Formation of oligomeric alkenylperoxides during the oxidation of unsaturated fatty acids: an electrospray ionization tandem mass spectrometry study.

PubMed

Villaverde, Juan José; Santos, Sónia A O; Maciel, Elisabete; Simões, Mário M Q; Pascoal Neto, Carlos; Domingues, M Rosário M; Silvestre, Armando J D

2012-02-01

This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS(2)), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe(2+)/H(2)O(2)) and Fe(2+)/O(2) systems. The reactions were followed by ferrous oxidation-xylenol orange method together with GC-MS and GC-FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH(·) radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI-MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra. Copyright © 2012 John Wiley & Sons, Ltd.

Static Longitudinal Stability of a Tandem-Coupled Bomber-Fighter Airplane Configuration Similar to One Proposed by Douglas Aircraft Company, Inc.

NASA Technical Reports Server (NTRS)

Hewes, Donald E.

1950-01-01

At the request of the Air Materiel Command, an investigation was made in the Langley free-flight tunnel to determine the longitudinal stability and control characteristics of models coupled together in a tandem configuration for aerial refueling similar to one proposed by the Douglas Aircraft Company, Inc. Static force tests were made with 1/20-scale models of the B-29 and F-80 airplanes to determine the effects of rigidly coupling the airplanes together. The Douglas configuration differs from the rigid configuration tested in that it provides for some freedom in pitch and vertical displacement. The force tests showed that, for the bomber alone, the aerodynamic center was 0.21 mean aerodynamic chord behind the center of gravity (stable) but that for the tandem configuration with rigid coupling the aerodynamic center was 0.28 mean aerodynamic chord forward of the center of gravity of the combination (unstable). This reduction in stability was caused by the downwash of the bomber on the fighter. The pitching moment produced by elevator deflection of the bomber was reduced approximately 50 percent by addition of the fighter. Some recent flight tests made in the free-flight tunnel on models in a similar tandem configuration indicated that, with a hinged coupling permitting freedom in pitch, the stability of the combination was better than that obtained with a rigid coupling and was about the same as that for the bomber alone.

Synthesis of extended polycyclic aromatic hydrocarbons by oxidative tandem spirocyclization and 1,2-aryl migration

NASA Astrophysics Data System (ADS)

Zhang, Xuan; Xu, Zhanqiang; Si, Weili; Oniwa, Kazuaki; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan

2017-04-01

The extended polycyclic aromatic hydrocarbons (PAHs) have received significant interdisciplinary attention due to their semiconducting applications in diverse organic electronics as well as intriguing structural interests of well-defined graphene segments. Herein, a highly efficient oxidative spirocyclization and 1,2-aryl migration tandem synthetic method for the construction of extended polyaromatic hydrocarbons (PAHs) has been developed. The CuCl-catalyst/PhCO3 tBu or DDQ oxidation system in the presence of trifluoroacetic acid enables the selective single-electron oxidation to take place preferentially at the more electron-rich alkene moiety of o-biphenylyl-substituted methylenefluorenes, giving rise to the subsequent tandem process. A variety of structurally diverse extended PAHs including functionalized dibenzo[g,p]chrysenes, benzo[f]naphtho[1,2-s]picene, hexabenzo[a,c,fg,j,l,op]tetracene, tetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene, tetrabenzo[a,c,f,k]phenanthro[9,10-m]tetraphene, tetrabenzo[a,c,f,o]phenanthro[9,10-m]picene and S-type helicene have been readily synthesized.

Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.): Influence of Caffeic Acid Derivatives, Oxidative Coupling, and Coupled Oxidation.

PubMed

Vissers, Anne; Kiskini, Alexandra; Hilgers, Roelant; Marinea, Marina; Wierenga, Peter Alexander; Gruppen, Harry; Vincken, Jean-Paul

2017-06-21

Sugar beet (Beta vulgaris L.) leaves of 8 month (8 m ) plants showed more enzymatic browning than those of 3 month (3 m ). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3 m and 8 m , respectively, quantitated by reverse-phase-ultrahigh-performance liquid chromatography-ultraviolet-mass spectrometry (RP-UHPLC-UV-MS). The PPO activity was 6.7 times higher in extracts from 8 m than from 3 m leaves. Substrate content increased from 0.53 to 2.45 mg/g FW in 3 m and 8 m , respectively, of which caffeic acid glycosyl esters were most important, increasing 10-fold with age. Caffeic acid glycosides and vitexin derivatives were no substrates. In 3 m and 8 m, nonsubstrate-to-substrate ratios were 8:1 and 3:1, respectively. A model system showed browning at 3:1 ratio due to formation of products with extensive conjugated systems through oxidative coupling and coupled oxidation. The 8:1 ratio did not turn brown as oxidative coupling occurred without much coupled oxidation. We postulate that differences in nonsubstrate-to-substrate ratio and therewith extent of coupled oxidation explain browning.

Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.): Influence of Caffeic Acid Derivatives, Oxidative Coupling, and Coupled Oxidation

PubMed Central

2017-01-01

Sugar beet (Beta vulgaris L.) leaves of 8 month (8m) plants showed more enzymatic browning than those of 3 month (3m). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3m and 8m, respectively, quantitated by reverse-phase-ultrahigh-performance liquid chromatography–ultraviolet-mass spectrometry (RP-UHPLC–UV-MS). The PPO activity was 6.7 times higher in extracts from 8m than from 3m leaves. Substrate content increased from 0.53 to 2.45 mg/g FW in 3m and 8m, respectively, of which caffeic acid glycosyl esters were most important, increasing 10-fold with age. Caffeic acid glycosides and vitexin derivatives were no substrates. In 3m and 8m, nonsubstrate-to-substrate ratios were 8:1 and 3:1, respectively. A model system showed browning at 3:1 ratio due to formation of products with extensive conjugated systems through oxidative coupling and coupled oxidation. The 8:1 ratio did not turn brown as oxidative coupling occurred without much coupled oxidation. We postulate that differences in nonsubstrate-to-substrate ratio and therewith extent of coupled oxidation explain browning. PMID:28570816

Tandem mobile robot system

DOEpatents

Buttz, James H.; Shirey, David L.; Hayward, David R.

2003-01-01

A robotic vehicle system for terrain navigation mobility provides a way to climb stairs, cross crevices, and navigate across difficult terrain by coupling two or more mobile robots with a coupling device and controlling the robots cooperatively in tandem.

Tandem robot control system and method for controlling mobile robots in tandem

DOEpatents

Hayward, David R.; Buttz, James H.; Shirey, David L.

2002-01-01

A control system for controlling mobile robots provides a way to control mobile robots, connected in tandem with coupling devices, to navigate across difficult terrain or in closed spaces. The mobile robots can be controlled cooperatively as a coupled system in linked mode or controlled individually as separate robots.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

PubMed

Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

2015-04-01

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

Orthogonal tandem catalysis

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

Lohr, Tracy L.; Marks, Tobin J.

2015-05-20

Tandem catalysis is a growing field that is beginning to yield important scientific and technological advances toward new and more efficient catalytic processes. 'One-pot' tandem reactions, where multiple catalysts and reagents, combined in a single reaction vessel undergo a sequence of precisely staged catalytic steps, are highly attractive from the standpoint of reducing both waste and time. Orthogonal tandem catalysis is a subset of one-pot reactions in which more than one catalyst is used to promote two or more mechanistically distinct reaction steps. This Perspective summarizes and analyses some of the recent developments and successes in orthogonal tandem catalysis, withmore » particular focus on recent strategies to address catalyst incompatibility. We also highlight the concept of thermodynamic leveraging by coupling multiple catalyst cycles to effect challenging transformations not observed in single-step processes, and to encourage application of this technique to energetically unfavourable or demanding reactions.« less

CFD-CAA Coupled Calculations of a Tandem Cylinder Configuration to Assess Facility Installation Effects

NASA Technical Reports Server (NTRS)

Redonnet, Stephane; Lockard, David P.; Khorrami, Mehdi R.; Choudhari, Meelan M.

2011-01-01

This paper presents a numerical assessment of acoustic installation effects in the tandem cylinder (TC) experiments conducted in the NASA Langley Quiet Flow Facility (QFF), an open-jet, anechoic wind tunnel. Calculations that couple the Computational Fluid Dynamics (CFD) and Computational Aeroacoustics (CAA) of the TC configuration within the QFF are conducted using the CFD simulation results previously obtained at NASA LaRC. The coupled simulations enable the assessment of installation effects associated with several specific features in the QFF facility that may have impacted the measured acoustic signature during the experiment. The CFD-CAA coupling is based on CFD data along a suitably chosen surface, and employs a technique that was recently improved to account for installed configurations involving acoustic backscatter into the CFD domain. First, a CFD-CAA calculation is conducted for an isolated TC configuration to assess the coupling approach, as well as to generate a reference solution for subsequent assessments of QFF installation effects. Direct comparisons between the CFD-CAA calculations associated with the various installed configurations allow the assessment of the effects of each component (nozzle, collector, etc.) or feature (confined vs. free jet flow, etc.) characterizing the NASA LaRC QFF facility.

Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.

PubMed

Ye, Fei; Qu, Shuanglin; Zhou, Lei; Peng, Cheng; Wang, Chengpeng; Cheng, Jiajia; Hossain, Mohammad Lokman; Liu, Yizhou; Zhang, Yan; Wang, Zhi-Xiang; Wang, Jianbo

2015-04-08

Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).

Tandem ion mobility spectrometry coupled to laser excitation

NASA Astrophysics Data System (ADS)

Simon, Anne-Laure; Chirot, Fabien; Choi, Chang Min; Clavier, Christian; Barbaire, Marc; Maurelli, Jacques; Dagany, Xavier; MacAleese, Luke; Dugourd, Philippe

2015-09-01

This manuscript describes a new experimental setup that allows to perform tandem ion mobility spectrometry (IMS) measurements and which is coupled to a high resolution time-of-flight mass spectrometer. It consists of two 79 cm long drift tubes connected by a dual ion funnel assembly. The setup was built to permit laser irradiation of the ions in the transfer region between the two drift tubes. This geometry allows selecting ions according to their ion mobility in the first drift tube, to irradiate selected ions, and examine the ion mobility of the product ions in the second drift tube. Activation by collision is possible in the same region (between the two tubes) and between the second tube and the time-of-flight. IMS-IMS experiments on Ubiquitin are reported. We selected a given isomer of charge state +7 and explored its structural rearrangement following collisional activation between the two drift tubes. An example of IMS-laser-IMS experiment is reported on eosin Y, where laser irradiation was used to produce radical ions by electron photodetachment starting from doubly deprotonated species. This allowed measuring the collision cross section of the radical photo-product, which cannot be directly produced with an electrospray source.

High-performance liquid chromatography coupled with tandem mass spectrometry technology in the analysis of Chinese Medicine Formulas: A bibliometric analysis (1997-2015).

PubMed

He, Xi-Ran; Li, Chun-Guang; Zhu, Xiao-Shu; Li, Yuan-Qing; Jarouche, Mariam; Bensoussan, Alan; Li, Ping-Ping

2017-01-01

There is a recognized challenge in analyzing traditional Chinese medicine formulas because of their complex chemical compositions. The application of modern analytical techniques such as high-performance liquid chromatography coupled with a tandem mass spectrometry has improved the characterization of various compounds from traditional Chinese medicine formulas significantly. This study aims to conduct a bibliometric analysis to recognize the overall trend of high-performance liquid chromatography coupled with tandem mass spectrometry approaches in the analysis of traditional Chinese medicine formulas, its significance and possible underlying interactions between individual herbs in these formulas. Electronic databases were searched systematically, and the identified studies were collected and analyzed using Microsoft Access 2010, Graph Pad 5.0 software and Ucinet software package. 338 publications between 1997 and 2015 were identified, and analyzed in terms of annual growth and accumulated publications, top journals, forms of traditional Chinese medicine preparations and highly studied formulas and single herbs, as well as social network analysis of single herbs. There is a significant increase trend in using high-performance liquid chromatography coupled with tandem mass spectrometry related techniques in analysis of commonly used forms of traditional Chinese medicine formulas in the last 3 years. Stringent quality control is of great significance for the modernization and globalization of traditional Chinese medicine, and this bibliometric analysis provided the first and comprehensive summary within this field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of oxidation products of 5-methylcytosine in plants by chemical derivatization coupled with liquid chromatography/tandem mass spectrometry analysis.

PubMed

Tang, Yang; Xiong, Jun; Jiang, Han-Peng; Zheng, Shu-Jian; Feng, Yu-Qi; Yuan, Bi-Feng

2014-08-05

Cytosine methylation (5-methylcytosine, 5-mC) in DNA is an important epigenetic mark that has regulatory roles in various biological processes. In plants, active DNA demethylation can be achieved through direct cleavage by DNA glycosylases, followed by replacement of 5-mC with cytosine by base excision repair (BER) machinery. Recent studies in mammals have demonstrated 5-mC can be sequentially oxidized to 5-hydroxymethylcytosine (5-hmC), 5-formylcytosine (5-foC), and 5-carboxylcytosine (5-caC) by Ten-eleven translocation (TET) proteins. The consecutive oxidations of 5-mC constitute the active DNA demethylation pathway in mammals, which raised the possible presence of oxidation products of 5-mC (5-hmC, 5-foC, and 5-caC) in plant genomes. However, there is no definitive evidence supporting the presence of these modified bases in plant genomic DNA, especially for 5-foC and 5-caC. Here we developed a chemical derivatization strategy combined with liquid chromatography-electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method to determine 5-formyl-2'-deoxycytidine (5-fodC) and 5-carboxyl-2'-deoxycytidine (5-cadC). Derivatization of 5-fodC and 5-cadC by Girard's reagents (GirD, GirT, and GirP) significantly increased the detection sensitivities of 5-fodC and 5-cadC by 52-260-fold. Using this method, we demonstrated the widespread existence of 5-fodC and 5-cadC in genomic DNA of various plant tissues, indicating that active DNA demethylation in plants may go through an alternative pathway similar to mammals besides the pathway of direct DNA glycosylases cleavage combined with BER. Moreover, we found that environmental stresses of drought and salinity can change the contents of 5-fodC and 5-cadC in plant genomes, suggesting the functional roles of 5-fodC and 5-cadC in response to environmental stresses.

Effect of interface reaction and diffusion on stress-oxidation coupling at high temperature

NASA Astrophysics Data System (ADS)

Yue, Mengkun; Dong, Xuelin; Fang, Xufei; Feng, Xue

2018-04-01

High-temperature structural materials undergo oxidation during the service, and stress would generate in the oxide film. Understanding the coupling effect between stress and oxidation contributes to the understanding of material degradation and failure during the oxidation process. Here, we propose a model to investigative the coupling effect of stress and oxidation at high temperature by considering the three-stage oxidation process, where both the interface reaction and the diffusion process are present. The governing equations including the oxidation kinetics and stress equilibrium for isothermal oxidation under stress-oxidation coupling effect have been derived. The theory is validated by comparing with the experimental results of SiO2 grown on Si substrate. Results show that the coupling of stress and oxidation influences the growth of the oxide film by affecting all three stages of the oxidation process.

Perovskite catalysts for oxidative coupling

DOEpatents

Campbell, K.D.

1991-06-25

Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

Perovskite catalysts for oxidative coupling

DOEpatents

Campbell, Kenneth D.

1991-01-01

Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

Nitrous Oxide-dependent Iron-catalyzed Coupling Reactions of Grignard Reagents.

PubMed

Döhlert, Peter; Weidauer, Maik; Enthaler, Stephan

2015-01-01

The formation of carbon-carbon bonds is one of the fundamental transformations in chemistry. In this regard the application of palladium-based catalysts has been extensively investigated during recent years, but nowadays research focuses on iron catalysis, due to sustainability, costs and toxicity issues; hence numerous examples for iron-catalyzed cross-coupling reactions have been established, based on the coupling of electrophiles (R(1)-X, X = halide) with nucleophiles (R(2)-MgX). Only a small number of protocols deals with the iron-catalyzed oxidative coupling of nucleophiles (R(1)-MgX + R(2)-MgX) with the aid of oxidants (1,2-dihaloethanes). However, some issues arise with these oxidants; hence more recently the potential of the industrial waste product nitrous oxide (N(2)O) was investigated, because the unproblematic side product N(2) is formed. Based on that, we demonstrate the catalytic potential of easily accessible iron complexes in the oxidative coupling of Grignard reagents. Importantly, nitrous oxide was essential to obtain yields up to >99% at mild conditions (e.g. 1 atm, ambient temperature) and low catalyst loadings (0.1 mol%) Excellent catalyst performance is realized with turnover numbers of up to 1000 and turnover frequencies of up to 12000 h(-1). Moreover, a good functional group tolerance is observed (e.g. amide, ester, nitrile, alkene, alkyne). Afterwards the reaction of different Grignard reagents revealed interesting results with respect to the selectivity of cross-coupling product formation.

Solar hydrogen production by tandem cell system composed of metal oxide semiconductor film photoelectrode and dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Arakawa, H.; Shiraishi, C.; Tatemoto, M.; Kishida, H.; Usui, D.; Suma, A.; Takamisawa, A.; Yamaguchi, T.

2007-09-01

Photocatalytic and photoelectrochemical approaches to solar hydrogen production in our group were introduced. In photocatalytic water splitting system using NiO x/ TiO II powder photocatalyst with concentrated Na IICO 3 aqueous solution, solar energy conversion efficiency to H II and O II production (STH efficiency) was 0.016%. In addition, STH efficiency of visible light responding photocatalyst, NiOx/ promoted In 0.9Ni 0.1TaO 4, was estimated at 0.03%. In photoelectrochemical system using an oxide semiconductor film phptoelectrode, STH efficiencies of meosporous TiO II (Anatase) , mesoporous visible light responding S-doped TiO II (Anatase) and WO 3 film were 0.32-0.44% at applied potential of 0.35 V vs NHE, 0.14% at 0.55 V and 0.44% at 0.9 V, respectively. Finally, solar hydrogen production by tandem cell system composed of an oxide semiconductor photoelectrode, a Pt wire counter electrode and a dye-sensitized solar cell (DSC) was investigated. As photoelectrodes, meosporous TiO II (Anatase), mesoporous S-doped TiO II (Anatase), WO 3, BiVO 4 and Fe IIO 3 film were tested. STH efficiency of tandem cell system composed of a WO 3 film photoelectrode, and a two-series-connected DSC (Voc = 1.4 V) was 2.5-2.8%. In conclusion, it is speculated that more than 5% STH efficiency will be obtained by tandem cell system composed of an oxide semiconductor photoelectrode and a two-series-connected DSC in near future. This suggests a cost-effective and practical application of this system for solar hydrogen production.

Tandem SN2' nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds.

PubMed

Zhang, Zhen; Li, Cheng; Wang, Shao-Hua; Zhang, Fu-Min; Han, Xue; Tu, Yong-Qiang; Zhang, Xiao-Ming

2017-04-11

A novel and efficient tandem S N 2' nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc) 3 as an oxidant, which enables the expeditious synthesis of polysubstituted dihydrofuran (DHF) derivatives in moderate to high yields. The use of weakly acidic hexafluoroisopropanol (HFIP) as the solvent rather than AcOH has successfully improved the yields and expanded the substrate scope of this type of radical cyclization reactions. Mechanistic studies confirmed the cascade reaction process involving a final radical cyclization.

Plasma-Chemical Synthesis of Oxide Powders Using Transformer-Coupled Discharge

NASA Astrophysics Data System (ADS)

M. Ulanov, I.; V. Isupov, M.; Yu Litvinsev, A.; A. Mischenko, P.

2013-04-01

An experimental investigation of transformer-coupled discharge in an Ar-O2 mixture with the addition of SiCl4, TiCl4 and ZrCl4 has been carried out under the atmospheric pressure of plasma-forming gases. Discharge power and discharge heat losses have been determined, and the dispersion and phase composition of reaction products (oxide powders) has been analyzed with SEM and X-ray diffraction analysis. Investigations reveal the formation of ultrafine oxide powders in the case of vaporized chloride (SiCl4 and TiCl4) injecting into the transformer coupled discharge. In the case of fine powder (ZrCl4) injection, full oxidation was not observed and reaction products consisted of a mixture of ZrO2 and ZrOCl2. A conclusion has been made regarding the perspectives of using transformer-coupled discharge to produce ultrafine oxide powders.

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, R.B.; Warren, B.K.

1991-12-17

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using a catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, Richard B.; Warren, Barbara K.

1991-01-01

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

Biquadratic coupling through nano-oxide layers in pinned layers of IrMn-based spin valves

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Lu, K. H.

2003-05-01

We have investigated the coupling between top and bottom pinned layers through various nano-oxide layers (NOLs) in IrMn-based spin valves. The NOLs were formed by using oxygen-plasma oxidation or natural oxidation on 1 nm metallic layers. By inserting naturally oxidized Co-NOLs in the pinned layer, strong ferromagnetic coupling through NOLs and high specularity at the NOL interface were achieved. In contrast, when the plasma-oxidized Co-NOLs were inserted, ferromagnetic coupling through NOLs disappeared, plausibly due to the formation of nonferromagnetic oxides, which led to a low magnetoresistance (MR). Insertion of naturally oxidized Ni80Fe20-NOLs showed the same results as that of naturally oxidized Co-NOLs. On the other hand, biquadratic coupling between top and bottom pinned-Co90Fe10 layers was observed by inserting plasma-oxidized Ni80Fe20-NOLs. The highest MR was obtained when the field was applied along the direction perpendicular to the field-annealing direction. Similar biquadratic coupling was also found with naturally oxidized or plasma-oxidized Fe-NOLs. We suggest that the biquadratic coupling between pinned Co90Fe10 layers through NOLs results from the coupling between Fe (or Co90Fe10) and Fe+3 oxides

Oxidation of aromatic contaminants coupled to microbial iron reduction

USGS Publications Warehouse

Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

1989-01-01

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

Infrared photocurrent management in monolithic perovskite/silicon heterojunction tandem solar cells by using a nanocrystalline silicon oxide interlayer.

PubMed

Mazzarella, Luana; Werth, Matteo; Jäger, Klaus; Jošt, Marko; Korte, Lars; Albrecht, Steve; Schlatmann, Rutger; Stannowski, Bernd

2018-05-14

We performed optical simulations using hydrogenated nanocrystalline silicon oxide (nc-SiO x :H) as n-doped interlayer in monolithic perovskite/c-Si heterojunction tandem solar cells. Depending on the adjustable value of its refractive index (2.0 - 2.7) and thickness, nc-SiO x :H allows to optically manage the infrared light absorption in the c-Si bottom cell minimizing reflection losses. We give guidelines for nc-SiO x :H optimization in tandem devices in combination with a systematic investigation of the effect of the surface morphology (flat or textured) on the photocurrent density. For full-flat and rear textured devices, we found matched photocurrents higher than 19 and 20 mA/cm 2 , respectively, using a 90 nm nc-SiO x :H interlayer with a refractive index of 2.7.

A novel solution for hydroxylated PAHs removal by oxidative coupling reaction using Mn oxide.

PubMed

Kang, Ki-Hoon; Lim, Dong-Min; Shin, Hyun-Sang

2008-01-01

In this study, removals of 1-naphthol by oxidative-coupling reaction using birnessite, one of the natural Mn oxides present in soil, was investigated in various experimental conditions (reaction time, Mn oxide loadings, pH). The removal efficiency of 1-naphthol by birnessite was high in all the experimental conditions, and UV-visible and mass spectrometric analyses on the supernatant after reaction confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Pseudo-first order rate constants, k, for the oxidative transformation of 1-naphthol by birnessite was derived from the kinetic experiments under various amounts of birnessite loadings, and using the observed pseudo-first order rate constants with respect to birnessite loadings, the surface area normalised specific rate constant, k(surf), was also determined to be 9.3 x 10(-4) (L/m(2).min) for 1-naphthol. In addition, the oxidative transformation of 1-naphthol was found to be dependent on solution pH, and the pseudo-first order rate constants were increased from 0.129 at pH 10 to 0.187 at pH 4. (c) IWA Publishing 2008.

Heterobimetallic Catalysis: Platinum-Gold-Catalyzed Tandem Cyclization/C-X Coupling Reaction of (Hetero)Arylallenes with Nucleophiles.

PubMed

Alonso, José Miguel; Muñoz, María Paz

2018-04-16

Heterobimetallic catalysis offers new opportunities for reactivity and selectivity but still presents challenges, and only a few metal combinations have been explored so far. Reported here is a Pt-Au heterobimetallic catalyst system for the synthesis of a family of multi-heteroaromatic structures through tandem cyclization/C-X coupling reaction. Au-catalyzed 6-endo-cyclization takes place as the first fast step. Pt-Au clusters are proposed to be responsible for the increased reactivity in the second step, that is, the intermolecular nucleophilic addition which occurs through an outer-sphere mechanism by hybrid homogeneous-heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Characterisation of Acetogenins from Annona muricata by Supercritical Fluid Chromatography Coupled to High-Resolution Tandem Mass Spectrometry.

PubMed

Laboureur, Laurent; Bonneau, Natacha; Champy, Pierre; Brunelle, Alain; Touboul, David

2017-11-01

Acetogenins are plant polyketides known to be cytotoxic and proposed as antitumor candidates. They are also suspected to be alimentary neurotoxins. Their occurrence as complex mixtures renders their dereplication and structural identification difficult using liquid chromatography coupled to tandem mass spectrometry and efforts are required to improve the methodology. To develop a supercritical fluid chromatography (SFC) high-resolution tandem mass spectrometry method, involving lithium post-column cationisation, for the structural characterisation of Annonaceous acetogenins in crude extracts. The seeds of Annona muricata L. were extracted with methanol. Supercritical fluid chromatography of the extract, using a 2-ethylpyridine stationary phase column, was monitored using a high-resolution quadrupole time-of-flight mass spectrometer. Lithium iodide was added post-column in the make-up solvent. For comparison, the same extract was analysed using high-pressure liquid chromatography coupled to the same mass spectrometer, with a column based on solid core particles. Sensitivity was similar for both HPLC and SFC approaches. Retention behaviour and fragmentation pathways of three different isomer groups are described. A previously unknown group of acetogenins was also evidenced for the first time. The use of SFC-MS/MS allows the reduction of the time of analysis, of environmental impact and an increase in the chromatographic resolution, compared to liquid chromatography. This new methodology enlightened a new group of acetogenins, isomers of montanacin-D. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Hidden Interface Driven Exchange Coupling in Oxide Heterostructures

DOE PAGES

Chen, Aiping; Wang, Qiang; Fitzsimmons, Michael R.; ...

2017-05-02

In a variety of emergent phenomena have been enabled by interface engineering in complex oxides. The existence of an intrinsic interfacial layer has often been found at oxide heterointerfaces. But, the role of such an interlayerin controlling functionalities is not fully explored. Here, we report the control of the exchange bias (EB) in single-phase manganite thin films with nominallyuniform chemical composition across the interfaces. The sign of EB depends on the magnitude of the cooling field. A pinned layer, confirmed by polarized neutron reflectometry, provides the source of unidirectional anisotropy. The origin of the exchange bias coupling is discussed inmore » terms of magnetic interactions between the interfacial ferromagnetically reduced layer and the bulk ferromagnetic region. The sign of EB is related to the frustration of antiferromagnetic coupling between the ferromagnetic region and the pinned layer. These results shed new light on using oxide interfaces to design functional spintronic devices.« less

PDZ Ligand Binding-Induced Conformational Coupling of the PDZ-SH3-GK Tandems in PSD-95 Family MAGUKs.

PubMed

Zeng, Menglong; Ye, Fei; Xu, Jia; Zhang, Mingjie

2018-01-05

Discs large (DLG) MAGUKs are abundantly expressed in glutamatergic synapses, crucial for synaptic transmission, and plasticity by anchoring various postsynaptic components including glutamate receptors, downstream scaffold proteins and signaling enzymes. Different DLG members have shared structures and functions, but also contain unique features. How DLG family proteins function individually and cooperatively is largely unknown. Here, we report that PSD-95 PDZ3 directly couples with SH3-GK tandem in a PDZ ligand binding-dependent manner, and the coupling can promote PSD-95 dimerization and multimerization. Aided by sortase-mediated protein ligation and selectively labeling, we elucidated the PDZ3/SH3-GK conformational coupling mechanism using NMR spectroscopy. We further demonstrated that PSD-93, but not SAP102, can also undergo PDZ3 ligand binding-induced conformational coupling with SH3-GK and form homo-oligomers. Interestingly, PSD-95 and PSD-93 can also form ligand binding-induced hetero-oligomers, suggesting a cooperative assembly mechanism for the mega-N-methyl-d-aspartate receptor synaptic signaling complex. Finally, we provide evidence showing that ligand binding-induced conformational coupling between PDZ and SH3-GK is a common feature for other MAGUKs including CASK and PALS1. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Enantioselective oxidative biaryl coupling reactions catalyzed by 1,5-diazadecalin metal complexes.

PubMed

Li, X; Yang, J; Kozlowski, M C

2001-04-19

[reaction: see text]. Chiral 1,5-diaza-cis-decalins have been examined as ligands in the enantioselective oxidative biaryl coupling of substituted 2-naphthol derivatives. Under the optimal conditions employing a 1,5-diaza-cis-decalin copper(I) iodide complex with oxygen as the oxidant, rapid and highly selective couplings could be achieved (90-93% ee, 85% yield).

Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

2017-09-01

Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant 13C nuclei coupled to the observer spins.

Solar-to-Chemical Energy Conversion with Photoelectrochemical Tandem Cells.

PubMed

Sivula, Kevin

2013-01-01

Efficiently and inexpensively converting solar energy into chemical fuels is an important goal towards a sustainable energy economy. An integrated tandem cell approach could reasonably convert over 20% of the sun's energy directly into chemical fuels like H2 via water splitting. Many different systems have been investigated using various combinations of photovoltaic cells and photoelectrodes, but in order to be economically competitive with the production of H2 from fossil fuels, a practical water splitting tandem cell must optimize cost, longevity and performance. In this short review, the practical aspects of solar fuel production are considered from the perspective of a semiconductor-based tandem cell and the latest advances with a very promising technology - metal oxide photoelectrochemical tandem cells - are presented.

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

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

Powell, M.A.; Somero, G.N.

1986-08-01

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide asmore » an inorganic energy source.« less

Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

PubMed Central

Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

2015-01-01

Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

Thermal-mechanical coupling effect on initial stage oxidation of Si(100) surface

NASA Astrophysics Data System (ADS)

Sun, Yu; Liu, Yilun; Chen, Xuefeng; Zhai, Zhi; Izumi, Satoshi

2018-04-01

The initial stage oxidation of biaxially strained Si(100) at temperatures ranging from 300 K to 1200 K has been investigated by Reactive Force Field Molecular Dynamics simulations. We reported that the oxidation process involving the reaction rate and the amount of absorbed O atoms could be enhanced by the coupling effect of higher temperatures and larger external tension. By fitting the simulation results, the relationship between absorbed oxygen and the coupling of temperature and strain was obtained. In probing the mechanism, we observed that there was a ballistic transport of O atoms, displaying an enhancement of inward penetration by external tension. Since such an inward transport was favored by thermal actuation, more O atoms penetrated into deeper layers when the 9% strained Si oxidized at 1200 K. Moreover, the evolution of stress in the surface region during the oxidation process was discussed, as well as the related oxide structure and the film quality. These present results may provide a way to understand the thermally-mechanically coupled chemical reactions and propose an effective approach to optimize microscale component processing in the electronic field.

Oxidative coupling of sp 2 and sp 3 carbon-hydrogen bonds to construct dihydrobenzofurans.

PubMed

Shi, Jiang-Ling; Wang, Ding; Zhang, Xi-Sha; Li, Xiao-Lei; Chen, Yu-Qin; Li, Yu-Xue; Shi, Zhang-Jie

2017-08-10

Metal-catalyzed cross-couplings provide powerful, concise, and accurate methods to construct carbon-carbon bonds from organohalides and organometallic reagents. Recent developments extended cross-couplings to reactions where one of the two partners connects with an aryl or alkyl carbon-hydrogen bond. From an economic and environmental point of view, oxidative couplings between two carbon-hydrogen bonds would be ideal. Oxidative coupling between phenyl and "inert" alkyl carbon-hydrogen bonds still awaits realization. It is very difficult to develop successful strategies for oxidative coupling of two carbon-hydrogen bonds owning different chemical properties. This article provides a solution to this challenge in a convenient preparation of dihydrobenzofurans from substituted phenyl alkyl ethers. For the phenyl carbon-hydrogen bond activation, our choice falls on the carboxylic acid fragment to form the palladacycle as a key intermediate. Through careful manipulation of an additional ligand, the second "inert" alkyl carbon-hydrogen bond activation takes place to facilitate the formation of structurally diversified dihydrobenzofurans.Cross-dehydrogenative coupling is finding increasing application in synthesis, but coupling two chemically distinct sites remains a challenge. Here, the authors report an oxidative coupling between sp 2 and sp 3 carbons by sequentially activating the more active aryl site followed by the alkyl position.

Electrically coupling complex oxides to semiconductors: A route to novel material functionalities

DOE PAGES

Ngai, J. H.; Ahmadi-Majlan, K.; Moghadam, J.; ...

2017-01-12

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. In this paper, we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypicalmore » heterostructures, Ba 1-xSr xTiO 3/Ge and SrZr xTi 1-xO 3/Ge, will be discussed. In the case of Ba 1-xSr xTiO 3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZr xTi 1-xO 3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Finally, analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.« less

Electrically coupling complex oxides to semiconductors: A route to novel material functionalities

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

Ngai, J. H.; Ahmadi-Majlan, K.; Moghadam, J.

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. In this paper, we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypicalmore » heterostructures, Ba 1-xSr xTiO 3/Ge and SrZr xTi 1-xO 3/Ge, will be discussed. In the case of Ba 1-xSr xTiO 3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZr xTi 1-xO 3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Finally, analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.« less

TRedD—A database for tandem repeats over the edit distance

PubMed Central

Sokol, Dina; Atagun, Firat

2010-01-01

A ‘tandem repeat’ in DNA is a sequence of two or more contiguous, approximate copies of a pattern of nucleotides. Tandem repeats are common in the genomes of both eukaryotic and prokaryotic organisms. They are significant markers for human identity testing, disease diagnosis, sequence homology and population studies. In this article, we describe a new database, TRedD, which contains the tandem repeats found in the human genome. The database is publicly available online, and the software for locating the repeats is also freely available. The definition of tandem repeats used by TRedD is a new and innovative definition based upon the concept of ‘evolutive tandem repeats’. In addition, we have developed a tool, called TandemGraph, to graphically depict the repeats occurring in a sequence. This tool can be coupled with any repeat finding software, and it should greatly facilitate analysis of results. Database URL: http://tandem.sci.brooklyn.cuny.edu/ PMID:20624712

Microfluidic chip based nano liquid chromatography coupled to tandem mass spectrometry for the determination of abused drugs and metabolites in human hair.

PubMed

Zhu, Kevin Y; Leung, K Wing; Ting, Annie K L; Wong, Zack C F; Ng, Winki Y Y; Choi, Roy C Y; Dong, Tina T X; Wang, Tiejie; Lau, David T W; Tsim, Karl W K

2012-03-01

A microfluidic chip based nano-HPLC coupled to tandem mass spectrometry (nano-HPLC-Chip-MS/MS) has been developed for simultaneous measurement of abused drugs and metabolites: cocaine, benzoylecgonine, cocaethylene, norcocaine, morphine, codeine, 6-acetylmorphine, phencyclidine, amphetamine, methamphetamine, MDMA, MDA, MDEA, and methadone in the hair of drug abusers. The microfluidic chip was fabricated by laminating polyimide films and it integrated an enrichment column, an analytical column and a nanospray tip. Drugs were extracted from hairs by sonication, and the chromatographic separation was achieved in 15 min. The drug identification and quantification criteria were fulfilled by the triple quardropule tandem mass spectrometry. The linear regression analysis was calibrated by deuterated internal standards with all of the R(2) at least over 0.993. The limit of detection (LOD) and the limit of quantification (LOQ) were from 0.1 to 0.75 and 0.2 to 1.25 pg/mg, respectively. The validation parameters including selectivity, accuracy, precision, stability, and matrix effect were also evaluated here. In conclusion, the developed sample preparation method coupled with the nano-HPLC-Chip-MS/MS method was able to reveal the presence of drugs in hairs from the drug abusers, with the enhanced sensitivity, compared with the conventional HPLC-MS/MS.

Oxidative coupling of methane using inorganic membrane reactor

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

Ma, Y.H.; Moser, W.R.; Dixon, A.G.

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gasmore » phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.« less

Benzene oxidation coupled to sulfate reduction

USGS Publications Warehouse

Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

1995-01-01

Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

Lipid Identification by Untargeted Tandem Mass Spectrometry Coupled with Ultra-High-Pressure Liquid Chromatography.

PubMed

Gugiu, Gabriel B

2017-01-01

Lipidomics refers to the large-scale study of lipids in biological systems (Wenk, Nat Rev Drug Discov 4(7):594-610, 2005; Rolim et al., Gene 554(2):131-139, 2015). From a mass spectrometric point of view, by lipidomics we understand targeted or untargeted mass spectrometric analysis of lipids using either liquid chromatography (LC) (Castro-Perez et al., J Proteome Res 9(5):2377-2389, 2010) or shotgun (Han and Gross, Mass Spectrom Rev 24(3):367-412, 2005) approaches coupled with tandem mass spectrometry. This chapter describes the former methodology, which is becoming rapidly the preferred method for lipid identification owing to similarities with established omics workflows, such as proteomics (Washburn et al., Nat Biotechnol 19(3):242-247, 2001) or genomics (Yadav, J Biomol Tech: JBT 18(5):277, 2007). The workflow described consists in lipid extraction using a modified Bligh and Dyer method (Bligh and Dyer, Can J Biochem Physiol 37(8):911-917, 1959), ultra high pressure liquid chromatography fractionation of lipid samples on a reverse phase C18 column, followed by tandem mass spectrometric analysis and in silico database search for lipid identification based on MSMS spectrum matching (Kind et al., Nat Methods 10(8):755-758, 2013; Yamada et al., J Chromatogr A 1292:211-218, 2013; Taguchi and Ishikawa, J Chromatogr A 1217(25):4229-4239, 2010; Peake et al., Thermoscientifices 1-3, 2015) and accurate mass of parent ion (Sud et al., Nucleic Acids Res 35(database issue):D527-D532, 2007; Wishart et al., Nucleic Acids Res 35(database):D521-D526, 2007).

External control of electron energy distributions in a dual tandem inductively coupled plasma

NASA Astrophysics Data System (ADS)

Liu, Lei; Sridhar, Shyam; Zhu, Weiye; Donnelly, Vincent M.; Economou, Demetre J.; Logue, Michael D.; Kushner, Mark J.

2015-08-01

The control of electron energy probability functions (EEPFs) in low pressure partially ionized plasmas is typically accomplished through the format of the applied power. For example, through the use of pulse power, the EEPF can be modulated to produce shapes not possible under continuous wave excitation. This technique uses internal control. In this paper, we discuss a method for external control of EEPFs by transport of electrons between separately powered inductively coupled plasmas (ICPs). The reactor incorporates dual ICP sources (main and auxiliary) in a tandem geometry whose plasma volumes are separated by a grid. The auxiliary ICP is continuously powered while the main ICP is pulsed. Langmuir probe measurements of the EEPFs during the afterglow of the main ICP suggests that transport of hot electrons from the auxiliary plasma provided what is effectively an external source of energetic electrons. The tail of the EEPF and bulk electron temperature were then elevated in the afterglow of the main ICP by this external source of power. Results from a computer simulation for the evolution of the EEPFs concur with measured trends.

Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

PubMed

Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

2015-11-01

Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

Synthesis of Benzannulated Medium-ring Lactams via a Tandem Oxidative Dearomatization-Ring Expansion Reaction.

PubMed

Guney, Tezcan; Wenderski, Todd A; Boudreau, Matthew W; Tan, Derek S

2018-06-23

Medium-ring natural products exhibit diverse biological activities but such scaffolds are underrepresented in probe and drug discovery efforts due to the limitations of classical macrocyclization reactions. We report herein a tandem oxidative dearomatization-ring-expanding rearoma¬tization (ODRE) reaction that generates benzannulated medium-ring lactams directly from simple bicyclic substrates. The reaction accommodates diverse aryl substrates (haloarenes, aryl ethers, aryl amides, heterocycles) and strategic incorporation of a bridgehead alcohol generates a versatile ketone moiety in the products amenable to downstream modifications. Cheminformatic analysis indicates that these medium rings access regions of chemical space that overlap with related natural products and are distinct from synthetic drugs, setting the stage for their use in discovery screening against novel biological targets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

PubMed

Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

2012-11-16

In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

PubMed Central

Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

2014-01-01

Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

Copper-catalyzed, C-C coupling-based one-pot tandem reactions for the synthesis of benzofurans using o-iodophenols, acyl chlorides, and phosphorus ylides.

PubMed

Liu, Yunyun; Wang, Hang; Wan, Jie-Ping

2014-11-07

One-pot reactions involving acyl chlorides, phosphorus ylides, and o-iodophenols with copper catalysis have been established for the rapid synthesis of functionalized benzofurans. With all of these easily available and stable reactants, the construction of the target products has been accomplished via tandem transformations involving a key C-C coupling, leading to the formation of one C(sp(2))-C bond, one C(sp(2))-O bond, and one C ═ C bond.

Controlling site selectivity in Pd-catalyzed oxidative cross-coupling reactions.

PubMed

Lyons, Thomas W; Hull, Kami L; Sanford, Melanie S

2011-03-30

This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl-H) with cyclometalating substrates (L~C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.

Sputtered Metal Oxide Broken Gap Junctions for Tandem Solar Cells

NASA Astrophysics Data System (ADS)

Johnson, Forrest

Broken gap metal oxide junctions have been created for the first time by sputtering using ZnSnO3 for the n-type material and Cu 2O or CuAlO2 for the p-type material. Films were sputtered from either ceramic or metallic targets at room temperature from 10nm to 220nm thick. The band structure of the respective materials have theoretical work functions which line up with the band structure for tandem CIAGS/CIGS solar cell applications. Multiple characterization methods demonstrated consistent ohmic I-V profiles for devices on rough surfaces such as ITO/glass and a CIAGS cell. Devices with total junction specific contact resistance of under 0.001 Ohm-cm2 have been achieved with optical transmission close to 100% using 10nm films. Devices showed excellent stability up to 600°C anneals over 1hr using ZnSnO3 and CuAlO2. These films were also amorphous -a great diffusion barrier during top cell growth at high temperatures. Rapid Thermal Anneal (RTA) demonstrated the ability to shift the band structure of the whole device, allowing for tuning it to align with adjacent solar layers. These results remove a key barrier for mass production of multi-junction thin film solar cells.

Copper-catalyzed oxidative homo- and cross-coupling of Grignard reagents using diaziridinone.

PubMed

Zhu, Yingguang; Xiong, Tao; Han, Wenyong; Shi, Yian

2014-12-05

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)-C(sp(3)) coupling.

Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

PubMed Central

Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

2016-01-01

Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene. PMID:27181191

IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

EPA Science Inventory

The presence of molecular oxygen in the test environment promotes oxidative coupling (polymer formation) of phenolic compounds on the surface of granular activated carbon (GAC). Both adsorption equilibria and adsorption kinetics are affected by these chemical reactions. Lack of...

Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye‐sensitized Solar Cells

PubMed Central

Cong, Jiayan; Hao, Yan; Boschloo, Gerrit

2014-01-01

Abstract A new TEMPO–Co tandem redox system with TEMPO and Co(bpy)3 2+/3+ has been investigated for the use in dye‐sensitized solar cells (DSSCs). A large open‐circuit voltage (V OC) increase, from 862 mV to 965 mV, was observed in the tandem redox system, while the short‐circuit current density (J SC) was maintained. The conversion efficiency was observed to increase from 7.1 % for cells containing the single Co(bpy)3 2+/3+ redox couple, to 8.4 % for cells containing the TEMPO–Co tandem redox system. The reason for the increase in V OC and overall efficiency is ascribed to the involvement of partial regeneration of the sensitizing dye molecules by TEMPO. This assumption can be verified through the observed much faster regeneration dynamics exhibited in the presence of the tandem system. Using the tandem redox system, the faster recombination problem of the single TEMPO redox couple is resolved and the mass‐transport of the metal‐complex‐based electrolyte is also improved. This TEMPO–Co tandem system is so far the most effienct tandem redox electrolyte reported not involving iodine. The current results show a promising future for tandem system as replacements for single redox systems in electrolytes for DSSCs. PMID:25504818

Copper-Catalyzed Oxidative Homo- and Cross-Coupling of Grignard Reagents Using Diaziridinone

PubMed Central

2015-01-01

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)–C(sp3) coupling. PMID:25420218

Coupling Between the Thermosphere and the Stratosphere: the Role of Nitric Oxide

NASA Technical Reports Server (NTRS)

Brasseur, G.

1984-01-01

In order to understand the lower ionosphere and its probable control by dynamical processes, the behavior of nitric oxide below 100 km was investigated. A two dimensional model with coupled chemical and dynamical processes was constructed. Calculations based on the model reveal that the chemical conditions at the stratopause are related to the state of the thermosphere. This coupling mechanism can be partly explained by the downward transport of nitric oxide during the winter season, and consequently depends on the dynamical conditions in the mesosphere and in the lower thermosphere (mean circulation and waves). In summer, the photodissociation of nitric oxide plays an important role and the thermospheric NO abundance modulates the radiation field reaching the upper stratosphere. Perturbations in the nitric oxide concentration above the mesopause could therefore have an impact in the vicinity of the stratopause.

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

PubMed Central

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Electro-mechanical coupling of semiconductor film grown on stainless steel by oxidation

NASA Astrophysics Data System (ADS)

Lin, M. C.; Wang, G.; Guo, L. Q.; Qiao, L. J.; Volinsky, Alex A.

2013-09-01

Electro-mechanical coupling phenomenon in oxidation film on stainless steel has been discovered by using current-sensing atomic force microscopy, along with the I-V curves measurements. The oxidation films exhibit either ohmic, n-type, or p-type semiconductor properties, according to the obtained I-V curves. This technique allows characterizing oxidation films with high spatial resolution. Semiconductor properties of oxidation films must be considered as additional stress corrosion cracking mechanisms.

Synthesis of 1-methyleneindenes via palladium-catalyzed tandem reactions.

PubMed

Ye, Shengqing; Gao, Ke; Zhou, Haibo; Yang, Xiaodi; Wu, Jie

2009-09-28

Palladium-catalyzed tandem reactions of 2-alkenylphenyl-acetylenes with CuCl2 or CuBr2 afforded 3-chloro- or 3-bromo-1-methyleneindenes in good yields; these compounds could be further elaborated via palladium-catalyzed coupling reactions.

47 CFR 69.111 - Tandem-switched transport and tandem charge.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 3 2011-10-01 2011-10-01 false Tandem-switched transport and tandem charge. 69... SERVICES (CONTINUED) ACCESS CHARGES Computation of Charges § 69.111 Tandem-switched transport and tandem...-switched transport shall consist of two rate elements, a transmission charge and a tandem switching charge...

White-emissive tandem-type hybrid organic/polymer diodes with (0.33, 0.33) chromaticity coordinates.

PubMed

Guo, Tzung-Fang; Wen, Ten-Chin; Huang, Yi-Shun; Lin, Ming-Wei; Tsou, Chuan-Cheng; Chung, Chia-Tin

2009-11-09

This study reports fabrication of white-emissive, tandem-type, hybrid organic/polymer light-emitting diodes (O/PLED). The tandem devices are made by stacking a blue-emissive OLED on a yellow-emissive phenyl-substituted poly(para-phenylene vinylene) copolymer-based PLED and applying an organic oxide/Al/molybdenum oxide (MoO(3)) complex structure as a connecting structure or charge-generation layer (CGL). The organic oxide/Al/MoO(3) CGL functions as an effective junction interface for the transport and injection of opposite charge carriers through the stacked configuration. The electroluminescence (EL) spectra of the tandem-type devices can be tuned by varying the intensity of the emission in each emissive component to yield the visible-range spectra from 400 to 750 nm, with Commission Internationale de l'Eclairage chromaticity coordinates of (0.33, 0.33) and a high color rendering capacity as used for illumination. The EL spectra also exhibit good color stability under various bias conditions. The tandem-type device of emission with chromaticity coordinates, (0.30, 0.31), has maximum brightness and luminous efficiency over 25,000 cd/m(2) and approximately 4.2 cd/A, respectively.

The direct analysis of drug distribution of rotigotine-loaded microspheres from tissue sections by LESA coupled with tandem mass spectrometry.

PubMed

Xu, Li-Xiao; Wang, Tian-Tian; Geng, Yin-Yin; Wang, Wen-Yan; Li, Yin; Duan, Xiao-Kun; Xu, Bin; Liu, Charles C; Liu, Wan-Hui

2017-09-01

The direct analysis of drug distribution of rotigotine-loaded microspheres (RoMS) from tissue sections by liquid extraction surface analysis (LESA) coupled with tandem mass spectrometry (MS/MS) was demonstrated. The RoMS distribution in rat tissues assessed by the ambient LESA-MS/MS approach without extensive or tedious sample pretreatment was compared with that obtained by a conventional liquid chromatography tandem mass spectrometry (LC-MS/MS) method in which organ excision and subsequent solvent extraction were commonly employed before analysis. Results obtained from the two were well correlated for a majority of the organs, such as muscle, liver, stomach, and hippocampus. The distribution of RoMS in the brain, however, was found to be mainly focused in the hippocampus and striatum regions as shown by the LESA-imaged profiles. The LESA approach we developed is sensitive enough, with an estimated LLOQ at 0.05 ng/mL of rotigotine in brain tissue, and information-rich with minimal sample preparation, suitable, and promising in assisting the development of new drug delivery systems for controlled drug release and protection. Graphical abstract Workflow for the LESA-MS/MS imaging of brain tissue section after intramuscular RoMS administration.

Quantitative multiresidue analysis of antibiotics in milk and milk powder by ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometry.

PubMed

Tian, He; Wang, Jiaqi; Zhang, Yangdong; Li, Songli; Jiang, Jindou; Tao, Dali; Zheng, Nan

2016-10-15

A simple and fast multiresidue extraction and purification method was developed for the determination of 61 veterinary drugs, belonging to seven classes, in milk and milk powder. The extraction depends on the acetonitrile solvent, followed by a single step to remove lipids with fatty acid chains using a new reversed phase SPE without traditional pre-equilibration and washing steps before eluting SPE. The purifying lipid effect of the present preparation method was evaluated by comparing the response changes of ion peak areas of the milk endogenous metabolites before and after SPE treatment using ultra-fast LC coupled to tandem quadrupole and TOF MS. Subsequently, UPLC coupled to tandem quadrupole MS was performed for the quantitative analysis of milk and milk powder samples spiked with 61 veterinary drugs, including β-lactam, macrolide, amide alcohol, forest amine, sulfanilamide, tetracyclines, and quinolones antibiotics. This method is very simple, fast, sensitive, and selective, and allows the good recoveries of all compounds, with a recovery range of 61.5-118.6%, and coefficients of variation of less than 11.6%. The 61 compounds behave in the dynamic range 0.01-200μgkg(-1), with correlation coefficient >0.99. The limits of quantification for the analytes are in the range 0.01-5.18μgkg(-1). Finally, this method has been successfully applied to the screening of veterinary drugs in 50 commercial bovine milk and milk powder samples, and ceftiofur and ciprofloxacin were detected in some brand samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Fabrication of visible light-triggered photocatalytic materials from the coupling of n-type zinc oxide and p-type copper oxide

NASA Astrophysics Data System (ADS)

Gorospe, A. B.; Herrera, M. U.

2017-04-01

Coupling of copper oxide (CuO) and zinc oxide (ZnO) was done by chemical precipitation method. In this method, copper sulfate pentahydrate and zinc sulfate heptahydrate salt precursors were separately dissolved in distilled water; then were mixed together. The copper sulfate-zinc sulfate solution was then combined with a sodium hydroxide solution. The precipitates were collected and washed in distilled water and ethanol several times, then filtered and dried. The dried sample was grounded, and then undergone heat treatment. After heating, the sample was grounded again. Zinc oxide powder and copper oxide powder were also fabricated using chemical precipitation method. X-Ray Diffraction measurements of the coupled CuO/ZnO powder showed the presence of CuO and ZnO in the fabricated sample. Furthermore, other peaks shown by XRD were also identified corresponding to copper, copper (II) oxide, copper sulfate and zinc sulfate. Results of the photocatalytic activity investigation show that the sample exhibited superior photocatalytic degradation of methyl orange under visible light illumination compared to copper oxide powder and zinc oxide powder. This may be attributed to the lower energy gap at the copper oxide-zinc oxide interface, compared to zinc oxide, allowing visible light to trigger its photocatalytic activity.

R&D issues in scale-up and manufacturing of amorphous silicon tandem modules

NASA Astrophysics Data System (ADS)

Arya, R. R.; Carlson, D. E.; Chen, L. F.; Ganguly, G.; He, M.; Lin, G.; Middya, R.; Wood, G.; Newton, J.; Bennett, M.; Jackson, F.; Willing, F.

1999-03-01

R & D on amorphous silicon based tandem junction devices has improved the throughtput, the material utilization, and the performance of devices on commercial tin oxide coated glass. The tandem junction technology has been scaled-up to produce 8.6 Ft2 monolithically integrated modules in manufacturing at the TF1 plant. Optimization of performance and stability of these modules is ongoing.

Mobility platform coupling device and method for coupling mobility platforms

DOEpatents

Shirey, David L.; Hayward, David R.; Buttz, James H.

2002-01-01

A coupling device for connecting a first mobility platform to a second mobility platform in tandem. An example mobility platform is a robot. The coupling device has a loose link mode for normal steering conditions and a locking position, tight link mode for navigation across difficult terrain and across obstacles, for traversing chasms, and for navigating with a reduced footprint in tight steering conditions.

Fast quantification of endogenous carbohydrates in plasma using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry.

PubMed

Zhu, Bangjie; Liu, Feng; Li, Xituo; Wang, Yan; Gu, Xue; Dai, Jieyu; Wang, Guiming; Cheng, Yu; Yan, Chao

2015-01-01

Endogenous carbohydrates in biosamples are frequently highlighted as the most differential metabolites in many metabolomics studies. A simple, fast, simultaneous quantitative method for 16 endogenous carbohydrates in plasma has been developed using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry. In order to quantify 16 endogenous carbohydrates in plasma, various conditions, including columns, chromatographic conditions, mass spectrometry conditions, and plasma preparation methods, were investigated. Different conditions in this quantified analysis were performed and optimized. The reproducibility, precision, recovery, matrix effect, and stability of the method were verified. The results indicated that a methanol/acetonitrile (50:50, v/v) mixture could effectively and reproducibly precipitate rat plasma proteins. Cold organic solvents coupled with vortex for 1 min and incubated at -20°C for 20 min were the most optimal conditions for protein precipitation and extraction. The results, according to the linearity, recovery, precision, matrix effect, and stability, showed that the method was satisfactory in the quantification of endogenous carbohydrates in rat plasma. The quantified analysis of endogenous carbohydrates in rat plasma performed excellently in terms of sensitivity, high throughput, and simple sample preparation, which met the requirement of quantification in specific expanded metabolomic studies after the global metabolic profiling research. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of aniline containing proteins using an oxidative coupling strategy.

PubMed

Hooker, Jacob M; Esser-Kahn, Aaron P; Francis, Matthew B

2006-12-13

A new bioconjugation reaction has been developed based on the chemoselective modification of anilines through an oxidative coupling pathway. Aryl amines were installed on the surface of protein substrates through lysine acylation reactions or through the use of native chemical ligation techniques. Upon exposure to NaIO4 in aqueous buffer, the anilines coupled rapidly to the aromatic rings of N,N-dialkyl-N'-acyl-p-phenylenediamines. The identities of the reaction products were confirmed using ESI-MS and through comparison to small molecule analogs. Control experiments indicated that none of the native amino acids participated in the reaction. The resulting bioconjugates were found to be stable toward hydrolysis from pH 4 to pH 11 and in the presence of many commonly used oxidants, reductants, and nucleophiles. A fluorescent phenylenediamine reagent was synthesized for the selective detection of aniline labeled proteins in mixtures, and the reaction was used to append the C-terminus of the green fluorescent protein with a single PEG chain. When combined with techniques for the incorporation of unnatural amino acids into proteins, this bioorthogonal coupling method should prove useful for a number of applications requiring a high degree of labeling specificity.

Determination of azithromycin residue in pork using a molecularly imprinted monolithic microcolumn coupled to liquid chromatography with tandem mass spectrometry.

PubMed

Zhou, Tong; Yang, Haicui; Jin, Zhen; Liu, Qingying; Song, Xuqin; He, Limin; Fang, Binghu; Meng, Chenying

2016-04-01

Using spiramycin as a dummy template, a molecularly imprinted polymer monolithic micro-column with high selection to azithromycin was prepared in a micropipette tip. The imprinting factor of the monolithic micro-column prepared was approximately 2.67 and the morphological structure of the polymers was characterized by scanning electron microscopy. A simple, sensitive, and reproducible method based on the imprinted monolithic micro-column coupled to liquid chromatography with tandem mass spectrometry was developed for determining the residues of azithromycin in pork. Pork samples were extracted with acetonitrile, cleaned up under the optimal monolithic micro-column conditions, and analyzed using liquid chromatography with tandem mass spectrometry in the multiple reaction monitoring mode. The assay exhibited a linear dynamic range of 0.50-50 μg/L with the correlation coefficient (r(2) ) above 0.99. In the three spiking levels of 0.50, 1.0, and 10 μg/kg, the average recoveries of azithromycin from pork samples were between 85.8 and 96.5% with a relative standard deviation below 10%. The limit of detection and limit of quantitation were 0.03 and 0.1 μg/kg, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective Ether/Ester C–O Cleavage of an Acetylated Lignin Model via Tandem Catalysis

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

Lohr, Tracy L.; Li, Zhi; Marks, Tobin J.

2015-11-06

Lignin, a heterogeneous phenolic polymer which constitutes roughly 15 to 20 wt % of lignocellulosic biomass (cellulose, hemicellose, and lignin), represents one of the few renewable sources of aromatic monomers.(1) Current lignin depolymerization methodologies, including base-catalyzed,(2) acid-catalyzed,(3) metal-catalyzed,(4) ionic liquid (IL)-assisted,(5) and supercritical-fluid-assisted(2b, 6) approaches, typically afford low yields (~10–20% or less) of low molecular weight aromatics under relatively harsh reaction conditions (>300 °C).(7) Recent advances include using oxidized lignin and lignin models,(8) where oxidation of the Cα alcohol facilitates depolymerizaton, with aromatic monomer yields reaching up to 52% for aspen “hardwood” lignin.(9) The most common structural lignin motifs containmore » a β-O-4 aryl-ether linkage,(10) a primary alcohol in the γ skeletal position, and a secondary alcohol in the α position (Scheme 1). Our laboratory has previously demonstrated an effective strategy for thermodynamically leveraged etheric and esteric C–O bond hydrogenolysis using a tandem metal triflate + supported palladium catalytic system.(11) A homogeneous M(OTf)n catalyst mediates endothermic ether or near thermoneutral ester C–O bond scission (the reverse of hydroelementation), which is coupled to exothermic Pd-catalyzed hydrogenation of the resulting C=C unsaturation, driving the overall process downhill. We next asked whether this tandem system might be applicable to cleaving the β-O-4 aryl-ether bond in lignin and lignin models. The promising results of that investigation are communicated here.« less

R&D issues in scale-up and manufacturing of amorphous silicon tandem modules

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

Arya, R.R.; Carlson, D.E.; Chen, L.F.

1999-03-01

R & D on amorphous silicon based tandem junction devices has improved the throughtput, the material utilization, and the performance of devices on commercial tin oxide coated glass. The tandem junction technology has been scaled-up to produce 8.6&hthinsp;Ft{sup 2} monolithically integrated modules in manufacturing at the TF1 plant. Optimization of performance and stability of these modules is ongoing. {copyright} {ital 1999 American Institute of Physics.}

DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Chaban, Galina M.; Wang, Dunyou; Dateo, Christopher E.

2005-01-01

Oxidative damages by ionizing radiation are the source of radiation-induced carcinogenesis, damage to the central nervous system, lowering of the immune response, as well as other radiation-induced damages to human health. Monte Carlo track simulations and kinetic modeling of radiation damages to the DNA employ available molecular and cellular data to simulate the biological effect of high and low LET radiation io the DNA. While the simulations predict single and double strand breaks and base damages, so far all complex lesions are the result of stochastic coincidence from independent processes. Tandem double lesions have not yet been taken into account. Unlike the standard double lesions that are produced by two separate attacks by charged particles or radicals, tandem double lesions are produced by one single attack. The standard double lesions dominate at the high dosage regime. On the other hand, tandem double lesions do not depend on stochastic coincidences and become important at the low dosage regime of particular interest to NASA. Tandem double lesions by hydroxyl radical attack of guanine in isolated DNA have been reported at a dosage of radiation as low as 10 Gy. The formation of two tandem base lesions was found to be linear with the applied doses, a characteristic of tandem lesions. However, tandem double lesions from attack by a charged particle have not been reported.

Simulation study of GaAsP/Si tandem cells including the impact of threading dislocations on the luminescent coupling between the cells

NASA Astrophysics Data System (ADS)

Onno, Arthur; Harder, Nils-Peter; Oberbeck, Lars; Liu, Huiyun

2016-03-01

A model, derived from the detailed balance model from Shockley and Queisser, has been adapted to monolithically grown GaAsP/Si tandem dual junction solar cells. In this architecture, due to the difference of lattice parameters between the silicon bottom cell - acting as the substrate - and the GaAsP top cell, threading dislocations (TDs) arise at the IIIV/ Si interface and propagate in the top cell. These TDs act as non-radiative recombination centers, degrading the performances of the tandem cell. Our model takes into account the impact of TDs by integrating the NTT model developed by Yamaguchi et. al.. Two surface geometries have been investigated: flat and ideally textured. Finally the model considers the luminescent coupling (LC) between the cells due to reemitted photons from the top cell cascading to the bottom cell. Without dislocations, LC allows a greater flexibility in the cell design by rebalancing the currents between the two cells when the top cell presents a higher short-circuit current. However we show that, as the TD density (TDD) increases, nonradiative recombinations take over radiative recombinations in the top cell and the LC is quenched. As a result, nonoptimized tandem cells with higher short-circuit current in the top cell experience a very fast degradation of efficiency for TDDs over 104cm-2. On the other hand optimized cells with matching currents only experience a small efficiency drop for TDDs up to 105cm-2. High TDD cells therefore need to be current-matched for optimal performances as the flexibility due to LC is lost.

MR-Tandem: parallel X!Tandem using Hadoop MapReduce on Amazon Web Services.

PubMed

Pratt, Brian; Howbert, J Jeffry; Tasman, Natalie I; Nilsson, Erik J

2012-01-01

MR-Tandem adapts the popular X!Tandem peptide search engine to work with Hadoop MapReduce for reliable parallel execution of large searches. MR-Tandem runs on any Hadoop cluster but offers special support for Amazon Web Services for creating inexpensive on-demand Hadoop clusters, enabling search volumes that might not otherwise be feasible with the compute resources a researcher has at hand. MR-Tandem is designed to drop in wherever X!Tandem is already in use and requires no modification to existing X!Tandem parameter files, and only minimal modification to X!Tandem-based workflows. MR-Tandem is implemented as a lightly modified X!Tandem C++ executable and a Python script that drives Hadoop clusters including Amazon Web Services (AWS) Elastic Map Reduce (EMR), using the modified X!Tandem program as a Hadoop Streaming mapper and reducer. The modified X!Tandem C++ source code is Artistic licensed, supports pluggable scoring, and is available as part of the Sashimi project at http://sashimi.svn.sourceforge.net/viewvc/sashimi/trunk/trans_proteomic_pipeline/extern/xtandem/. The MR-Tandem Python script is Apache licensed and available as part of the Insilicos Cloud Army project at http://ica.svn.sourceforge.net/viewvc/ica/trunk/mr-tandem/. Full documentation and a windows installer that configures MR-Tandem, Python and all necessary packages are available at this same URL. brian.pratt@insilicos.com

Rapid residue analysis of four triazolopyrimidine herbicides in soil, water, and wheat by ultra-performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Liu, Xingang; Xu, Jun; Li, Yuanbo; Dong, Fengshou; Li, Jing; Song, Wenchen; Zheng, Yongquan

2011-03-01

A sensitive and effective method for simultaneous determination of triazolopyrimidine sulfonamide herbicide residues in soil, water, and wheat was developed using ultra-performance liquid chromatography coupled with tandem mass spectrometry. The four herbicides (pyroxsulam, flumetsulam, metosulam, and diclosulam) were cleaned up with an off-line C18 SPE cartridge and detected by tandem mass spectrometry using an electrospray ionization source in positive mode (ESI+). The determination of the target compounds was achieved in <2.0 min. The limits of detection were below 1 μg kg(-1), while the limits of quantification did not exceed 3 μg kg(-1) in different matrices. Quantitation was determined from calibration curves of standards containing 0.05-100 μg L(-1) with r(2) > 0.997. Recovery studies were conducted at three spiked levels (0.2, 1, and 5 μg kg(-1) for water; 5, 10, and 100 μg kg(-1) for soil and wheat). The overall average recoveries for this method in water, soil, wheat plants, and seeds at three levels ranged from 75.4% to 106.0%, with relative standard deviations in the range of 2.1-12.5% (n = 5) for all analytes.

Identification of oxidative coupling products of xylenols arising from laboratory-scale phytoremediation.

PubMed

Poerschmann, J; Schultze-Nobre, L; Ebert, R U; Górecki, T

2015-01-01

Oxidative coupling reactions take place during the passage of xylenols through a laboratory-scale helophyte-based constructed wetland system. Typical coupling product groups including tetramethyl-[1,1'-biphenyl] diols and tetramethyl diphenylether monools as stable organic intermediates could be identified by a combination of pre-chromatographic derivatization and GC/MS analysis. Structural assignment of individual analytes was performed by an increment system developed by Zenkevich to pre-calculate retention sequences. The most abundant analyte turned out to be 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, which can be formed by a combination of radicals based on 2,6-xylenol or by an attack of a 2,6-xylenol-based radical on 2,6-xylenol. Organic intermediates originating from oxidative coupling could also be identified in anaerobic constructed wetland systems. This finding suggested the presence of (at least partly) oxic conditions in the rhizosphere. Copyright © 2014 Elsevier Ltd. All rights reserved.

MR-Tandem: parallel X!Tandem using Hadoop MapReduce on Amazon Web Services

PubMed Central

Pratt, Brian; Howbert, J. Jeffry; Tasman, Natalie I.; Nilsson, Erik J.

2012-01-01

Summary: MR-Tandem adapts the popular X!Tandem peptide search engine to work with Hadoop MapReduce for reliable parallel execution of large searches. MR-Tandem runs on any Hadoop cluster but offers special support for Amazon Web Services for creating inexpensive on-demand Hadoop clusters, enabling search volumes that might not otherwise be feasible with the compute resources a researcher has at hand. MR-Tandem is designed to drop in wherever X!Tandem is already in use and requires no modification to existing X!Tandem parameter files, and only minimal modification to X!Tandem-based workflows. Availability and implementation: MR-Tandem is implemented as a lightly modified X!Tandem C++ executable and a Python script that drives Hadoop clusters including Amazon Web Services (AWS) Elastic Map Reduce (EMR), using the modified X!Tandem program as a Hadoop Streaming mapper and reducer. The modified X!Tandem C++ source code is Artistic licensed, supports pluggable scoring, and is available as part of the Sashimi project at http://sashimi.svn.sourceforge.net/viewvc/sashimi/trunk/trans_proteomic_pipeline/extern/xtandem/. The MR-Tandem Python script is Apache licensed and available as part of the Insilicos Cloud Army project at http://ica.svn.sourceforge.net/viewvc/ica/trunk/mr-tandem/. Full documentation and a windows installer that configures MR-Tandem, Python and all necessary packages are available at this same URL. Contact: brian.pratt@insilicos.com PMID:22072385

Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1989-01-01

The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

Lignins : natural polymers from oxidative coupling of 4-hydroxyphenyl-propanoids

Treesearch

John Ralph; Knut Lundquist; Gosta Brunow; Fachuang Lu; Hoon Kim; Paul F. Schatz; Jane M. Marita; Ronald D. Hatfield; Sally A. Ralph; Jorgen Holst Christensen; Wout Boerjan

2004-01-01

Lignins are complex natural polymers resulting from oxidative coupling of, primarily, 4-hydroxyphenylpropanoids. An understanding of their nature is evolving as a result of detailed structural studies, recently aided by the availability of lignin-biosynthetic-pathway mutants and transgenics. The currently accepted theory is that the lignin polymer is formed by...

Polarization-coupled tunable resistive behavior in oxide ferroelectric heterostructures

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

Gruverman, Alexei; Tsymbal, Evgeny Y.; Eom, Chang-Beom

2017-05-03

This research focuses on investigation of the physical mechanism of the electrically and mechanically tunable resistive behavior in oxide ferroelectric heterostructures with engineered interfaces realized via a strong coupling of ferroelectric polarization with tunneling electroresistance and metal-insulator (M-I) transitions. This report describes observation of electrically conductive domain walls in semiconducting ferroelectrics, voltage-free control of resistive switching and demonstration of a new mechanism of electrical control of 2D electron gas (2DEG) at oxide interfaces. The research goals are achieved by creating strong synergy between cutting-edge fabrication of epitaxial single-crystalline complex oxides, nanoscale electrical characterization by scanning probe microscopy and theoretical modelingmore » of the observed phenomena. The concept of the ferroelectric devices with electrically and mechanically tunable nonvolatile resistance represents a new paradigm shift in realization of the next-generation of non-volatile memory devices and low-power logic switches.« less

Ternary and coupled binary zinc tin oxide nanopowders: Synthesis, characterization, and potential application in photocatalytic processes

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

Ivetić, T.B., E-mail: tamara.ivetic@df.uns.ac.rs; Finčur, N.L.; Đačanin, Lj. R.

2015-02-15

Highlights: • Mechanochemically synthesized nanocrystalline zinc tin oxide (ZTO) powders. • Photocatalytic degradation of alprazolam in the presence of ZTO water suspensions. • Coupled binary ZTO exhibits enhanced photocatalytic activity compared to ternary ZTO. - Abstract: In this paper, ternary and coupled binary zinc tin oxide nanocrystalline powders were prepared via simple solid-state mechanochemical method. X-ray diffraction, scanning electron microscopy, Raman and reflectance spectroscopy were used to study the structure and optical properties of the obtained powder samples. The thermal behavior of zinc tin oxide system was examined through simultaneous thermogravimetric-differential scanning calorimetric analysis. The efficiencies of ternary (Zn{sub 2}SnO{submore » 4} and ZnSnO{sub 3}) and coupled binary (ZnO/SnO{sub 2}) zinc tin oxide water suspensions in the photocatalytic degradation of alprazolam, short-acting anxiolytic of the benzodiazepine class of psychoactive drugs, under UV irradiation were determined and compared with the efficiency of pure ZnO and SnO{sub 2}.« less

Spatially coupled catalytic ignition of CO oxidation on Pt: mesoscopic versus nano-scale

PubMed Central

Spiel, C.; Vogel, D.; Schlögl, R.; Rupprechter, G.; Suchorski, Y.

2015-01-01

Spatial coupling during catalytic ignition of CO oxidation on μm-sized Pt(hkl) domains of a polycrystalline Pt foil has been studied in situ by PEEM (photoemission electron microscopy) in the 10−5 mbar pressure range. The same reaction has been examined under similar conditions by FIM (field ion microscopy) on nm-sized Pt(hkl) facets of a Pt nanotip. Proper orthogonal decomposition (POD) of the digitized FIM images has been employed to analyze spatiotemporal dynamics of catalytic ignition. The results show the essential role of the sample size and of the morphology of the domain (facet) boundary in the spatial coupling in CO oxidation. PMID:26021411

Enhanced spin-phonon-electronic coupling in a 5d oxide

DOE PAGES

Calder, Stuart A.; Yamaura, K.; Tsujimoto, Y.; ...

2015-11-26

Enhanced coupling of material properties offers new fundamental insights and routes to multifunctional devices. In this context 5d oxides provide new paradigms of cooperative interactions that drive novel emergent behaviour. This is exemplified in osmates that host metal insulator transitions where magnetic order appears intimately entwined. Here we consider such a material, the 5d perovskite NaOsO 3, and observe a coupling between spin and phonon manifested in a frequency shift of 40 cm 1, the largest measured in any material. The anomalous modes are shown to involve solely Os O interactions and magnetism is revealed as the driving microscopic mechanismmore » for the phonon renormalization. The magnitude of the coupling in NaOsO 3 is primarily due to a property common to all 5d materials: the large spatial extent of the ion. This allows magnetism to couple to phonons on an unprecedented scale and in general offers multiple new routes to enhanced coupled phenomena in 5d materials.« less

Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks

DOE PAGES

Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian; ...

2014-08-25

A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH 2, this catalyst (Pd@UiO-66-NH 2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found thatmore » alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. As a result, we further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.« less

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

DOE PAGES

Parkison, Adam J.; Nelson, Andrew Thomas

2016-01-11

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

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

Parkison, Adam J.; Nelson, Andrew Thomas

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Hybrid tandem quantum dot/organic photovoltaic cells with complementary near infrared absorption

NASA Astrophysics Data System (ADS)

Kim, Taesoo; Palmiano, Elenita; Liang, Ru-Ze; Hu, Hanlin; Murali, Banavoth; Kirmani, Ahmad R.; Firdaus, Yuliar; Gao, Yangqin; Sheikh, Arif; Yuan, Mingjian; Mohammed, Omar F.; Hoogland, Sjoerd; Beaujuge, Pierre M.; Sargent, Edward H.; Amassian, Aram

2017-05-01

Monolithically integrated hybrid tandem solar cells that effectively combine solution-processed colloidal quantum dot (CQD) and organic bulk heterojunction subcells to achieve tandem performance that surpasses the individual subcell efficiencies have not been demonstrated to date. In this work, we demonstrate hybrid tandem cells with a low bandgap PbS CQD subcell harvesting the visible and near-infrared photons and a polymer:fullerene—poly (diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C60-butyric acid methyl ester (PC61BM)—top cell absorbing effectively the red and near-infrared photons of the solar spectrum in a complementary fashion. The two subcells are connected in series via an interconnecting layer (ICL) composed of a metal oxide layer, a conjugated polyelectrolyte, and an ultrathin layer of Au. The ultrathin layer of Au forms nano-islands in the ICL, reducing the series resistance, increasing the shunt resistance, and enhancing the device fill-factor. The hybrid tandems reach a power conversion efficiency (PCE) of 7.9%, significantly higher than the PCE of the corresponding individual single cells, representing one of the highest efficiencies reported to date for hybrid tandem solar cells based on CQD and polymer subcells.

Characterization of solution-phase and gas-phase reactions in on-line electrochemistry-thermospray tandem mass spectrometry.

PubMed

Volk, K J; Yost, R A; Brajter-Toth, A

1989-07-14

Electrochemistry was used on-line with high-performance liquid chromatography-thermospray tandem mass spectrometry to provide insight into the solution-phase decomposition reactions of electrochemically generated oxidation products. Products formed during electrooxidation were monitored as the electrode potential was varied. The solution reactions which follow the initial electron transfer at the electrode are affected by the vaporizer tip temperature of the thermospray probe and the composition of the thermospray buffer. Either hydrolysis or ammonolysis reactions of the initial electrochemical oxidation products can occur with pH 7 ammonium acetate buffer. Both the electrochemically generated and the synthesized disulfide of 6-thiopurine decompose under thermospray conditions to produce 6-thiopurine and purine-6-sulfinate. Solution-phase studies indicate that nucleophilic and electrophilic substitution reactions with purine-6-sulfinate result in the formation of purine, adenine, and hypoxanthine. Products were identified and characterized by tandem mass spectrometry. This work shows the first example of high-performance liquid chromatography used on-line with electrochemistry to separate stable oxidation products prior to analysis by thermospray tandem mass spectrometry. In addition, solution-phase and gas-phase studies with methylamine show that the site of the nucleophilic and electrophilic reactions is probably inside the thermospray probe. Most importantly, these results also show that the on-line combination of electrochemistry with thermospray tandem mass spectrometry provides valuable information about redox and associated chemical reactions of biological molecules such as the structures of intermediates or products as well as providing insight into reaction pathways.

Nitrite oxidation in ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS).

PubMed

Farhat, Ali; Dooley, Alek N; Ahmad, Farrukh

2011-07-01

Nitrite anions are formed in the human body and in the natural environment as intermediate chemical compounds during the reduction of nitrate, a ubiquitous anthropogenic contaminant introduced into the environment primarily through fertilizer use. Multiple reaction monitoring (MRM) in ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS) is a promising new technique for quantifying and confirming the identity of anions in complex aqueous mixtures. In this article, we present the results of a short investigation devised to: (1) compare the signal generated by the MRM transitions for nitrite with those for nitrate, (2) isolate the source of the signal from these MRM transitions occurring within the IC-ESI-MS/MS instrument and (3) assess the relationship between the observed MRM signals for nitrite. The MRM transitions used in this study were m/z 62 (NO(3)(-))→m/z 46 (NO(2)(-)) and m/z 46 (NO(2)(-))→m/z 46 (NO(2)(-)). Results of the investigation revealed the association of both MRM transitions with the nitrite chromatographic peak, indicating the occurrence of nitrite oxidation to nitrate at the ESI interface before the first quadrupole. Calibrations for both MRM signals, as well as their sum, were found to be linear. However, the ratio of m/z 62→m/z 46 to m/z 46→m/z 46 (indicating an extent of oxidation) ranged from 35 to 56% over a nitrite concentration range of 10 to 100 ppm, showing no clear trend associated with concentration. Copyright © 2011 John Wiley & Sons, Ltd.

Improved Tandem Measurement Techniques for Aerosol Particle Analysis

NASA Astrophysics Data System (ADS)

Rawat, Vivek Kumar

Non-spherical, chemically inhomogeneous (complex) nanoparticles are encountered in a number of natural and engineered environments, including combustion systems (which produces highly non-spherical aggregates), reactors used in gas-phase materials synthesis of doped or multicomponent materials, and in ambient air. These nanoparticles are often highly diverse in size, composition and shape, and hence require determination of property distribution functions for accurate characterization. This thesis focuses on development of tandem mobility-mass measurement techniques coupled with appropriate data inversion routines to facilitate measurement of two dimensional size-mass distribution functions while correcting for the non-idealities of the instruments. Chapter 1 provides the detailed background and motivation for the studies performed in this thesis. In chapter 2, the development of an inversion routine is described which is employed to determine two dimensional size-mass distribution functions from Differential Mobility Analyzer-Aerosol Particle Mass analyzer tandem measurements. Chapter 3 demonstrates the application of the two dimensional distribution function to compute cumulative mass distribution function and also evaluates the validity of this technique by comparing the calculated total mass concentrations to measured values for a variety of aerosols. In Chapter 4, this tandem measurement technique with the inversion routine is employed to analyze colloidal suspensions. Chapter 5 focuses on application of a transverse modulation ion mobility spectrometer coupled with a mass spectrometer to study the effect of vapor dopants on the mobility shifts of sub 2 nm peptide ion clusters. These mobility shifts are then compared to models based on vapor uptake theories. Finally, in Chapter 6, a conclusion of all the studies performed in this thesis is provided and future avenues of research are discussed.

Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko; Concepcion, Javier J.

2016-08-18

Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy) 2(phen-imidazole-Ph(OH)( tBu) 2)] 2+, in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the Ru III/IIcouple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with k ET = 2.7 × 10 7more » s ₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λ DA = 1.16 eV and 280 < H DA < 540 cm ₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol ₋1. In conclusion, the reaction is nonadiabatic (V PCET ~ 22 cm ₋1 (H) and 49 cm ₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.« less

Exercise coupled with dietary restriction reduces oxidative stress in male adolescents with obesity.

PubMed

Li, Chunyan; Feng, Feihu; Xiong, Xiaoling; Li, Rui; Chen, Ning

2017-04-01

The increased oxidative stress is usually observed in obese population, but the control of body weight by calorie restriction and/or exercise training can ameliorate oxidative stress. In order to evaluate oxidative stress in response to exercise and dietary restriction in obese adolescents, a total of 20 obese volunteers were enrolled in a 4-week intervention program including exercise training and dietary restriction. Body compositions and blood samples were analysed before and after 4-week intervention, and biomarkers associated with oxidative stress were examined. After 4-week exercise training coupled with dietary restriction, physical composition parameters including body mass, body mass index (BMI), lean body mass, body fat mass and fat mass ratio had obvious reduction by 12.43%, 13.51%, 5.83%, 25.05% and 14.52%, respectively. In addition, the activities of antioxidant enzymes, such as superoxide dismutase (SOD) and glutathione peroxidase (GPx) revealed a remarkable enhancement. On the other hand, protein carbonyls (PC) exhibited an obvious reduction. Moreover, total thiols and nitrites with respect to baseline revealed a reducing trend although no significant difference was observed. Therefore, the 4-week exercise intervention coupled with dietary restriction is benefit for the loss of body weight and the mitigation of oxidative stress in obese population so that it can be a recommendable intervention prescription for the loss of body weight.

Progress in Tandem Solar Cells Based on Hybrid Organic-Inorganic Perovskites

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

Chen, Bo; Zheng, Xiaopeng; Bai, Yang

Owing to their high efficiency, low-cost solution-processability, and tunable bandgap, perovskite solar cells (PSCs) made of hybrid organic-inorganic perovskite (HOIP) thin films are promising top-cell candidates for integration with bottom-cells based on Si or other low-bandgap solar-cell materials to boost the power conversion efficiency (PCE) beyond the Shockley-Quiesser (S-Q) limit. In this review, recent progress in such tandem solar cells based on the emerging PSCs is summarized and reviewed critically. Notable achievements for different tandem solar cell configurations including mechanically-stacked, optical coupling, and monolithically-integrated with PSCs as top-cells are described in detail. Highly-efficient semitransparent PSC top-cells with high transmittance inmore » near-infrared (NIR) region are critical for tandem solar cells. Different types of transparent electrodes with high transmittance and low sheet-resistance for PSCs are reviewed, which presents a grand challenge for PSCs. The strategies to obtain wide-bandgap PSCs with good photo-stability are discussed. In conclusion, the PCE reduction due to reflection loss, parasitic absorption, electrical loss, and current mismatch are analyzed to provide better understanding of the performance of PSC-based tandem solar cells.« less

Progress in Tandem Solar Cells Based on Hybrid Organic-Inorganic Perovskites

DOE PAGES

Chen, Bo; Zheng, Xiaopeng; Bai, Yang; ...

2017-03-06

Owing to their high efficiency, low-cost solution-processability, and tunable bandgap, perovskite solar cells (PSCs) made of hybrid organic-inorganic perovskite (HOIP) thin films are promising top-cell candidates for integration with bottom-cells based on Si or other low-bandgap solar-cell materials to boost the power conversion efficiency (PCE) beyond the Shockley-Quiesser (S-Q) limit. In this review, recent progress in such tandem solar cells based on the emerging PSCs is summarized and reviewed critically. Notable achievements for different tandem solar cell configurations including mechanically-stacked, optical coupling, and monolithically-integrated with PSCs as top-cells are described in detail. Highly-efficient semitransparent PSC top-cells with high transmittance inmore » near-infrared (NIR) region are critical for tandem solar cells. Different types of transparent electrodes with high transmittance and low sheet-resistance for PSCs are reviewed, which presents a grand challenge for PSCs. The strategies to obtain wide-bandgap PSCs with good photo-stability are discussed. In conclusion, the PCE reduction due to reflection loss, parasitic absorption, electrical loss, and current mismatch are analyzed to provide better understanding of the performance of PSC-based tandem solar cells.« less

Towards a zero-waste oxidative coupling of nonactivated aromatics by supported gold nanoparticles.

PubMed

Serna, Pedro; Corma, Avelino

2014-08-01

We show that gold nanoparticles are able to perform the direct oxidative coupling of nonactivated aromatics with O2 as the only co-reagent. In this reaction, the aromatic acts both as reactant and solvent. Biphenyl, for example, can be obtained from benzene with high selectivity and a turnover number (TON) of 230 per pass. Similarly, several substituted biaryls can be prepared. Pd performs only one TON and even when a second catalytic functionality is introduced, together with strong acidic conditions, TON is always lower than 100. Other catalysts require iodine for performing the reaction, leading to 2 kg of waste for 1 kg of biphenyl formed, whereas no waste is created by the oxidative coupling with gold nanoparticles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling characteristics of thin-film metal-oxide-metal diodes at 10.6 microns

NASA Technical Reports Server (NTRS)

Wang, S. Y.; Gustafson, T. K.; Izawa, T.

1975-01-01

Direct detection experiments have demonstrated the coherent coupling of 10.6 micrometer radiation into photolithographically fabricated metal-oxide-metal tunnel junctions. A CO2 laser beam mechanically chopped at 1 KHz was focused at a variable angle of incidence with a power density of about 10 W/sq cm at the diodes. Diodes in which the junction resistance was much greater than the lead resistance displayed angular characteristics dominated by coherent antenna coupling.

SU-D-BRF-05: A Novel System to Provide Real-Time Image-Guidance for Intrauterine Tandem Insertion and Placement

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

Price, M; Fontenot, J

Purpose: To develop a system that provides real-time image-guidance for intrauterine tandem insertion and placement for brachytherapy. Methods: The conceptualized system consists of an intrauterine tandem with a transparent, lensed tip, a flexible miniature fiber optic scope, light source and interface for CCD coupling. The tandem tip was designed to act as a lens providing a wide field-of-view (FOV) with minimal image distortion and focus length appropriate for the application. The system is designed so that once inserted, the image-guidance component of the system can be removed and brachytherapy can be administered without interfering with source transport or disturbing tandemmore » placement. Proof-of-principle studies were conducted to assess the conceptualized system's (1) lens functionality (clarity, focus and FOV) (2) and ability to visualize the cervical os of a female placed in the lithotomy position. Results: A prototype of this device was constructed using a commercial tandem modified to incorporate a transparent tip that internally coupled with a 1.9mm diameter fiber optic cable. The 900mm-long cable terminated at an interface that provided illumination as well as facilitated visualization of patient anatomy on a computer. The system provided a 23mm FOV with a focal length of 1cm and provided clear visualization of the cervix, cervical fornix and cervical os. The optical components of the system are easily removed without perturbing the position of a tandem placed in a common fixation clamp. Conclusion: Clinicians frequently encounter difficulty inserting an intrauterine tandem through the cervical os, circumventing fibrotic tissue or masses within the uterus, and positioning the tandem without perforating the uterus. To mitigate these challenges, we have designed and conducted proof-of- principle studies to discern the utility of a prototype device that provides real-time image-guidance for intrauterine tandem placement using fiber optic components.« less

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.

Multi-element analysis of water decoction of medicine food homology plants using inductively coupled plasma-tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Fu, Liang; Shi, Shu-Yun; Chen, Xiao-Qing

2017-07-01

The concentration of twelve trace elements in the water decoction of medicine food homology plants (MFHP) was determined by inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). Water decoctions of MFHP were analyzed directly using the MS/MS mode after acidification by 1% (v/v) nitric acid. The polyatomic interferences were eliminated by oxygen mass shift, oxygen on-mass, and ammonia mass shift. The accuracy of the method was verified by analysis of standard reference materials. This method was utilized to investigate the water decoction composition of 16 common Chinese MFHPs. The trace elements in the water decoctions of different MFHPs presented significantly different dissolution ratios. The dissolution ratio of V was the lowest (4.21%-14.86%), whereas Zn showed the highest dissolution ratio (24.87%-86.80%). In addition, the dissolution ratio of heavy metallic elements in most MFHP was equal to or was lower than 30%. Therefore, consumption of MHFP decoction could decrease the heavy metal intake associated with MFHP use and reduce the risk of heavy metal poisoning.

Covalently Linked Tandem Lesions in DNA

PubMed Central

Patrzyc, Helen B.; Dawidzik, Jean B.; Budzinski, Edwin E.; Freund, Harold G.; Wilton, John H.; Box, Harold C.

2013-01-01

Reactive oxygen species (ROS) generate a type of DNA damage called tandem lesions, two adjacent nucleotides both modified. A subcategory of tandem lesions consists of adjacent nucleotides linked by a covalent bond. Covalently linked tandem lesions generate highly characteristic liquid chromotography-tandem mass spectrometry (LC-MS/MS) elution profiles. We have used this property to comprehensively survey X-irradiated DNA for covalently linked tandem lesions. A total of 15 tandem lesions were detected in DNA irradiated in deoxygenated aqueous solution, five tandem lesions were detected in DNA that was irradiated in oxygenated solution. PMID:23106212

Quantitation of zoledronic acid in murine bone by liquid chromatography coupled with tandem mass spectrometry.

PubMed

Raccor, Brianne S; Sun, Jianxun; Lawrence, Ross F; Li, Lei; Zhang, Hai; Somerman, Martha J; Totah, Rheem A

2013-09-15

An in vitro method for extraction and quantification of zoledronic acid (ZA) from murine bone was developed. Whole mouse bones were incubated in ZA solutions with predetermined concentrations and bound ZA was subsequently extracted from bone with phosphoric acid and derivatized using trimethylsilyl diazomethane (TMS-DAM). ZA tetra-methyl phosphonate was quantified by liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). This resulted in a sensitive, accurate, and precise method that was linear over three orders of magnitude (0.0250-50.0μg/mL ZA). For quality control (QC) samples, intra-and inter-day coefficients of variance were calculated and were less than 10%. This method was then applied to an in vivo model to quantitate ZA from the femur and mandible of three mice treated with ZA for two weeks. The mean ZA extracted from the mandible was four fold higher than that extracted from the femur (3.06±0.52 vs. 0.76±0.09ng/mg, respectively) indicating that ZA did not distribute equally in the skeleton and had a preference to the mandible. In conclusion, a highly sensitive method to measure ZA from mouse skeleton was developed, which can be easily adapted to multiple mammalian models including humans receiving ZA treatment. Copyright © 2013 Elsevier B.V. All rights reserved.

Perchlorate-Coupled Carbon Monoxide (CO) Oxidation: Evidence for a Plausible Microbe-Mediated Reaction in Martian Brines.

PubMed

Myers, Marisa R; King, Gary M

2017-01-01

The presence of hydrated salts on Mars indicates that some regions of its surface might be habitable if suitable metabolizable substrates are available. However, several lines of evidence have shown that Mars' regolith contains only trace levels of the organic matter needed to support heterotrophic microbes. Due to the scarcity of organic carbon, carbon monoxide (CO) at a concentration of about 700 parts per million (about 0.4 Pa) might be the single most abundant readily available substrate that could support near-surface bacterial activity. Although a variety of electron acceptors can be coupled to CO oxidation, perchlorate is likely the most abundant potential oxidant in Mars' brines. Whether perchlorate, a potent chaotrope, can support microbial CO oxidation has not been previously documented. We report here the first evidence for perchlorate-coupled CO oxidation based on assays with two distinct euryarchaeal extreme halophiles. CO oxidation occurred readily in 3.8 M NaCl brines with perchlorate concentrations from 0.01 to 1 M. Both isolates were able to couple CO with perchlorate or chlorate under anaerobic conditions with or without nitrate as an inducer for nitrate reductase, which serves as a perchlorate reductase in extreme halophiles. In the presence of perchlorate, CO concentrations were reduced to levels well below those found in Mars' atmosphere. This indicates that CO could contribute to the survival of microbial populations in hydrated salt formations or brines if water activities are suitably permissive.

Coupling Surfactants/Cosolvents with Oxidants: Effects on Site Characterization and DNAPL Remediation

NASA Astrophysics Data System (ADS)

Dugan, P. J.; Siegrist, R. L.; Crimi, M. L.

2004-12-01

Within the last decade, surfactant-enhanced aquifer remediation \\(SEAR\\), and more recently, in-situ chemical oxidation \\(ISCO\\) show promise for remediation of dense nonaqueous phase liquid \\(DNAPL\\) contamination in the subsurface. DNAPL removal is typically difficult to achieve with one remedial technique; however, coupling of treatments can be a highly effective method for remediation of DNAPL contamination. Little research has been completed to date to evaluate such coupling and the factors that impact appropriate engineering design and remediation performance assessment. Partitioning tracer tests (PTTs) are a promising method for estimating the volume and distribution of DNAPL. PTTs have several useful purposes: locating subsurface DNAPL zones, estimating NAPL saturation or volume within these contaminated zones, and providing a quantitative and qualitative means of assessing remediation performance. PTT theory permits direct calculation of the NAPL saturation from the chromatographic separation of a tracer pulse consisting of suites of partitioning and non-partitioning tracers that travel with the advecting groundwater. The PTT has been used with limited success after surfactant/cosolvent recovery but has not been assessed as a performance assessment tool after ISCO. There are several factors that could potentially impact the feasibility of the PTT after ISCO. First, previous batch experiments indicate that partitioning tracers degrade in the presence of the oxidant potassium permanganate. Secondly, tracer partitioning could be inhibited by manganese dioxide film formation after chemical oxidation of DNAPL. Both of these factors have potential to influence partitioning tracer transport, which could lead to inaccurate estimates of the post-remediation NAPL saturation, and therefore remediation efficiency. There is a need for researching PTTs after surfactant/cosolvent coupling with ISCO. In general, DNAPL-zone characterization methods have significant

Coupling Oxygen Consumption with Hydrocarbon Oxidation in Bacterial Multicomponent Monooxygenases.

PubMed

Wang, Weixue; Liang, Alexandria D; Lippard, Stephen J

2015-09-15

A fundamental goal in catalysis is the coupling of multiple reactions to yield a desired product. Enzymes have evolved elegant approaches to address this grand challenge. A salient example is the biological conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily. sMMO is a dynamic protein complex of three components: a hydroxylase, a reductase, and a regulatory protein. The active site, a carboxylate-rich non-heme diiron center, is buried inside the 251 kDa hydroxylase component. The enzyme processes four substrates: O2, protons, electrons, and methane. To couple O2 activation to methane oxidation, timely control of substrate access to the active site is critical. Recent studies of sMMO, as well as its homologues in the BMM superfamily, have begun to unravel the mechanism. The emerging and unifying picture reveals that each substrate gains access to the active site along a specific pathway through the hydroxylase. Electrons and protons are delivered via a three-amino-acid pore located adjacent to the diiron center; O2 migrates via a series of hydrophobic cavities; and hydrocarbon substrates reach the active site through a channel or linked set of cavities. The gating of these pathways mediates entry of each substrate to the diiron active site in a timed sequence and is coordinated by dynamic interactions with the other component proteins. The result is coupling of dioxygen consumption with hydrocarbon oxidation, avoiding unproductive oxidation of the reductant rather than the desired hydrocarbon. To initiate catalysis, the reductase delivers two electrons to the diiron(III) center by binding over the pore of the hydroxylase. The regulatory component then displaces the reductase, docking onto the same surface of the hydroxylase. Formation of the hydroxylase-regulatory component complex (i) induces conformational changes of pore residues that may bring protons to the

Characterization via liquid chromatography coupled to diode array detector and tandem mass spectrometry of supercritical fluid antioxidant extracts of Spirulina platensis microalga.

PubMed

Mendiola, Jose A; Marín, Francisco R; Hernández, S Francisco; Arredondo, Bertha O; Señoráns, F Javier; Ibañez, Elena; Reglero, Guillermo

2005-06-01

Spirulina platensis microalga has been extracted on a pilot scale plant using supercritical fluid extraction (SFE) under various extraction conditions. The extraction yield and the antioxidant activity of the extracts were evaluated in order to select those extracts with both the highest antioxidant capacity and a good extraction yield. These extracts were characterized using LC coupled to diode array detection (DAD) and LC coupled to mass spectrometry (MS) with two different interfaces, atmospheric pressure chemical ionization (APCI) and electrospray (ESI) which allowed us to perform tandem MS by using an ion trap analyzer. The best extraction conditions were as follows: CO2 with 10% of modifier (ethanol) as extraction solvent, 55 degrees C (extraction temperature) and 220 bar (extraction pressure). Fractionation was achieved by cascade depressurization providing two extracts with different activity and chemical composition. Several compounds have been identified in the extracts, corresponding to different carotenoids previously identified in Spirulina platensis microalga along with chlorophyll a and some degradation products. Also, the structure of some phenolic compounds could be tentatively identified. The antioxidant activity of the extracts could be attributed to some of the above mentioned compounds.

Copper-catalyzed tandem reactions of 1-(2-iodoary)-2-yn-1-ones with isocyanides for the synthesis of 4-oxo-indeno[1,2-b]pyrroles.

PubMed

Cai, Qian; Zhou, Fengtao; Xu, Tianfeng; Fu, Liangbing; Ding, Ke

2011-01-21

A novel copper-catalyzed tandem reaction of 1-(2-iodoaryl)-2-yn-1-ones with isocyanides is described. The reaction is through a formal [3 + 2] cycloaddition/coupling tandem process and leads to efficient formation of 4-oxo-indeno[1,2-b]pyrroles.

A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

PubMed

Largeron, Martine; Fleury, Maurice-Bernard

2015-02-23

The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced Coupling of Oxidative Phosphorylation In Vivo Precedes Electron Transport Chain Defects Due to Mild Oxidative Stress in Mice

PubMed Central

Siegel, Michael P.; Kruse, Shane E.; Knowels, Gary; Salmon, Adam; Beyer, Richard; Xie, Hui; Van Remmen, Holly; Smith, Steven R.; Marcinek, David J.

2011-01-01

Oxidative stress and mitochondrial function are at the core of many degenerative conditions. However, the interaction between oxidative stress and in vivo mitochondrial function is unclear. We used both pharmacological (2 week paraquat (PQ) treatment of wild type mice) and transgenic (mice lacking Cu, Zn-superoxide dismutase (SOD1−/−)) models to test the effect of oxidative stress on in vivo mitochondrial function in skeletal muscle. Magnetic resonance and optical spectroscopy were used to measure mitochondrial ATP and oxygen fluxes and cell energetic state. In both models of oxidative stress, coupling of oxidative phosphorylation was significantly lower (lower P/O) at rest in vivo in skeletal muscle and was dose-dependent in the PQ model. Despite this reduction in efficiency, in vivo mitochondrial phosphorylation capacity (ATPmax) was maintained in both models, and ex vivo mitochondrial respiration in permeabilized muscle fibers was unchanged following PQ treatment. In association with the reduced P/O, PQ treatment led to a dose-dependent reduction in PCr/ATP ratio and increased phosphorylation of AMPK. These results indicate that oxidative stress uncouples oxidative phosphorylation in vivo and results in energetic stress in the absence of defects in the mitochondrial electron transport chain. PMID:22132085

23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability

NASA Astrophysics Data System (ADS)

Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.; Boccard, Mathieu; Cheacharoen, Rongrong; Mailoa, Jonathan P.; McMeekin, David P.; Hoye, Robert L. Z.; Bailie, Colin D.; Leijtens, Tomas; Peters, Ian Marius; Minichetti, Maxmillian C.; Rolston, Nicholas; Prasanna, Rohit; Sofia, Sarah; Harwood, Duncan; Ma, Wen; Moghadam, Farhad; Snaith, Henry J.; Buonassisi, Tonio; Holman, Zachary C.; Bent, Stacey F.; McGehee, Michael D.

2017-02-01

As the record single-junction efficiencies of perovskite solar cells now rival those of copper indium gallium selenide, cadmium telluride and multicrystalline silicon, they are becoming increasingly attractive for use in tandem solar cells due to their wide, tunable bandgap and solution processability. Previously, perovskite/silicon tandems were limited by significant parasitic absorption and poor environmental stability. Here, we improve the efficiency of monolithic, two-terminal, 1-cm2 perovskite/silicon tandems to 23.6% by combining an infrared-tuned silicon heterojunction bottom cell with the recently developed caesium formamidinium lead halide perovskite. This more-stable perovskite tolerates deposition of a tin oxide buffer layer via atomic layer deposition that prevents shunts, has negligible parasitic absorption, and allows for the sputter deposition of a transparent top electrode. Furthermore, the window layer doubles as a diffusion barrier, increasing the thermal and environmental stability to enable perovskite devices that withstand a 1,000-hour damp heat test at 85 ∘C and 85% relative humidity.

Simultaneous determination of 9 heterocyclic aromatic amines in pork products by liquid chromatography coupled with triple quadrupole tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Shen, X. C.; Zhang, Y. L.; Cui, Y. Q.; Xu, L. Y.; Li, X.; Qi, J. H.

2017-07-01

Heterocyclic aromatic amines (HAAs) are potent mutagens that formed at high temperature in cooked, protein-rich food. Owing to their frequent intake, an accurate method is essential to access human health risk of HAAs exposure through detecting these compounds in various heat-treated meat products. In this study, a liquid chromatography-electrospray tandem mass spectrometry (LC--ESI-MS/MS) method was developed to perform the determination of 9 mutagenic heterocyclic amines (HAAs) in meat samples with multiple reaction monitoring (MRM) mode. Ultrasound assisted extraction and diatomaceous earth was employed to extract HAAs from food samples, and the analytes were purified and enriched using tandem solid phase extraction, with propyl sulfonic acid coupled to a C18 cartridge. Two parameters, extraction time and eluent, were carefully optimized to improve the extraction and purification efficiency. The LC separation was carried out using a Zorbax SB-C18 (3.5 μm particle size, 2.1 × 150 mm i.d.) column and optimized some parameters, such as pH, concentration and volume. Under the optimal experimental conditions, recoveries ranged from 52.97% to 97.11% with good quality parameters: limit of detection values between 0.02 and 0.24 ng mL-1, linearity (R2>0.998), and run-to-run and day-to-day precisions lower than 9.81% achieved. To evaluate the performance of the method in high throughput analysis of complex meat samples, the LC-MS/MS method was applied to the analysis of HAAs in three food samples, and the results demonstrated that the method can be used for the trace determination of HAAs in pork samples.

Determination of tetrabromobisphenol-A/S and their main derivatives in water samples by high performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry.

PubMed

Liu, Lihong; Liu, Aifeng; Zhang, Qinghua; Shi, Jianbo; He, Bin; Yun, Zhaojun; Jiang, Guibin

2017-05-12

As the most widely used brominated flame retardants (BFRs), Tetrabromobisphenol-A (TBBPA) as well as its alternative Tetrabromobisphenol-S (TBBPS) and their derivatives have raised wide concerns due to their adverse effects on human health and hence the sensitive detection of those BFRs was urgently needed. Herein, a novel analytical method based on high-performance liquid chromatography (HPLC) coupled with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) has been developed for the determination of TBBPA/S and their derivatives, including TBBPA-bis(2-hydroxyethyl ether) (TBBPA-BHEE), TBBPA-bis(allylether) (TBBPA-BAE), TBBPA-bis(glycidyl ether) (TBBPA-BGE), TBBPA-bis(2,3-dibromopropyl ether) (TBBPA-BDBPE) and TBBPS-bis(2,3-dibromopropyl ether) (TBBPS-BDBPE) in water samples. After optimization, the TBBPA/S and their derivatives, especially the TBBPA-BAE and TBBPA-BDBPE were simultaneously and sensitively quantified by determination of bromine (m/z=79) by using the ICP-MS. The instrument limits of detection (LODs) for the TBBPA, TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE, TBBPA-BDBPE, TBBPS and TBBPS-BDBPE were determined to be 0.12, 0.14, 0.19, 0.14, 0.12, 0.17 and 0.13μgL -1 , respectively, which was close to or much better than the reported methods. The relative standard deviations (RSDs, n=5) of peak area and retention time were better than 2.2% and 0.2% for intra-day analysis, indicating good repeatability and high precision. The proposed method had been successfully applied for the analysis of TBBPA/S and their derivatives in water samples with satisfactory recoveries (67.7%-113%). Copyright © 2017 Elsevier B.V. All rights reserved.

Spin Hall driven domain wall motion in magnetic bilayers coupled by a magnetic oxide interlayer

NASA Astrophysics Data System (ADS)

Liu, Yang; Furuta, Masaki; Zhu, Jian-Gang Jimmy

2018-05-01

mCell, previously proposed by our group, is a four-terminal magnetoresistive device with isolated write- and read-paths for all-spin logic and memory applications. A mCell requires an electric-insulating magnetic layer to couple the spin Hall driven write-path to the magnetic free layer of the read-path. Both paths are magnetic layers with perpendicular anisotropy and their perpendicularly oriented magnetization needs to be maintained with this insertion layer. We have developed a magnetic oxide (FeOx) insertion layer to serve for these purposes. We show that the FeOx insertion layer provides sufficient magnetic coupling between adjacent perpendicular magnetic layers. Resistance measurement shows that this magnetic oxide layer can act as an electric-insulating layer. In addition, spin Hall driven domain wall motion in magnetic bi-layers coupled by the FeOx insertion layer is significantly enhanced compared to that in magnetic single layer; it also requires low voltage threshold that poses possibility for power-efficient device applications.

Clonazepam quantification in human plasma by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry in a bioequivalence study.

PubMed

Cavedal, Luiz E; Mendes, Fabiana D; Domingues, Claudia C; Patni, Anil K; Monif, Tausif; Reyar, Simrit; Pereira, Alberto Dos S; Mendes, Gustavo D; De Nucci, Gilberto

2007-01-01

A rapid, sensitive and specific method for quantifying clonazepam in human plasma using diazepam as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using a hexane/diethylether (20 : 80, v/v) solution. The extracts were analysed by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS-MS). Chromatography was performed on a Jones Genesis C8 4 microm analytical column (100 x 2.1 mm i.d.). The method had a chromatographic run time of 3.0 min and a linear calibration curve over the range 0.5-50 ng/ml (r2 > 0.9965). The limit of quantification was 0.5 ng/ml. This HPLC/MS/MS procedure was used to assess the bioequivalence of two clonazepam 2 mg tablet formulations (clonazepam test formulation from Ranbaxy Laboratories Ltd and Rivotril from Roche Laboratórios Ltda as standard reference formulation). Copyright 2006 John Wiley & Sons, Ltd.

Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

NASA Astrophysics Data System (ADS)

Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

2018-01-01

In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

PubMed

He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

2015-08-15

Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 μM for methane and 8.7 ± 1.5 μM for nitrite. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Perovskite Solar Cells for High-Efficiency Tandems

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

McGehee, Michael; Buonassisi, Tonio

The first monolithic perovskite/silicon tandem was made with a diffused silicon p-n junction, a tunnel junction made of n ++ hydrogenated amorphous silicon, a titania electron transport layer, a methylammonium lead iodide absorber, and a Spiro-OMeTAD hole transport layer (HTL). The power conversion efficiency (PCE) was only 13.7% due to excessive parasitic absorption of light in the HTL, limiting the matched current density to 11.5 mA/cm 2. Werner et al. 15 raised the PCE to a record 21.2% by switching to a silicon heterojunction bottom cell and carefully tuning layer thicknesses to achieve lower optical loss and a higher currentmore » density of 15.9 mA/cm 2. It is clear from these reports that minimizing parasitic absorption in the window layers is crucial to achieving higher current densities and efficiencies in monolithic tandems. To this end, the window layers through which light first passes before entering the perovskite and silicon absorber materials must be highly transparent. The front electrode must also be conductive to carry current laterally across the top of the device. Indium tin oxide (ITO) is widely utilized as a transparent electrode in optoelectronic devices such as flat-panel displays, smart windows, organic light-emitting diodes, and solar cells due to its high conductivity and broadband transparency. ITO is typically deposited through magnetron sputtering; however, the high kinetic energy of sputtered particles can damage underlying layers. In perovskite solar cells, a sputter buffer layer is required to protect the perovskite and organic carrier extraction layers from damage during sputter deposition. The ideal buffer layer should also be energetically well aligned so as to act as a carrier-selective contact, have a wide bandgap to enable high optical transmission, and have no reaction with the halides in the perovskite. Additionally, this buffer layer should act as a diffusion barrier layer to prevent both organic cation evolution and

Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment.

PubMed

Rubalcaba, A; Suárez-Ojeda, M E; Stüber, F; Fortuny, A; Bengoa, C; Metcalfe, I; Font, J; Carrera, J; Fabregat, A

2007-01-01

Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested batch wise, while catalytic wet air oxidation and H2O2-promoted catalytic wet air oxidation processes were studied in a trickle bed reactor, the last two using over activated carbon as catalyst. Effluent characterisation was made by means of substrate conversion (using high liquid performance chromatography), chemical oxygen demand and total organic carbon. Biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) were obtained from respirometric tests using activated sludge from an urban biological wastewater treatment plant (WWTP). The main goal was to find the proper conditions in terms of biodegradability enhancement, so that these phenolic effluents could be successfully treated in an urban biological WWTP. Results show promising research ways for the development of efficient coupled processes for the treatment of wastewater containing toxic or biologically non-degradable compounds.

Determination of Flavonoids and Anthocyanins in Nitraria tangutorum by High Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry.

PubMed

Zhe, Gao; Ying-Chun, Wang; Yan-Xu, Chang

2016-01-01

Using high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-MSn) method, qualitative and quantitative analysis of flavonoids of stems, leaves, fruits and seeds, and anthocyanidin of fresh fruits in Nitraria tangutorum were performed. A total of 14 flavonoid components were identified from the seeds of N. tangutorum including three quercetin derivatives, three kaempferol derivatives, and eight isorhamnetin derivatives. A total of 12, 10, and 7 flavonoid components were identified from leaves, stems, and fruits of N. tangutorum, respectively; all were present in seeds also. The total content of flavonoids in leaves was the highest, up to 42.43 mg/g·dry weight. A total of 12 anthocyanidin components were identified from the fresh fruits of N. tangutorum, belonging to five anthocyanidin. The total content of anthocyanidin in fresh fruits was up to 45.83 mg/100 g· fresh weight, of which the acylated anthocyanidin accounted for 65.7%. The HPLC-DAD-MS(n) method can be operated easily, rapidly, and accurately, and is feasible for qualitative and quantitative analysis of flavone glycosides in N. tangutorum.

Analysis of anabolic androgenic steroids as sulfate conjugates using high performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Rzeppa, S; Heinrich, G; Hemmersbach, P

2015-01-01

Improvements in doping analysis can be effected by speeding up analysis time and extending the detection time. Therefore, direct detection of phase II conjugates of doping agents, especially anabolic androgenic steroids (AAS), is proposed. Besides direct detection of conjugates with glucuronic acid, the analysis of sulfate conjugates, which are usually not part of the routine doping control analysis, can be of high interest. Sulfate conjugates of methandienone and methyltestosterone metabolites have already been identified as long-term metabolites. This study presents the synthesis of sulfate conjugates of six commonly used AAS and their metabolites: trenbolone, nandrolone, boldenone, methenolone, mesterolone, and drostanolone. In the following these sulfate conjugates were used for development of a fast and easy analysis method based on sample preparation using solid phase extraction with a mixed-mode sorbent and detection by high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). Validation demonstrated the suitability of the method with regard to the criteria given by the technical documents of the World Anti-Doping Agency (WADA). In addition, suitability has been proven by successful detection of the synthesized sulfate conjugates in excretion urines and routine doping control samples. Copyright © 2015 John Wiley & Sons, Ltd.

Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

PubMed Central

Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel MM; Schubert, Carsten J

2015-01-01

Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

NASA Astrophysics Data System (ADS)

Chen, Lin; Yueming, Li

2018-06-01

In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

EPA Science Inventory

In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

Photo-induced oxidant-free oxidative C-H/N-H cross-coupling between arenes and azoles

NASA Astrophysics Data System (ADS)

Niu, Linbin; Yi, Hong; Wang, Shengchun; Liu, Tianyi; Liu, Jiamei; Lei, Aiwen

2017-02-01

Direct cross-coupling between simple arenes and heterocyclic amines under mild conditions is undoubtedly important for C-N bonds construction. Selective C(sp2)-H amination is more valuable. Herein we show a selective C(sp2)-H amination of arenes (alkyl-substituted benzenes, biphenyl and anisole derivatives) accompanied by hydrogen evolution by using heterocyclic azoles as nitrogen sources. The reaction is selective for C(sp2)-H bonds, providing a mild route to N-arylazoles. The KIE (kinetic isotope effect) experiment reveals the cleavage of C-H bond is not involved in the rate-determining step. Kinetic studies indicate the first-order behaviour with respect to the arene component. It is interesting that this system works without the need for any sacrificial oxidant and is highly selective for C(sp2)-H activation, whereas C(sp3)-H bonds are unaffected. This study may have significant implications for the functionalization of methylarenes which are sensitive to oxidative conditions.

Zwitterionic-hydrophilic interaction capillary liquid chromatography coupled to tandem mass spectrometry for the characterization of human alpha-acid-glycoprotein N-glycan isomers.

PubMed

Mancera-Arteu, Montserrat; Giménez, Estela; Barbosa, José; Peracaula, Rosa; Sanz-Nebot, Victòria

2017-10-23

In this work, a μZIC-HILIC-MS/MS methodology was established in negative ion mode for the characterization of glycan isomers. The possibility to separate the glycan isomers by the μZIC-HILIC strategy coupled to a high resolution tandem mass spectrometry detection permitted us to obtain valuable information about each glycan structure. The most important diagnostic ion fragments previously described to characterize structural features of glycans, were evaluated in this study using hAGP as model glycoprotein. The assignation of hAGP glycan isomers performed in our previous work using the GRIL strategy in combination with exoglycosidase digestion [1] was used in this paper to confirm or discard some ion fragments reported in the literature and delve into the structural characterization of glycan isomers. Sialic acid as well as fucose linkage-type glycan isomers were assigned using this approach and daughter ions with higher diagnostic value were determined. The location of α2-3/α2-6 sialic acids on antennas and a deeper characterization of several highly sialylated tri- and tetraantennary glycans was also possible using the established MS/MS method. Moreover, relying on the characterization performed in Ref. [1], core and antenna fucosylation were differentiated in this work using specific ion fragments obtained in the tandem mass spectra. This methodology was also applied to hAGP purified from control and pathological serum samples, which corroborated its robustness and its potential for finding novel glycan-based biomarkers in patho-glycomic studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Low-Energy, Low-Cost Production of Ethylene by Low- Temperature Oxidative Coupling of Methane

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

Radaelli, Guido; Chachra, Gaurav; Jonnavittula, Divya

In this project, we develop a catalytic process technology for distributed small-scale production of ethylene by oxidative coupling of methane at low temperatures using an advanced catalyst. The Low Temperature Oxidative Coupling of Methane (LT-OCM) catalyst system is enabled by a novel chemical catalyst and process pioneered by Siluria, at private expense, over the last six years. Herein, we develop the LT-OCM catalyst system for distributed small-scale production of ethylene by identifying and addressing necessary process schemes, unit operations and process parameters that limit the economic viability and mass penetration of this technology to manufacture ethylene at small-scales. The outputmore » of this program is process concepts for small-scale LT-OCM catalyst based ethylene production, lab-scale verification of the novel unit operations adopted in the proposed concept, and an analysis to validate the feasibility of the proposed concepts.« less

Accurate determination of non-metallic impurities in high purity tetramethylammonium hydroxide using inductively coupled plasma tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Fu, Liang; Xie, Hualin; Shi, Shuyun; Chen, Xiaoqing

2018-06-01

The content of non-metallic impurities in high-purity tetramethylammonium hydroxide (HPTMAH) aqueous solution has an important influence on the yield, electrical properties and reliability of the integrated circuit during the process of chip etching and cleaning. Therefore, an efficient analytical method to directly quantify the content of non-metallic impurities in HPTMAH aqueous solutions is necessary. The present study was aimed to develop a novel method that can accurately determine seven non-metallic impurities (B, Si, P, S, Cl, As, and Se) in an aqueous solution of HPTMAH by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). The samples were measured using a direct injection method. In the MS/MS mode, oxygen and hydrogen were used as reaction gases in the octopole reaction system (ORS) to eliminate mass spectral interferences during the analytical process. The detection limits of B, Si, P, S, Cl, As, and Se were 0.31, 0.48, 0.051, 0.27, 3.10, 0.008, and 0.005 μg L-1, respectively. The samples were analyzed by the developed method and the sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was used for contrastive analysis. The values of these seven elements measured using ICP-MS/MS were consistent with those measured by SF-ICP-MS. The proposed method can be utilized to analyze non-metallic impurities in HPTMAH aqueous solution. Table S2 Multiple potential interferences on the analytes. Table S3 Parameters of calibration curve and the detection limit (DL). Table S4 Results obtained for 25% concentration high-purity grade TMAH aqueous solution samples (μg L-1, mean ± standard deviation, n = 10).

Determination of steroid hormones in fish tissues by microwave-assisted extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry.

PubMed

Guedes-Alonso, Rayco; Sosa-Ferrera, Zoraida; Santana-Rodríguez, José Juan

2017-12-15

Steroid hormones produce adverse effects on biota as well as bioaccumulation in fish and seafood, making it necessary to develop methodologies to evaluate these compounds in samples related to the food chain. This work presents an analytical method for evaluating 15 steroid hormones in fish tissue. It is based on microwave-assisted extraction and solid-phase extraction coupled to ultra-high-performance liquid chromatography tandem mass spectrometry (MAE-SPE-UHPLC-MS/MS). The proposed method shows appropriate detection limits (0.14-49.0ngg -1 ), recoveries in the range of 50% and good repeatability. After optimization, the method was applied to different tissues from two small fishes of the Canary Islands that constitute an important level of the food web (Boops boops and Sphoeroides marmoratus) and were exposed to the outfall of the Las Palmas de Gran Canaria wastewater treatment plant. The concentrations of eight detected compounds ranged from below the quantification limits to 3.95μgg -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

The application of headspace gas chromatography coupled to tandem quadrupole mass spectrometry for the analysis of furan in baby food samples.

PubMed

Pugajeva, Iveta; Rozentale, Irina; Viksna, Arturs; Bartkiene, Elena; Bartkevics, Vadims

2016-12-01

Selective methodology employing a tandem quadrupole mass spectrometer coupled to a gas chromatograph with headspace autosampler (HS-GC-MS/MS) was elaborated in this study. Application of the elaborated procedure resulted in a limit of detection of 0.021μgkg(-1) and a limit of quantification of 0.071μgkg(-1). The mean recoveries during in-house validation ranged from 89% to 109%, and coefficients of variation for repeatability ranged from 4% to 11%. The proposed analytical method was applied for monitoring the furan content of 30 commercial baby food samples available on the Latvian retail market. The level of furan found in these samples varied from 0.45 to 81.9μgkg(-1), indicating that infants whose sole diet comprises baby food sold in jars and cans are exposed constantly to furan. Samples containing vegetables and meat had higher levels of furan than those containing only fruits. Copyright © 2016 Elsevier Ltd. All rights reserved.

Perovskite/c-Si tandem solar cell with inverted nanopyramids: realizing high efficiency by controllable light trapping

PubMed Central

Shi, Dai; Zeng, Yang; Shen, Wenzhong

2015-01-01

Perovskite/c-Si tandem solar cells (TSCs) have become a promising candidate in recent years for achieving efficiency over 30%. Although general analysis has shown very high upper limits for such TSCs, it remains largely unclear what specific optical structures could best approach these limits. Here we propose the combination of perovskite/c-Si tandem structure with inverted nanopyramid morphology as a practical way of achieving efficiency above 31% based on realistic solar cell parameters. By full-field simulation, we have shown that an ultra-low surface reflectance can be achieved by tuning the pyramid geometry within the range of experimental feasibility. More importantly, we have demonstrated that the index-guided modes can be excited within the top cell layer by introducing a TCO interlayer that prevents coupling of guided light energy into the bottom cell. This light trapping scheme has shown superior performance over the Bragg stack intermediate reflector utilized in previous micropyramid-based TSCs. Finally, by controlling the coupling between the top and bottom cell through the thickness of the interlayer, current generation within the tandem can be optimized for both two- and four-terminal configurations, yielding efficiencies of 31.9% and 32.0%, respectively. These results have provided useful guidelines for the fabrication of perovskite/c-Si TSCs. PMID:26566176

Perovskite/c-Si tandem solar cell with inverted nanopyramids: realizing high efficiency by controllable light trapping.

PubMed

Shi, Dai; Zeng, Yang; Shen, Wenzhong

2015-11-13

Perovskite/c-Si tandem solar cells (TSCs) have become a promising candidate in recent years for achieving efficiency over 30%. Although general analysis has shown very high upper limits for such TSCs, it remains largely unclear what specific optical structures could best approach these limits. Here we propose the combination of perovskite/c-Si tandem structure with inverted nanopyramid morphology as a practical way of achieving efficiency above 31% based on realistic solar cell parameters. By full-field simulation, we have shown that an ultra-low surface reflectance can be achieved by tuning the pyramid geometry within the range of experimental feasibility. More importantly, we have demonstrated that the index-guided modes can be excited within the top cell layer by introducing a TCO interlayer that prevents coupling of guided light energy into the bottom cell. This light trapping scheme has shown superior performance over the Bragg stack intermediate reflector utilized in previous micropyramid-based TSCs. Finally, by controlling the coupling between the top and bottom cell through the thickness of the interlayer, current generation within the tandem can be optimized for both two- and four-terminal configurations, yielding efficiencies of 31.9% and 32.0%, respectively. These results have provided useful guidelines for the fabrication of perovskite/c-Si TSCs.

Biological reduction of uranium coupled with oxidation of ammonium by Acidimicrobiaceae bacterium A6 under iron reducing conditions.

PubMed

Gilson, Emily R; Huang, Shan; Jaffé, Peter R

2015-11-01

This study investigated the possibility of links between the biological immobilization of uranium (U) and ammonium oxidation under iron (Fe) reducing conditions. The recently-identified Acidimicrobiaceae bacterium A6 (ATCC, PTA-122488) derives energy from ammonium oxidation coupled with Fe reduction. This bacterium has been found in various soil and wetland environments, including U-contaminated wetland sediments. Incubations of Acidimicrobiaceae bacteria A6 with nontronite, an Fe(III)-rich clay, and approximately 10 µM U indicate that these bacteria can use U(VI) in addition to Fe(III) as an electron acceptor in the presence of ammonium. Measurements of Fe(II) production and ammonium oxidation support this interpretation. Concentrations of approximately 100 µM U were found to entirely inhibit Acidimicrobiaceae bacteria A6 activity. These results suggest that natural sites of active ammonium oxidation under Fe reducing conditions by Acidimicrobiaceae bacteria A6 could be hotspots of U immobilization by bioreduction. This is the first report of biological U reduction that is not coupled to carbon oxidation.

Achieving 15% Tandem Polymer Solar Cells

DTIC Science & Technology

2015-06-23

solar cell structures – both polymer only and hybrid tandem cells to constantly pushing the envelope of solution processed solar cell ...performance – 11.6% polymer tandem cell , 7% transparent tandem polymer cell , and over 10% PCE hybrid tandem solar cells were achieved. In addition, AFOSR’s...final support also enabled us to explore novel hybrid perovskite solar cells in depth. For example, single junction cell efficiency

A high-performance liquid chromatography-tandem mass spectrometry method coupled with protein precipitation for determination of granisetron in human plasma and its application to a comparative pharmacokinetic study.

PubMed

Zhou, Ying; Jiang, Ji; Hu, Pei; Wang, Hongyun

2014-12-01

A rapid, simple and validated method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) has been developed for the determination of granisetron in human plasma. Plasma samples were pre-purified by protein precipitation procedure. The chromatographic separation was achieved with Synergi Polar-RP (75 × 2 mm, 4 µm) column using a mixture of 5 mm pH4.0 ammonium formate and methanol (300:316, v/v) under isocratic conditions at a flow rate of 0.3 mL/min. The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring mode using positive electrospray ionization. The analysis time was about 2.5 min. The method was fully validated over the concentration range 0.1-10 ng/mL. The lower limit of quantification was 0.1 ng/mL. Inter- and intra-batch precision was <6.1% and the accuracy was within 95.6-100.0%. The mean extraction recovery was 96.3%. Selectivity, matrix effect and stability were also validated. The method was applied to the comparative pharmacokinetic study of granisetron in Chinese healthy subjects. Copyright © 2014 John Wiley & Sons, Ltd.

Ubiquitous long-range antiferromagnetic coupling across the interface between superconducting and ferromagnetic oxides

DOE PAGES

De Luca, G. M.; Ghiringhelli, G.; Perroni, C. A.; ...

2014-11-24

The so-called proximity effect is the manifestation, across an interface, of the systematic competition between magnetic order and superconductivity. This phenomenon has been well documented and understood for conventional superconductors coupled with metallic ferromagnets; however it is still less known for oxide materials, where much higher critical temperatures are offered by copper oxide-based superconductors. In this paper, we show that, even in the absence of direct Cu–O–Mn covalent bonding, the interfacial CuO 2 planes of superconducting La 1.85Sr 0.15CuO 4 thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La 0.66Sr 0.33MnO 3 ferromagnet.more » Theoretical modelling confirms that this effect is general to all cuprate/manganite heterostructures and the presence of direct bonding only affects the strength of the coupling. Finally, the Dzyaloshinskii–Moriya interaction, also at the origin of the weak ferromagnetism of bulk cuprates, propagates the magnetisation from the interface CuO 2 planes into the superconductor, eventually depressing its critical temperature.« less

Double [3 + 2]-dimerisation cascade synthesis of bis(triazolyl)bisphosphanes, a new scaffold for bidentate bisphosphanes.

PubMed

Laborde, Coralie; Wei, Muh-Mei; van der Lee, Arie; Deydier, Eric; Daran, Jean-Claude; Volle, Jean-Noël; Poli, Rinaldo; Pirat, Jean-Luc; Manoury, Eric; Virieux, David

2015-07-28

A highly convergent synthesis of bis(triazolylphosphane oxides) was developed by a tandem copper-mediated Huisgen reaction-oxidative coupling. The phosphane oxides were reduced by trichlorosilane and the coordination of the resulting bisphosphanes was studied with various transition metals.

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents.

PubMed

Fayad, Paul B; Zamyadi, Arash; Broseus, Romain; Prévost, Michèle; Sauvé, Sébastien

2013-01-01

This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. This

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

PubMed Central

2013-01-01

Background This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. Results The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M-1 sec-1 in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M-1 sec-1 in ultrapure water and 26 to 149 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M-1 sec-1 in ultrapure water and 180 to 368 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L-1 after contact times of 10 to 60�

Endogenous influences on anammox and sulfocompound-oxidizing autotrophic denitrification coupling system (A/SAD) and dynamic operating strategy.

PubMed

Sun, Xinbo; Du, Lingfeng; Hou, Yuqian; Cheng, Shaoju; Zhang, Xuxiang; Liu, Bo

2018-02-21

The anaerobic ammonia oxidation (anammox) and sulfocompound-oxidizing autotrophic denitrification coupling system (A/SAD) was initiated in an expanded granular sludge bed (EGSB) reactor for nitrogen removal from high-strength wastewater. Owing to cooperation between anammox and partial sulfocompound-oxidation autotrophic denitrification coupling system (PSAD), the highest nitrogen removal efficiency (NRE) of 98.1% ± 0.4% achieved at the optimal influent conditions of conversion efficiency of ammonium (CEA) of 55% and S 2 O 3 2- -S/NO 3 - -N (S/N) of 1.4 mol mol -1 . The activity of the short-cut sulfocompound-oxidizing autotrophic denitrification (SSAD) was also regulated to cope with dynamic CEA in the influent by changing the S/N, which was demonstrated to be effective in alleviating nitrite accumulation when the CEA was between 57% and 61%. Both the anammox and SAD bacteria enriched in the reactor after long-term incubation. Candidatus Brocadia and Candidatus Jettenia might be potentially contributing the most to anammox, while the Thiobacillus was the dominant taxa related to SAD. Copyright © 2018. Published by Elsevier Ltd.

Simultaneous targeted analysis of trimethylamine-N-oxide, choline, betaine, and carnitine by high performance liquid chromatography tandem mass spectrometry.

PubMed

Liu, Jia; Zhao, Mingming; Zhou, Juntuo; Liu, Changjie; Zheng, Lemin; Yin, Yuxin

2016-11-01

Trimethylamine-N-oxide (TMAO) is a metabolite generated from choline, betaine and carnitine in a gut microbiota-dependent way. This molecule is associated with development of atherosclerosis and cardiovascular events. A sensitive liquid chromatographic electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) has been developed and validated for the simultaneous determination of TMAO related molecules including TMAO, betaine, choline, and carnitine in mouse plasma. Analytes are extracted after protein precipitation by methanol and subjected to LC-ESI-MS/MS without preliminary derivatization. Separation of analytes was achieved on an amide column with acetonitrile-water as the mobile phase. This method has been fully validated in this study in terms of selectivity, linearity, sensitivity, precision, accuracy, and carryover effect, and the stability of the analyte under various conditions has been confirmed. This developed method has successfully been applied to plasma samples of our mouse model. Copyright © 2016 Elsevier B.V. All rights reserved.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution.

PubMed

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Reduction of intergranular exchange coupling and grain size for high Ku CoPt-based granular media: Metal-oxide buffer layer and multiple oxide boundary materials

NASA Astrophysics Data System (ADS)

Tham, Kim Kong; Kushibiki, Ryosuke; Kamada, Tomonari; Hinata, Shintaro; Saito, Shin

2018-05-01

Investigation of magnetic properties and microstructure of granular media with various multiple oxides as the grain boundary material is reported. Saturation magnetization (Ms), uniaxial magnetocrystalline anisotropy (Ku), and magnetic grain diameter (GD) of the granular media show linear correlation with volume weighted average for melting point (Tm) of each oxides (Tmave). Ku of magnetic grains (Kugrain) shows a trade-off relation with GD that it is a big challenge to satisfy both high Kugrain and small GD by only controlling Tmave. To obtain a granular medium with appropriate Kugrain, GD, and low degree of intergranular exchange coupling, the combination of Tmave control of grain boundary material by mixing oxides and employment of a buffer layer are required. Here the degree of intergranular exchange coupling is estimated from the slope of M-H loop at around coercivity (α). By applying this technique, a typical granular medium with Kugrain of 1.0×107 erg/cm3, GD of 5.1 nm, and α of 1.2 is realized.

Simultaneous determination of 24 polycyclic aromatic hydrocarbons in edible oil by tandem solid-phase extraction and gas chromatography coupled/tandem mass spectrometry.

PubMed

Xu, Ting; Tang, Hua; Chen, Dazhou; Dong, Haifeng; Li, Lei

2015-01-01

An efficient and fast tandem SPE method followed by GC/MS/MS has been developed for the determination and the quantification of 24 polycyclic aromatic hydrocarbons (PAHs) in edible oil. This method includes the monitoring of 15 + 1 PAHs designated as a priority by the European Union in their 2005/108/EC recommendation and 16 PAHs listed by the U. S. Environmental Protection Agency. The sample preparation procedures were based on SPE in which PAH-dedicated cartridges with molecularly imprinted polymers and graphitized carbon black were used in series. The novel tandem SPE combination of selective extraction and purification of light and heavy PAHs provided highly purified analytes. Identification and quantification of 24 target PAHs were performed using GC/MS/MS with the isotope dilution approaches using D-labeled and (13)C-labeled PAHs. The advantages of GC/MS/MS as compared to other detection methods include high sensitivity, selectivity, and interpretation ability. The method showed satisfactory linearity (R(2) > 0.998) over the range assayed (0.5-200 μg/kg); the LODs ranged from 0.03 to 0.6 μg/kg, and LOQs from 0.1 to 2.0 μg/kg. The recoveries using this method at three spiked concentration levels (2, 10, and 50 μg/kg) ranged from 56.8 to 117.7%. The RSD was lower than 12.7% in all cases. The proposed analytical method has been successfully applied for the analysis of the 24 PAHs in edible oil.

Control of Sulfidogenesis Through Bio-oxidation of H 2S Coupled to (per)chlorate Reduction

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

Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G.

2014-04-04

Here, we investigate H 2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H 2S coupled to (per)chlorate reduction without sustaining growth. H 2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H 2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

Quantitative determination of risperidone, paliperidone and olanzapine in human serum by liquid chromatography-tandem mass spectrometry coupled with on-line solid-phase extraction.

PubMed

Ruan, Can-Jun; Guo, Wei; Zhou, Miao; Guo, Gui-Xin; Wang, Chuan-Yue; Li, Wen-Biao; de Leon, Jose

2018-07-01

A recent guideline recommends therapeutic drug monitoring for risperidone, paliperidone and olanzapine, which are frequently used second-generation antipsychotics. We developed a simple high-performance liquid chromatography-tandem mass spectrometry coupled with an online solid-phase extraction method that can be used to measure risperidone, paliperidone and olanzapine using small (40 μL) samples. The analytes were extracted from serum samples automatically pre-concentrated and purified by C 8 (5 μm, 2.1 × 30 mm) solid-phase extraction cartridges, then chromatographed on an Xbidge™ C 18 column (3.5 μm, 100 × 2.1 mm) thermostatted at 30°C with a mobile phase consisting of 70% acetonitrile and 30% ammonium hydroxide 1% solution at an isocratic flow rate of 0.3 mL/min, and detected with tandem mass spectrometry. The assay was validated in the concentration range from 2.5 to 160 ng/mL. Intra- and inter-day precision for all analytes was between 1.1 and 8.2%; method accuracy was between 6.6 and 7.6%. The risperidone and paliperidone assay was compared with a high-performance liquid chromatography-ultraviolet assay currently used in our hospital for risperidone and paliperidone therapeutic drug monitoring, and the results of weighted Deming regression analysis showed good agreement. For the olanzapine assay, we compared 20 samples in separate re-assays on different days; all the relative errors were within the 20% recommended limit. Copyright © 2018 John Wiley & Sons, Ltd.

Spin-Orbit Coupling Controlled J = 3 / 2 Electronic Ground State in 5 d 3 Oxides

DOE PAGES

Taylor, A. E.; Calder, S.; Morrow, R.; ...

2017-05-16

Spin-orbit entanglement in 5d-based transition metal oxides (TMOs) has been identified as a route to a host of unconventional physical states including quantum spin liquids, Weyl semimetals, and axion insulators. Yet despite intense interest, no clear rules have emerged for the treatment of spin-orbit coupling (SOC) in 5d TMOs outside of idealised LS or jj coupling paradigms. This is exemplified in 5d 3 oxides in which an orbitally-quenched singlet ground state is anticipated, yet SOC is manifest in the observed magnetic properties. Here we solve this long-outstanding puzzle by revealing that the electronic ground state of Os5+ 5d 3 ionsmore » is an unquenched J = 3/2 state. Resonant inelastic x-ray scattering (RIXS) in Ca3LiOsO6 and Ba 2YOsO 6 exposes a SOC-controlled splitting of the t 2g manifold. The results are successfully described using an intermediate-coupling framework in which oxygen hybridisation promotes the breakdown of the orbital singlet. This framework opens the door to realistic treatment of SOC across a range of 5d TMOs beyond the 5d 3 case.« less

Spin-Orbit Coupling Controlled J = 3 / 2 Electronic Ground State in 5 d 3 Oxides

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

Taylor, A. E.; Calder, S.; Morrow, R.

Spin-orbit entanglement in 5d-based transition metal oxides (TMOs) has been identified as a route to a host of unconventional physical states including quantum spin liquids, Weyl semimetals, and axion insulators. Yet despite intense interest, no clear rules have emerged for the treatment of spin-orbit coupling (SOC) in 5d TMOs outside of idealised LS or jj coupling paradigms. This is exemplified in 5d 3 oxides in which an orbitally-quenched singlet ground state is anticipated, yet SOC is manifest in the observed magnetic properties. Here we solve this long-outstanding puzzle by revealing that the electronic ground state of Os5+ 5d 3 ionsmore » is an unquenched J = 3/2 state. Resonant inelastic x-ray scattering (RIXS) in Ca3LiOsO6 and Ba 2YOsO 6 exposes a SOC-controlled splitting of the t 2g manifold. The results are successfully described using an intermediate-coupling framework in which oxygen hybridisation promotes the breakdown of the orbital singlet. This framework opens the door to realistic treatment of SOC across a range of 5d TMOs beyond the 5d 3 case.« less

TANDEM: matching proteins with tandem mass spectra.

PubMed

Craig, Robertson; Beavis, Ronald C

2004-06-12

Tandem mass spectra obtained from fragmenting peptide ions contain some peptide sequence specific information, but often there is not enough information to sequence the original peptide completely. Several proprietary software applications have been developed to attempt to match the spectra with a list of protein sequences that may contain the sequence of the peptide. The application TANDEM was written to provide the proteomics research community with a set of components that can be used to test new methods and algorithms for performing this type of sequence-to-data matching. The source code and binaries for this software are available at http://www.proteome.ca/opensource.html, for Windows, Linux and Macintosh OSX. The source code is made available under the Artistic License, from the authors.

Identification and High-Resolution Imaging of α-Tocopherol from Human Cells to Whole Animals by TOF-SIMS Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Bruinen, Anne L.; Fisher, Gregory L.; Balez, Rachelle; van der Sar, Astrid M.; Ooi, Lezanne; Heeren, Ron M. A.

2018-06-01

A unique method for identification of biomolecular components in different biological specimens, while preserving the capability for high speed 2D and 3D molecular imaging, is employed to investigate cellular response to oxidative stress. The employed method enables observing the distribution of the antioxidant α-tocopherol and other molecules in cellular structures via time-of-flight secondary ion mass spectrometry (TOF-SIMS (MS1)) imaging in parallel with tandem mass spectrometry (MS2) imaging, collected simultaneously. The described method is employed to examine a network formed by neuronal cells differentiated from human induced pluripotent stem cells (iPSCs), a model for investigating human neurons in vitro. The antioxidant α-tocopherol is identified in situ within different cellular layers utilizing a 3D TOF-SIMS tandem MS imaging analysis. As oxidative stress also plays an important role in mediating inflammation, the study was expanded to whole body tissue sections of M. marinum-infected zebrafish, a model organism for tuberculosis. The TOF-SIMS tandem MS imaging results reveal an increased presence of α-tocopherol in response to the pathogen. [Figure not available: see fulltext.

Charge generation layers for solution processed tandem organic light emitting diodes with regular device architecture.

PubMed

Höfle, Stefan; Bernhard, Christoph; Bruns, Michael; Kübel, Christian; Scherer, Torsten; Lemmer, Uli; Colsmann, Alexander

2015-04-22

Tandem organic light emitting diodes (OLEDs) utilizing fluorescent polymers in both sub-OLEDs and a regular device architecture were fabricated from solution, and their structure and performance characterized. The charge carrier generation layer comprised a zinc oxide layer, modified by a polyethylenimine interface dipole, for electron injection and either MoO3, WO3, or VOx for hole injection into the adjacent sub-OLEDs. ToF-SIMS investigations and STEM-EDX mapping verified the distinct functional layers throughout the layer stack. At a given device current density, the current efficiencies of both sub-OLEDs add up to a maximum of 25 cd/A, indicating a properly working tandem OLED.

Fast determination of four polar contaminants in soy nutraceutical products by liquid chromatography coupled to tandem mass spectrometry.

PubMed

Domingos Alves, Renata; Romero-González, Roberto; López-Ruiz, Rosalía; Jiménez-Medina, M L; Garrido Frenich, Antonia

2016-11-01

An analytical method based on a modified QuPPe (quick polar pesticide) extraction procedure coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was evaluated for the determination of four polar compounds (chlorate, fosetyl-Al, maleic hydrazide, and perchlorate) in nutraceutical products obtained from soy. Experimental conditions including extraction such as solvent, acidification, time, and clean-up sorbents were varied. Acidified acetonitrile (1 % formic acid, v/v) was used as extraction solvent instead of methanol (conventional QuPPe), which provides a doughy mixture which cannot be injected into the LC. Clean-up or derivatization steps were avoided. For analysis, several stationary phases were evaluated and Hypercarb (porous graphitic carbon) provided the best results. The optimized method was validated and recoveries ranged between 46 and 119 %, and correction factors can be used for quantification purposes bearing in mind that inter-day precision was equal to or lower than 17 %. Limits of quantification (LOQs) ranged from 4 to 100 μg kg -1 . Soy-based nutraceutical products were analyzed and chlorate was detected in five samples at concentrations between 63 and 1642 μg kg -1 . Graphical Abstract Analysis of polar compounds in soy-based nutraceutical products.

Three-dimensional photonic crystals as intermediate filter for thin-film tandem solar cells

NASA Astrophysics Data System (ADS)

Bielawny, Andreas; Miclea, Paul T.; Wehrspohn, Ralf B.; Lee, Seung-Mo; Knez, Mato; Rockstuhl, Carsten; Lisca, Marian; Lederer, Falk L.; Carius, Reinhard

2008-04-01

The concept of a 3D photonic crystal structure as diffractive and spectrally selective intermediate filter within 'micromorphous' (a-Si/μc-Si) tandem solar cells has been investigated numerically and experimentally. Our device aims for the enhancement of the optical pathway of incident light within the amorphous silicon top cell in its spectral region of low absorption. From our previous simulations, we expect a significant improvement of the tandem cell efficiency of about absolutely 1.3%. This increases the efficiency for a typical a-Si / μc-Si tandem cell from 11.1% to 12.4%, as a result of the optical current-matching of the two junctions. We suggest as wavelength-selective optical element a 3D-structured optical thin-film, prepared by self-organized artificial opal templates and replicated with atomic layer deposition. The resulting samples are highly periodic thin-film inverted opals made of conducting and transparent zinc-oxide. We describe the fabrication processes and compare experimental data on the optical properties in reflection and transmission with our simulations and photonic band structure calculations.

A dye-sensitized photoelectrochemical tandem cell for light driven hydrogen production from water

DOE PAGES

Sherman, Benjamin D.; Sheridan, Matthew V.; Wee, Kyung -Ryang; ...

2016-12-02

Here, tandem junction photoelectrochemical water-splitting devices, whereby two light absorbing electrodes targeting separate portions of the solar spectrum generate the voltage required to convert water to oxygen and hydrogen, enable much higher possible efficiencies than single absorber systems. We report here on the development of a tandem system consisting of a dye-sensitized photoelectrochemical cell (DSPEC) wired in series with a dye-sensitized solar cell (DSC). The DSPEC photoanode incorporates a tris(bipyridine)ruthenium(II)-type chromophore and molecular ruthenium based water oxidation catalyst. The DSPEC was tested with two more-red absorbing DSC variations, one utilizing N719 dye with an I 3 –/I – redox mediatormore » solution and the other D35 dye with a tris(bipyridine)cobalt ([Co(bpy) 3] 3+/2+) based mediator. The tandem configuration consisting of the DSPEC and D35/[Co(bpy) 3] 3+/2+ based DSC gave the best overall performance and demonstrated the production of H 2 from H 2O with the only energy input from simulated solar illumination.« less

Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover.

PubMed

Feng, S; Ng, C W W; Leung, A K; Liu, H W

2017-10-01

Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄.

PubMed

Mancuso, Raffaella; Maner, Asif; Ziccarelli, Ida; Pomelli, Christian; Chiappe, Cinzia; Della Ca', Nicola; Veltri, Lucia; Gabriele, Bartolo

2016-07-08

A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

Proton translocation coupled to trimethylamine N-oxide reduction in anaerobically grown Escherichia coli.

PubMed Central

Takagi, M; Tsuchiya, T; Ishimoto, M

1981-01-01

Proton translocation coupled to trimethylamine N-oxide reduction was studied in Escherichia coli grown anaerobically in the presence of trimethylamine N-oxide. Rapid acidification of the medium was observed when trimethylamine N-oxide was added to anaerobic cell suspensions of E. coli K-10. Acidification was sensitive to the proton conductor 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile (SF6847). No pH change was shown in a strain deficient in trimethylamine N-oxide reductase activity. The apparent H+/trimethylamine N-oxide ratio in cells oxidizing endogenous substrates was 3 to 4 g-ions of H+ translocated per mol of trimethylamine N-oxide added. The addition of trimethylamine N-oxide and formate to ethylenediaminetetraacetic acid-treated cell suspension caused fluorescence quenching of 3,3'-dipropylthiacarbocyanine [diS-C3-(5)], indicating the generation of membrane potential. These results indicate that the reduction of trimethylamine N-oxide in E. coli is catalyzed by an anaerobic electron transfer system, resulting in formation of a proton motive force. Trimethylamine N-oxide reductase activity and proton extrusion were also examined in chlorate-resistant mutants. Reduction of trimethylamine N-oxide occurred in chlC, chlG, and chlE mutants, whereas chlA, chlB, and chlD mutants, which are deficient in the molybdenum cofactor, could not reduce it. Protons were extruded in chlC and chlG mutants, but not in chlA, chlB, and chlD mutants. Trimethylamine N-oxide reductase activity in a chlD mutant was restored to the wild-type level by the addition of 100 microM molybdate to the growth medium, indicating that the same molybdenum cofactor as used by nitrate reductase is required for the trimethylamine N-oxide reductase system. PMID:7031034

Waste-free synthesis of condensed heterocyclic compounds by rhodium-catalyzed oxidative coupling of substituted arene or heteroarene carboxylic acids with alkynes.

PubMed

Shimizu, Masaki; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2009-05-01

The direct oxidative coupling of 2-amino- and 2-hydroxybenzoic acids with internal alkynes proceeds efficiently in the presence of a rhodium/copper catalyst system under air to afford the corresponding 8-substituted isocoumarin derivatives, some of which exhibit solid-state fluorescence. Depending on conditions, 4-ethenylcarbazoles can be synthesized selectively from 2-(arylamino)benzoic acids. The oxidative coupling reactions of heteroarene carboxylic acids as well as aromatic diacids with an alkyne are also described.

Detecting long tandem duplications in genomic sequences.

PubMed

Audemard, Eric; Schiex, Thomas; Faraut, Thomas

2012-05-08

Detecting duplication segments within completely sequenced genomes provides valuable information to address genome evolution and in particular the important question of the emergence of novel functions. The usual approach to gene duplication detection, based on all-pairs protein gene comparisons, provides only a restricted view of duplication. In this paper, we introduce ReD Tandem, a software using a flow based chaining algorithm targeted at detecting tandem duplication arrays of moderate to longer length regions, with possibly locally weak similarities, directly at the DNA level. On the A. thaliana genome, using a reference set of tandem duplicated genes built using TAIR,(a) we show that ReD Tandem is able to predict a large fraction of recently duplicated genes (dS  <  1) and that it is also able to predict tandem duplications involving non coding elements such as pseudo-genes or RNA genes. ReD Tandem allows to identify large tandem duplications without any annotation, leading to agnostic identification of tandem duplications. This approach nicely complements the usual protein gene based which ignores duplications involving non coding regions. It is however inherently restricted to relatively recent duplications. By recovering otherwise ignored events, ReD Tandem gives a more comprehensive view of existing evolutionary processes and may also allow to improve existing annotations.

Evaluating the economic viability of CdTe/CIS and CIGS/CIS tandem photovoltaic modules

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

Nanayakkara, Sanjini U.; Horowitz, Kelsey; Kanevce, Ana

In this paper, we analyze the potential cost competitiveness of two frameless, glass–glass thin-film tandem photovoltaic module structures, cadmium telluride (CdTe)/CuInSe 2 (CIS) and CuIn 0.3Ga 0.7Se 2 (CIGS)/CIS, based on the demonstrated cost of manufacturing the respective component cell technologies in high volume. To consider multiple economic scenarios, we base the CdTe/CIS module efficiency on the current industrial production of CdTe modules, while for CIGS/CIS, we use an aspirational estimate for CIGS efficiency. We focus on four-terminal mechanically stacked structures, thus avoiding the need to achieve current matching between the two cells. The top cell in such a tandemmore » must have a transparent back contact, which has not been successfully implemented to date. However, for the purpose of understanding the economic viability of both tandems, we assume that this can be implemented at a cost similar to that of sputtered indium tin oxide. The cost of both tandem module structures was found to be nearly identical on an equal-area basis and approximately $30/m 2 higher than the single-junction alternatives. Both tandem modules are about 4% (absolute) more efficient than a module by using the top-cell material alone. We find that these tandem modules might reduce total system cost by as much as 11% in applications having a high area-related balance-of-system cost, such as area-constrained residential systems; however, the relative advantage of tandems decreases in the cases where balance-of-system costs are lower, such as in commercial and utility scale systems.« less

Evaluating the economic viability of CdTe/CIS and CIGS/CIS tandem photovoltaic modules

DOE PAGES

Nanayakkara, Sanjini U.; Horowitz, Kelsey; Kanevce, Ana; ...

2017-01-20

In this paper, we analyze the potential cost competitiveness of two frameless, glass–glass thin-film tandem photovoltaic module structures, cadmium telluride (CdTe)/CuInSe 2 (CIS) and CuIn 0.3Ga 0.7Se 2 (CIGS)/CIS, based on the demonstrated cost of manufacturing the respective component cell technologies in high volume. To consider multiple economic scenarios, we base the CdTe/CIS module efficiency on the current industrial production of CdTe modules, while for CIGS/CIS, we use an aspirational estimate for CIGS efficiency. We focus on four-terminal mechanically stacked structures, thus avoiding the need to achieve current matching between the two cells. The top cell in such a tandemmore » must have a transparent back contact, which has not been successfully implemented to date. However, for the purpose of understanding the economic viability of both tandems, we assume that this can be implemented at a cost similar to that of sputtered indium tin oxide. The cost of both tandem module structures was found to be nearly identical on an equal-area basis and approximately $30/m 2 higher than the single-junction alternatives. Both tandem modules are about 4% (absolute) more efficient than a module by using the top-cell material alone. We find that these tandem modules might reduce total system cost by as much as 11% in applications having a high area-related balance-of-system cost, such as area-constrained residential systems; however, the relative advantage of tandems decreases in the cases where balance-of-system costs are lower, such as in commercial and utility scale systems.« less

Mitochondrial coupling and capacity of oxidative phosphorylation in skeletal muscle of Inuit and Caucasians in the arctic winter.

PubMed

Gnaiger, E; Boushel, R; Søndergaard, H; Munch-Andersen, T; Damsgaard, R; Hagen, C; Díez-Sánchez, C; Ara, I; Wright-Paradis, C; Schrauwen, P; Hesselink, M; Calbet, J A L; Christiansen, M; Helge, J W; Saltin, B

2015-12-01

During evolution, mitochondrial DNA haplogroups of arctic populations may have been selected for lower coupling of mitochondrial respiration to ATP production in favor of higher heat production. We show that mitochondrial coupling in skeletal muscle of traditional and westernized Inuit habituating northern Greenland is identical to Danes of western Europe haplogroups. Biochemical coupling efficiency was preserved across variations in diet, muscle fiber type, and uncoupling protein-3 content. Mitochondrial phenotype displayed plasticity in relation to lifestyle and environment. Untrained Inuit and Danes had identical capacities to oxidize fat substrate in arm muscle, which increased in Danes during the 42 days of acclimation to exercise, approaching the higher level of the Inuit hunters. A common pattern emerges of mitochondrial acclimatization and evolutionary adaptation in humans at high latitude and high altitude where economy of locomotion may be optimized by preservation of biochemical coupling efficiency at modest mitochondrial density, when submaximum performance is uncoupled from VO2max and maximum capacities of oxidative phosphorylation. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Highly efficient and tunable spin-to-charge conversion through Rashba coupling at oxide interfaces

NASA Astrophysics Data System (ADS)

Lesne, E.; Fu, Yu; Oyarzun, S.; Rojas-Sánchez, J. C.; Vaz, D. C.; Naganuma, H.; Sicoli, G.; Attané, J.-P.; Jamet, M.; Jacquet, E.; George, J.-M.; Barthélémy, A.; Jaffrès, H.; Fert, A.; Bibes, M.; Vila, L.

2016-12-01

The spin-orbit interaction couples the electrons’ motion to their spin. As a result, a charge current running through a material with strong spin-orbit coupling generates a transverse spin current (spin Hall effect, SHE) and vice versa (inverse spin Hall effect, ISHE). The emergence of SHE and ISHE as charge-to-spin interconversion mechanisms offers a variety of novel spintronic functionalities and devices, some of which do not require any ferromagnetic material. However, the interconversion efficiency of SHE and ISHE (spin Hall angle) is a bulk property that rarely exceeds ten percent, and does not take advantage of interfacial and low-dimensional effects otherwise ubiquitous in spintronic hetero- and mesostructures. Here, we make use of an interface-driven spin-orbit coupling mechanism--the Rashba effect--in the oxide two-dimensional electron system (2DES) LaAlO3/SrTiO3 to achieve spin-to-charge conversion with unprecedented efficiency. Through spin pumping, we inject a spin current from a NiFe film into the oxide 2DES and detect the resulting charge current, which can be strongly modulated by a gate voltage. We discuss the amplitude of the effect and its gate dependence on the basis of the electronic structure of the 2DES and highlight the importance of a long scattering time to achieve efficient spin-to-charge interconversion.

Oxidative tandem nitrosation/cyclization of N-aryl enamines with nitromethane toward 3-(trifluoromethyl)quinoxalines.

PubMed

Yang, Zhi-Jun; Liu, Chuan-Zhuo; Hu, Bo-Lun; Deng, Chen-Liang; Zhang, Xing-Guo

2014-12-04

A novel one-pot strategy for the synthesis of 3-trifluoromethylquinoxalines from N-aryl enamines and nitromethane was developed. The tandem reaction is achieved through nitrosation of alkenes, tautomerization and cyclization, which can be applicable to a wide range of enamines with excellent functional group tolerance and afford quinoxalines in moderate to good yields.

Rapid Chemoselective Bioconjugation Through the Oxidative Coupling of Anilines and Aminophenols

PubMed Central

Behrens, Christopher R.; Hooker, Jacob M.; Obermeyer, Allie C.; Romanini, Dante W.; Katz, Elan M.; Francis, Matthew B.

2012-01-01

A highly efficient protein bioconjugation method is described involving the addition of anilines to o-aminophenols in the presence of sodium periodate. The reaction takes place in aqueous buffer at pH 6.5 and can reach high levels of completion in 2–5 min. The product of the reaction has been characterized using X-ray crystallography, which revealed that an unprecedented oxidative ring contraction occurs after the coupling step. The compatibility of the reaction with protein substrates has been demonstrated through the attachment of small molecules, polymer chains, and peptides to p-aminophenylalanine residues introduced into viral capsids through amber stop codon suppression. The coupling of anilines to o-aminophenol groups derived from tyrosine residues is also described. The compatibility of this method with thiol modification chemistry is shown through the attachment of a near-IR fluorescent chromophore to cysteine residues inside the viral capsid shells, followed by the attachment of integrin-targeting RGD peptides to anilines on the exterior surface. PMID:21919497

QEPAS nitric oxide sensor based on a mid-infrared fiber-coupled quantum cascade laser

NASA Astrophysics Data System (ADS)

Ren, Wei; Shi, Chao; Wang, Zhen; Yao, Chenyu

2017-04-01

We report a quartz-enhanced photoacoustic sensor (QEPAS) for nitric oxide (NO) detection using a mid-infrared fibercoupled quantum cascade laser (QCL) near 5.2 μm. The QCL radiation was coupled into an InF3 fiber (100 μm core diameter) for light delivery to the quartz tuning fork, a tiny piezoelectric element converting the acoustic wave induced mechanical vibration to the gas-absorption associated electrical signal. This mid-infrared fiber can achieve nearly single-mode light delivery for the target wavelength. The off-beam configuration was adopted for the fiber-coupled detection considering its simpler installation, optical alignment and comparative sensitivity to the traditional on-beam setup.

Analysis of chloramphenicol residues in the macroalgae Ulva lactuca through ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS).

PubMed

Leston, Sara; Freitas, Andreia; Nunes, Margarida; Barbosa, Jorge; Pardal, Miguel Ângelo; Ramos, Fernando

2015-02-15

Antibiotic use is a well-described practice to promote animal health whether for prevention or treatment. Nonetheless, it can also cause a number of potentially harmful effects that dictate the need to implement regulation to assure a reduction of hazards to the consumers and the environment. Chloramphenicol (CAP) is a broad-spectrum antibacterial excluded from use in animal food production but despite this, reports of illegal use still persist. More recently, awareness has risen that the surrounding natural ecosystems can potentially be contaminated by pharmaceuticals and the extent of their effects in non-target organisms is already under the scope of researchers. To face the demanding new challenges a methodology for the determination of CAP in the green macroalgae Ulva lactuca by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was developed, optimized and fully validated following the guidelines of the EC Decision 2002/657. Copyright © 2014 Elsevier Ltd. All rights reserved.

Determination of pyrethrin and pyrethroid residues in animal fat using liquid chromatography coupled to tandem mass spectrometry.

PubMed

Moloney, M; Tuck, S; Ramkumar, A; Furey, A; Danaher, M

2018-03-01

A method was developed for the confirmatory and quantitative analysis of one pyrethrin and 18 pyrethroid residues in animal fat. Fat was extracted was collected from adipose tissue melted in an oven at 65 °C for 2 h. Fat samples (1 g) were dispersed with deactivated Florisil ® sorbent and extracted with MeCN. Sample extracts were purified by cold temperature precipitation at -30 °C for 4 h and further purified using dispersive solid-phase extraction (d-SPE) clean-up in tubes containing 500 mg of Z-SEP+ and 125 mg of PSA bonded silica. Purified samples were analysed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) detection. Chromatographic separation was carried out on a Acquity C 8 BEH column, using a binary gradient separation comprising of mobile phase A, 5 mM ammonium formate in water:MeOH (80:20, v/v,) and mobile phase B, 5 mM ammonium formate in MeOH. The mass spectrometer was operated in the positive electrospray ionisation mode (ESI(+)). Validation was performed following the 2002/657/EC guidelines. Trueness ranged between 84% and 143% and precision ranged between 3.9% and 29%. The developed method is particularly advantageous because the sample preparation procedure does not require complex sample extraction equipment and uses less solvent compared to other sample preparation protocols. Copyright © 2017 Elsevier B.V. All rights reserved.

Determinations of airborne synthetic musks by polyurethane foam coupled with triple quadrupole gas chromatography tandem mass spectrometer.

PubMed

Wang, I-Ting Ivy; Cheng, Shu-Fang; Tsai, Shih-Wei

2014-02-21

Synthetic musk is widely used in various scented consumer products. However, the exposure via inhalation is often ignored due to pleasant smells. In addition, the information regarding the distribution of synthetic musk in air is limited. Hence, this research is aimed to develop a highly sensitive and widely applicable method for the determination of airborne synthetic musk. In this study, polyurethane foam (PUF) and filter were employed for active air sampling. Microwave assisted extraction (MAE) and nitrogen evaporator were performed for sample preparation. A gas chromatography coupled with triple quadrupole tandem mass spectrometer (GC/MS-MS) with specific multiple reaction monitoring (MRM) transition pairs was applied for sample analysis. Compared with using selected ion monitoring (SIM) mode traditionally, the sensitivities were improved in this study about an order at least. In terms of air concentration, as low as 0.48ngm(-3) can be determined when sampling at 3.5Lmin(-1) for 8h. The method established was further applied to the analysis of synthetic musk compounds in air samples collected in a cosmetics plant. The results showed that the airborne concentrations of gaseous polycyclic musk, gaseous nitro-musk, and particle-phase polycyclic musk were 6.4×10(2), 4.0×10(1) and 3.1×10(2)ngm(-3), respectively. Meanwhile, Cashmeran, Celstolide, Galaxolide, and Tonalide were found as the dominant musk compounds in the factory investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

PubMed

Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

2017-09-01

Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Progress towards a 30% efficient GaInP/Si tandem solar cells

DOE PAGES

Essig, Stephanie; Ward, Scott; Steiner, Myles A.; ...

2015-08-28

The performance of dual-junction solar cells with a Si bottom cell has been investigated both theoretically and experimentally. Simulations show that adding a top junction with an energy bandgap of 1.6 -1.9 eV to a standard silicon solar cell enables efficiencies over 38%. Currently, top junctions of GaInP (1.8 eV) are the most promising as they can achieve 1-sun efficiencies of 20.8% [1]. We fabricated mechanically stacked, four terminal GaInP/Si tandem solar cells using a transparent adhesive between the subcells. These tandem devices achieved an efficiency of 27% under AM1.5 g spectral conditions. Furthermore, higher efficiencies can be achieved bymore » using an improved Si-bottom cell and by optimizing the dual-junction device for long-wavelength light and luminescent coupling between the two junctions.« less

All-silicon tandem solar cells: Practical limits for energy conversion and possible routes for improvement

NASA Astrophysics Data System (ADS)

Jia, Xuguang; Puthen-Veettil, Binesh; Xia, Hongze; Yang, Terry Chien-Jen; Lin, Ziyun; Zhang, Tian; Wu, Lingfeng; Nomoto, Keita; Conibeer, Gavin; Perez-Wurfl, Ivan

2016-06-01

Silicon nanocrystals (Si NCs) embedded in a dielectric matrix is regarded as one of the most promising materials for the third generation photovoltaics, owing to their tunable bandgap that allows fabrication of optimized tandem devices. Previous work has demonstrated fabrication of Si NCs based tandem solar cells by sputter-annealing of thin multi-layers of silicon rich oxide and SiO2. However, these device efficiencies were much lower than expected given that their theoretical values are much higher. Thus, it is necessary to understand the practical conversion efficiency limits for these devices. In this article, practical efficiency limits of Si NC based double junction tandem cells determined by fundamental material properties such as minority carrier, mobility, and lifetime are investigated. The practical conversion efficiency limits for these devices are significantly different from the reported efficiency limits which use Shockley-Queisser assumptions. Results show that the practical efficiency limit of a double junction cell (1.6 eV Si NC top cell and a 25% efficient c-Si PERL cell as the bottom cell) is 32%. Based on these results suggestions for improvement to the performance of Si nanocrystal based tandem solar cells in terms of the different parameters that were simulated are presented.

Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

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

Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina

Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

DOE PAGES

Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina; ...

2017-09-21

Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

Infrared rectification in a nanoantenna-coupled metal-oxide-semiconductor tunnel diode.

PubMed

Davids, Paul S; Jarecki, Robert L; Starbuck, Andrew; Burckel, D Bruce; Kadlec, Emil A; Ribaudo, Troy; Shaner, Eric A; Peters, David W

2015-12-01

Direct rectification of electromagnetic radiation is a well-established method for wireless power conversion in the microwave region of the spectrum, for which conversion efficiencies in excess of 84% have been demonstrated. Scaling to the infrared or optical part of the spectrum requires ultrafast rectification that can only be obtained by direct tunnelling. Many research groups have looked to plasmonics to overcome antenna-scaling limits and to increase the confinement. Recently, surface plasmons on heavily doped Si surfaces were investigated as a way of extending surface-mode confinement to the thermal infrared region. Here we combine a nanostructured metallic surface with a heavily doped Si infrared-reflective ground plane designed to confine infrared radiation in an active electronic direct-conversion device. The interplay of strong infrared photon-phonon coupling and electromagnetic confinement in nanoscale devices is demonstrated to have a large impact on ultrafast electronic tunnelling in metal-oxide-semiconductor (MOS) structures. Infrared dispersion of SiO2 near a longitudinal optical (LO) phonon mode gives large transverse-field confinement in a nanometre-scale oxide-tunnel gap as the wavelength-dependent permittivity changes from 1 to 0, which leads to enhanced electromagnetic fields at material interfaces and a rectified displacement current that provides a direct conversion of infrared radiation into electric current. The spectral and electrical signatures of the nanoantenna-coupled tunnel diodes are examined under broadband blackbody and quantum-cascade laser (QCL) illumination. In the region near the LO phonon resonance, we obtained a measured photoresponsivity of 2.7 mA W(-1) cm(-2) at -0.1 V.

Characterization of procyanidin B2 oxidation products in an apple juice model solution and confirmation of their presence in apple juice by high-performance liquid chromatography coupled to electrospray ion trap mass spectrometry.

PubMed

Poupard, Pascal; Sanoner, Philippe; Baron, Alain; Renard, Catherine M G C; Guyot, Sylvain

2011-11-01

Procyanidins (i.e. condensed tannins) are polyphenols commonly found in fruits. During juice and cider making, apple polyphenol oxidase catalyzes the oxidation of caffeoylquinic acid (CQA) into its corresponding o-quinone which further reacts with procyanidins and other polyphenols, leading to the formation of numerous oxidation products. However, the structure and the reaction pathways of these neoformed phenolic compounds are still largely unknown. Experiments were carried out on a model system to gain insights into the chemical processes occurring during the initial steps of fruit processing. Procyanidin B2 was oxidized by caffeoylquinic acid o-quinone (CQAoq) in an apple juice model solution. The reaction products were monitored using high performance liquid chromatography (HPLC) coupled to ultraviolet (UV)-visible and electrospray tandem mass spectrometry (ESI-MS/MS) in the negative mode. Oxidative conversion of procyanidin B2 ([M-H](-) at m/z 577) into procyanidin A2 at m/z 575 was unambiguously confirmed. In addition, several classes of products were characterized by their deprotonated molecules ([M-H](-)) and their MS/MS fragmentation patterns: hetero-dimers (m/z 929) and homo-dimers (m/z 1153 and 705) resulting from dimerization involving procyanidin and CQA molecules; intramolecular addition products at m/z 575, 573, 927, 1151 and 703. Interestingly, no extensive polymerization was observed. Analysis of a cider apple juice enabled comparison with the results obtained on a biosynthetic model solution. However, procyanidin A2 did not accumulate but seemed to be an intermediate in the formation of an end-product at m/z 573 for which two structural hypotheses are given. These structural modifications of native polyphenols as a consequence of oxidation probably have an impact on the organoleptic and nutritional properties of apple juices and other apple-derived foods. Copyright © 2011 John Wiley & Sons, Ltd.

Improved out-coupling efficiency of organic light emitting diodes fabricated on a TiO2 planarization layer with embedded Si oxide nanostructures

NASA Astrophysics Data System (ADS)

Sung, Young Hoon; Jung, Pil-Hoon; Han, Kyung-Hoon; Kim, Yang Doo; Kim, Jang-Joo; Lee, Heon

2017-10-01

In order to increase the out-coupling efficiency of organic light emitting diodes, conical Si oxide nanostructures were formed on a glass substrate using nanoimprint lithography with hydrogen silsesquioxane. Then, the substrate was planarized with TiO2 nanoparticles. Since TiO2 nanoparticles have a higher refractive index than Si oxide, the surface of substrate is physically flat, but optically undulated in a manner that enables optical scattering and suppression of total internal reflection. Subsequently, OLEDs formed on a substrate with nanostructured Si oxide and a TiO2 planarization layer exhibit a 25% increase in out-coupling efficiency by suppressing total internal reflection.

Efficient semitransparent perovskite solar cells for 23.0%-efficiency perovskite/silicon four-terminal tandem cells

DOE PAGES

Chen, Bo; Bai, Yang; Yu, Zhengshan; ...

2016-07-19

Here, we have investigated semi-transparent perovskite solar cells and infrared enhanced silicon heterojunction cells for high-efficiency tandem devices. A semi-transparent metal electrode with good electrical conductivity and optical transparency has been fabricated by thermal evaporation of 7 nm of Au onto a 1-nm-thick Cu seed layer. For this electrode to reach its full potential, MAPbI3 thin films were formed by a modified one-step spin-coating method, resulting in a smooth layer that allowed the subsequent metal thin film to remain continuous. The fabricated semi-transparent perovskite solar cells demonstrated 16.5% efficiency under one-sun illumination, and were coupled with infrared-enhanced silicon heterojunction cellsmore » tuned specifically for perovskite/Si tandem devices. A double-layer antireflection coating at the front side and MgF2 reflector at rear side of the silicon heterojunction cells reduced parasitic absorption of near-infrared light, leading to 6.5% efficiency after filtering with a perovskite device and 23.0% summed efficiency for the perovskite/Si tandem device.« less

Efficient semitransparent perovskite solar cells for 23.0%-efficiency perovskite/silicon four-terminal tandem cells

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

Chen, Bo; Bai, Yang; Yu, Zhengshan

Here, we have investigated semi-transparent perovskite solar cells and infrared enhanced silicon heterojunction cells for high-efficiency tandem devices. A semi-transparent metal electrode with good electrical conductivity and optical transparency has been fabricated by thermal evaporation of 7 nm of Au onto a 1-nm-thick Cu seed layer. For this electrode to reach its full potential, MAPbI3 thin films were formed by a modified one-step spin-coating method, resulting in a smooth layer that allowed the subsequent metal thin film to remain continuous. The fabricated semi-transparent perovskite solar cells demonstrated 16.5% efficiency under one-sun illumination, and were coupled with infrared-enhanced silicon heterojunction cellsmore » tuned specifically for perovskite/Si tandem devices. A double-layer antireflection coating at the front side and MgF2 reflector at rear side of the silicon heterojunction cells reduced parasitic absorption of near-infrared light, leading to 6.5% efficiency after filtering with a perovskite device and 23.0% summed efficiency for the perovskite/Si tandem device.« less

Short Tandem Repeat DNA Internet Database

National Institute of Standards and Technology Data Gateway

SRD 130 Short Tandem Repeat DNA Internet Database (Web, free access)   Short Tandem Repeat DNA Internet Database is intended to benefit research and application of short tandem repeat DNA markers for human identity testing. Facts and sequence information on each STR system, population data, commonly used multiplex STR systems, PCR primers and conditions, and a review of various technologies for analysis of STR alleles have been included.

A Study on Organic-Metal Halide Perovskite Film Morphology, Interfacial Layers, Tandem Applications, and Encapsulation

NASA Astrophysics Data System (ADS)

Fisher, Dallas A.

Organic-metal halide perovskites have brought about a new wave of research in the photovoltaic community due to their ideally suited optical and electronic parameters. In less than a decade, perovskite solar cell performance has skyrocketed to unprecedented efficiencies with numerous reported methodologies. Perovskites face many challenges with high-quality film morphology, interfacial layers, and long-term stability. In this work, these active areas are explored through a combination of studies. First, the importance of perovskite film precursor ratios is explored with an in-depth study of carrier lifetime and solvent-grain effects. It was found that excess lead iodide precursor greatly improves the film morphology by reducing pinholes in the solar absorber. Dimethyl sulfoxide (DMSO) solvent was found to mend grains, as well as improve carrier lifetime and device performance, possibly by passivation of grain boundary traps. Second, applications of perovskite with tandem cells is investigated, with an emphasis for silicon devices. Perovskites can easily be integrated with silicon, which already has strong market presence. Additionally, both materials' bandgaps are ideally suited for maximum tandem efficiency. The silicon/perovskite tandem device structure necessitated the optimization of inverted (p-i-n) structure devices. PEDOT:PSS, copper oxide, and nickel oxide p-type layers were explored through a combination of photoluminescent, chemical reactivity, and solar simulation results. Results were hindered due to resistive ITO and rough silicon substrates, but tandem devices displayed Voc indicative of proper monolithic performance. Third, replacement of titanium dioxide n-type layer with iron oxide (Fe 2O3, common rust) was studied. Iron oxide experiences less ultraviolet instability than that of titanium dioxide under solar illumination. It was found that current density slightly decreased due to parasitic absorption from the rust, but that open circuit voltage

Simple and fast analysis of tetrabromobisphenol A, hexabromocyclododecane isomers, and polybrominated diphenyl ethers in serum using solid-phase extraction or QuEChERS extraction followed by tandem mass spectrometry coupled to HPLC and GC.

PubMed

Li, Jian; Chen, Tian; Wang, Yuwei; Shi, Zhixiong; Zhou, Xianqing; Sun, Zhiwei; Wang, Dejun; Wu, Yongning

2017-02-01

Two simplified sample preparation procedures for simultaneous extraction and clean-up of tetrabromobisphenol A, α-, β-, and γ-hexabromocyclododecane and polybrominated diphenyl ethers in human serum were developed and validated. The first procedure was based on solid-phase extraction. Sample extraction, purification, and lipid removal were carried out directly on an Oasis HLB cartridge. The second procedure was a quick, easy, cheap, effective, rugged, and safe-based approach using octadecyl-modified silica particles as a sorbent. After sample extraction and cleanup, tetrabromobisphenol A/hexabromocyclododecane was separated from polybrominated diphenyl ethers by using a Si-based cartridge. Tetrabromobisphenol A and hexabromocyclododecane were then detected by high-performance liquid chromatography coupled to tandem mass spectrometry, while polybrominated diphenyl ethers were detected by gas chromatography coupled to tandem mass spectrometry. The results of the spike recovery test using fetal bovine serum showed that the average recoveries of the analytes ranged from 87.3 to 115.3% with relative standard deviations equal to or lower than 13.4 %. Limits of detection of the analytes were in the range of 0.4-19 pg/mL except for decabromodiphenyl ether. The developed method was successfully applied to routine analysis of human serum samples from occupational workers and the general population. Extremely high serum polybrominated diphenyl ethers levels up to 3.32 × 10 4 ng/g lipid weight were found in occupational workers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance tandem organic light-emitting diodes based on a buffer-modified p/n-type planar organic heterojunction as charge generation layer

NASA Astrophysics Data System (ADS)

Wu, Yukun; Sun, Ying; Qin, Houyun; Hu, Shoucheng; Wu, Qingyang; Zhao, Yi

2017-04-01

High-performance tandem organic light-emitting diodes (TOLEDs) were realized using a buffer-modified p/n-type planar organic heterojunction (OHJ) as charge generation layer (CGL) consisting of common organic materials, and the configuration of this p/n-type CGL was "LiF/N,N'-diphenyl-N,N'-bis(1-napthyl)-1,1'-biphenyl-4,4'-diamine (NPB)/4,7-diphenyl-1,10-phenanthroline (Bphen)/molybdenum oxide (MoOx)". The optimized TOLED exhibited a maximum current efficiency of 77.6 cd/A without any out-coupling techniques, and the efficiency roll-off was greatly improved compared to the single-unit OLED. The working mechanism of the p/n-type CGL was discussed in detail. It is found that the NPB/Bphen heterojunction generated enough charges under a forward applied voltage and the carrier extraction was a tunneling process. These results could provide a new method to fabricate high-performance TOLEDs.

Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

NASA Astrophysics Data System (ADS)

Gonzalez, Julia; Peña, Jasquelin

2016-04-01

Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

Insight into the epitaxial encapsulation of Pd catalysts in an oriented metalloporphyrin network thin film for tandem catalysis.

PubMed

Vohra, M Ismail; Li, De-Jing; Gu, Zhi-Gang; Zhang, Jian

2017-06-14

A palladium catalyst (Pd-Cs) encapsulated metalloporphyrin network PIZA-1 thin film with bifunctional properties has been developed through a modified epitaxial layer-by-layer encapsulation approach. Combining the oxidation activity of Pd-Cs and the acetalization activity of the Lewis acidic sites in the PIZA-1 thin film, this bifunctional catalyst of the Pd-Cs@PIZA-1 thin film exhibits a good catalytic activity in a one-pot tandem oxidation-acetalization reaction. Furthermore, the surface components can be controlled by ending the top layer with different precursors in the thin film preparation procedures. The catalytic performances of these thin films with different surface composites were studied under the same conditions, which showed different reaction conversions. The result revealed that the surface component can influence the catalytic performance of the thin films. This epitaxial encapsulation offers a good understanding of the tandem catalysis for thin film materials and provides useful guidance to develop new thin film materials with catalytic properties.

Matrix interference evaluation employing GC and LC coupled to triple quadrupole tandem mass spectrometry.

PubMed

Uclés, S; Lozano, A; Sosa, A; Parrilla Vázquez, P; Valverde, A; Fernández-Alba, A R

2017-11-01

Gas and liquid chromatography coupled to triple quadrupole tandem mass spectrometry are currently the most powerful tools employed for the routine analysis of pesticide residues in food control laboratories. However, whatever the multiresidue extraction method, there will be a residual matrix effect making it difficult to identify/quantify some specific compounds in certain cases. Two main effects stand out: (i) co-elution with isobaric matrix interferents, which can be a major drawback for unequivocal identification, and therefore false negative detections, and (ii) signal suppression/enhancement, commonly called the "matrix effect", which may cause serious problems including inaccurate quantitation, low analyte detectability and increased method uncertainty. The aim of this analytical study is to provide a framework for evaluating the maximum expected errors associated with the matrix effects. The worst-case study contrived to give an estimation of the extreme errors caused by matrix effects when extraction/determination protocols are applied in routine multiresidue analysis. Twenty-five different blank matrices extracted with the four most common extraction methods used in routine analysis (citrate QuEChERS with/without PSA clean-up, ethyl acetate and the Dutch mini-Luke "NL" methods) were evaluated by both GC-QqQ-MS/MS and LC-QqQ-MS/MS. The results showed that the presence of matrix compounds with isobaric transitions to target pesticides was higher in GC than under LC in the experimental conditions tested. In a second study, the number of "potential" false negatives was evaluated. For that, ten matrices with higher percentages of natural interfering components were checked. Additionally, the results showed that for more than 90% of the cases, pesticide quantification was not affected by matrix-matched standard calibration when an interferent was kept constant along the calibration curve. The error in quantification depended on the concentration level. In a

Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

PubMed

Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-05-09

Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-catalyzed Huisgen and oxidative Huisgen coupling reactions controlled by polysiloxane-supported amines (AFPs) for the divergent synthesis of triazoles and bistriazoles.

PubMed

Zheng, Zhan-Jiang; Ye, Fei; Zheng, Long-Sheng; Yang, Ke-Fang; Lai, Guo-Qiao; Xu, Li-Wen

2012-10-29

An interesting example of a divergent catalysis with a copper(I) and amine-functional macromolecular polysiloxanes system was successfully presented in click chemistry. In this manuscript, we demonstrate the remarkable ability of the secondary amine-functional polysiloxane to induce oxidative coupling in the copper-mediated Huisgen reactions of azides and alkynes, thereby achieving good yields and selectivities. The click reactions mediated by a polysiloxane-supported secondary amine allow the preparation of novel heterocyclic compounds, that is, bistriazoles. Comparably, it is also surprising that the use of a diamine-functional polysiloxane as ligand led to a classic Huisgen [3+2] cycloaddition in excellent yields. From the results of the present amine-functional polysiloxanes-controlled Huisgen reaction or oxidative Huisgen coupling reaction to divergent products and the proposed mechanism, we suggested that the mononuclear bistriazole-copper complex stabilized and dispersed by the secondary amine-functional polysiloxane was beneficial to prevalent the way to oxidative coupling. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vibro-Shock Dynamics Analysis of a Tandem Low Frequency Resonator-High Frequency Piezoelectric Energy Harvester.

PubMed

Žižys, Darius; Gaidys, Rimvydas; Ostaševičius, Vytautas; Narijauskaitė, Birutė

2017-04-27

Frequency up-conversion is a promising technique for energy harvesting in low frequency environments. In this approach, abundantly available environmental motion energy is absorbed by a Low Frequency Resonator (LFR) which transfers it to a high frequency Piezoelectric Vibration Energy Harvester (PVEH) via impact or magnetic coupling. As a result, a decaying alternating output signal is produced, that can later be collected using a battery or be transferred directly to the electric load. The paper reports an impact-coupled frequency up-converting tandem setup with different LFR to PVEH natural frequency ratios and varying contact point location along the length of the harvester. RMS power output of different frequency up-converting tandems with optimal resistive values was found from the transient analysis revealing a strong relation between power output and LFR-PVEH natural frequency ratio as well as impact point location. Simulations revealed that higher power output is obtained from a higher natural frequency ratio between LFR and PVEH, an increase of power output by one order of magnitude for a doubled natural frequency ratio and up to 150% difference in power output from different impact point locations. The theoretical results were experimentally verified.

Antioxidant ability of fractionated apple peel phenolics to inhibit fish oil oxidation.

PubMed

Sekhon-Loodu, Satvir; Warnakulasuriya, Sumudu N; Rupasinghe, H P Vasantha; Shahidi, Fereidoon

2013-09-01

Polyphenols isolated from frozen and dried apple peels were studied as potential natural antioxidants to stabilize omega-3 polyunsaturated fatty acid (ω3 PUFA) enriched fish oil. The ethanolic extracts of apple peels were fractionated by reversed phase chromatography using gradient elution of 20-100% aqueous ethanol. The collected fractions were analyzed by ultra pressure liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The total phenolic content and antioxidant capacity of each fraction were evaluated by Folin-Ciocalteu (FC), ferric reducing antioxidant power (FRAP) and 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) scavenging assays. Inhibition of fish oil oxidation was studied using the thiobarbituric acid reactive substances (TBARS) assay. Polyphenols fractionated using frozen apple peel extract had significantly higher FC, FRAP and DPPH(·) scavenging values than those of dried apple peel (p<0.05). The flavonol-rich fractions inhibited fish oil oxidation by 40-62% at a total phenolic concentration of 200 μg/ml. The fractionated polyphenols from both dried and frozen apple peel showed higher inhibition of lipid oxidation compared to α-tocopherol, butylated hydroxytoluene and crude apple peel extracts. Copyright © 2013 Elsevier Ltd. All rights reserved.

Classification of type 2 diabetes rats based on urine amino acids metabolic profiling by liquid chromatography coupled with tandem mass spectrometry.

PubMed

Wang, Chunyan; Zhu, Hongbin; Pi, Zifeng; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

2013-09-15

An analytical method for quantifying underivatized amino acids (AAs) in urine samples of rats was developed by using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Classification of type 2 diabetes rats was based on urine amino acids metabolic profiling. LC-MS/MS analysis was applied through chromatographic separation and multiple reactions monitoring (MRM) transitions of MS/MS. Multivariate profile-wide predictive models were constructed using partial least squares discriminant analysis (PLS-DA) by SIMAC-P 11.5 version software package and hierarchical cluster analysis (HCA) by SPSS 18.0 version software. Some amino acids in urine of rats have significant change. The results of the present study prove that this method could perform the quantification of free AAs in urine of rats by using LC-MS/MS. In summary, the PLS-DA and HCA statistical analysis in our research were preferable to differentiate healthy rats and type 2 diabetes rats by the quantification of AAs in their urine samples. In addition, comparing with health group the seven increased amino acids in urine of type 2 rats were returned to normal under the treatment of acarbose. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of Hund's coupling in 5 d oxides using resonant inelastic x-ray scattering

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

Yuan, Bo; Clancy, J. P.; Cook, A. M.

2017-06-01

We report resonant inelastic x-ray scattering (RIXS) measurements on ordered double-perovskite samples containing Re5+ and Ir5+ with 5d(2) and 5d(4) electronic configurations, respectively. In particular, the observedRIXS spectra of Ba2YReO6 and Sr2MIrO6 (M = Y, Gd) show sharp intra-t(2g) transitions, which can be quantitatively understood using a minimal "atomic" Hamiltonian incorporating spin-orbit coupling. and Hund's coupling J(H). Our analysis yields lambda = 0.38(2) eV with J(H) = 0.26(2) eV for Re5+ and lambda = 0.42(2) eV with J(H) = 0.25(4) eV for Ir5+. Our results provide sharp estimates for Hund's coupling in 5d oxides and suggest that it should bemore » treated on equal footing with spin-orbit interaction in multiorbital 5d transition-metal compounds.« less

Tandem Organic Light-Emitting Diodes.

PubMed

Fung, Man-Keung; Li, Yan-Qing; Liao, Liang-Sheng

2016-12-01

A tandem organic light-emitting diode (OLED) is an organic optoelectronic device that has two or more electroluminescence (EL) units connected electrically in series with unique intermediate connectors within the device. Researchers have studied this new OLED architecture with growing interest and have found that the current efficiency of a tandem OLED containing N EL units (N > 1) should be N times that of a conventional OLED containing only a single EL unit. Therefore, this new architecture is potentially useful for constructing high-efficiency, high-luminance, and long-lifetime OLED displays and organic solid-state lighting sources. In a tandem OLED, the intermediate connector plays a crucial role in determining the effectiveness of the stacked EL units. The interfaces in the connector control the inner charge generation and charge injection into the adjacent EL units. Meanwhile, the transparency and the thickness of the connector affect the light output of the device. Therefore, the intermediate connector should be made to meet both the electrical and optical requirements for achieving optimal performance. Here, recent advances in the research of the tandem OLEDs is discussed, with the main focus on material selection and interface studies in the intermediate connectors, as well as the optical design of the tandem OLEDs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tandem array of nanoelectronic readers embedded coplanar to a fluidic nanochannel for correlated single biopolymer analysis

PubMed Central

Lesser-Rojas, Leonardo; Sriram, K. K.; Liao, Kuo-Tang; Lai, Shui-Chin; Kuo, Pai-Chia; Chu, Ming-Lee; Chou, Chia-Fu

2014-01-01

We have developed a two-step electron-beam lithography process to fabricate a tandem array of three pairs of tip-like gold nanoelectronic detectors with electrode gap size as small as 9 nm, embedded in a coplanar fashion to 60 nm deep, 100 nm wide, and up to 150 μm long nanochannels coupled to a world-micro-nanofluidic interface for easy sample introduction. Experimental tests with a sealed device using DNA-protein complexes demonstrate the coplanarity of the nanoelectrodes to the nanochannel surface. Further, this device could improve transverse current detection by correlated time-of-flight measurements of translocating samples, and serve as an autocalibrated velocimeter and nanoscale tandem Coulter counters for single molecule analysis of heterogeneous samples. PMID:24753731

Iron-Coupled Anaerobic Oxidation of Methane Performed by a Mixed Bacterial-Archaeal Community Based on Poorly Reactive Minerals.

PubMed

Bar-Or, Itay; Elvert, Marcus; Eckert, Werner; Kushmaro, Ariel; Vigderovich, Hanni; Zhu, Qingzeng; Ben-Dov, Eitan; Sivan, Orit

2017-11-07

Anaerobic oxidation of methane (AOM) was shown to reduce methane emissions by over 50% in freshwater systems, its main natural contributor to the atmosphere. In these environments iron oxides can become main agents for AOM, but the underlying mechanism for this process has remained enigmatic. By conducting anoxic slurry incubations with lake sediments amended with 13 C-labeled methane and naturally abundant iron oxides the process was evidenced by significant 13 C-enrichment of the dissolved inorganic carbon pool and most pronounced when poorly reactive iron minerals such as magnetite and hematite were applied. Methane incorporation into biomass was apparent by strong uptake of 13 C into fatty acids indicative of methanotrophic bacteria, associated with increasing copy numbers of the functional methane monooxygenase pmoA gene. Archaea were not directly involved in full methane oxidation, but their crucial participation, likely being mediators in electron transfer, was indicated by specific inhibition of their activity that fully stopped iron-coupled AOM. By contrast, inhibition of sulfur cycling increased 13 C-methane turnover, pointing to sulfur species involvement in a competing process. Our findings suggest that the mechanism of iron-coupled AOM is accomplished by a complex microbe-mineral reaction network, being likely representative of many similar but hidden interactions sustaining life under highly reducing low energy conditions.

Interactions of soil-derived dissolved organic matter with phenol in peroxidase-catalyzed oxidative coupling reactions.

PubMed

Huang, Qingguo; Weber, Walter J

2004-01-01

The influence of dissolved soil organic matter (DSOM) derived from three geosorbents of different chemical composition and diagenetic history on the horseradish peroxidase (HRP) catalyzed oxidative coupling reactions of phenol was investigated. Phenol conversion and precipitate-product formation were measured, respectively, by HPLC and radiolabeled species analysis. Fourier transform infrared (FTIR) spectroscopy and capillary electrophoresis (CE) were used to characterize the products of enzymatic coupling, and the acute toxicities of the soluble products were determined by Microtox assay. Phenol conversion and precipitate formation were both significantly influenced by cross-coupling of phenol with dissolved organic matter, particularly in the cases of the more reactive and soluble DSOMs derived from two diagenetically "young" humic-type geosorbents. FTIR and CE characterizations indicate that enzymatic cross-coupling in these two cases leads to incorporation of phenol in DSOM macromolecules, yielding nontoxic soluble products. Conversely, cross-coupling appears to proceed in parallel with self-coupling in the presence of the relatively inert and more hydrophobic DSOM derived from a diagenetically "old" kerogen-type shale material. The products formed in this system have lower solubility and precipitate more readily, although their soluble forms tend to be more toxic than those formed by dominant cross-coupling reactions in the humic-type DSOM solutions. Several of the findings reported may be critically important with respect to feasibility evaluations and the engineering design of associated remediation schemes.

Simultaneous Quantification of Seven Bioactive Flavonoids in Citri Reticulatae Pericarpium by Ultra-Fast Liquid Chromatography Coupled with Tandem Mass Spectrometry.

PubMed

Zhao, Lian-Hua; Zhao, Hong-Zheng; Zhao, Xue; Kong, Wei-Jun; Hu, Yi-Chen; Yang, Shi-Hai; Yang, Mei-Hua

2016-05-01

Citri Reticulatae Pericarpium (CRP) is a commonly-used traditional Chinese medicine with flavonoids as the major bioactive components. Nevertheless, the contents of the flavonoids in CRP of different sources may significantly vary affecting their therapeutic effects. Thus, the setting up of a reliable and comprehensive quality assessment method for flavonoids in CRP is necessary. To set up a rapid and sensitive ultra-fast liquid chromatography coupled with tandem mass spectrometry (UFLC-MS/MS) method for simultaneous quantification of seven bioactive flavonoids in CRP. A UFLC-MS/MS method coupled to ultrasound-assisted extraction was developed for simultaneous separation and quantification of seven flavonoids including hesperidin, neohesperidin, naringin, narirutin, tangeretin, nobiletin and sinensetin in 16 batches of CRP samples from different sources in China. The established method showed good linearity for all analytes with correlation coefficient (R) over 0.9980, together with satisfactory accuracy, precision and reproducibility. Furthermore, the recoveries at the three spiked levels were higher than 89.71% with relative standard deviations (RSDs) lower than 5.19%. The results indicated that the contents of seven bioactive flavonoids in CRP varied significantly among different sources. Among the samples under study, hesperidin showed the highest contents in 16 samples ranged from 27.50 to 86.30 mg/g, the contents of hesperidin in CRP-15 and CRP-9 were 27.50 and 86.30 mg/g, respectively, while, the amount of narirutin was too low to be measured in some samples. This study revealed that the developed UFLC-MS/MS method was simple, sensitive and reliable for simultaneous quantification of multi-components in CRP with potential perspective for quality control of complex matrices. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Oxidation pattern of curdlan with TEMPO-mediated system.

PubMed

Tang, Rong; Hao, Jie; Zong, Ruijie; Wu, Fangxia; Zeng, Yangyang; Zhang, Zhenqing

2018-04-15

In this study, the TEMPO-mediated (TEMPO/NaBr/NaClO) oxidation pattern of curdlan was investigated through comprehensively structural analysis of the corresponding oxidized products. During the structural analysis, infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography tandem multiple angle laser scattering (GPC-MALS) and ultra-high performance liquid chromatography tandem quadrupole time of flight mass spectrometry (UHPLC-Q/TOF-MS) were applied. As a result, the homogenous β1-3 polyglucuronic acids (MW, 49.8, 29.8 and 7.0 kDa) were obtained with proper amount of oxidant (5.36 mmol NaClO) at various temperatures (4, 25, 50 °C), respectively. Compared to the oxidation of 1-4 linked glucan (starch and cellulose) with TEMPO-mediated system at same reaction conditions, higher degree of specific oxidation and less degradation were observed in that of 1-3 linked curdlan. The glycosylation at position 3 could stabilize the sugar ring, which inactivates the non-specific oxidation related hydroxyl groups on the sugar ring. Thus, the TEMPO-mediated system has higher selectivity to oxidize the primary hydroxyl groups of 1-3 linked curdlan and form polyglucuronic acid than those observed in the oxidation of starch and cellulose. In addition, same as those observed in previous work about starch, higher the temperature was used in the oxidation with TEMPO system, higher the activity of oxidant (NaClO solution) was, more non-specific oxidation occurred, and more the degradation were observed. Copyright © 2018 Elsevier Ltd. All rights reserved.

High voltage series connected tandem junction solar battery

DOEpatents

Hanak, Joseph J.

1982-01-01

A high voltage series connected tandem junction solar battery which comprises a plurality of strips of tandem junction solar cells of hydrogenated amorphous silicon having one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon, arranged in a tandem configuration, can have the same bandgap or differing bandgaps. The tandem junction strip solar cells are series connected to produce a solar battery of any desired voltage.

Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides.

PubMed

You, Qing; Wang, Fei; Wu, Chaoting; Shi, Tianchao; Min, Dewen; Chen, Huajun; Zhang, Wu

2015-06-28

Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.

Comparison of analytical performances of inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry for trace analysis of bismuth and bismuth oxide

NASA Astrophysics Data System (ADS)

Medvedev, Nickolay S.; Shaverina, Anastasiya V.; Tsygankova, Alphiya R.; Saprykin, Anatoly I.

2018-04-01

The paper presents а comparison of analytical performances of inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) for trace analysis of high purity bismuth and bismuth oxide. Matrix effects in the ICP-MS and ICP-AES methods were studied as a function of Bi concentration, ICP power and nebulizer flow rate. For ICP-MS the strong dependence of the matrix effects versus the atomic mass of analytes was observed. For ICP-AES the minimal matrix effects were achieved for spectral lines of analytes with low excitation potentials. The optimum degree of sample dilution providing minimum values of the limits of detection (LODs) was chosen. Both methods let us to reach LODs from n·10-7 to n·10-4 wt% for more than 50 trace elements. For most elements the LODs of ICP-MS were lower in comparison to ICP-AES. Validation of accuracy of the developed techniques was performed by "added-found" experiments and by comparison of the results of ICP-MS and ICP-AES analysis of high-purity bismuth oxide.

Occurrence, Biological Consequences, and Human Health Relevance of Oxidative Stress-Induced DNA Damage.

PubMed

Yu, Yang; Cui, Yuxiang; Niedernhofer, Laura J; Wang, Yinsheng

2016-12-19

A variety of endogenous and exogenous agents can induce DNA damage and lead to genomic instability. Reactive oxygen species (ROS), an important class of DNA damaging agents, are constantly generated in cells as a consequence of endogenous metabolism, infection/inflammation, and/or exposure to environmental toxicants. A wide array of DNA lesions can be induced by ROS directly, including single-nucleobase lesions, tandem lesions, and hypochlorous acid (HOCl)/hypobromous acid (HOBr)-derived DNA adducts. ROS can also lead to lipid peroxidation, whose byproducts can also react with DNA to produce exocyclic DNA lesions. A combination of bioanalytical chemistry, synthetic organic chemistry, and molecular biology approaches have provided significant insights into the occurrence, repair, and biological consequences of oxidatively induced DNA lesions. The involvement of these lesions in the etiology of human diseases and aging was also investigated in the past several decades, suggesting that the oxidatively induced DNA adducts, especially bulky DNA lesions, may serve as biomarkers for exploring the role of oxidative stress in human diseases. The continuing development and improvement of LC-MS/MS coupled with the stable isotope-dilution method for DNA adduct quantification will further promote research about the clinical implications and diagnostic applications of oxidatively induced DNA adducts.

Characterization of Disulfide-Linked Peptides Using Tandem Mass Spectrometry Coupled with Automated Data Analysis Software

NASA Astrophysics Data System (ADS)

Liang, Zhidan; McGuinness, Kenneth N.; Crespo, Alejandro; Zhong, Wendy

2018-05-01

Disulfide bond formation is critical for maintaining structure stability and function of many peptides and proteins. Mass spectrometry has become an important tool for the elucidation of molecular connectivity. However, the interpretation of the tandem mass spectral data of disulfide-linked peptides has been a major challenge due to the lack of appropriate tools. Developing proper data analysis software is essential to quickly characterize disulfide-linked peptides. A thorough and in-depth understanding of how disulfide-linked peptides fragment in mass spectrometer is a key in developing software to interpret the tandem mass spectra of these peptides. Two model peptides with inter- and intra-chain disulfide linkages were used to study fragmentation behavior in both collisional-activated dissociation (CAD) and electron-based dissociation (ExD) experiments. Fragments generated from CAD and ExD can be categorized into three major types, which result from different S-S and C-S bond cleavage patterns. DiSulFinder is a computer algorithm that was newly developed based on the fragmentation observed in these peptides. The software is vendor neutral and capable of quickly and accurately identifying a variety of fragments generated from disulfide-linked peptides. DiSulFinder identifies peptide backbone fragments with S-S and C-S bond cleavages and, more importantly, can also identify fragments with the S-S bond still intact to aid disulfide linkage determination. With the assistance of this software, more comprehensive disulfide connectivity characterization can be achieved. [Figure not available: see fulltext.

Characterization of Disulfide-Linked Peptides Using Tandem Mass Spectrometry Coupled with Automated Data Analysis Software

NASA Astrophysics Data System (ADS)

Liang, Zhidan; McGuinness, Kenneth N.; Crespo, Alejandro; Zhong, Wendy

2018-01-01

Disulfide bond formation is critical for maintaining structure stability and function of many peptides and proteins. Mass spectrometry has become an important tool for the elucidation of molecular connectivity. However, the interpretation of the tandem mass spectral data of disulfide-linked peptides has been a major challenge due to the lack of appropriate tools. Developing proper data analysis software is essential to quickly characterize disulfide-linked peptides. A thorough and in-depth understanding of how disulfide-linked peptides fragment in mass spectrometer is a key in developing software to interpret the tandem mass spectra of these peptides. Two model peptides with inter- and intra-chain disulfide linkages were used to study fragmentation behavior in both collisional-activated dissociation (CAD) and electron-based dissociation (ExD) experiments. Fragments generated from CAD and ExD can be categorized into three major types, which result from different S-S and C-S bond cleavage patterns. DiSulFinder is a computer algorithm that was newly developed based on the fragmentation observed in these peptides. The software is vendor neutral and capable of quickly and accurately identifying a variety of fragments generated from disulfide-linked peptides. DiSulFinder identifies peptide backbone fragments with S-S and C-S bond cleavages and, more importantly, can also identify fragments with the S-S bond still intact to aid disulfide linkage determination. With the assistance of this software, more comprehensive disulfide connectivity characterization can be achieved. [Figure not available: see fulltext.

Combined remediation of pyrene-contaminated soil with a coupled system of persulfate oxidation and phytoremediation with ryegrass.

PubMed

Chen, Xiao; Li, Hongbing; Liu, Xiaoyan; Zhang, Xinying; Liang, Xia; He, Chiquan; Cao, Liya

2016-10-01

The in situ chemical oxidation technology (ISCO) and phytoremediation for PAHs have been studied respectively, but few focus on the feasibility of combining persulfate with ryegrass. This literature revealed the effect of persulfate oxidation on the growth of ryegrass and the removal ratios of pyrene in the couple system of persulfate oxidation and phytoremediation. The results demonstrated that half of pyrene in test soil was oxidized by persulfate in 7 days and then the residual pyrene concentration was decreased to a lower level by ryegrass in the following 2 months in oxidation treatment and drip washing and plants (OWP) and oxidation treatment and drip washing and plants and fertilization (OWFP) treatment. Ryegrass could grow well after persulfate oxidation with the oxidized soil washed by water. Ryegrass in OWP and OWFP treatments had higher ratios of overground and underground biomass. However, the seeds of ryegrass cannot germinate when drip washing was omitted. Pyrene together with residual persulfate changed soil enzyme activities. Drip washing and the growth of ryegrass made soil enzyme activities tend to returned to normal levels. Persulfate oxidation and phytoremediation were compatible to make contributions to the dissipation of pyrene. Persulfate oxidation activated by heat had higher removal efficiency of PAHs and phytoremediation could further decrease the pyrene concentration in spiked soil.

Axisymmetric Tandem Mirrors: Stabilization and Confinement Studies

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

Post, R.F.; Fowler, T.K.; Bulmer, R.

2005-01-15

The 'Kinetic Stabilizer' has been proposed as a means of MHD stabilizing an axisymmetric tandem mirror system. The K-S concept is based on theoretical studies by Ryutov, confirmed experimentally in the Gas Dynamic Trap experiment in Novosibirsk. In the K-S beams of ions are directed into the end of an 'expander' region outside the outer mirror of a tandem mirror. These ions, slowed, stagnated, and reflected as they move up the magnetic gradient, produce a low-density stabilizing plasma.At the Lawrence Livermore National Laboratory we have been conducting theoretical and computational studies of the K-S Tandem Mirror. These studies have employedmore » a low-beta code written especially to analyze the beam injection/stabilization process,and a new code SYMTRAN (by Hua and Fowler)that solves the coupled radial and axial particle and energy transport in a K-S T-M. Also, a 'legacy' MHD stability code, FLORA, has been upgraded and employed to benchmark the injection/stabilization code and to extend its results to high beta values.The FLORA code studies so far have confirmed the effectiveness of the K-S in stabilizing high-beta (40%) plasmas with stabilizer plasmas the peak pressures of which are several orders of magnitude smaller than those of the confined plasma.Also the SYMTRAN code has shown D-T plasma ignition from alpha particle energy deposition in T-M regimes with strong end plugging.Our studies have confirmed the viability of the K-S T-M concept with respect to MHD stability and radial and axial confinement. We are continuing these studies in order to optimize the parameters and to examine means for the stabilization of possible residual instability modes, such as drift modes and 'trapped-particle' modes. These modes may in principle be controlled by tailoring the stabilizer plasma distribution and/or the radial potential distribution.In the paper the results to date of our studies are summarized and projected to scope out possible fusion-power versions of the

Axisymmetric Tandem Mirrors: Stabilization and Confinement Studies

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

Post, R F; Fowler, T K; Bulmer, R

2004-07-15

The 'Kinetic Stabilizer' has been proposed as a means of MHD stabilizing an axisymmetric tandem mirror system. The K-S concept is based on theoretical studies by Ryutov, confirmed experimentally in the Gas Dynamic Trap experiment in Novosibirsk. In the K-S beams of ions are directed into the end of an 'expander' region outside the outer mirror of a tandem mirror. These ions, slowed, stagnated, and reflected as they move up the magnetic gradient, produce a low-density stabilizing plasma. At the Lawrence Livermore National Laboratory we have been conducting theoretical and computational studies of the K-S Tandem Mirror. These studies havemore » employed a low-beta code written especially to analyze the beam injection/stabilization process, and a new code SYMTRAN (by Hua and Fowler) that solves the coupled radial and axial particle and energy transport in a K-S TM. Also, a 'legacy' MHD stability code, FLORA, has been upgraded and employed to benchmark the injection/stabilization code and to extend its results to high beta values. The FLORA code studies so far have confirmed the effectiveness of the K-S in stabilizing high-beta (40%) plasmas with stabilizer plasmas the peak pressures of which are several orders of magnitude smaller than those of the confined plasma. Also the SYMTRAN code has shown D-T plasma ignition from alpha particle energy deposition in T-M regimes with strong end plugging. Our studies have confirmed the viability of the K-S-T-M concept with respect to MHD stability and radial and axial confinement. We are continuing these studies in order to optimize the parameters and to examine means for the stabilization of possible residual instability modes, such as drift modes and 'trapped-particle' modes. These modes may in principle be controlled by tailoring the stabilizer plasma distribution and/or the radial potential distribution. In the paper the results to date of our studies are summarized and projected to scope out possible fusion-power versions

Neurovascular-neuroenergetic coupling axis in the brain: master regulation by nitric oxide and consequences in aging and neurodegeneration.

PubMed

Lourenço, Cátia F; Ledo, Ana; Barbosa, Rui M; Laranjinha, João

2017-07-01

The strict energetic demands of the brain require that nutrient supply and usage be fine-tuned in accordance with the specific temporal and spatial patterns of ever-changing levels of neuronal activity. This is achieved by adjusting local cerebral blood flow (CBF) as a function of activity level - neurovascular coupling - and by changing how energy substrates are metabolized and shuttled amongst astrocytes and neurons - neuroenergetic coupling. Both activity-dependent increase of CBF and O 2 and glucose utilization by active neural cells are inextricably linked, establishing a functional metabolic axis in the brain, the neurovascular-neuroenergetic coupling axis. This axis incorporates and links previously independent processes that need to be coordinated in the normal brain. We here review evidence supporting the role of neuronal-derived nitric oxide ( • NO) as the master regulator of this axis. Nitric oxide is produced in tight association with glutamatergic activation and, diffusing several cell diameters, may interact with different molecular targets within each cell type. Hemeproteins such as soluble guanylate cyclase, cytochrome c oxidase and hemoglobin, with which • NO reacts at relatively fast rates, are but a few of the key in determinants of the regulatory role of • NO in the neurovascular-neuroenergetic coupling axis. Accordingly, critical literature supporting this concept is discussed. Moreover, in view of the controversy regarding the regulation of catabolism of different neural cells, we further discuss key aspects of the pathways through which • NO specifically up-regulates glycolysis in astrocytes, supporting lactate shuttling to neurons for oxidative breakdown. From a biomedical viewpoint, derailment of neurovascular-neuroenergetic axis is precociously linked to aberrant brain aging, cognitive impairment and neurodegeneration. Thus, we summarize current knowledge of how both neurovascular and neuroenergetic coupling are compromised in

G protein-coupled estrogen receptor (GPER) deficiency induces cardiac remodeling through oxidative stress.

PubMed

Wang, Hao; Sun, Xuming; Lin, Marina S; Ferrario, Carlos M; Van Remmen, Holly; Groban, Leanne

2018-04-25

Oxidative stress has been implicated in the unfavorable changes in cardiac function and remodeling that occur after ovarian estrogen loss. Using ovariectomized rat models, we previously reported that the cardioprotective actions of estrogen are mediated by the G protein-coupled estrogen receptor (GPER). Here, in 9-month-old, female cardiomyocyte-specific GPER knockout (KO) mice vs sex- and age-matched wild-type (WT) mice, we found increased cardiac oxidative stress and oxidant damage, measured as a decreased ratio of reduced glutathione to oxidized glutathione, increased 4-hydroxynonenal and 8-hydroxy-2'-deoxyguanosine (8-oxo-DG) staining, and increased expression of oxidative stress-related genes. GPER KO mice also displayed increased heart weight, cardiac collagen deposition, and Doppler-derived filling pressure, and decreased percent fractional shortening and early mitral annular velocity compared with WT controls. Treatment of GPER KO mice for 8 weeks with phosphonium [10-(4,5-dimethoxy-2-methyl 3,6-dioxo-1,4-cyclohexadien-1-yl)decyl] triphenyl-,mesylate (MitoQ), a mitochondria-targeted antioxidant, significantly attenuated these measures of cardiac dysfunction, and MitoQ decreased 8-oxo-DG intensity compared with treatment with an inactive comparator compound, (1-decyl)triphenylphosphonium bromide (P <0.05). A real-time polymerase chain reaction array analysis of 84 oxidative stress and antioxidant defense genes revealed that MitoQ attenuates the increase in NADPH oxidase 4 and prostaglandin-endoperoxide synthase 2 and the decrease in uncoupling protein 3 and glutathione S-transferase kappa 1 seen in GPER KO mice. Our findings suggest that the cardioprotective effects of GPER include an antioxidant role and that targeted strategies to limit oxidative stress after early noncancerous surgical extirpation of ovaries or menopause may help limit alterations in cardiac structure and function related to estrogen loss. Copyright © 2018 Elsevier Inc. All rights

Assaying Oxidative Coupling Activity of CYP450 Enzymes.

PubMed

Agarwal, Vinayak

2018-01-01

Cytochrome P450 (CYP450) enzymes are ubiquitous catalysts in natural product biosynthetic schemes where they catalyze numerous different transformations using radical intermediates. In this protocol, we describe procedures to assay the activity of a marine bacterial CYP450 enzyme Bmp7 which catalyzes the oxidative radical coupling of polyhalogenated aromatic substrates. The broad substrate tolerance of Bmp7, together with rearrangements of the aryl radical intermediates leads to a large number of products to be generated by the enzymatic action of Bmp7. The complexity of the product pool generated by Bmp7 thus presents an analytical challenge for structural elucidation. To address this challenge, we describe mass spectrometry-based procedures to provide structural insights into aryl crosslinked products generated by Bmp7, which can complement subsequent spectroscopic experiments. Using the procedures described here, for the first time, we show that Bmp7 can efficiently accept polychlorinated aryl substrates, in addition to the physiological polybrominated substrates for the biosynthesis of polyhalogenated marine natural products. © 2018 Elsevier Inc. All rights reserved.

Strain-induced topological quantum phase transition in phosphorene oxide

NASA Astrophysics Data System (ADS)

Kang, Seoung-Hun; Park, Jejune; Woo, Sungjong; Kwon, Young-Kyun

Using ab initio density functional theory, we investigate the structural stability and electronic properties of phosphorene oxides (POx) with different oxygen compositions x. A variety of configurations are modeled and optimized geometrically to search for the equilibrium structure for each x value. Our electronic structure calculations on the equilibrium configuration obtained for each x reveal that the band gap tends to increase with the oxygen composition of x < 0.5, and then to decrease with x > 0.5. We further explore the strain effect on the electronic structure of the fully oxidized phosphorene, PO, with x = 1. At a particular strain without spin-orbit coupling (SOC) is observed a band gap closure near the Γ point in the k space. We further find the strain in tandem with SOC induces an interesting band inversion with a reopened very small band gap (5 meV), and thus gives rise to a topological quantum phase transition from a normal insulator to a topological insulator. Such a topological phase transition is confirmed by the wave function analysis and the band topology identified by the Z2 invariant calculation.

Coupling of bias-induced crystallographic shear planes with charged domain walls in ferroelectric oxide thin films

DOE PAGES

Han, Myung-Geun; Garlow, Joseph A.; Bugnet, Matthieu; ...

2016-09-02

Polar discontinuity at interfaces plays deterministic roles in charge transport, magnetism, and even superconductivity of functional oxides. To date, most polar discontinuity problems have been explored in hetero-interfaces between two dissimilar materials. Here, we show that charged domain walls (CDWs) in epitaxial thin films of ferroelectric PbZr 0.2Ti 0.8O 3 are strongly coupled to polar interfaces through the formation of ½<101>{h0l} type crystallographic shear planes (CSPs). Using atomic resolution imaging and spectroscopy we illustrate that the CSPs consist of both conservative and nonconservative segments when coupled to the CDWs, where necessary compensating charges for stabilizing the CDWs are associated withmore » vacancies at the CSPs. Lasly, the CDW/CSP coupling yields an atomically narrow domain walls, consisting of a single atomic layer of oxygen. This study shows that the CDW/CSP coupling is a fascinating venue to develop emergent material properties.« less

Ammonia oxidation coupled to CO2 fixation by archaea and bacteria in an agricultural soil.

PubMed

Pratscher, Jennifer; Dumont, Marc G; Conrad, Ralf

2011-03-08

Ammonia oxidation is an essential part of the global nitrogen cycling and was long thought to be driven only by bacteria. Recent findings expanded this pathway also to the archaea. However, most questions concerning the metabolism of ammonia-oxidizing archaea, such as ammonia oxidation and potential CO(2) fixation, remain open, especially for terrestrial environments. Here, we investigated the activity of ammonia-oxidizing archaea and bacteria in an agricultural soil by comparison of RNA- and DNA-stable isotope probing (SIP). RNA-SIP demonstrated a highly dynamic and diverse community involved in CO(2) fixation and carbon assimilation coupled to ammonia oxidation. DNA-SIP showed growth of the ammonia-oxidizing bacteria but not of archaea. Furthermore, the analysis of labeled RNA found transcripts of the archaeal acetyl-CoA/propionyl-CoA carboxylase (accA/pccB) to be expressed and labeled. These findings strongly suggest that ammonia-oxidizing archaeal groups in soil autotrophically fix CO(2) using the 3-hydroxypropionate-4-hydroxybutyrate cycle, one of the two pathways recently identified for CO(2) fixation in Crenarchaeota. Catalyzed reporter deposition (CARD)-FISH targeting the gene encoding subunit A of ammonia monooxygenase (amoA) mRNA and 16S rRNA of archaea also revealed ammonia-oxidizing archaea to be numerically relevant among the archaea in this soil. Our results demonstrate a diverse and dynamic contribution of ammonia-oxidizing archaea in soil to nitrification and CO(2) assimilation and that their importance to the overall archaeal community might be larger than previously thought.

Ammonia oxidation coupled to CO2 fixation by archaea and bacteria in an agricultural soil

PubMed Central

Pratscher, Jennifer; Dumont, Marc G.; Conrad, Ralf

2011-01-01

Ammonia oxidation is an essential part of the global nitrogen cycling and was long thought to be driven only by bacteria. Recent findings expanded this pathway also to the archaea. However, most questions concerning the metabolism of ammonia-oxidizing archaea, such as ammonia oxidation and potential CO2 fixation, remain open, especially for terrestrial environments. Here, we investigated the activity of ammonia-oxidizing archaea and bacteria in an agricultural soil by comparison of RNA- and DNA-stable isotope probing (SIP). RNA-SIP demonstrated a highly dynamic and diverse community involved in CO2 fixation and carbon assimilation coupled to ammonia oxidation. DNA-SIP showed growth of the ammonia-oxidizing bacteria but not of archaea. Furthermore, the analysis of labeled RNA found transcripts of the archaeal acetyl-CoA/propionyl-CoA carboxylase (accA/pccB) to be expressed and labeled. These findings strongly suggest that ammonia-oxidizing archaeal groups in soil autotrophically fix CO2 using the 3-hydroxypropionate–4-hydroxybutyrate cycle, one of the two pathways recently identified for CO2 fixation in Crenarchaeota. Catalyzed reporter deposition (CARD)-FISH targeting the gene encoding subunit A of ammonia monooxygenase (amoA) mRNA and 16S rRNA of archaea also revealed ammonia-oxidizing archaea to be numerically relevant among the archaea in this soil. Our results demonstrate a diverse and dynamic contribution of ammonia-oxidizing archaea in soil to nitrification and CO2 assimilation and that their importance to the overall archaeal community might be larger than previously thought. PMID:21368116

Ultra-Trace Analysis of Nine Macrolides, including Tulathromycin A (Draxxin), in Edible Animal Tissues with Mini-Column Liquid Chromatography Tandem Mass Spectrometry

USDA-ARS?s Scientific Manuscript database

Analysis of 9 macrolides is presented, including tulathromycin A (Draxxin), in beef, poultry and pork muscle with a simple multi-residue extraction and analysis method using high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. The extraction method inv...

Palladium-Catalyzed Oxidative Couplings and Applications to the Synthesis of Macrocycles and Strained Cyclic Dienes

NASA Astrophysics Data System (ADS)

Boon, Byron Adrian

The palladium(II)-catalyzed oxidative macrocyclization of bis(vinylboronate esters) is demonstrated as an efficient method for the synthesis of macrocyclic dienes. The macrocyclization reactions feature mild conditions due to a palladium(II) catalytic cycle which obviates the need for a high energy oxidative addition step of standard palladium(0) catalytic cycles. Instead, this oxidative coupling is promoted by chloroacetone as a terminal re-oxidant in the catalytic cycle. An extension of the oxidative coupling/macrocyclization strategy is highlighted where molecular oxygen may be used in place of chloroacetone as the terminal re-oxidant. Homocoupling reactions of vinylboronate esters served as a template to screen reaction conditions for this method. From these experiments, multiple reaction conditions gave the oxidative homocoupling product in high yield. These reaction conditions were successfully applied to the oxidative macrocyclization of a bis(vinylboronate ester) using molecular oxygen as a re-oxidant. Syntheses of strained cyclic dienes were accomplished via the palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generated strained (E,E)-1,3-dienes that underwent spontaneous 4?-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by strain in the medium-ring (E,E)-1,3-diene intermediates. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. These results are in contrast with typical acyclic trans-3,4-dialkyl cyclobutenes, which favor outward torquoselective ring-openings to give (E,E)-1,3-dienes. DFT calculations verified the thermodynamic versus kinetic control of the reactions and kinetic studies are in excellent agreement with the calculated energy changes. Investigations on the transannular Pauson-Khand reaction are also highlighted. The Pauson-Khand reaction is a powerful tool for the synthesis of cyclopentenones

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 3 2011-10-01 2011-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 47 Telecommunication 3 2010-10-01 2010-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 47 Telecommunication 3 2013-10-01 2013-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 47 Telecommunication 3 2012-10-01 2012-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

Li-doped MgO as catalysts for oxidative coupling of methane: A positron annihilation study

NASA Astrophysics Data System (ADS)

Dai, G. H.; Yan, Q. J.; Wang, Y.; Liu, Q. S.

1991-08-01

Magnesium oxides intentionally doped with lithium (with a maximum Li content of 40 tool%) for use as catalysts for oxidative coupling of methane were characterized by means of positron annihilation. The positron lifetime spectra, which could be reasonably well interpreted within the framework of the well-known trapping model, depend on the amount of Li doping of the MgO suggesting that positrons are trapped at dispersed small Li 2CO 3 precipitates. Very similar dependencies on lithium doping of the C 2 selectivity and the positron trapping rate ϰ imply an intimate relationship between the concentration of [Li] 0-centers (also referred to as [Li +O -] centers) and the selective activity of Li/MgO during catalytic reactions.

High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

PubMed

Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

2015-03-01

Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 μmol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 μmol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation.

Determination of ketamine and its main metabolites by liquid chromatography coupled to tandem mass spectrometry in pig plasma: Comparison of extraction methods.

PubMed

Ramiole, Cindy; D'Hayer, Benoit; Boudy, Vincent; Legagneux, Josette; Fonsart, Julien; Houzé, Pascal

2017-11-30

A rapid, sensitive and specific liquid chromatography coupled to tandem mass spectrometry method was developed for the simultaneous quantification pig plasma of ketamine and its two principal metabolites, norketamine and dehydronorketamine. Three extraction procoles were assessed including acetonitrile precipitation, Oase™ microplate extraction, and liquid-liquid extraction. Oase™ microplate extraction induced no significant matrix effect, important signal/noise ratio and good recoveries, ranging from 82 to 87% for the considered compounds. Using this extraction procedure, the assay was linear in the dynamic range 10-3000ng/mL (R 2 >0.99) regardless of the analytes. Intra- and inter-day accuracies were less than 12% for all compounds and intra- and inter-day precisions expressed as RSD were within <9.9%. Samples were stable in different storage conditions. High ketamine, norketamine and dehydronorketamine concentrations up to 15,000ng/mL can be determined with good precision using appropriate sample dilution. The assay was successfully applied to pig plasma samples to determine the pharmacokinetics of ketamine and the consecutive metabolites after buccal administration of a 4mg/kg ketamine base solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO3 microwires.

PubMed

Fountaine, Katherine T; Atwater, Harry A

2014-10-20

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.

Determination of type A trichothecenes in coix seed by magnetic solid-phase extraction based on magnetic multi-walled carbon nanotubes coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

PubMed

Dong, Maofeng; Si, Wenshuai; Wang, Weimin; Bai, Bing; Nie, Dongxia; Song, Weiguo; Zhao, Zhihui; Guo, Yirong; Han, Zheng

2016-09-01

Magnetic solid-phase extraction (m-SPE) is a promising sample preparation approach due to its convenience, speed, and simplicity. For the first time, a rapid and reliable m-SPE approach using magnetic multi-walled carbon nanotubes (m-MWCNTs) as the adsorbent was proposed for purification of type A trichothecenes including T-2 toxins (T2), HT-2 toxins (HT-2), diacetoxyscirpenol (DAS), and neosolaniol (NEO) in coix seed. The m-MWCNTs were synthesized by assembling the magnetic nanoparticles (Fe3O4) with MWCNTs by sonication through an aggregation wrap mechanism, and characterized by transmission electron microscope. Several key parameters affecting the performance of the procedure were extensively investigated including extraction solutions, desorption solvents, and m-MWCNT amounts. Under the optimal sample preparation conditions followed by analysis with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), high sensitivity (limit of quantification in the range of 0.3-1.5 μg kg(-1)), good linearity (R (2) > 0.99), satisfactory recovery (73.6-90.6 %), and acceptable precision (≤2.5 %) were obtained. The analytical performance of the developed method has also been successfully evaluated in real coix seed samples. Graphical Abstract Flow chart of determination of type A trichothecenes in coix seed by magnetic solid-phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

PubMed

Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

2016-09-21

The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous detection of low and high molecular weight carbonylated compounds derived from lipid peroxidation by electrospray ionization-tandem mass spectrometry.

PubMed

Milic, Ivana; Hoffmann, Ralf; Fedorova, Maria

2013-01-02

Reactive oxygen species (ROS) and other oxidative agents such as free radicals can oxidize polyunsaturated fatty acids (PUFA) as well as PUFA in lipids. The oxidation products can undergo consecutive reactions including oxidative cleavages to yield a chemically diverse group of products, such as lipid peroxidation products (LPP). Among them are aldehydes and ketones ("reactive carbonyls") that are strong electrophiles and thus can readily react with nucleophilic side chains of proteins, which can alter the protein structure, function, cellular distribution, and antigenicity. Here, we report a novel technique to specifically derivatize both low molecular and high molecular weight carbonylated LPP with 7-(diethylamino)coumarin-3-carbohydrazide (CHH) and analyze all compounds by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. CHH-derivatized compounds were identified by specific neutral losses or fragment ions. The fragment ion spectra displayed additional signals that allowed unambiguous identification of the lipid, fatty acids, cleavage sites, and oxidative modifications. Oxidation of docosahexaenoic (DHA, 22:6), arachidonic (AA, 20:4), linoleic (LA, 18:2), and oleic acids (OA, 18:1) yielded 69 aliphatic carbonyls, whose structures were all deduced from the tandem mass spectra. When four phosphatidylcholine (PC) vesicles containing the aforementioned unsaturated fatty acids were oxidized, we were able to deduce the structures of 122 carbonylated compounds from the tandem mass spectra of a single shotgun analysis acquired within 15 min. The high sensitivity (LOD ∼ 1 nmol/L for 4-hydroxy-2-nonenal, HNE) and a linear range of more than 3 orders of magnitude (10 nmol/L to 10 μmol/L for HNE) will allow further studies on complex biological samples including plasma.

Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

PubMed

Wigger, Tina; Seidel, Albrecht; Karst, Uwe

2017-06-01

Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H 2 , quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

Side-pumping combiner for high-power fiber laser based on tandem pumping

NASA Astrophysics Data System (ADS)

Gu, Yanran; Lei, Chengmin; Liu, Jun; Li, Ruixian; Liu, Le; Xiao, Hu; Chen, Zilun

2017-11-01

We investigate a (2+1)×1 side-pumping combiner numerically and experimentally for high-power fiber laser based on tandem pumping for the first time. The influence of taper ratio and launch mode on the 1018-nm pump coupling efficiency and the leakage power into the coating of the signal fiber (LPC) is analyzed numerically. A side-pumping combiner is developed successfully by tapered-fused splicing technique based on the numerical analysis, consisting of two pump fibers (220/242 μm, NA=0.22) and a signal fiber (40/400 μm, NA=0.06/0.46). The total 1018-nm pump efficiency of the combiner is 98.1%, and the signal light insertion loss is <3%. The results show that, compared with laser diodes pumping, the combiner appears to have a better LPC performance and power handling capability when using 1018-nm fiber as the pump light. Meanwhile, an all-fiber MOPA laser based on tandem pumping with 1080-nm output of 2533 W and the slope efficiency of 82.8% is achieved based on the home-made combiner.

Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

USGS Publications Warehouse

Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

2015-01-01

Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

Simultaneous determination of eugenol, isoeugenol and methyleugenol in fish fillet using gas chromatography coupled to tandem mass spectrometry.

PubMed

Ke, Changliang; Liu, Qi; Li, Liudong; Chen, Jiewen; Wang, Xunuo; Huang, Ke

2016-09-15

Gas chromatography (GC) coupled with triple quadrupole tandem mass spectrometry (MS/MS) operated in electron ionization mode (EI) has been shown to have advantages in the trace analysis of chemical compounds. Employing the instrument, a method has been built to simultaneously determine eugenol, isoeugenol' and methyleugenol, which have been widely used as fish anesthetic, in the fish fillet. Procedure for the sample preparation was achieved by using hexane extraction followed by phenyl solid phase extraction (SPE) cleanup, which was free of such steps as rotary evaporation and nitrogen blowing by taking the volatility of eugenol and its isomers into consideration. The method was validated by conducting recovery studies on fortified fish fillet samples at four concentrations. The linearity in the range of 5-500μg·L(-1) was forced through the origin giving a coefficient of determination (r(2)) greater than 0.9982. Limits of detection (LODs) for eugenol, isoeugenol' and methyleugenol were 0.4, 1.2' and 0.2μg·kg(-1), respectively. The limits of quantification (LOQs) were 1.2, 4' and 0.7μg·kg(-1) for eugenol, isoeugenol' and methyleugenol, respectively. The recoveries for eugenol and its isomers ranged from 76.4 to 99.9% with relative standard deviations (RSD) in a range from 2.18 to 15.5%. This method is quick, simple and suitable for determining the residues of eugenol, isoeugenol and methyleugenol simultaneously in batch samples of fish fillet. Copyright © 2016 Elsevier B.V. All rights reserved.

Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

PubMed

Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

2016-05-25

A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.

Direct and sensitive determination of glyphosate and aminomethylphosphonic acid in environmental water samples by high performance liquid chromatography coupled to electrospray tandem mass spectrometry.

PubMed

Guo, Hongyue; Riter, Leah S; Wujcik, Chad E; Armstrong, Daniel W

2016-04-22

A novel method based on high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) was developed for the sensitive determination of glyphosate and its major degradation product, AMPA in environmental water samples. The method involves the use of MS compatible mobile phases (0.1% formic acid in water and acetonitrile) for HPLC and direct analysis of water samples without sample derivatization. The method has been validated in different types of water matrices (drinking, surface and groundwater) by accuracy and precision studies with samples spiked at 0.1, 7.5 and 90 ppb. All mean accuracy values ranged from 85% to 112% for glyphosate and AMPA using both primary and secondary quantitative ion transitions (RSD ≤ 10%). Moreover, both primary and secondary ion transitions for glyphosate and AMPA can achieve the quantitation limits at 0.1 ppb. The linear dynamic range of the calibration curves were from 0.1 to 100 ppb for each analyte at each ion transitions with correlation coefficient higher than 0.997. Copyright © 2016 Elsevier B.V. All rights reserved.

Rapid quantification of underivatized amino acids in plasma by hydrophilic interaction liquid chromatography (HILIC) coupled with tandem mass-spectrometry.

PubMed

Prinsen, Hubertus C M T; Schiebergen-Bronkhorst, B G M; Roeleveld, M W; Jans, J J M; de Sain-van der Velden, M G M; Visser, G; van Hasselt, P M; Verhoeven-Duif, N M

2016-09-01

Amino acidopathies are a class of inborn errors of metabolism (IEM) that can be diagnosed by analysis of amino acids (AA) in plasma. Current strategies for AA analysis include cation exchange HPLC with post-column ninhydrin derivatization, GC-MS, and LC-MS/MS-related methods. Major drawbacks of the current methods are time-consuming procedures, derivative problems, problems with retention, and MS-sensitivity. The use of hydrophilic interaction liquid chromatography (HILIC) columns is an ideal separation mode for hydrophilic compounds like AA. Here we report a HILIC-method for analysis of 36 underivatized AA in plasma to detect defects in AA metabolism that overcomes the major drawbacks of other methods. A rapid, sensitive, and specific method was developed for the analysis of AA in plasma without derivatization using HILIC coupled with tandem mass-spectrometry (Xevo TQ, Waters). Excellent separation of 36 AA (24 quantitative/12 qualitative) in plasma was achieved on an Acquity BEH Amide column (2.1×100 mm, 1.7 μm) in a single MS run of 18 min. Plasma of patients with a known IEM in AA metabolism was analyzed and all patients were correctly identified. The reported method analyzes 36 AA in plasma within 18 min and provides baseline separation of isomeric AA such as leucine and isoleucine. No separation was obtained for isoleucine and allo-isoleucine. The method is applicable to study defects in AA metabolism in plasma.

Tandem Translation Classroom: A Case Study

ERIC Educational Resources Information Center

Kim, Dohun; Koh, Taejin

2018-01-01

The transition to student-centred learning, advances in teleconferencing tools, and active international student exchange programmes have stimulated tandem learning in many parts of the world. This pedagogical model is based on a mutual language exchange between tandem partners, where each student is a native speaker in the language the…

Self-assembly of a superparamagnetic raspberry-like silica/iron oxide nanocomposite using epoxy-amine coupling chemistry.

PubMed

Cano, Manuel; de la Cueva-Méndez, Guillermo

2015-02-28

The fabrication of colloidal nanocomposites would benefit from controlled hetero-assembly of ready-made particles through covalent bonding. Here we used epoxy-amine coupling chemistry to promote the self-assembly of superparamagnetic raspberry-like nanocomposites. This adaptable method induced the covalent attachment of iron oxide nanoparticles sparsely coated with amine groups onto epoxylated silica cores in the absence of other reactants.

Electrochemistry coupled online to liquid chromatography-mass spectrometry for fast simulation of biotransformation reactions of the insecticide chlorpyrifos.

PubMed

Mekonnen, Tessema F; Panne, Ulrich; Koch, Matthias

2017-05-01

An automated method is presented for fast simulation of (bio)transformation products (TPs) of the organophosphate insecticide chlorpyrifos (CPF) based on electrochemistry coupled online to liquid chromatography-mass spectrometry (EC-LC-MS). Oxidative TPs were produced by a boron doped diamond (BDD) electrode, separated by reversed phase HPLC and online detected by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, EC oxidative TPs were investigated by HPLC-tandem mass spectrometry (LC-MS/MS) and FT-ICR high resolution mass spectrometry (HRMS) and compared to in vitro assay metabolites (rat and human liver microsomes). Main phase I metabolites of CPF: chlorpyrifos oxon (CPF oxon), trichloropyridinol (TCP), diethylthiophosphate (DETP), diethylphosphate (DEP), desethyl chlorpyrifos (De-CPF), and desethyl chlorpyrifos oxon (De-CPF oxon), were successfully identified by the developed EC-LC-MS method. The EC-LC-MS method showed similar metabolites compared to the in vitro assay with possibilities of determining reactive species. Our results reveal that online EC-(LC)-MS brings an advantage on time of analysis by eliminating sample preparation steps and matrix complexity compared to conventional in vivo or in vitro methods.

Rapid separation and identification of phenolics in crude red grape skin extracts by high performance liquid chromatography coupled to diode array detection and tandem mass spectrometry.

PubMed

Ji, Mei; Li, Chen; Li, Qiang

2015-10-02

A rapid and efficient method was established for the simultaneous determination of structures and configurations for 45 phenolics isolated from crude red grape skin extracts without extensive sample preparation. Separation and compound assignments were achieved using high performance liquid chromatography coupled to diode array detection and tandem mass spectrometry (HPLC-DAD-MS(2)). A Poroshell 120 EC-C18 (100mm×3.0mm, 2.7μm) column was employed to separate the phenolics, which were eluted using a gradient of acetonitrile and water acidified with 0.2% formic acid. Phenolics were identified by comparison of their UV-vis spectra, mass spectra and MS(2) data with those in the literature. Using this procedure, five compounds were detected for the first time in Vitis amurensis. Good separation of most phenolics was achieved in 26min. The methods described here can be used for the characterization of phenolics in a variety of grapes and grape products. Copyright © 2015 Elsevier B.V. All rights reserved.

Monitoring and determination of sulfonamide antibiotics (sulfamethoxydiazine, sulfamethazine, sulfamethoxazole and sulfadiazine) in imported Pangasius catfish products in Thailand using liquid chromatography coupled with tandem mass spectrometry.

PubMed

Jansomboon, Worawat; Boontanon, Suwanna Kitpati; Boontanon, Narin; Polprasert, Chongrak; Thi Da, Chau

2016-12-01

This research aimed to monitor the concentrations of sulfamethoxydiazine (SMD), sulfamethazine (SMT), sulfamethoxazole (SMX) and sulfadiazine (SDZ) in imported Pangasius catfish products in Thailand. The residues of the four sulfonamides (SAs) were analyzed by extraction process and liquid chromatography coupled with tandem mass spectrometry. The highest concentrations found were 10.97ng/g for SMD, 6.23ng/g for SMT, 11.13ng/g for SDZ and 245.91ng/g for SMX, which was higher than the European Union (EU) standard (100ng/g). Moreover, all samples contaminated with SMX also contained SMT, indicating that more than one antibiotic was used for production in the country of origin. Because Thai standards for antibiotics in food have not been completely set, all contaminated discovered would not be considered to be an illegal food, in which antibiotic residues may affect human health in the long term. Therefore, antibiotic residues in Pangasius catfish products should be continually regulated and monitored. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamic characterization of tandem mismatches found in naturally occurring RNA

PubMed Central

Christiansen, Martha E.; Znosko, Brent M.

2009-01-01

Although all sequence symmetric tandem mismatches and some sequence asymmetric tandem mismatches have been thermodynamically characterized and a model has been proposed to predict the stability of previously unmeasured sequence asymmetric tandem mismatches [Christiansen,M.E. and Znosko,B.M. (2008) Biochemistry, 47, 4329–4336], experimental thermodynamic data for frequently occurring tandem mismatches is lacking. Since experimental data is preferred over a predictive model, the thermodynamic parameters for 25 frequently occurring tandem mismatches were determined. These new experimental values, on average, are 1.0 kcal/mol different from the values predicted for these mismatches using the previous model. The data for the sequence asymmetric tandem mismatches reported here were then combined with the data for 72 sequence asymmetric tandem mismatches that were published previously, and the parameters used to predict the thermodynamics of previously unmeasured sequence asymmetric tandem mismatches were updated. The average absolute difference between the measured values and the values predicted using these updated parameters is 0.5 kcal/mol. This updated model improves the prediction for tandem mismatches that were predicted rather poorly by the previous model. This new experimental data and updated predictive model allow for more accurate calculations of the free energy of RNA duplexes containing tandem mismatches, and, furthermore, should allow for improved prediction of secondary structure from sequence. PMID:19509311

A finite element analysis modeling tool for solid oxide fuel cell development: coupled electrochemistry, thermal and flow analysis in MARC®

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

Khaleel, Mohammad A.; Lin, Zijing; Singh, Prabhakar

2004-05-03

A 3D simulation tool for modeling solid oxide fuel cells is described. The tool combines the versatility and efficiency of a commercial finite element analysis code, MARC{reg_sign}, with an in-house developed robust and flexible electrochemical (EC) module. Based upon characteristic parameters obtained experimentally and assigned by the user, the EC module calculates the current density distribution, heat generation, and fuel and oxidant species concentration, taking the temperature profile provided by MARC{reg_sign} and operating conditions such as the fuel and oxidant flow rate and the total stack output voltage or current as the input. MARC{reg_sign} performs flow and thermal analyses basedmore » on the initial and boundary thermal and flow conditions and the heat generation calculated by the EC module. The main coupling between MARC{reg_sign} and EC is for MARC{reg_sign} to supply the temperature field to EC and for EC to give the heat generation profile to MARC{reg_sign}. The loosely coupled, iterative scheme is advantageous in terms of memory requirement, numerical stability and computational efficiency. The coupling is iterated to self-consistency for a steady-state solution. Sample results for steady states as well as the startup process for stacks with different flow designs are presented to illustrate the modeling capability and numerical performance characteristic of the simulation tool.« less

Tyrosine oxidation in heme oxygenase: examination of long-range proton-coupled electron transfer.

PubMed

Smirnov, Valeriy V; Roth, Justine P

2014-10-01

Heme oxygenase is responsible for the degradation of a histidine-ligated ferric protoporphyrin IX (Por) to biliverdin, CO, and the free ferrous ion. Described here are studies of tyrosyl radical formation reactions that occur after oxidizing Fe(III)(Por) to Fe(IV)=O(Por(·+)) in human heme oxygenase isoform-1 (hHO-1) and the structurally homologous protein from Corynebacterium diphtheriae (cdHO). Site-directed mutagenesis on hHO-1 probes the reduction of Fe(IV)=O(Por(·+)) by tyrosine residues within 11 Å of the prosthetic group. In hHO-1, Y58· is implicated as the most likely site of oxidation, based on the pH and pD dependent kinetics. The absence of solvent deuterium isotope effects in basic solutions of hHO-1 and cdHO contrasts with the behavior of these proteins in the acidic solution, suggesting that long-range proton-coupled electron transfer predominates over electron transfer.

Measurement of the surface charge accumulation using anodic aluminum oxide(AAO) structure in an inductively coupled plasma

NASA Astrophysics Data System (ADS)

Park, Ji-Hwan; Oh, Seung-Ju; Lee, Hyo-Chang; Kim, Yu-Sin; Kim, Young-Cheol; Kim, June Young; Ha, Chang-Seoung; Kwon, Soon-Ho; Lee, Jung-Joong; Chung, Chin-Wook

2014-10-01

As the critical dimension of the nano-device shrinks, an undesired etch profile occurs during plasma etch process. One of the reasons is the local electric field due to the surface charge accumulation. To demonstrate the surface charge accumulation, an anodic aluminum oxide (AAO) membrane which has high aspect ratio is used. The potential difference between top electrode and bottom electrode in an anodic aluminum oxide contact structure is measured during inductively coupled plasma exposure. The voltage difference is changed with external discharge conditions, such as gas pressure, input power, and gas species and the result is analyzed with the measured plasma parameters.

Solar water oxidation using nickel-borate coupled BiVO4 photoelectrodes.

PubMed

Choi, Sung Kyu; Choi, Wonyong; Park, Hyunwoong

2013-05-07

A naturally abundant nickel-borate (Ni-Bi) complex is demonstrated to successfully catalyze the photoelectrochemical (PEC) water oxidation of BiVO4 electrodes at 1.23 VRHE with nearly 100% faradaic efficiency for oxygen evolution. Ni-Bi is electrodeposited (ED) and photodeposited (PD) for varying times on BiVO4 electrodes in the 0.1 M borate electrolyte with 1 mM Ni(2+) at pH 9.2. Surprisingly, optimally deposited Ni-Bi films (ED-10 s and PD-30 min) display the same layer thickness of ca. 40 nm. Both Ni-Bi films enhance the photocurrent generation of BiVO4 at 1.23 VRHE by a factor of 3-4 under AM 1.5-light irradiation (100 mW cm(-2)) along with ca. 250% increase in the incident and absorbed photon-to-current efficiencies. Impedance analysis further reveals that the charge transfer resistance at BiVO4 is markedly decreased by Ni-Bi deposits. The primary role of Ni-Bi has been suggested to be a hole-conductor making photogenerated electrons more mobile and catalyzing a four-hole transfer to water through cyclic changes between the lower and higher Ni oxidation states. However, thick Ni-Bi films (>~40 nm) significantly reduce the PEC performance of BiVO4 due to the kinetic bottleneck and charge recombination. Under identical PEC conditions (0.1 M, pH 9.2), the borate electrolyte (good proton acceptor) is found to be better than nitrate (poor proton acceptor), indicative of a proton-coupled electron transfer pathway in PEC water oxidation.

Selecting tandem partners for silicon solar cells [Selecting tandem partners for silicon solar cells using spectral efficiency

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

Yu, Zhengshan; Leilaeioun, Mehdi; Holman, Zachary

Combining silicon and other materials in tandem solar cells is one approach to enhancing the overall power conversion efficiency of the cells. Here, we argue that top cell partners for silicon tandem solar cells should be selected on the basis of their spectral efficiency — their efficiency resolved by wavelength.

Selecting tandem partners for silicon solar cells [Selecting tandem partners for silicon solar cells using spectral efficiency

DOE PAGES

Yu, Zhengshan; Leilaeioun, Mehdi; Holman, Zachary

2016-09-26

Combining silicon and other materials in tandem solar cells is one approach to enhancing the overall power conversion efficiency of the cells. Here, we argue that top cell partners for silicon tandem solar cells should be selected on the basis of their spectral efficiency — their efficiency resolved by wavelength.

Identification of glyceollin metabolites derived from conjugation with glutathione and glucuronic acid in rats by on-line liquid chromatography-electrospray ionization tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

Glyceollin-related metabolites produced in rats following oral glyceollin administration were screened and identified by precursor and product ion scanning using liquid chromatography, coupled on-line with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), to identify all glyceollin me...

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE PAGES

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

2017-09-01

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

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

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

PubMed

Shaffer, David W; Xie, Yan; Concepcion, Javier J

2017-10-16

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

Electromagnetic resonance modes on a two-dimensional tandem grating and its application for broadband absorption in the visible spectrum.

PubMed

Han, Sunwoo; Lee, Bong Jae

2016-01-25

In this work, we numerically investigate the electromagnetic resonances on two-dimensional tandem grating structures. The base of a tandem grating consists of an opaque Au substrate, a SiO(2) spacer, and a Au grating (concave type); that is, a well-known fishnet structure forming Au/SiO(2)/Au stack. A convex-type Au grating (i.e., topmost grating) is then attached on top of the base fishnet structure with or without additional SiO(2) spacer, resulting in two types of tandem grating structures. In order to calculate the spectral reflectance and local magnetic field distribution, the finite-difference time-domain method is employed. When the topmost Au grating is directly added onto the base fishnet structure, the surface plasmon and magnetic polariton in the base structure are branched out due to the geometric asymmetry with respect to the SiO(2) spacer. If additional SiO(2) spacer is added between the topmost Au grating and the base fishnet structure, new magnetic resonance modes appear due to coupling between two vertically aligned Au/SiO(2)/Au stacks. With the understanding of multiple electromagnetic resonance modes on the proposed tandem grating structures, we successfully design a broadband absorber made of Au and SiO(2) in the visible spectrum.

Tandem junction amorphous silicon solar cells

DOEpatents

Hanak, Joseph J.

1981-01-01

An amorphous silicon solar cell has an active body with two or a series of layers of hydrogenated amorphous silicon arranged in a tandem stacked configuration with one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon arranged in tandem configuration can have the same bandgap or differing bandgaps.

Forensic analysis of printing inks using tandem Laser Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

NASA Astrophysics Data System (ADS)

Subedi, Kiran; Trejos, Tatiana; Almirall, José

2015-01-01

Elemental analysis, using either LA-ICP-MS or LIBS, can be used for the chemical characterization of materials of forensic interest to discriminate between source materials originating from different sources and also for the association of materials known to originate from the same source. In this study, a tandem LIBS/LA-ICP-MS system that combines the benefits of both LIBS and LA-ICP-MS was evaluated for the characterization of samples of printing inks (toners, inkjets, intaglio and offset.). The performance of both laser sampling methods is presented. A subset of 9 black laser toners, 10 colored (CMYK) inkjet samples, 12 colored (CMYK) offset samples and 12 intaglio inks originating from different manufacturing sources were analyzed to evaluate the discrimination capability of the tandem method. These samples were selected because they presented a very similar elemental profile by LA-ICP-MS. Although typical discrimination between different ink sources is found to be > 99% for a variety of inks when only LA-ICP-MS was used for the analysis, additional discrimination was achieved by combining the elemental results from the LIBS analysis to the LA-ICP-MS analysis in the tandem technique, enhancing the overall discrimination capability of the individual laser ablation methods. The LIBS measurements of the Ca, Fe, K and Si signals, in particular, improved the discrimination for this specific set of different ink samples previously shown to exhibit very similar LA-ICP-MS elemental profiles. The combination of these two techniques in a single setup resulted in better discrimination of the printing inks with two distinct fingerprint spectra, providing information from atomic/ionic emissions and isotopic composition (m/z) for each ink sample.

Microbiology and potential applications of aerobic methane oxidation coupled to denitrification (AME-D) process: A review.

PubMed

Zhu, Jing; Wang, Qian; Yuan, Mengdong; Tan, Giin-Yu Amy; Sun, Faqian; Wang, Cheng; Wu, Weixiang; Lee, Po-Heng

2016-03-01

Aerobic methane oxidation coupled to denitrification (AME-D) is an important link between the global methane and nitrogen cycles. This mini-review updates discoveries regarding aerobic methanotrophs and denitrifiers, as a prelude to spotlight the microbial mechanism and the potential applications of AME-D. Until recently, AME-D was thought to be accomplished by a microbial consortium where denitrifying bacteria utilize carbon intermediates, which are excreted by aerobic methanotrophs, as energy and carbon sources. Potential carbon intermediates include methanol, citrate and acetate. This mini-review presents microbial thermodynamic estimations and postulates that methanol is the ideal electron donor for denitrification, and may serve as a trophic link between methanotrophic bacteria and denitrifiers. More excitingly, new discoveries have revealed that AME-D is not only confined to the conventional synergism between methanotrophic bacteria and denitrifiers. Specifically, an obligate aerobic methanotrophic bacterium, Methylomonas denitrificans FJG1, has been demonstrated to couple partial denitrification with methane oxidation, under hypoxia conditions, releasing nitrous oxide as a terminal product. This finding not only substantially advances the understanding of AME-D mechanism, but also implies an important but unknown role of aerobic methanotrophs in global climate change through their influence on both the methane and nitrogen cycles in ecosystems. Hence, further investigation on AME-D microbiology and mechanism is essential to better understand global climate issues and to develop niche biotechnological solutions. This mini-review also presents traditional microbial techniques, such as pure cultivation and stable isotope probing, and powerful microbial techniques, such as (meta-) genomics and (meta-) transcriptomics, for deciphering linked methane oxidation and denitrification. Although AME-D has immense potential for nitrogen removal from wastewater, drinking

Templating Routes to Supported Oxide Catalysts by Design

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

Notestein, Justin M.

2016-09-08

The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas.more » First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MO x-SiO 2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO 2-Al 2O 3 acid catalysts and to control reactant selectivity in Al 2O 3-TiO 2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported oxide catalysts for energy applications.« less

High-Efficiency Polycrystalline Thin Film Tandem Solar Cells.

PubMed

Kranz, Lukas; Abate, Antonio; Feurer, Thomas; Fu, Fan; Avancini, Enrico; Löckinger, Johannes; Reinhard, Patrick; Zakeeruddin, Shaik M; Grätzel, Michael; Buecheler, Stephan; Tiwari, Ayodhya N

2015-07-16

A promising way to enhance the efficiency of CIGS solar cells is by combining them with perovskite solar cells in tandem devices. However, so far, such tandem devices had limited efficiency due to challenges in developing NIR-transparent perovskite top cells, which allow photons with energy below the perovskite band gap to be transmitted to the bottom cell. Here, a process for the fabrication of NIR-transparent perovskite solar cells is presented, which enables power conversion efficiencies up to 12.1% combined with an average sub-band gap transmission of 71% for photons with wavelength between 800 and 1000 nm. The combination of a NIR-transparent perovskite top cell with a CIGS bottom cell enabled a tandem device with 19.5% efficiency, which is the highest reported efficiency for a polycrystalline thin film tandem solar cell. Future developments of perovskite/CIGS tandem devices are discussed and prospects for devices with efficiency toward and above 27% are given.

Solid-state synthesis of YAG powders through microwave coupling of oxide/carbon particulate mixtures

DOE PAGES

Wildfire, Christina; Sabolsky, Edward M.; Spencer, Michael J.; ...

2017-06-14

The rapid synthesis of yttrium aluminum garnet (Y 3Al 15O 12, YAG) powder was investigated through the use of microwave irradiation of the oxide precursor system. For this investigation, an external hybrid heating source was not used. Instead, the rapid heating of the precursor materials (yttria and alumina powders, which are typically transparent to 2.45 GHz microwaves) was initiated by mixing an intrinsic absorbing material (carbon) into the original oxide precursors. The effect of the carbon characteristics, such as carbon source, concentration, particle size, and agglomerate microstructure were evaluated on the efficiency of coupling and resultant oxide reaction. The microwavemore » power was varied to optimize the YAG conversion and eliminate intermediate phase formation. Interactions between the conductive carbon particles and the dielectric oxides within the microwave exposure produced local arching and micro-plasma formation within the powder bed, resulting in the rapid formation of the refractory YAG composition. This optimal conduction led to temperatures of 1000°C that could be achieved in less than 5 min resulting in the formation of > 90 vol% YAG. The understanding of a conductor/dielectric particulate system here, provided insight into possible application of similar systems where microwave irradiation could be used for enhanced solid-state formation, local melting events, and gas phase reactions with a composite powder media.« less

Oxidized zirconium on ceramic; Catastrophic coupling.

PubMed

Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

2017-02-01

Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Microscopic theory of Dzyaloshinsky-Moriya interaction in pyrochlore oxides with spin-orbit coupling

NASA Astrophysics Data System (ADS)

Arakawa, Naoya

2016-10-01

Pyrochlore oxides show several fascinating phenomena, such as the formation of heavy fermions and the thermal Hall effect. Although a key to understanding some phenomena may be the Dzyaloshinsky-Moriya (DM) interaction, its microscopic origin is unclear. To clarify the microscopic origin, we constructed a t2 g-orbital model with the kinetic energy, the trigonal-distortion potential, the multiorbital Hubbard interactions, and the L S coupling, and derived the low-energy effective Hamiltonian for a d1 Mott insulator with the weak L S coupling. We first show that lack of the inversion center of each nearest-neighbor V-V bond causes the odd-mirror interorbital hopping integrals. Those are qualitatively different from the even-mirror hopping integrals, existing even with the inversion center. We next show that the second-order perturbation using the kinetic terms leads to the ferromagnetic and the antiferromagnetic superexchange interactions, whose competition is controllable by tuning the Hubbard interactions. Then, we show the most important result: the third-order perturbation terms using the combination of the even-mirror hopping integral, the odd-mirror hopping integral, and the L S coupling causes the DM interaction due to the mirror-mixing effect, where those hopping integrals are necessary to obtain the antisymmetric kinetic exchange and the L S coupling is necessary to excite the orbital angular momentum at one of two sites. We also show that the magnitude and sign of the DM interaction can be controlled by changing the positions of the O ions and the strength of the Hubbard interactions. We discuss the advantages in comparison with the phenomenological theory and Moriya's microscopic theory, applicability of our mechanism, and the similarities and differences between our case and the strong-L S -coupling case.

The ASTRO-1 preliminary design review coupled load analysis

NASA Technical Reports Server (NTRS)

Mcghee, D. S.

1984-01-01

Results of the ASTRO-1 preliminary design review coupled loads analysis are presented. The M6.0Y Generic Shuttle mathematical models were used. Internal accelerations, interface forces, relative displacements, and net e.g., accelerations were recovered for two ASTRO-1 payloads in a tandem configuration. Twenty-seven load cases were computed and summarized. Load exceedences were found and recommendations made.

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

DOE PAGES

Gent, William E.; Lim, Kipil; Liang, Yufeng; ...

2017-12-01

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

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

Gent, William E.; Lim, Kipil; Liang, Yufeng

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Determination of 21 antibiotics in sea cucumber using accelerated solvent extraction with in-cell clean-up coupled to ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhu, Minghua; Zhao, Hongxia; Xia, Deming; Du, Juan; Xie, Huaijun; Chen, Jingwen

2018-08-30

An accelerated solvent extraction (ASE) with in-cell clean-up method coupled to ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed to determine 21 antibiotics in sea cucumber. The analytes include 10 sulfonamides, 4 fluoroquinolones, 3 amphenicols, 2 beta-lactams, 1 lincosamide and trimethoprim. Optimal parameters of ASE method were obtained at 80 °C, 1 static cycle of 5 min with methanol/acetonitrile (1/1, v/v) using 2 g of C18 as adsorbent. Recoveries at 50.1-129.2% were achieved with RSD under 20%. Method detection limits ranged from 0.03 to 2.9 μg kg -1 . Compared to the reported ultrasound-assisted extraction method, the proposed method offered comparable extraction efficiency for sulfonamides from sea cucumber, but higher for other categories of antibiotics. This validated method was then successfully applied to sea cucumber samples and 9 antibiotics were detected with the highest concentration up to 57.7 μg kg -1 for norfloxacin. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

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

Werner, R.W.

1982-11-01

This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

Copper-Catalyzed Tandem Reactions for Synthesis of Pyrazolo[5,1-a]isoquinolines with Heterocyclic Ketene Aminals as Ligands.

PubMed

Wen, Li-Rong; Jin, Xian-Jun; Niu, Xiao-Dong; Li, Ming

2015-01-02

A CuI-catalyzed tandem reaction of 5-(2-bromoaryl)-N-aryl-1H-pyrazol-3-amines with active acetonitrile derivatives to prepare pyrazolo[5,1-a]isoquinolines in good to excellent yields has been successfully developed under mild conditions with heterocyclic ketene aminals (HKAs) as new ligands. This is the first time HKAs have been used as ligands for copper-catalyzed coupling reactions.

Form-Focused Interaction in Online Tandem Learning

ERIC Educational Resources Information Center

O'Rourke, Breffni

2005-01-01

Tandem language learning--a configuration involving pairs of learners with complementary target/native languages--is an underexploited but potentially very powerful use of computer-mediated communication (CMC) in second-language pedagogy. Tandem offers the benefits of authentic, culturally grounded interaction, while also promoting a pedagogical…

Assessment of the stoichiometry and efficiency of CO2 fixation coupled to reduced sulfur oxidation

PubMed Central

Klatt, Judith M.; Polerecky, Lubos

2015-01-01

Chemolithoautotrophic sulfur oxidizing bacteria (SOB) couple the oxidation of reduced sulfur compounds to the production of biomass. Their role in the cycling of carbon, sulfur, oxygen, and nitrogen is, however, difficult to quantify due to the complexity of sulfur oxidation pathways. We describe a generic theoretical framework for linking the stoichiometry and energy conservation efficiency of autotrophic sulfur oxidation while accounting for the partitioning of the reduced sulfur pool between the energy generating and energy conserving steps as well as between the main possible products (sulfate vs. zero-valent sulfur). Using this framework, we show that the energy conservation efficiency varies widely among SOB with no apparent relationship to their phylogeny. Aerobic SOB equipped with reverse dissimilatory sulfite reductase tend to have higher efficiency than those relying on the complete Sox pathway, whereas for anaerobic SOB the presence of membrane-bound, as opposed to periplasmic, nitrate reductase systems appears to be linked to higher efficiency. We employ the framework to also show how limited rate measurements can be used to estimate the primary productivity of SOB without the knowledge of the sulfate-to-zero-valent-sulfur production ratio. Finally, we discuss how the framework can help researchers gain new insights into the activity of SOB and their niches. PMID:26052315

[Determination of deoxynivalenol in grain and its products by solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry].

PubMed

Huang, Juan; Chen, Guosong; Zhang, Xiaoyan; Shen, Chongyu; Lü, Chen; Wu, Bin; Liu, Yan; Chen, Huilan; Ding, Tao

2012-11-01

A method was established for the determination of deoxynivalenol (vomitoxin) in grain and its products based on solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The sample was firstly extracted by acetonitrile-water (84:16, v/v). The extract was then cleaned-up by an HLB solid phase extraction cartridge. The separation was carried out on a Phenomenex Kinetex C18 column (100 mm x4. 6 mm, 2.6 microm) with a gradient elution using 0.3% per hundred ammonia solution-acetonitrile as mobile phases. The analysis of deoxynivalenol was performed under electrospray negative ionization mode. The limit of detection (LOD, S/N= 3) and the limit of quantification (LOQ, S/N = 10) were 20 microg/kg and 50 microg/kg, respectively. A good linearity (r > 0.99) was achieved for the target compound over the range of 20-1000 pg/L. The recoveries at the three spiked levels (50, 100, 500 microg/kg) in the blank matrices such as flour, barley, soybean, rice, cornmeal, cassava and wheat, were varied from 75.6% to 111.0% with the relative standard deviations no more than 13. 0%. The method is accurate, efficient, sensitive and practical. The cost of pretreatment is obviously reduced by replacing immunoaffinity columns and Mycosep columns with HLB columns which have the same purification effect.

Electronic Tandem Language Learning (eTandem): A Third Approach to Second Language Learning for the 21st Century

ERIC Educational Resources Information Center

Cziko, Gary A.

2004-01-01

Tandem language learning occurs when two learners of different native languages work together to help each other learn the other language. First used in face-to-face contexts, Tandem is now increasingly being used by language-learning partners located in different countries who are linked via various forms of electronic communication, a context…

Determination of caffeine, myosmine, and nicotine in chocolate by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry.

PubMed

Müller, Christoph; Vetter, Florian; Richter, Elmar; Bracher, Franz

2014-02-01

The occurrence of the bioactive components caffeine (xanthine alkaloid), myosmine and nicotine (pyridine alkaloids) in different edibles and plants is well known, but the content of myosmine and nicotine is still ambiguous in milk/dark chocolate. Therefore, a sensitive method for determination of these components was established, a simple separation of the dissolved analytes from the matrix, followed by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry (HS-SPME-GC-MS/MS). This is the first approach for simultaneous determination of caffeine, myosmine, and nicotine with a convenient SPME technique. Calibration curves were linear for the xanthine alkaloid (250 to 3000 mg/kg) and the pyridine alkaloids (0.000125 to 0.003000 mg/kg). Residuals of the calibration curves were lower than 15%, hence the limits of detection were set as the lowest points of the calibration curves. The limits of detection calculated from linearity data were for caffeine 216 mg/kg, for myosmine 0.000110 mg/kg, and for nicotine 0.000120 mg/kg. Thirty samples of 5 chocolate brands with varying cocoa contents (30% to 99%) were analyzed in triplicate. Caffeine and nicotine were detected in all samples of chocolate, whereas myosmine was not present in any sample. The caffeine content ranged from 420 to 2780 mg/kg (relative standard deviation 0.1 to 11.5%) and nicotine from 0.000230 to 0.001590 mg/kg (RSD 2.0 to 22.1%). © 2014 Institute of Food Technologists®

The structure of a one-electron oxidized Mn(iii)-bis(phenolate)dipyrrin radical complex and oxidation catalysis control via ligand-centered redox activity.

PubMed

Lecarme, Laureline; Chiang, Linus; Moutet, Jules; Leconte, Nicolas; Philouze, Christian; Jarjayes, Olivier; Storr, Tim; Thomas, Fabrice

2016-10-18

The tetradentate ligand dppH3, which features a half-porphyrin and two electron-rich phenol moieties, was prepared and chelated to manganese. The mononuclear Mn(iii)-dipyrrophenolate complex 1 was structurally characterized. The metal ion lies in a square pyramidal environment, the apical position being occupied by a methanol molecule. Complex 1 displays two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc + /Fc, which are assigned to ligand-centered processes. The one-electron oxidized species 1+ SbF6- was crystallized, showing an octahedral Mn(iii) center with two water molecules coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that the radical is delocalized over the whole aromatic framework. Complex 1+ SbF6- exhibits an S tot = 3/2 spin state due to the antiferromagnetic coupling between Mn(iii) and the ligand radical. The zero field splitting parameters are D = 1.6 cm -1 , E/D = 0.18(1), g ⊥ = 1.99 and g ∥ = 1.98. The dication 12+ is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a Mn(iii) metal center. Both 1 and 1+ SbF6- catalyze styrene oxidation in the presence of PhIO, but the nature of the main reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed predominantly when using 1+ SbF6-. We examined the ability of complex 1+ SbF6- to catalyze the isomerization of styrene oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case of 1+ SbF6-. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a catalyst based on a redox-active ligand.

Development of High Efficiency Four-Terminal Perovskite-Silicon Tandems

NASA Astrophysics Data System (ADS)

Duong, The Duc

This thesis is concerned with the development of high efficiency four-terminal perovskite-silicon tandem solar cells with the potential to reduce the cost of solar energy. The work focuses on perovskite top cells and can be divided into three main parts: developing low parasitic absorption and efficient semi-transparent perovskite cells, doping perovskite materials with rubidium, and optimizing perovskite material's bandgap with quadruple-cation and mixed-halide. A further section investigates the light stability of optimized bandgap perovskite cells. In a four-terminal mechanically stacked tandem, the perovskite top cell requires two transparent contacts at both the front and rear sides. Through detailed optical and electrical power loss analysis of the tandem efficiency due to non-ideal properties of the two transparent contacts, optimal contact parameters in term of sheet resistance and transparency are identified. Indium doped tin oxide by sputtering is used for both two transparent contacts and their deposition parameters are optimized separately. The semi-transparent perovskite cell using MAPbI3 has an efficiency of more than 12% with less than 12% parasitic absorption and up to 80% transparency in the long wavelength region. Using a textured foil as anti-reflection coating, an outstanding average transparency of 84% in the long wavelength is obtained. The low parasitic absorption allows an opaque version of the semi-transparent perovskite cell to operate efficiently in a filterless spectrum splitting perovskite-silicon tandem configuration. To further enhance the performance of perovskite cells, it is essential to improve the quality of perovskite films. This can be achieved with mixed-perovskite FAPbI3/MAPbBr3. However, mixed-perovskite films normally contain small a small amount of a non-perovskite phase, which is detrimental for the cell performance. Rb-doping is found to eliminate the formation of the non-perovskite phase and enhance the crystallinity of

III-V/Si Tandem Cells Utilizing Interdigitated Back Contact Si Cells and Varying Terminal Configurations: Preprint

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

Schnabel, Manuel; Klein, Talysa R.; Jain, Nikhil

Solar cells made from bulk crystalline silicon (c-Si) dominate the market, but laboratory efficiencies have stagnated because the current record efficiency of 26.3% is already very close to the theoretical limit of 29.4% for a single-junction c-Si cell. In order to substantially boost the efficiency of Si solar cells we have been developing stacked III-V/Si tandem cells, recently attaining efficiencies above 32% in four-terminal configuration. In this contribution, we use state-of-the-art III-V cells coupled with equivalent circuit simulations to compare four-terminal (4T) to three- and two-terminal (3T, 2T) operation. Equivalent circuit simulations are used to show that tandem cells canmore » be operated just as efficiently using three terminals as with four terminals. However, care must be taken not to overestimate 3T efficiency, as the two circuits used to extract current interact, and a method is described to accurately determine this efficiency. Experimentally, a 4T GaInP/Si tandem cell utilizing an interdigitated back contact cell is shown, exhibiting a 4T efficiency of 31.5% and a 2T efficiency of 28.1%. In 3T configuration, it is used to verify the finding from simulation that 3T efficiency is overestimated when interactions between the two circuits are neglected. Considering these, a 3T efficiency approaching the 4T efficiency is found, showing that 3T operation is efficient, and an outlook on fully integrated high-efficiency 3T and 2T tandem cells is given.« less

47 CFR 69.111 - Tandem-switched transport and tandem charge.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., geographically averaged on a study-area-wide basis, that the incumbent local exchange carrier experiences based... exchange carrier experiences based on the prior year's annual use. Tandem-switched transport transmission..., geographically averaged on a study-area-wide basis, that the incumbent local exchange carrier experiences based...

Spin-Orbit Coupling Controlled J = 3 / 2 Electronic Ground State in 5 d 3 Oxides

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

Taylor, A. E.; Calder, S.; Morrow, R.

Entanglement of spin and orbital degrees of freedom drives the formation of novel quantum and topological physical states. Here we report resonant inelastic x-ray scattering measurements of the transition metal oxides Ca3LiOsO6 and Ba2YOsO6, which reveals a dramatic spitting of the t2g manifold. We invoke an intermediate coupling approach that incorporates both spin-orbit coupling and electron-electron interactions on an even footing and reveal that the ground state of 5d3-based compounds, which has remained elusive in previously applied models, is a novel spin-orbit entangled J=3/2 electronic ground state. This work reveals the hidden diversity of spin-orbit controlled ground states in 5dmore » systems and introduces a new arena in the search for spin-orbit controlled phases of matter.« less

Indium/TFA-catalyzed synthesis of tetracyclic [6,5,5,6] indole ring, via a tandem cycloannulation of β-oxodithioester with tryptamine.

PubMed

Singh, Thokchom Prasanta; Bhattarcharya, Suman; Singh, Okram Mukherjee

2013-04-19

The cycloannulation of β-oxodithioesters and tryptamine in dichloromethane in the presence of a catalytic amount of InCl3 and TFA gave the novel 5-aryl/heteroaryl 2a(1),9b-dihydro-1H-2a,5a-diaza-cyclopenta[jk]fluorene-3(2H)-thiones in moderate to good yields. The reaction was proposed to involve a tandem transformation of thioamide, protonation, and dehydrative cyclization. KMnO4-oxidation of these newly prepared compounds yielded oxidative desulfurization products in good yields.

In situ high temperature oxidation analysis of Zircaloy-4 using acoustic emission coupled with thermogravimetry

NASA Astrophysics Data System (ADS)

Omar, Al Haj; Véronique, Peres; Eric, Serris; François, Grosjean; Jean, Kittel; François, Ropital; Michel, Cournil

2015-06-01

Zircaloy-4 oxidation behavior at high temperature (900 °C), which can be reached in case of severe accidental situations in nuclear pressurised water reactor, was studied using acoustic emission analysis coupled with thermogravimetry. Two different atmospheres were used to study the oxidation of Zircaloy-4: (a) helium and pure oxygen, (b) helium and oxygen combined with slight addition of air. The experiments with 20% of oxygen confirm the dependence on oxygen anions diffusion in the oxide scale. Under a mixture of oxygen and air in helium, an acceleration of the corrosion was observed due to the detrimental effect of nitrogen. The kinetic rate increased significantly after a kinetic transition (breakaway). This acceleration was accompanied by an acoustic emission activity. Most of the acoustic emission bursts were recorded after the kinetic transition (post-transition) or during the cooling of the sample. The characteristic features of the acoustic emission signals appear to be correlated with the different populations of cracks and their occurrence in the ZrO2 layer or in the α-Zr(O) layer. Acoustic events were recorded during the isothermal dwell time at high temperature under air. They were associated with large cracks in the zirconia porous layer. Acoustic events were also recorded during cooling after oxidation tests both under air or oxygen. For the latter, cracks were observed in the oxygen enriched zirconium metal phase and not in the dense zirconia layer after 5 h of oxidation.

FORUM: Bioinspired Heme, Heme/non-heme Diiron, Heme/copper and Inorganic NOx Chemistry: ·NO(g) Oxidation, Peroxynitrite-Metal Chemistry and ·NO(g) Reductive Coupling

PubMed Central

Schopfer, Mark P.; Wang, Jun; Karlin, Kenneth D.

2010-01-01

The focus of this Forum review highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide (nitrogen monoxide, ·NO(g)) and its biological roles and reactions. The latter focus is on (i) oxidation of ·NO(g) to nitrate by nitric oxide dioxygenases (NOD’s), and (ii) reductive coupling of two molecules of ·NO(g) to give N2O(g). In the former case, NOD’s are described and the highlighting of possible peroxynitrite-heme intermediates and consequences of this are given by discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with ·NO(g) and O2(g) leading to peroxynitrite species are given. The coverage of biological reductive coupling of ·NO(g) deals with bacterial nitric oxide reductases (NOR’s) with heme/non-heme diiron active sites, and on heme/Cu oxidases such as cytochrome c oxidase which can mediate the same chemistry. Recent designed protein and synthetic model compound (heme/non-heme diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, which describe the oxidation of ·NO(g) to nitrate (or nitrite) and possible peroxynitrite intermediates, or reductive coupling of ·NO(g) to give nitrous oxide. PMID:20666386

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

Cross dehydrogenative coupling of N-aryltetrahydroisoquinolines (sp3 C–H) with indoles (sp2 C–H) using a heterogeneous mesoporous manganese oxide catalyst

DOE PAGES

Dutta, B.; Sharma, Vinit K.; Sassu, N.; ...

2017-09-01

We disclose a novel, heterogeneous catalytic approach for selective coupling of C1 of N-aryltetrahydroisoquinolines with C3 of indoles in the presence of mesoporous manganese oxides. Our work involves a detailed mechanistic investigation of the reaction on the catalyst surface, backed by DFT computational studies, to understand the superior catalytic activity of manganese oxides.

Potential coupling effects of ammonia-oxidizing and anaerobic ammonium-oxidizing bacteria on completely autotrophic nitrogen removal over nitrite biofilm formation induced by the second messenger cyclic diguanylate.

PubMed

Wang, Chao; Liu, Sitong; Xu, Xiaochen; Zhao, Chuanqi; Yang, Fenglin; Wang, Dong

2017-05-01

The objective of this study was to investigate the influence of extracellular polymeric substance (EPS) on the coupling effects between ammonia-oxidizing bacteria (AOB) and anaerobic ammonium-oxidizing (anammox) bacteria for the completely autotrophic nitrogen removal over nitrite (CANON) biofilm formation in a moving bed biofilm reactor (MBBR). Analysis of the quantity of EPS and cyclic diguanylate (c-di-GMP) confirmed that the contents of polysaccharides and c-di-GMP were correlated in the AOB sludge, anammox sludge, and CANON biofilm. The anammox sludge secreted more EPS (especially polysaccharides) than AOB with a markedly higher c-di-GMP content, which could be used by the bacteria to regulate the synthesis of exopolysaccharides that are ultimately used as a fixation matrix, for the adhesion of biomass. Indeed, increased intracellular c-di-GMP concentrations in the anammox sludge enhanced the regulation of polysaccharides to promote the adhesion of AOB and formation of the CANON biofilm. Overall, the results of this study provide new comprehensive information regarding the coupling effects of AOB and anammox bacteria for the nitrogen removal process.

Tandem catalysis: a new approach to polymers.

PubMed

Robert, Carine; Thomas, Christophe M

2013-12-21

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

Peptide Analysis Using Tandem Mass Spectrometry

DTIC Science & Technology

1989-06-01

to give pyroglutamic acid during storage, eliminating ammonia. It is almost absent in the spectrum of a freshly-prepared sample and is not seen in...USING TANDEM MASS SPECTROMETRY INTRODUCTION S The objective of the project was to determine the complete amino acid sequence of the large polypeptide...Ubiquitin by use of fast atom bombardment (FAB) ionization and tandem mass spectrometry. The peptide containing 76 amino acid residues was available

Competition Between Resonant Plasmonic Coupling and Electrostatic Interaction in Reduced Graphene Oxide Quantum Dots.

PubMed

Karna, Sanjay; Mahat, Meg; Choi, Tae-Youl; Shimada, Ryoko; Wang, Zhiming; Neogi, Arup

2016-11-22

The light emission from reduced graphene oxide quantum dots (rGO-QDs) exhibit a significant enhancement in photoluminescence (PL) due to localized surface plasmon (LSP) interactions. Silver and gold nanoparticles (NPs) coupled to rGO nanoparticles exhibit the effect of resonant LSP coupling on the emission processes. Enhancement of the radiative recombination rate in the presence of Ag-NPs induced LSP tuned to the emission energy results in a four-fold increase in PL intensity. The localized field due to the resonantly coupled LSP modes induces n-π* transitions that are not observed in the absence of the resonant interaction of the plasmons with the excitons. An increase in the density of the Ag-NPs result in a detuning of the LSP energy from the emission energy of the nanoparticles. The detuning is due to the cumulative effect of the red-shift in the LSP energy and the electrostatic field induced blue shift in the PL energy of the rGO-QDs. The detuning quenches the PL emission from rGO-QDs at higher concentration of Ag NPs due to non-dissipative effects unlike plasmon induced Joule heating that occurs under resonance conditions. An increase in Au nanoparticles concentration results in an enhancement of PL emission due to electrostatic image charge effect.

The use of ultra-high pressure liquid chromatography with tandem mass spectrometric detection of analysis of agrochemical residues and mycotoxines in food - challenges and applications

USDA-ARS?s Scientific Manuscript database

In the field of food contaminant analysis, the most significant development of recent years has been the integration of ultra-high pressure liquid chromatography (UHPLC), coupled to tandem quadrupole mass spectrometry (MS/MS), into analytical applications. In this review, we describe the emergence o...

In vivo study on the neurotransmitters and their metabolites change in depressive disorder rat plasma by ultra high performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Zhao, Longshan; Zheng, Shuning; Su, Guangyue; Lu, Xiumei; Yang, Jingyu; Xiong, Zhili; Wu, Chunfu

2015-04-15

A sensitive and versatile, ultra-high performance, liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method coupled to pre-column derivatization for the simultaneous determination of 5-hydroxytryptamine (5-HT), 5-hydroxyindoleacetic acid (5-HIAA), dopamine (DA), norepinephrine (NE), homovanillic acid (HVA), γ-aminobutyric acid (GABA) and glutamic acid (Glu) was developed and validated in rat plasma. The analytes were dansylated under strong alkaline conditions after protein precipitation extraction, which were analyzed on a BEH C18 column using a gradient elution. The lower limit of quantification (LLOQ) values for 5-HT, 5-HIAA, DA, NE, HVA, GABA and Glu were 1.00, 1.00, 0.991, 0.992, 1.02, 1000, and 5030 pmol/mL, respectively. Good linearity was obtained (r > 0.99) and the intra- and inter-day precisions of the method (relative standard deviation, RSD%) were lower than 12%. The method was novel, sensitive and specific which can provide an alternative method for the quantification of neurotransmitters and their metabolites in plasma samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrophilic interaction ultra-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry for highly rapid and sensitive analysis of underivatized amino acids in functional foods.

PubMed

Zhou, Guisheng; Pang, Hanqing; Tang, Yuping; Yao, Xin; Mo, Xuan; Zhu, Shaoqing; Guo, Sheng; Qian, Dawei; Qian, Yefei; Su, Shulan; Zhang, Li; Jin, Chun; Qin, Yong; Duan, Jin-ao

2013-05-01

This work presented a new analytical methodology based on hydrophilic interaction ultra-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry in multiple-reaction monitoring mode for analysis of 24 underivatized free amino acids (FAAs) in functional foods. The proposed method was first reported and validated by assessing the matrix effects, linearity, limit of detections and limit of quantifications, precision, repeatability, stability and recovery of all target compounds, and it was used to determine the nutritional substances of FAAs in ginkgo seeds and further elucidate the nutritional value of this functional food. The result showed that ginkgo seed turned out to be a good source of FAAs with high levels of several essential FAAs and to have a good nutritional value. Furthermore, the principal component analysis was performed to classify the ginkgo seed samples on the basis of 24 FAAs. As a result, the samples could be mainly clustered into three groups, which were similar to areas classification. Overall, the presented method would be useful for the investigation of amino acids in edible plants and agricultural products.

Remarkable co-catalysis by copper(I) oxide in the palladium catalyzed cross-coupling of arylboronic acids with ethyl bromoacetate.

PubMed

Liu, Xing-xin; Deng, Min-zhi

2002-03-21

Copper(I) oxide can effectively co-catalyze the Suzuki type cross-coupling reactions of arylboronic acids with ethyl bromoacetate. As an alternative protocol for introducing the methylenecarboxy group into functionalized molecules, this reaction occurs in the absence of highly toxic thallium compounds or special ligands and should be convenient and practical.

Identification of Polish cochineal (Porphyrophora polonica L.) in historical textiles by high-performance liquid chromatography coupled with spectrophotometric and tandem mass spectrometric detection.

PubMed

Lech, Katarzyna; Jarosz, Maciej

2016-05-01

The present work reports a method for identification of Polish cochineal (Porphyrophora polonica L.) in historical fabrics by the use of high-performance liquid chromatography coupled with diode array and tandem mass spectrometric detection with electrospray ionization (HPLC-DAD-ESI MS/MS). This hyphened technique allows detection and identification of 16 new minor colorants present in the discussed scale insect (including two previously observed by Wouters and Verhecken (Ann Soc Entomol Fr. 1989;25:393-410), but specified only as compounds of unknown structures) that do not occur (e.g., in American cochineal). The MS/MS experiments, complemented with UV-VIS data, enable identification of mono- and di-, C- and O-hexosides of kermesic and flavokermesic acids or their derivatives. The present paper introduces a fingerprint of color compounds present in Polish cochineal and defines them, particularly pp6 (ppI, O-hexoside of flavokermesic acid), as its markers allow distinguishing of Polish-cochineal reds from the American ones. Usefulness of the selected set of markers for identification of Polish cochineal has been demonstrated in the examination of textiles from the collection of the National Museum in Warsaw using the multiple reaction monitoring (MRM) method, originally elaborated on the basis of this study.

Biochemical establishment and characterization of EncM's flavin-N5-oxide cofactor

PubMed Central

Teufel, Robin; Stull, Frederick; Meehan, Michael J.; Michaudel, Quentin; Dorrestein, Pieter C.; Palfey, Bruce; Moore, Bradley S.

2016-01-01

The ubiquitous flavin-dependent monooxygenases commonly catalyze oxygenation reactions by means of a transient C4a-peroxyflavin. A recent study, however, suggested an unprecedented flavin-oxygenating species - proposed as the flavin-N5-oxide (FlN5[O]) - as key to an oxidative Favorskii-type rearrangement in the biosynthesis of the bacterial polyketide antibiotic enterocin. This stable superoxidized flavin is covalently tethered to the enzyme EncM and converted into FADH2 (Flred) during substrate turnover. Subsequent reaction of Flred with molecular oxygen restores the postulated FlN5[O] via an unknown pathway. Here we provide direct evidence for the FlN5[O] species via isotope labeling, proteolytic digestion, and high-resolution tandem mass spectrometry of EncM. We propose that formation of this species occurs by hydrogen-transfer from Flred to molecular oxygen, allowing radical coupling of the formed protonated superoxide and anionic flavin semiquinone at N5, before elimination of water affords the FlN5[O] cofactor. Further biochemical and spectroscopic investigations reveal important features of the FlN5[O] species and the EncM catalytic mechanism. We speculate that flavin-N5-oxides may be intermediates or catalytically active species in other flavoproteins that form the anionic semiquinone and promote access of oxygen to N5. PMID:26067765

PTGBase: an integrated database to study tandem duplicated genes in plants.

PubMed

Yu, Jingyin; Ke, Tao; Tehrim, Sadia; Sun, Fengming; Liao, Boshou; Hua, Wei

2015-01-01

Tandem duplication is a wide-spread phenomenon in plant genomes and plays significant roles in evolution and adaptation to changing environments. Tandem duplicated genes related to certain functions will lead to the expansion of gene families and bring increase of gene dosage in the form of gene cluster arrays. Many tandem duplication events have been studied in plant genomes; yet, there is a surprising shortage of efforts to systematically present the integration of large amounts of information about publicly deposited tandem duplicated gene data across the plant kingdom. To address this shortcoming, we developed the first plant tandem duplicated genes database, PTGBase. It delivers the most comprehensive resource available to date, spanning 39 plant genomes, including model species and newly sequenced species alike. Across these genomes, 54 130 tandem duplicated gene clusters (129 652 genes) are presented in the database. Each tandem array, as well as its member genes, is characterized in complete detail. Tandem duplicated genes in PTGBase can be explored through browsing or searching by identifiers or keywords of functional annotation and sequence similarity. Users can download tandem duplicated gene arrays easily to any scale, up to the complete annotation data set for an entire plant genome. PTGBase will be updated regularly with newly sequenced plant species as they become available. © The Author(s) 2015. Published by Oxford University Press.

Hybrid Tandem Solar Cells | Photovoltaic Research | NREL

Science.gov Websites

Hybrid Tandem Solar Cells Hybrid Tandem Solar Cells To achieve aggressive cost reductions in photovoltaics (PV) beyond the 6¢/kWh SunShot Initiative 2020 goal, module efficiency must be increased beyond on a silicon platform and that aim to provide viable prototypes for commercialization. PV Research

Monolithic Parallel Tandem Organic Photovoltaic Cell with Transparent Carbon Nanotube Interlayer

NASA Technical Reports Server (NTRS)

Tanaka, S.; Mielczarek, K.; Ovalle-Robles, R.; Wang, B.; Hsu, D.; Zakhidov, A. A.

2009-01-01

We demonstrate an organic photovoltaic cell with a monolithic tandem structure in parallel connection. Transparent multiwalled carbon nanotube sheets are used as an interlayer anode electrode for this parallel tandem. The characteristics of front and back cells are measured independently. The short circuit current density of the parallel tandem cell is larger than the currents of each individual cell. The wavelength dependence of photocurrent for the parallel tandem cell shows the superposition spectrum of the two spectral sensitivities of the front and back cells. The monolithic three-electrode photovoltaic cell indeed operates as a parallel tandem with improved efficiency.

Design and performance of an instrument for electron impact tandem mass spectrometry and action spectroscopy of mass/charge selected macromolecular ions stored in RF ion trap*

NASA Astrophysics Data System (ADS)

Ranković, Milos Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

2016-06-01

A new apparatus was designed, coupling an electron gun with a linear quadrupole ion trap mass spectrometer, to perform m/ z (mass over charge) selected ion activation by electron impact for tandem mass spectrometry and action spectroscopy. We present in detail electron tracing simulations of a 300 eV electron beam inside the ion trap, design of the mechanical parts, electron optics and electronic circuits used in the experiment. We also report examples of electron impact activation tandem mass spectra for Ubiquitin protein, Substance P and Melittin peptides, at incident electron energies in the range from 280 eV to 300 eV.

Three-dimensional fully-coupled electrical and thermal transport model of dynamic switching in oxide memristors

DOE PAGES

Gao, Xujiao; Mamaluy, Denis; Mickel, Patrick R.; ...

2015-09-08

In this paper, we present a fully-coupled electrical and thermal transport model for oxide memristors that solves simultaneously the time-dependent continuity equations for all relevant carriers, together with the time-dependent heat equation including Joule heating sources. The model captures all the important processes that drive memristive switching and is applicable to simulate switching behavior in a wide range of oxide memristors. The model is applied to simulate the ON switching in a 3D filamentary TaOx memristor. Simulation results show that, for uniform vacancy density in the OFF state, vacancies fill in the conduction filament till saturation, and then fill outmore » a gap formed in the Ta electrode during ON switching; furthermore, ON-switching time strongly depends on applied voltage and the ON-to-OFF current ratio is sensitive to the filament vacancy density in the OFF state.« less

Multiresidue determination of 114 multiclass pesticides in flue-cured tobacco by solid-phase extraction coupled with gas chromatography and tandem mass spectrometry.

PubMed

Cao, Jianmin; Sun, Na; Yu, Weisong; Pang, Xueli; Lin, Yingnan; Kong, Fanyu; Qiu, Jun

2016-12-01

A sensitive and robust multiresidue method for the simultaneous analysis of 114 pesticides in tobacco was developed based on solid-phase extraction coupled with gas chromatography and tandem mass spectrometry. In this strategy, tobacco samples were extracted with acetonitrile and cleaned up with a multilayer solid-phase extraction cartridge Cleanert TPT using acetonitrile/toluene (3:1) as the elution solvent. Two internal standards of different polarity were used to meet simultaneous pesticides quantification demands in the tobacco matrix. Satisfactory linearity in the range of 10-500 ng/mL was obtained for all 114 pesticides with linear regression coefficients higher than 0.994. The limit of detection and limit of quantification values were 0.02-5.27 and 0.06-17.6 ng/g, respectively. For most of the pesticides, acceptable recoveries in the range of 70-120% and repeatabilities (relative standard deviation) of <11% were achieved at spiking levels of 20, 100, and 400 ng/g. Compared with the reported multiresidue analytical method, the proposed method provided a cleaner test solution with smaller amounts of pigments, fatty acids as well as other undesirable interferences. The development and validation of the high sensitivity, high selectivity, easy automation, and high-throughput analytical method meant that it could be successfully used for the determination of pesticides in tobacco samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous Quantification of 11 Constituents in Wuji Pill Using Ultra Performance Liquid Chromatography Coupled With a Triple Quadrupole Electrospray Tandem Mass Spectrometry.

PubMed

Tian, Tingting; Jin, Yiran; Ma, Yinghua; Xie, Weiwei; Xu, Huijun; Du, Yingfeng

2016-02-01

An ultra performance liquid chromatography coupled with a triple quadrupole electrospray tandem mass spectrometry (UPLC-MS-MS) method was developed for analyzing and identifying the constituents of 11 compounds including berberine, epiberberine, berberrubine, jatrorrhizine, coptisine, palmatine, evodiamine, rutaecarpine, limonin, paeoniflorin and albiflorin in Wuji pill (WJ pill), a traditional Chinese medicine. The chromatographic separation was performed on a C18 column and the mobile phase was composed of water (0.1% formic acid and 2 mmol ammonium acetate) and methanol with a linear gradient elution. The detection was performed by multiple reaction monitoring mode, using electrospray ionization in the positive ion mode. The total run time was 14 min. The calibration curves were linear with all correlation coefficients higher than 0.9987 in the tested range. The intra- and interday precisions were no more than 4.9%, and the average recoveries were from 92.4 to 107.8% with the relative standard deviations no more than 7.8%. The developed method was successfully employed to analyze five batches of WJ pill samples. This is the first time to establish a method for the quality control of WJ pill to ensure the safety and efficacy in clinical applications effectively. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Early life low-level cadmium exposure is positively associated with increased oxidative stress

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

Kippler, Maria; Bakhtiar Hossain, Mohammad; Department of Laboratory Medicine, Section of Occupational and Environmental Medicine, Lund University, Lund

Environmental exposure to cadmium (Cd) is known to induce oxidative stress, a state of imbalance between the production of reactive oxygen species (ROS) and the ability to detoxify them, in adults. However, data are lacking on potential effects in early-life. We evaluated urinary concentrations of 8-oxo-7,8-dihydro-2 Prime -deoxyguanosine (8-oxodG), a recognized marker of oxidative DNA damage, in relation to Cd exposure in 96 predominantly breast-fed infants (11-17 weeks of age) in rural Bangladesh. Urinary 8-oxodG was measured using liquid chromatography tandem mass spectrometry and Cd in urine and breast milk by inductively coupled plasma mass spectrometry. Median concentration of 8-oxodGmore » was 3.9 nmol/L, urinary Cd 0.30 {mu}g/L, and breast-milk Cd 0.13 {mu}g/L. In linear regression analyses, urinary 8-oxodG was positively associated with Cd in both urine (p=0.00067) and breast milk (p=0.0021), and negatively associated with body weight (kg; p=0.0041). Adjustment for age, body weight, socio-economic status, urinary arsenic, as well as magnesium, calcium, and copper in breast milk did not change the association between Cd exposure and urinary 8-oxodG. These findings suggest that early-life low-level exposure to Cd via breast milk induces oxidative stress. Further studies are warranted to elucidate whether this oxidative stress is associated with impaired child health and development.« less

Inverted Three-Junction Tandem Thermophotovoltaic Modules

NASA Technical Reports Server (NTRS)

Wojtczuk, Steven

2012-01-01

An InGaAs-based three-junction (3J) tandem thermophotovoltaic (TPV) cell has been investigated to utilize more of the blackbody spectrum (from a 1,100 C general purpose heat source GPHS) efficiently. The tandem consists of three vertically stacked subcells, a 0.74-eV InGaAs cell, a 0.6- eV InGaAs cell, and a 0.55-eV InGaAs cell, as well as two interconnecting tunnel junctions. A greater than 20% TPV system efficiency was achieved by another group with a 1,040 C blackbody using a single-bandgap 0.6- eV InGaAs cell MIM (monolithic interconnected module) (30 lateral junctions) that delivered about 12 V/30 or 0.4 V/junction. It is expected that a three-bandgap tandem MIM will eventually have about 3 this voltage (1.15 V) and about half the current. A 4 A/cm2 would be generated by a single-bandgap 0.6-V InGaAs MIM, as opposed to the 2 A/cm2 available from the same spectrum when split among the three series-connected junctions in the tandem stack. This would then be about a 50% increase (3xVoc, 0.5xIsc) in output power if the proposed tandem replaced the single- bandgap MIM. The advantage of the innovation, if successful, would be a 50% increase in power conversion efficiency from radioisotope heat sources using existing thermophotovoltaics. Up to 50% more power would be generated for radioisotope GPHS deep space missions. This type of InGaAs multijunction stack could be used with terrestrial concentrator solar cells to increase efficiency from 41 to 45% or more.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): coupling model analysis.

PubMed

Ngai, K L; Wang, Li-Min

2011-11-21

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past t(c) = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at t(c). The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some t(c) determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): Coupling model analysis

NASA Astrophysics Data System (ADS)

Ngai, K. L.; Wang, Li-Min

2011-11-01

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past tc = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at tc. The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some tc determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Simultaneous determination of metolazone and valsartan in plasma by on-line SPE coupled with liquid chromatography/tandem mass spectrometry.

PubMed

Zhou, Jiezhao; Chen, Meiling; Li, Ying; Yu, Fanglin; Cheng, Xiaohui; Yang, Yang; Liu, Yan; Xie, Xiangyang; Li, Zhiping; Zhang, Hui; Mei, Xingguo

2017-10-01

Combination of metolazone (0.5 mg) and valsartan (80 mg) has been verified as a promising therapy treatment for hypertension. In order to facilitate to pharmacokinetic research, it needs a method for the simultaneously determination of metolazone and valsartan in biological samples. However, there are no relative reports so far. In order to facilitate to pharmacokinetic research, an on-line solid phase extraction coupled with liquid chromatography-tandem mass spectrometry method for the simultaneous determination of metolazone and valsartan in beagle dog plasma was developed and validated in this study. An on-line solid phase extraction column Retain PEP Javelin (10 mm × 2.1 mm) was used to remove impurities in plasma samples. The metolazone, valsartan and internal standard (losartan) were separated on a Poroshell 120 SB-C18 column (4.6 mm × 50 mm × 2.7 µm) with a gradient elution procedure. Acidified acetonitrile/water mixture was used as a mobile phase. The selected multiple-reaction monitoring mode in positive ion was performed and the parent to the product transitions m/z 366/259, m/z 436.2/291 and m/z 423.4/207 were used to measure the metolazone, valsartan and losartan. The method was linear over the range of 0.1-100 ng/mL and 1-1000 ng/mL for metolazone and valsartan, respectively. This method was validated in terms of specificity, linearity, sensitivity, precision, accuracy, matrix effect, and stability and then successfully applied to pharmacokinetic studies of the metolazone and valsartan combination tablets in beagle dogs.

All solution-processed lead halide perovskite-BiVO4 tandem assembly for photolytic solar fuels production.

PubMed

Chen, Yong-Siou; Manser, Joseph S; Kamat, Prashant V

2015-01-21

The quest for economic, large-scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. Here we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons, and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard AM 1.5G illumination, the photoanode-photovoltaic architecture, in conjunction with an earth-abundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially promising new frontier for solar water splitting research.

Metabolic Profile of Skimmianine in Rats Determined by Ultra-Performance Liquid Chromatography Coupled with Quadrupole Time-of-Flight Tandem Mass Spectrometry.

PubMed

Huang, Aihua; Xu, Hui; Zhan, Ruoting; Chen, Weiwen; Liu, Jiawei; Chi, Yuguang; Chen, Daidi; Ji, Xiaoyu; Luo, Chaoquan

2017-03-23

Skimmianine is a furoquinoline alkaloid present mainly in the Rutaceae family. It has been reported to have analgesic, antispastic, sedative, anti-inflammatory, and other pharmacologic activities. Despite its critical pharmacological function, its metabolite profiling is still unclear. In this study, the in vivo metabolite profiling of skimmianine in rats was investigated using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS). The metabolites were predicted using MetabolitePilot TM software. These predicted metabolites were further analyzed by MS² spectra, and compared with the detailed fragmentation pathway of the skimmianine standard and literature data. A total of 16 metabolites were identified for the first time in rat plasma, urine, and feces samples after oral administration of skimmianine. Skimmianine underwent extensive Phase I and Phase II metabolism in rats. The Phase I biotransformations of skimmianine consist of epoxidation of olefin on its furan ring (M1) followed by the hydrolysis of the epoxide ring (M4), hydroxylation (M2, M3), O -demethylation (M5-M7), didemethylation (M14-M16). The Phase II biotransformations include glucuronide conjugation (M8-M10) and sulfate conjugation (M11-M13). The epoxidation of 2,3-olefinic bond followed by the hydrolysis of the epoxide ring and O -demethylation were the major metabolic pathways of skimmianine. The results provide key information for understanding the biotransformation processes of skimmianine and the related furoquinoline alkaloids.

Oxidation Kinetics of Bromophenols by Nonradical Activation of Peroxydisulfate in the Presence of Carbon Nanotube and Formation of Brominated Polymeric Products.

PubMed

Guan, Chaoting; Jiang, Jin; Pang, Suyan; Luo, Congwei; Ma, Jun; Zhou, Yang; Yang, Yi

2017-09-19

This work demonstrated that bromophenols (BrPs) could be readily oxidized by peroxydisulfate (PDS) activated by a commercial carbon nanotube (CNT), while furfuryl alcohol (a chemical probe for singlet oxygen ( 1 O 2 )) was quite refractory. Results obtained by radical quenching experiments, electron paramagnetic resonance spectroscopy, and Fourier transform infrared spectroscopy further confirmed the involvement of nonradical PDS-CNT complexes rather than 1 O 2 . Bicarbonate and chloride ion exhibited negligible impacts on BrPs degradation by the PDS/CNT system, while a significant inhibitory effect was observed for natural organic matter. The oxidation of BrPs was influenced by solution pH with maximum rates occurring at neutral pH. Linear free energy relationships (LFERs) were established between the observed pseudo-first-order oxidation rates of various substituted phenols and the classical descriptor variables (i.e., Hammett constant σ + , and half-wave oxidation potential E 1/2 ). Products analyses by liquid chromatography tandem mass spectrometry clearly showed the formation of hydroxylated polybrominated diphenyl ethers and hydroxylated polybrominated biphenyls on CNT surface. Their formation pathway possibly involved the generation of bromophenoxyl radicals from BrPs one-electron oxidation and their subsequent coupling reactions. These results suggest that the novel nonradical PDS/CNT oxidation technology is a good alternative for selectively eliminating BrPs with alleviating toxic byproducts in treated water effluent.

Performance of a tandem-rotor/tandem-stator conical-flow compressor designed for a pressure ratio of 3

NASA Technical Reports Server (NTRS)

Wood, J. R.; Owen, A. K.; Schumann, L. F.

1982-01-01

A conical-flow compressor stage with a large radius change through the rotor was tested at three values of rotor tip clearance. The stage had a tandem rotor and a tandem stator. Peak efficiency at design speed was 0.774 at a pressure ratio of 2.613. The rotor was tested without the stator, and detailed survey data were obtained for each rotor blade row. Overall peak rotor efficiency was 0.871 at a pressure ratio of 2.952.

Poly(cyclohexylethylene)- block-poly(ethylene oxide) block polymers for metal oxide templating

DOE PAGES

Schulze, Morgan W.; Sinturel, Christophe; Hillmyer, Marc A.

2015-09-01

A series of poly(cyclohexylethylene)- block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation producesmore » an ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.« less

Applying Tandem Mass Spectral Libraries for Solving the Critical Assessment of Small Molecule Identification (CASMI) LC/MS Challenge 2012

PubMed Central

Oberacher, Herbert

2013-01-01

The “Critical Assessment of Small Molecule Identification” (CASMI) contest was aimed in testing strategies for small molecule identification that are currently available in the experimental and computational mass spectrometry community. We have applied tandem mass spectral library search to solve Category 2 of the CASMI Challenge 2012 (best identification for high resolution LC/MS data). More than 230,000 tandem mass spectra part of four well established libraries (MassBank, the collection of tandem mass spectra of the “NIST/NIH/EPA Mass Spectral Library 2012”, METLIN, and the ‘Wiley Registry of Tandem Mass Spectral Data, MSforID’) were searched. The sample spectra acquired in positive ion mode were processed. Seven out of 12 challenges did not produce putative positive matches, simply because reference spectra were not available for the compounds searched. This suggests that to some extent the limited coverage of chemical space with high-quality reference spectra is still a problem encountered in tandem mass spectral library search. Solutions were submitted for five challenges. Three compounds were correctly identified (kanamycin A, benzyldiphenylphosphine oxide, and 1-isopropyl-5-methyl-1H-indole-2,3-dione). In the absence of any reference spectrum, a false positive identification was obtained for 1-aminoanthraquinone by matching the corresponding sample spectrum to the structurally related compounds N-phenylphthalimide and 2-aminoanthraquinone. Another false positive result was submitted for 1H-benz[g]indole; for the 1H-benz[g]indole-specific sample spectra provided, carbazole was listed as the best matching compound. In this case, the quality of the available 1H-benz[g]indole-specific reference spectra was found to hamper unequivocal identification. PMID:24957994

A tandem-based compact dual-energy gamma generator.

PubMed

Persaud, A; Kwan, J W; Leitner, M; Leung, K-N; Ludewigt, B; Tanaka, N; Waldron, W; Wilde, S; Antolak, A J; Morse, D H; Raber, T

2010-02-01

A dual-energy tandem-type gamma generator has been developed at E. O. Lawrence Berkeley National Laboratory and Sandia National Laboratories. The tandem accelerator geometry allows higher energy nuclear reactions to be reached, thereby allowing more flexible generation of MeV-energy gammas for active interrogation applications. Both positively charged ions and atoms of hydrogen are created from negative ions via a gas stripper. In this paper, we show first results of the working tandem-based gamma generator and that a gas stripper can be utilized in a compact source design. Preliminary results of monoenergetic gamma production are shown.

TRAP: automated classification, quantification and annotation of tandemly repeated sequences.

PubMed

Sobreira, Tiago José P; Durham, Alan M; Gruber, Arthur

2006-02-01

TRAP, the Tandem Repeats Analysis Program, is a Perl program that provides a unified set of analyses for the selection, classification, quantification and automated annotation of tandemly repeated sequences. TRAP uses the results of the Tandem Repeats Finder program to perform a global analysis of the satellite content of DNA sequences, permitting researchers to easily assess the tandem repeat content for both individual sequences and whole genomes. The results can be generated in convenient formats such as HTML and comma-separated values. TRAP can also be used to automatically generate annotation data in the format of feature table and GFF files.

Coupling of tandem Smad ubiquitination regulatory factor (Smurf) WW domains modulates target specificity.

PubMed

Chong, P Andrew; Lin, Hong; Wrana, Jeffrey L; Forman-Kay, Julie D

2010-10-26

Smad ubiquitination regulatory factor 2 (Smurf2) is an E3 ubiquitin ligase that participates in degradation of TGF-β receptors and other targets. Smurf2 WW domains recognize PPXY (PY) motifs on ubiquitin ligase target proteins or on adapters, such as Smad7, that bind to E3 target proteins. We previously demonstrated that the isolated WW3 domain of Smurf2, but not the WW2 domain, can directly bind to a Smad7 PY motif. We show here that the WW2 augments this interaction by binding to the WW3 and making auxiliary contacts with the PY motif and a novel E/D-S/T-P motif, which is N-terminal to all Smad PY motifs. The WW2 likely enhances the selectivity of Smurf2 for the Smad proteins. NMR titrations confirm that Smad1 and Smad2 are bound by Smurf2 with the same coupled WW domain arrangement used to bind Smad7. The analogous WW domains in the short isoform of Smurf1 recognize the Smad7 PY peptide using the same coupled mechanism. However, a longer Smurf1 isoform, which has an additional 26 residues in the inter-WW domain linker, is only partially able to use the coupled WW domain binding mechanism. The longer linker results in a decrease in affinity for the Smad7 peptide. Interdomain coupling of WW domains enhances selectivity and enables the tuning of interactions by isoform switching.

Coupling of tandem Smad ubiquitination regulatory factor (Smurf) WW domains modulates target specificity

PubMed Central

Chong, P. Andrew; Lin, Hong; Wrana, Jeffrey L.; Forman-Kay, Julie D.

2010-01-01

Smad ubiquitination regulatory factor 2 (Smurf2) is an E3 ubiquitin ligase that participates in degradation of TGF-β receptors and other targets. Smurf2 WW domains recognize PPXY (PY) motifs on ubiquitin ligase target proteins or on adapters, such as Smad7, that bind to E3 target proteins. We previously demonstrated that the isolated WW3 domain of Smurf2, but not the WW2 domain, can directly bind to a Smad7 PY motif. We show here that the WW2 augments this interaction by binding to the WW3 and making auxiliary contacts with the PY motif and a novel E/D-S/T-P motif, which is N-terminal to all Smad PY motifs. The WW2 likely enhances the selectivity of Smurf2 for the Smad proteins. NMR titrations confirm that Smad1 and Smad2 are bound by Smurf2 with the same coupled WW domain arrangement used to bind Smad7. The analogous WW domains in the short isoform of Smurf1 recognize the Smad7 PY peptide using the same coupled mechanism. However, a longer Smurf1 isoform, which has an additional 26 residues in the inter-WW domain linker, is only partially able to use the coupled WW domain binding mechanism. The longer linker results in a decrease in affinity for the Smad7 peptide. Interdomain coupling of WW domains enhances selectivity and enables the tuning of interactions by isoform switching. PMID:20937913

MEASUREMENT OF PYRETHROID RESIDUES IN ENVIRONMENTAL AND FOOD SAMPLES BY ENHANCED SOLVENT EXTRACTION/SUPERCRITICAL FLUID EXTRACTION COUPLED WITH GAS CHROMATOGRAPHY-TANDEM MASS SPECTROMETRY

EPA Science Inventory

The abstract summarizes pyrethorid methods development research. It provides a summary of sample preparation and analytical techniques such as supercritical fluid extraction, enhance solvent extraction, gas chromatography and tandem mass spectrometry.

Structural Characterization of New Peptide Variants Produced by Cyanobacteria from the Brazilian Atlantic Coastal Forest Using Liquid Chromatography Coupled to Quadrupole Time-of-Flight Tandem Mass Spectrometry

PubMed Central

Sanz, Miriam; Andreote, Ana Paula Dini; Fiore, Marli Fatima; Dörr, Felipe Augusto; Pinto, Ernani

2015-01-01

Cyanobacteria from underexplored and extreme habitats are attracting increasing attention in the search for new bioactive substances. However, cyanobacterial communities from tropical and subtropical regions are still largely unknown, especially with respect to metabolite production. Among the structurally diverse secondary metabolites produced by these organisms, peptides are by far the most frequently described structures. In this work, liquid chromatography/electrospray ionization coupled to high resolution quadrupole time-of-flight tandem mass spectrometry with positive ion detection was applied to study the peptide profile of a group of cyanobacteria isolated from the Southeastern Brazilian coastal forest. A total of 38 peptides belonging to three different families (anabaenopeptins, aeruginosins, and cyanopeptolins) were detected in the extracts. Of the 38 peptides, 37 were detected here for the first time. New structural features were proposed based on mass accuracy data and isotopic patterns derived from full scan and MS/MS spectra. Interestingly, of the 40 surveyed strains only nine were confirmed to be peptide producers; all of these strains belonged to the order Nostocales (three Nostoc sp., two Desmonostoc sp. and four Brasilonema sp.). PMID:26096276

Structural Characterization of Oxidized Glycerophosphatidylserine: Evidence of Polar Head Oxidation

NASA Astrophysics Data System (ADS)

Maciel, Elisabete; da Silva, Raquel Nunes; Simões, Cláudia; Domingues, Pedro; Domingues, M. Rosário M.

2011-10-01

Non-oxidized phosphatidylserine (PS) is known to play a key role in apoptosis but there is considerable research evidence suggesting that oxidized PS also plays a role in this event, leading to the increasing interest in studying PS oxidative modifications. In this work, different PS (1-palmitoyl-2-linoleoyl-sn-glycero-3-phospho-L-serine (PLPS), 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine (POPS), and 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine (DPPS) were oxidized in vitro by hydroxyl radical, generated under Fenton reaction conditions, and the reactions were monitored by ESI-MS in negative mode. Oxidation products were then fractionated by thin layer chromatography (TLC) and characterized by tandem mass spectrometry (MS/MS). This approach allowed the identification of hydroxyl, peroxy, and keto derivatives due to oxidation of unsaturated fatty acyl chains. Oxidation products due to oxidation of serine polar head were also identified. These products, with lower molecular weight than the non-modified PS, were identified as [M - 29 - H]- (terminal acetic acid), [M - 30 - H]- (terminal acetamide), [M - 13 - H]- (terminal hydroperoxyacetaldehyde), and [M - 13 - H]- (terminal hydroxyacetaldehyde plus hydroxy fatty acyl chain). Phosphatidic acid was also formed in these conditions. These findings confirm the oxidation of the serine polar head induced by the hydroxyl radical. The identification of these modifications may be a valuable tool to evaluate phosphatidylserine alteration under physiopathologic conditions and also to help understand the biological role of phosphatidylserine oxidation in the apoptotic process and other biological functions.

Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

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

Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.

Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. Themore » extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.« less

An alternative pathway for marine nitrous oxide production at oxic-anoxic interfaces from coupled biotic-abiotic reactions

NASA Astrophysics Data System (ADS)

Glass, J. B.; Stanton, C. L.; Ochoa, H.; Haslun, J. A.; Gandhi, H.; Taillefert, M.; Dichristina, T. J.; Stewart, F. J.; Klotz, M. G.; Ostrom, N. E.

2016-02-01

Marine emissions of nitrous oxide (N2O), a potent greenhouse gas, comprise approximately a third of global sources. Recent evidence suggests that the dominant source of N2O in seawater is the activity of ammonia-oxidizing Thaumarchaeota that lack characterized N2O-generating enzymes. Nitrous oxide may arise from a novel enzyme and/or abiotic reactions between nitrification intermediates, hydroxylamine (NH2OH) and nitric oxide (NO), and redox-active metals in seawater. Isotopic site preference, or difference in δ15N between the two nitrogen atoms in N2O, has been used as tracer for microbial N2O production pathways (-10 to 0‰ for nitrifier-denitrification and denitrification vs. 30-37‰ for nitrification via NH2OH oxidation). Seawater N2O site preference falls in between these two characterized end members, suggesting simultaneous production via a combination of both microbial pathways or via a novel mechanism with intermediate site preference. Here we show significant N2O production in abiotic experiments after addition of iron to seawater containing NH2OH and NO. The N2O produced from chemical reduction of NO by Fe(II) had a site preference of 16‰ whereas N2O produced from abiotic NH2OH oxidation had a site preference of 31‰. We propose that coupled biotic-abiotic N2O production pathways could contribute significant sources of N2O at marine oxic-anoxic interfaces.

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

NASA Astrophysics Data System (ADS)

Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

2017-01-01

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks

Stellar MHD and Nuclear Physics Coupled Together Solve the Puzzle of Oxide Grain Composition

NASA Astrophysics Data System (ADS)

Palmerini, Sara; Trippella, Oscar; Busso, Maurizio; La Cognata, Marco; Petrelli, Maurizio; Zucchini, Azzurra

Oxide grains, enclosed in meteorites, give us very precise information about the stars in which they formed. Grains belonging to group 1 and 2 are characterized by values of 17O/16O and 18O/16O inconsistent with explosive nucleosynthesis scenarios, and are then believed to form in low mass stars. Nowadays, models of non convective mixing coupled with nuclear burning succeed in reproducing the oxygen isotopic mix found in these ancient solids thanks to the more accurate nuclear physics inputs employed in calculations. However, a large part of oxide grains shows values of the 26Al/27Al isotopic ratio too high to be accounted for by the mixing models mentioned above. Recently, [1] demonstrated that the stellar magnetic field might promote the transport of material across the stellar radiative layers. We apply this magnetic mixing model to a 1.2M ⊙ AGB star of solar metallicity. It turns out that the oxygen and aluminum isotopic ratios shown by group 1 and 2 grains are perfectly reproduced.

Biotransformation and metabolic profile of Xian-Ling-Gu-Bao capsule, a traditional Chinese medicine prescription, with rat intestinal microflora by ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry analysis.

PubMed

Gao, Meng-Xue; Tang, Xi-Yang; Zhang, Feng-Xiang; Yao, Zhi-Hong; Yao, Xin-Sheng; Dai, Yi

2018-04-01

Xian-Ling-Gu-Bao capsule (XLGB), a well-known traditional Chinese medicine prescription, has been used for the prevention and treatment of osteoporosis. The safety and efficacy of XLGB have been confirmed based on the principle of evidence-based medicine. XLGB is usually administered orally, after which its multiple components are brought into contact with intestinal microflora in the alimentary tract and biotransformed. However, investigations on the comprehensive metabolic profile of XLGB are absent. In this study, 12 representative compounds bearing different typical structures (including iridoid glycosides, prenylated flavonol glycosides, prenylated flavonoids, triterpenoid saponins, steroidal saponins, coumarins and monoterpene phenols) were selected and then investigated for their biotransformation in rat intestinal microflora. In addition, the metabolic profile of XLGB in rat intestinal microflora was investigated by ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. As a result, a total of 87 biotransformation components were identified from incubated solutions of 12 representative compounds and XLGB, which underwent 16 metabolic reactions (including deglycosylation, glycosylation, dehydrogenation, hydrogenation, oxidation, epoxidation, hydroxylation, dehydration, hydration, hydrolysis, methylation, isomerization, cyclization, pyrolysis reaction, amino acid conjugation and nucleophilic addition reaction with NH 3 ). This demonstrated that the deglycosylation reaction by cleavage of the sugar moieties is the main metabolic pathway of a variety of glycosides, including prenylated flavonol glycosides, coumarin glycosides, iridoid glycosides and saponins. In addition, compared with the biotransformation of 12 representative compounds, a different biotransformed fate was observed in the XLGB incubated samples of rat intestinal microflora. It is worth noting that the amino acid conjugation was first discovered

Microstructural study of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer (PEO-b-PS) by electrospray tandem mass spectrometry.

PubMed

Girod, Marion; Phan, Trang N T; Charles, Laurence

2008-08-01

Electrospray ionization tandem mass spectrometry has been used to characterize the microstructure of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer, called SG1-capped PEO-b-PS. The main dissociation route of co-oligomers adducted with lithium or silver cation was observed to proceed via the homolytic cleavage of a C-ON bond, aimed at undergoing reversible homolysis during nitroxide mediated polymerization. This cleavage results in the elimination of the terminal SG1 end-group as a radical, inducing a complete depolymerization process of the PS block from the so-formed radical cation. These successive eliminations of styrene molecules allowed a straightforward determination of the PS block size. An alternative fragmentation pathway of the radical cation was shown to provide structural information on the junction group between the two blocks. Proposed dissociation mechanisms were supported by accurate mass measurements. Structural information on the SG1 end-group could be reached from weak abundance fragment ions detected in the low m/z range of the MS/MS spectrum. Amongst fragments typically expected from PS dissociation, only beta ions were produced. Moreover, specific dissociation of the PEO block was not observed to occur in MS/MS, suggesting that these rearrangement reactions do not compete effectively with dissociations of the odd-electron fragment ions. Information about the PEO block length and the initiated end-group were obtained in MS(3) experiments.

Targeted tandem duplication of a large chromosomal segment in Aspergillus oryzae.

PubMed

Takahashi, Tadashi; Sato, Atsushi; Ogawa, Masahiro; Hanya, Yoshiki; Oguma, Tetsuya

2014-08-01

We describe here the first successful construction of a targeted tandem duplication of a large chromosomal segment in Aspergillus oryzae. The targeted tandem chromosomal duplication was achieved by using strains that had a 5'-deleted pyrG upstream of the region targeted for tandem chromosomal duplication and a 3'-deleted pyrG downstream of the target region. Consequently,strains bearing a 210-kb targeted tandem chromosomal duplication near the centromeric region of chromosome 8 and strains bearing a targeted tandem chromosomal duplication of a 700-kb region of chromosome 2 were successfully constructed. The strains bearing the tandem chromosomal duplication were efficiently obtained from the regenerated protoplast of the parental strains. However, the generation of the chromosomal duplication did not depend on the introduction of double-stranded breaks(DSBs) by I-SceI. The chromosomal duplications of these strains were stably maintained after five generations of culture under nonselective conditions. The strains bearing the tandem chromosomal duplication in the 700-kb region of chromosome 2 showed highly increased protease activity in solid-state culture, indicating that the duplication of large chromosomal segments could be a useful new breeding technology and gene analysis method.

Advances in ultra-high performance liquid chromatography coupled to tandem mass spectrometry for sensitive detection of several food allergens in complex and processed foodstuffs.

PubMed

Planque, M; Arnould, T; Dieu, M; Delahaut, P; Renard, P; Gillard, N

2016-09-16

Sensitive detection of food allergens is affected by food processing and foodstuff complexity. It is therefore a challenge to detect cross-contamination in food production that could endanger an allergic customer's life. Here we used ultra-high performance liquid chromatography coupled to tandem mass spectrometry for simultaneous detection of traces of milk (casein, whey protein), egg (yolk, white), soybean, and peanut allergens in different complex and/or heat-processed foodstuffs. The method is based on a single protocol (extraction, trypsin digestion, and purification) applicable to the different tested foodstuffs: chocolate, ice cream, tomato sauce, and processed cookies. The determined limits of quantitation, expressed in total milk, egg, peanut, or soy proteins (and not soluble proteins) per kilogram of food, are: 0.5mg/kg for milk (detection of caseins), 5mg/kg for milk (detection of whey), 2.5mg/kg for peanut, 5mg/kg for soy, 3.4mg/kg for egg (detection of egg white), and 30.8mg/kg for egg (detection of egg yolk). The main advantage is the ability of the method to detect four major food allergens simultaneously in processed and complex matrices with very high sensitivity and specificity. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Thieno[3,2-b]indoles via Halogen Dance and Ligand-Controlled One-Pot Sequential Coupling Reaction.

PubMed

Hayashi, Yuki; Okano, Kentaro; Mori, Atsunori

2018-02-16

A two-pot synthesis of thieno[3,2-b]indole from 2,5-dibromothiophene is described. A halogen dance of 2,5-dibromothiophene was performed with LDA, and subsequent Negishi coupling was performed with 2-iodoaniline derivatives to provide the corresponding coupling products. The resulting two bromo groups have different reactivities, which were utilized for the one-pot Suzuki-Miyaura coupling/intramolecular Buchwald-Hartwig amination to produce thieno[3,2-b]indole via an assisted tandem catalysis that involved in situ ligand exchange.

Nitro-fatty acid metabolome: saturation, desaturation, beta-oxidation, and protein adduction.

PubMed

Rudolph, Volker; Schopfer, Francisco J; Khoo, Nicholas K H; Rudolph, Tanja K; Cole, Marsha P; Woodcock, Steven R; Bonacci, Gustavo; Groeger, Alison L; Golin-Bisello, Franca; Chen, Chen-Shan; Baker, Paul R S; Freeman, Bruce A

2009-01-16

Nitrated derivatives of fatty acids (NO2-FA) are pluripotent cell-signaling mediators that display anti-inflammatory properties. Current understanding of NO2-FA signal transduction lacks insight into how or if NO2-FA are modified or metabolized upon formation or administration in vivo. Here the disposition and metabolism of nitro-9-cis-octadecenoic (18:1-NO2) acid was investigated in plasma and liver after intravenous injection in mice. High performance liquid chromatography-tandem mass spectrometry analysis showed that no 18:1-NO2 or metabolites were detected under basal conditions, whereas administered 18:1-NO2 is rapidly adducted to plasma thiol-containing proteins and glutathione. NO2-FA are also metabolized via beta-oxidation, with high performance liquid chromatography-tandem mass spectrometry analysis of liver lipid extracts of treated mice revealing nitro-7-cis-hexadecenoic acid, nitro-5-cis-tetradecenoic acid, and nitro-3-cis-dodecenoic acid and corresponding coenzyme A derivatives of 18:1-NO2 as metabolites. Additionally, a significant proportion of 18:1-NO2 and its metabolites are converted to nitroalkane derivatives by saturation of the double bond, and to a lesser extent are desaturated to diene derivatives. There was no evidence of the formation of nitrohydroxyl or conjugated ketone derivatives in organs of interest, metabolites expected upon 18:1-NO2 hydration or nitric oxide (*NO) release. Plasma samples from treated mice had significant extents of protein-adducted 18:1-NO2 detected by exchange to added beta-mercaptoethanol. This, coupled with the observation of 18:1-NO2 release from glutathione-18:1-NO2 adducts, supports that reversible and exchangeable NO2-FA-thiol adducts occur under biological conditions. After administration of [3H]18:1-NO2, 64% of net radiolabel was recovered 90 min later in plasma (0.2%), liver (18%), kidney (2%), adipose tissue (2%), muscle (31%), urine (6%), and other tissue compartments, and may include metabolites not yet

Low-temperature-processed efficient semi-transparent planar perovskite solar cells for bifacial and tandem applications

PubMed Central

Fu, Fan; Feurer, Thomas; Jäger, Timo; Avancini, Enrico; Bissig, Benjamin; Yoon, Songhak; Buecheler, Stephan; Tiwari, Ayodhya N.

2015-01-01

Semi-transparent perovskite solar cells are highly attractive for a wide range of applications, such as bifacial and tandem solar cells; however, the power conversion efficiency of semi-transparent devices still lags behind due to missing suitable transparent rear electrode or deposition process. Here we report a low-temperature process for efficient semi-transparent planar perovskite solar cells. A hybrid thermal evaporation–spin coating technique is developed to allow the introduction of PCBM in regular device configuration, which facilitates the growth of high-quality absorber, resulting in hysteresis-free devices. We employ high-mobility hydrogenated indium oxide as transparent rear electrode by room-temperature radio-frequency magnetron sputtering, yielding a semi-transparent solar cell with steady-state efficiency of 14.2% along with 72% average transmittance in the near-infrared region. With such semi-transparent devices, we show a substantial power enhancement when operating as bifacial solar cell, and in combination with low-bandgap copper indium gallium diselenide we further demonstrate 20.5% efficiency in four-terminal tandem configuration. PMID:26576667

Low-temperature-processed efficient semi-transparent planar perovskite solar cells for bifacial and tandem applications.

PubMed

Fu, Fan; Feurer, Thomas; Jäger, Timo; Avancini, Enrico; Bissig, Benjamin; Yoon, Songhak; Buecheler, Stephan; Tiwari, Ayodhya N

2015-11-18

Semi-transparent perovskite solar cells are highly attractive for a wide range of applications, such as bifacial and tandem solar cells; however, the power conversion efficiency of semi-transparent devices still lags behind due to missing suitable transparent rear electrode or deposition process. Here we report a low-temperature process for efficient semi-transparent planar perovskite solar cells. A hybrid thermal evaporation-spin coating technique is developed to allow the introduction of PCBM in regular device configuration, which facilitates the growth of high-quality absorber, resulting in hysteresis-free devices. We employ high-mobility hydrogenated indium oxide as transparent rear electrode by room-temperature radio-frequency magnetron sputtering, yielding a semi-transparent solar cell with steady-state efficiency of 14.2% along with 72% average transmittance in the near-infrared region. With such semi-transparent devices, we show a substantial power enhancement when operating as bifacial solar cell, and in combination with low-bandgap copper indium gallium diselenide we further demonstrate 20.5% efficiency in four-terminal tandem configuration.

Alpha particle confinement in tandem mirrors

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

Devoto, R.S.; Ohnishi, M.; Kerns, J.

1980-10-10

Mechanisms leading to loss of alpha particles from non-axisymmetric tandem mirrors are considered. Stochastic diffusion due to bounce-drift resonances, which can cause rapid radial losses of high-energy alpha particles, can be suppressed by imposing a 20% rise in axisymmetric fields before the quadrupole transition sections. Alpha particles should then be well-confined until thermal energies when they enter the resonant plateau require. A fast code for computation of drift behavior in reactors is described. Sample calculations are presented for resonant particles in a proposed coil set for the Tandem Mirror Next Step.

Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

DOE PAGES

Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; ...

2014-09-30

G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62).more » These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10 –19 to 25 × 10 –19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn 2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.« less

Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation

PubMed Central

Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan

2015-01-01

COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd0 nanoparticles into it. An 18–20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) <0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using ‘non-boronic acid’ substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable. PMID:26057044

Coupling Drosophila melanogaster Cryptochrome Light Activation and Oxidation of the Kvβ Subunit Hyperkinetic NADPH Cofactor.

PubMed

Hong, Gongyi; Pachter, Ruth; Ritz, Thorsten

2018-06-28

Motivated by the observations on the involvement of light-induced processes in the Drosophila melanogaster cryptochrome (DmCry) in regulation of the neuronal firing rate, which is achieved by a redox-state change of its voltage-dependent K + channel Kvβ subunit hyperkinetic (Hk) reduced nicotinamide adenine dinucleotide phosphate (NADPH) cofactor, we propose in this work two hypothetical pathways that may potentially enable such coupling. In the first pathway, triggered by blue-light-induced formation of a radical pair [FAD •- TRP •+ ] in DmCry, the hole (TRP •+ ) may hop to Hk, for example, through a tryptophan chain and oxidize NADPH, possibly leading to inhibition of the N-terminus inactivation in the K + channel. In a second possible pathway, DmCry's FAD •- is reoxidized by molecular oxygen, producing H 2 O 2 , which then diffuses to Hk and oxidizes NADPH. In this work, by applying a combination of quantum and empirical-based methods for free-energy calculations, we find that the oxidation of NADPH by TRP •+ or H 2 O 2 and the reoxidation of FAD •- by O 2 are thermodynamically feasible. Our results may have an implication in identifying a magnetic sensing signal transduction pathway, specifically upon Drosophila's Hk NADPH cofactor oxidation, with a subsequent inhibition of the K + channel N-terminus inactivation gate, permitting K + flux.

Tandem internal models execute motor learning in the cerebellum.

PubMed

Honda, Takeru; Nagao, Soichi; Hashimoto, Yuji; Ishikawa, Kinya; Yokota, Takanori; Mizusawa, Hidehiro; Ito, Masao

2018-06-25

In performing skillful movement, humans use predictions from internal models formed by repetition learning. However, the computational organization of internal models in the brain remains unknown. Here, we demonstrate that a computational architecture employing a tandem configuration of forward and inverse internal models enables efficient motor learning in the cerebellum. The model predicted learning adaptations observed in hand-reaching experiments in humans wearing a prism lens and explained the kinetic components of these behavioral adaptations. The tandem system also predicted a form of subliminal motor learning that was experimentally validated after training intentional misses of hand targets. Patients with cerebellar degeneration disease showed behavioral impairments consistent with tandemly arranged internal models. These findings validate computational tandemization of internal models in motor control and its potential uses in more complex forms of learning and cognition. Copyright © 2018 the Author(s). Published by PNAS.

Quality evaluation of tandem mass spectral libraries.

PubMed

Oberacher, Herbert; Weinmann, Wolfgang; Dresen, Sebastian

2011-06-01

Tandem mass spectral libraries are gaining more and more importance for the identification of unknowns in different fields of research, including metabolomics, forensics, toxicology, and environmental analysis. Particularly, the recent invention of reliable, robust, and transferable libraries has increased the general acceptance of these tools. Herein, we report on results obtained from thorough evaluation of the match reliabilities of two tandem mass spectral libraries: the MSforID library established by the Oberacher group in Innsbruck and the Weinmann library established by the Weinmann group in Freiburg. Three different experiments were performed: (1) Spectra of the libraries were searched against their corresponding library after excluding either this single compound-specific spectrum or all compound-specific spectra prior to searching; (2) the libraries were searched against each other using either library as reference set or sample set; (3) spectra acquired on different mass spectrometric instruments were matched to both libraries. Almost 13,000 tandem mass spectra were included in this study. The MSforID search algorithm was used for spectral matching. Statistical evaluation of the library search results revealed that principally both libraries enable the sensitive and specific identification of compounds. Due to higher mass accuracy of the QqTOF compared with the QTrap instrument, matches to the MSforID library were more reliable when comparing spectra with both libraries. Furthermore, only the MSforID library was shown to be efficiently transferable to different kinds of tandem mass spectrometers, including "tandem-in-time" instruments; this is due to the coverage of a large range of different collision energy settings-including the very low range-which is an outstanding characteristics of the MSforID library.

Solution for blank and matrix difficulties encountered during phthalate analysis of edible oils by high performance liquid chromatography coupled with tandem mass spectrometry.

PubMed

Vavrouš, Adam; Pavloušková, Jana; Ševčík, Václav; Vrbík, Karel; Čabala, Radomír

2016-07-22

Worldwide production of phthalates has led to their undesirable presence in the food chain. Particularly edible oils have become an area of growing concern owing to numerous reported occurrences of phthalates. The analytical methods used in this field face difficulties associated mainly with matrix complexity or phthalate contamination which this study has aimed to describe and resolve. The proposed procedure consisting of liquid-liquid extraction, solid phase extraction and high performance liquid chromatography coupled with tandem mass spectrometry allowed us to analyze simultaneously 6 individual phthalates and 2 phthalate isomeric mixtures. DSC-18 SPE phase was selected for cleanup owing to the most efficient co-extract removal (assessed using high resolution mass spectrometry). Several sources of phthalate contamination were identified, however, the mobile phase was the most serious. The key improvement was achieved by equipping a contamination trap, a 50-mm reverse phase HPLC column, generating a delay between target and mobile phase peaks of the same compounds. RSDs ranging between 2.4 and 16 % confirm good precision and LOQs between 5.5 and 110μgkg(-1) reflect satisfactory blank management. With up to 19 occurrences in 25 analyzed edible oil samples and levels up to 33mgkg(-1), bis(2-ethylhexyl), diisononyl and diisodecyl phthalates were the most important contaminants. Copyright © 2016 Elsevier B.V. All rights reserved.

Calculation of the Lateral Stability of a Directly Coupled Tandem-Towed Fighter Airplane and Correlation with Experimental Data

NASA Technical Reports Server (NTRS)

Shanks, Robert E.

1958-01-01

A theoretical method is presented for predicting the dynamic lateral stability characteristics of an airplane towed in tandem by a much larger airplane. Values of period and time to damp to one-half amplitude and rolling motions calculated by an analog computer have been correlated with results of two experimental investigations conducted in the Langley free-flight tunnel which were part of a U.S. Air Force program (Project FICON) to develop a satisfactory arrangement by which a bomber could tow a parasite fighter. In general, the theoretical results agree with the experimental results.

Single-task and dual-task tandem gait test performance after concussion.

PubMed

Howell, David R; Osternig, Louis R; Chou, Li-Shan

2017-07-01

To compare single-task and dual-task tandem gait test performance between athletes after concussion with controls on observer-timed, spatio-temporal, and center-of-mass (COM) balance control measurements. Ten participants (19.0±5.5years) were prospectively identified and completed a tandem gait test protocol within 72h of concussion and again 1 week, 2 weeks, 1 month, and 2 months post-injury. Seven uninjured controls (20.0±4.5years) completed the same protocol in similar time increments. Tandem gait test trials were performed with (dual-task) and without (single-task) concurrently performing a cognitive test as whole-body motion analysis was performed. Outcome variables included test completion time, average tandem gait velocity, cadence, and whole-body COM frontal plane displacement. Concussion participants took significantly longer to complete the dual-task tandem gait test than controls throughout the first 2 weeks post-injury (mean time=16.4 [95% CI: 13.4-19.4] vs. 10.1 [95% CI: 6.4-13.7] seconds; p=0.03). Single-task tandem gait times were significantly lower 72h post-injury (p=0.04). Dual-task cadence was significantly lower for concussion participants than controls (89.5 [95% CI: 68.6-110.4] vs. 127.0 [95% CI: 97.4-156.6] steps/minute; p=0.04). Moderately-high to high correlations between tandem gait test time and whole-body COM medial-lateral displacement were detected at each time point during dual-task gait (r s =0.70-0.93; p=0.03-0.001). Adding a cognitive task during the tandem gait test resulted in longer detectable deficits post-concussion compared to the traditional single-task tandem gait test. As a clinical tool to assess dynamic motor function, tandem gait may assist with return to sport decisions after concussion. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Oxidative coupling of a feruloyl-arabinoxylan trisaccharide (FAXX) in the walls of living maize cells requires endogenous hydrogen peroxide and is controlled by a low-Mr apoplastic inhibitor.

PubMed

Encina, Antonio; Fry, Stephen C

2005-12-01

Feruloyl-polysaccharides can be oxidatively coupled in isolated cell walls by peroxidase plus exogenous H(2)O(2) in vitro, but the extent to which similar reactions may occur in the apoplast in vivo was unclear. Numerous cellular factors potentially control feruloyl coupling in vivo, and their net controlling influence is not readily studied in vitro. Therefore, we have monitored apoplastic feruloyl coupling in cultured maize cells in vivo using a radiolabelled model substrate, 5-O-feruloyl-alpha-L: -arabinofuranosyl-(1-->3)-beta-D: -xylopyranosyl-(1-->4)-D: -xylose (FAXX). FAXX was expected to permeate the wall and to undergo reactions analogous to those normally exhibited by apoplastic feruloyl-polysaccharides in vivo. Little difference was found between the fates of [feruloyl-(14)C]FAXX and [pentosyl-(3)H]FAXX, indicating negligible apoplastic hydrolase or transferase activities. Very little radioactivity entered the protoplasm. Maize cells that had recently been washed in fresh medium were able to bind most of the FAXX (90%) in their cell walls, regardless of the age of the culture. During wall-binding, the [(14)C]feruloyl groups were converted to [(14)C]dehydrodiferulates and larger coupling products, as revealed by TLC after alkaline hydrolysis. As expected for an oxidative reaction, wall-binding was delayed by added anti-oxidants (ascorbate, ferulate, sinapate, chlorogenate or rutin). It was also completely inhibited by iodide, an H(2)O(2)-scavenger, indicating a role for peroxidase rather than oxidase. The observations indicate that oxidative coupling of feruloyl groups occurred within the cell wall, dependent on endogenous apoplastic H(2)O(2) and wall-localised peroxidase, in vivo. Cells that had not recently been washed in fresh medium were much less able to bind FAXX, indicating the presence in the apoplast of an endogenous inhibitor of oxidative coupling. This inhibitor was of low M(r), was destroyed by heating, and remained in the aqueous phase (p

Structural characterization of electrochemically and in vitro biologically generated oxidation products of atorvastatin using UHPLC/MS/MS.

PubMed

Jirásko, Robert; Mikysek, Tomáš; Chagovets, Vitaliy; Vokřál, Ivan; Holčapek, Michal

2013-09-01

Ultrahigh-performance liquid chromatography coupled with high-mass-accuracy tandem mass spectrometry (UHPLC-MS-MS) has been used for elucidation of the structures of oxidation products of atorvastatin (AT), one of the most popular commercially available drugs. The purpose of the study was identification of AT metabolites in rat hepatocytes and comparison with electrochemically generated oxidation products. AT was incubated with rat hepatocytes for 24 h. Electrochemical oxidation of AT was performed by use of a three-electrode off-line system with a glassy carbon working electrode. Three supporting electrolytes (0.1 mol L(-1) H2SO4, 0.1 mol L(-1) HCl, and 0.1 mol L(-1) NaCl) were tested, and dependence on pH was also investigated. AT undergoes oxidation by a single irreversible process at approximately +1.0 V vs. Ag/AgCl electrode. The results obtained revealed a simple and relatively fast way of determining the type of oxidation and its position, on the basis of characteristic neutral losses (NLs) and fragment ions. Unfortunately, different products were obtained by electrochemical oxidation and biotransformation of AT. High-mass-accuracy measurement combined with different UHPLC-MS-MS scans, for example reconstructed ion-current chromatograms, constant neutral loss chromatograms, or exact mass filtering, enable rapid identification of drug-related compounds. β-Oxidation, aromatic hydroxylation of the phenylaminocarbonyl group, sulfation, AT lactone and glycol formation were observed in rat biotransformation samples. In contrast, a variety of oxidation reactions on the conjugated skeleton of isopropyl substituent of AT were identified as products of electrolysis.

Perovskite/silicon-based heterojunction tandem solar cells with 14.8% conversion efficiency via adopting ultrathin Au contact

NASA Astrophysics Data System (ADS)

Fan, Lin; Wang, Fengyou; Liang, Junhui; Yao, Xin; Fang, Jia; Zhang, Dekun; Wei, Changchun; Zhao, Ying; Zhang, Xiaodan

2017-01-01

A rising candidate for upgrading the performance of an established narrow-bandgap solar technology without adding much cost is to construct the tandem solar cells from a crystalline silicon bottom cell and a high open-circuit voltage top cell. Here, we present a four-terminal tandem solar cell architecture consisting of a self-filtered planar architecture perovskite top cell and a silicon heterojunction bottom cell. A transparent ultrathin gold electrode has been used in perovskite solar cells to achieve a semi-transparent device. The transparent ultrathin gold contact could provide a better electrical conductivity and optical reflectance-scattering to maintain the performance of the top cell compared with the traditional metal oxide contact. The four-terminal tandem solar cell yields an efficiency of 14.8%, with contributions of the top (8.98%) and the bottom cell (5.82%), respectively. We also point out that in terms of optical losses, the intermediate contact of self-filtered tandem architecture is the uppermost problem, which has been addressed in this communication, and the results show that reducing the parasitic light absorption and improving the long wavelength range transmittance without scarifying the electrical properties of the intermediate hole contact layer are the key issues towards further improving the efficiency of this architecture device. Project supported by the International Cooperation Projects of the Ministry of Science and Technology (No. 2014DFE60170), the National Natural Science Foundation of China (Nos. 61474065, 61674084), the Tianjin Research Key Program of Application Foundation and Advanced Technology (No. 15JCZDJC31300), the Key Project in the Science & Technology Pillar Program of Jiangsu Province (No. BE2014147-3), and the 111 Project (No. B16027).

Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: significant influence of the order of combining aryl Grignard reagents with titanate.

PubMed

Liu, Kun Ming; Wei, Juan; Duan, Xin Fang

2015-03-18

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant.

Control of the neurovascular coupling by nitric oxide-dependent regulation of astrocytic Ca2+ signaling

PubMed Central

Muñoz, Manuel F.; Puebla, Mariela; Figueroa, Xavier F.

2015-01-01

Neuronal activity must be tightly coordinated with blood flow to keep proper brain function, which is achieved by a mechanism known as neurovascular coupling. Then, an increase in synaptic activity leads to a dilation of local parenchymal arterioles that matches the enhanced metabolic demand. Neurovascular coupling is orchestrated by astrocytes. These glial cells are located between neurons and the microvasculature, with the astrocytic endfeet ensheathing the vessels, which allows fine intercellular communication. The neurotransmitters released during neuronal activity reach astrocytic receptors and trigger a Ca2+ signaling that propagates to the endfeet, activating the release of vasoactive factors and arteriolar dilation. The astrocyte Ca2+ signaling is coordinated by gap junction channels and hemichannels formed by connexins (Cx43 and Cx30) and channels formed by pannexins (Panx-1). The neuronal activity-initiated Ca2+ waves are propagated among neighboring astrocytes directly via gap junctions or through ATP release via connexin hemichannels or pannexin channels. In addition, Ca2+ entry via connexin hemichannels or pannexin channels may participate in the regulation of the astrocyte signaling-mediated neurovascular coupling. Interestingly, nitric oxide (NO) can activate connexin hemichannel by S-nitrosylation and the Ca2+-dependent NO-synthesizing enzymes endothelial NO synthase (eNOS) and neuronal NOS (nNOS) are expressed in astrocytes. Therefore, the astrocytic Ca2+ signaling triggered in neurovascular coupling may activate NO production, which, in turn, may lead to Ca2+ influx through hemichannel activation. Furthermore, NO release from the hemichannels located at astrocytic endfeet may contribute to the vasodilation of parenchymal arterioles. In this review, we discuss the mechanisms involved in the regulation of the astrocytic Ca2+ signaling that mediates neurovascular coupling, with a special emphasis in the possible participation of NO in this process

Negotiating Multiple Identities through eTandem Learning Experiences

ERIC Educational Resources Information Center

Yang, Se Jeong; Yi, Youngjoo

2017-01-01

Much of eTandem research has investigated either linguistic or cross-cultural aspects of second language (L2) learning, but relatively little is known about issues of identity construction in an eTandem context. Situating the study within theories and research of language learner identity, we examined ways in which two adult L2 learners (a Korean…

Observation of T-2 and HT-2 glucosides from Fusarium sporotrichioides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS)

USDA-ARS?s Scientific Manuscript database

Cultures of Fusarium sporotrichioides were extracted and subjected to evaluation by high performance liquid chromatography – tandem mass spectrometry (LC-MS/MS). Along with the expected T-2 and HT-2 toxins, compounds 162 m/z higher than the toxins were observed. Fragmentation behavior of the larger ...

Two stacked tandem white organic light-emitting diodes employing WO3 as a charge generation layer

NASA Astrophysics Data System (ADS)

Bin, Jong-Kwan; Lee, Na Yeon; Lee, SeungJae; Seo, Bomin; Yang, JoongHwan; Kim, Jinook; Yoon, Soo Young; Kang, InByeong

2016-09-01

Recently, many studies have been conducted to improve the electroluminescence (EL) performance of organic lightemitting diodes (OLEDs) by using appropriate organic or inorganic materials as charge generation layer (CGL) for their application such as full color displays, backlight units, and general lighting source. In a stacked tandem white organic light-emitting diodes (WOLEDs), a few emitting units are electrically interconnected by a CGL, which plays the role of generating charge carriers, and then facilitate the injection of it into adjacent emitting units. In the present study, twostacked WOLEDs were fabricated by using tungsten oxide (WO3) as inorganic charge generation layer and 1,4,5,8,9,11- hexaazatriphenylene hexacarbonitrile (HAT-CN) as organic charge generation layer (P-CGL). Organic P-CGL materials were used due to their ease of use in OLED fabrication as compared to their inorganic counterparts. To obtain high efficiency, we demonstrate two-stacked tandem WOLEDs as follows: ITO/HIL/HTL/HTL'/B-EML/ETL/N-CGL/P-CGL (WO3 or HAT-CN)/HTL″/YG-EML/ETL/LiF/Al. The tandem devices with blue- and yellow-green emitting layers were sensitive to the thickness of an adjacent layer, hole transporting layer for the YG emitting layer. The WOLEDs containing the WO3 as charge generation layer reach a higher power efficiency of 19.1 lm/W and the current efficiency of 51.2 cd/A with the white color coordinate of (0.316, 0.318) than the power efficiency of 13.9 lm/W, and the current efficiency of 43.7 cd/A for organic CGL, HAT-CN at 10 mA/cm2, respectively. This performance with inserting WO3 as CGL exhibited the highest performance with excellent CIE color coordinates in the two-stacked tandem OLEDs.

SYMTRAN - A Time-dependent Symmetric Tandem Mirror Transport Code

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

Hua, D; Fowler, T

2004-06-15

A time-dependent version of the steady-state radial transport model in symmetric tandem mirrors in Ref. [1] has been coded up and first tests performed. Our code, named SYMTRAN, is an adaptation of the earlier SPHERE code for spheromaks, now modified for tandem mirror physics. Motivated by Post's new concept of kinetic stabilization of symmetric mirrors, it is an extension of the earlier TAMRAC rate-equation code omitting radial transport [2], which successfully accounted for experimental results in TMX. The SYMTRAN code differs from the earlier tandem mirror radial transport code TMT in that our code is focused on axisymmetric tandem mirrorsmore » and classical diffusion, whereas TMT emphasized non-ambipolar transport in TMX and MFTF-B due to yin-yang plugs and non-symmetric transitions between the plugs and axisymmetric center cell. Both codes exhibit interesting but different non-linear behavior.« less

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake.

PubMed

Deutzmann, Joerg S; Stief, Peter; Brandes, Josephin; Schink, Bernhard

2014-12-23

Anaerobic methane oxidation coupled to denitrification, also known as "nitrate/nitrite-dependent anaerobic methane oxidation" (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660-4,890 µmol CH4⋅m(-2)⋅d(-1)) and actual rates calculated from microsensor profiles (31-437 µmol CH4⋅m(-2)⋅d(-1)) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones.

Quantitative characterization of colloidal assembly of graphene oxide-silver nanoparticle hybrids using aerosol differential mobility-coupled mass analyses.

PubMed

Nguyen, Thai Phuong; Chang, Wei-Chang; Lai, Yen-Chih; Hsiao, Ta-Chih; Tsai, De-Hao

2017-10-01

In this work, we develop an aerosol-based, time-resolved ion mobility-coupled mass characterization method to investigate colloidal assembly of graphene oxide (GO)-silver nanoparticle (AgNP) hybrid nanostructure on a quantitative basis. Transmission electron microscopy (TEM) and zeta potential (ZP) analysis were used to provide visual information and elemental-based particle size distributions, respectively. Results clearly show a successful controlled assembly of GO-AgNP by electrostatic-directed heterogeneous aggregation between GO and bovine serum albumin (BSA)-functionalized AgNP under an acidic environment. Additionally, physical size, mass, and conformation (i.e., number of AgNP per nanohybrid) of GO-AgNP were shown to be proportional to the number concentration ratio of AgNP to GO (R) and the selected electrical mobility diameter. An analysis of colloidal stability of GO-AgNP indicates that the stability increased with its absolute ZP, which was dependent on R and environmental pH. The work presented here provides a proof of concept for systematically synthesizing hybrid colloidal nanomaterials through the tuning of surface chemistry in aqueous phase with the ability in quantitative characterization. Graphical Abstract Colloidal assembly of graphene oxide-silver nanoparticle hybrids characterized by aerosol differential mobility-coupled mass analyses.

Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[ de]chromenes.

PubMed

Fang, Feifei; Zhang, Chunmei; Zhou, Chaofan; Li, Yazhou; Zhou, Yu; Liu, Hong

2018-04-06

Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[ de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloaddition with another diazo compound. Intriguingly, synthesis of substituted benzo[ de]chromenes and their decarboxylation products could be realized by controlling the reaction conditions. These reactions have a broad range of substrates, moderate to good yields, and high regioselectivity.

A novel mechanism of tandem activation of ryanodine receptors by cytosolic and SR luminal Ca2+ during excitation-contraction coupling in atrial myocytes.

PubMed

Maxwell, Joshua T; Blatter, Lothar A

2017-06-15

In atrial myocytes excitation-contraction coupling is strikingly different from ventricle because atrial myocytes lack a transverse tubule membrane system: Ca 2+ release starts in the cell periphery and propagates towards the cell centre by Ca 2+ -induced Ca 2+ release from the sarcoplasmic reticulum (SR) Ca 2+ store. The cytosolic Ca 2+ sensitivity of the ryanodine receptor (RyRs) Ca 2+ release channel is low and it is unclear how Ca 2+ release can be activated in the interior of atrial cells. Simultaneous confocal imaging of cytosolic and intra-SR calcium revealed a transient elevation of store Ca 2+ that we termed 'Ca 2+ sensitization signal'. We propose a novel paradigm of atrial ECC that is based on tandem activation of the RyRs by cytosolic and luminal Ca 2+ through a 'fire-diffuse-uptake-fire' (or FDUF) mechanism: Ca 2+ uptake by SR Ca 2+ pumps at the propagation front elevates Ca 2+ inside the SR locally, leading to luminal RyR sensitization and lowering of the cytosolic Ca 2+ activation threshold. In atrial myocytes Ca 2+ release during excitation-contraction coupling (ECC) is strikingly different from ventricular myocytes. In many species atrial myocytes lack a transverse tubule system, dividing the sarcoplasmic reticulum (SR) Ca 2+ store into the peripheral subsarcolemmnal junctional (j-SR) and the much more abundant central non-junctional (nj-SR) SR. Action potential (AP)-induced Ca 2+ entry activates Ca 2+ -induced Ca 2+ release (CICR) from j-SR ryanodine receptor (RyR) Ca 2+ release channels. Peripheral elevation of [Ca 2+ ] i initiates CICR from nj-SR and sustains propagation of CICR to the cell centre. Simultaneous confocal measurements of cytosolic ([Ca 2+ ] i ; with the fluorescent Ca 2+ indicator rhod-2) and intra-SR ([Ca 2+ ] SR ; fluo-5N) Ca 2+ in rabbit atrial myocytes revealed that Ca 2+ release from j-SR resulted in a cytosolic Ca 2+ transient of higher amplitude compared to release from nj-SR; however, the degree of depletion of j-SR [Ca 2

Cooperative cell motility during tandem locomotion of amoeboid cells

PubMed Central

Bastounis, Effie; Álvarez-González, Begoña; del Álamo, Juan C.; Lasheras, Juan C.; Firtel, Richard A.

2016-01-01

Streams of migratory cells are initiated by the formation of tandem pairs of cells connected head to tail to which other cells subsequently adhere. The mechanisms regulating the transition from single to streaming cell migration remain elusive, although several molecules have been suggested to be involved. In this work, we investigate the mechanics of the locomotion of Dictyostelium tandem pairs by analyzing the spatiotemporal evolution of their traction adhesions (TAs). We find that in migrating wild-type tandem pairs, each cell exerts traction forces on stationary sites (∼80% of the time), and the trailing cell reuses the location of the TAs of the leading cell. Both leading and trailing cells form contractile dipoles and synchronize the formation of new frontal TAs with ∼54-s time delay. Cells not expressing the lectin discoidin I or moving on discoidin I–coated substrata form fewer tandems, but the trailing cell still reuses the locations of the TAs of the leading cell, suggesting that discoidin I is not responsible for a possible chemically driven synchronization process. The migration dynamics of the tandems indicate that their TAs’ reuse results from the mechanical synchronization of the leading and trailing cells’ protrusions and retractions (motility cycles) aided by the cell–cell adhesions. PMID:26912787

A tandem mirror hybrid plume plasma propulsion facility

NASA Technical Reports Server (NTRS)

Yang, T. F.; Krueger, W. A.; Peng, S.; Urbahn, J.; Chang-Diaz, F. R.

1988-01-01

This paper discusses a novel concept in electrodeless plasma propulsion, in which the materials problems are ameliorated by an electrodeless magnetic confinement scheme borrowed from the tandem mirror approach to controlled thermonuclear fusion. The concept also features a two-stage magnetic nozzle with an annular hypersonic coaxial gas injector near the throat. The nozzle produces hybrid plume by the coaxial injection of hypersonic neutral gas, and the gas layer thus formed protects the material walls from the hot plasma and, through increased collisions, helps detach it from the diverging magnetic field. The tandem mirror plasma propulsion facility is capable of delivering a variable I(sp). The results of numerical simulation of this concept are presented together with those from an experimental tandem-mirror plasma propulsion device.

Reduction of bonding resistance of two-terminal III-V/Si tandem solar cells fabricated using smart-stack technology

NASA Astrophysics Data System (ADS)

Baba, Masaaki; Makita, Kikuo; Mizuno, Hidenori; Takato, Hidetaka; Sugaya, Takeyoshi; Yamada, Noboru

2017-12-01

This paper describes a method that remarkably reduces the bonding resistance of mechanically stacked two-terminal GaAs/Si and InGaP/Si tandem solar cells, where the top and bottom cells are bonded using a Pd nanoparticle array. A transparent conductive oxide (TCO) layer, which partially covers the surface of the Si bottom cell below the electrodes of the III-V top cell, significantly enhances the fill factor (FF) and cell conversion efficiency. The partial TCO layer reduces the bonding resistance and thus, increases the FF and efficiency of InGaP/Si by factors of 1.20 and 1.11, respectively. Eventually, the efficiency exceeds 15%. Minimizing the optical losses at the bonding interfaces of the TCO layer is important in the fabrication of high-efficiency solar cells. To help facilitate this, the optical losses in the tandem solar cells are thoroughly characterized through optical simulations and experimental verifications.

[Determination of 23 antibiotics and 3 β-agonists in livestock drinking water by ultra performance liquid chromatography-tandem mass spectrometry coupled with solid-phase extraction].

PubMed

Shi, Ao

2016-02-01

A method has been developed for the simultaneous determination of 23 antibiotics (four categories) and 3 β-agonists in livestock drinking water using solid-phase extraction and ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS). The samples were adjusted pH to 5. 0, added Na2EDTA, enriched and cleaned-up by an HLB solid-phase extraction cartridge. The target compounds were confirmed and quantified by UPLC-ESI MS/MS with external standard method for the anti- biotics and internal standard method for the β-agonists. The recoveries were assessed by using lab tap water as matrix. The average recoveries of the 23 antibiotics and the 3 β-agonists were in the range of 50. 7%-104. 6% and the relative standard deviations (RSDs) were 2. 6%-8. 8% (n= 3). Under the optimal conditions, the calibration curves of the 23 antibiotics and the 3 β-agonists showed good linearity with the correlation coefficients better than 0. 994. The limits of detection (LODs, S/N≥3) ranged from 0. 01-0. 20 ng/L. The developed method was applied to analyze the livestock drinking waters in 36 Beijing intensive livestock farms. The results showed that some antibiotics were detected.

Monitoring Bilingualism: Pedagogical Implications of the Bilingual Tandem Analyser

ERIC Educational Resources Information Center

Schwienhorst, Klaus; Borgia, Alexandre

2006-01-01

Tandem learning is the collaborative learning partnership of two language learners with complementary language combinations, for example an Irish student learning German and a German student learning English. One of the major principles in tandem learning, apart from reciprocity and learner autonomy, is balanced bilingualism. While learners may…

High Performance Tandem Perovskite/Polymer Solar Cells

NASA Astrophysics Data System (ADS)

Liu, Yao; Bag, Monojit; Page, Zachariah; Renna, Lawrence; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D.; Russell, Thomas

Combining perovskites with other inorganic materials, such as copper indium gallium diselenide (CIGS) or silicon, is enabling significant improvement in solar cell device performance. Here, we demonstrate a highly efficient hybrid tandem solar cell fabricated through a facile solution deposition approach to give a perovskite front sub-cell and a polymer:fullerene blend back sub-cell. This methodology eliminates the adverse effects of thermal annealing during perovskite fabrication on polymer solar cells. The record tandem solar cell efficiency of 15.96% is 40% greater than the corresponding perovskite-based single junction device and 65% greater than the polymer-based single junction device, while mitigating deleterious hysteresis effects often associated with perovskite solar cells. The hybrid tandem devices demonstrate the synergistic effects arising from the combination of perovskite and polymer-based materials for solar cells. This work was supported by the Department of Energy-supported Energy Frontier Research Center at the University of Massachusetts (DE-SC0001087). The authors acknowledge the W.M. Keck Electron Microscopy.

Synthesis of Ce doped ZnO nanoparticles coupled with graphene oxide as efficient photocatalyst for the degradation of dye under day light

NASA Astrophysics Data System (ADS)

Labhane, P. K.; Patle, L. B.; Huse, V. R.; Sonawane, G. H.

2018-05-01

Ce doped ZnO nanoparticles coupled with graphene oxide (Ce-ZnO/GO) photocatalyst was prepared by co-precipitation and wet impregnation method. The effect of Ce doping on ZnO and ZnO-GO composite has been evaluated by using XRD, Williamson-Hall Plot, FESEM and EDX data. Solar light photocatalytic activities of samples were evaluated spectrophotometrically by the degradation of methylene blue (MB). Ce doped ZnO coupled with GO shows excellent catalytic efficiency compared to other samples, degrading MB completely within 120 min under day light.

Development and validation of rapid multiresidue and multi-class analysis for antibiotics and anthelmintics in feed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Robert, Christelle; Brasseur, Pierre-Yves; Dubois, Michel; Delahaut, Philippe; Gillard, Nathalie

2016-08-01

A new multi-residue method for the analysis of veterinary drugs, namely amoxicillin, chlortetracycline, colistins A and B, doxycycline, fenbendazole, flubendazole, ivermectin, lincomycin, oxytetracycline, sulfadiazine, tiamulin, tilmicosin and trimethoprim, was developed and validated for feed. After acidic extraction, the samples were centrifuged, purified by SPE and analysed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. Quantitative validation was done in accordance with the guidelines laid down in European Commission Decision 2002/657/CE. Matrix-matched calibration with internal standards was used to reduce matrix effects. The target level was set at the authorised carryover level (1%) and validation levels were set at 0.5%, 1% and 1.5%. Method performances were evaluated by the following parameters: linearity (0.986 < R(2) < 0.999), precision (repeatability < 12.4% and reproducibility < 14.0%), accuracy (89% < recovery < 107%), sensitivity, decision limit (CCα), detection capability (CCβ), selectivity and expanded measurement uncertainty (k = 2).This method has been used successfully for three years for routine monitoring of antibiotic residues in feeds during which period 20% of samples were found to exceed the 1% authorised carryover limit and were deemed non-compliant.

On the nature of organic and inorganic centers that bifurcate electrons, coupling exergonic and endergonic oxidation-reduction reactions.

PubMed

Peters, John W; Beratan, David N; Schut, Gerrit J; Adams, Michael W W

2018-04-19

Bifurcating electrons to couple endergonic and exergonic electron-transfer reactions has been shown to have a key role in energy conserving redox enzymes. Bifurcating enzymes require a redox center that is capable of directing electron transport along two spatially separate pathways. Research into the nature of electron bifurcating sites indicates that one of the keys is the formation of a low potential oxidation state to satisfy the energetics required of the endergonic half reaction, indicating that any redox center (organic or inorganic) that can exist in multiple oxidation states with sufficiently separated redox potentials should be capable of electron bifurcation. In this Feature Article, we explore a paradigm for bifurcating electrons down independent high and low potential pathways, and describe redox cofactors that have been demonstrated or implicated in driving this unique biochemistry.

Determination of pesticide residues in samples of green minor crops by gas chromatography and ultra performance liquid chromatography coupled to tandem quadrupole mass spectrometry.

PubMed

Walorczyk, Stanisław; Drożdżyński, Dariusz; Kierzek, Roman

2015-01-01

A method was developed for pesticide analysis in samples of high chlorophyll content belonging to the group of minor crops. A new type of sorbent, known as ChloroFiltr, was employed for dispersive-solid phase extraction cleanup (dispersive-SPE) to reduce the unwanted matrix background prior to concurrent analysis by gas chromatography and ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometry (GC-MS/MS and UPLC-MS/MS). Validation experiments were carried out on green, unripe plants of lupin, white mustard and sorghum. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.5 mg kg(-1) fell in the range between 68 and 120% (98% on average) and 72-104% (93% on average) with relative standard deviation (RSD) values between 2 and 19% (7% on average) and 3-16% (6% on average) by GC-MS/MS and UPLC-MS/MS technique, respectively. Because of strong enhancement or suppression matrix effects (absolute values >20%) which were exhibited by about 80% of the pesticide and matrix combinations, acceptably accurate quantification was achieved by using matrix-matched standards. Up to now, the proposed method has been successfully used to study the dissipation patterns of pesticides after application on lupin, white mustard, soya bean, sunflower and field bean in experimental plot trials conducted in Poland. Copyright © 2014 Elsevier B.V. All rights reserved.

Automated Lipid A Structure Assignment from Hierarchical Tandem Mass Spectrometry Data

NASA Astrophysics Data System (ADS)

Ting, Ying S.; Shaffer, Scott A.; Jones, Jace W.; Ng, Wailap V.; Ernst, Robert K.; Goodlett, David R.

2011-05-01

Infusion-based electrospray ionization (ESI) coupled to multiple-stage tandem mass spectrometry (MS n ) is a standard methodology for investigating lipid A structural diversity (Shaffer et al. J. Am. Soc. Mass. Spectrom. 18(6), 1080-1092, 2007). Annotation of these MS n spectra, however, has remained a manual, expert-driven process. In order to keep up with the data acquisition rates of modern instruments, we devised a computational method to annotate lipid A MS n spectra rapidly and automatically, which we refer to as hierarchical tandem mass spectrometry (HiTMS) algorithm. As a first-pass tool, HiTMS aids expert interpretation of lipid A MS n data by providing the analyst with a set of candidate structures that may then be confirmed or rejected. HiTMS deciphers the signature ions (e.g., A-, Y-, and Z-type ions) and neutral losses of MS n spectra using a species-specific library based on general prior structural knowledge of the given lipid A species under investigation. Candidates are selected by calculating the correlation between theoretical and acquired MS n spectra. At a false discovery rate of less than 0.01, HiTMS correctly assigned 85% of the structures in a library of 133 manually annotated Francisella tularensis subspecies novicida lipid A structures. Additionally, HiTMS correctly assigned 85% of the structures in a smaller library of lipid A species from Yersinia pestis demonstrating that it may be used across species.

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

USGS Publications Warehouse

Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

2017-01-01

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several

Role of gap junctional coupling in astrocytic networks in the determination of global ischaemia-induced oxidative stress and hippocampal damage.

PubMed

Perez Velazquez, Jose L; Kokarovtseva, Larisa; Sarbaziha, Raheleh; Jeyapalan, Zina; Leshchenko, Yevgen

2006-01-01

While there is evidence that gap junctions play important roles in the determination of cell injuries, there is not much known about mechanisms by which gap junctional communication may exert these functions. Using a global model of transient ischaemia in rats, we found that pretreatment with the gap junctional blockers carbenoxolone, 18alpha-glycyrrhetinic acid and endothelin, applied via cannulae implanted into the hippocampus in one hemisphere, resulted in decreased numbers of TUNEL-positive neurons, as compared with the contralateral hippocampus that received saline injection. Post-treatment with carbenoxolone for up to 30 min after the stroke injury still resulted in decreased cell death, but post-treatment at 90 min after the ischaemic insult did not result in differences in cell death. However, quinine, an inhibitor of Cx36-mediated gap junctional coupling, did not result in appreciable neuroprotection. Searching for a possible mechanism for the observed protective effects, possible actions of the gap junctional blockers in the electrical activity of the hippocampus during the ischaemic insult were assessed using intracerebral recordings, with no differences observed between the saline-injected and the contralateral drug-injected hippocampus. However, a significant reduction in lipid peroxides, a measure of free radical formation, in the hippocampus treated with carbenoxolone, revealed that the actions of gap junctional coupling during injuries may be causally related to oxidative stress. These observations suggest that coupling in glial networks may be functionally important in determining neuronal vulnerability to oxidative injuries.

Wing-wake interaction reduces power consumption in insect tandem wings

NASA Astrophysics Data System (ADS)

Lehmann, Fritz-Olaf

Insects are capable of a remarkable diversity of flight techniques. Dragonflies, in particular, are notable for their powerful aerial manoeuvres and endurance during prey catching or territory flights. While most insects such as flies, bees and wasps either reduced their hinds wings or mechanically coupled fore and hind wings, dragonflies have maintained two independent-controlled pairs of wings throughout their evolution. An extraordinary feature of dragonfly wing kinematics is wing phasing, the shift in flapping phase between the fore and hind wing periods. Wing phasing has previously been associated with an increase in thrust production, readiness for manoeuvrability and hunting performance. Recent studies have shown that wing phasing in tandem wings produces a twofold modulation in hind wing lift, but slightly reduces the maximum combined lift of fore and hind wings, compared to two wings flapping in isolation. Despite this disadvantage, however, wing phasing is effective in improving aerodynamic efficiency during flight by the removal of kinetic energy from the wake. Computational analyses demonstrate that this increase in flight efficiency may save up to 22% aerodynamic power expenditure compared to insects flapping only two wings. In terms of engineering, energetic benefits in four-wing flapping are of substantial interest in the field of biomimetic aircraft design, because the performance of man-made air vehicles is often limited by high-power expenditure rather than by lift production. This manuscript provides a summary on power expenditures and aerodynamic efficiency in flapping tandem wings by investigating wing phasing in a dynamically scaled robotic model of a hovering dragonfly.

Wing-wake interaction reduces power consumption in insect tandem wings

NASA Astrophysics Data System (ADS)

Lehmann, Fritz-Olaf

2009-05-01

Insects are capable of a remarkable diversity of flight techniques. Dragonflies, in particular, are notable for their powerful aerial manoeuvres and endurance during prey catching or territory flights. While most insects such as flies, bees and wasps either reduced their hinds wings or mechanically coupled fore and hind wings, dragonflies have maintained two independent-controlled pairs of wings throughout their evolution. An extraordinary feature of dragonfly wing kinematics is wing phasing, the shift in flapping phase between the fore and hind wing periods. Wing phasing has previously been associated with an increase in thrust production, readiness for manoeuvrability and hunting performance. Recent studies have shown that wing phasing in tandem wings produces a twofold modulation in hind wing lift, but slightly reduces the maximum combined lift of fore and hind wings, compared to two wings flapping in isolation. Despite this disadvantage, however, wing phasing is effective in improving aerodynamic efficiency during flight by the removal of kinetic energy from the wake. Computational analyses demonstrate that this increase in flight efficiency may save up to 22% aerodynamic power expenditure compared to insects flapping only two wings. In terms of engineering, energetic benefits in four-wing flapping are of substantial interest in the field of biomimetic aircraft design, because the performance of man-made air vehicles is often limited by high-power expenditure rather than by lift production. This manuscript provides a summary on power expenditures and aerodynamic efficiency in flapping tandem wings by investigating wing phasing in a dynamically scaled robotic model of a hovering dragonfly.

Rapid separation and characterization of diterpenoid alkaloids in processed roots of Aconitum carmichaeli using ultra high performance liquid chromatography coupled with hybrid linear ion trap-Orbitrap tandem mass spectrometry.

PubMed

Xu, Wen; Zhang, Jing; Zhu, Dayuan; Huang, Juan; Huang, Zhihai; Bai, Junqi; Qiu, Xiaohui

2014-10-01

The lateral root of Aconitum carmichaeli, a popular traditional Chinese medicine, has been widely used to treat rheumatic diseases. For decades, diterpenoid alkaloids have dominated the phytochemical and biomedical research on this plant. In this study, a rapid and sensitive method based on ultra high performance liquid chromatography coupled with linear ion trap-Orbitrap tandem mass spectrometry was developed to characterize the diterpenoid alkaloids in Aconitum carmichaeli. Based on an optimized chromatographic condition, more than 120 diterpenoid alkaloids were separated with good resolution. Using a systematic strategy that combines high resolution separation, highly accurate mass measurements and a good understanding of the diagnostic fragment-based fragmentation patterns, these diterpenoid alkaloids were identified or tentatively identified. The identification of these chemicals provided essential data for further phytochemical studies and toxicity research of Aconitum carmichaeli. Moreover, the ultra high performance liquid chromatography with linear ion trap-Orbitrap mass spectrometry platform was an effective and accurate tool for rapid qualitative analysis of secondary metabolite productions from natural resources. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

rTANDEM, an R/Bioconductor package for MS/MS protein identification.

PubMed

Fournier, Frédéric; Joly Beauparlant, Charles; Paradis, René; Droit, Arnaud

2014-08-01

rTANDEM is an R/Bioconductor package that interfaces the X!Tandem protein identification algorithm. The package can run the multi-threaded algorithm on proteomic data files directly from R. It also provides functions to convert search parameters and results to/from R as well as functions to manipulate parameters and automate searches. An associated R package, shinyTANDEM, provides a web-based graphical interface to visualize and interpret the results. Together, those two packages form an entry point for a general MS/MS-based proteomic pipeline in R/Bioconductor. rTANDEM and shinyTANDEM are distributed in R/Bioconductor, http://bioconductor.org/packages/release/bioc/. The packages are under open licenses (GPL-3 and Artistice-1.0). frederic.fournier@crchuq.ulaval.ca or arnaud.droit@crchuq.ulaval.ca Supplementary data are available at Bioinformatics online. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Building mechanism for a high open-circuit voltage in an all-solution-processed tandem polymer solar cell.

PubMed

Kong, Jaemin; Lee, Jongjin; Kim, Geunjin; Kang, Hongkyu; Choi, Youna; Lee, Kwanghee

2012-08-14

Additional post-processing techniques, such as post-thermal annealing and UV illumination, were found to be required to obtain desirable values of the cell parameters in a tandem polymer solar cell incorporated with solution-processed basic n-type titanium sub-oxide (TiO(x))/acidic p-type poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) interlayers. Subsequent to the fabrication of the tandem polymer solar cells, the open-circuit voltage (V(OC)) of the cells exhibited half of the expected value. Only after the application of the post-treatments, the V(OC) of a tandem cell increased from the initial half-cell value (∼0.6 V) to its full-cell value (∼1.2 V). The selective light-biased incident photon-to-current efficiency (IPCE) measurements indicated that the initial V(OC) originated from the back subcell and that the application of the post-processing treatments revived the front subcell, such that the net photocurrent of the tandem cell was finally governed by a recombination process of holes from the back subcell and electrons from the front subcell. Based on our experimental results, we suggest that a V(OC) enhancement could be ascribed to two types of subsequent junction formations at the interface between the TiO(x) and PEDOT:PSS interlayers: an 'ion-mediated dipole junction', resulting from the electro-kinetic migration of cationic ions in the interlayers during post-thermal annealing in the presence of a low-work-function metal cathode, and a 'photoinduced Schottky junction', formed by increasing the charge carrier density in the n-type TiO(x) interlayer during UV illumination process. The two junctions separately contributed to the formation of a recombination junction through which the electrons in TiO(x) and the holes in PEDOT:PSS were able to recombine without substantial voltage drops.

Semi-transparent perovskite solar cells for tandems with silicon and CIGS

DOE PAGES

Bailie, Colin D.; Christoforo, M. Greyson; Mailoa, Jonathan P.; ...

2014-12-23

A promising approach for upgrading the performance of an established low-bandgap solar technology without adding much cost is to deposit a high bandgap polycrystalline semiconductor on top to make a tandem solar cell. We use a transparent silver nanowire electrode on perovskite solar cells to achieve a semi-transparent device. We place the semi-transparent cell in a mechanically-stacked tandem configuration onto copper indium gallium diselenide (CIGS) and low-quality multicrystalline silicon (Si) to achieve solid-state polycrystalline tandem solar cells with a net improvement in efficiency over the bottom cell alone. Furthermore, this work paves the way for integrating perovskites into a low-costmore » and high-efficiency (>25%) tandem cell.« less

Development of a method for the simultaneous determination of multi-class pesticides in earthworms by liquid chromatography coupled to tandem electrospray mass spectrometry.

PubMed

Daniele, Gaëlle; Lafay, Florent; Pelosi, Céline; Fritsch, Clémentine; Vulliet, Emmanuelle

2018-06-04

Agricultural intensification, and in particular the use of pesticides, leads over the years to a loss of biodiversity and a decline of ecosystem services in cultivated zones and agricultural landscapes. Among the animal communities involved in the functioning of agro-ecosystems, earthworms are ubiquitous and recognized as indicators of land uses and cultural practices. However, little data is available on the levels of pesticides in such organisms in natura, which would allow estimating their actual exposure and the potentially resulting impacts. Thus, the objective of this study was to develop a sensitive analytical methodology to detect and quantify 27 currently used pesticides in earthworms (Allolobophora chlorotica). A modified QuEChERS extraction was implemented on individual earthworms. This step was followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The whole analytical method was validated on spiked earthworm blank samples, with regard to linearity (from 1 to 100 method limit of quantification, r 2  > 0.95), intra-day precision (relative standard deviation (RSD) < 15%), inter-day precision (RSD < 20%), recoveries (mainly in the range 70-110%), and limits of detection and of quantification (inferior to 5 ng/g for most of the pesticides). The developed method was successfully applied to determine the concentrations of pesticides in nine individuals collected in natura. Up to five of the selected pesticides have been detected in one individual. Graphical abstract.

Complete Nutrient Removal Coupled to Nitrous Oxide Production as a Bioenergy Source by Denitrifying Polyphosphate-Accumulating Organisms.

PubMed

Gao, Han; Liu, Miaomiao; Griffin, James S; Xu, Longcheng; Xiang, Da; Scherson, Yaniv D; Liu, Wen-Tso; Wells, George F

2017-04-18

Coupled aerobic-anoxic nitrous decomposition operation (CANDO) is a promising emerging bioprocess for wastewater treatment that enables direct energy recovery from nitrogen (N) in three steps: (1) ammonium oxidation to nitrite; (2) denitrification of nitrite to nitrous oxide (N 2 O); and (3) N 2 O conversion to N 2 with energy generation. However, CANDO does not currently target phosphorus (P) removal. Here, we demonstrate that denitrifying polyphosphate-accumulating organism (PAO) enrichment cultures are capable of catalyzing simultaneous biological N and P removal coupled to N 2 O generation in a second generation CANDO process, CANDO+P. Over 7 months (>300 cycles) of operation of a prototype lab-scale CANDO+P sequencing batch reactor treating synthetic municipal wastewater, we observed stable and near-complete N removal accompanied by sustained high-rate, high-yield N 2 O production with partial P removal. A substantial increase in abundance of the PAO Candidatus Accumulibacter phosphatis was observed, increasing from 5% of the total bacterial community in the inoculum to over 50% after 4 months. PAO enrichment was accompanied by a strong shift in the dominant Accumulibacter population from clade IIC to clade IA, based on qPCR monitoring of polyphosphate kinase 1 (ppk1) gene variants. Our work demonstrates the feasibility of combining high-rate, high-yield N 2 O production for bioenergy production with combined N and P removal from wastewater, and it further suggests a putative denitrifying PAO niche for Accumulibacter clade IA.

Economic viability of thin-film tandem solar modules in the United States

NASA Astrophysics Data System (ADS)

Sofia, Sarah E.; Mailoa, Jonathan P.; Weiss, Dirk N.; Stanbery, Billy J.; Buonassisi, Tonio; Peters, I. Marius

2018-05-01

Tandem solar cells are more efficient but more expensive per unit area than established single-junction (SJ) solar cells. To understand when specific tandem architectures should be utilized, we evaluate the cost-effectiveness of different II-VI-based thin-film tandem solar cells and compare them to the SJ subcells. Levelized cost of electricity (LCOE) and energy yield are calculated for four technologies: industrial cadmium telluride and copper indium gallium selenide, and their hypothetical two-terminal (series-connected subcells) and four-terminal (electrically independent subcells) tandems, assuming record SJ quality subcells. Different climatic conditions and scales (residential and utility scale) are considered. We show that, for US residential systems with current balance-of-system costs, the four-terminal tandem has the lowest LCOE because of its superior energy yield, even though it has the highest US per watt (US W-1) module cost. For utility-scale systems, the lowest LCOE architecture is the cadmium telluride single junction, the lowest US W-1 module. The two-terminal tandem requires decreased subcell absorber costs to reach competitiveness over the four-terminal one.

Typing Clostridium difficile strains based on tandem repeat sequences

PubMed Central

2009-01-01

Background Genotyping of epidemic Clostridium difficile strains is necessary to track their emergence and spread. Portability of genotyping data is desirable to facilitate inter-laboratory comparisons and epidemiological studies. Results This report presents results from a systematic screen for variation in repetitive DNA in the genome of C. difficile. We describe two tandem repeat loci, designated 'TR6' and 'TR10', which display extensive sequence variation that may be useful for sequence-based strain typing. Based on an investigation of 154 C. difficile isolates comprising 75 ribotypes, tandem repeat sequencing demonstrated excellent concordance with widely used PCR ribotyping and equal discriminatory power. Moreover, tandem repeat sequences enabled the reconstruction of the isolates' largely clonal population structure and evolutionary history. Conclusion We conclude that sequence analysis of the two repetitive loci introduced here may be highly useful for routine typing of C. difficile. Tandem repeat sequence typing resolves phylogenetic diversity to a level equivalent to PCR ribotypes. DNA sequences may be stored in databases accessible over the internet, obviating the need for the exchange of reference strains. PMID:19133124

Asymmetric allylation of ketones and subsequent tandem reactions catalyzed by a novel polymer-supported titanium-BINOLate complex.

PubMed

Yadav, Jagjit; Stanton, Gretchen R; Fan, Xinyuan; Robinson, Jerome R; Schelter, Eric J; Walsh, Patrick J; Pericas, Miquel A

2014-06-02

By using a novel, simple, and convenient synthetic route, enantiopure 6-ethynyl-BINOL (BINOL = 1,1-binaphthol) was synthesized and anchored to an azidomethylpolystyrene resin through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The polystyrene (PS)-supported BINOL ligand was converted into its diisopropoxytitanium derivative in situ and used as a heterogeneous catalyst in the asymmetric allylation of ketones. The catalyst showed good activity and excellent enantioselectivity, typically matching the results obtained in the corresponding homogeneous reaction. The allylation reaction mixture could be submitted to epoxidation by simple treatment with tert-butyl hydroperoxide (TBHP), and the tandem asymmetric allylation epoxidation process led to a highly enantioenriched epoxy alcohol with two adjacent quaternary centers as a single diastereomer. A tandem asymmetric allylation/Pauson-Khand reaction was also performed, involving simple treatment of the allylation reaction mixture with Co2(CO)8/N-methyl morpholine N-oxide. This cascade process resulted in the formation of two diastereomeric tricyclic enones in high yields and enantioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thiol oxidation and di-tyrosine formation in human plasma proteins induced by inflammatory concentrations of hypochlorous acid.

PubMed

Colombo, Graziano; Clerici, Marco; Altomare, Alessandra; Rusconi, Francesco; Giustarini, Daniela; Portinaro, Nicola; Garavaglia, Maria Lisa; Rossi, Ranieri; Dalle-Donne, Isabella; Milzani, Aldo

2017-01-30

In this study, we assessed the oxidative damage occurring in plasma proteins when human blood was exposed to inflammatory concentrations of hypochlorous acid (HOCl). We used specific thiol labelling and Western blot analyses to determine protein thiol oxidation, as well as analytical gel filtration HPLC coupled to fluorescence detection to explore formation of high molecular weight (HMW) protein aggregates. Thiol-containing proteins oxidized by HOCl were identified by redox proteomics. Mass spectrometry (MS) analysis was performed to elucidate the protein composition of HMW aggregates. α1-antitrypsin, transthyretin, and haptoglobin showed thiol oxidation at HOCl concentrations higher than those causing complete oxidation of albumin. At the highest HOCl concentrations, formation of carbonylated and di-tyrosine cross-linked HMW protein aggregates also occurred. MS analysis identified fibrinogen, complement C3 and apolipoprotein A-I as components of HMW protein aggregates. These results could be relevant for human diseases characterized by inflammatory conditions in which myeloperoxidase and HOCl are involved. In this study we evaluated the oxidative damage occurring on plasma proteins when reconstituted human blood was exposed to inflammatory concentrations of hypochlorous acid (HOCl). Pathophysiological concentrations of HOCl are able to induce different modifications on plasma proteins such as carbonylation, sulfhydryl oxidation and formation of high molecular weight (HMW) protein aggregates characterized by di-tyrosine fluorescence. There are two relevant aspects emerging from this paper. The first one consists on identifying low abundant proteins undergoing sulfhydryl oxidation by biotin-maleimide derivatization followed by MALDI-TOF mass spectrometry. This approach suggests three low-abundant proteins undergoing HOCl-induced oxidation: transthyretin, α1-antitrypsin, and haptoglobin. In addition, we analysed HMW protein aggregates forming after HOCl exposure

Tandem Payne/Dakin Reaction: A New Strategy for Hydrogen Peroxide Detection and Molecular Imaging.

PubMed

Yang, Dan; Ye, Sen; Hu, Jun Jacob

2018-06-22

Hydrogen peroxide (H2O2) has been recognized as one of the most significant ROS (reactive oxygen species) in human health and disease. Due to the intrinsic attributes of H2O2 such as low reactivity under physiological pH, it is exceedingly challenging to develop small molecule fluorescent probes with high selectivity and sensitivity to visualize H2O2 in intricate biological milieux. To address this gap, we report a rationally designed tandem Payne/Dakin reaction that is specific to molecular recognition of H2O2, and demonstrate its application in developing novel biocompatible fluorescent probes. New H2O2 probes based on this unique chemical strategy can be facilely synthesized by a general coupling reaction, and the practical applicability of those probes has been confirmed by the visualization of endogenously produced H2O2 in living cells. In particular, starvation induced H2O2 production in mouse macrophages has been detected by our novel probe in both confocal imaging and flow cytometry. This tandem Payne/Dakin reaction provides a basis for developing more sophisticated molecular tools to interrogate H2O2 functions in biological phenomena. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode.

PubMed

Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

2014-12-23

Tandem architecture is the most relevant concept to overcome the efficiency limit of single-junction photovoltaic solar cells. Series-connected tandem polymer solar cells (PSCs) have advanced rapidly during the past decade. In contrast, the development of parallel-connected tandem cells is lagging far behind due to the big challenge in establishing an efficient interlayer with high transparency and high in-plane conductivity. Here, we report all-solution fabrication of parallel tandem PSCs using silver nanowires as intermediate charge collecting electrode. Through a rational interface design, a robust interlayer is established, enabling the efficient extraction and transport of electrons from subcells. The resulting parallel tandem cells exhibit high fill factors of ∼60% and enhanced current densities which are identical to the sum of the current densities of the subcells. These results suggest that solution-processed parallel tandem configuration provides an alternative avenue toward high performance photovoltaic devices.

Tandem Repeated Irritation Test (TRIT) Studies and Clinical Relevance: Post 2006.

PubMed

Reddy, Rasika; Maibach, Howard

2018-06-11

Single or multiple applications of irritants can lead to occupational contact dermatitis, and most commonly irritant contact dermatitis (ICD). Tandem irritation, the sequential application of two irritants to a target skin area, has been studied using the Tandem Repeated Irritation Test (TRIT) to provide a more accurate representation of skin irritation. Here we present an update to Kartono's review on tandem irritation studies since 2006 [1]. We surveyed the literature available on PubMed, Embase, Google Scholar, and the UCSF Dermatology library databases since 2006. The studies included discuss the tandem effects of common chemical irritants, organic solvents, occlusion as well as clinical relevance - and enlarge our ability to discern whether multiple chemical exposures are more or less likely to enhance irritation.

An examination of the origin and evolution of additional tandem repeats in the mitochondrial DNA control region of Japanese sika deer (Cervus Nippon).

PubMed

Ba, Hengxing; Wu, Lang; Liu, Zongyue; Li, Chunyi

2016-01-01

Tandem repeat units are only detected in the left domain of the mitochondrial DNA control region in sika deer. Previous studies showed that Japanese sika deer have more tandem repeat units than its cousins from the Asian continent and Taiwan, which often have only three repeat units. To determine the origin and evolution of these additional repeat units in Japanese sika deer, we obtained the sequence of repeat units from an expanded dataset of the control region from all sika deer lineages. The functional constraint is inferred to act on the first repeat unit because this repeat has the least sequence divergence in comparison to the other units. Based on slipped-strand mispairing mechanisms, the illegitimate elongation model could account for the addition or deletion of these additional repeat units in the Japanese sika deer population. We also report that these additional repeat units could be occurring in the internal positions of tandem repeat regions, possibly via coupling with a homogenization mechanism within and among these lineages. Moreover, the increased number of repeat units in the Japanese sika deer population could reflect a balance between mutation and selection, as well as genetic drift.

Identification of mutagenic transformation products generated during oxidation of 3-methyl-4-nitrophenol solutions by orbitrap tandem mass spectrometry and quantitative structure-activity relationship analyses.

PubMed

Matsushita, Taku; Honda, Shiho; Kuriyama, Taisuke; Fujita, Yuki; Kondo, Takashi; Matsui, Yoshihiko; Shirasaki, Nobutaka; Takanashi, Hirokazu; Kameya, Takashi

2018-02-01

We used Ames assays to investigate the effects of ozonation (designated O 3 ), ozonation followed by chlorination (O 3 /Cl), an advanced oxidation process (AOP, UV/H 2 O 2 ), and AOP followed by chlorination (AOP/Cl) on the mutagenicity of solutions of 3-methyl-4-nitrophenol (3M4NP), a major environmental degradation product of the organophosphorus insecticide fenitrothion. Whereas O 3 did not induce mutagenicity, O 3 /Cl, AOP, and AOP/Cl converted 3M4NP into mutagenic transformation products (TPs). Using liquid chromatography-mass spectrometry, we detected a total of 138 peaks in the solutions subjected to O 3 /Cl, AOP, and AOP/Cl. To elucidate the TPs responsible for the observed mutagenicity, we performed simple regression analyses of the relationship between the area of each peak and the observed mutagenicity of samples withdrawn periodically during each oxidation process. The area of each of 10 peaks was found to be positively correlated (r 2  ≥ 0.8) with the observed mutagenicity, suggesting that the TPs corresponding to these peaks contributed to the mutagenicity. After taking into account the consistency of mutagenicity induction by the oxidation processes and analyzing the peaks by tandem mass spectrometry, we identified 3 TPs, corresponding to 6 peaks, as candidate mutagens. These TPs were assessed by means of 4 quantitative structure-activity relationship (QSAR) models, and all 3 were predicted to be mutagenic by at least one model. This result was consistent with our assumption that these TPs were mutagens. Ames assays of an authentic sample of one of the 3 TPs revealed that it did not contribute to the mutagenicity. This left 3-methoxy-4-nitrophenol and 2-[(E)-[(2,5-dihydroxyphenyl) methylidene]amino]-5-dihydroxybenzaldehyde on the list of mutagens suspected of contributing to the mutagenicity induced by AOP. No TPs were identified as candidate mutagens responsible for the mutagenicity induced by O 3 /Cl and AOP/Cl. Copyright © 2017 Elsevier Ltd

Flow field interactions between two tandem cyclists

NASA Astrophysics Data System (ADS)

Barry, Nathan; Burton, David; Sheridan, John; Thompson, Mark; Brown, Nicholas A. T.

2016-12-01

Aerodynamic drag is the primary resistive force acting on cyclists at racing speeds. Many events involve cyclists travelling in very close proximity. Previous studies have shown that interactions result in significant drag reductions for inline cyclists. However, the interaction between cyclist leg position (pedalling) and the vortical flow structures that contribute significantly to the drag on an isolated cyclist has not previously been quantified or described for tandem cyclists of varying separation. To this end, scale model cyclists were constructed for testing in a water channel for inline tandem configurations. Particle image velocimetry was used to capture time-averaged velocity fields around two tandem cyclists. Perhaps surprisingly, the wake of a trailing cyclist maintains strong similarity to the characteristic wake of a single cyclist despite a significant disturbance to the upstream flow. Together with streamwise velocity measurements through the wake and upstream of the trailing cyclist, this work supports previous findings, which showed that the trailing cyclist drag reduction is primarily due to upstream sheltering effects reducing the stagnation pressure on forward-facing surfaces.

Stacking multiple connecting functional materials in tandem organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Zhang, Tao; Wang, Deng-Ke; Jiang, Nan; Lu, Zheng-Hong

2017-02-01

Tandem device is an important architecture in fabricating high performance organic light-emitting diodes and organic photovoltaic cells. The key element in making a high performance tandem device is the connecting materials stack, which plays an important role in electric field distribution, charge generation and charge injection. For a tandem organic light-emitting diode (OLED) with a simple Liq/Al/MoO3 stack, we discovered that there is a significant current lateral spreading causing light emission over an extremely large area outside the OLED pixel when the Al thickness exceeds 2 nm. This spread light emission, caused by an inductive electric field over one of the device unit, limits one’s ability to fabricate high performance tandem devices. To resolve this issue, a new connecting materials stack with a C60 fullerene buffer layer is reported. This new structure permits optimization of the Al metal layer in the connecting stack and thus enables us to fabricate an efficient tandem OLED having a high 155.6 cd/A current efficiency and a low roll-off (or droop) in current efficiency.

Oxidation Numbers in the Study of Metabolism

ERIC Educational Resources Information Center

Bentley, Ronald; Franzen, James; Chasteen, Thomas G.

2002-01-01

The calculation and use of oxidation numbers in the study of metabolic reactions are discussed for normal oxidations (alcohol dehydrogenase and the NAD+/NADH couple, propanediol dehydratase) and for enzymatic reactions with a "hidden" redox component (transamination, the coupled conversion of ethylamine to ethanol, and the biomethylation of…

[Polymorphic loci and polymorphism analysis of short tandem repeats within XNP gene].

PubMed

Liu, Qi-Ji; Gong, Yao-Qin; Guo, Chen-Hong; Chen, Bing-Xi; Li, Jiang-Xia; Guo, Yi-Shou

2002-01-01

To select polymorphic short tandem repeat markers within X-linked nuclear protein (XNP) gene, genomic clones which contain XNP gene were recognized by homologous analysis with XNP cDNA. By comparing the cDNA with genomic DNA, non-exonic sequences were identified, and short tandem repeats were selected from non-exonic sequences by using BCM search Launcher. Polymorphisms of the short tandem repeats in Chinese population were evaluated by PCR amplification and PAGE. Five short tandem repeats were identified from XNP gene, two of which were polymorphic. Four and 11 alleles were observed in Chinese population for XNPSTR1 and XNPSTR4, respectively. Heterozygosities were 47% for XNPSTR1 and 70% for XNPSTR4. XNPSTR1 and XNPSTR4 localized within 3' end and intron 10, respectively. Two polymorphic short tandem repeats have been identified within XNP gene and will be useful for linkage analysis and gene diagnosis of XNP gene.

Low-Cost CdTe/Silicon Tandem Solar Cells

DOE PAGES

Tamboli, Adele C.; Bobela, David C.; Kanevce, Ana; ...

2017-09-06

Achieving higher photovoltaic efficiency in single-junction devices is becoming increasingly difficult, but tandem modules offer the possibility of significant efficiency improvements. By device modeling we show that four-terminal CdTe/Si tandem solar modules offer the prospect of 25%-30% module efficiency, and technoeconomic analysis predicts that these efficiency gains can be realized at costs per Watt that are competitive with CdTe and Si single junction alternatives. The cost per Watt of the modeled tandems is lower than crystalline silicon, but slightly higher than CdTe alone. But, these higher power modules reduce area-related balance of system costs, providing increased value especially in area-constrainedmore » applications. This avenue for high-efficiency photovoltaics enables improved performance on a near-term timeframe, as well as a path to further reduced levelized cost of electricity as module and cell processes continue to advance.« less

Low-Cost CdTe/Silicon Tandem Solar Cells

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

Tamboli, Adele C.; Bobela, David C.; Kanevce, Ana

Achieving higher photovoltaic efficiency in single-junction devices is becoming increasingly difficult, but tandem modules offer the possibility of significant efficiency improvements. By device modeling we show that four-terminal CdTe/Si tandem solar modules offer the prospect of 25%-30% module efficiency, and technoeconomic analysis predicts that these efficiency gains can be realized at costs per Watt that are competitive with CdTe and Si single junction alternatives. The cost per Watt of the modeled tandems is lower than crystalline silicon, but slightly higher than CdTe alone. But, these higher power modules reduce area-related balance of system costs, providing increased value especially in area-constrainedmore » applications. This avenue for high-efficiency photovoltaics enables improved performance on a near-term timeframe, as well as a path to further reduced levelized cost of electricity as module and cell processes continue to advance.« less

Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea.

PubMed

Ma, Guicen; Zhang, Minglu; Zhu, Li; Chen, Hongping; Liu, Xin; Lu, Chengyin

2018-01-05

Amine-functional reduced graphene oxide (amine-rGO) with different carbon chain length amino groups were successfully synthesized. The graphene oxides (GO) reduction as well as amino grafting were achieved simultaneously in one step via a facile solvothermal synthetic strategy. The obtained materials were characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectrometry and X-ray photoelectron spectroscopy to confirm the modification of GO with different amino groups. The adsorption performance of catechins and caffeine from tea acetonitrile extracts on different amine functional rGO samples were evaluated. It was found that tributylamine-functional rGO (tri-BuA-rGO) exhibited the highest adsorption ability for catechins and caffeine compared to GO and other amino group functional rGO samples. It was worth to note that the adsorption capacity of catechins on tri-BuA-rGO was 11 times higher than that of GO (203.7mgg -1 vs 18.7mgg -1 ). Electrostatic interaction, π-π interaction and surface hydrophilic-hydrophobic properties of tri-BuA-rGO played important roles in the adsorption of catechins as well as caffeine. The gravimetric analysis confirmed that the tri-BuA-rGO achieved the highest efficient cleanup preformance compared with traditional dispersive solid phase extraction (dSPE) adsorbents like primary-secondary amine (PSA), graphitized carbon black (GCB) or C18. A multi-pesticides analysis method based on tri-BuA-rGO is validated on 33 representative pesticides in tea using gas chromatography coupled to tandem mass spectrometry or high-performance liquid chromatography coupled with tandem mass spectrometry. The analysis method gave a high coefficient of determination (r 2 >0.99) for each pesticide and satisfactory recoveries in a range of 72.1-120.5%. Our study demonstrated that amine functional rGO as a new type of QuEChERS adsorbent is expected to be widely applied for analysis of pesticides at trace levels. Copyright © 2017

Proteomic analysis of Taenia ovis metacestodes by high performance liquid chromatography-coupled tandem mass spectrometry.

PubMed

Zheng, Yadong

2017-03-15

Taenia ovis metacestodes reside in the muscle of sheep and goats, and may cause great economic loss due to condemnation of carcasses if not effectively controlled. Although advances have been made in the control of T. ovis infection, our knowledge of T. ovis biology is limited. Herein the protein profiling of T. ovis metacestodes was determined by liquid chromatography-linked tandem mass spectrometry. A total of 966 proteins were identified and 25.1% (188/748) were annotated to be associated with metabolic pathways. Consistently, GO analysis returned a metabolic process (16.27%) as one of two main biological process terms. Moreover, it was found that 24 proteins, including very low-density lipoprotein receptor, enolase, paramyosin and endophilin B1, were abundant in T. ovis metacestodes. These proteins may be associated with motility, metabolism, signaling, stress, drug resistance and immune responses. Furthermore, comparative analysis of 5 cestodes revealed the presence of Taenia-specific enolases. These data provide clues for better understanding of T. ovis biology, which is informative for effective control of infection. Copyright © 2017 Elsevier B.V. All rights reserved.

Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake

PubMed Central

Deutzmann, Joerg S.; Stief, Peter; Brandes, Josephin; Schink, Bernhard

2014-01-01

Anaerobic methane oxidation coupled to denitrification, also known as “nitrate/nitrite-dependent anaerobic methane oxidation” (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660–4,890 µmol CH4⋅m−2⋅d−1) and actual rates calculated from microsensor profiles (31–437 µmol CH4⋅m−2⋅d−1) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones. PMID:25472842

Oxidative C-H/C-H Cross-Coupling Reactions between N-Acylanilines and Benzamides Enabled by a Cp*-Free RhCl3/TFA Catalytic System.

PubMed

You, Jingsong; Shi, Yang; Zhang, Luoqiang; Lan, Jingbo; Zhang, Min; Zhou, Fulin; Wei, Wenlong

2018-06-03

Using the dual chelation-assisted strategy, a completely regiocontrolled oxidative C-H/C-H cross-coupling reaction between an N-acylaniline and a benzamide has been accomplished for the first time, which enables a step-economical and highly efficient pathway to 2-amino-2'-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3/TFA catalytic system has been developed to replace the generally used [Cp*RhCl2]2/AgSbF6 (Cp* = pentamethyl cyclopentadienyl) in oxidative C-H/C-H cross-coupling reactions between two (hetero)arenes. The RhCl3/TFA system avoids the use of expensive Cp* ligand and AgSbF6. As an illustrative example, the protocol developed herein greatly streamlines access to naturally occurring benzo[c]phenanthridine alkaloid oxynitidine in an excellent overall yield. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Skeletal Muscle Neurovascular Coupling, Oxidative Capacity, and Microvascular Function with 'One Stop Shop' Near-infrared Spectroscopy.

PubMed

Rosenberry, Ryan; Chung, Susie; Nelson, Michael D

2018-02-20

Exercise represents a major hemodynamic stress that demands a highly coordinated neurovascular response in order to match oxygen delivery to metabolic demand. Reactive hyperemia (in response to a brief period of tissue ischemia) is an independent predictor of cardiovascular events and provides important insight into vascular health and vasodilatory capacity. Skeletal muscle oxidative capacity is equally important in health and disease, as it determines the energy supply for myocellular processes. Here, we describe a simple, non-invasive approach using near-infrared spectroscopy to assess each of these major clinical endpoints (reactive hyperemia, neurovascular coupling, and muscle oxidative capacity) during a single clinic or laboratory visit. Unlike Doppler ultrasound, magnetic resonance images/spectroscopy, or invasive catheter-based flow measurements or muscle biopsies, our approach is less operator-dependent, low-cost, and completely non-invasive. Representative data from our lab taken together with summary data from previously published literature illustrate the utility of each of these end-points. Once this technique is mastered, application to clinical populations will provide important mechanistic insight into exercise intolerance and cardiovascular dysfunction.

Partners in crime: The role of tandem modules in gene transcription.

PubMed

Sharma, Rajal; Zhou, Ming-Ming

2015-09-01

Histones and their modifications play an important role in the regulation of gene transcription. Numerous modifications, such as acetylation, phosphorylation, methylation, ubiquitination, and SUMOylation, have been described. These modifications almost always co-occur and thereby increase the combinatorial complexity of post-translational modification detection. The domains that recognize these histone modifications often occur in tandem in the context of larger proteins and complexes. The presence of multiple modifications can positively or negatively regulate the binding of these tandem domains, influencing downstream cellular function. Alternatively, these tandem domains can have novel functions from their independent parts. Here we summarize structural and functional information known about major tandem domains and their histone binding properties. An understanding of these interactions is key for the development of epigenetic therapy. © 2015 The Protein Society.

Specular spin-valve films with an FeCo nano-oxide layer by ion-assisted oxidation

NASA Astrophysics Data System (ADS)

Fukuzawa, Hideaki; Koi, Katsuhiko; Tomita, Hiroshi; Fuke, Hiromi Niu; Iwasaki, Hitoshi; Sahashi, Masashi

2002-05-01

We compared the specular spin-valve films with an Fe50Co50 nano-oxide layer (NOL) and a Co90Fe10 NOL in a pinned layer, prepared by natural oxidation (NO) and ion-assisted oxidation (IAO). For the IAO, an Ar-ion beam was used for the energy-assist effect during the oxidation, resulting in thermally stable NOL formation. With small oxygen exposures during the oxidation for the Fe50Co50 NOL by IAO, good ferromagnetic coupling through the NOL and high specularity at the NOL interface were concurrently obtained. Moreover, twisted coupling through the NOL was observed for the Fe50Co50 NOL by IAO for higher oxygen exposures. On the other hand, the NO did not cause large magnetoresistance (MR) enhancement for either the Co90Fe10 or Fe50Co50 NOLs, and the Co90Fe10 NOL by IAO caused weak magnetic coupling through the NOL, resulting in a small MR ratio. The Fe50Co50 NOL for small oxygen exposures is a good candidate for a final specular spin-valve film head for 100-Giga-bit per square inch recording.

Nitro-fatty Acid Metabolome: Saturation, Desaturation, β-Oxidation, and Protein Adduction*

PubMed Central

Rudolph, Volker; Schopfer, Francisco J.; Khoo, Nicholas K. H.; Rudolph, Tanja K.; Cole, Marsha P.; Woodcock, Steven R.; Bonacci, Gustavo; Groeger, Alison L.; Golin-Bisello, Franca; Chen, Chen-Shan; Baker, Paul R. S.; Freeman, Bruce A.

2009-01-01

Nitrated derivatives of fatty acids (NO2-FA) are pluripotent cell-signaling mediators that display anti-inflammatory properties. Current understanding of NO2-FA signal transduction lacks insight into how or if NO2-FA are modified or metabolized upon formation or administration in vivo. Here the disposition and metabolism of nitro-9-cis-octadecenoic (18:1-NO2) acid was investigated in plasma and liver after intravenous injection in mice. High performance liquid chromatography-tandem mass spectrometry analysis showed that no 18:1-NO2 or metabolites were detected under basal conditions, whereas administered 18:1-NO2 is rapidly adducted to plasma thiol-containing proteins and glutathione. NO2-FA are also metabolized via β-oxidation, with high performance liquid chromatography-tandem mass spectrometry analysis of liver lipid extracts of treated mice revealing nitro-7-cis-hexadecenoic acid, nitro-5-cis-tetradecenoic acid, and nitro-3-cis-dodecenoic acid and corresponding coenzyme A derivatives of 18:1-NO2 as metabolites. Additionally, a significant proportion of 18:1-NO2 and its metabolites are converted to nitroalkane derivatives by saturation of the double bond, and to a lesser extent are desaturated to diene derivatives. There was no evidence of the formation of nitrohydroxyl or conjugated ketone derivatives in organs of interest, metabolites expected upon 18:1-NO2 hydration or nitric oxide (•NO) release. Plasma samples from treated mice had significant extents of protein-adducted 18:1-NO2 detected by exchange to added β-mercaptoethanol. This, coupled with the observation of 18:1-NO2 release from glutathione-18:1-NO2 adducts, supports that reversible and exchangeable NO2-FA-thiol adducts occur under biological conditions. After administration of [3H]18:1-NO2, 64% of net radiolabel was recovered 90 min later in plasma (0.2%), liver (18%), kidney (2%), adipose tissue (2%), muscle (31%), urine (6%), and other tissue compartments, and may include metabolites not yet

Structure Annotation and Quantification of Wheat Seed Oxidized Lipids by High-Resolution LC-MS/MS.

PubMed

Riewe, David; Wiebach, Janine; Altmann, Thomas

2017-10-01

Lipid oxidation is a process ubiquitous in life, but the direct and comprehensive analysis of oxidized lipids has been limited by available analytical methods. We applied high-resolution liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (MS/MS) to quantify oxidized lipids (glycerides, fatty acids, phospholipids, lysophospholipids, and galactolipids) and implemented a platform-independent high-throughput-amenable analysis pipeline for the high-confidence annotation and acyl composition analysis of oxidized lipids. Lipid contents of 90 different naturally aged wheat ( Triticum aestivum ) seed stocks were quantified in an untargeted high-resolution LC-MS experiment, resulting in 18,556 quantitative mass-to-charge ratio features. In a posthoc liquid chromatography-tandem mass spectrometry experiment, high-resolution MS/MS spectra (5 mD accuracy) were recorded for 8,957 out of 12,080 putatively monoisotopic features of the LC-MS data set. A total of 353 nonoxidized and 559 oxidized lipids with up to four additional oxygen atoms were annotated based on the accurate mass recordings (1.5 ppm tolerance) of the LC-MS data set and filtering procedures. MS/MS spectra available for 828 of these annotations were analyzed by translating experimentally known fragmentation rules of lipids into the fragmentation of oxidized lipids. This led to the identification of 259 nonoxidized and 365 oxidized lipids by both accurate mass and MS/MS spectra and to the determination of acyl compositions for 221 nonoxidized and 295 oxidized lipids. Analysis of 15-year aged wheat seeds revealed increased lipid oxidation and hydrolysis in seeds stored in ambient versus cold conditions. © 2017 The author(s). All Rights Reserved.

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

PubMed

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Simultaneous determination of blonanserin and its four metabolites in human plasma using ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhou, Ying; Liu, Ming; Jiang, Ji; Wang, Hongyun; Hu, Pei

2013-11-15

A sensitive and rapid method based on ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was developed and validated for the simultaneous determination of blonanserin, its major active metabolite (N-deethyl form) and other three metabolites (N-oxide form, Ethylenediamine form and Carboxylate form) in human plasma. Plasma samples were pre-purified by solid-phase extraction (SPE) and analyzed using a gradient chromatographic separation over an Acquity UPLC CSH C18 column. The mobile phase consisted of acetonitrile-water containing 5mM ammonium formate and 0.1% formic acid at a flow rate of 0.5mL/min. Positive electrospray ionization was employed as the ionization source in the multiple reaction monitoring (MRM) mode. The analysis time was about 3.5min. The method was fully validated over the concentration range of 0.01-1ng/mL for all analytes. The lower limit of quantification (LLOQ) was 0.01ng/mL. Inter- and intra-batch precision was less than 15% and the accuracy was within 85-115%. The mean extraction recoveries of all analytes at two concentration levels were consistent. Selectivity, matrix effect and stability were also validated. The method was applied to the pharmacokinetic study of blonanserin in Chinese healthy subjects. Copyright © 2013 Elsevier B.V. All rights reserved.

Tear proteomic analysis of patients with type 2 diabetes and dry eye syndrome by two-dimensional nano-liquid chromatography coupled with tandem mass spectrometry.

PubMed

Li, Bing; Sheng, Minjie; Xie, Liqi; Liu, Feng; Yan, Guoquan; Wang, Weifang; Lin, Anjuan; Zhao, Fei; Chen, Yihui

2014-01-09

Diabetes mellitus has been shown to be associated with and complicated by dry eye syndrome. We sought to examine and compare the tear film proteome of type 2 diabetic patients with or without dry eye syndrome and normal subjects using two-dimensional nano-liquid chromatography coupled with tandem mass spectrometry (MS)-based proteomics. Tears were collected from eight type 2 diabetes patients with dry eye syndrome, eight type 2 diabetes patients without dry eye syndrome, and eight normal subjects. Tear breakup time (BUT) was determined, and tear proteins were prepared and analyzed using two-dimensional strong cation-exchange/reversed-phase nano-scale liquid chromatography MS. All MS/MS spectra were identified by using SEQUEST against the human International Protein Index (IPI) database and the relative abundance of individual proteins was assessed by spectral counting. Tear BUT was significantly lower in patients with diabetes and dry eye syndrome than in patients with diabetes only and normal subjects. Analysis of spectral counts of tear proteins showed that, compared to healthy controls, patients with diabetes and dry eye syndrome had increased expression of apoptosis-related proteins, like annexin A1, and immunity- and inflammation-related proteins, including neutrophil elastase 2 and clusterin, and glycometabolism-related proteins, like apolipoprotein A-II. Dry eye syndrome in diabetic patients is associated with aberrant expression of tear proteins, and the findings could lead to identification of novel pathways for therapeutic targeting and new diagnostic markers.

Perovskite-perovskite tandem photovoltaics with optimized band gaps

NASA Astrophysics Data System (ADS)

Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

2016-11-01

We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

Stacking multiple connecting functional materials in tandem organic light-emitting diodes

PubMed Central

Zhang, Tao; Wang, Deng-Ke; Jiang, Nan; Lu, Zheng-Hong

2017-01-01

Tandem device is an important architecture in fabricating high performance organic light-emitting diodes and organic photovoltaic cells. The key element in making a high performance tandem device is the connecting materials stack, which plays an important role in electric field distribution, charge generation and charge injection. For a tandem organic light-emitting diode (OLED) with a simple Liq/Al/MoO3 stack, we discovered that there is a significant current lateral spreading causing light emission over an extremely large area outside the OLED pixel when the Al thickness exceeds 2 nm. This spread light emission, caused by an inductive electric field over one of the device unit, limits one’s ability to fabricate high performance tandem devices. To resolve this issue, a new connecting materials stack with a C60 fullerene buffer layer is reported. This new structure permits optimization of the Al metal layer in the connecting stack and thus enables us to fabricate an efficient tandem OLED having a high 155.6 cd/A current efficiency and a low roll-off (or droop) in current efficiency. PMID:28225028

Electrical and optical analyses of tandem organic light-emitting diodes with organic charge-generation layer

NASA Astrophysics Data System (ADS)

Kim, Bong Sung; Chae, Heeyeop; Chung, Ho Kyoon; Cho, Sung Min

2018-06-01

The electrical and optical properties of tandem organic light-emitting diodes (OLEDs), in which a fluorescent and phosphorescent emitting units are connected by an organic charge-generation layer (CGL), were experimentally analyzed. To investigate the internal properties of the tandem OLEDs, we fabricated and compared two single, two homo-tandem, and two hetero-tandem OLEDs using the fluorescent and phosphorescent units. From the experimental results of the OLEDs obtained at the same current density, the voltage across the CGL as well as the individual emission spectra and luminance of each unit of tandem OLEDs were obtained and compared with the theoretical simulation results. The analysis method proposed in this study can be utilized as a method to verify the accuracy of optical or electrical computer simulation of tandem OLED and it will be useful to understand the overall electrical and optical characteristics of tandem OLEDs.

Coupled adsorption-photocatalytic degradation of crystal violet under sunlight using chemically synthesized grafted sodium alginate/ZnO/graphene oxide composite.

PubMed

Mohamed, S K; Hegazy, Sh H; Abdelwahab, N A; Ramadan, A M

2018-03-01

This research aimed to synthesize natural polymer nanocomposite and employ it for coupled adsorption- photocatalytic degradation of crystal violet. Sodium alginate-g-poly (acrylic acid-co-cinnamic acid) and its composites with ZnO nanorods and graphene oxide sheets were synthesized and characterized using FT-IR, XRD, SEM, HR-TEM and DR/UV-vis spectroscopy. The adsorption efficiency of samples for crystal violet has been studied in the dark. The effect of different parameters as pH, initial dye concentration, contact time and temperature on the adsorption efficiency of the synthesized sample has been examined. Kinetics studies showed that the adsorption of all samples was well described by the pseudo-second-order model and the equilibrium adsorption results fitted Freundlich model. The maximum adsorption capacity achieved at pH 5.0 was 13.85 mg g -1 . Thermodynamic studies exhibited that the adsorption is spontaneous, endothermic in nature and leads to higher entropy. Coupled adsorption-photocatalytic degradation studies under sunlight showed an enhancement in the removal efficiency by 10%. In the case of sodium alginate-g-poly (acrylic acid-co-cinnamic acid)/ZnO/graphene oxide composite, the removal efficiency after 5 h under sunlight was 94% versus 84% in the dark. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous Determination of Oleanolic Acid and Ursolic Acid by in Vivo Microdialysis via UHPLC-MS/MS Using Magnetic Dispersive Solid Phase Extraction Coupling with Microwave-Assisted Derivatization and Its Application to a Pharmacokinetic Study of Arctiumlappa L. Root Extract in Rats.

PubMed

Zheng, Zhenjia; Zhao, Xian-En; Zhu, Shuyun; Dang, Jun; Qiao, Xuguang; Qiu, Zhichang; Tao, Yanduo

2018-04-18

Simultaneous detection of oleanolic acid and ursolic acid in rat blood by in vivo microdialysis can provide important pharmacokinetics information. Microwave-assisted derivatization coupled with magnetic dispersive solid phase extraction was established for the determination of oleanolic acid and ursolic acid by liquid chromatography tandem mass spectrometry. 2'-Carbonyl-piperazine rhodamine B was first designed and synthesized as the derivatization reagent, which was easily adsorbed onto the surface of Fe 3 O 4 /graphene oxide. Simultaneous derivatization and extraction of oleanolic acid and ursolic acid were performed on Fe 3 O 4 /graphene oxide. The permanent positive charge of the derivatization reagent significantly improved the ionization efficiencies. The limits of detection were 0.025 and 0.020 ng/mL for oleanolic acid and ursolic acid, respectively. The validated method was shown to be promising for sensitive, accurate, and simultaneous determination of oleanolic acid and ursolic acid. It was used for their pharmacokinetics study in rat blood after oral administration of Arctiumlappa L. root extract.

TandEM: Titan and Enceladus mission

USGS Publications Warehouse

Coustenis, A.; Atreya, S.K.; Balint, T.; Brown, R.H.; Dougherty, M.K.; Ferri, F.; Fulchignoni, M.; Gautier, D.; Gowen, R.A.; Griffith, C.A.; Gurvits, L.I.; Jaumann, R.; Langevin, Y.; Leese, M.R.; Lunine, J.I.; McKay, C.P.; Moussas, X.; Muller-Wodarg, I.; Neubauer, F.; Owen, T.C.; Raulin, F.; Sittler, E.C.; Sohl, F.; Sotin, Christophe; Tobie, G.; Tokano, T.; Turtle, E.P.; Wahlund, J.-E.; Waite, J.H.; Baines, K.H.; Blamont, J.; Coates, A.J.; Dandouras, I.; Krimigis, T.; Lellouch, E.; Lorenz, R.D.; Morse, A.; Porco, C.C.; Hirtzig, M.; Saur, J.; Spilker, T.; Zarnecki, J.C.; Choi, E.; Achilleos, N.; Amils, R.; Annan, P.; Atkinson, D.H.; Benilan, Y.; Bertucci, C.; Bezard, B.; Bjoraker, G.L.; Blanc, M.; Boireau, L.; Bouman, J.; Cabane, M.; Capria, M.T.; Chassefiere, E.; Coll, P.; Combes, M.; Cooper, J.F.; Coradini, A.; Crary, F.; Cravens, T.; Daglis, I.A.; de Angelis, E.; De Bergh, C.; de Pater, I.; Dunford, C.; Durry, G.; Dutuit, O.; Fairbrother, D.; Flasar, F.M.; Fortes, A.D.; Frampton, R.; Fujimoto, M.; Galand, M.; Grasset, O.; Grott, M.; Haltigin, T.; Herique, A.; Hersant, F.; Hussmann, H.; Ip, W.; Johnson, R.; Kallio, E.; Kempf, S.; Knapmeyer, M.; Kofman, W.; Koop, R.; Kostiuk, T.; Krupp, N.; Kuppers, M.; Lammer, H.; Lara, L.-M.; Lavvas, P.; Le, Mouelic S.; Lebonnois, S.; Ledvina, S.; Li, Ji; Livengood, T.A.; Lopes, R.M.; Lopez-Moreno, J. -J.; Luz, D.; Mahaffy, P.R.; Mall, U.; Martinez-Frias, J.; Marty, B.; McCord, T.; Salvan, C.M.; Milillo, A.; Mitchell, D.G.; Modolo, R.; Mousis, O.; Nakamura, M.; Neish, Catherine D.; Nixon, C.A.; Mvondo, D.N.; Orton, G.; Paetzold, M.; Pitman, J.; Pogrebenko, S.; Pollard, W.; Prieto-Ballesteros, O.; Rannou, P.; Reh, K.; Richter, L.; Robb, F.T.; Rodrigo, R.; Rodriguez, S.; Romani, P.; Bermejo, M.R.; Sarris, E.T.; Schenk, P.; Schmitt, B.; Schmitz, N.; Schulze-Makuch, D.; Schwingenschuh, K.; Selig, A.; Sicardy, B.; Soderblom, L.; Spilker, L.J.; Stam, D.; Steele, A.; Stephan, K.; Strobel, D.F.; Szego, K.; Szopa,

2009-01-01

TandEM was proposed as an L-class (large) mission in response to ESA’s Cosmic Vision 2015–2025 Call, and accepted for further studies, with the goal of exploring Titan and Enceladus. The mission concept is to perform in situ investigations of two worlds tied together by location and properties, whose remarkable natures have been partly revealed by the ongoing Cassini–Huygens mission. These bodies still hold mysteries requiring a complete exploration using a variety of vehicles and instruments. TandEM is an ambitious mission because its targets are two of the most exciting and challenging bodies in the Solar System. It is designed to build on but exceed the scientific and technological accomplishments of the Cassini–Huygens mission, exploring Titan and Enceladus in ways that are not currently possible (full close-up and in situ coverage over long periods of time). In the current mission architecture, TandEM proposes to deliver two medium-sized spacecraft to the Saturnian system. One spacecraft would be an orbiter with a large host of instruments which would perform several Enceladus flybys and deliver penetrators to its surface before going into a dedicated orbit around Titan alone, while the other spacecraft would carry the Titan in situ investigation components, i.e. a hot-air balloon (Montgolfière) and possibly several landing probes to be delivered through the atmosphere.

TandEM: Titan and Enceladus mission

NASA Astrophysics Data System (ADS)

Coustenis, A.; Atreya, S. K.; Balint, T.; Brown, R. H.; Dougherty, M. K.; Ferri, F.; Fulchignoni, M.; Gautier, D.; Gowen, R. A.; Griffith, C. A.; Gurvits, L. I.; Jaumann, R.; Langevin, Y.; Leese, M. R.; Lunine, J. I.; McKay, C. P.; Moussas, X.; Müller-Wodarg, I.; Neubauer, F.; Owen, T. C.; Raulin, F.; Sittler, E. C.; Sohl, F.; Sotin, C.; Tobie, G.; Tokano, T.; Turtle, E. P.; Wahlund, J.-E.; Waite, J. H.; Baines, K. H.; Blamont, J.; Coates, A. J.; Dandouras, I.; Krimigis, T.; Lellouch, E.; Lorenz, R. D.; Morse, A.; Porco, C. C.; Hirtzig, M.; Saur, J.; Spilker, T.; Zarnecki, J. C.; Choi, E.; Achilleos, N.; Amils, R.; Annan, P.; Atkinson, D. H.; Bénilan, Y.; Bertucci, C.; Bézard, B.; Bjoraker, G. L.; Blanc, M.; Boireau, L.; Bouman, J.; Cabane, M.; Capria, M. T.; Chassefière, E.; Coll, P.; Combes, M.; Cooper, J. F.; Coradini, A.; Crary, F.; Cravens, T.; Daglis, I. A.; de Angelis, E.; de Bergh, C.; de Pater, I.; Dunford, C.; Durry, G.; Dutuit, O.; Fairbrother, D.; Flasar, F. M.; Fortes, A. D.; Frampton, R.; Fujimoto, M.; Galand, M.; Grasset, O.; Grott, M.; Haltigin, T.; Herique, A.; Hersant, F.; Hussmann, H.; Ip, W.; Johnson, R.; Kallio, E.; Kempf, S.; Knapmeyer, M.; Kofman, W.; Koop, R.; Kostiuk, T.; Krupp, N.; Küppers, M.; Lammer, H.; Lara, L.-M.; Lavvas, P.; Le Mouélic, S.; Lebonnois, S.; Ledvina, S.; Li, J.; Livengood, T. A.; Lopes, R. M.; Lopez-Moreno, J.-J.; Luz, D.; Mahaffy, P. R.; Mall, U.; Martinez-Frias, J.; Marty, B.; McCord, T.; Menor Salvan, C.; Milillo, A.; Mitchell, D. G.; Modolo, R.; Mousis, O.; Nakamura, M.; Neish, C. D.; Nixon, C. A.; Nna Mvondo, D.; Orton, G.; Paetzold, M.; Pitman, J.; Pogrebenko, S.; Pollard, W.; Prieto-Ballesteros, O.; Rannou, P.; Reh, K.; Richter, L.; Robb, F. T.; Rodrigo, R.; Rodriguez, S.; Romani, P.; Ruiz Bermejo, M.; Sarris, E. T.; Schenk, P.; Schmitt, B.; Schmitz, N.; Schulze-Makuch, D.; Schwingenschuh, K.; Selig, A.; Sicardy, B.; Soderblom, L.; Spilker, L. J.; Stam, D.; Steele, A.; Stephan, K.; Strobel, D. F.; Szego, K.; Szopa, C.; Thissen, R.; Tomasko, M. G.; Toublanc, D.; Vali, H.; Vardavas, I.; Vuitton, V.; West, R. A.; Yelle, R.; Young, E. F.

2009-03-01

TandEM was proposed as an L-class (large) mission in response to ESA’s Cosmic Vision 2015-2025 Call, and accepted for further studies, with the goal of exploring Titan and Enceladus. The mission concept is to perform in situ investigations of two worlds tied together by location and properties, whose remarkable natures have been partly revealed by the ongoing Cassini-Huygens mission. These bodies still hold mysteries requiring a complete exploration using a variety of vehicles and instruments. TandEM is an ambitious mission because its targets are two of the most exciting and challenging bodies in the Solar System. It is designed to build on but exceed the scientific and technological accomplishments of the Cassini-Huygens mission, exploring Titan and Enceladus in ways that are not currently possible (full close-up and in situ coverage over long periods of time). In the current mission architecture, TandEM proposes to deliver two medium-sized spacecraft to the Saturnian system. One spacecraft would be an orbiter with a large host of instruments which would perform several Enceladus flybys and deliver penetrators to its surface before going into a dedicated orbit around Titan alone, while the other spacecraft would carry the Titan in situ investigation components, i.e. a hot-air balloon (Montgolfière) and possibly several landing probes to be delivered through the atmosphere.

Photo-induced water oxidation at the aqueous GaN (101¯0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

DOE PAGES

Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; ...

2015-03-12

Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys ( e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101¯0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigationmore » of free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O˙⁻ requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101¯0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.« less

Illumina sequencing-based analysis of a microbial community enriched under anaerobic methane oxidation condition coupled to denitrification revealed coexistence of aerobic and anaerobic methanotrophs.

PubMed

Siniscalchi, Luciene Alves Batista; Leite, Laura Rabelo; Oliveira, Guilherme; Chernicharo, Carlos Augusto Lemos; de Araújo, Juliana Calabria

2017-07-01

Methane is produced in anaerobic environments, such as reactors used to treat wastewaters, and can be consumed by methanotrophs. The composition and structure of a microbial community enriched from anaerobic sewage sludge under methane-oxidation condition coupled to denitrification were investigated. Denaturing gradient gel electrophoresis (DGGE) analysis retrieved sequences of Methylocaldum and Chloroflexi. Deep sequencing analysis revealed a complex community that changed over time and was affected by methane concentration. Methylocaldum (8.2%), Methylosinus (2.3%), Methylomonas (0.02%), Methylacidiphilales (0.45%), Nitrospirales (0.18%), and Methanosarcinales (0.3%) were detected. Despite denitrifying conditions provided, Nitrospirales and Methanosarcinales, known to perform anaerobic methane oxidation coupled to denitrification (DAMO) process, were in very low abundance. Results demonstrated that aerobic and anaerobic methanotrophs coexisted in the reactor together with heterotrophic microorganisms, suggesting that a diverse microbial community was important to sustain methanotrophic activity. The methanogenic sludge was a good inoculum to enrich methanotrophs, and cultivation conditions play a selective role in determining community composition.

Tandem microwave waste remediation and decontamination system

DOEpatents

Wicks, George G.; Clark, David E.; Schulz, Rebecca L.

1999-01-01

The invention discloses a tandem microwave system consisting of a primary chamber in which microwave energy is used for the controlled combustion of materials. A second chamber is used to further treat the off-gases from the primary chamber by passage through a susceptor matrix subjected to additional microwave energy. The direct microwave radiation and elevated temperatures provide for significant reductions in the qualitative and quantitative emissions of the treated off gases. The tandem microwave system can be utilized for disinfecting wastes, sterilizing materials, and/or modifying the form of wastes to solidify organic or inorganic materials. The simple design allows on-site treatment of waste by small volume waste generators.

Optimizing a tandem disk model

NASA Astrophysics Data System (ADS)

Healey, J. V.

1983-08-01

The optimum values of the solidity ratio, tip speed ratio (TSR), and the preset angle of attack, the corresponding distribution, and the breakdown mechanism for a tandem disk model for a crosswind machine such as a Darrieus are examined analytically. Equations are formulated for thin blades with zero drag in consideration of two plane rectangular disks, both perpendicular to the wind flow. Power coefficients are obtained for both disks and comparisons are made between a single-disk system and a two-disk system. The power coefficient for the tandem disk model is shown to be a sum of the coefficients of the individual disks, with a maximum value of twice the Betz limit at an angle of attack of -1 deg and the TSR between 4-7. The model, applied to the NACA 0012 profile, gives a maximum power coefficient of 0.967 with a solidity ratio of 0.275 and highly limited ranges for the angle of attack and TSR.

Tandem mass spectrometric analysis of cyclophosphamide, ifosfamide and their metabolites.

PubMed

Liu, Zhongfa; Chan, Kenneth K; Wang, Jeffrey J

2005-01-01

A detailed multi-stage (MSn) fragmentation study of cyclophosphamide (CP), ifosfamide (IF) and their major metabolites, using an ion-trap mass spectrometer and a Q-TOF mass spectrometer, was performed with the aid of specifically deuterium-labeled analogs. The analytes showed good responses in positive-ion electrospray mass spectrometry as [MH]+ ions. Tandem mass spectra revealed a wealth of structurally specific ions, allowing characterization of the fragmentation pathways of these analytes. The major fragmentation pathways of the protonated CP and IF are elimination of ethylene from C5 and C6 of 1,3,2-oxazaphosphorine-2-oxide via a McLafferty rearrangement, and cleavage of the P-N bond. However, their activated 4-OOH and 4-OH metabolites primarily underwent hydrogen peroxide elimination and dehydration, respectively, followed by fragmentation pathways similar to those of CP and IF. These results should prove useful in structural elucidation of future analogs of CP and IF, and/or of their metabolites. Copyright (c) 2005 John Wiley & Sons, Ltd.

High-performance liquid chromatography with diode array detection coupled to electrospray time-of-flight and ion-trap tandem mass spectrometry to identify phenolic compounds from a lemon verbena extract.

PubMed

Quirantes-Piné, R; Funes, L; Micol, V; Segura-Carretero, A; Fernández-Gutiérrez, A

2009-07-10

High-performance liquid chromatography with diode array and electrospray ionization mass spectrometric detection was used to carry out the comprehensive characterization of a lemon verbena extract with demonstrated antioxidant and antiinflammatory activity. Two different MS techniques have been coupled to HPLC: on one hand, time-of-flight mass spectrometry, and on the other hand, tandem mass spectrometry on an ion-trap. The use of a small particle size C18 column (1.8 microm) provided a great resolution and made possible the separation of several isomers. The UV-visible spectrophotometry was used to delimit the class of phenolic compound and the accurate mass measurements on time-of-flight spectrometer enabled to identify the compounds present in the extract. Finally, the fragmentation pattern obtained in MS-MS experiments confirmed the proposed structures. This procedure was able to determine many well-known phenolic compounds present in lemon verbena such as verbascoside and its derivatives, diglucuronide derivatives of apigenin and luteolin, and eukovoside. Also gardoside, verbasoside, cistanoside F, theveside, campneoside I, chrysoeriol-7-diglucuronide, forsythoside A and acacetin-7-diglucuronide were found for the first time in lemon verbena.

Kinetic study on anaerobic oxidation of methane coupled to denitrification.

PubMed

Yu, Hou; Kashima, Hiroyuki; Regan, John M; Hussain, Abid; Elbeshbishy, Elsayed; Lee, Hyung-Sool

2017-09-01

Monod kinetic parameters provide information required for kinetic analysis of anaerobic oxidation of methane coupled to denitrification (AOM-D). This information is critical for engineering AOM-D processes in wastewater treatment facilities. We first experimentally determined Monod kinetic parameters for an AOM-D enriched culture and obtained the following values: maximum specific growth rate (μ max ) 0.121/d, maximum substrate-utilization rate (q max ) 28.8mmol CH 4 /g cells-d, half maximum-rate substrate concentration (K s ) 83μΜ CH 4 , growth yield (Y) 4.76gcells/mol CH 4 , decay coefficient (b) 0.031/d, and threshold substrate concentration (S min ) 28.8μM CH 4 . Clone library analysis of 16S rRNA and mcrA gene fragments suggested that AOM-D reactions might have occurred via the syntrophic interaction between denitrifying bacteria (e.g., Ignavibacterium, Acidovorax, and Pseudomonas spp.) and hydrogenotrophic methanogens (Methanobacterium spp.), supporting reverse methanogenesis-dependent AOM-D in our culture. High μ max and q max , and low K s for the AOM-D enrichment imply that AOM-D could play a significant role in mitigating atmospheric methane efflux. In addition, these high kinetic features suggest that engineered AOM-D systems may provide a sustainable alternative to nitrogen removal in wastewater treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

A serially coupled stationary phase method for the determination of urinary 8-oxo-7,8-dihydro-2′-deoxyguanosine by liquid chromatography ion trap tandem mass spectrometry☆

PubMed Central

Rota, Cristina; Cristoni, Simone; Trenti, Tommaso; Cariani, Elisabetta

2013-01-01

Oxidative attack to DNA is of particular interest since DNA modifications can lead to heritable mutations. The most studied product of DNA oxidation is 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG). While 8-oxodG determination in blood and tissue cells is prone to artifacts, its measurement in urine employing liquid chromatography tandem mass spectrometry (LC-MS/MS) has gained more and more interest for increased reliability. LC-MS/MS can be affected by matrix effects and this is particularly true when ion trap is used as MS analyzer, due to ion accumulation in the trap and related space charge effect. In the present work, we have developed a LC-MS/MS method where the combination of cation exchange and reverse phase solid phases resulted in LC separation optimization. This together with the employment of an isotopically labeled internal standard, allowed the usage of ion trap LC-MS/MS, typically not employed for quantitative measurement in biological samples, for the measurement of 8-oxodG in urine samples from control populations. Four different urine matrices were employed for method validation. Limit of quantitation was set at least at 0.5 ng/ml. While analyzing urine samples from healthy volunteers, 8-oxodG levels reported as ng/ml were statistically different comparing males with females (p<0.05, Mann Whitney test); while comparing results normalized for creatinine no statistical significant difference was found. Mean urinary 8-oxodG level found in healthy volunteers was 1.16±0.46 nmol/mmol creatinine. The present method by enhancing at best the chromatographic performances allows the usage of ion trap LC-MS/MS for the measurement of 8-oxodG in urine samples from control populations. PMID:24251117

Dynamics of tandem bubble interaction in a microfluidic channel

PubMed Central

Yuan, Fang; Sankin, Georgy; Zhong, Pei

2011-01-01

The dynamics of tandem bubble interaction in a microfluidic channel (800 × 21 μm, W × H) have been investigated using high-speed photography, with resultant fluid motion characterized by particle imaging velocimetry. A single or tandem bubble is produced reliably via laser absorption by micron-sized gold dots (6 μm in diameter with 40 μm in separation distance) coated on a glass surface of the microfluidic channel. Using two pulsed Nd:YAG lasers at λ = 1064 nm and ∼10 μJ/pulse, the dynamics of tandem bubble interaction (individual maximum bubble diameter of 50 μm with a corresponding collapse time of 5.7 μs) are examined at different phase delays. In close proximity (i.e., interbubble distance = 40 μm or γ = 0.8), the tandem bubbles interact strongly with each other, leading to asymmetric deformation of the bubble walls and jet formation, as well as the production of two pairs of vortices in the surrounding fluid rotating in opposite directions. The direction and speed of the jet (up to 95 m/s), as well as the orientation and strength of the vortices can be varied by adjusting the phase delay. PMID:22088007

Dynamics of tandem bubble interaction in a microfluidic channel.

PubMed

Yuan, Fang; Sankin, Georgy; Zhong, Pei

2011-11-01

The dynamics of tandem bubble interaction in a microfluidic channel (800  ×  21 μm, W × H) have been investigated using high-speed photography, with resultant fluid motion characterized by particle imaging velocimetry. A single or tandem bubble is produced reliably via laser absorption by micron-sized gold dots (6 μm in diameter with 40 μm in separation distance) coated on a glass surface of the microfluidic channel. Using two pulsed Nd:YAG lasers at λ = 1064 nm and ∼10 μJ/pulse, the dynamics of tandem bubble interaction (individual maximum bubble diameter of 50 μm with a corresponding collapse time of 5.7 μs) are examined at different phase delays. In close proximity (i.e., interbubble distance = 40 μm or γ = 0.8), the tandem bubbles interact strongly with each other, leading to asymmetric deformation of the bubble walls and jet formation, as well as the production of two pairs of vortices in the surrounding fluid rotating in opposite directions. The direction and speed of the jet (up to 95 m/s), as well as the orientation and strength of the vortices can be varied by adjusting the phase delay.

Method for heat treating and sintering metal oxides with microwave radiation

DOEpatents

Holcombe, Cressie E.; Dykes, Norman L.; Meek, Thomas T.

1989-01-01

A method for microwave sintering materials, primarily metal oxides, is described. Metal oxides do not normally absorb microwave radiation at temperatures ranging from about room temperature to several hundred degrees centrigrade are sintered with microwave radiation without the use of the heretofore required sintering aids. This sintering is achieved by enclosing a compact of the oxide material in a housing or capsule formed of a oxide which has microwave coupling properties at room temprature up to at least the microwave coupling temperature of the oxide material forming the compact. The heating of the housing effects the initial heating of the oxide material forming the compact by heat transference and then functions as a thermal insulator for the encased oxide material after the oxide material reaches a sufficient temperature to adequately absorb or couple with microwave radiation for heating thereof to sintering temperature.

On the Relativistic Correction of Particles Trajectory in Tandem Type Electrostatic Accelerator

NASA Astrophysics Data System (ADS)

Minárik, Stanislav

2015-08-01

A constant potential is applied to the acceleration of the ion-beam in the tandem type electrostatic accelerator. However, not just one voltage is applied, but instead a number of applications can be made in succession by means of the tandem arrangement of high voltage tubes. This number of voltage applications, which is the number of so-called "stages" of a tandem accelerator, may be two, three, or four, depending on the chosen design. Electrostatic field with approximately constant intensity acts on ions in any stage. In general, non-relativistic dynamics is used for the description of the ion transport in tandem accelerator. Energies of accelerated ions are too low and relativistic effects cannot be commonly observed by standard experimental technique. Estimation of possible relativistic correction of ion trajectories is therefore only a matter of calculation. In this note, we briefly present such calculation. Our aim is to show how using the relativistic dynamics modifies the particles trajectory in tandem type accelerator and what parameters determine this modification.

Simulation of two dimensional electrophoresis and tandem mass spectrometry for teaching proteomics.

PubMed

Fisher, Amanda; Sekera, Emily; Payne, Jill; Craig, Paul

2012-01-01

In proteomics, complex mixtures of proteins are separated (usually by chromatography or electrophoresis) and identified by mass spectrometry. We have created 2DE Tandem MS, a computer program designed for use in the biochemistry, proteomics, or bioinformatics classroom. It contains two simulations-2D electrophoresis and tandem mass spectrometry. The two simulations are integrated together and are designed to teach the concept of proteome analysis of prokaryotic and eukaryotic organisms. 2DE-Tandem MS can be used as a freestanding simulation, or in conjunction with a wet lab, to introduce proteomics in the undergraduate classroom. 2DE Tandem MS is a free program available on Sourceforge at https://sourceforge.net/projects/jbf/. It was developed using Java Swing and functions in Mac OSX, Windows, and Linux, ensuring that every student sees a consistent and informative graphical user interface no matter the computer platform they choose. Java must be installed on the host computer to run 2DE Tandem MS. Example classroom exercises are provided in the Supporting Information. Copyright © 2012 Wiley Periodicals, Inc.

Nitroethylation of Vinyl Triflates and Bromides

PubMed Central

Padilla–Salinas, Rosaura; Walvoord, Ryan R.; Tcyrulnikov, Sergei

2013-01-01

A two-carbon homologation of vinyl triflates and bromides for the synthesis of homoallylic nitro products is described. This palladium-catalyzed double coupling of nitromethane exploits the anion stabilizing and leaving group properties of nitromethane, generating the homo allyl nitro products via a tandem cross-coupling/π-allylation sequence. The resultant process provides a mild and convenient entry of nitroethylated products, which are versatile precursors to β,γ-unsaturated carbonyls, homoallylic amines, and nitrile oxides. PMID:23885976

Scanning electron microscopy coupled with energy-dispersive X-ray spectrometry for quick detection of sulfur-oxidizing bacteria in environmental water samples

NASA Astrophysics Data System (ADS)

Sun, Chengjun; Jiang, Fenghua; Gao, Wei; Li, Xiaoyun; Yu, Yanzhen; Yin, Xiaofei; Wang, Yong; Ding, Haibing

2017-01-01

Detection of sulfur-oxidizing bacteria has largely been dependent on targeted gene sequencing technology or traditional cell cultivation, which usually takes from days to months to carry out. This clearly does not meet the requirements of analysis for time-sensitive samples and/or complicated environmental samples. Since energy-dispersive X-ray spectrometry (EDS) can be used to simultaneously detect multiple elements in a sample, including sulfur, with minimal sample treatment, this technology was applied to detect sulfur-oxidizing bacteria using their high sulfur content within the cell. This article describes the application of scanning electron microscopy imaging coupled with EDS mapping for quick detection of sulfur oxidizers in contaminated environmental water samples, with minimal sample handling. Scanning electron microscopy imaging revealed the existence of dense granules within the bacterial cells, while EDS identified large amounts of sulfur within them. EDS mapping localized the sulfur to these granules. Subsequent 16S rRNA gene sequencing showed that the bacteria detected in our samples belonged to the genus Chromatium, which are sulfur oxidizers. Thus, EDS mapping made it possible to identify sulfur oxidizers in environmental samples based on localized sulfur within their cells, within a short time (within 24 h of sampling). This technique has wide ranging applications for detection of sulfur bacteria in environmental water samples.

Forensic applications of direct analysis in real time (DART) coupled to Q-orbitrap tandem mass spectrometry for the in situ analysis of pigments from paint evidence.

PubMed

Chen, Tai-Hung; Wu, Shu-Pao

2017-08-01

The accurate examination of paint fragments obtained from an accident, such as those obtained from vehicles involved in a hit-and-run case, is often critical in forensic investigations. However, organic pigments are typically minor components of automotive coatings, which makes discrimination difficult. In this study, direct analysis in real time coupled to Q-orbitrap tandem mass spectrometry (DART-MS) was employed to detect a wide range of common organic pigments in vehicle paints. Twelve common organic pigments used in vehicle paints, such as red, yellow, orange, and purple, were tested, and a database was constructed for future examinations of vehicle paint. Two hit-and-run vehicle accident cases, which occurred in New Taipei City, were investigated by Fourier transform infrared (FTIR) spectroscopy and DART-MS. First, FTIR spectroscopy was employed to study the paint samples as a preliminary screening step. Most of the observed IR peaks were attributed to binder and extenders present in paints. The IR peaks corresponding to the organic pigments were found to be weak and overlapped with those corresponding to resins. On the other hand, DART-MS successfully characterized the organic pigments. DART-MS was found to be excellent for rapidly determining the presence of organic pigments in paint samples without the need for a complicated pre-treatment process or lengthy analysis time. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of an advanced spacecraft tandem mass spectrometer

NASA Astrophysics Data System (ADS)

Drew, Russell C.

1992-03-01

The purpose of this research was to apply current advanced technology in electronics and materials to the development of a miniaturized Tandem Mass Spectrometer that would have the potential for future development into a package suitable for spacecraft use. The mass spectrometer to be used as a basis for the tandem instrument would be a magnetic sector instrument, of Nier-Johnson configuration, as used on the Viking Mars Lander mission. This instrument configuration would then be matched with a suitable second stage MS to provide the benefits of tandem MS operation for rapid identification of unknown organic compounds. This tandem instrument is configured with a newly designed GC system to aid in separation of complex mixtures prior to MS analysis. A number of important results were achieved in the course of this project. Among them were the development of a miniaturized GC subsystem, with a unique desorber-injector, fully temperature feedback controlled oven with powered cooling for rapid reset to ambient conditions, a unique combination inlet system to the MS that provides for both membrane sampling and direct capillary column sample transfer, a compact and ruggedized alignment configuration for the MS, an improved ion source design for increased sensitivity, and a simple, rugged tandem MS configuration that is particularly adaptable to spacecraft use because of its low power and low vacuum pumping requirements. The potential applications of this research include use in manned spacecraft like the space station as a real-time detection and warning device for the presence of potentially harmful trace contaminants of the spacecraft atmosphere, use as an analytical device for evaluating samples collected on the Moon or a planetary surface, or even use in connection with monitoring potentially hazardous conditions that may exist in terrestrial locations such as launch pads, environmental test chambers or other sensitive areas. Commercial development of the technology

Development of an advanced spacecraft tandem mass spectrometer

NASA Technical Reports Server (NTRS)

Drew, Russell C.

1992-01-01

The purpose of this research was to apply current advanced technology in electronics and materials to the development of a miniaturized Tandem Mass Spectrometer that would have the potential for future development into a package suitable for spacecraft use. The mass spectrometer to be used as a basis for the tandem instrument would be a magnetic sector instrument, of Nier-Johnson configuration, as used on the Viking Mars Lander mission. This instrument configuration would then be matched with a suitable second stage MS to provide the benefits of tandem MS operation for rapid identification of unknown organic compounds. This tandem instrument is configured with a newly designed GC system to aid in separation of complex mixtures prior to MS analysis. A number of important results were achieved in the course of this project. Among them were the development of a miniaturized GC subsystem, with a unique desorber-injector, fully temperature feedback controlled oven with powered cooling for rapid reset to ambient conditions, a unique combination inlet system to the MS that provides for both membrane sampling and direct capillary column sample transfer, a compact and ruggedized alignment configuration for the MS, an improved ion source design for increased sensitivity, and a simple, rugged tandem MS configuration that is particularly adaptable to spacecraft use because of its low power and low vacuum pumping requirements. The potential applications of this research include use in manned spacecraft like the space station as a real-time detection and warning device for the presence of potentially harmful trace contaminants of the spacecraft atmosphere, use as an analytical device for evaluating samples collected on the Moon or a planetary surface, or even use in connection with monitoring potentially hazardous conditions that may exist in terrestrial locations such as launch pads, environmental test chambers or other sensitive areas. Commercial development of the technology

Comprehensive analysis of ß-lactam antibiotics including penicillins, cephalosporins, and carbapenems in poultry muscle using liquid chromatography coupled to tandem mass spectrometry.

PubMed

Berendsen, Bjorn J A; Gerritsen, Henk W; Wegh, Robin S; Lameris, Steven; van Sebille, Ralph; Stolker, Alida A M; Nielen, Michel W F

2013-09-01

A comprehensive method for the quantitative residue analysis of trace levels of 22 ß-lactam antibiotics, including penicillins, cephalosporins, and carbapenems, in poultry muscle by liquid chromatography in combination with tandem mass spectrometric detection is reported. The samples analyzed for ß-lactam residues are hydrolyzed using piperidine in order to improve compound stability and to include the total residue content of the cephalosporin ceftifour. The reaction procedure was optimized using a full experimental design. Following detailed isotope labeling, tandem mass spectrometry studies and exact mass measurements using high-resolution mass spectrometry reaction schemes could be proposed for all ß-lactams studied. The main reaction occurring is the hydrolysis of the ß-lactam ring under formation of the piperidine substituted amide. For some ß-lactams, multiple isobaric hydrolysis reaction products are obtained, in accordance with expectations, but this did not hamper quantitative analysis. The final method was fully validated as a quantitative confirmatory residue analysis method according to Commission Decision 2002/657/EC and showed satisfactory quantitative performance for all compounds with trueness between 80 and 110% and within-laboratory reproducibility below 22% at target level, except for biapenem. For biapenem, the method proved to be suitable for qualitative analysis only.

[Determination of biurea in flour and its products by liquid chromatography-tandem mass spectrometry].

PubMed

Wang, Ya; Wang, Junsu; Xiang, Lu; Xi, Cunxian; Chen, Dongdong; Peng, Tao; Wang, Guomin; Mu, Zhaode

2014-05-01

A novel method was established for the determination and identification of biurea in flour and its products using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The biurea was extracted with water and oxidized to azodicarbonamide by potassium permanganate. The azodicarbonamide was then derivatized using sodium p-toluene sulfinate solution. The separation was performed on a Shimpak XR-ODS II column (150 mm x 2.0 mm, 2.2 microm) using the mobile phase composed of acetonitrile and 2 mmol/L ammonium acetate aqueous solution (containing 0.2% (v/v) formic acid) with a gradient elution program. Tandem mass spectrometric detection was performed in multiple reaction monitoring (MRM) scan mode with a positive electrospray ionization (ESI(+)) source. The method used stable isotope internal standard quantitation. The calibration curve showed good linearity over the range of 1-20 000 microg/kg (R2 = 0.999 9). The limit of quantification was 5 microg/kg for biurea spiked in flour and its products. At the spiking levels of 5.0, 10.0 and 50.0 microg/kg in different matrices, the average recovery o biurea was 78.3%-108.0% with the relative standard deviations (RSDs) < or = 5.73%. The method developed is novel, reliable and sensitive with wide linear range, and can be used to determine the biurea in flour and its products.

Design and long-term monitoring of DSC/CIGS tandem solar module

NASA Astrophysics Data System (ADS)

Vildanova, M. F.; Nikolskaia, A. B.; Kozlov, S. S.; Shevaleevskiy, O. I.

2015-11-01

This paper describes the design and development of tandem dye-sensitized/Cu(In, Ga)Se (DSC/CIGS) PV modules. The tandem PV module comprised of the top DSC module and a bottom commercial 0,8 m2 CIGS module. The top DSC module was made of 10 DSC mini-modules with the field size of 20 × 20 cm2 each. Tandem DSC/CIGS PV modules were used for providing the long-term monitoring of energy yield and electrical parameters in comparison with standalone CIGS modules under outdoor conditions. The outdoor test facility, containing solar modules of both types and a measurement unit, was located on the roof of the Institute of Biochemical Physics in Moscow. The data obtained during monitoring within the 2014 year period has shown the advantages of the designed tandem DSC/CIGS PV-modules over the conventional CIGS modules, especially for cloudy weather and low-intensity irradiation conditions.

Heterobimetallic Pd-Sn catalysis: a Suzuki, tandem ring-closing sequence toward indeno[2,1-b]thiophenes and indeno[2,1-b]indoles.

PubMed

Das, Debjit; Pratihar, Sanjay; Roy, Sujit

2012-09-21

Indeno[2,1-b]thiophene and indeno[1,2-b]indole motifs have been obtained in moderate to good yields from easily available substituted boronic acids, 2-bromo aryl/vinyl aldehydes, and nucleophiles such as arenes/heteroarenes and others using a catalytic combination of bimetallic "Pd-Sn" and AgPF(6). This formal three-component coupling involves a Suzuki reaction followed by nucleophile assisted tandem ring closure. The sequential synthesis of substituted heterocycle-fused indenes, benzofluorene, and fluorenes was also accomplished.

An Efficient Glycoblotting-Based Analysis of Oxidized Lipids in Liposomes and a Lipoprotein.

PubMed

Furukawa, Takayuki; Hinou, Hiroshi; Takeda, Seiji; Chiba, Hitoshi; Nishimura, Shin-Ichiro; Hui, Shu-Ping

2017-10-05

Although widely occurring lipid oxidation, which is triggered by reactive oxygen species (ROS), produces a variety of oxidized lipids, practical methods to efficiently analyze oxidized lipids remain elusive. Herein, it is shown that the glycoblotting platform can be used to analyze oxidized lipids. Analysis is based on the principle that lipid aldehydes, one of the oxidized lipid species, can be captured selectively, enriched, and detected. Moreover, 3-methyl-1-p-tolyltriazene (MTT) methylates phosphoric and carboxylic acids, and this MTT-mediated methylation is, in combination with conventional tandem mass spectrometry (MS/MS) analysis, an effective method for the structural analysis of oxidized lipids. By using three classes of standards, liposomes, and a lipoprotein, it is demonstrated that glycoblotting represents a powerful approach for focused lipidomics, even in complex macromolecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

De novo protein sequencing by combining top-down and bottom-up tandem mass spectra.

PubMed

Liu, Xiaowen; Dekker, Lennard J M; Wu, Si; Vanduijn, Martijn M; Luider, Theo M; Tolić, Nikola; Kou, Qiang; Dvorkin, Mikhail; Alexandrova, Sonya; Vyatkina, Kira; Paša-Tolić, Ljiljana; Pevzner, Pavel A

2014-07-03

There are two approaches for de novo protein sequencing: Edman degradation and mass spectrometry (MS). Existing MS-based methods characterize a novel protein by assembling tandem mass spectra of overlapping peptides generated from multiple proteolytic digestions of the protein. Because each tandem mass spectrum covers only a short peptide of the target protein, the key to high coverage protein sequencing is to find spectral pairs from overlapping peptides in order to assemble tandem mass spectra to long ones. However, overlapping regions of peptides may be too short to be confidently identified. High-resolution mass spectrometers have become accessible to many laboratories. These mass spectrometers are capable of analyzing molecules of large mass values, boosting the development of top-down MS. Top-down tandem mass spectra cover whole proteins. However, top-down tandem mass spectra, even combined, rarely provide full ion fragmentation coverage of a protein. We propose an algorithm, TBNovo, for de novo protein sequencing by combining top-down and bottom-up MS. In TBNovo, a top-down tandem mass spectrum is utilized as a scaffold, and bottom-up tandem mass spectra are aligned to the scaffold to increase sequence coverage. Experiments on data sets of two proteins showed that TBNovo achieved high sequence coverage and high sequence accuracy.

Single P-N junction tandem photovoltaic device

DOEpatents

Walukiewicz, Wladyslaw [Kensington, CA; Ager, III, Joel W.; Yu, Kin Man [Lafayette, CA

2012-03-06

A single P-N junction solar cell is provided having two depletion regions for charge separation while allowing the electrons and holes to recombine such that the voltages associated with both depletion regions of the solar cell will add together. The single p-n junction solar cell includes an alloy of either InGaN or InAlN formed on one side of the P-N junction with Si formed on the other side in order to produce characteristics of a two junction (2J) tandem solar cell through only a single P-N junction. A single P-N junction solar cell having tandem solar cell characteristics will achieve power conversion efficiencies exceeding 30%.

Single P-N junction tandem photovoltaic device

DOEpatents

Walukiewicz, Wladyslaw [Kensington, CA; Ager, III, Joel W.; Yu, Kin Man [Lafayette, CA

2011-10-18

A single P-N junction solar cell is provided having two depletion regions for charge separation while allowing the electrons and holes to recombine such that the voltages associated with both depletion regions of the solar cell will add together. The single p-n junction solar cell includes an alloy of either InGaN or InAlN formed on one side of the P-N junction with Si formed on the other side in order to produce characteristics of a two junction (2J) tandem solar cell through only a single P-N junction. A single P-N junction solar cell having tandem solar cell characteristics will achieve power conversion efficiencies exceeding 30%.

Efficient Monolithic Perovskite/Silicon Tandem Solar Cell with Cell Area >1 cm(2).

PubMed

Werner, Jérémie; Weng, Ching-Hsun; Walter, Arnaud; Fesquet, Luc; Seif, Johannes Peter; De Wolf, Stefaan; Niesen, Bjoern; Ballif, Christophe

2016-01-07

Monolithic perovskite/crystalline silicon tandem solar cells hold great promise for further performance improvement of well-established silicon photovoltaics; however, monolithic tandem integration is challenging, evidenced by the modest performances and small-area devices reported so far. Here we present first a low-temperature process for semitransparent perovskite solar cells, yielding efficiencies of up to 14.5%. Then, we implement this process to fabricate monolithic perovskite/silicon heterojunction tandem solar cells yielding efficiencies of up to 21.2 and 19.2% for cell areas of 0.17 and 1.22 cm(2), respectively. Both efficiencies are well above those of the involved subcells. These single-junction perovskite and tandem solar cells are hysteresis-free and demonstrate steady performance under maximum power point tracking for several minutes. Finally, we present the effects of varying the intermediate recombination layer and hole transport layer thicknesses on tandem cell photocurrent generation, experimentally and by transfer matrix simulations.

Confirmatory and quantitative analysis of fatty acid esters of hydroxy fatty acids in serum by solid phase extraction coupled to liquid chromatography tandem mass spectrometry.

PubMed

López-Bascón, María Asunción; Calderón-Santiago, Mónica; Priego-Capote, Feliciano

2016-11-02

A novel class of endogenous mammalian lipids endowed with antidiabetic and anti-inflammatory properties has been recently discovered. These are fatty acid esters of hydroxy fatty acids (FAHFAs) formed by condensation between a hydroxy fatty acid and a fatty acid. FAHFAs are present in human serum and tissues at low nanomolar concentrations. Therefore, high sensitivity and selectivity profiling analysis of these compounds in clinical samples is demanded. An automated qualitative and quantitative method based on on-line coupling between solid phase extraction and liquid chromatography-tandem mass spectrometry has been here developed for determination of FAHFAs in serum with the required sensitivity and selectivity. Matrix effects were evaluated by preparation of calibration models in serum and methanol. Recovery factors ranged between 73.8 and 100% in serum. The within-day variability ranged from 7.1 to 13.8%, and the between-days variability varied from 9.3 to 21.6%, which are quite acceptable values taking into account the low concentration levels at which the target analytes are found. The method has been applied to a cohort of human serum samples to estimate the concentrations profiles as a function of the glycaemic state and obesity. Statistical analysis revealed three FAHFAs with levels significantly different depending on the glycaemic state or the body mass index. This automated method could be implemented in high-throughput analysis with minimum user assistance. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of haloacetic acids, bromate, and dalapon in natural waters by ion chromatography-tandem mass spectrometry.

PubMed

Wu, Shimin; Anumol, Tarun; Gandhi, Jay; Snyder, Shane A

2017-03-03

The addition of oxidants for disinfecting water can lead to the formation of potentially carcinogenic compounds referred to as disinfection byproducts (DBPs). Haloacetic acids (HAAs) are one of the most widely detected DBPs in US water utilities and some of them are regulated by the US Environmental Protection Agency (USEPA). The present study developed a method to analyze all the compounds in the USEPA method 557 (nine HAAs, bromate and dalapon) plus four potentially more toxic iodinated HAAs in water by coupling ion chromatography with tandem mass spectrometry (IC-MS/MS). This aqueous direct injection method has significant advantages over traditional GC methods, which require a derivatization and sample extraction that are laborious, time-consuming, and can negatively impact reproducibility. The method developed in this study requires half the time of the current USEPA method 557 on IC-MS/MS while including more compounds and achieving sub-μg/L level method detection limits (MDLs) for all 15 target analytes. The single laboratory lowest concentration minimum reporting level (LCMRL) has also been determined in reagent water, which ranged from 0.011 to 0.62μg/L for the analytes. The mean recoveries of the analytes during matrix spike recovery tests were 77-125% in finished drinking water and 81-112% in surface water. This method was then applied to untreated, chlorinated, and chloraminated groundwater and surface water samples. Bromate and 9 HAAs were detected at different levels in some of these samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultra-performance liquid chromatography-tandem mass spectrometry for the determination of atypical antipsychotics and some metabolites in in vitro samples.

PubMed

Li, Kun-Yan; Zhou, Yan-Gang; Ren, Hua-Yi; Wang, Feng; Zhang, Bi-Kui; Li, Huan-De

2007-05-01

The ultra-performance liquid chromatography-electrospray tandem mass spectrometry (UPLC-ESI-MS/MS) method has been developed to perform the determination of quetiapine, perospirone, aripiprazole and quetiapine sulfoxide in in vitro samples in less than 3 min. The UPLC separation was carried out using an Acquity UPLC BEH C18 column (100 mm x 2.1mm i.d., 1.7 microm particle size) that provided high efficiency and resolution in combination with high linear velocities. The UPLC system was coupled to a Waters Micromass Quattro Premier XE tandem quadrupole mass spectrometer. This system permits high-speed data acquisition without peak intensity degradation, and produces sharp and narrow chromatographic peaks (w(h) about 2.5s) of compounds. The determination was performed in multiple reaction monitoring (MRM) mode. The quantification parameters of the developed method were established, obtaining instrumental LODs lower than 0.005 microg/l and a repeatability at a low concentration level lower than 10% CV (n=10). Finally, the method was successfully applied to the analysis of atypical antipsychotics and some metabolites in in vitro samples.

Base-Free Photoredox/Nickel Dual-Catalytic Cross-Coupling of Ammonium Alkylsilicates.

PubMed

Jouffroy, Matthieu; Primer, David N; Molander, Gary A

2016-01-20

Single-electron transmetalation is recognized as an enabling technology for the mild transfer of alkyl groups to transition metal catalysts in cross-coupling reactions. Hypercoordinate silicates represent a new and improved class of radical precursors because of their low oxidation potentials and the innocuous byproducts generated upon oxidation. Herein, we report the cross-coupling of secondary and primary ammonium alkylsilicates with (hetero)aryl bromides in good to excellent yields. The base-free conditions have exceptional protic group tolerance on both partners, permitting the cross-coupling of unprotected primary and secondary amines.

Isolation and Characterization of Microbes Mediating Thermodynamically Favorable Coupling of Anaerobic Oxidation of Methane and Metal Reduction

NASA Astrophysics Data System (ADS)

Glass, J. B.; Reed, B. C.; Sarode, N. D.; Kretz, C. B.; Bray, M. S.; DiChristina, T. J.; Stewart, F. J.; Fowle, D. A.; Crowe, S.

2014-12-01

Methane is the third most reduced environmentally relevant electron donor for microbial metabolisms after organic carbon and hydrogen. In anoxic ecosystems, the major sink for methane is anaerobic oxidation of methane (AOM) mediated by syntrophic microbial consortia that couple AOM to reduction of an oxidized electron acceptor to yield free energy. In marine sediments, AOM is generally coupled to reduction of sulfate despite an extremely small amount of free energy yield because sulfate is the most abundant electron acceptor in seawater. While AOM coupled to Fe(III) and Mn(IV) reduction (Fe- and Mn-AOM) is 10-30x more thermodynamically favorable than sulfate-AOM, and geochemical data suggests that it occurs in diverse environments, the microorganisms mediating Fe- and Mn-AOM remain unknown. Lake Matano, Indonesia is an ideal ecosystem to enrich for Fe- and Mn-AOM microbes because its anoxic ferruginous deep waters and sediments contain abundant Fe(III), Mn(IV) and methane, and extremely low sulfate and nitrate. Our research aims to isolate and characterize the microbes mediating Fe- and Mn-AOM from three layers of Lake Matano sediments through serial enrichment cultures in minimal media lacking nitrate and sulfate. 16S rRNA amplicon sequencing of sediment inoculum revealed the presence of the Fe(III)-reducing bacterium Geobacter (5-10% total microbial community in shallow sediment and 35-60% in deeper sediment) as well as 1-2% Euryarchaeota implicated in methane cycling, including ANME-1 and 2d and Methanosarcinales. After 90 days of primary enrichment, all three sediment layers showed high levels of Fe(III) reduction (60-90 μM Fe(II) d-1) in the presence of methane compared to no methane and heat-killed controls. Treatments with added Fe(III) as goethite contained higher abundances of Geobacter than the inoculum (60-80% in all layers), suggesting that Geobacter may be mediating Fe(III) reduction in these enrichments. Quantification of AOM rates is underway, and

Simultaneous determination of three pesticides and their metabolites in unprocessed foods using ultraperformance liquid chromatography-tandem mass spectrometry.