substrate fatty acid, multiplied by 100. A mixed linear model was fitted under REML for the statistical analysis of milk fatty acid unsaturation indices. The statistical model included the fixed effects of parity, age at calving, and stage of lactation, each nested within parity, and the random effects of herd-year-season of calving, animal, and residual. Estimates of heritabilities for the C14, C16, C18, conjugated linoleic acid, and total unsaturation indices were 0.48, 0.25, 0.29, 0.14, and 0.19, respectively. Phenotypic and genetic correlation estimates among unsaturation indices were all positive and ranged from 0.20 to 0.65 and 0.23 to 0.81, respectively. The estimates of heritabilities and genetic correlations for milk fatty acid unsaturation indices suggest that genetic variation exists among cows in milk fatty acid unsaturation, and the proportions of desirable unsaturated fatty acids from a human health point of view may be increased in bovine milk through genetic selection. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Field investigation into unsaturated flow and transport in a fault: Model analyses

USGS Publications Warehouse

Liu, H.-H.; Salve, R.; Wang, J.-S.; Bodvarsson, G.S.; Hudson, D.

2004-01-01

Results of a fault test performed in the unsaturated zone of Yucca Mountain, Nevada, were analyzed using a three-dimensional numerical model. The fault was explicitly represented as a discrete feature and the surrounding rock was treated as a dual-continuum (fracture-matrix) system. Model calibration against seepage and water-travel-velocity data suggests that lithophysal cavities connected to fractures can considerably enhance the effective fracture porosity and therefore retard water flow in fractures. Comparisons between simulation results and tracer concentration data also indicate that matrix diffusion is an important mechanism for solute transport in unsaturated fractured rock. We found that an increased fault-matrix and fracture-matrix interface areas were needed to match the observed tracer data, which is consistent with previous studies. The study results suggest that the current site-scale model for the unsaturated zone of Yucca Mountain may underestimate radionuclide transport time within the unsaturated zone, because an increased fracture-matrix interface area and the increased effective fracture porosity arising from lithophysal cavities are not considered in the current site-scale model. ?? 2004 Published by Elsevier B.V.

Contribution To Degradation Study, Behavior Of Unsaturated Polyester Resin Under Neutron Irradiation

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

Abellache, D.; Lounis, A.; Taiebi, K.

2010-01-05

Applications of unsaturated polyester thermosetting resins are numerous in construction sector, in transport, electric spare parts manufactures, consumer goods, and anticorrosive materials. This survey reports the effect of thermosetting polymer degradation (unsaturated polyester): degradation by neutrons irradiation. In order to evaluate the deterioration of our material, some comparative characterizations have been done between standard samples and damaged ones. Scanning electron microscopy (SEM), ultrasonic scanning, hardness test (Shore D) are the techniques which have been used. The exposure to a neutrons flux is carried out in the column of the nuclear research reactor of Draria (Algiers-Algeria). The energetic profile of themore » incidental fluxes is constituted of fast neutrons (PHI{sub R} = 3.10{sup 12} n.cm{sup -2}.s{sup -1}, E = 2 Mev) of thermal neutrons (PHI{sub TH} = 10{sup 13} n.cm{sup -2}.s{sup -1}; E = 0.025 ev) and epithermal neutrons (PHI{sub epi} = 7.10{sup 11} n.cm{sup -2}.s{sup -1}; E>4,9 ev). The received dose flow is 0,4 Kgy. We notice only a few scientific investigations can be found in this field. In comparison with the standard sample (no exposed) it is shown that the damage degree is an increasing process with the exposure. Concerning the description of irradiation effects on polymers, we can advance that several reactions are in competition: reticulation, chain break, and oxidation by radical mechanism. In our case the incidental particle of high energy fast neutrons whose energy is greater or equal to 2 Mev, is braked by the target with a nuclear shock during which the incidental particle transmits a part of its energy to an atom. If the energy transfer is sufficient, the nuclear shock permits to drive out an atom of its site the latter will return positioning interstitially, the energy that we used oversteps probably the energy threshold (displacement energy). This fast neutrons collision with target cores proceeds to an indirect

Deep installations of monitoring instrumentation in unsaturated welded tuff

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

Tyler, S.

1985-12-31

The major goal of this research is to develop low cost techniques to measure matric potential, moisture content, and to sample liquid and vapor for chemical analysis in the deep unsaturated zones of the arid areas of Nevada. This work has been prompted by the high level waste repository proposed in the unsaturated zone of Yucca Mountain. The work presented focuses on two deep (250 meter) boreholes planned for completion at the southern end of Yucca Mountain in fractured tuff. One borehole will be drilled without water and cased to slightly below the zone of saturation in order to measuremore » the depth to saturation and to collect water samples for analysis. This hole will also be used for routine quarterly neutron logging. Between loggings, vapor liquid water samplers will be suspended in the borehole and packed off at selective screened intervals to collect water vapor for isotopic analysis. The second borehole will be drilled to slightly above the water table and serve as a multiple interval psychrometer installation. Thermocouple psychrometers will be placed in isolated screened intervals within the casing. These boreholes will be used for instrument testing, interference and permeability testing, and to monitor short term fluctuations of soil and rock moisture due to precipitation and recharge.« less

Creep model of unsaturated sliding zone soils and long-term deformation analysis of landslides

NASA Astrophysics Data System (ADS)

Zou, Liangchao; Wang, Shimei; Zhang, Yeming

2015-04-01

Sliding zone soil is a special soil layer formed in the development of a landslide. Its creep behavior plays a significant role in long-term deformation of landslides. Due to rainfall infiltration and reservoir water level fluctuation, the soils in the slide zone are often in unsaturated state. Therefore, the investigation of creep behaviors of the unsaturated sliding zone soils is of great importance for understanding the mechanism of the long-term deformation of a landslide in reservoir areas. In this study, the full-process creep curves of the unsaturated soils in the sliding zone in different net confining pressure, matric suctions and stress levels were obtained from a large number of laboratory triaxial creep tests. A nonlinear creep model for unsaturated soils and its three-dimensional form was then deduced based on the component model theory and unsaturated soil mechanics. This creep model was validated with laboratory creep data. The results show that this creep model can effectively and accurately describe the nonlinear creep behaviors of the unsaturated sliding zone soils. In order to apply this creep model to predict the long-term deformation process of landslides, a numerical model for simulating the coupled seepage and creep deformation of unsaturated sliding zone soils was developed based on this creep model through the finite element method (FEM). By using this numerical model, we simulated the deformation process of the Shuping landslide located in the Three Gorges reservoir area, under the cycling reservoir water level fluctuation during one year. The simulation results of creep displacement were then compared with the field deformation monitoring data, showing a good agreement in trend. The results show that the creeping deformations of landslides have strong connections with the changes of reservoir water level. The creep model of unsaturated sliding zone soils and the findings obtained by numerical simulations in this study are conducive to

Fractal Analysis of Permeability of Unsaturated Fractured Rocks

PubMed Central

Jiang, Guoping; Shi, Wei; Huang, Lili

2013-01-01

A physical conceptual model for water retention in fractured rocks is derived while taking into account the effect of pore size distribution and tortuosity of capillaries. The formula of calculating relative hydraulic conductivity of fractured rock is given based on fractal theory. It is an issue to choose an appropriate capillary pressure-saturation curve in the research of unsaturated fractured mass. The geometric pattern of the fracture bulk is described based on the fractal distribution of tortuosity. The resulting water content expression is then used to estimate the unsaturated hydraulic conductivity of the fractured medium based on the well-known model of Burdine. It is found that for large enough ranges of fracture apertures the new constitutive model converges to the empirical Brooks-Corey model. PMID:23690746

Fractal analysis of permeability of unsaturated fractured rocks.

PubMed

Jiang, Guoping; Shi, Wei; Huang, Lili

2013-01-01

A physical conceptual model for water retention in fractured rocks is derived while taking into account the effect of pore size distribution and tortuosity of capillaries. The formula of calculating relative hydraulic conductivity of fractured rock is given based on fractal theory. It is an issue to choose an appropriate capillary pressure-saturation curve in the research of unsaturated fractured mass. The geometric pattern of the fracture bulk is described based on the fractal distribution of tortuosity. The resulting water content expression is then used to estimate the unsaturated hydraulic conductivity of the fractured medium based on the well-known model of Burdine. It is found that for large enough ranges of fracture apertures the new constitutive model converges to the empirical Brooks-Corey model.

Ion Diffusion Within Water Films in Unsaturated Porous Media.

PubMed

Tokunaga, Tetsu K; Finsterle, Stefan; Kim, Yongman; Wan, Jiamin; Lanzirotti, Antonio; Newville, Matthew

2017-04-18

Diffusion is important in controlling local solute transport and reactions in unsaturated soils and geologic formations. Although it is commonly assumed that thinning of water films controls solute diffusion at low water contents, transport under these conditions is not well understood. We conducted experiments in quartz sands at low volumetric water contents (θ) to quantify ion diffusion within adsorbed films. At the lowest water contents, we employed fixed relative humidities to control water films at nm thicknesses. Diffusion profiles for Rb + and Br - in unsaturated sand packs were measured with a synchrotron X-ray microprobe, and inverse modeling was used to determine effective diffusion coefficients, D e, as low as ∼9 × 10 -15 m 2 s -1 at θ = 1.0 × 10 -4 m 3 m -3 , where the film thickness = 0.9 nm. Given that the diffusion coefficients (D o ) of Rb + and Br - in bulk water (30 °C) are both ∼2.4 × 10 -9 m 2 s -1 , we found the impedance factor f = D e /(θD o ) is equal to 0.03 ± 0.02 at this very low saturation, in agreement with the predicted influence of interface tortuosity (τ a ) for diffusion along grain surfaces. Thus, reduced cross-sectional area (θ) and tortuosity largely accounted for the more than 5 orders of magnitude decrease in D e relative to D o as desaturation progressed down to nanoscale films.

Occurrence of Agricultural Chemicals in Shallow Ground Water and the Unsaturated Zone, Northeast Nebraska Glacial Till, 2002-04

USGS Publications Warehouse

Stanton, Jennifer S.; Steele, Gregory V.; Vogel, Jason R.

2007-01-01

Agricultural chemicals applied at the land surface in northeast Nebraska can move downward, past the crop root zone, to ground water. Because agricultural chemicals applied at the land surface are more likely to be observed in the shallowest part of an aquifer, an assessment of shallow ground-water and unsaturated zone quality in the northeast Nebraska glacial till was completed between 2002 and 2004. Ground-water samples were collected at the first occurrence of ground water or just below the water table at 32 sites located in areas likely affected by agriculture. Four of the 32 sites were situated along a ground-water flow path with its downgradient end next to Maple Creek. Twenty-eight sites were installed immediately adjacent to agricultural fields throughout the glacial-till area. In addition to those 32 sites, two sites were installed in pastures to represent ground-water conditions in a non-cropland setting. Ground-water samples were analyzed for physical properties and concentrations of nitrogen and phosphorus compounds, selected pesticides and pesticide degradates, dissolved solids, major ions, trace elements, and dissolved organic carbon. Chlorofluorocarbons (CFCs) or sulfur hexafluoride (SF6) concentrations were analyzed at about 70 percent of the monitoring wells to estimate the residence time of ground water. Borehole-core samples were collected from 28 of the well boreholes. Sediment in the unsaturated zone was analyzed for nitrate, chloride, and ammonia concentrations. Analytical results indicated that the agricultural chemicals most often detected during this study were nitrates and herbicides. Nitrate as nitrogen (nitrate-N) concentrations (2003 median 9.53 milligrams per liter) indicated that human activity has affected the water quality of recently recharged ground water in approximately two-thirds of the wells near corn and soybean fields. The principal pesticide compounds that were detected reflect the most-used pesticides in the area and

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-12-14

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adaptive probabilistic collocation based Kalman filter for unsaturated flow problem

NASA Astrophysics Data System (ADS)

Man, J.; Li, W.; Zeng, L.; Wu, L.

2015-12-01

The ensemble Kalman filter (EnKF) has gained popularity in hydrological data assimilation problems. As a Monte Carlo based method, a relatively large ensemble size is usually required to guarantee the accuracy. As an alternative approach, the probabilistic collocation based Kalman filter (PCKF) employs the Polynomial Chaos to approximate the original system. In this way, the sampling error can be reduced. However, PCKF suffers from the so called "cure of dimensionality". When the system nonlinearity is strong and number of parameters is large, PCKF is even more computationally expensive than EnKF. Motivated by recent developments in uncertainty quantification, we propose a restart adaptive probabilistic collocation based Kalman filter (RAPCKF) for data assimilation in unsaturated flow problem. During the implementation of RAPCKF, the important parameters are identified and active PCE basis functions are adaptively selected. The "restart" technology is used to alleviate the inconsistency between model parameters and states. The performance of RAPCKF is tested by unsaturated flow numerical cases. It is shown that RAPCKF is more efficient than EnKF with the same computational cost. Compared with the traditional PCKF, the RAPCKF is more applicable in strongly nonlinear and high dimensional problems.

The effect of nitrification inhibitors on NH3 and N2O emissions in highly N fertilized irrigated Mediterranean cropping systems.

PubMed

Recio, Jaime; Vallejo, Antonio; Le-Noë, Julia; Garnier, Josette; García-Marco, Sonia; Álvarez, José Manuel; Sanz-Cobena, Alberto

2018-09-15

There is an increasing concern about the negative impacts associated to the release of reactive nitrogen (N) from highly fertilized agro-ecosystems. Ammonia (NH 3 ) and nitrous oxide (N 2 O) are harmful N pollutants that may contribute both directly and indirectly to global warming. Surface applied manure, urea and ammonium (NH 4 + ) based fertilizers are important anthropogenic sources of these emissions. Nitrification inhibitors (NIs) have been proposed as a useful technological approach to reduce N 2 O emission although they can lead to large NH 3 losses due to increasing NH 4 + pool in soils. In this context, a field experiment was carried out in a maize field with aiming to simultaneously quantify NH 3 volatilization and N 2 O emission, assessing the effect of two NIs 3,4‑dimethilpyrazol phosphate (DMPP) and 3,4‑dimethylpyrazole succinic acid (DMPSA). The first treatment was pig slurry (PS) before seeding (50 kg N ha -1 ) and calcium ammonium nitrate (CAN) at top-dressing (150 kg N ha -1 ), and the second was DMPP diluted in PS (PS + DMPP) (50 kg N ha -1 ) and CAN + DMPSA (150 kg N ha -1 ) also before seeding and at top-dressing, respectively. Ammonia emissions were quantified by a micrometeorological method during 20 days after fertilization and N 2 O emissions were assessed using manual static chambers during all crop period. The treatment with NIs was effective in reducing c. 30% cumulative N 2 O losses. However, considering only direct N 2 O emissions after second fertilization event, a significant reduction was not observed using CAN+DMPSA, probably because high WFPS of soil, driven by irrigation, favored denitrification. Cumulative NH 3 losses were not significantly affected by NIs. Indeed, NH 3 volatilization accounted 14% and 10% of N applied in PS + DMPP and PS plots, respectively and c. 2% of total N applied in CAN+DMPSA and CAN plots. Since important NH 3 losses still exist even although abating strategies

Friction and wear performance of some thermoplastic polymers and polymer composites against unsaturated polyester

NASA Astrophysics Data System (ADS)

Unal, H.; Mimaroglu, A.; Arda, T.

2006-09-01

Wear experiments have been carried out with a range of unfilled and filled engineering thermoplastic polymers sliding against a 15% glass fibre reinforced unsaturated polyester polymer under 20, 40 and 60 N loads and 0.5 m/s sliding speed. Pin materials used in this experimental investigation are polyamide 66 (PA 66), poly-ether-ether-ketone (PEEK) and aliphatic polyketone (APK), glass fibre reinforced polyamide 46 (PA 46 + 30% GFR), glass fibre reinforced polytetrafluoroethylene (PTFE + 17% GFR), glass fibre reinforced poly-ether-ether-ketone (PEEK + 20% GFR), glass fibre reinforced poly-phylene-sulfide (PPS + 30% GFR), polytetrafluoroethylene filled polyamide 66 (PA 66 + 10% PTFE) and bronze filled pofytetrafluoroethylene (PTFE + 25% bronze) engineering polymers. The disc material is a 15% glass fibre reinforced unsaturated polyester thermoset polymer produced by Bulk Moulding Compound (BMC). Sliding wear tests were carried out on a pin-on-disc apparatus under 0.5 m/s sliding speed and load values of 20, 40 and 60 N. The results showed that the highest specific wear rate is for PPS + 30% GFR with a value of 1 × 10 -11 m 2/N and the lowest wear rate is for PTFE + 17% GFR with a value of 9.41 × 10 -15 m 2/N. For the materials and test conditions of this investigation, apart from polyamide 66 and PA 46 + 30% GFR polymers, the coefficient of friction and specific wear rates are not significantly affected by the change in load value. For polyamide 66 and PA 46 + 30% GFR polymers the coefficient of friction and specific wear rates vary linearly with the variation in load values.

Unsaturated fatty acids protect trophoblast cells from saturated fatty acid-induced autophagy defects.

PubMed

Hong, Ye-Ji; Ahn, Hyo-Ju; Shin, Jongdae; Lee, Joon H; Kim, Jin-Hoi; Park, Hwan-Woo; Lee, Sung Ki

2018-02-01

Dysregulated serum fatty acids are associated with a lipotoxic placental environment, which contributes to increased pregnancy complications via altered trophoblast invasion. However, the role of saturated and unsaturated fatty acids in trophoblastic autophagy has yet to be explored. Here, we demonstrated that prolonged exposure of saturated fatty acids interferes with the invasiveness of human extravillous trophoblasts. Saturated fatty acids (but not unsaturated fatty acids) inhibited the fusion of autophagosomes and lysosomes, resulting in the formation of intracellular protein aggregates. Furthermore, when the trophoblast cells were exposed to saturated fatty acids, unsaturated fatty acids counteracted the effects of saturated fatty acids by increasing degradation of autophagic vacuoles. Saturated fatty acids reduced the levels of the matrix metalloproteinases (MMP)-2 and MMP-9, while unsaturated fatty acids maintained their levels. In conclusion, saturated fatty acids induced decreased trophoblast invasion, of which autophagy dysfunction plays a major role. Copyright © 2017 Elsevier B.V. All rights reserved.

Bioreduction of α,β-unsaturated ketones and aldehydes by non-conventional yeast (NCY) whole-cells.

PubMed

Goretti, Marta; Ponzoni, Chiara; Caselli, Elisa; Marchegiani, Elisabetta; Cramarossa, Maria Rita; Turchetti, Benedetta; Forti, Luca; Buzzini, Pietro

2011-03-01

The bioreduction of α,β-unsaturated ketones (ketoisophorone, 2-methyl- and 3-methyl-cyclopentenone) and aldehydes [(S)-(-)-perillaldehyde and α-methyl-cinnamaldehyde] by 23 "non-conventional" yeasts (NCYs) belonging to 21 species of the genera Candida, Cryptococcus, Debaryomyces, Hanseniaspora, Kazachstania, Kluyveromyces, Lindnera, Nakaseomyces, Vanderwaltozyma, and Wickerhamomyces was reported. The results highlight the potential of NCYs as whole-cell biocatalysts for selective biotransformation of electron-poor alkenes. A few NCYs exhibited extremely high (>90%) or even total ketoisophorone and 2-methyl-cyclopentenone bioconversion yields via asymmetric reduction of the conjugated CC bond catalyzed by enoate reductases. Catalytic efficiency declined after switching from ketones to aldehydes. High chemoselectivity due to low competing carbonyl reductases was also sometimes observed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Renewable unsaturated polyesters from muconic acid

DOE PAGES

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.; ...

2016-09-27

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a

Renewable unsaturated polyesters from muconic acid

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

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a

High Fat Diet-Induced Changes in Mouse Muscle Mitochondrial Phospholipids Do Not Impair Mitochondrial Respiration Despite Insulin Resistance

PubMed Central

Hulshof, Martijn F. M.; van den Berg, Sjoerd A. A.; Schaart, Gert; van Dijk, Ko Willems; Smit, Egbert; Mariman, Edwin C. M.

2011-01-01

Background Type 2 diabetes mellitus and muscle insulin resistance have been associated with reduced capacity of skeletal muscle mitochondria, possibly as a result of increased intake of dietary fat. Here, we examined the hypothesis that a prolonged high-fat diet consumption (HFD) increases the saturation of muscle mitochondrial membrane phospholipids causing impaired mitochondrial oxidative capacity and possibly insulin resistance. Methodology C57BL/6J mice were fed an 8-week or 20-week low fat diet (10 kcal%; LFD) or HFD (45 kcal%). Skeletal muscle mitochondria were isolated and fatty acid (FA) composition of skeletal muscle mitochondrial phospholipids was analyzed by thin-layer chromatography followed by GC. High-resolution respirometry was used to assess oxidation of pyruvate and fatty acids by mitochondria. Insulin sensitivity was estimated by HOMA-IR. Principal Findings At 8 weeks, mono-unsaturated FA (16∶1n7, 18∶1n7 and 18∶1n9) were decreased (−4.0%, p<0.001), whereas saturated FA (16∶0) were increased (+3.2%, p<0.001) in phospholipids of HFD vs. LFD mitochondria. Interestingly, 20 weeks of HFD descreased mono-unsaturated FA while n-6 poly-unsaturated FA (18∶2n6, 20∶4n6, 22∶5n6) showed a pronounced increase (+4.0%, p<0.001). Despite increased saturation of muscle mitochondrial phospholipids after the 8-week HFD, mitochondrial oxidation of both pyruvate and fatty acids were similar between LFD and HFD mice. After 20 weeks of HFD, the increase in n-6 poly-unsaturated FA was accompanied by enhanced maximal capacity of the electron transport chain (+49%, p = 0.002) and a tendency for increased ADP-stimulated respiration, but only when fuelled by a lipid-derived substrate. Insulin sensitivity in HFD mice was reduced at both 8 and 20 weeks. Conclusions/Interpretation Our findings do not support the concept that prolonged HF feeding leads to increased saturation of skeletal muscle mitochondrial phospholipids resulting in a decrease in

Unsaturation of Very-Long-Chain Ceramides Protects Plant from Hypoxia-Induced Damages by Modulating Ethylene Signaling in Arabidopsis

PubMed Central

Yu, Lu-Jun; Huang, Li; Chen, Liang; Wang, Feng-Zhu; Xia, Fan-Nv; Zhu, Tian-Ren; Wu, Jian-Xin; Yin, Jian; Liao, Bin; Shi, Jianxin; Zhang, Jian-Hua; Aharoni, Asaph; Yao, Nan; Shu, Wensheng; Xiao, Shi

2015-01-01

Lipid remodeling is crucial for hypoxic tolerance in animals, whilst little is known about the hypoxia-induced lipid dynamics in plants. Here we performed a mass spectrometry-based analysis to survey the lipid profiles of Arabidopsis rosettes under various hypoxic conditions. We observed that hypoxia caused a significant increase in total amounts of phosphatidylserine, phosphatidic acid and oxidized lipids, but a decrease in phosphatidylcholine (PC) and phosphatidylethanolamine (PE). Particularly, significant gains in the polyunsaturated species of PC, PE and phosphatidylinositol, and losses in their saturated and mono-unsaturated species were evident during hypoxia. Moreover, hypoxia led to a remarkable elevation of ceramides and hydroxyceramides. Disruption of ceramide synthases LOH1, LOH2 and LOH3 enhanced plant sensitivity to dark submergence, but displayed more resistance to submergence under light than wild type. Consistently, levels of unsaturated very-long-chain (VLC) ceramide species (22:1, 24:1 and 26:1) predominantly declined in the loh1, loh2 and loh3 mutants under dark submergence. In contrast, significant reduction of VLC ceramides in the loh1-1 loh3-1 knockdown double mutant and lacking of VLC unsaturated ceramides in the ads2 mutants impaired plant tolerance to both dark and light submergences. Evidence that C24:1-ceramide interacted with recombinant CTR1 protein and inhibited its kinase activity in vitro, enhanced ER-to-nucleus translocation of EIN2-GFP and stabilization of EIN3-GFP in vivo, suggests a role of ceramides in modulating CTR1-mediated ethylene signaling. The dark submergence-sensitive phenotypes of loh mutants were rescued by a ctr1-1 mutation. Thus, our findings demonstrate that unsaturation of VLC ceramides is a protective strategy for hypoxic tolerance in Arabidopsis. PMID:25822663

The Fe-C-O-H-N system at 6.3-7.8 GPa and 1200-1400 °C: implications for deep carbon and nitrogen cycles

NASA Astrophysics Data System (ADS)

Sokol, Alexander G.; Tomilenko, Anatoly A.; Bul'bak, Taras A.; Kruk, Alexey N.; Zaikin, Pavel A.; Sokol, Ivan A.; Seryotkin, Yurii V.; Palyanov, Yury N.

2018-06-01

Interactions in a Fe-C-O-H-N system that controls the mobility of siderophile nitrogen and carbon in the Fe0-saturated upper mantle are investigated in experiments at 6.3-7.8 GPa and 1200-1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe3C with an N-rich fluid in a graphite-saturated system produce the ɛ-Fe3N phase (space group P63/ mmc or P6322) at subsolidus conditions of 1200-1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity ( fH2), fluids vary from NH3- to H2O-rich compositions (NH3/N2 > 1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H2O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH2 and carboxylic acids at unbuffered fH2 conditions. In unbuffered conditions, N2 is the principal nitrogen host (NH3/N2 ≤ 0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe3N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.

Ordered Nanostructured Amphiphile Self-Assembly Materials from Endogenous Nonionic Unsaturated Monoethanolamide Lipids in Water

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

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

2010-08-23

The self-assembly, solid state and lyotropic liquid crystalline phase behavior of a series of endogenous n-acylethanolamides (NAEs) with differing degrees of unsaturation, viz., oleoyl monoethanolamide, linoleoyl monoethanolamide, and linolenoyl monoethanolamide, have been examined. The studied molecules are known to possess inherent biological function. Both the monoethanolamide headgroup and the unsaturated hydrophobe are found to be important in dictating the self-assembly behavior of these molecules. In addition, all three molecules form lyotropic liquid crystalline phases in water, including the inverse bicontinuous cubic diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) phases. The ability of the NAE's to form inverse cubicmore » phases and to be dispersed into ordered nanostructured colloidal particles, cubosomes, in excess water, combined with their endogenous nature and natural medicinal properties, makes this new class of soft mesoporous amphiphile self-assembly materials suitable candidates for investigation in a variety of advanced multifunctional applications, including encapsulation and controlled release of therapeutic agents and incorporation of medical imaging agents.« less

Saturated-unsaturated flow to a partially penetrating well with storage in a compressible aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2010-12-01

Mishra and Neuman [2010] developed an analytical solution for flow to a partially penetrating well of zero radius in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from responses recorded in the saturated and/or the unsaturated zone. We extend their solution to the case of a finite diameter pumping well with storage. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of storage in the pumping well and delayed piezometer response on drawdowns in the saturated and unsaturated zones as functions of position and time; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten - Mualem constitutive model; and use our solution to analyze drawdown data from a pumping test conducted at the Borden site in Ontario, Canada.

Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation.

PubMed

Brouyère, Serge; Dassargues, Alain; Hallet, Vincent

2004-08-01

This paper presents the results of a detailed field investigation that was performed for studying groundwater recharge processes and solute downward migration mechanisms prevailing in the unsaturated zone overlying a chalk aquifer in Belgium. Various laboratory measurements were performed on core samples collected during the drilling of boreholes in the experimental site. In the field, experiments consisted of well logging, infiltration tests in the unsaturated zone, pumping tests in the saturated zone and tracer tests in both the saturated and unsaturated zones. Results show that gravitational flows govern groundwater recharge and solute migration mechanisms in the unsaturated zone. In the variably saturated chalk, the migration and retardation of solutes is strongly influenced by recharge conditions. Under intense injection conditions, solutes migrate at high speed along the partially saturated fissures, downward to the saturated zone. At the same time, they are temporarily retarded in the almost immobile water located in the chalk matrix. Under normal recharge conditions, fissures are inactive and solutes migrate slowly through the chalk matrix. Results also show that concentration dynamics in the saturated zone are related to fluctuations of groundwater levels in the aquifer. A conceptual model is proposed to explain the hydrodispersive behaviour of the variably saturated chalk. Finally, the vulnerability of the chalk to contamination issues occurring at the land surface is discussed.

Stimulation by unsaturated fatty acid of squalene uptake in rat liver microsomes.

PubMed

Chin, J; Bloch, K

1985-07-01

Supernatant protein factor (SPF) and anionic phospholipids such as phosphatidylglycerol (PG) stimulate squalene epoxidase activity in rat liver microsomes by promoting [3H]squalene uptake as well as substrate translocation (Chin, J., and K. Bloch. 1984. J. Biol. Chem. 259: 11735-11738). This process is postulated to be membrane-mediated and not carrier-mediated. Here we show that treatment of PG with phospholipase A2 in the presence of bovine serum albumin abolishes the stimulatory effect of SPF on epoxidase activity. Disaturated fatty acyl-PGs are not as effective as egg yolk lecithin PG in the SPF effect. These findings suggest an important role for the unsaturated fatty acid moiety of PG. We also show that at submicellar concentrations, cis-unsaturated fatty acids stimulate microsomal epoxidase activity whereas saturated fatty acids do not. This effect is due to an increase in substrate uptake which in turn may facilitate substrate availability to the enzyme.

n-Aldehydes (C6-C10) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

NASA Astrophysics Data System (ADS)

Sieg, K.; Starokozhev, E.; Fries, E.; Sala, S.; Püttmann, W.

2009-04-01

C6-C10 n-aldehydes were analyzed in samples of freshly fallen snow collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace - solid phase dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify n-aldehydes in melted snow samples. n-Hexanal was identified as the most abundant n-aldehyde (median concentration 1.324 µg L-1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460 and 0.304 µg L-1, respectively). A wide range of concentrations of n-aldehydes was found in snow samples from Jungfraujoch, even for samples collected at the same time during the same snowfall event. According to their physical and chemical characteristics, n-aldehydes are expected to be primarily linked to aerosol particles in the atmosphere suggesting the uptake of n-aldehydes into snow via the particle phase. Particle scavenging can occur during snow formation in clouds. The high concentration variations of the n-aldehydes among the snow samples can be explained assuming that aerosol particles, which are loaded with n-aldehydes, are heterogeneously distributed throughout the snow samples. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. The sources of atmospheric n-aldehydes present at Jungfraujoch are most likely to be related to direct and indirect biogenic emissions. The presence of n-aldehydes as semivolatile constituents of direct biogenic emissions from vegetation has been reported previously in studies of Ciccioli et al. [1], Yokouchi et al. [2] and Kesselmeier and Staudt [3]. The distribution pattern of the n-aldehydes in emissions from vegetation largely matches with the n

Fingering and Intermittent Flow in Unsaturated Fractured Porous Media

NASA Astrophysics Data System (ADS)

Or, D.; Ghezzehei, T. A.

2003-12-01

Because of the dominance of gravitational forces over capillary and viscous forces in relatively large fracture apertures, flow processes in unsaturated fractures are considerably different from flow in rock matrix or in unsaturated soils. Additionally, variations in fracture geometry and properties perturb the delicate balance between gravitational, capillary, and viscous forces, leading to liquid fragmentation, fingering and intermittent flows. We developed a quantitative framework for modeling fluid fragmentation and the subsequent flow behavior of discrete fluid elements (slugs). The transition from a slowly growing but stationary liquid cluster to a finger-forming mobile slug in a non horizontal fracture is estimated from the force balance between retarding capillary forces dominated by contact angle hysteresis, and the weight and shape of the cluster. For a steady flux we developed a model for liquid fragmentation within the fracture plane that gives rise to intermittent discharge, as has been observed experimentally. Intermittency is shown to be a result of interplay between capillary, viscous, and gravitational forces, much like internal dripping. Liquid slug size, detachment interval, and travel velocity are dependent primarily on the local fracture-aperture geometry shaping the seed cluster, rock-surface roughness and wetness, and liquid flux feeding the bridge (either by film flow or from the rock matrix). We show that the presence of even a few irregularities in a vertical fracture surface could affect liquid cluster formation and growth, resulting in complicated flux patterns at the fracture bottom. Such chaotic-like behavior has been observed in previous studies involving gravity-driven unsaturated flow. Inferences based on statistical description of fracture-aperture variations and simplified representation of the fragmentation processes yield insights regarding magnitude and frequency of liquid avalanches. The study illustrates that attempts at

Chemical Kinetic Influences of Alkyl Chain Structure on the High Pressure and Temperature Oxidation of a Representative Unsaturated Biodiesel: Methyl Nonenoate.

PubMed

Fridlyand, Aleksandr; Goldsborough, S Scott; Brezinsky, Kenneth

2015-07-16

The high pressure and temperature oxidation of methyl trans-2-nonenoate, methyl trans-3-nonenoate, 1-octene, and trans-2-octene are investigated experimentally to probe the influence of the double bond position on the chemical kinetics of long esters and alkenes. Single pulse shock tube experiments are performed in the ranges p = 3.8-6.2 MPa and T = 850-1500 K, with an average reaction time of 2 ms. Gas chromatographic measurements indicate increased reactivity for trans-2-octene compared to 1-octene, whereas both methyl nonenoate isomers have reactivities similar to that of 1-octene. A difference in the yield of stable intermediates is observed for the octenes when compared to the methyl nonenoates. Chemical kinetic models are developed with the aid of the Reaction Mechanism Generator to interpret the experimental results. The models are created using two different base chemistry submodels to investigate the influence of the foundational chemistry (i.e., C0-C4), whereas Monte Carlo simulations are performed to examine the quality of agreement with the experimental results. Significant uncertainties are found in the chemistry of unsaturated esters with the double bonds located close to the ester groups. This work highlights the importance of the foundational chemistry in predictive chemical kinetics of biodiesel combustion at engine relevant conditions.

Data from a thick unsaturated zone in Joshua Tree, San Bernardino County, California, 2007--09

USGS Publications Warehouse

Burgess, Matthew; Izbicki, John; Teague, Nicholas; O'Leary, David R.; Clark, Dennis; Land, Michael

2012-01-01

Data were collected on the physical properties of unsaturated alluvial deposits, the chemical composition of leachate extracted from unsaturated alluvial deposits, the chemical and isotopic composition of groundwater and unsaturated-zone water, and the chemical composition of unsaturated-zone gas at four monitoring sites in the southwestern part of the Mojave Desert in the town of Joshua Tree, San Bernardino County, California. The presence of denitrifying and nitrate-reducing bacteria from unsaturated alluvial deposits was evaluated for two of these monitoring sites that underlie unsewered residential development. Four unsaturated-zone monitoring sites were installed in the Joshua Tree area—two in an unsewered residential development and two adjacent to a proposed artificial-recharge site in an undeveloped area. The two boreholes in residential development areas were installed by using the ODEX air-hammer method. One borehole was drilled through the unsaturated zone to a depth of 541 ft (feet) below land surface; a well screened across the water table was installed. Groundwater was sampled from this well. The second borehole was drilled to a depth of 81 ft below land surface. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described. Core material was analyzed for water content, bulk density, matric potential, particle size, and water retention. The leachate from over 500 subsamples of cores and cuttings was analyzed for soluble anions, including fluoride, sulfate, bromide, chloride, nitrate, nitrite, and orthophosphate. Groundwater was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone water from suction-cup lysimeters was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone gas samples were analyzed for argon, oxygen, nitrogen, methane, carbon dioxide, ethane

Improved solution for saturated-unsaturated flow to a partially penetrating well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2009-12-01

Tartakovsky and Neuman [2007] developed an analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering an unsaturated zone of infinite thickness. In their solution three-dimensional, axially symmetric unsaturated flow was described by a linearized version of Richards’ equation in which both relative hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value. Both exponential functions were characterized by a common exponent. We present an improved solution in which relative hydraulic conductivity and water content are characterized by separate parameters and the unsaturated zone has finite thickness. Our four-parameter representation of these functions is more flexible than the three-parameter version of Mathias and Butler [2006], who consider flow in the unsaturated zone to be strictly vertical and the pumping well to be fully penetrating. We investigate the effects of unsaturated zone thickness and constitutive parameters on drawdown in the unsaturated and saturated zones as functions of position and time. We then use our new solution to analyze data from synthetic and real pumping tests.

Combined effects of endurance training and dietary unsaturated fatty acids on physical performance, fat oxidation and insulin sensitivity.

PubMed

Boss, Andreas; Lecoultre, Virgile; Ruffieux, Christiane; Tappy, Luc; Schneiter, Philippe

2010-04-01

Endurance training improves exercise performance and insulin sensitivity, and these effects may be in part mediated by an enhanced fat oxidation. Since n-3 and n-9 unsaturated fatty acids may also increase fat oxidation, we hypothesised that a diet enriched in these fatty acids may enhance the effects of endurance training on exercise performance, insulin sensitivity and fat oxidation. To assess this hypothesis, sixteen normal-weight sedentary male subjects were randomly assigned to an isoenergetic diet enriched with fish and olive oils (unsaturated fatty acid group (UFA): 52 % carbohydrates, 34 % fat (12 % SFA, 12 % MUFA, 5 % PUFA), 14 % protein), or a control diet (control group (CON): 62 % carbohydrates, 24 % fat (12 % SFA, 6 % MUFA, 2 % PUFA), 14 % protein) and underwent a 10 d gradual endurance training protocol. Exercise performance was evaluated by measuring VO2max and the time to exhaustion during a cycling exercise at 80 % VO2max; glucose homeostasis was assessed after ingestion of a test meal. Fat oxidation was assessed by indirect calorimetry at rest and during an exercise at 50 % VO2max. Training significantly increased time to exhaustion, but not VO2max, and lowered incremental insulin area under the curve after the test meal, indicating improved insulin sensitivity. Those effects were, however, of similar magnitude in UFA and CON. Fat oxidation tended to increase in UFA, but not in CON. This difference was, however, not significant. It is concluded that a diet enriched with fish- and olive oil does not substantially enhance the effects of a short-term endurance training protocol in healthy young subjects.

Volatile organic compounds in the unsaturated zone from radioactive wastes

USGS Publications Warehouse

Baker, Ronald J.; Andraski, Brian J.; Stonestrom, David A.; Luo, Wentai

2012-01-01

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0–2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m-2 yr-1. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.

Nickel-catalyzed cycloadditions of unsaturated hydrocarbons, aldehydes, and ketones.

PubMed

Tekavec, Thomas N; Louie, Janis

2008-04-04

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon-carbon bond is formed, prior to a competitive beta-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No beta-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C-O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon-carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr).

Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones

PubMed Central

Tekavec, Thomas N.

2014-01-01

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3, 3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon–carbon bond is formed, prior to a competitive β-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No β-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C–O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon–carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr). PMID:18318544

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

NASA Astrophysics Data System (ADS)

Adamson, Aiko; Kaljurand, Ivari; Guillemin, Jean-Claude; Burk, Peeter

2016-09-01

The typical Gibbs free energy difference between hydrocarbon substituted isocyanides and the corresponding cyanides is 25 to 28 kcal/mol in favor of the cyanides and is mostly independent of the substituent. Triple bonded species with a -C ≡ C-RN,C (RN,C = CN, NC) structure can be considered as exceptions. Because isocyanide and cyanide species have very similar structures, the relative energy is independent of the pressure and temperature conditions. Theoretical and experimental gas-phase investigations show that basicity of isocyanides ranges from 182.1 to 198.2 kcal/mol which is 14.0 to 19.7 kcal/mol higher than the basicity of respective cyanides. The most favored protonation centers are located on isocyanide or cyanide group depending on the species. The biggest increase of basicity was caused by bulkier substituents. The substitutions have greater influence on the basicity of cyanides than on the basicity of isocyanides. In regard to deprotonation, the cyanides are more acidic than the corresponding isocyanides. For most of the unsaturated cyanide and isocyanide species the (N,C)-CHR' hydrogen (the one connected to the carbon next to cyanide/isocyanide group) is the most acidic. Our work suggests that for derivatives bearing unsaturated substituent the favored deprotonation center may be different and some cyanides and isocyanides are unstable towards gas-phase deprotonation equilibrium as the formed anion tends to isomerize.

Ultra-low loss Si3N4 waveguides with low nonlinearity and high power handling capability.

PubMed

Tien, Ming-Chun; Bauters, Jared F; Heck, Martijn J R; Blumenthal, Daniel J; Bowers, John E

2010-11-08

We investigate the nonlinearity of ultra-low loss Si3N4-core and SiO2-cladding rectangular waveguides. The nonlinearity is modeled using Maxwell's wave equation with a small amount of refractive index perturbation. Effective n2 is used to describe the third-order nonlinearity, which is linearly proportional to the optical intensity. The effective n2 measured using continuous-wave self-phase modulation shows agreement with the theoretical calculation. The waveguide with 2.8-μm wide and 80-nm thick Si3N4 core has low loss and high power handling capability, with an effective n2 of about 9×10(-16) cm2/W.

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2011 CFR

2011-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2014 CFR

2014-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

40 CFR 264.278 - Unsaturated zone monitoring.

Code of Federal Regulations, 2010 CFR

2010-07-01

... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not been...

Anacardic Acid Constituents from Cashew Nut Shell Liquid: NMR Characterization and the Effect of Unsaturation on Its Biological Activities

PubMed Central

Morais, Selene M.; Silva, Katherine A.; Araujo, Halisson; Vieira, Icaro G.P.; Alves, Daniela R.; Fontenelle, Raquel O.S.; Silva, Artur M.S.

2017-01-01

Anacardic acids are the main constituents of natural cashew nut shell liquid (CNSL), obtained via the extraction of cashew shells with hexane at room temperature. This raw material presents high technological potential due to its various biological properties. The main components of CNSL are the anacardic acids, salicylic acid derivatives presenting a side chain of fifteen carbon atoms with different degrees of unsaturation (monoene–15:1, diene–15:2, and triene–15:3). Each constituent was isolated by column chromatography using silica gel impregnated with silver nitrate. The structures of the compounds were characterized by nuclear magnetic resonance through complete and unequivocal proton and carbon assignments. The effect of the side chain unsaturation was also evaluated in relation to antioxidant, antifungal and anticholinesterase activities, and toxicity against Artemia salina. The triene anacardic acid provided better results in antioxidant activity assessed by the inhibition of the free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH), higher cytotoxicity against A. salina, and acetylcholinesterase (AChE) inhibition. Thus, increasing the unsaturation of the side chain of anacardic acid increases its action against free radicals, AChE enzyme, and A. salina nauplii. In relation to antifungal activity, an inverse result was obtained, and the linearity of the molecule plays an important role, with monoene being the most active. In conclusion, the changes in structure of anacardic acids, which cause differences in polarity, contribute to the increase or decrease in the biological activity assessed. PMID:28300791

Coupled hydromechanical and electromagnetic disturbances in unsaturated porous materials

NASA Astrophysics Data System (ADS)

Revil, A.; Mahardika, H.

2013-02-01

A theory of cross-coupled flow equations in unsaturated soils is necessary to predict (1) electroosmotic flow with application to electroremediation and agriculture, (2) the electroseismic and the seismoelectric effects to develop new geophysical methods to characterize the vadose zone, and (3) the streaming current, which can be used to investigate remotely ground water flow in unsaturated conditions in the capillary water regime. To develop such a theory, the cross-coupled generalized Darcy and Ohm constitutive equations of transport are extended to unsaturated conditions. This model accounts for inertial effects and for the polarization of porous materials. Rather than using the zeta potential, like in conventional theories for the saturated case, the key parameter used here is the quasi-static volumetric charge density of the pore space, which can be directly computed from the quasi-static permeability. The apparent permeability entering Darcy's law is also frequency dependent with a critical relaxation time that is, in turn, dependent on saturation. A decrease of saturation increases the associated relaxation frequency. The final form of the equations couples the Maxwell equations and a simplified form of two-fluid phases Biot theory accounting for water saturation. A generalized expression of the Richard equation is derived, accounting for the effect of the vibration of the skeleton during the passage of seismic waves and the electrical field. A new expression is obtained for the effective stress tensor. The model is tested against experimental data regarding the saturation and frequency dependence of the streaming potential coupling coefficient. The model is also adapted for two-phase flow conditions and a numerical application is shown for water flooding of a nonaqueous phase liquid (NAPL, oil) contaminated aquifer. Seismoelectric conversions are mostly taking place at the NAPL (oil)/water encroachment front and can be therefore used to remotely track the

Coupled hydromechanical and electromagnetic disturbances in unsaturated porous materials

PubMed Central

Revil, A; Mahardika, H

2013-01-01

A theory of cross-coupled flow equations in unsaturated soils is necessary to predict (1) electroosmotic flow with application to electroremediation and agriculture, (2) the electroseismic and the seismoelectric effects to develop new geophysical methods to characterize the vadose zone, and (3) the streaming current, which can be used to investigate remotely ground water flow in unsaturated conditions in the capillary water regime. To develop such a theory, the cross-coupled generalized Darcy and Ohm constitutive equations of transport are extended to unsaturated conditions. This model accounts for inertial effects and for the polarization of porous materials. Rather than using the zeta potential, like in conventional theories for the saturated case, the key parameter used here is the quasi-static volumetric charge density of the pore space, which can be directly computed from the quasi-static permeability. The apparent permeability entering Darcy's law is also frequency dependent with a critical relaxation time that is, in turn, dependent on saturation. A decrease of saturation increases the associated relaxation frequency. The final form of the equations couples the Maxwell equations and a simplified form of two-fluid phases Biot theory accounting for water saturation. A generalized expression of the Richard equation is derived, accounting for the effect of the vibration of the skeleton during the passage of seismic waves and the electrical field. A new expression is obtained for the effective stress tensor. The model is tested against experimental data regarding the saturation and frequency dependence of the streaming potential coupling coefficient. The model is also adapted for two-phase flow conditions and a numerical application is shown for water flooding of a nonaqueous phase liquid (NAPL, oil) contaminated aquifer. Seismoelectric conversions are mostly taking place at the NAPL (oil)/water encroachment front and can be therefore used to remotely track the

TiAlN/TiAlON/Si{sub 3}N{sub 4} tandem absorber for high temperature solar selective applications

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

Barshilia, Harish C.; Selvakumar, N.; Rajam, K. S.

2006-11-06

A tandem absorber of TiAlN/TiAlON/Si{sub 3}N{sub 4} is prepared using a magnetron sputtering process. The graded composition of the individual component layers of the tandem absorber produces a film with a refractive index increasing from the surface to the substrate, which exhibits a high absorptance (0.95) and a low emittance (0.07). The tandem absorber is stable in air up to 600 deg. C for 2 h, indicating its importance for high temperature solar selective applications. The thermal stability of the tandem absorber is attributed to high oxidation resistance and microstructural stability of the component materials at higher temperatures.

DASH-like diets high in protein or monounsaturated fats improve metabolic syndrome and calculated vascular risk.

PubMed

Root, Martin M; Dawson, Hannah R

2013-01-01

Weight-loss diets with varying proportions of macronutrients have had varying effects on weight loss, and components of metabolic syndrome and risk factors for vascular diseases. However, little work has examined the effect of weight-neutral dietary changes in macronutrients on these factors. This is an investigation using the OMNI Heart datasets available from the NHLBI BioLINCC program. This study compared a DASH-like diet high in carbohydrates with similar diets high in protein and high in unsaturated fats. Measures of metabolic syndrome, except waist, and measures of risk factors for vascular diseases were taken at the end of each dietary period. All 3 diets significantly lowered the number of metabolic syndrome components (p ≤ 0.002) with a standardized measure of changes in metabolic syndrome components, suggesting that the high-protein, high-fat diet was most efficacious overall (p = 0.035). All 3 diets lowered a calculated 10-year risk of cardiovascular disease, with the high-protein and unsaturated fat diet being the most efficacious (p < 0.001). Only the unsaturated fat diet showed a slightly decreased calculated 9-year risk of diabetes (p = 0.11). Of the 3 weight-neutral diets, those high in protein and unsaturated fats appeared partially or wholly most beneficial.

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

PubMed Central

Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

2014-01-01

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

Asymmetric epoxidation of unsaturated ketones catalyzed by heterobimetallic rare earth-lithium complexes bearing phenoxy-functionalized chiral diphenylprolinolate ligand.

PubMed

Qian, Qinqin; Tan, Yufang; Zhao, Bei; Feng, Tao; Shen, Qi; Yao, Yingming

2014-09-05

Four novel heterobimetallic complexes [REL2]{[(THF)3Li]2(μ-Cl)} stabilized by chiral phenoxy-functionalized prolinolate (RE = Yb (1), Y (2), Sm (3), Nd (4), H2L = (S)-2,4-di-tert-butyl-6-[[2-(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol have been synthesized and characterized. These readily available complexes are highly active in catalyzing the epoxidation of α,β-unsaturated ketones, while the enantioselectivity varies according to the ionic radii of the rare earth center. A series of chalcone derivatives were converted to chiral epoxides in 80 → 99% ee at 0 °C using TBHP as the oxidant in the presence of 10 mol % of 1.

Documentation of the Streamflow-Routing (SFR2) Package to Include Unsaturated Flow Beneath Streams - A Modification to SFR1

USGS Publications Warehouse

Niswonger, Richard G.; Prudic, David E.

2005-01-01

Many streams in the United States, especially those in semiarid regions, have reaches that are hydraulically disconnected from underlying aquifers. Ground-water withdrawals have decreased water levels in valley aquifers beneath streams, increasing the occurrence of disconnected streams and aquifers. The U.S. Geological Survey modular ground-water model (MODFLOW-2000) can be used to model these interactions using the Streamflow-Routing (SFR1) Package. However, the approach does not consider unsaturated flow between streams and aquifers and may not give realistic results in areas with significantly deep unsaturated zones. This documentation describes a method for extending the capabilities of MODFLOW-2000 by incorporating the ability to simulate unsaturated flow beneath streams. A kinematic-wave approximation to Richards' equation was solved by the method of characteristics to simulate unsaturated flow beneath streams in SFR1. This new package, called SFR2, includes all the capabilities of SFR1 and is designed to be used with MODFLOW-2000. Unlike SFR1, seepage loss from the stream may be restricted by the hydraulic conductivity of the unsaturated zone. Unsaturated flow is simulated independently of saturated flow within each model cell corresponding to a stream reach whenever the water table (head in MODFLOW) is below the elevation of the streambed. The relation between unsaturated hydraulic conductivity and water content is defined by the Brooks-Corey function. Unsaturated flow variables specified in SFR2 include saturated and initial water contents; saturated vertical hydraulic conductivity; and the Brooks-Corey exponent. These variables are defined independently for each stream reach. Unsaturated flow in SFR2 was compared to the U.S. Geological Survey's Variably Saturated Two-Dimensional Flow and Transport (VS2DT) Model for two test simulations. For both test simulations, results of the two models were in good agreement with respect to the magnitude and downward

Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

PubMed Central

Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

2009-01-01

A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

Effect of unsaturations on the physical properties of a model membrane with the highly polyunsaturated docosahexaenoic fatty acid

NASA Astrophysics Data System (ADS)

Saiz, Leonor; Klein, Michael L.

2001-03-01

Polyunsaturated fatty acids are an essential component of biomembranes. The docosahexaenoic fatty acid (DHA), in particular, is found in high concentrations in retinal and neuronal tissue and in the olfactory bulb. Furthermore, it is well known the ability of DHA rich membranes to modulate membrane protein function, in some situations, by modifying the membrane physical properties. A particularly well studied situation is the DHA effect onthe activity of the visual receptor (protein) rhodopsin. Here, we study at a microscopic level this type of complex systems under physiological conditions. In this way, we can probe the molecular origin of the peculiarities that the system confers to membranes. To this purpose, the structure of a fully hydrated mixed (saturated/polyunsaturated) chain lipid bilayer in the biologically relevant liquid crystalline phase has been examined by performing molecular dynamics simulations. The model membrane, a 1-stearoyl- 2-docosahexaenoic- sn-glycero- 3-phosphatidylcholine (18:0/22:6 PC) lipid bilayer, was investigated at room temperature and ambient pressure and the results obtained in the nanosecond time scale were in good agreement with the available experimental data. Among the effects of the multiple unsaturations on the physical properties of these membranes, we focus on the enhanced permeability to water and small organic solvents, the decreased area compressibility modulus, and the domain formation and chain segregation.

A Similarity Theory for Unsaturated Downdrafts within Clouds.

NASA Astrophysics Data System (ADS)

Emanuel, Kerry A.

1981-08-01

Recent observations of cumulus clouds strongly support the hypothesis of Squires (1958) that much of the mixing within such clouds is associated with downward propagating currents initiated near their tops. A similarity theory is here proposed to describe the properties of such currents; the use of similarity is defended on the basis of the observed and predicted scale of the downdrafts. The theory suggests that downward-propagating unsaturated thermals are pervasive throughout all but the largest convective clouds and that quasi-steady unsaturated downdraft plumes may exist in the lower portions of cumulonimbi. In addition to providing a reasonable explanation for the microstructure of and liquid water distribution within cumulus clouds, the theory appears to account for certain severe convective phenomena, including down-bursts. A new but related cloud instability is proposed to account for the occurrence of mamma.

Unsaturated fatty acyl recognition by Frizzled receptors mediates dimerization upon Wnt ligand binding

PubMed Central

Nile, Aaron H.; Mukund, Susmith; Stanger, Karen; Wang, Weiru; Hannoush, Rami N.

2017-01-01

Frizzled (FZD) receptors mediate Wnt signaling in diverse processes ranging from bone growth to stem cell activity. Moreover, high FZD receptor expression at the cell surface contributes to overactive Wnt signaling in subsets of pancreatic, ovarian, gastric, and colorectal tumors. Despite the progress in biochemical understanding of Wnt–FZD receptor interactions, the molecular basis for recognition of Wnt cis-unsaturated fatty acyl groups by the cysteine-rich domain (CRD) of FZD receptors remains elusive. Here, we determined a crystal structure of human FZD7 CRD unexpectedly bound to a 24-carbon fatty acid. We also report a crystal structure of human FZD5 CRD bound to C16:1 cis-Δ9 unsaturated fatty acid. Both structures reveal a dimeric arrangement of the CRD. The lipid-binding groove exhibits flexibility and spans both monomers, adopting a U-shaped geometry that accommodates the fatty acid. Re-evaluation of the published mouse FZD8 CRD structure reveals that it also shares the same architecture as FZD5 and FZD7 CRDs. Our results define a common molecular mechanism for recognition of the cis-unsaturated fatty acyl group, a necessary posttranslational modification of Wnts, by multiple FZD receptors. The fatty acid bridges two CRD monomers, implying that Wnt binding mediates FZD receptor dimerization. Our data uncover possibilities for the arrangement of Wnt–FZD CRD complexes and shed structural insights that could aide in the identification of pharmacological strategies to modulate FZD receptor function. PMID:28377511

High-performance enhancement-mode Al2O3/InAlGaN/GaN MOS high-electron mobility transistors with a self-aligned gate recessing technology

NASA Astrophysics Data System (ADS)

Zhang, Kai; Kong, Cen; Zhou, Jianjun; Kong, Yuechan; Chen, Tangsheng

2017-02-01

The paper reports high-performance enhancement-mode MOS high-electron mobility transistors (MOS-HEMTs) based on a quaternary InAlGaN barrier. Self-aligned gate technology is used for gate recessing, dielectric deposition, and gate electrode formation. An improved digital recessing process is developed, and an Al2O3 gate dielectric grown with O2 plasma is used. Compared to results with AlGaN barrier, the fabricated E-mode MOS-HEMT with InAlGaN barrier delivers a record output current density of 1.7 A/mm with a threshold voltage (V TH) of 1.5 V, and a small on-resistance (R on) of 2.0 Ω·mm. Excellent V TH hysteresis and greatly improved gate leakage characteristics are also demonstrated.

Hall effect measurements of high-quality M n3CuN thin films and the electronic structure

NASA Astrophysics Data System (ADS)

Matsumoto, Toshiki; Hatano, Takafumi; Urata, Takahiro; Iida, Kazumasa; Takenaka, Koshi; Ikuta, Hiroshi

2017-11-01

The physical properties of M n3CuN were studied using thin films. We found that an annealing process was very effective to improve the film quality, the key of which was the use of Ti that prevented the formation of oxide impurities. Using these high-quality thin films, we found strong strain dependence for the ferromagnetic transition temperature (TC) and a sign change of the Hall coefficient at TC. The analysis of Hall coefficient data revealed a sizable decrease of hole concentration and a large increase of electron mobility below TC, which is discussed in relation to the electronic structure of this material.

Stabilizing benzene-like planar N6 rings to form a single atomic honeycomb BeN3 sheet with high carrier mobility.

PubMed

Li, Xiaoyin; Zhang, Shunhong; Zhang, Cunzhi; Wang, Qian

2018-01-18

It is a longstanding quest to use the planar N 6 ring as a structural unit to build stable atomic sheets. However, unlike C 6 H 6 , the neutral N 6 ring is unstable due to the strong repulsion of the lone-pair of electrons. Using first-principles calculations and the global structure search method, we show that the N 6 unit can be stabilized by the linkage of Be atoms, forming a h-BeN 3 honeycomb monolayer, in which the geometry and the π-molecular orbitals of the N 6 rings are well kept. This sheet is not only energetically, dynamically and thermally stable, but also can withstand high temperatures up to 1000 K. Band structure calculation combined with a group theory analysis and a tight-binding model uncover that h-BeN 3 has a π-band dominated band structure with an indirect band gap of 1.67 eV. While it possesses a direct band gap of 2.07 eV at the Γ point lying in the photon energy region of visual light, its interband dipole transition is symmetrically allowed so that electrons can be excited by photons free of phonons. Based on deformation potential theory, a systematic study of the transport properties reveals that the h-BeN 3 sheet possesses a high carrier mobility of ∼10 3 cm 2 V -1 s -1 , superior to the extensively studied transition metal dichalcogenide monolayers. We further demonstrate that this sheet can be rolled up into either zigzag or armchair nanotubes. These nanotubes are also dynamically stable, and are all direct band gap semiconductors with carrier mobility comparable to that of their 2D counterparts, regardless of their chirality and diameter. The robust stability and novel electronic and transport properties of the h-BeN 3 sheet and its tubular derivatives endow them with great potential for applications in nanoelectronic devices.

Optimality and Conductivity for Water Flow: From Landscapes, to Unsaturated Soils, to Plant Leaves

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

Liu, H.H.

2012-02-23

Optimality principles have been widely used in many areas. Based on an optimality principle that any flow field will tend toward a minimum in the energy dissipation rate, this work shows that there exists a unified form of conductivity relationship for three different flow systems: landscapes, unsaturated soils and plant leaves. The conductivity, the ratio of water flux to energy gradient, is a power function of water flux although the power value is system dependent. This relationship indicates that to minimize energy dissipation rate for a whole system, water flow has a small resistance (or a large conductivity) at amore » location of large water flux. Empirical evidence supports validity of the relationship for landscape and unsaturated soils (under gravity dominated conditions). Numerical simulation results also show that the relationship can capture the key features of hydraulic structure for a plant leaf, although more studies are needed to further confirm its validity. Especially, it is of interest that according to this relationship, hydraulic conductivity for gravity-dominated unsaturated flow, unlike that defined in the classic theories, depends on not only capillary pressure (or saturation), but also the water flux. Use of the optimality principle allows for determining useful results that are applicable to a broad range of areas involving highly non-linear processes and may not be possible to obtain from classic theories describing water flow processes.« less

BIODEGRADATION OF HYDROCARBON VAPORS IN THE UNSATURATED ZONE

EPA Science Inventory

The time-averaged concentration of hydrocarbon and oxygen vapors were measured in the unsaturated zone above the residually contaminated capillary fringe at the U.S. Coast Guard Air Station in Traverse City, Michigan. Total hydrocarbon and oxygen vapor concentrations were observe...

Synthesis, antimycobacterial and cytotoxic activity of α,β-unsaturated amides and 2,4-disubstituted oxazoline derivatives.

PubMed

Avalos-Alanís, Francisco G; Hernández-Fernández, Eugenio; Carranza-Rosales, Pilar; López-Cortina, Susana; Hernández-Fernández, Jorge; Ordóñez, Mario; Guzmán-Delgado, Nancy E; Morales-Vargas, Alejandro; Velázquez-Moreno, Víctor M; Santiago-Mauricio, María G

2017-02-15

The synthesis of six α,β,-unsaturated amides and six 2,4-disubstituted oxazolines derivatives and their evaluation against two Mycobacterium tuberculosis strains (sensitive H37Rv and a resistant clinical isolate) is reported. 2,4-Disubstituted oxazolines (S)-3b,d,e were the most active in the sensitive strain with a MIC of 14.2, 13.6 and 10.8μM, respectively, and the compounds (S)-3d,f were the most active against resistant strain with a MIC of 6.8 and 7.4μM. The ex-vivo evaluation of hepatotoxicity on precision-cut rat liver slices was also tested for the α,β-unsaturated amides (S)-2b and (S)-2d,f and for the oxazolines (S)-3b and (S)-3d,f at different concentrations (5, 15 and 30μg/mL). The results indicate that these compounds possess promising antimycobacterial activity and at the same time are not hepatotoxic. These findings open the possibility for development of new drugs against tuberculosis. Copyright © 2017 Elsevier Ltd. All rights reserved.

On Unsaturated Soil Mechanics - Personal Views on Current Research

NASA Astrophysics Data System (ADS)

Pande, G. N.; Pietruszczak, S.

2015-09-01

This paper presents the authors' personal views on current research being conducted by various research groups around the world in the broad area of mechanics of unsaturated geomaterials in general and soils in particular. The topic is of interest to a wide spectrum of scientists and engineers working in diverse areas such as geology and geophysics, powder technology, agricultural, petroleum, chemical, geotechnical, civil, environmental and nuclear engineering. Even if we restrict ourselves to civil, geotechnical and environmental engineering, it is noted that a plethora of hypotheses as well as a number of empirical and semi-empirical relations have been introduced for describing the mechanics of unsaturated porous media. However, many of these proposed advances as well as methods of testing may lack sound theoretical basis.

Rapid, transient, and highly localized induction of plastidial ω-3 fatty acid desaturase mRNA at fungal infection sites in Petroselinum crispum

PubMed Central

Kirsch, Christoph; Takamiya-Wik, Monica; Reinold, Susanne; Hahlbrock, Klaus; Somssich, Imre E.

1997-01-01

Parsley (Petroselinum crispum) plants and suspension-cultured cells have been used extensively for studies of non-host-resistance mechanisms in plant/pathogen interactions. We now show that treatment of cultured parsley cells with a defined peptide elicitor of fungal origin causes rapid and large changes in the levels of various unsaturated fatty acids. While linoleic acid decreased and linolenic acid increased steadily for several hours, comparatively sharp increases in oleic acid followed a biphasic time course. In contrast, the overall level of stearic acid remained unaffected. Using a PCR-based approach, a parsley cDNA was isolated sharing high sequence similarity with ω-3 fatty acid desaturases. Subsequent isolation and characterization of a full-length cDNA enabled its functional identification as a plastid-localized ω-3 fatty acid desaturase by complementation of the Arabidopsis thaliana fad7/8 double mutant which is low in trienoic fatty acids. ω-3 Fatty acid desaturase mRNA accumulated rapidly and transiently in elicitor-treated cultured parsley cells, protoplasts, and leaves, as well as highly localized around fungal infection sites in parsley leaf buds. These results indicate that unsaturated fatty acid metabolism is yet another component of the highly complex, transcriptionally regulated pathogen defense response in plants. PMID:9050908

Effect of a High-Protein Diet on Kidney Function in Healthy Adults: Results From the OmniHeart Trial

PubMed Central

Juraschek, Stephen P.; Appel, Lawrence J.; Anderson, Cheryl A.M.; Miller, Edgar R.

2013-01-01

Background Consumption of a diet high in protein can cause glomerular hyperfiltration, a potentially maladaptive response, which may accelerate the progression of kidney disease. Study Design An ancillary study of the OmniHeart trial, a randomized 3-period crossover feeding trial testing the effects of partial replacement of carbohydrate with protein on kidney function. Setting & Participants Healthy adults (N=164) with prehypertension or stage 1 hypertension at a community-based research clinic with a metabolic kitchen. Intervention Participants were fed each of 3 diets for 6 weeks. Feeding periods were separated by a 2- to 4-week washout period. Weight was held constant on each diet. The 3 diets emphasized carbohydrate, protein, or unsaturated fat; dietary protein was either 15% (carbohydrate and unsaturated fat diets) or 25% (protein diet) of energy intake. Outcomes Fasting serum creatinine, cystatin C, and β2-microglobulin levels, estimated glomerular filtration rate (eGFR). Measurements Serum creatinine, cystatin C, and β2-microglobulin collected at the end of each feeding period. Results Baseline cystatin C-based eGFR was 92.0±16.3 (SD) mL/min/1.73 m2. Compared with the carbohydrate and unsaturated fat diets, the protein diet increased cystatin C-based eGFR by ~4 mL/min/1.73 m2 (P < 0.001). The effects of the protein diet on kidney function were independent of changes in blood pressure. There was no significant difference between the carbohydrate and unsaturated fat diets. Limitations Participants did not have kidney disease at baseline. Conclusions A healthy diet rich in protein increased eGFR. Whether long-term consumption of a high-protein diet leads to kidney disease is uncertain. PMID:23219108

Isolation and Characterization of the cis-trans-Unsaturated Fatty Acid Isomerase of Pseudomonas oleovorans GPo12

PubMed Central

Pedrotta, Valerian; Witholt, Bernard

1999-01-01

Pseudomonas oleovorans contains an isomerase which catalyzes the cis-trans conversion of the abundant unsaturated membrane fatty acids 9-cis-hexadecenoic acid (palmitoleic acid) and 11-cis-octadecenoic acid (vaccenic acid). We purified the isomerase from the periplasmic fraction of Pseudomonas oleovorans. The molecular mass of the enzyme was estimated to be 80 kDa under denaturing conditions and 70 kDa under native conditions, suggesting a monomeric structure of the active enzyme. N-terminal sequencing showed that the isomerase derives from a precursor with a signal sequence which is cleaved from the primary translation product in accord with the periplasmic localization of the enzyme. The purified isomerase acted only on free unsaturated fatty acids and not on esterified fatty acids. In contrast to the in vivo cis-trans conversion of lipids, this in vitro isomerization of free fatty acids did not require the addition of organic solvents. Pure phospholipids, even in the presence of organic solvents, could not serve as substrate for the isomerase. However, when crude membranes from Pseudomonas or Escherichia coli cells were used as phospholipid sources, a cis-trans isomerization was detectable which occurred only in the presence of organic solvents. These results indicate that isolated membranes from Pseudomonas or E. coli cells must contain factors which, activated by the addition of organic solvents, enable and control the cis-trans conversion of unsaturated acyl chains of membrane phospholipids by the periplasmic isomerase. PMID:10322030

Air-stable n-channel organic thin-film transistors with high field-effect mobility based on N ,N'-bis(heptafluorobutyl)-3,4:9,10-perylene diimide

NASA Astrophysics Data System (ADS)

Oh, Joon Hak; Liu, Shuhong; Bao, Zhenan; Schmidt, Rüdiger; Würthner, Frank

2007-11-01

The thin-film transistor characteristics of n-channel organic semiconductor, N ,N'-bis(2,2,3,3,4,4,4-heptafluorobutyl)-perylene tetracarboxylic diimide, are described. The slip-stacked face-to-face molecular packing allows a very dense parallel arrangement of the molecules, leading to field-effect mobility as high as 0.72cm2V-1s-1. The mobility only slightly decreased after exposure to air and remained stable for more than 50days. Our results reveal that molecular packing effects such as close stacking of perylene diimide units and segregation effects imparted by the fluorinated side chains are crucial for the air stability.

On the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells in unconfined aquifers

NASA Astrophysics Data System (ADS)

Liang, Xiuyu; Zhan, Hongbin; Zhang, You-Kuan; Liu, Jin

2017-03-01

Conventional models of pumping tests in unconfined aquifers often neglect the unsaturated flow process. This study concerns the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells positioned in an unconfined aquifer. A mathematical model is established with special consideration of the coupled unsaturated-saturated flow process and the well orientation. Groundwater flow in the saturated zone is described by a three-dimensional governing equation and a linearized three-dimensional Richards' equation in the unsaturated zone. A solution in the Laplace domain is derived by the Laplace-finite-Fourier-transform and the method of separation of variables, and the semi-analytical solutions are obtained using a numerical inverse Laplace method. The solution is verified by a finite-element numerical model. It is found that the effects of the unsaturated zone on the drawdown of a pumping test exist at any angle of inclination of the pumping well, and this impact is more significant in the case of a horizontal well. The effects of the unsaturated zone on the drawdown are independent of the length of the horizontal well screen. The vertical well leads to the largest water volume drained from the unsaturated zone (W) during the early pumping time, and the effects of the well orientation on W values become insignificant at the later time. The screen length of the horizontal well does not affect W for the whole pumping period. The proposed solutions are useful for the parameter identification of pumping tests with a general well orientation (vertical, horizontal, and slant) in unconfined aquifers affected from above by the unsaturated flow process.

Unsaturated hydraulic properties of porous sedimentary rocks explained by mercury porosimetry

NASA Astrophysics Data System (ADS)

Clementina Caputo, Maria; Turturro, Celeste; Gerke, Horst H.

2016-04-01

The understanding of hydraulic properties is essential in the modeling of flow and solute transport including contaminants through the vadose zone, which consists of the soil as well as of the underlying porous sediments or rocks. The aim of this work is to study the relationships between unsaturated hydraulic properties of porous rocks and their pore size distribution. For this purpose, two different lithotypes belonging to Calcarenite di Gravina Formation, a Plio-Pleistocene sedimentary rock of marine origin, were investigated. The two lithotypes differ mainly in texture and came from two distinct quarry districts, Canosa di Puglia (C) and Massafra (M) in southern Italy, respectively. This relatively porous rock formation (porosities range between 43% for C and 41% for M) often constitutes a thick layer of vadose zone in several places of Mediterranean basin. The water retention curves (WRCs) and the unsaturated hydraulic conductivity functions were determined using four different experimental methods that cover the full range from low to high water contents: the WP4 psychrometer test, the Wind's evaporation method, the Stackman's method and the Quasi-steady centrifuge method. Pore size estimation by means of mercury intrusion porosimetry (MIP) was performed. WRCs were compared with the pore size distributions to understand the influence of fabric, in terms of texture and porosity, features of pores and pore size distribution on the hydraulic behavior of rocks. The preliminary results show that the pore size distributions obtained by MIP do not cover the entire pore size range of the investigated Calcarenite. In fact, some pores in the rock samples of both lithotypes were larger than the maximum size that could be investigated by MIP. This implies that for explaining the unsaturated hydraulic properties over the full moisture range MIP results need to be combined with results obtained by other methods such as image analysis and SEM.

Conformational Change in the Active Site of Streptococcal Unsaturated Glucuronyl Hydrolase Through Site-Directed Mutagenesis at Asp-115.

PubMed

Nakamichi, Yusuke; Oiki, Sayoko; Mikami, Bunzo; Murata, Kousaku; Hashimoto, Wataru

2016-08-01

Bacterial unsaturated glucuronyl hydrolase (UGL) degrades unsaturated disaccharides generated from mammalian extracellular matrices, glycosaminoglycans, by polysaccharide lyases. Two Asp residues, Asp-115 and Asp-175 of Streptococcus agalactiae UGL (SagUGL), are completely conserved in other bacterial UGLs, one of which (Asp-175 of SagUGL) acts as a general acid and base catalyst. The other Asp (Asp-115 of SagUGL) also affects the enzyme activity, although its role in the enzyme reaction has not been well understood. Here, we show substitution of Asp-115 in SagUGL with Asn caused a conformational change in the active site. Tertiary structures of SagUGL mutants D115N and D115N/K370S with negligible enzyme activity were determined at 2.00 and 1.79 Å resolution, respectively, by X-ray crystallography. The side chain of Asn-115 is drastically shifted in both mutants owing to the interaction with several residues, including Asp-175, by formation of hydrogen bonds. This interaction between Asn-115 and Asp-175 probably prevents the mutants from triggering the enzyme reaction using Asp-175 as an acid catalyst.

Heterojunction p-Cu2O/n-Ga2O3 diode with high breakdown voltage

NASA Astrophysics Data System (ADS)

Watahiki, Tatsuro; Yuda, Yohei; Furukawa, Akihiko; Yamamuka, Mikio; Takiguchi, Yuki; Miyajima, Shinsuke

2017-11-01

Heterojunction p-Cu2O/n-β-Ga2O3 diodes were fabricated on an epitaxially grown β-Ga2O3(001) layer. The reverse breakdown voltage of these p-n diodes reached 1.49 kV with a specific on-resistance of 8.2 mΩ cm2. The leakage current of the p-n diodes was lower than that of the Schottky barrier diode due to the higher barrier height against the electron. The ideality factor of the p-n diode was 1.31. It indicated that some portion of the recombination current at the interface contributed to the forward current, but the diffusion current was the dominant. The forward current more than 100 A/cm2 indicated the lower conduction band offset at the hetero-interface between Cu2O and Ga2O3 layers than that predicted from the bulk properties, resulting in such a high forward current without limitation. These results open the possibility of advanced device structures for wide bandgap Ga2O3 to achieve higher breakdown voltage and lower on-resistance.

The Soil Foam Drainage Equation - an alternative model for unsaturated flow in porous media

NASA Astrophysics Data System (ADS)

Assouline, Shmuel; Lehmann, Peter; Hoogland, Frouke; Or, Dani

2017-04-01

The analogy between the geometry and dynamics of wet foam drainage and gravity drainage of unsaturated porous media expands modeling capabilities for capillary flows and supplements the standard Richards equation representation. The governing equation for draining foam (or a soil variant termed the soil foam drainage equation - SFDE) obviates the need for macroscopic unsaturated hydraulic conductivity function by an explicit account of diminishing flow pathway sizes as the medium gradually drains. Potential advantages of the proposed drainage foam formalism include direct description of transient flow without requiring constitutive functions; evolution of capillary cross sections that provides consistent description of self-regulating internal fluxes (e.g., towards field capacity); and a more intuitive geometrical picture of capillary flow across textural boundaries. We will present new and simple analytical expressions for drainage rates and volumes from unsaturated porous media subjected to different boundary conditions that are in good agreement with the numerical solution of the SFDE and experimental results. The foam drainage methodology expands the range of tools available for describing and quantifying unsaturated flows and provides geometrically tractable links between evolution of liquid configuration and flow dynamics in unsaturated porous media. The resulting geometrical representation of capillary drainage could improve understanding of colloid and pathogen transport. The explicit geometrical interpretation of flow pathways underlying the hydraulic functions used by the Richards equation offers new insights that benefit both approaches.

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

PubMed

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolution of strain localization in variable-width three-dimensional unsaturated laboratory-scale cut slopes

USGS Publications Warehouse

Morse, Michael S.; Lu, Ning; Wayllace, Alexandra; Godt, Jonathan W.

2017-01-01

To experimentally validate a recently developed theory for predicting the stability of cut slopes under unsaturated conditions, the authors measured increasing strain localization in unsaturated slope cuts prior to abrupt failure. Cut slope width and moisture content were controlled and varied in a laboratory, and a sliding door that extended the height of the free face of the slope was lowered until the cut slope failed. A particle image velocimetry tool was used to quantify soil displacement in the x-y">x-y (horizontal) and x-z">x-z (vertical) planes, and strain was calculated from the displacement. Areas of maximum strain localization prior to failure were shown to coincide with the location of the eventual failure plane. Experimental failure heights agreed with the recently developed stability theory for unsaturated cut slopes (within 14.3% relative error) for a range of saturation and cut slope widths. A theoretical threshold for sidewall influence on cut slope failures was also proposed to quantify the relationship between normalized sidewall width and critical height. The proposed relationship was consistent with the cut slope experiment results, and is intended for consideration in future geotechnical experiment design. The experimental data of evolution of strain localization presented herein provide a physical basis from which future numerical models of strain localization can be validated.

Investigations of novel unsaturated bile salts of male sea lamprey as potential chemical cues

USGS Publications Warehouse

Johnson, Nicholas S.; Yun, Sang-Seon; Li, Weiming

2014-01-01

Sulfated bile salts function as chemical cues that coordinate reproduction in sea lamprey, Petromyzon marinus. 7α, 12α, 24-trihydroxy-5α-cholan-3-one 24-sulfate (3kPZS) is the most abundant known bile salt released by sexually mature male sea lampreys and attracts ovulated females. However, previous studies showed that the male-produced pheromone consists of unidentified components in addition to 3kPZS. Here, analysis of water conditioned with mature male sea lampreys indicated the presence of 4 oxidized, unsaturated compounds with molecular weights of 466 Da, 468 Da, and 2 of 470 Da. These compounds were not detectable in water conditioned with immature male sea lampreys. By using mass spectrometry, 4 A-ring unsaturated sulfated bile salts were tentatively identified from male washings as 2 4-ene, a 1-ene, and a 1,4-diene analogs. These were synthesized to determine if they attracted ovulated female sea lampreys to spawning nests in natural streams. One of the novel synthetic bile salts, 3 keto-1-ene PZS, attracted ovulated females to the point of application at a concentration of 10-12 M. This study reveals the structural diversity of bile salts in sea lamprey, some of which have been demonstrated to be pheromonal cues.

Vegetables, unsaturated fats, moderate alcohol intake, and mild cognitive impairment.

PubMed

Roberts, Rosebud O; Geda, Yonas E; Cerhan, James R; Knopman, David S; Cha, Ruth H; Christianson, Teresa J H; Pankratz, V Shane; Ivnik, Robert J; Boeve, Bradley F; O'Connor, Helen M; Petersen, Ronald C

2010-01-01

To investigate associations of the Mediterranean diet (MeDi) components and the MeDi score with mild cognitive impairment (MCI). Participants (aged 70-89 years) were clinically evaluated to assess MCI and dementia, and completed a 128-item food frequency questionnaire. 163 of 1,233 nondemented persons had MCI. The odds ratio of MCI was reduced for high vegetable intake [0.66 (95% CI = 0.44-0.99), p = 0.05] and for high mono- plus polyunsaturated fatty acid to saturated fatty acid ratio [0.52 (95% CI = 0.33-0.81), p = 0.007], adjusted for confounders. The risk of incident MCI or dementia was reduced in subjects with a high MeDi score [hazard ratio = 0.75 (95% CI = 0.46-1.21), p = 0.24]. Vegetables, unsaturated fats, and a high MeDi score may be beneficial to cognitive function.

An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

PubMed

Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

2017-10-05

Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

In chronic fatigue syndrome, the decreased levels of omega-3 poly-unsaturated fatty acids are related to lowered serum zinc and defects in T cell activation.

PubMed

Maes, Michael; Mihaylova, Ivana; Leunis, Jean-Claude

2005-12-01

There is now evidence that major depression is accompanied by decreased levels of omega3 poly-unsaturated fatty acids (PUFA), such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). There is a strong comorbidity between major depression and chronic fatigue syndrome (CFS). The present study has been carried out in order to examine PUFA levels in CFS. In twenty-two CFS patients and 12 normal controls we measured serum PUFA levels using gas chromatography and mass spectrometry. We found that CFS was accompanied by increased levels of omega6 PUFAs, i.e. linoleic acid and arachidonic acid (AA), and mono-unsaturated fatty acids (MUFAs), i.e. oleic acid. The EPA/AA and total omega3/omega6 ratios were significantly lower in CFS patients than in normal controls. The omega3/omega6 ratio was significantly and negatively correlated to the severity of illness and some items of the FibroFatigue scale, i.e. aches and pain, fatigue and failing memory. The severity of illness was significantly and positively correlated to linoleic and arachidonic acid, oleic acid, omega9 fatty acids and one of the saturated fatty acids, i.e. palmitic acid. In CFS subjects, we found significant positive correlations between the omega3/omega6 ratio and lowered serum zinc levels and the lowered mitogen-stimulated CD69 expression on CD3+, CD3+ CD4+, and CD3+ CD8+ T cells, which indicate defects in early T cell activation. The results of this study show that a decreased availability of omega3 PUFAs plays a role in the pathophysiology of CFS and is related to the immune pathophysiology of CFS. The results suggest that patients with CFS should respond favourably to treatment with--amongst other things--omega3 PUFAs, such as EPA and DHA.

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

PubMed

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

C–H Functionalization of Cyclic Amines: Redox-Annulations with α,β-Unsaturated Carbonyl Compounds

PubMed Central

Kang, YoungKu; Richers, Matthew T.; Sawicki, Conrad H.; Seidel, Daniel

2015-01-01

Cyclic amines such as pyrrolidine and 1,2,3,4-tetrahydroisoquinoline undergo redox-annulations with α,β-unsaturated aldehydes and ketones. Carboxylic acid promoted generation of a conjugated azomethine ylide is followed by 6π-electrocylization, and, in some cases, tautomerization. The resulting ring-fused pyrrolines are readily oxidized to the corresponding pyrroles or reduced to pyrrolidines. PMID:26051897

Monitoring radionuclide contamination in the unsaturated zone - Lessons learned at the Amargosa Desert Research Site, Nye County, Nevada

USGS Publications Warehouse

Stonestrom, David A.; Abraham, Jared D.; Andraski, Brian J.; Baker, Ronald J.; Mayers, C. Justin; Michel, Robert L.; Prudic, David E.; Striegl, Robert G.; Walvoord, Michelle Ann

2004-01-01

Contaminant-transport processes are being investigated at the U.S. Geological Survey’s Amargosa Desert Research Site (A DRS), adjacent to the Nation’s first commercial disposal facility for low-level radioactive waste. Gases containing tritium and radiocarbon are migrating through a 110-m thick unsaturated zone from unlined trenches that received waste from 1962 to 1992. Results relevant to long- term monitoring of radionuclides are summarized as follows. Contaminant plumes have unexpected histories and spatial configurations due to uncertainties in the: (1) geologic framework, (2) biochemical reactions involving waste components, (3) interactions between plume components and unsaturated-zone materials, (4) disposal practices, and (5) physical transport processes. Information on plume dynamics depends on ex-situ wet-chemical techniques because in-situ sensors for the radionuclides of interest do not exist. As at other radioactive-waste disposal facilities, radionuclides at the ADRS are mixed with varying amounts of volatile organic compounds (VOCs). Carbon-dioxide and VOC anomalies provide proxies for radioactive contamination. Contaminants in the unsaturated zone migrate along preferential pathways. Effective monitoring thus requires accurate geologic characterization. Direct- current electrical-resistivity imaging successfully mapped geologic units controlling preferential transport at the ADRS. Direct sampling of water from the unsaturated zone is complex and time consuming. Sampling plant water is an efficient alternative for mapping shallow tritium contamination.

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

PubMed

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

Acyl chain unsaturation modulates distribution of lecithin molecular species between mixed micelles and vesicles in model bile. Implications for particle structure and metastable cholesterol solubilities.

PubMed

Cohen, D E; Carey, M C

1991-08-01

We determined the distribution of lecithin molecular species between vesicles and mixed micelles in cholesterol super-saturated model biles (molar taurocholate-lecithin-cholesterol ratio 67:23:10, 3 g/dl, 0.15 M NaCl, pH approximately 6-7) that contained equimolar synthetic lecithin mixtures or egg yolk or soybean lecithins. After apparent equilibration (48 h), biles were fractionated by Superose 6 gel filtration chromatography at 20 degrees C, and lecithin molecular species in the vesicle and mixed micellar fractions were quantified as benzoyl diacylglycerides by high performance liquid chromatography. With binary lecithin mixtures, vesicles were enriched with lecithins containing the most saturated sn-1 or sn-2 chains by as much as 2.4-fold whereas mixed micelles were enriched in the more unsaturated lecithins. Vesicles isolated from model biles composed of egg yolk (primarily sn-1 16:0 and 18:0 acyl chains) or soy bean (mixed saturated and unsaturated sn-1 acyl chains) lecithins were selectively enriched (6.5-76%) in lecithins with saturated sn-1 acyl chains whereas mixed micelles were enriched with lecithins composed of either sn-1 18:1, 18:2, and 18:3 unsaturated or sn-2 20:4, 22:4, and 22:6 polyunsaturated chains. Gel filtration, lipid analysis, and quasielastic light scattering revealed that apparent micellar cholesterol solubilities and metastable vesicle cholesterol/lecithin molar ratios were as much as 60% and 100% higher, respectively, in biles composed of unsaturated lecithins. Acyl chain packing constraints imposed by distinctly different particle geometries most likely explain the asymmetric distribution of lecithin molecular species between vesicles and mixed micelles in model bile as well as the variations in apparent micellar cholesterol solubilities and vesicle cholesterol/lecithin molar ratios.(ABSTRACT TRUNCATED AT 250 WORDS)

Fabrication of Highly Ordered and Well-Aligned PbTiO 3/TiN Core–Shell Nanotube Arrays

DOE PAGES

Yoon, Jaesung; Kim, Sangjoon; Kim, Dongjin; ...

2015-04-30

Highly ordered and well-aligned PbTiO 3/TiN core–shell nanotubes are fabricated in this paper via an anodic aluminum oxide templating route followed by TiN and TiO 2 atomic layer deposition deposition and a subsequent PbO vapor reaction. Finally, PbTiO 3/TiN nanotubes keep their original shape after the vapor phase reaction, and they display well-defined piezoresponse hysteresis curves with remnant piezoresponse of 38 pm V -1.

Development of N- and P- Types of Semiconducting Polymers

DTIC Science & Technology

2015-03-05

Luyao Lu, Tao Xu, Ju Min Lee, Zhiqiang Luo, Feng He, Hyung Il Park, In Hwan Jung, Sang Ouk Kim, Luping Yu, “The Role of N- Doped Multi-wall Carbon...Luping Yu, Di-Jia Liu, Improving Hydrogen Adsorption Enthalpy Through Coordinatively 23 Unsaturated Cobalt in Porous Polymers, Macromolecular...Sang Ouk Kim, Luping Yu, “The Role of N- Doped Multi-wall Carbon Nanotubes in Achieving Highly Efficient Polymer Bulk Heterojunction Solar Cells

Mechanical Properties of Unsaturated Polyester / Montmorillonite Composites

DTIC Science & Technology

2001-11-01

Montmorillonite Composites DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: Nanophase and...Mechanical Properties of Unsaturated Polyester / Montmorillonite Composites A. Baran Inceoglu and Ulku Yilmazer Middle East Technical University, Chemical...analysed the nature of the curing agent on structure. Kornmann, Berglund and Giannelis [8] studied nanocomposites based on montmorillonite modified

Characterization of high-{kappa} LaLuO{sub 3} thin film grown on AlGaN/GaN heterostructure by molecular beam deposition

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

Yang Shu; Huang Sen; Chen Hongwei

2011-10-31

We report the study of high-dielectric-constant (high-{kappa}) dielectric LaLuO{sub 3} (LLO) thin film that is grown on AlGaN/GaN heterostructure by molecular beam deposition (MBD). The physical properties of LLO on AlGaN/GaN heterostrucure have been investigated with atomic force microscopy, x-ray photoelectron spectroscopy, and TEM. It is revealed that the MBD-grown 16 nm-thick LLO film is polycrystalline with a thin ({approx}2 nm) amorphous transition layer at the LLO/GaN interface. The bandgap of LLO is derived as 5.3 {+-} 0.04 eV from O1s energy loss spectrum. Capacitance-voltage (C-V) characteristics of a Ni-Au/LLO/III-nitride metal-insulator-semiconductor diode exhibit small frequency dispersion (<2%) and reveal amore » high effective dielectric constant of {approx}28 for the LLO film. The LLO layer is shown to be effective in suppressing the reverse and forward leakage current in the MIS diode. In particular, the MIS diode forward current is reduced by 7 orders of magnitude at a forward bias of 1 V compared to a conventional Ni-Au/III-nitride Schottky diode.« less

Determination of nitroaromatic explosives and their degradation products in unsaturated-zone water samples by high-performance liquid chromatography with photodiode-array, mass spectrometric, and tandem mass spectrometric detection

USGS Publications Warehouse

Gates, Paul M.; Furlong, E.T.; Dorsey, T.F.; Burkhardt, M.R.

1996-01-01

Mass spectrometry and tandem mass spectrometry, coupled by a thermospray interface to a high-performance liguid chromatography system and equipped with a photodiode array detector, were used to determine the presence of nitroaromatic explosives and their degradation products in USA unsaturated-zone water samples. Using this approach, the lower limits of quantitation for explosives determined by mass spectrometry in this study typically ranged from 10 to 100 ng/l.

Structural analyses of polymorphic transitions of sn-1, 3-distearoyl-2-oleoylglycerol (SOS) and sn-1, 3-dioleoyl-2-stearoylglycerol (OSO): assessment on steric hindrance of unsaturated and saturated acyl chain interactions.

PubMed

Yano, J; Sato, K; Kaneko, F; Small, D M; Kodali, D R

1999-01-01

Polymorphic transformations in two saturated-unsaturated mixed acid triacylglycerols, SOS (sn -1,3-distearoyl-2-oleoylglycerol) and OSO (sn -1,3-dioleoyl-2-stearoylglycerol), have been studied by FT-IR spectroscopy using deuterated specimens in which stearoyl chains are fully deuterated. A reversible phase transition between sub alpha and alpha and a series of irreversible transitions (alpha-->gamma-->beta'-->beta (beta2, beta1) for SOS and alpha-->beta'-->beta for OSO) were studied with an emphasis on the conformational ordering process of stearoyl and oleoyl chains. The alpha-->sub alpha reversible transition was due to the orientational change of stearoyl chains in the lateral directions from the hexagonal subcell to a perpendicularly packed one. As the first stage of the series of irreversible transitions from alpha to beta, the conformational ordering of saturated chains took place in the alpha-->gamma transition of SOS and in the alpha-->beta' transition of OSO; one stearoyl chain in SOS and OSO takes the all-trans conformation and the second stearoyl chain in SOS takes the bent conformation like those observed in the most stable beta-type. As the final stage, the ordering of unsaturated chains occurred in the beta'-->beta transition both for SOS and OSO. A conversion in the layered structure from bilayer to trilayer was also accompanied by the conformational ordering in the alpha-->gamma transition of SOS and in the beta'-->beta transition of OSO.

Quasi‐steady centrifuge method for unsaturated hydraulic properties

USGS Publications Warehouse

Caputo, Maria C.; Nimmo, John R.

2005-01-01

We have developed the quasi‐steady centrifuge (QSC) method as a variation of the steady state centrifuge method that can be implemented simply and inexpensively with greater versatility in terms of sample size and other features. It achieves these advantages by somewhat relaxing the criterion for steadiness of flow through the sample. This compromise entails an increase in measurement uncertainty but to a degree that is tolerable in most applications. We have tested this new approach with an easily constructed apparatus to establish a quasi‐steady flow of water in unsaturated porous rock samples spinning in a centrifuge, obtaining measurements of unsaturated hydraulic conductivity and water retention that agree with results of other methods. The QSC method is adaptable to essentially any centrifuge suitable for hydrogeologic applications, over a wide range of sizes and operating speeds. The simplified apparatus and greater adaptability of this method expands the potential for exploring situations that are common in nature but have been the subject of few laboratory investigations.

Application of Silver Ion High-Performance Liquid Chromatography for Quantitative Analysis of Selected n-3 and n-6 PUFA in Oil Supplements.

PubMed

Czajkowska-Mysłek, Anna; Siekierko, Urszula; Gajewska, Magdalena

2016-04-01

The aim of this study was to develop a simple method for simultaneous determination of selected cis/cis PUFA-LNA (18:2), ALA (18:3), GLA (18:3), EPA (20:5), and DHA (22:6) by silver ion high-performance liquid chromatography coupled to a diode array detector (Ag-HPLC-DAD). The separation was performed on three Luna SCX Silver Loaded columns connected in series maintained at 10 °C with isocratic elution by 1% acetonitrile in n-hexane. The applied chromatographic system allowed a baseline separation of standard mixture of n-3 and n-6 fatty acid methyl esters containing LNA, DHA, and EPA and partial separation of ALA and GLA positional isomers. The method was validated by means of linearity, precision, stability, and recovery. Limits of detection (LOD) for considered PUFA standard solutions ranged from 0.27 to 0.43 mg L(-1). The developed method was used to evaluate of n-3 and n-6 fatty acids contents in plant and fish softgel oil capsules, results were compared with reference GC-FID based method.

40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (PMNs...

Manipulating the Ordered Nanostructure of Self-Assembled Monoolein and Phytantriol Nanoparticles with Unsaturated Fatty Acids.

PubMed

Tran, Nhiem; Mulet, Xavier; Hawley, Adrian M; Fong, Celesta; Zhai, Jiali; Le, Tu C; Ratcliffe, Julian; Drummond, Calum J

2018-02-27

Mesophase structures of self-assembled lyotropic liquid crystalline nanoparticles are important factors that directly influence their ability to encapsulate and release drugs and their biological activities. However, it is difficult to predict and precisely control the mesophase behavior of these materials, especially in complex systems with several components. In this study, we report the controlled manipulation of mesophase structures of monoolein (MO) and phytantriol (PHYT) nanoparticles by adding unsaturated fatty acids (FAs). By using high throughput formulation and small-angle X-ray scattering characterization methods, the effects of FAs chain length, cis-trans isomerism, double bond location, and level of chain unsaturation on self-assembled systems are determined. Additionally, the influence of temperature on the phase behavior of these nanoparticles is analyzed. We found that in general, the addition of unsaturated FAs to MO and PHYT induces the formation of mesophases with higher Gaussian surface curvatures. As a result, a rich variety of lipid polymorphs are found to correspond with the increasing amounts of FAs. These phases include inverse bicontinuous cubic, inverse hexagonal, and discrete micellar cubic phases and microemulsion. However, there are substantial differences between the phase behavior of nanoparticles with trans FA, cis FAs with one double bond, and cis FAs with multiple double bonds. Therefore, the material library produced in this study will assist the selection and development of nanoparticle-based drug delivery systems with desired mesophase.

Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

NASA Astrophysics Data System (ADS)

Safi Shalamzari, Mohammad; Vermeylen, Reinhilde; Blockhuys, Frank; Kleindienst, Tadeusz E.; Lewandowski, Michael; Szmigielski, Rafal; Rudzinski, Krzysztof J.; Spólnik, Grzegorz; Danikiewicz, Witold; Maenhaut, Willy; Claeys, Magda

2016-06-01

We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles (GLVs) 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack), and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS) and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements) to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfooxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α,β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013). The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl group at the

High external quantum efficiency and fill-factor InGaN/GaN heterojunction solar cells grown by NH3-based molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Lang, J. R.; Neufeld, C. J.; Hurni, C. A.; Cruz, S. C.; Matioli, E.; Mishra, U. K.; Speck, J. S.

2011-03-01

High external quantum efficiency (EQE) p-i-n heterojunction solar cells grown by NH3-based molecular beam epitaxy are presented. EQE values including optical losses are greater than 50% with fill-factors over 72% when illuminated with a 1 sun AM0 spectrum. Optical absorption measurements in conjunction with EQE measurements indicate an internal quantum efficiency greater than 90% for the InGaN absorbing layer. By adjusting the thickness of the top p-type GaN window contact layer, it is shown that the short-wavelength (<365 nm) quantum efficiency is limited by the minority carrier diffusion length in highly Mg-doped p-GaN.

Highly pathogenic avian influenza H5N1 virus delays apoptotic responses via activation of STAT3

PubMed Central

Hui, Kenrie P. Y.; Li, Hung Sing; Cheung, Man Chun; Chan, Renee W. Y.; Yuen, Kit M.; Mok, Chris K. P.; Nicholls, John M.; Peiris, J. S. Malik; Chan, Michael C. W.

2016-01-01

Highly pathogenic avian influenza (HPAI) H5N1 virus continues to pose pandemic threat, but there is a lack of understanding of its pathogenesis. We compared the apoptotic responses triggered by HPAI H5N1 and low pathogenic H1N1 viruses using physiologically relevant respiratory epithelial cells. We demonstrated that H5N1 viruses delayed apoptosis in primary human bronchial and alveolar epithelial cells (AECs) compared to H1N1 virus. Both caspase-8 and -9 were activated by H5N1 and H1N1 viruses in AECs, while H5N1 differentially up-regulated TRAIL. H5N1-induced apoptosis was reduced by TRAIL receptor silencing. More importantly, STAT3 knock-down increased apoptosis by H5N1 infection suggesting that H5N1 virus delays apoptosis through activation of STAT3. Taken together, we demonstrate that STAT3 is involved in H5N1-delayed apoptosis compared to H1N1. Since delay in apoptosis prolongs the duration of virus replication and production of pro-inflammatory cytokines and TRAIL from H5N1-infected cells, which contribute to orchestrate cytokine storm and tissue damage, our results suggest that STAT3 may play a previously unsuspected role in H5N1 pathogenesis. PMID:27344974

Fourier transform infrared imaging showing reduced unsaturated lipid content in the hippocampus of a mouse model of Alzheimer's disease.

PubMed

Leskovjan, Andreana C; Kretlow, Ariane; Miller, Lisa M

2010-04-01

Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer's disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier transform infrared imaging (FTIRI) to visualize the unsaturated lipid content in specific regions of the hippocampus in the PSAPP mouse model of AD as a function of plaque formation. Specifically, the unsaturated lipid content was imaged using the olefinic =CH stretching mode at 3012 cm(-1). The axonal, dendritic, and somatic layers of the hippocampus were examined in the mice at 13, 24, 40, and 56 weeks old. Results showed that lipid unsaturation in the axonal layer was significantly increased with normal aging in control (CNT) mice (p < 0.01) but remained low and relatively constant in PSAPP mice. Thus, these findings indicate that unsaturated lipid content is reduced in hippocampal white matter during amyloid pathogenesis and that maintaining unsaturated lipid content early in the disease may be critical in avoiding progression of the disease.

Unsaturated flow dynamics during irrigation with wastewater: field and modelling study

NASA Astrophysics Data System (ADS)

Martinez-Hernandez, V.; de Miguel, A.; Meffe, R.; Leal, M.; González-Naranjo, V.; de Bustamante, I.

2012-04-01

To deal with water scarcity combined with a growing water demand, the reuse of wastewater effluents of wastewater treatment plants (WWTP) for industrial and agricultural purposes is considered as a technically and economically feasible solution. In agriculture, irrigation with wastewater emerges as a sustainable practice that should be considered in such scenarios. Water infiltration, soil moisture storage and evapotranspiration occurring in the unsaturated zone are fundamental processes that play an important role in soil water balance. An accurate estimation of unsaturated flow dynamics (during and after irrigation) is essential to improve wastewater management (i.e. estimating groundwater recharge or maximizing irrigation efficiency) and to avoid possible soil and groundwater affections (i.e. predicting contaminant transport). The study site is located in the Experimental Plant of Carrión de los Céspedes (Seville, Spain). Here, treated wastewater is irrigated over the soil to enhance plants growth. To obtain physical characteristics of the soil (granulometry, bulk density and water retention curve), soil samples were collected at different depths. A drain gauge passive capillary lysimeter was installed to determine the volume of water draining from the vadose zone. Volumetric water content of the soil was monitored by measuring the dielectric constant using capacitance/frequency domain technology. Three soil moisture probes were located at different depths (20, 50 and 70 cm below the ground surface) to control the variation of the volumetric water content during infiltration. The main aim of this study is to understand water flow dynamics through the unsaturated zone during irrigation by using the finite element model Hydrus-1D. The experimental conditions were simulated by a 90 cm long, one dimensional solution domain. Specific climatic conditions, wastewater irrigation rates and physical properties of the soil were introduced in the model as input parameters

Effect of hydrofracking fluid on colloid transport in the unsaturated zone.

PubMed

Sang, Wenjing; Stoof, Cathelijne R; Zhang, Wei; Morales, Verónica L; Gao, Bin; Kay, Robert W; Liu, Lin; Zhang, Yalei; Steenhuis, Tammo S

2014-07-15

Hydraulic fracturing is expanding rapidly in the US to meet increasing energy demand and requires high volumes of hydrofracking fluid to displace natural gas from shale. Accidental spills and deliberate land application of hydrofracking fluids, which return to the surface during hydrofracking, are common causes of environmental contamination. Since the chemistry of hydrofracking fluids favors transport of colloids and mineral particles through rock cracks, it may also facilitate transport of in situ colloids and associated pollutants in unsaturated soils. We investigated this by subsequently injecting deionized water and flowback fluid at increasing flow rates into unsaturated sand columns containing colloids. Colloid retention and mobilization was measured in the column effluent and visualized in situ with bright field microscopy. While <5% of initial colloids were released by flushing with deionized water, 32-36% were released by flushing with flowback fluid in two distinct breakthrough peaks. These peaks resulted from 1) surface tension reduction and steric repulsion and 2) slow kinetic disaggregation of colloid flocs. Increasing the flow rate of the flowback fluid mobilized an additional 36% of colloids, due to the expansion of water filled pore space. This study suggests that hydrofracking fluid may also indirectly contaminate groundwater by remobilizing existing colloidal pollutants.

Effect of Hydrofracking Fluid on Colloid Transport in the Unsaturated Zone

PubMed Central

2014-01-01

Hydraulic fracturing is expanding rapidly in the US to meet increasing energy demand and requires high volumes of hydrofracking fluid to displace natural gas from shale. Accidental spills and deliberate land application of hydrofracking fluids, which return to the surface during hydrofracking, are common causes of environmental contamination. Since the chemistry of hydrofracking fluids favors transport of colloids and mineral particles through rock cracks, it may also facilitate transport of in situ colloids and associated pollutants in unsaturated soils. We investigated this by subsequently injecting deionized water and flowback fluid at increasing flow rates into unsaturated sand columns containing colloids. Colloid retention and mobilization was measured in the column effluent and visualized in situ with bright field microscopy. While <5% of initial colloids were released by flushing with deionized water, 32–36% were released by flushing with flowback fluid in two distinct breakthrough peaks. These peaks resulted from 1) surface tension reduction and steric repulsion and 2) slow kinetic disaggregation of colloid flocs. Increasing the flow rate of the flowback fluid mobilized an additional 36% of colloids, due to the expansion of water filled pore space. This study suggests that hydrofracking fluid may also indirectly contaminate groundwater by remobilizing existing colloidal pollutants. PMID:24905470

Protective efficacy of a high-growth reassortant swine H3N2 inactivated vaccine constructed by reverse genetic manipulation

PubMed Central

Wen, Feng; Ma, Ji-Hong; Yang, Fu-Ru; Huang, Meng; Zhou, Yan-Jun; Li, Ze-Jun

2014-01-01

Novel reassortant H3N2 swine influenza viruses (SwIV) with the matrix gene from the 2009 H1N1 pandemic virus have been isolated in many countries as well as during outbreaks in multiple states in the United States, indicating that H3N2 SwIV might be a potential threat to public health. Since southern China is the world's largest producer of pigs, efficient vaccines should be developed to prevent pigs from acquiring H3N2 subtype SwIV infections, and thus limit the possibility of SwIV infection at agricultural fairs. In this study, a high-growth reassortant virus (GD/PR8) was generated by plasmid-based reverse genetics and tested as a candidate inactivated vaccine. The protective efficacy of this vaccine was evaluated in mice by challenging them with another H3N2 SwIV isolate [A/Swine/Heilongjiang/1/05 (H3N2) (HLJ/05)]. Prime and booster inoculation with GD/PR8 vaccine yielded high-titer serum hemagglutination inhibiting antibodies and IgG antibodies. Complete protection of mice against H3N2 SwIV was observed, with significantly reduced lung lesion and viral loads in vaccine-inoculated mice relative to mock-vaccinated controls. These results suggest that the GD/PR8 vaccine may serve as a promising candidate for rapid intervention of H3N2 SwIV outbreaks in China. PMID:24675833

Occurrence of nitrous oxide in the central High Plains aquifer, 1999

USGS Publications Warehouse

McMahon, P.B.; Bruch, B.W.; Becker, M.F.; Pope, L.M.; Dennehy, K.F.

2000-01-01

Nitrogen-enriched groundwater has been proposed as an important anthropogenic source of atmospheric nitrous oxide (N2O), yet few measurements of N2O in large aquifer systems have been made. Concentrations of N2O in water samples collected from the 124 000 km2 central High Plains aquifer in 1999 ranged from < 1 to 940 nM, with a median concentration of 29 nM (n = 123). Eighty percent of the N20 concentrations exceeded the aqueous concentration expected from equilibration with atmospheric N2O. Measurements of N2O, NO3-, and 3H in unsaturated-zone sediments, recently recharged groundwater, and older groundwater indicate that concentrations of N2O in groundwater increased over time and will likely continue to increase in the future as N-enriched water recharges the aquifer. Large concentrations of O2 and NO3- and small concentrations of NH4+ and dissolved organic carbon in the aquifer indicate that N2O in the central High Plains aquifer was produced primarily by nitrification. Calculations indicate that the flux of N2O from the central High Plains aquifer to the atmosphere from well pumping and groundwater discharge to streams was not a significant source of atmospheric N2O.Nitrogen-enriched groundwater has been proposed as an important anthropogenic source of atmospheric nitrous oxide (N2O), yet few measurements of N2O in large aquifer systems have been made. Concentrations of N2O in water samples collected from the 124000 km2 central High Plains aquifer in 1999 ranged from < 1 to 940 nM, with a median concentration of 29 nM (n = 123). Eighty percent of the N2O concentrations exceeded the aqueous concentration expected from equilibration with atmospheric N2O. Measurements of N2O, NO3-, and 3H in unsaturated-zone sediments, recently recharged groundwater, and older groundwater indicate that concentrations of N2O in groundwater increased over time and will likely continue to increase in the future as N-enriched water recharges the aquifer. Large concentrations of O2 and

Actual ratios of triacylglycerol positional isomers and enantiomers comprising saturated fatty acids and highly unsaturated fatty acids in fishes and marine mammals.

PubMed

Nagai, Toshiharu; Matsumoto, Yumiko; Jiang, Yanying; Ishikawa, Keiko; Wakatabe, Tokuhisa; Mizobe, Hoyo; Yoshinaga, Kazuaki; Kojima, Koichi; Kuroda, Ikuma; Saito, Tadao; Beppu, Fumiaki; Gotoh, Naohiro

2013-01-01

It has been previously shown that the positional isomers of triacylglycerol (TAG) containing palmitic acid (P) and highly unsaturated fatty acids (HUFAs) such as DHA (D) and EPA (E) vary between fishes and marine mammals. However, it has not yet been understood why in marine mammals HUFAs are located only at the α position when two palmitic acid chains combine, and not in fishes. In order to gain further understanding of the biosynthetic pathways involved in the formation of these asymmetric TAGs, we investigated whether the HUFA in the TAG of marine mammals exists predominantly at the sn-1 or sn-3 position. We examined the TAG positional isomers and enantiomers in marine organisms in detail. As a result, while PDP and PEP were not detected, sn-PPD and sn-PPE were found in abundance in marine mammals. For fishes, on the other hand, PDP, PEP, sn-PPD, and sn-PPE were all identified. In the case of TAGs that contain two HUFAs and one palmitic acid, marine mammals were rich in DPD and EPE whereas fishes were rich in sn-PDD and sn-PEE.

Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2.

PubMed

Lalrempuia, Ralte; Breivik, Frida; Törnroos, Karl W; Le Roux, Erwan

2017-06-27

Tetravalent zirconium complexes supported by tridentate bis-phenolate imidazolidin-2-ylidene (L1), imidazol-2-ylidene (L2) and benzimidazol-2-ylidene (L3) NHC ligands were synthesized and evaluated as precursors for the copolymerization of cyclohexene oxide (CHO) with CO 2 . While the reactivity of the imidazolidinium [H 3 L1] chloride salt with Zr(OiPr) 4 (HOiPr), and subsequent ligand exchanges with either (CH 3 ) 3 SiCl or LiOiPr lead to a series of heteroleptic compounds (κ 3 -O,C,O-L1)Zr(X) 2 (THF) (X = Cl, OiPr), both imidazolium [H 3 L2] and benzimidazolium [H 3 L3] chloride salts give a mixture of homoleptic (κ 3 -O,C,O-NHC) 2 Zr and zwitterionic (κ 2 -O,O-HL)ZrCl 2 (OiPr) compounds along with traces or the absence of the heteroleptic intermediate (κ 3 -O,C,O-NHC)Zr(Cl)(OiPr)(THF). Such dissimilar reactivity between the unsaturated and saturated NHC ligands is predominantly ascribed to the increased acidity of azolium salts along with the π-donor strength of the C carbene in L2 and L3-Zr moieties. The reactivity with the more acidic azolium salts (H 3 L2/3) and the destabilized Zr-X trans to NHC carbene bond results in a significant increase in the amount of homoleptic compounds generating HCl. The released HCl reacts preferentially with the heteroleptic intermediates having non-planar NHC ligands (i.e. L2/3) promoting the formation of zwitterionic complexes. The in situ deprotonation of the isolated zwitterionic (κ 2 -O,O-HL3)ZrCl 2 (OiPr) compound by using Ag 2 O gives the homoleptic complex as the major component along with a bimetallic hydroxo-bridged [(κ 3 -O,C,O-L3)Zr(μ-OH)(OiPr)] 2 compound. Of particular interest is that only the heteroleptic NHC-Zr(iv) complexes were identified to be active and highly selective towards the copolymerization of CHO with CO 2 independently of the co-catalysts used (both anionic and neutral) under mild conditions (P CO 2 < 1 bar, T = 60 °C), and gave atactic and completely alternating copolymers in a

Acrolein with an alpha, beta-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

USDA-ARS?s Scientific Manuscript database

Acrolein is a highly electrophilic a,ß-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear factor-kB (NF-kB) activation by lipopolysac...

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

NASA Astrophysics Data System (ADS)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Modeling Raw Sewage Leakage and Transport in the Unsaturated Zone of Carbonate Aquifer Using Carbamazepine as an Indicator

NASA Astrophysics Data System (ADS)

Yakirevich, A.; Kuznetsov, M.; Livshitz, Y.; Gasser, G.; Pankratov, I.; Lev, O.; Adar, E.; Dvory, N. Z.

2016-12-01

Fast contamination of groundwater in karstic aquifers can be caused due to leaky sewers, for example, or overflow from sewer networks. When flowing through a karst system, wastewater has the potential to reach the aquifer in a relatively short time. The Western Mountain Aquifer (Yarkon-Taninim) of Israel is one of the country's major water resources. During late winter 2013, maintenance actions were performed on a central sewage pipe that caused raw sewage to leak into the creek located in the study area. The subsequent infiltration of sewage through the thick ( 100 m) fractured/karst unsaturated zone led to a sharp increase in contaminant concentrations in the groundwater, which was monitored in a well located 29 meters from the center of the creek. Carbamazepine (CBZ) was used as an indicator for the presence of untreated raw sewage and its quantification in groundwater. The ultimate research goal was to develop a mathematical model for quantifying flow and contaminant transport processes in the fractured-porous unsaturated zone and karstified groundwater system. A quasi-3D dual permeability numerical model, representing the 'vadose zone - aquifer' system, was developed by a series of 1D equations solved in variably-saturated zone and by 3D-saturated flow and transport equation in groundwater. The 1D and 3D equations were coupled at the moving phreatic surface. The model was calibrated and applied to a simulated water flow scenario and CBZ transport during and after the observed sewage leakage event. The results of simulation showed that after the leakage stopped, significant amounts of CBZ were retained in the porous matrix of the unsaturated zone below the creek. Water redistribution and slow recharge during the dry summer season contributed to elevated CBZ concentrations in the groundwater in the vicinity of the creek and tens of meters downstream. The resumption of autumn rains enhanced flushing of CBZ from the unsaturated zone and led to an increase in

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

USGS Publications Warehouse

Gates, J.B.; Böhlke, J.K.; Edmunds, W.M.

2008-01-01

Aerobic conditions in desert aquifers commonly allow high nitrate (NO 3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (??15N NO3 and ??18ONO3) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Oesert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO 3- is generally higher than groundwater NO 3- in terms of both concentration (up to 15 476 ??M, corresponding to 3.6 mg NO3--N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation. ?? 2008 American Chemical Society.

Fe(OTf)3-catalysed Friedel–Crafts reaction of benzenoid arenes with α,β-unsaturated carbonyl compounds: easy access to 1,1-diarylalkanes

PubMed Central

Bhattacharya, Aditya; Shukla, Pushpendra Mani

2017-01-01

A simple and efficient method for the synthesis of 1,1-diarylalkanes via the Friedel–Crafts-type alkylation reaction of electron-rich arenes with cinnamic acid ester derivatives or chalcones is reported. Iron triflate has been found to be the best catalyst for the Friedel–Crafts-type alkylation reaction with α,β-unsaturated carbonyl compounds. This reaction afforded β,β-diaryl carbonyl compounds in good yields (65–93%) and with excellent regioselectivities. Remarkably, this method is also compatible with a variety of indoles to provide 3-indolyl-aryl carbonyl compounds in excellent yields. Great efforts have been made to deduce a plausible reaction mechanism based on isotopic labelling experiments. PMID:29134078

Effect of saturated and unsaturated fatty acid supplementation on bio-plastic production under submerged fermentation.

PubMed

Srivastava, S K; Tripathi, Abhishek Dutt

2013-10-01

Polyhydroxyalkanoates (PHAs) are intracellular reserve material stored by gram-negative bacteria under nutrient-limited condition. PHAs are utilized in biodegradable plastics (bio-plastics) synthesis due to their similarity with conventional synthetic plastic. In the present study, the effect of addition of saturated and unsaturated fatty acids (palmitic acid, stearic acid, oleic acid and linoleic acid) on the production of PHAs by the soil bacterium Alcaligenes sp. NCIM 5085 was studied. Fatty acid supplementation in basal media produced saturated and unsaturated PHAs of medium and short chain length. Gas chromatography analysis of palmitic acid-supplemented media showed the presence of short chain length (scl) PHAs which could potentially serve as precursors for bio-plastic production. The scl PHA was subsequently characterized as PHB by NMR and FTIR. On the other hand, oleic acid and linoleic acid addition showed both saturated and unsaturated PHAs of different chain lengths. Palmitic acid showed maximum PHB content of 70.8 % at concentration of 15 g l -1 under shake flask cultivation. When shake flask cultivation was scaled up in a 7.5-l bioreactor (working volume 3 l), 7.6 g l -1 PHA was produced with a PHB yield (Y P/X ) and productivity of 75.89 % and 0.14 g l -1  h, respectively.

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

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

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.

2016-03-04

Here we demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. Our results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order tomore » achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

DOE PAGES

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.; ...

2016-02-02

We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achievemore » comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Dietary unsaturated fatty acids differently affect catecholamine handling by adrenal chromaffin cells.

PubMed

Gomes, Andreia; Correia, Gustavo; Coelho, Marisa; Araújo, João Ricardo; Pinho, Maria João; Teixeira, Ana Luisa; Medeiros, Rui; Ribeiro, Laura

2015-05-01

Catecholamines (CA) play an important role in cardiovascular (CDV) disease risk. Namely, noradrenaline (NA) levels positively correlate whereas adrenaline (AD) levels negatively correlate with obesity and/or CDV disease. Western diets, which are tipically rich in Ω-6 fatty acids (FAs) and deficient in Ω-3 FAs, may contribute to the development of obesity, type 2 diabetes and/or coronary artery disease. Taking this into consideration and the fact that our group has already described that saturated FAs affect catecholamine handling by adrenal chromaffin cells, this work aimed to investigate the effect of unsaturated FAs upon catecholamine handling in the same model. Our results showed that chronic exposure to unsaturated FAs differently modulated CA cellular content and release, regardless of both FA series and number of carbon atoms. Namely, the Ω-6 arachidonic and linoleic acids, based on their effect on CA release and cellular content, seemed to impair NA and AD vesicular transport, whereas γ-linolenic acid selectively impaired AD synthesis and release. Within the Ω-9 FAs, oleic acid was devoid of effect, and elaidic acid behaved similarly to γ-linolenic acid. Eicosapentaenoic and docosahexaenoic acids (Ω-3 series) impaired the synthesis and release of both NA and AD. These results deserve attention and future development, namely, in what concerns the mechanisms involved and correlative effects in vivo. Copyright © 2015 Elsevier Inc. All rights reserved.

High-Efficiency InGaN/GaN Quantum Well-Based Vertical Light-Emitting Diodes Fabricated on β-Ga2O3 Substrate.

PubMed

Muhammed, Mufasila M; Alwadai, Norah; Lopatin, Sergei; Kuramata, Akito; Roqan, Iman S

2017-10-04

We demonstrate a state-of-the-art high-efficiency GaN-based vertical light-emitting diode (VLED) grown on a transparent and conductive (-201)-oriented (β-Ga 2 O 3 ) substrate, obtained using a straightforward growth process that does not require a high-cost lift-off technique or complex fabrication process. The high-resolution scanning transmission electron microscopy (STEM) images confirm that we produced high quality upper layers, including a multiquantum well (MQW) grown on the masked β-Ga 2 O 3 substrate. STEM imaging also shows a well-defined MQW without InN diffusion into the barrier. Electroluminescence (EL) measurements at room temperature indicate that we achieved a very high internal quantum efficiency (IQE) of 78%; at lower temperatures, IQE reaches ∼86%. The photoluminescence (PL) and time-resolved PL analysis indicate that, at a high carrier injection density, the emission is dominated by radiative recombination with a negligible Auger effect; no quantum-confined Stark effect is observed. At low temperatures, no efficiency droop is observed at a high carrier injection density, indicating the superior VLED structure obtained without lift-off processing, which is cost-effective for large-scale devices.

Complex binding of the FabR repressor of bacterial unsaturated fatty acid biosynthesis to its cognate promoters.

PubMed

Feng, Youjun; Cronan, John E

2011-04-01

Two transcriptional regulators, the FadR activator and the FabR repressor, control biosynthesis of unsaturated fatty acids in Escherichia coli. FabR represses expression of the two genes, fabA and fabB, required for unsaturated fatty acid synthesis and has been reported to require the presence of an unsaturated thioester (of either acyl carrier protein or CoA) in order to bind the fabA and fabB promoters in vitro. We report in vivo experiments in which unsaturated fatty acid synthesis was blocked in the absence of exogenous unsaturated fatty acids in a ΔfadR strain and found that the rates of transcription of fabA and fabB were unaffected by the lack of unsaturated thioesters. To examine the discrepancy between our in vivo results and the prior in vitro results we obtained active, natively folded forms of the E. coli and Vibrio cholerae FabRs by use of an in vitro transcription-translation system. We report that FabR bound the intact promoter regions of both fabA and fabB in the absence of unsaturated acyl thioesters, but bound the two promoters differently. Native FabR bound the fabA promoter region provided that the canonical FabR binding site is extended by inclusion of flanking sequences that overlap the neighbouring FadR binding site. In contrast, although binding to the fabB operator also required a flanking sequence, a non-specific sequence could suffice. However, unsaturated thioesters did allow FabR binding to the minimal FabR operator sites of both promoters which otherwise were not bound. Thus unsaturated thioester ligands were not essential for FabR/target DNA interaction, but acted to enhance binding. The gel mobility shift data plus in vivo expression data indicate that despite the remarkably similar arrangements of promoter elements, FadR predominately regulates fabA expression whereas FabR is the dominant regulator of fabB expression. We also report that E. coli fabR expression is not autoregulated. Complementation, qRT-PCR and fatty acid

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

NASA Astrophysics Data System (ADS)

Rivett, Michael O.; Wealthall, Gary P.; Dearden, Rachel A.; McAlary, Todd A.

2011-04-01

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone — VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site — VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes — e.g., multi-mechanistic sorption phase partitioning, and

High current density 2D/3D MoS2/GaN Esaki tunnel diodes

NASA Astrophysics Data System (ADS)

Krishnamoorthy, Sriram; Lee, Edwin W.; Lee, Choong Hee; Zhang, Yuewei; McCulloch, William D.; Johnson, Jared M.; Hwang, Jinwoo; Wu, Yiying; Rajan, Siddharth

2016-10-01

The integration of two-dimensional materials such as transition metal dichalcogenides with bulk semiconductors offer interesting opportunities for 2D/3D heterojunction-based device structures without any constraints of lattice matching. By exploiting the favorable band alignment at the GaN/MoS2 heterojunction, an Esaki interband tunnel diode is demonstrated by transferring large area Nb-doped, p-type MoS2 onto heavily n-doped GaN. A peak current density of 446 A/cm2 with repeatable room temperature negative differential resistance, peak to valley current ratio of 1.2, and minimal hysteresis was measured in the MoS2/GaN non-epitaxial tunnel diode. A high current density of 1 kA/cm2 was measured in the Zener mode (reverse bias) at -1 V bias. The GaN/MoS2 tunnel junction was also modeled by treating MoS2 as a bulk semiconductor, and the electrostatics at the 2D/3D interface was found to be crucial in explaining the experimentally observed device characteristics.

A shallow water table fluctuation model in response to precipitation with consideration of unsaturated gravitational flow

NASA Astrophysics Data System (ADS)

Park, E.; Jeong, J.

2017-12-01

A precise estimation of groundwater fluctuation is studied by considering delayed recharge flux (DRF) and unsaturated zone drainage (UZD). Both DRF and UZD are due to gravitational flow impeded in the unsaturated zone, which may nonnegligibly affect groundwater level changes. In the validation, a previous model without the consideration of unsaturated flow is benchmarked where the actual groundwater level and precipitation data are divided into three periods based on the climatic condition. The estimation capability of the new model is superior to the benchmarked model as indicated by the significantly improved representation of groundwater level with physically interpretable model parameters.

A new and efficient synthetic method for 15N3-labeled cytosine nucleosides: Dimroth rearrangement of cytidine N3-oxides.

PubMed

Sako, Magoichi; Kawada, Hiroyoshi

2004-11-12

The treatment of (15)N(4)-labeled cytidine N(3)-oxide and (15)N(4)-labeled 2'-deoxycytidine N(3)-oxide, prepared from the appropriate unprotected uridines in three reaction steps, with benzyl bromide in the presence of excess lithium methoxide allowed the smooth occurrence of their Dimroth rearrangement even under mild conditions leading to the corresponding (15)N(3)-labeled uridine 4-O-benzyloximes which can easily undergo the reductive N-O bond cleavage to give the desirable (15)N(3)-labeled cytosine nucleosides in high total yields.

Pork as a Source of Omega-3 (n-3) Fatty Acids

PubMed Central

Dugan, Michael E.R.; Vahmani, Payam; Turner, Tyler D.; Mapiye, Cletos; Juárez, Manuel; Prieto, Nuria; Beaulieu, Angela D.; Zijlstra, Ruurd T.; Patience, John F.; Aalhus, Jennifer L.

2015-01-01

Pork is the most widely eaten meat in the world, but typical feeding practices give it a high omega-6 (n-6) to omega-3 (n-3) fatty acid ratio and make it a poor source of n-3 fatty acids. Feeding pigs n-3 fatty acids can increase their contents in pork, and in countries where label claims are permitted, claims can be met with limited feeding of n-3 fatty acid enrich feedstuffs, provided contributions of both fat and muscle are included in pork servings. Pork enriched with n-3 fatty acids is, however, not widely available. Producing and marketing n-3 fatty acid enriched pork requires regulatory approval, development costs, quality control costs, may increase production costs, and enriched pork has to be tracked to retail and sold for a premium. Mandatory labelling of the n-6/n-3 ratio and the n-3 fatty acid content of pork may help drive production of n-3 fatty acid enriched pork, and open the door to population-based disease prevention polices (i.e., food tax to provide incentives to improve production practices). A shift from the status-quo, however, will require stronger signals along the value chain indicating production of n-3 fatty acid enriched pork is an industry priority. PMID:26694475