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Sample records for high-performance esi fticr

  1. High-Throughput Proteomics Using High Efficiency Multiple-Capillary Liquid Chromatography With On-Line High-Performance ESI FTICR Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Yufeng (BATTELLE (PACIFIC NW LAB)); Tolic, Nikola (BATTELLE (PACIFIC NW LAB)); Zhao, Rui (ASSOC WESTERN UNIVERSITY); Pasa Tolic, Ljiljana (BATTELLE (PACIFIC NW LAB)); Li, Lingjun (Illinois Univ Of-Urbana/Champa); Berger, Scott J.(ASSOC WESTERN UNIVERSITY); Harkewicz, Richard (BATTELLE (PACIFIC NW LAB)); Anderson, Gordon A.(BATTELLE (PACIFIC NW LAB)); Belov, Mikhail E.(BATTELLE (PACIFIC NW LAB)); Smith, Richard D.(BATTELLE (PACIFIC NW LAB))

    2000-12-01

    We report on the design and application of a high-efficiency multiple-capillary liquid chromatography (LC) system for high-throughput proteome analysis. The multiple-capillary LC system was operated at the pressure of 10,000 psi using commercial LC pumps to deliver the mobile phase and newly developed passive feedback valves to switch the mobile phase flow and introduce samples. The multiple-capillary LC system was composed of several serially connected dual-capillary column devices. The dual-capillary column approach was designed to eliminate the time delay for regeneration (or equilibrium) of the capillary column after its use under the mobile phase gradient condition (i.e. one capillary column was used in separation and the other was washed using mobile phase A). The serially connected dual-capillary columns and ESI sources were operated independently, and could be used for either''backup'' operation or with other mass spectrometer(s). This high-efficiency multiple-capillary LC system uses switching valves for all operations and is highly amenable to automation. The separations efficiency of dual-capillary column device, optimal capillary dimensions (column length and packed particle size), suitable mobile phases for electrospray, and the capillary re-generation were investigated. A high magnetic field (11.5 tesla) Fourier transform ion cyclotron resonance (FTICR) mass spectrometer was coupled on-line with this high-efficiency multiple-capillary LC system through an electrospray ionization source. The capillary LC provided a peak capacity of {approx}600, and the 2-D capillary LC-FTICR provided a combined resolving power of > 6 x 10 7 polypeptide isotopic distributions. For yeast cellular tryptic digests, > 100,000 polypeptides were typically detected, and {approx}1,000 proteins can be characterized in a single run.

  2. Determination of soyasaponins in Fagioli di Sarconi beans (Phaseolus vulgaris L.) by LC-ESI-FTICR-MS and evaluation of their hypoglycemic activity.

    Science.gov (United States)

    Bianco, Giuliana; Pascale, Raffaella; Carbone, Cecilia F; Acquavia, Maria A; Cataldi, Tommaso R I; Schmitt-Kopplin, Philippe; Buchicchio, Alessandro; Russo, Daniela; Milella, Luigi

    2018-02-01

    Soyasaponins are oleanene-type triterpenoid saponins, naturally occurring in many edible plants that have attracted a great deal of attention for their role in preventing chronic diseases. The aim of this study was to establish the distribution and the content of soyasaponins in 21 ecotypes of Fagioli di Sarconi beans (Phaseolus vulgaris, Leguminosae). High-performance reversed-phase liquid chromatography (RPLC) with positive electrospray ionization (ESI(+)) and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS) in conjunction with infrared multiphoton dissociation (IRMPD) was applied for the unambiguous identification of soyasaponins Ba (m/z 959.5213, [C 48 H 79 O 19 ] + ), Bb (m/z 943.5273, [C 48 H 79 O 18 ] + ), Bd (m/z 957.5122, [C 48 H 77 O 19 ] + ), and Be (m/z 941.5166, [C 48 H 77 O 18 ] + ), which are the only commercially available reference standards. In addition, the several diagnostic product ions generated by IRMPD in the ICR-MS cell allowed us the putative identification of soyasaponins Bb' (m/z 797.4680, [C 42 H 69 O 14 ] + ), αg (m/z 1085.5544, [C 54 H 85 O 22 ] + ), βg (m/z 1069.5600, [C 54 H 85 O 21 ] + ), and γg (m/z 923.5009, [C 48 H 75 O 17 ] + ), establishing thus their membership in the soyasaponin group. Quantitative and semiquantitative analysis of identified soyasaponins were also performed by RPLC-ESI(+) FTICR-MS; the total concentration levels were found ranging from 83.6 ± 9.3 to 767 ± 37 mg/kg. In vitro hypoglycemic outcomes of four soyasaponin standards were evaluated; significant inhibitory activities were obtained with IC 50 values ranging from 1.5 ± 0.1 to 2.3 ± 0.2 μg/mL and 12.0 ± 1.1 to 29.4 ± 1.4 μg/mL for α-glucosidase and α-amylase, respectively. This study represents the first detailed investigation on the antidiabetic activity of bioactive constituents found in Fagioli di Sarconi beans. Graphical abstract The first detailed RPLC-ESI(+) FTICR-MS investigation of

  3. Use of ESI-FTICR-MS to Characterize Dissolved Organic Matter in Headwater Streams Draining Forest-Dominated and Pasture-Dominated Watersheds.

    Directory of Open Access Journals (Sweden)

    YueHan Lu

    Full Text Available Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest- or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8-87.9%, with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C = 0.7-1.5, O/C = 0.1-0.67, suggesting the predominance of allochthonous, terrestrial plant-derived DOM. Relative to the two pasture streams, DOM formulas in the two forest streams were more similar, based on Jaccard similarity coefficients and nonmetric multidimensional scaling calculated from Bray-Curtis distance. Formulas from the pasture streams were characterized by lower proportions of aromatic formulas and lower unsaturation, suggesting that the allochthonous versus autochthonous contributions of organic matter to streams were modified by pasture land use. The number of condensed aromatic structures (CAS was higher for the forest streams, which is possibly due to the controlled burning in the forest-dominated watersheds and suggests that black carbon was mobilized from soils to streams. During 15-day biodegradation experiments, DOM from the two pasture streams was altered to a greater extent than DOM from the forest streams, with formulas with H/C and O/C ranges similar to protein (H/C = 1.5-2.2, O/C = 0.3-0.67, lipid (H/C = 1.5-2.0, O/C = 0-0.3, and unsaturated hydrocarbon (H/C = 0.7-1.5, O/C = 0-0.1 being the most bioreactive groups. Aromatic compound formulas including CAS were preferentially removed during combined light

  4. Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool

    Science.gov (United States)

    Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

    2018-03-01

    Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H]-. Nevertheless, NH3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous CxHyOz bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. [Figure not available: see fulltext.

  5. Organic environments on Saturn's moon, Titan: simulating chemical reactions and analyzing products by FT-ICR and ion-trap mass spectrometry.

    Science.gov (United States)

    Somogyi, Arpad; Oh, Chu-Ha; Smith, Mark A; Lunine, Jonathan I

    2005-06-01

    Laboratory simulations have been carried out to model chemical reactions that possibly take place in the stratosphere of Saturn's moon, Titan. The aerosol products of these reactions (tholin samples) have been systematically analyzed by mass spectrometry using electrospray ionization (ESI) and laser desorption (LD). A wide variety of ions with a general formula C(x)H(y)N(z) detected by ultrahigh resolution and accurate mass measurements in a Fourier transform/ion cyclotron resonance (FT-ICR) cell reflect the complexity of these polymeric products, both in chemical compositions and isomeric distributions. As a common feature, however, tandem mass spectral (MS/MS) data and H/D exchange products in the solution phase support the presence of amino and nitrile functionalities in these (highly unsaturated) "tholin" compounds. The present work demonstrates that ESI-MS coupled with FT-ICR is a suitable and "intact" method to analyze tholin components formed under anaerobic conditions; only species with C(x)H(y)N(z) are detected for freshly prepared and harvested samples. However, when intentionally exposed to water, oxygen-containing compounds are unambiguously detected.

  6. An Automated High Performance Capillary Liquid Chromatography Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for High-Throughput Proteomics

    International Nuclear Information System (INIS)

    Belov, Mikhail E.; Anderson, Gordon A.; Wingerd, Mark A.; Udseth, Harold R.; Tang, Keqi; Prior, David C.; Swanson, Kenneth R.; Buschbach, Michael A.; Strittmatter, Eric F.; Moore, Ronald J.; Smith, Richard D.

    2004-01-01

    We report on a fully automated 9.4 tesla Fourier transform ion resonance cyclotron (FTICR) mass spectrometer coupled to reverse-phase chromatography for high-throughput proteomic studies. Modifications made to the front-end of a commercial FTICR instrument--a dual-ESI-emitter ion source; dual-channel electrodynamic ion funnel; and collisional-cooling, selection and accumulation quadrupoles--significantly improved the sensitivity, dynamic range and mass measurement accuracy of the mass spectrometer. A high-pressure capillary liquid chromatography (LC) system was incorporated with an autosampler that enabled 24 h/day operation. A novel method for accumulating ions in the ICR cell was also developed. Unattended operation of the instrument revealed the exceptional reproducibility (1-5% deviation in elution times for peptides from a bacterial proteome), repeatability (10-20% deviation in detected abundances for peptides from the same aliquot analyzed a few weeks apart) and robustness (high-throughput operation for 5 months without downtime) of the LC/FTICR system. When combined with modulated-ion-energy gated trapping, the internal calibration of FTICR mass spectra decreased dispersion of mass measurement errors for peptide identifications in conjunction with high resolution capillary LC separations to < 5 ppm over a dynamic range for each spectrum of 10 3

  7. Hydrothermal liquefaction oil and hydrotreated product from pine feedstock characterized by heteronuclear two-dimensional NMR spectroscopy and FT-ICR mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sudasinghe, Nilusha; Cort, John R.; Hallen, Richard T.; Olarte, Mariefel V.; Schmidt, Andrew J.; Schaub, Tanner

    2014-12-01

    Hydrothermal liquefaction (HTL) crude oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution twodimensional heteronuclear 1H-13C NMR spectroscopy. FT-ICR MS resolves thousands of compounds in complex oils and provides unparalleled compositional details for individual molecules for identification of compound class (heteroatom content), type (number of rings plus double bonds to carbon or double bond equivalents (DBE) and carbon number (degree of alkylation). Heteronuclear 1H-13C NMR spectroscopy provides one-bond and multiple-bond correlations between pairs of 1H and 13C chemical shifts that are characteristic of different organic functional groups. Taken together this information provides a picture of the chemical composition of these oils. Pyrolysis crude oil product from pine wood was characterized for comparison. Generally, pyrolysis oil is comprised of a more diverse distribution of heteroatom classes with higher oxygen number relative to HTL oil as shown by both positive- and negative-ion ESI FT-ICR MS. A total of 300 N1, 594 O1 and 267 O2 compounds were observed as products of hydrotreatment. The relative abundance of N1O1, N1O2, N1O3, N2, N2O1, N2O2 and O3 compounds are reduced to different degrees after hydrotreatment and other higher heteroatom containing species (O4-O10, N1O4, N1O5 and N2O3) are completely removed by hydrotreatment.

  8. Next-generation technologies for spatial proteomics: Integrating ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR imaging mass spectrometry for protein analysis.

    Science.gov (United States)

    Spraggins, Jeffrey M; Rizzo, David G; Moore, Jessica L; Noto, Michael J; Skaar, Eric P; Caprioli, Richard M

    2016-06-01

    MALDI imaging mass spectrometry is a powerful analytical tool enabling the visualization of biomolecules in tissue. However, there are unique challenges associated with protein imaging experiments including the need for higher spatial resolution capabilities, improved image acquisition rates, and better molecular specificity. Here we demonstrate the capabilities of ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR IMS platforms as they relate to these challenges. High spatial resolution MALDI-TOF protein images of rat brain tissue and cystic fibrosis lung tissue were acquired at image acquisition rates >25 pixels/s. Structures as small as 50 μm were spatially resolved and proteins associated with host immune response were observed in cystic fibrosis lung tissue. Ultra-high speed MALDI-TOF enables unique applications including megapixel molecular imaging as demonstrated for lipid analysis of cystic fibrosis lung tissue. Additionally, imaging experiments using MALDI FTICR IMS were shown to produce data with high mass accuracy (z 5000) for proteins up to ∼20 kDa. Analysis of clear cell renal cell carcinoma using MALDI FTICR IMS identified specific proteins localized to healthy tissue regions, within the tumor, and also in areas of increased vascularization around the tumor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Developments in FT-ICR MS instrumentation, ionization techniques, and data interpretation methods for petroleomics.

    Science.gov (United States)

    Cho, Yunju; Ahmed, Arif; Islam, Annana; Kim, Sunghwan

    2015-01-01

    Because of the increasing importance of heavy and unconventional crude oil as an energy source, there is a growing need for petroleomics: the pursuit of more complete and detailed knowledge of the chemical compositions of crude oil. Crude oil has an extremely complex nature; hence, techniques with ultra-high resolving capabilities, such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), are necessary. FT-ICR MS has been successfully applied to the study of heavy and unconventional crude oils such as bitumen and shale oil. However, the analysis of crude oil with FT-ICR MS is not trivial, and it has pushed analysis to the limits of instrumental and methodological capabilities. For example, high-resolution mass spectra of crude oils may contain over 100,000 peaks that require interpretation. To visualize large data sets more effectively, data processing methods such as Kendrick mass defect analysis and statistical analyses have been developed. The successful application of FT-ICR MS to the study of crude oil has been critically dependent on key developments in FT-ICR MS instrumentation and data processing methods. This review offers an introduction to the basic principles, FT-ICR MS instrumentation development, ionization techniques, and data interpretation methods for petroleomics and is intended for readers having no prior experience in this field of study. © 2014 Wiley Periodicals, Inc.

  10. High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food

    International Nuclear Information System (INIS)

    Midey, Anthony J.; Camacho, Amanda; Sampathkumaran, Jayanthi; Krueger, Clinton A.; Osgood, Mark A.; Wu, Ching

    2013-01-01

    Graphical abstract: -- Highlights: •A new ESI source was built for direct ionization from syringe. •Phthalates, food dyes, and sweeteners detected with high-performance IMS. •Phthalates directly detected in cola, soy bubble tea matrices with simple treatment. -- Abstract: High-performance ion mobility spectrometry (HPIMS) with an electrospray ionization (ESI) source detected a series of food contaminants and additive compounds identified as critical to monitoring the safety of food samples. These compounds included twelve phthalate plasticizers, legal and illegal food and cosmetic dyes, and artificial sweeteners that were all denoted as detection priorities. HPIMS separated and detected the range of compounds with a resolving power better than 60 in both positive and negative ion modes, comparable to the commonly used high-performance liquid chromatography (HPLC) methods, but with most acquisition times under a minute. The reduced mobilities, K 0 , have been determined, as have the linear response ranges for ESI-HPIMS, which are 1.5–2 orders of magnitude for concentrations down to sub-ng μL −1 levels. At least one unique mobility peak was seen for two subsets of the phthalates grouped by the country where they were banned. Furthermore, ESI-HPIMS successfully detected low nanogram levels of a phthalate at up to 30 times lower concentration than international detection levels in both a cola matrix and a soy-based bubble tea beverage using only a simplified sample treatment. A newly developed direct ESI source (Directspray) was combined with HPIMS to detect food-grade dyes and industrial dye adulterants, as well as the sweeteners sodium saccharin and sodium cyclamate, with the same good performance as with the phthalates. However, the Directspray method eliminated sources of carryover and decreased the time between sample runs. Limits-of-detection (LOD) for the analyte standards were estimated to be sub-ng μL −1 levels without extensive sample handling

  11. High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food

    Energy Technology Data Exchange (ETDEWEB)

    Midey, Anthony J., E-mail: anthony.midey@excellims.com; Camacho, Amanda; Sampathkumaran, Jayanthi; Krueger, Clinton A.; Osgood, Mark A.; Wu, Ching

    2013-12-04

    Graphical abstract: -- Highlights: •A new ESI source was built for direct ionization from syringe. •Phthalates, food dyes, and sweeteners detected with high-performance IMS. •Phthalates directly detected in cola, soy bubble tea matrices with simple treatment. -- Abstract: High-performance ion mobility spectrometry (HPIMS) with an electrospray ionization (ESI) source detected a series of food contaminants and additive compounds identified as critical to monitoring the safety of food samples. These compounds included twelve phthalate plasticizers, legal and illegal food and cosmetic dyes, and artificial sweeteners that were all denoted as detection priorities. HPIMS separated and detected the range of compounds with a resolving power better than 60 in both positive and negative ion modes, comparable to the commonly used high-performance liquid chromatography (HPLC) methods, but with most acquisition times under a minute. The reduced mobilities, K{sub 0}, have been determined, as have the linear response ranges for ESI-HPIMS, which are 1.5–2 orders of magnitude for concentrations down to sub-ng μL{sup −1} levels. At least one unique mobility peak was seen for two subsets of the phthalates grouped by the country where they were banned. Furthermore, ESI-HPIMS successfully detected low nanogram levels of a phthalate at up to 30 times lower concentration than international detection levels in both a cola matrix and a soy-based bubble tea beverage using only a simplified sample treatment. A newly developed direct ESI source (Directspray) was combined with HPIMS to detect food-grade dyes and industrial dye adulterants, as well as the sweeteners sodium saccharin and sodium cyclamate, with the same good performance as with the phthalates. However, the Directspray method eliminated sources of carryover and decreased the time between sample runs. Limits-of-detection (LOD) for the analyte standards were estimated to be sub-ng μL{sup −1} levels without extensive

  12. 2D FT-ICR MS of Calmodulin: A Top-Down and Bottom-Up Approach.

    Science.gov (United States)

    Floris, Federico; van Agthoven, Maria; Chiron, Lionel; Soulby, Andrew J; Wootton, Christopher A; Lam, Yuko P Y; Barrow, Mark P; Delsuc, Marc-André; O'Connor, Peter B

    2016-09-01

    Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS) allows data-independent fragmentation of all ions in a sample and correlation of fragment ions to their precursors through the modulation of precursor ion cyclotron radii prior to fragmentation. Previous results show that implementation of 2D FT-ICR MS with infrared multi-photon dissociation (IRMPD) and electron capture dissociation (ECD) has turned this method into a useful analytical tool. In this work, IRMPD tandem mass spectrometry of calmodulin (CaM) has been performed both in one-dimensional and two-dimensional FT-ICR MS using a top-down and bottom-up approach. 2D IRMPD FT-ICR MS is used to achieve extensive inter-residue bond cleavage and assignment for CaM, using its unique features for fragment identification in a less time- and sample-consuming experiment than doing the same thing using sequential MS/MS experiments. Graphical Abstract ᅟ.

  13. Environmental Forensics: Molecular Insight into Oil Spill Weathering Helps Advance High Magnetic Field FT-ICR Mass Spectrometry

    Science.gov (United States)

    McKenna, Amy

    2013-03-01

    events in the FT-ICR experiment. For example, the high density of peaks at each nominal mass unit provides unprecedented insight into how excitation conditions affect ion motion during detection. Aggregated oil (i.e., tar balls, tar mats) that reached the surface exhibits a more than two-fold increase in the total number of detected species, with an increased number of oxygenated species. Principal component analysis (PCA) applied to two possible source oils (contained within the same ship) and weathered samples provide the first application of FT-ICR MS for source identification. Molecular formulae from parent and weathered oil indicate that the lightest petroleum fractions (saturated hydrocarbons) are the most readily oxidized components, and can serve as a template to determine chemical transformations that occur throughout the water column. The ability to differentiate and catalogue compositional changes that occur to oil after its release into the environment relies heavily on gains achieved in nearly all steps in the FT-ICR mass spectral experiment required to accommodate larger ion populations inherent to heavily weathered crude oil. Here, we present the requirement for FT-ICR MS for comprehensive oil spill characterization, and highlight advances made to FT-ICR MS experimental conditions developed from petroleum characterization. Work supported by DMR-06-54118, NSF CHE-10-49753 (RAPID), BP/The Gulf of Mexico Research Initiative, and the State of Florida

  14. RAPID AND AUTOMATED PROCESSING OF MALDI-FTICR/MS DATA FOR N-METABOLIC LABELING IN A SHOTGUN PROTEOMICS ANALYSIS.

    Science.gov (United States)

    Jing, Li; Amster, I Jonathan

    2009-10-15

    Offline high performance liquid chromatography combined with matrix assisted laser desorption and Fourier transform ion cyclotron resonance mass spectrometry (HPLC-MALDI-FTICR/MS) provides the means to rapidly analyze complex mixtures of peptides, such as those produced by proteolytic digestion of a proteome. This method is particularly useful for making quantitative measurements of changes in protein expression by using (15)N-metabolic labeling. Proteolytic digestion of combined labeled and unlabeled proteomes produces complex mixtures that with many mass overlaps when analyzed by HPLC-MALDI-FTICR/MS. A significant challenge to data analysis is the matching of pairs of peaks which represent an unlabeled peptide and its labeled counterpart. We have developed an algorithm and incorporated it into a compute program which significantly accelerates the interpretation of (15)N metabolic labeling data by automating the process of identifying unlabeled/labeled peak pairs. The algorithm takes advantage of the high resolution and mass accuracy of FTICR mass spectrometry. The algorithm is shown to be able to successfully identify the (15)N/(14)N peptide pairs and calculate peptide relative abundance ratios in highly complex mixtures from the proteolytic digest of a whole organism protein extract.

  15. Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

    Science.gov (United States)

    Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

    2006-02-01

    Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

  16. Distributed computing strategies for processing of FT-ICR MS imaging datasets for continuous mode data visualization

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Donald F.; Schulz, Carl; Konijnenburg, Marco; Kilic, Mehmet; Heeren, Ronald M.

    2015-03-01

    High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry imaging enables the spatial mapping and identification of biomolecules from complex surfaces. The need for long time-domain transients, and thus large raw file sizes, results in a large amount of raw data (“big data”) that must be processed efficiently and rapidly. This can be compounded by largearea imaging and/or high spatial resolution imaging. For FT-ICR, data processing and data reduction must not compromise the high mass resolution afforded by the mass spectrometer. The continuous mode “Mosaic Datacube” approach allows high mass resolution visualization (0.001 Da) of mass spectrometry imaging data, but requires additional processing as compared to featurebased processing. We describe the use of distributed computing for processing of FT-ICR MS imaging datasets with generation of continuous mode Mosaic Datacubes for high mass resolution visualization. An eight-fold improvement in processing time is demonstrated using a Dutch nationally available cloud service.

  17. Evaluation of analytical performance and reliability of direct nanoLC-nanoESI-high resolution mass spectrometry for profiling the (xeno)metabolome.

    Science.gov (United States)

    Chetwynd, Andrew J; David, Arthur; Hill, Elizabeth M; Abdul-Sada, Alaa

    2014-10-01

    Mass spectrometry (MS) profiling techniques are used for analysing metabolites and xenobiotics in biofluids; however, detection of low abundance compounds using conventional MS techniques is poor. To counter this, nanoflow ultra-high-pressure liquid chromatography-nanoelectrospray ionization-time-of-flight MS (nUHPLC-nESI-TOFMS), which has been used primarily for proteomics, offers an innovative prospect for profiling small molecules. Compared to conventional UHPLC-ESI-TOFMS, nUHPLC-nESI-TOFMS enhanced detection limits of a variety of (xeno)metabolites by between 2 and 2000-fold. In addition, this study demonstrates for the first time excellent repeatability and reproducibility for analysis of urine and plasma samples using nUHPLC-nESI-TOFMS, supporting implementation of this platform as a novel approach for high-throughput (xeno)metabolomics. Copyright © 2014 John Wiley & Sons, Ltd.

  18. Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Analysis of Large Polymerases Chain Reaction Products

    International Nuclear Information System (INIS)

    Wunschel, David S.; Pasa Tolic, Ljiljana; Feng, Bingbing; Smith, Richard D.

    2000-01-01

    We have attempted to expand the size range of PCR products that can be analyzed by electroscopy ionization (ESI) Fourier transformion cyclotron resonance (FTICR) mass spectrometry. The mass measurement accuracy obtained illustrates that a signel base substitution could be identified at the size of PCR product with a 7 tesla ESI-FTICR

  19. TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil

    KAUST Repository

    Elbaz, Ayman M.; Abdul Jameel, Abdul Gani; Hourani, Nadim; Emwas, Abdul-Hamid M.; Sarathy, Mani; Roberts, William L.

    2015-01-01

    infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC

  20. MALDI FTICR IMS of Intact Proteins: Using Mass Accuracy to Link Protein Images with Proteomics Data

    Science.gov (United States)

    Spraggins, Jeffrey M.; Rizzo, David G.; Moore, Jessica L.; Rose, Kristie L.; Hammer, Neal D.; Skaar, Eric P.; Caprioli, Richard M.

    2015-06-01

    MALDI imaging mass spectrometry is a highly sensitive and selective tool used to visualize biomolecules in tissue. However, identification of detected proteins remains a difficult task. Indirect identification strategies have been limited by insufficient mass accuracy to confidently link ion images to proteomics data. Here, we demonstrate the capabilities of MALDI FTICR MS for imaging intact proteins. MALDI FTICR IMS provides an unprecedented combination of mass resolving power (~75,000 at m/z 5000) and accuracy (differentiate a series of oxidation products of S100A8 ( m/z 10,164.03, -2.1ppm), a subunit of the heterodimer calprotectin, in kidney tissue from mice infected with Staphylococcus aureus. S100A8 - M37O/C42O3 ( m/z 10228.00, -2.6ppm) was found to co-localize with bacterial microcolonies at the center of infectious foci. The ability of MALDI FTICR IMS to distinguish S100A8 modifications is critical to understanding calprotectin's roll in nutritional immunity.

  1. SIEMENS ADVANCED QUANTRA FTICR MASS SPECTROMETER FOR ULTRA HIGH RESOLUTION AT LOW MASS

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, W; Laura Tovo, L

    2008-07-08

    The Siemens Advanced Quantra Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometer was evaluated as an alternative instrument to large double focusing mass spectrometers for gas analysis. High resolution mass spectrometers capable of resolving the common mass isomers of the hydrogen isotopes are used to provide data for accurate loading of reservoirs and to monitor separation of tritium, deuterium, and helium. Conventional double focusing magnetic sector instruments have a resolution that is limited to about 5000. The Siemens FTICR instrument achieves resolution beyond 400,000 and could possibly resolve the tritium ion from the helium-3 ion, which differ by the weight of an electron, 0.00549 amu. Working with Y-12 and LANL, SRNL requested Siemens to modify their commercial Quantra system for low mass analysis. To achieve the required performance, Siemens had to increase the available waveform operating frequency from 5 MHz to 40 MHz and completely redesign the control electronics and software. However, they were able to use the previous ion trap, magnet, passive pump, and piezo-electric pulsed inlet valve design. NNSA invested $1M in this project and acquired four systems, two for Y-12 and one each for SRNL and LANL. Siemens claimed a $10M investment in the Quantra systems. The new Siemens Advanced Quantra demonstrated phenomenal resolution in the low mass range. Resolution greater than 400,000 was achieved for mass 2. The new spectrometer had a useful working mass range to 500 Daltons. However, experiments found that a continuous single scan from low mass to high was not possible. Two useful working ranges were established covering masses 1 to 6 and masses 12 to 500 for our studies. A compromise performance condition enabled masses 1 to 45 to be surveyed. The instrument was found to have a dynamic range of about three orders of magnitude and quantitative analysis is expected to be limited to around 5 percent without using complex fitting algorithms

  2. Online quench-flow electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for elucidating kinetic and chemical enzymatic reaction mechanisms.

    Science.gov (United States)

    Clarke, David J; Stokes, Adam A; Langridge-Smith, Pat; Mackay, C Logan

    2010-03-01

    We have developed an automated quench-flow microreactor which interfaces directly to an electrospray ionization (ESI) mass spectrometer. We have used this device in conjunction with ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to demonstrate the potential of this approach for studying the mechanistic details of enzyme reactions. For the model system chosen to test this device, namely, the pre-steady-state hydrolysis of p-nitrophenyl acetate by the enzyme chymotrypsin, the kinetic parameters obtained are in good agreement with those in the literature. To our knowledge, this is the first reported use of online quench-flow coupled with FTICR MS. Furthermore, we have exploited the power of FTICR MS to interrogate the quenched covalently bound enzyme intermediate using top-down fragmentation. The accurate mass capabilities of FTICR MS permitted the nature of the intermediate to be assigned with high confidence. Electron capture dissociation (ECD) fragmentation allowed us to locate the intermediate to a five amino acid section of the protein--which includes the known catalytic residue, Ser(195). This experimental approach, which uniquely can provide both kinetic and chemical details of enzyme mechanisms, is a potentially powerful tool for studies of enzyme catalysis.

  3. Molecular Characterization and Reactivity of Dissolved Organic Matter by High Resolution Nanospray Ionization Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS)

    Science.gov (United States)

    Sleighter, R. L.; Hatcher, S. A.; Hatcher, P. G.

    2006-12-01

    The ultrahigh resolving power of FTICR-MS allows for the intense characterization of dissolved organic matter (DOM). DOM is the largest reactive component of the global carbon cycle, and an improved understanding of its composition is necessary to determine the transport and eventual fate of pollutants. The seasonal and spatial variations in DOM composition are investigated by taking surface water samples from five different sampling sites, four times a year. Water sampling begins at the Dismal Swamp in North Carolina, continues north up the Elizabeth River to the Chesapeake Bay, and concludes approximately ten miles off the coast in the Atlantic Ocean. DOM was extracted from the water samples using C18 extraction disks and were prepared in 50:50 methanol:water. Ammonium hydroxide was added prior to nanospray in order to solubilize the DOM as well as to increase the ionization efficiency. The samples were continuously infused into the Apollo II ion source with an Advion TriVersa NanoMate system of a Bruker 12 Tesla Apex QE FTICR-MS with resolving powers exceeding 400,000. All samples were analyzed in negative ion mode and were externally and internally calibrated prior to data analysis. Our DOM mass spectra consist of a multitude of peaks spanning the range of 200-850 m/z. Complexity is apparent from the detection of up to 20 peaks per nominal mass at nearly every mass throughout that range. A molecular formula calculator generated molecular formula matches from which van Krevelen plots were constructed for characterization purposes. A wide range of molecules were observed each containing oxygen, sulfur and nitrogen functional groups. We utilize the van Krevelen diagram to assist in clustering the molecules according to their functional group compositions. To test the hypothesis that formation of adducts to DOM serve to protect peptides from bacterial degradation, microcosm experiments were performed with a small isotopically enriched peptide, GGGR. This peptide

  4. Bioconversion of red ginseng saponins in the gastro-intestinal tract in vitro model studied by high-performance liquid chromatography-high resolution Fourier transform ion cyclotron resonance mass spectrometry

    NARCIS (Netherlands)

    Kong, H.; Wang, M.; Venema, K.; Maathuis, A.; Heijden, R. van der; Greef, J. van der; Xu, G.; Hankemeier, T.

    2009-01-01

    A high-performance liquid chromatography-high resolution Fourier transform ion cyclotron resonance mass spectrometry (HPLC-FTICR-MS) method was developed to investigate the metabolism of ginsenosides in in vitro models of the gastro-intestinal tract. The metabolites were identified by

  5. Improved detection of drugs of abuse using high-performance ion mobility spectrometry with electrospray ionization (ESI-HPIMS) for urine matrices.

    Science.gov (United States)

    Midey, Anthony J; Patel, Aesha; Moraff, Carol; Krueger, Clinton A; Wu, Ching

    2013-11-15

    High-performance ion mobility spectrometry (HPIMS) with electrospray ionization (ESI) has been used to separate drugs of abuse compounds as a function of drift time (ion mobility), which is based on their size, structural shape, and mass-to-charge. HPIMS has also been used to directly detect and identify a variety of the most commonly encountered illegal drugs, as well as a mixture of opiates in a urine matrix without extra sample pretreatment. HPIMS has shown resolving power greater than 65 comparable to that of high-performance liquid chromatography (HPLC) with only 1 mL of solvent and sample required using air as the IMS separation medium. The HPIMS method can achieve two-order of magnitude linear response, precise drift times, and high peak area precision with percent relative standard deviations (%RSD) less than 3% for sample quantitation. The reduced mobilities measured agree very well with other IMS measurements, allowing a simple "dilute-and-shoot" method to be used to detect a mixture of codeine and morphine in urine matrix. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. High-field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter

    Directory of Open Access Journals (Sweden)

    N. Hertkorn

    2013-03-01

    Full Text Available High-performance, non-target, high-resolution organic structural spectroscopy was applied to solid phase extracted marine dissolved organic matter (SPE-DOM isolated from four different depths in the open South Atlantic Ocean off the Angola coast (3° E, 18° S; Angola Basin and provided molecular level information with extraordinary coverage and resolution. Sampling was performed at depths of 5 m (Angola Current; near-surface photic zone, 48 m (Angola Current; fluorescence maximum, 200 m (still above Antarctic Intermediate Water, AAIW; upper mesopelagic zone and 5446 m (North Atlantic Deep Water, NADW; abyssopelagic, ~30 m above seafloor and produced SPE-DOM with near 40% carbon yield and beneficial nuclear magnetic resonance (NMR relaxation properties, a crucial prerequisite for the acquisition of NMR spectra with excellent resolution. 1H and 13C NMR spectra of all four marine SPE-DOM showed smooth bulk envelopes, reflecting intrinsic averaging from massive signal overlap, with a few percent of visibly resolved signatures and variable abundances for all major chemical environments. The abundance of singly oxygenated aliphatics and acetate derivatives in 1H NMR spectra declined from surface to deep marine SPE-DOM, whereas C-based aliphatics and carboxyl-rich alicyclic molecules (CRAM increased in abundance. Surface SPE-DOM contained fewer methyl esters than all other samples, likely a consequence of direct exposure to sunlight. Integration of 13C NMR spectra revealed continual increase of carboxylic acids and ketones from surface to depth, reflecting a progressive oxygenation, with concomitant decline of carbohydrate-related substructures. Aliphatic branching increased with depth, whereas the fraction of oxygenated aliphatics declined for methine, methylene and methyl carbon. Lipids in the oldest SPE-DOM at 5446 m showed a larger share of ethyl groups and methylene carbon than observed in the other samples. Two-dimensional NMR spectra showed

  7. ICR studies of some anionic gas phase reactions and FTICR software design

    International Nuclear Information System (INIS)

    Noest, A.J.

    1983-01-01

    This thesis consists of two parts. Part one (Chs. 1-5) reports experimental results from mostly drift-cell ICR studies of negative ion-molecule reactions; part two (Chs. 6-11) concerns the design of software for an FTICR instrument. The author discusses successively: 1. ion cyclotron resonance spectrometry; 2. the gas phase allyl anion; 3. the (M-H) and (M-H2) anions from acetone; 4. negative ion-molecule reactions of aliphatic nitrites studied by cyclotron resonance; 5. homoconjugation versus charge-dipole interaction effects in the stabilization of carbanions in the gas phase; 6. the Fourier Transform ICR method; 7. the FTICR-software; 8. an efficient adaptive matcher filter for fast transient signals; 9. reduction of spectral peak height errors by time-domain weighing; 10. Chirp excitation; 11. Compact data storage. The book concludes with a Dutch and English summary (G.J.P.)

  8. Petroleomics by electrospray ionization FT-ICR mass spectrometry coupled to partial least squares with variable selection methods: prediction of the total acid number of crude oils.

    Science.gov (United States)

    Terra, Luciana A; Filgueiras, Paulo R; Tose, Lílian V; Romão, Wanderson; de Souza, Douglas D; de Castro, Eustáquio V R; de Oliveira, Mirela S L; Dias, Júlio C M; Poppi, Ronei J

    2014-10-07

    Negative-ion mode electrospray ionization, ESI(-), with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was coupled to a Partial Least Squares (PLS) regression and variable selection methods to estimate the total acid number (TAN) of Brazilian crude oil samples. Generally, ESI(-)-FT-ICR mass spectra present a power of resolution of ca. 500,000 and a mass accuracy less than 1 ppm, producing a data matrix containing over 5700 variables per sample. These variables correspond to heteroatom-containing species detected as deprotonated molecules, [M - H](-) ions, which are identified primarily as naphthenic acids, phenols and carbazole analog species. The TAN values for all samples ranged from 0.06 to 3.61 mg of KOH g(-1). To facilitate the spectral interpretation, three methods of variable selection were studied: variable importance in the projection (VIP), interval partial least squares (iPLS) and elimination of uninformative variables (UVE). The UVE method seems to be more appropriate for selecting important variables, reducing the dimension of the variables to 183 and producing a root mean square error of prediction of 0.32 mg of KOH g(-1). By reducing the size of the data, it was possible to relate the selected variables with their corresponding molecular formulas, thus identifying the main chemical species responsible for the TAN values.

  9. Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Directory of Open Access Journals (Sweden)

    R. M. Dickhut

    2008-09-01

    Full Text Available Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223 component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia and 78% (New York of these peaks were assigned molecular formulas using only carbon (C, hydrogen (H, oxygen (O, nitrogen (N, and sulfur (S as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.

  10. Metabolic profiling of Vitex agnus castus leaves, fruits and sprouts: analysis by LC/ESI/(QqQ)MS and (HR) LC/ESI/(Orbitrap)/MS n.

    Science.gov (United States)

    Mari, Angela; Montoro, Paola; D'Urso, Gilda; Macchia, Mario; Pizza, Cosimo; Piacente, Sonia

    2015-01-01

    Food supplements based on Vitex agnus castus L. (Verbenaceae) fruits, also known as chasteberry, are routinely used by women against somatic and psychic premenstrual symptoms such as depression, sadness or irritability. With the aim of highlighting the differences in the chemical profiles of cultivated fruits and different parts of wild plants (fruits, leaves and sprouts) of V. agnus castus, a method concerning with the quali-quantitative study of the derived hydroalcoholic extracts was carried out by using high-performance liquid chromatography coupled to electrospray negative ionization Orbitrap multicollisional high resolution mass spectrometry (LC/ESI/(Orbitrap)MS(n)) and high-performance liquid chromatography coupled to electrospray negative ionization triple quadrupole tandem mass spectrometry (LC/ESI/(QqQ)MS) in multiple reaction monitoring (MRM) mode. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Identification and determination of flavonoids in astragali radix by high performance liquid chromatography coupled with DAD and ESI-MS detection.

    Science.gov (United States)

    Lv, Yan-Wen; Hu, Wei; Wang, Yu-Ling; Huang, Lan-Fang; He, Yun-Biao; Xie, Xian-Zhen

    2011-03-09

    A method for the analysis of flavonoids in Astragali Radix by high-performance liquid chromatography (HPLC) combined with photodiode-array detection (DAD) and an electrospray ionization (ESI)--mass spectrometry (MS) was developed. After the samples were extracted with ethanol, the optimum separation conditions for these analytes were achieved using a gradient elution system and a 2.0 x 150 mm Shimadzu VP-ODS column. Eight flavonoids were identified to exist in Astragali Radix based on their characteristic UV data and mass spectra. The concentrations of three major components in this herb--ononin, calycosin and formononetin--were determined by LC/ESI-MS in positive selective ion monitoring (SIM) mode. The calibration curves were linear in the range of 0.9~180.0 μg·mL⁻¹ for ononin, 1.8~360.0 μg·mL⁻¹ for calycosin and 1.4~280 μg·mL⁻¹ for formononetin, respectively. The limits of quantification (LOQ) and detection (LOD) were 0.9 μg· mL⁻¹ and 0.2 μg mL⁻¹ for ononin, 1.8 μg mL⁻¹ and 0.5 μg·mL-1 for calycosin, 1.4 μg mL⁻¹ and 0.5 μg·mL⁻¹ for formononetin, respectively. The standard recoveries were between 95.4~104.7%. The developed method was proven to be useful for the quantitative and qualitative analysis of flavonoid constituents in various resources of Astragali Radix.

  12. Identification and Determination of Flavonoids in Astragali Radix by High Performance Liquid Chromatography Coupled with DAD and ESI-MS Detection

    Directory of Open Access Journals (Sweden)

    Yu-Ling Wang

    2011-03-01

    Full Text Available A method for the analysis of flavonoids in Astragali Radix by high-performance liquid chromatography (HPLC combined with photodiode-array detection (DAD and an electrospray ionization (ESI - mass spectrometry (MS was developed. After the samples were extracted with ethanol, the optimum separation conditions for these analytes were achieved using a gradient elution system and a 2.0 × 150 mm Shimadzu VP-ODS column. Eight flavonoids were identified to exist in Astragali Radix based on their characteristic UV data and mass spectra. The concentrations of three major components in this herb—ononin, calycosin and formononetin—were determined by LC/ESI-MS in positive selective ion monitoring (SIM mode. The calibration curves were linear in the range of 0.9~180.0 μg·mL−1 for ononin, 1.8~360.0 μg·mL−1 for calycosin and 1.4~280 μg·mL−1 for formononetin, respectively. The limits of quantification (LOQ and detection (LOD were 0.9 μg· mL−1 and 0.2 μg mL−1 for ononin, 1.8 μg mL−1 and 0.5 μg·mL−1 for calycosin, 1.4 μg mL−1 and 0.5 μg·mL−1 for formononetin, respectively. The standard recoveries were between 95.4~104.7%. The developed method was proven to be useful for the quantitative and qualitative analysis of flavonoid constituents in various resources of Astragali Radix.

  13. Mass measurements on neutron-deficient nuclides at SHIPTRAP and commissioning of a cryogenic narrow-band FT-ICR mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Ferrer Garcia, R.

    2007-07-01

    The dissertation presented here deals with high-precision Penning trap mass spectrometry on short-lived radionuclides. Owed to the ability of revealing all nucleonic interactions, mass measurements far off the line of {beta}-stability are expected to bring new insight to the current knowledge of nuclear properties and serve to test the predictive power of mass models and formulas. In nuclear astrophysics, atomic masses are fundamental parameters for the understanding of the synthesis of nuclei in the stellar environments. This thesis presents ten mass values of radionuclides around A=90 interspersed in the predicted rp-process pathway. Six of them have been experimentally determined for the first time. The measurements have been carried out at the Penning-trap mass spectrometer SHIPTRAP using the destructive time-of-flight ion-cyclotron-resonance (TOF-ICR) detection technique. Given the limited performance of the TOF-ICR detection when trying to investigate heavy/superheavy species with small production cross sections ({sigma} <1 {mu}b), a new detection system is found to be necessary. Thus, the second part of this thesis deals with the commissioning of a cryogenic double-Penning trap system for the application of a highly-sensitive, narrow-band Fourier-transform ion-cyclotron-resonance (FT-ICR) detection technique. With the non-destructive FT-ICR detection method a single singly-charged trapped ion will provide the required information to determine its mass. First off-line tests of a new detector system based on a channeltron with an attached conversion dynode, of a cryogenic pumping barrier, to guarantee ultra-high vacuum conditions during mass determination, and of the detection electronics for the required single-ion sensitivity are reported. (orig.)

  14. Is a mobile emergency severity index (ESI) triage better than the paper ESI?

    Science.gov (United States)

    Savatmongkorngul, Sorravit; Yuksen, Chaiyaporn; Suwattanasilp, Chanakarn; Sawanyawisuth, Kittisak; Sittichanbuncha, Yuwares

    2017-12-01

    This study aims to evaluate the mobile emergency severity index (ESI) tool in terms of validity compared with the original ESI triage. The original ESI and mobile ESI were used with patients at the Department of Emergency Medicine, Ramathibodi Hospital, Thailand. Eligible patients were evaluated by sixth-year medical students/emergency physicians using either the original or mobile ESI. The ESI results for each patient were compared with the standard ESI. Concordance and kappa statistics were calculated for pairs of the evaluators. There were 486 patients enrolled in the study; 235 patients (48.4%) were assessed using the mobile ESI, and 251 patients (51.6%) were in the original ESI group. The baseline characteristics of patients in both groups were mostly comparable except for the ED visit time. The percentages of concordance and kappa statistics in the original ESI group were lower than in the mobile group in all three comparisons (medical students vs gold standard, emergency physicians vs gold standard, and medical students vs emergency physicians). The highest kappa in the original ESI group is 0.69, comparing emergency physicians vs gold standard, while the lowest kappa in the application group is 0.84 comparing the medical students vs gold standard. Both medical students and emergency physicians are more confident with the mobile ESI application triage. In conclusion, the mobile ESI has better inter-rater reliability, and is more user-friendly than the original paper form.

  15. Routine low-level monitoring of polar pesticides and pesticide degradates by HPLC/ESI-MS: Evaluating long-term performance

    Science.gov (United States)

    Furlong, E.T.; Martin, Jeffrey D.; Werner, S.L.; Gates, Paul M.

    2002-01-01

    The sensitivity and selective determination of polar pesticides were analyzed using high-performance liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS). The effects of multiple operators and instruments on method performance were evaluated using 440 pairs of fortified reagent-water and blank reagent-water samples. The influence of varying environmental matrices on recovery and precision were also analyzed using 200 fortified ambient water samples and duplicate ambient water samples. The results show that compound stability in filtered water was matrix-, chemical class- and compound-dependent which ranged from 1 day to 2 weeks.

  16. Automated Gain Control and Internal Calibration With External Ion Accumulation Capillary liquid chromatography-electrospray ionization-fourier transform ion cyclotron resonance.

    Energy Technology Data Exchange (ETDEWEB)

    Belov, Mikhail E.(VISITORS); Zhang, Rui (BATTELLE (PACIFIC NW LAB)); Strittmatter, Eric F.(BATTELLE (PACIFIC NW LAB)); Prior, David C.(BATTELLE (PACIFIC NW LAB)); Tang, Keqi (BATTELLE (PACIFIC NW LAB)); Smith, Richard D.(BATTELLE (PACIFIC NW LAB))

    2003-08-15

    When combined with capillary LC separations, Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICR MS) has increasingly been applied for advanced characterization of proteolytic digests. Incorporation of external (to the ICR cell) ion accumulation multipoles with FTICR for ion pre selection and accumulation has enhanced the dynamic range, sensitivity and duty cycle of measurements. However, the highly variable ion production rate from an LC separation can result in overfilling of the external trap, resulting in m/z discrimination and fragmentation of peptide ions. An excessive space charge trapped in the ICR cell causes significant shifts in the detected ion cyclotron frequencies, reducing the achievable mass measurement accuracy (MMA) for protein identification. To eliminate m/z discrimination in the external ion trap, further increase the duty cycle and improve MMA, we developed a capability for data-dependent adjustment of ion accumulation times in the course of an LC separation, referred to as Automated Gain Control (AGC), in combination with low kinetic energy gated ion trapping and internal calibration using a dual-channel electrodynamic ion funnel. The system was initially evaluated in the analysis of a 0.5 mg/mL tryptic digest of bovine serum albumin. The implementation of LC/ESI/AGC/FTICR with internal calibration gave rise to a {approx} 10-fold increase in the number of identified tryptic peptides within mass measurement accuracy of 2 ppm as compared to that detected during the conventional LC/FTICR run with a fixed ion accumulation time and external calibration.

  17. Forensic validation of the PowerPlex® ESI 16 STR Multiplex and comparison of performance with AmpFlSTR® SGM Plus®.

    Science.gov (United States)

    Tucker, Valerie C; Kirkham, Amanda J; Hopwood, Andrew J

    2012-05-01

    We describe the forensic validation of Promega's PowerPlex® European Standard Investigator 16 (ESI 16) multiplex kit and compare results generated with the AmpFlSTR® SGM Plus® (SGM+) multiplex. ESI 16 combines the loci contained within the SGM+ multiplex with five additional loci: D2S441, D10S1248, D22S1045, D1S1656, and D12S391. A relative reduction in amplicon size of the SGM+ loci facilitates an increased robustness and amplification success of these amplicons with degraded DNA samples. Tests performed herein supplement ESI 16 data published previously with sensitivity, profile quality, mock casework, inhibitor and mixture study data collected in our laboratories in alignment with our internal technical and quality guidelines and those issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM), the DNA Advisory Board (DAB) and the DNA working group (DNAWG) of the European Network of Forensic Science Institutes (ENFSI). Full profiles were routinely generated from a fully heterozygous single source DNA template using 62.5 pg for ESI 16 and 500 pg for SGM+. This increase in sensitivity has a consequent effect on mixture analyses and the detection of minor mixture components. The improved PCR chemistry confers enhanced tolerance to high levels of laboratory prepared inhibitors compared with SGM+ results. In summary, our results demonstrate that the ESI 16 multiplex kit is more robust and sensitive compared with SGM+ and will be a suitable replacement system for the analysis of forensic DNA samples providing compliance with the European standard set of STR loci.

  18. High field FT-ICR mass spectrometry for molecular characterization of snow board from Moscow regions.

    Science.gov (United States)

    Mazur, Dmitry M; Harir, Mourad; Schmitt-Kopplin, Philippe; Polyakova, Olga V; Lebedev, Albert T

    2016-07-01

    High field Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry analysis of eight snow samples from Moscow city allowed us to identify more than 2000 various elemental compositions corresponding to regional air pollutants. The hierarchical cluster analysis (HCA) of the data showed good concordance of three main groups of samples with the main wind directions. The North-West group (A1) is represented by several homologous CHOS series of aliphatic organic aerosols. They may form as a result of enhanced photochemical reactions including oxidation of hydrocarbons with sulfonations due to higher amount of SO2 emissions in the atmosphere in this region. Group A2, corresponding to the South-East part of Moscow, contains large amount of oxidized hydrocarbons of different sources that may form during oxidation in atmosphere. These hydrocarbons appear correlated to emissions from traffic, neighboring oil refinery, and power plants. Another family of compounds specific for this region involves CHNO substances formed during oxidation processes including NOx and NO3 radical since emissions of NOx are higher in this part of the city. Group A3 is rich in CHO type of compounds with high H/C and low O/C ratios, which is characteristic of oxidized hydrocarbon-like organic aerosol. CHNO types of compounds in A3 group are probably nitro derivatives of condensed hydrocarbons such as PAH. This non-targeted profiling revealed site specific distribution of pollutants and gives a chance to develop new strategies in air quality control and further studies of Moscow environment. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

    Science.gov (United States)

    Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  20. Prince William Sound, Alaska ESI: ESI (Environmental Sensitivity Index Shoreline Types)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  1. Characterization of ANFO explosive by high accuracy ESI(±)-FTMS with forensic identification on real samples by EASI(-)-MS.

    Science.gov (United States)

    Hernandes, Vinicius Veri; Franco, Marcos Fernado; Santos, Jandyson Machado; Melendez-Perez, Jose J; de Morais, Damila Rodrigues; Rocha, Werickson Fortunato de Carvalho; Borges, Rodrigo; de Souza, Wanderley; Zacca, Jorge Jardim; Logrado, Lucio Paulo Lima; Eberlin, Marcos Nogueira; Correa, Deleon Nascimento

    2015-04-01

    Ammonium nitrate fuel oil (ANFO) is an explosive used in many civil applications. In Brazil, ANFO has unfortunately also been used in criminal attacks, mainly in automated teller machine (ATM) explosions. In this paper, we describe a detailed characterization of the ANFO composition and its two main constituents (diesel and a nitrate explosive) using high resolution and accuracy mass spectrometry performed on an FT-ICR-mass spectrometer with electrospray ionization (ESI(±)-FTMS) in both the positive and negative ion modes. Via ESI(-)-MS, an ion marker for ANFO was characterized. Using a direct and simple ambient desorption/ionization technique, i.e., easy ambient sonic-spray ionization mass spectrometry (EASI-MS), in a simpler, lower accuracy but robust single quadrupole mass spectrometer, the ANFO ion marker was directly detected from the surface of banknotes collected from ATM explosion theft. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  2. Resveratrol and its oligomers from wine grapes are selective (1)O2 quenchers: mechanistic implication by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry and theoretical calculation.

    Science.gov (United States)

    Jiang, Li-Yan; He, Shan; Jiang, Ke-Zhi; Sun, Cui-Rong; Pan, Yuan-Jiang

    2010-08-25

    Resveratrol and its oligomers, abundantly present in wine grapes, are believed to be effective phytoalexins for the phenomenon "French paradox" partially by virtue of their powerful antiradical properties. EPR spin-trapping technique was utilized, demonstrating all polyphenols were selective (1)O2 quenchers but not effective (•)OH and O2(•¯) scavengers. On the basis of the HPLC-ESI-MS(2) analysis for the simulated reactions of polyphenols with (1)O2, the molecular weights of the resulting photochemical products were 14 or 28 Da higher than those of their substrates. No fragment C2H2O (42 Da), which was rather distinctive of the resorcinol rings in these cases, had been observed, whereas their MS/MS spectra displayed characteristic neutral fragments including carbon monoxide (CO, 28 Da) and 2-hydroxy[1,4]benzoquinone (C6H4O3, 124 Da). Finally, PM3 semiempirical calculations and HR-FTICR-MS experiments were performed, supporting the assertion that their quenching mechanism involved physical and chemical pathways. Chemical quenching underwent an endoperoxide intermediate form to generate quinones.

  3. Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Ren, Shuoyi; Yu, Jianwei; Ji, Feng; Luo, Wenbin; Yang, Min

    2012-10-15

    Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Front-End Electron Transfer Dissociation Coupled to a 21 Tesla FT-ICR Mass Spectrometer for Intact Protein Sequence Analysis

    Science.gov (United States)

    Weisbrod, Chad R.; Kaiser, Nathan K.; Syka, John E. P.; Early, Lee; Mullen, Christopher; Dunyach, Jean-Jacques; English, A. Michelle; Anderson, Lissa C.; Blakney, Greg T.; Shabanowitz, Jeffrey; Hendrickson, Christopher L.; Marshall, Alan G.; Hunt, Donald F.

    2017-09-01

    High resolution mass spectrometry is a key technology for in-depth protein characterization. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enables high-level interrogation of intact proteins in the most detail to date. However, an appropriate complement of fragmentation technologies must be paired with FTMS to provide comprehensive sequence coverage, as well as characterization of sequence variants, and post-translational modifications. Here we describe the integration of front-end electron transfer dissociation (FETD) with a custom-built 21 tesla FT-ICR mass spectrometer, which yields unprecedented sequence coverage for proteins ranging from 2.8 to 29 kDa, without the need for extensive spectral averaging (e.g., 60% sequence coverage for apo-myoglobin with four averaged acquisitions). The system is equipped with a multipole storage device separate from the ETD reaction device, which allows accumulation of multiple ETD fragment ion fills. Consequently, an optimally large product ion population is accumulated prior to transfer to the ICR cell for mass analysis, which improves mass spectral signal-to-noise ratio, dynamic range, and scan rate. We find a linear relationship between protein molecular weight and minimum number of ETD reaction fills to achieve optimum sequence coverage, thereby enabling more efficient use of instrument data acquisition time. Finally, real-time scaling of the number of ETD reactions fills during method-based acquisition is shown, and the implications for LC-MS/MS top-down analysis are discussed. [Figure not available: see fulltext.

  5. Developmental validation of the PowerPlex(®) ESI 16 and PowerPlex(®) ESI 17 Systems: STR multiplexes for the new European standard.

    Science.gov (United States)

    Tucker, Valerie C; Hopwood, Andrew J; Sprecher, Cynthia J; McLaren, Robert S; Rabbach, Dawn R; Ensenberger, Martin G; Thompson, Jonelle M; Storts, Douglas R

    2011-11-01

    In response to the ENFSI and EDNAP groups' call for new STR multiplexes for Europe, Promega(®) developed a suite of four new DNA profiling kits. This paper describes the developmental validation study performed on the PowerPlex(®) ESI 16 (European Standard Investigator 16) and the PowerPlex(®) ESI 17 Systems. The PowerPlex(®) ESI 16 System combines the 11 loci compatible with the UK National DNA Database(®), contained within the AmpFlSTR(®) SGM Plus(®) PCR Amplification Kit, with five additional loci: D2S441, D10S1248, D22S1045, D1S1656 and D12S391. The multiplex was designed to reduce the amplicon size of the loci found in the AmpFlSTR(®) SGM Plus(®) kit. This design facilitates increased robustness and amplification success for the loci used in the national DNA databases created in many countries, when analyzing degraded DNA samples. The PowerPlex(®) ESI 17 System amplifies the same loci as the PowerPlex(®) ESI 16 System, but with the addition of a primer pair for the SE33 locus. Tests were designed to address the developmental validation guidelines issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM), and those of the DNA Advisory Board (DAB). Samples processed include DNA mixtures, PCR reactions spiked with inhibitors, a sensitivity series, and 306 United Kingdom donor samples to determine concordance with data generated with the AmpFlSTR(®) SGM Plus(®) kit. Allele frequencies from 242 white Caucasian samples collected in the United Kingdom are also presented. The PowerPlex(®) ESI 16 and ESI 17 Systems are robust and sensitive tools, suitable for the analysis of forensic DNA samples. Full profiles were routinely observed with 62.5pg of a fully heterozygous single source DNA template. This high level of sensitivity was found to impact on mixture analyses, where 54-86% of unique minor contributor alleles were routinely observed in a 1:19 mixture ratio. Improved sensitivity combined with the robustness afforded by smaller amplicons

  6. Comparison of piracetam measured with HPLC-DAD, HPLC-ESI-MS, DIP-APCI-MS, and a newly developed and optimized DIP-ESI-MS.

    Science.gov (United States)

    Lenzen, Claudia; Winterfeld, Gottfried A; Schmitz, Oliver J

    2016-06-01

    The direct inlet probe-electrospray ionization (DIP-ESI) presented here was based on the direct inlet probe-atmospheric pressure chemical ionization (DIP-APCI) developed by our group. It was coupled to an ion trap mass spectrometer (MS) for the detection of more polar compounds such as degradation products from pharmaceuticals. First, the position of the ESI tip, the gas and solvent flow rates, as well as the gas temperature were optimized with the help of the statistic program Minitab® 17 and a caffeine standard. The ability to perform quantitative analyses was also tested by using different concentrations of caffeine and camphor. Calibration curves with a quadratic calibration regression of R (2) = 0.9997 and 0.9998 for caffeine and camphor, respectively, were obtained. The limit of detection of 2.5 and 1.7 ng per injection for caffeine and camphor were determined, respectively. Furthermore, a solution of piracetam was used to compare established analytical methods for this drug and its impurities such as HPLC-diode array detector (DAD) and HPLC-ESI-MS with the DIP-APCI and the developed DIP-ESI. With HPLC-DAD and 10 μg piracetam on column, no impurity could be detected. With HPLC-ESI-MS, two impurities (A and B) were identified with only 4.6 μg piracetam on column, while with DIP-ESI, an amount of 1.6 μg piracetam was sufficient. In the case of the DIP-ESI measurements, all detected impurities could be identified by MS/MS studies. Graphical Abstract Scheme of the DIP-ESI principle.

  7. Analysis of sesterterpenoids from Aspergillus terreus using ESI-QTOF and ESI-IT.

    Science.gov (United States)

    Wu, Zhi-Jun; Fang, Dong-Mei; Han, Dan; Li, Guo-You; Chen, Xiao-Zhen; Qi, Hua-Yi; Zhang, Guo-Lin

    2010-01-01

    Biosynthesis of terretonin was studied due to the interesting skeleton of this series of sesterterpenoids. Very recently, López-Gresa reported two new sesterterpenoids (terretonins E and F) which are inhibitors of the mammalian mitochondrial respiratory chain. Mass spectrometry (MS), especially tandem mass spectrometry, has been one of the most important physicochemical methods for the identification of trace natural products due to it rapidity, sensitivity and low levels of sample consumption. The potential application prospect and unique skeleton prompted us to study structural characterisation using MS. To obtain sufficient information for rapid structural elucidation of this class of compounds using MS. The elemental composition of the product ions was confirmed by low-energy ESI-CID-QTOF-MS/MS analyses. The fragmentation pathways were postulated on the basis of ESI-QTOF-MS/MS/MS and ESI-IT-MS(n) spectra. Common features and major differences between ESI-QTOF-MS/MS and IT-MS(n) spectra were compared. For ESI-QTOF-MS/MS/MS experiments, capillary exit voltage was raised to induce in-source dissociation. Ammonium acetate or acetic acid were added into solutions to improve the intensity of [M + H]+. The collision energy was optimised to achieve sufficient fragmentation. Some fragmentation pathways were unambiguously proposed by the variety of abundance of fragment ions at different collision energies even without MS(n) spectra. Fragmentation pathways of five representative sesterterpenoids were elucidated using ESI-QTOF-MS/MS/MS and ESI-IT-MS(n) in both positive- and negative-ion mode. The key group of characterising fragmentation profiles was ring B, and these fragmentation patterns are helpful to identify different types of sestertepenoids. Complementary information obtained from fragmentation experiments of [M + H]+ (or [M + NH4]+ and [M-H](-) precursor ions is especially valuable for rapid identification of this kind of sesterterpenoid.

  8. Production of highly charged ion beams Kr32+, Xe44+, Au54+ with Electron String Ion Source (ESIS) Krion-2 and corresponding basic and applied studies

    Science.gov (United States)

    Donets, D. E.; Donets, E. D.; Donets, E. E.; Salnikov, V. V.; Shutov, V. B.

    2010-09-01

    Electron String Ion Source (ESIS) Krion-2 (JINR, Dubna) was used for basic and applied research in various aspects of multiply charged heavy ions production. Energy recuperation mode in ESIS has been proofed first and used for production of highly charged ions 84Kr28+÷84Kr32+, 124Xe40÷124Xe44 and Au51+÷ Au54+. Krion-2 ESIS was mounted on high voltage (HV) platform of LU-20 Linac and used as an injector of highly charged ions during Nuclotron run N° 41. Krion-2 ESIS has produced 3.0.107 124Xe42+ ions per pulse of 7 μs duration. This ion beam was injected into LU-20 and Nuclotron, accelerated up to energy of 186 GeV and the extracted Xe beam was used for physics experiments. Electron String Ion Source Krion-2 demonstrated the high reliability and stability running during 30 days on HV platform. We believe that it is due to an extremely low electron beam power, provided by using the electron string mode of operation: 50 W pulse power and about 10 W average power. Other possible application of ESIS could be its use in injection complexes of synchrotrons and cyclotrons for cancer therapy. Slow and fast extraction of C4+ and C6+ beams from Krion-2 ESIS were preliminary studied towards ESIS optimization for medical accelerators requirements.

  9. Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2009-04-01

    Full Text Available Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS. Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO only, sulfur (S containing CHOS compounds, nitrogen (N containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

  10. Golfo de Fonseca ESI; Honduras and Nicaragua: ESI (Environmental Sensitivity Index Shoreline Types)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  11. Evaluation of microbial transformations of dissolved organic matter - what information can be extracted from high-field FTICR-MS elemental formula data sets?

    Science.gov (United States)

    Herzsprung, Peter; von Tümpling, Wolf; Harir, Mourad; Hertkorn, Norbert; Schmitt-Kopplin, Philippe; Norf, Helge; Weitere, Markus; Kamjunke, Norbert

    2017-04-01

    Transformation of DOC and DOM was and is widespread investigated (1-3). Due to the complex composition of DOC increased attention was payed to DOM quality change during degradation processes. In order to get a better insight in DOM transformation processes both resolution as a function of time and on a molecular level are promising. The observation of DOM quality changes requires sophisticated evaluation techniques. A new evaluation strategy of FTICR-MS elemental formula data sets is introduced. An experiment with seven flumes and leaf leachate was performed. All flumes were sampled on five dates (within 7 days) and the SPEDOM was characterized using high-field FTICR-MS analysis, resulting in together 35 elemental formula data sets. The time dependent change of components abundance was fitted by a simple linear regression model after normalization of mass peak intensities. All components were categorized by calculation of the slope (change of percent intensity per day) in all seven flumes. A positive slope means product formation, a negative slope means degradation of components. Specific data filtration was developed to find out components with relevant change of relative intensity. About 7000 different components were present in at least one of the 35 samples. Of those about 1800 components were present in all of the 35 samples. About 300 components with significant increase of intensity were identified. They were mainly unsaturated and oxygen-rich components (lignin-like or tannin-like) and had molecular masses less than 450 Dalton. A group of about 70 components was partially degraded (significant negative slope, present in all samples). These components were more saturated and less oxygen-rich compared to the product group and had molecular masses > 450 Dalton. A third group of about 150 components was identified with a tendency to total degradation (significant negative slope, not present in all samples, reduced or no abundance at the end of the experiment

  12. TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil

    KAUST Repository

    Elbaz, Ayman M.

    2015-11-12

    There is an increasing interest in the comprehensive study of heavy fuel oil (HFO) due to its growing use in furnaces, boilers, marines, and recently in gas turbines. In this work, the thermal combustion characteristics and chemical composition of HFO were investigated using a range of techniques. Thermogravimetric analysis (TGA) was conducted to study the nonisothermal HFO combustion behavior. Chemical characterization of HFO was accomplished using various standard methods in addition to direct infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC) spectroscopy. By analyzing thermogravimetry and differential thermogravimetry (TG/DTG) results, three different reaction regions were identified in the combustion of HFO with air, specifically, low temperature oxidation region (LTO), fuel deposition (FD), and high temperature oxidation (HTO) region. At the high end of the LTO region, a mass transfer resistance (skin effect) was evident. Kinetic analysis in LTO and HTO regions was conducted using two different kinetic models to calculate the apparent activation energy. In both models, HTO activation energies are higher than those for LTO. The FT-ICR MS technique resolved thousands of aromatic and sulfur containing compounds in the HFO sample and provided compositional details for individual molecules of three major class species. The major classes of compounds included species with one sulfur atom (S1), with two sulfur atoms (S2), and purely hydrocarbons (HC). The DBE (double bond equivalent) abundance plots established for S1 and HC provided additional information on their distributions in the HFO sample. The 1H NMR and 13C NMR results revealed that nearly 59% of the 1H nuclei were distributed as paraffinic CH2 and 5% were in aromatic groups. Nearly 21% of 13C nuclei were

  13. Behenic acid pyrolysis to produce diesel-like hydrocarbons

    International Nuclear Information System (INIS)

    Xu, Zhi-Xiang; Liu, Peng; Xu, Gui-Sheng; He, Zhi-Xia; Ji, Heng-Song; Wang, Qian

    2017-01-01

    Highlights: • Behenic acid is a suitable bio-renewable resource to produce bio-fuel oil using catalytic cracking. • Little fraction of aromatic compounds presented in bio-fuel oil. • Carbon chain of fatty acid was cracked to form short carbon chain carboxyl firstly. • ESI FT-ICR MS experiment was an effective method to analyze bio-fuel oil heavy compounds. - Abstract: In order to obtain diesel-like bio-fuel oil, behenic acid was selected to carry out fast pyrolysis. The decomposition temperature of behenic acid was in the range of 250–450 °C at 20 k/min according to TG experiment. The bio-fuel oil mainly contained alkane, alkene and fatty acid. Components of products were C_1_3–C_2_0 hydrocarbon. Little fraction of aromatic compounds was found in bio-fuel oil. According to ESI FT-ICR MS analysis results, the oxygen containing compounds in bio-fuel oil were mainly O_2–O_4 classes, with the O_3 being the major class. According to GC–MS and ESI FT-ICR MS results, it was found that the carbon chain of behenic acid was cracked to form short carbon chain carboxyl firstly. And then decarboxylation reaction carried out. In other means carboxyl groups were more stable than carbon chain of fatty acid. The probable mechanism of O_4 species was free radical reaction. The recommended pyrolysis path was also proposed. Diesel-like bio-fuel oil can be obtained using behenic acid catalytic cracking.

  14. High temperature liquid chromatography hyphenated with ESI-MS and ICP-MS detection for the structural characterization and quantification of halogen containing drug metabolites

    International Nuclear Information System (INIS)

    Vlieger, Jon S.B. de; Giezen, Mark J.N.; Falck, David; Tump, Cornelis; Heuveln, Fred van; Giera, Martin; Kool, Jeroen; Lingeman, Henk; Wieling, Jaap; Honing, Maarten; Irth, Hubertus; Niessen, Wilfried M.A.

    2011-01-01

    Highlights: → Hyphenation of high temperature liquid chromatography to ICP-MS and ESI-MS. → Structural characterization of kinase inhibitor metabolites with high resolution MS n experiments. → Quantification of drug metabolites with ICP-MS based on Iodine detection. → Significant changes in ESI-MS response after small structural changes. - Abstract: In this paper we describe the hyphenation of high temperature liquid chromatography with ICP-MS and ESI-MS for the characterization of halogen containing drug metabolites. The use of temperature gradients up to 200 deg. C enabled the separation of metabolites with low organic modifier content. This specific property allowed the use of detection methods that suffer from (significant) changes in analyte response factors as a function of the organic modifier content such as ICP-MS. Metabolites of two kinase inhibitors (SB-203580-Iodo and MAPK inhibitor VIII) produced by bacterial cytochrome P450 BM3 mutants and human liver microsomes were identified based on high resolution MS n data. Quantification was done using their normalized and elemental specific response in the ICP-MS. The importance of these kinds of quantification strategies is stressed by the observation that the difference of the position of one oxygen atom in a structure can greatly affect its response in ESI-MS and UV detection.

  15. 2001 Environmental Sustainability Index (ESI)

    Data.gov (United States)

    National Aeronautics and Space Administration — The 2001 Environmental Sustainability Index (ESI) utilizes a refined methodology based on the 2000 Pilot ESI effort, to construct an index covering 122 countries...

  16. Puerto Rico ESI/RSI: INDEX

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  17. Puerto Rico ESI/RSI: BIRDS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  18. Puerto Rico ESI/RSI: HABITATS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  19. Puerto Rico ESI/RSI: KARST

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  20. Identification of Reactive and Refractory Components of Dissolved Organic Nitrogen by FT-ICR Mass Spectrometry

    Science.gov (United States)

    Cooper, W. T.; Podgorski, D. C.; Osborne, D. M.; Corbett, J.; Chanton, J.

    2010-12-01

    Dissolved organic nitrogen is an often overlooked but potentially significant bioavailable component of dissolved organic matter. Studies of bulk DON turnover have been reported, but the compositions of the reactive and refractory components of DON are largely unknown. Here we show the unique ability of atmospheric pressure photoionization (APPI) coupled to ultrahigh resolution mass spectrometry to identify the reactive and refractory components of DON. Figure 1 is an isolated 0.30 m/z window from an ultrahigh resolution APPI FT-ICR mass spectrum of DON in surface waters draining an agricultural area in South Florida. Using this optimized, negative-ion APPI strategy we have been able to identify the reactive and refractory components of DON in these nitrogen-rich waters. Similar results were observed with samples from soil porewaters in sedge-dominated fens and sphagnum-dominated bogs within the Glacial Lake Agassiz Peatlands (GLAP) of northern Minnesota. Surprisingly, microbes appear to initially use similar enzymatic pathways to degrade DON and DOC, often with little release of nitrogen. Figure 1. Isolated 0.30 m/z window at nominal mass 432 from negative-ion APPI FT-ICR mass spectrum of DOM from waters draining an agricultural area in South Florida. Peaks marked contain nitrogen.

  1. U.S. Virgin Islands and British Virgin Islands ESI: ESI (Environmental Sensitivity Index Shoreline Types)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  2. Utilizing a Robotic Sprayer for High Lateral and Mass Resolution MALDI FT-ICR MSI of Microbial Cultures

    Energy Technology Data Exchange (ETDEWEB)

    Anderton, Christopher R.; Chu, Rosalie K.; Tolic, Nikola; Creissen, Alain V.; Pasa-Tolic, Ljiljana

    2016-01-07

    The ability to visualize biochemical interactions between microbial communities using MALDI MSI has provided tremendous insights into a variety of biological fields. Matrix application using a sieve proved to be incredibly useful, but it had many limitations that include uneven matrix coverage and limitation in the types of matrices one could employ in their studies. Recently, there has been a concerted effort to improve matrix application for studying agar plated microbial cultures, many of which utilized automated matrix sprayers. Here, we describe the usefulness of using a robotic sprayer for matrix application. The robotic sprayer has two-dimensional control over where matrix is applied and a heated capillary that allows for rapid drying of the applied matrix. This method provided a significant increase in MALDI sensitivity over the sieve method, as demonstrated by FT-ICR MS analysis, facilitating the ability to gain higher lateral resolution MS images of Bacillus Subtilis than previously reported. This method also allowed for the use of different matrices to be applied to the culture surfaces.

  3. Spatial Segmentation of MALDI FT-ICR MSI Data: A Powerful Tool to Explore the Head and Neck Tumor In Situ Lipidome

    Czech Academy of Sciences Publication Activity Database

    Krásný, Lukáš; Hoffmann, F.; Ernst, G.; Trede, D.; Alexandrov, T.; Havlíček, Vladimír; Guntinas-Lichius, O.; von Eggeling, F.; Crecelius, A.C.

    2015-01-01

    Roč. 26, č. 1 (2015), s. 36-43 ISSN 1044-0305 R&D Projects: GA MŠk(CZ) LD13038 Institutional support: RVO:61388971 Keywords : MALDI * MSI * FT-ICR Subject RIV: CE - Biochemistry Impact factor: 3.031, year: 2015

  4. Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

    Science.gov (United States)

    Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

  5. Systematic HPLC/ESI-High Resolution-qTOF-MS Methodology for Metabolomic Studies in Nonfluorescent Chlorophyll Catabolites Pathway

    Directory of Open Access Journals (Sweden)

    José Julián Ríos

    2015-01-01

    Full Text Available Characterization of nonfluorescent chlorophyll catabolites (NCCs and dioxobilane-type nonfluorescent chlorophyll catabolite (DNCC in peel extracts of ripened lemon fruits (Citrus limon L. was performed by HPLC/ESI-high resolution-qTOF-MS method. Compounds were identified in samples on the basis of measured accurate mass, isotopic pattern, and characteristic fragmentation profile with an implemented software postprocessing routine. Three NCC structures already identified in other vegetal tissues were present in the lemon fruit peels (Cl-NCC1; Cl-NCC2; Cl-NCC4 while a new structure not defined so far was characterized (Cl-NCC3. This catabolite exhibits an exceptional arrangement of the peripheral substituents, allowing concluding that the preferences for the NCC modifications could be a species-related matter.

  6. Puerto Rico ESI and RSI: WETLANDS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  7. Puerto Rico ESI/RSI: HYDRO (Hydrology)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  8. Prince William Sound, Alaska ESI: INDEX

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  9. Fabricating and Characterizing the Microfluidic Solid Phase Extraction Module Coupling with Integrated ESI Emitters

    Directory of Open Access Journals (Sweden)

    Hangbin Tang

    2018-05-01

    Full Text Available Microfluidic chips coupling with mass spectrometry (MS will be of great significance to the development of relevant instruments involving chemical and bio-chemical analysis, drug detection, food and environmental applications and so on. In our previous works, we proposed two types of microfluidic electrospray ionization (ESI chip coupling with MS: the two-phase flow focusing (FF ESI microfluidic chip and the corner-integrated ESI emitter, respectively. However the pretreatment module integrated with these ESI emitters is still a challenging problem. In this paper, we concentrated on integrating the solid phase micro-extraction (SPME module with our previous proposed on-chip ESI emitters; the fabrication processes of such SPME module are fully compatible with our previous proposed ESI emitters based on the multi-layer soft lithography. We optimized the structure of the integrated chip and characterized its performance using standard samples. Furthermore, we verified its abilities of salt removal, extraction of multiple analytes and separation through on-chip elution using mimic biological urine spiked with different drugs. The results indicated that our proposed integrated module with ESI emitters is practical and effective for real biological sample pretreatment and MS detection.

  10. Conformations of cationized linear oligosaccharides revealed by FTMS combined with in-ESI H/D exchange.

    Science.gov (United States)

    Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

    2015-10-01

    Previously (Kostyukevich et al. Anal Chem 2014, 86, 2595), we have reported that oligosaccharides anions are produced in the electrospray in two different conformations, which differ by the rate of gas phase hydrogen/deuterium (H/D) exchange reaction. In the present paper, we apply the in-electrospray ionization (ESI) source H/D exchange approach for the investigation of the oligosaccharides cations formed by attaching of metal ions (Na, K) to the molecule. It was observed that the formation of different conformers can be manipulated by varying the temperature of the desolvating capillary of the ESI interphase. Separation of the conformers was performed using gas phase H/D approach. Because the conformers have different rates of the H/D exchange reaction, the deuterium distribution spectrum becomes bimodal. It was found that the conformation corresponding to the slow H/D exchange rate dominates in the spectrum when the capillary temperature is low (~200 °C), and the conformation corresponding to the fast H/D exchange rate dominates at high (~400 °C) temperatures. In the intermediate temperature region, two conformers are present simultaneously. It was also observed that large oligosaccharide requires higher temperature for the formation of another conformer. It was found that the presence of the conformers considerably depends on the solvent used for ESI and the pH. We have compared these results with the previously performed in-ESI source H/D exchange experiments with peptides and proteins. Copyright © 2015 John Wiley & Sons, Ltd.

  11. Unambiguous metabolite identification in high-throughput metabolomics by hybrid 1D 1 H NMR/ESI MS 1 approach: Hybrid 1D 1 H NMR/ESI MS 1 metabolomics method

    Energy Technology Data Exchange (ETDEWEB)

    Walker, Lawrence R. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Hoyt, David W. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Walker, S. Michael [Department of Ecology and Evolutionary Biology, University of Kansas, Lawrence KS 66045 USA; Ward, Joy K. [Department of Ecology and Evolutionary Biology, University of Kansas, Lawrence KS 66045 USA; Nicora, Carrie D. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Bingol, Kerem [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA

    2016-09-16

    We present a novel approach to improve accuracy of metabolite identification by combining direct infusion ESI MS1 with 1D 1H NMR spectroscopy. The new approach first applies standard 1D 1H NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in metabolomics library. This generates a list of candidate metabolites. The list contains false positive and ambiguous identifications. Next, we constrained the list with the chemical formulas derived from high-resolution direct infusion ESI MS1 spectrum of the same sample. Detection of the signals of a metabolite both in NMR and MS significantly improves the confidence of identification and eliminates false positive identification. 1D 1H NMR and direct infusion ESI MS1 spectra of a sample can be acquired in parallel in several minutes. This is highly beneficial for rapid and accurate screening of hundreds of samples in high-throughput metabolomics studies. In order to make this approach practical, we developed a software tool, which is integrated to Chenomx NMR Suite. The approach is demonstrated on a model mixture, tomato and Arabidopsis thaliana metabolite extracts, and human urine.

  12. Characterization of fast pyrolysis products generated from several western USA woody species

    Science.gov (United States)

    Jacqueline M. Jarvis; Deborah S. Page-Dumroese; Nathaniel M. Anderson; Yuri Corilo; Ryan P. Rodgers

    2014-01-01

    Woody biomass has the potential to be utilized at an alternative fuel source through its pyrolytic conversion. Here, fast pyrolysis bio-oils derived from several western USA woody species are characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine molecular-level composition. The...

  13. Analysis of impact of temperature and saltwater on Nannochloropsis salina bio-oil production by ultra high resolution APCI FT-ICR MS

    KAUST Repository

    Sanguineti, Michael Mario

    2015-05-01

    Concentrated Nannochloropsis salina paste was reconstituted in distilled water and synthetic saltwater and processed at 250°C and 300°C via hydrothermal liquefaction. The resulting bio-oils yielded a diverse distribution of product classes, as analyzed by ultra high resolution APCI FT-ICR MS. The organic fractions were analyzed and both higher temperatures and distilled water significantly increase the number of total compounds present and the number of product classes. Major bio-oil products consisted of N1O1, hydrocarbon, and O2 classes, while O1, O4, S1, N1O2, and N2O2 classes represented the more significant minor classes. Both chlorine and sulfur containing compounds were detected in both distilled and saltwater reactions, while fewer numbers of chlorine and sulfur containing products were present in the organic fraction of the saltwater reactions. Further refinement to remove the chlorine and sulfur contents appears necessary with marine microalgal bio-oils produced via hydrothermal liquefaction. The higher heating value (MJ/kg) as calculated by the Boie equation of classes of interest in the bio-oil reveals a significant potential of algal hydrothermal liquefaction products as a sustainable and renewable fuel feedstock. © 2015.

  14. High-performance liquid chromatography electrospray mass spectrometry as a method in proteomic research

    International Nuclear Information System (INIS)

    Walcher, W.

    2003-06-01

    During the sequencing of the human genome it became clear, that a lot of human diseases and/or malfunctions don't base on genomic information, but on differences at the protein level. Therefore biochemistry, biology and medicine are faced to various novel problems where new and authentic analysis methods are needed. Miniaturized chromatographic separation methods are frequently the methods of choice for the separation of peptides and proteins, when the amount of sample is limited. Monolithic capillary columns were prepared by copolymerization of styrene and divinylbenzene in the presence of a suitable porogen mixture of 1-decanol and tetrahydrofuran. The synthesized columns enabled the highly efficient separation of peptides and proteins by reversed-phase high-performance liquid chromatography (RP-HPLC) with peak capacities of 80 and more in 10 minutes. By the hyphenation of RP-HPLC to electrospray mass spectrometry (ESI-MS) the potential of the analysis method was even extended. The monolithic column technology was further miniaturized from 200 μm to 100 and 50 μm inner diameters to improve detection limits by RP-HPLC-ESI-MS. After the optimization of the RP-HPLC-ESI-MS method, the ion source and the ion transfer optics of an ion trap mass spectrometer (LCQ classic, Thermofinnigan) have been advanced for protein and peptide analysis. The improved RP-HPLC-ESI-MS system was subsequently applied to the detection of posttranslational protein modifications at the example of the nitration of bovine serum albumin (BSA). The results of the RP-HPLC-ESI-MS analysis were found to be highly reproducible, which enabled the determination of nitration degrees for different tyrosine residues in the protein sequence. Y 1 60, Y 4 96 and Y 3 52 or Y369 were found to be the predominant positions of protein nitration in BSA. At last light harvesting proteins from the photosystem II (PSII) of higher plants have been analyzed by RP-HPLC-ESI-MS and RP-HPLC-ESI-MSMS. Beside the

  15. Cyclotron Phase-Coherent Ion Spatial Dispersion in a Non-Quadratic Trapping Potential is Responsible for FT-ICR MS at the Cyclotron Frequency

    Science.gov (United States)

    Nagornov, Konstantin O.; Kozhinov, Anton N.; Tsybin, Yury O.

    2018-01-01

    Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) at the cyclotron frequency instead of the reduced cyclotron frequency has been experimentally demonstrated using narrow aperture detection electrode (NADEL) ICR cells. Here, based on the results of SIMION simulations, we provide the initial mechanistic insights into the cyclotron frequency regime generation in FT-ICR MS. The reason for cyclotron frequency regime is found to be a new type of a collective motion of ions with a certain dispersion in the initial characteristics, such as pre-excitation ion velocities, in a highly non-quadratic trapping potential as realized in NADEL ICR cells. During ion detection, ions of the same m/z move in phase for cyclotron ion motion but out of phase for magnetron (drift) ion motion destroying signals at the fundamental and high order harmonics that comprise reduced cyclotron frequency components. After an initial magnetron motion period, ion clouds distribute into a novel type of structures - ion slabs, elliptical cylinders, or star-like structures. These structures rotate at the Larmor (half-cyclotron) frequency on a plane orthogonal to the magnetic field, inducing signals at the true cyclotron frequency on each of the narrow aperture detection electrodes. To eliminate the reduced cyclotron frequency peak upon dipolar ion detection, a number of slabs or elliptical cylinders organizing a star-like configuration are formed. In a NADEL ICR cell with quadrupolar ion detection, a single slab or an elliptical cylinder is sufficient to minimize the intensity of the reduced cyclotron frequency components, particularly the second harmonic. [Figure not available: see fulltext.

  16. Ellagitannin composition of blackberry as determined by HPLC-ESI-MS and MALDI-TOF-MS.

    Science.gov (United States)

    Hager, Tiffany J; Howard, Luke R; Liyanage, Rohana; Lay, Jackson O; Prior, Ronald L

    2008-02-13

    Blackberries ( Rubus sp.) were evaluated by high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF-MS) to identify the ellagitannins present in flesh, torus (receptacle tissue), and seeds. Most ellagitannins were present (or detectable) only in seed tissues. Ellagitannins identified by HPLC-ESI-MS in the seeds included pedunculagin, casuarictin/potentillin, castalagin/vescalagin, lambertianin A/sanguiin H-6, lambertianin C, and lambertianin D. For several of the ellagitannins, isomeric separation was also obtained. The MALDI-TOF-MS analysis was primarily utilized to evaluate and identify high molecular mass (>1000 Da) ellagitannins. The MALDI analysis verified the presence of the ellagitannins identified by HPLC-ESI-MS including lambertianin A/sanguiin H-6, lambertianin C, and lambertianin D, but the analysis also indicated the presence of several other compounds that were most likely ellagitannins based on the patterns observed in the masses (i.e., loss or addition of a gallic acid moiety to a known ellagitannin). This study determined the presence of several possible isomeric forms of ellagitannins previously unidentified in fruit and presents a possible analytical HPLC method for the analysis of the major ellagitannins present in the fruit.

  17. PIXE analysis of museum soapstone sculptures from Esie, south west Nigeria

    International Nuclear Information System (INIS)

    Olabanji, S.O.; Olarewaju, V.O.; Onabajo, O.

    1989-05-01

    The PIXE technique was employed for the study of Esie museum stone sculptures using 2.55 MeV protons from the 3 MeV tandem accelerator (NEC 3 UDH) in Lund, coupled with the geological and archaeological findings. The aim is to elucidate and decipher the prodigious but rather enigmatic and bewildering stone sculptures. PIXE results show that the composition of the stone sculptures are 40.69% talc-tremolite schist, 30.88% talc-chlorite schist, 15.20% talc-tremolite-anthophyllite schist and 13.24% talc-amphibolite schist. Thus the composition of Esie sculptures are found to be the same with the locally available talc-schists present around Esie. The geological evidence (mineralogical results) corroborated this as there was no textural or mineralogical difference between the talc-bearing country rock (outcrop) in Esie and the museum soapstone samples studied. Consequently, there is a very high probability that the sculptures were carved using the locally available talc-schists. (author). 7 refs, 4 figs, 2 tabs

  18. New and vintage solutions to enhance the plasma metabolome coverage by LC-ESI-MS untargeted metabolomics: the not-so-simple process of method performance evaluation.

    Science.gov (United States)

    Tulipani, Sara; Mora-Cubillos, Ximena; Jáuregui, Olga; Llorach, Rafael; García-Fuentes, Eduardo; Tinahones, Francisco J; Andres-Lacueva, Cristina

    2015-03-03

    Although LC-MS untargeted metabolomics continues to expand into exiting research domains, methodological issues have not been solved yet by the definition of unbiased, standardized and globally accepted analytical protocols. In the present study, the response of the plasma metabolome coverage to specific methodological choices of the sample preparation (two SPE technologies, three sample-to-solvent dilution ratios) and the LC-ESI-MS data acquisition steps of the metabolomics workflow (four RP columns, four elution solvent combinations, two solvent quality grades, postcolumn modification of the mobile phase) was investigated in a pragmatic and decision tree-like performance evaluation strategy. Quality control samples, reference plasma and human plasma from a real nutrimetabolomic study were used for intermethod comparisons. Uni- and multivariate data analysis approaches were independently applied. The highest method performance was obtained by combining the plasma hybrid extraction with the highest solvent proportion during sample preparation, the use of a RP column compatible with 100% aqueous polar phase (Atlantis T3), and the ESI enhancement by using UHPLC-MS purity grade methanol as both organic phase and postcolumn modifier. Results led to the following considerations: submit plasma samples to hybrid extraction for removal of interfering components to minimize the major sample-dependent matrix effects; avoid solvent evaporation following sample extraction if loss in detection and peak shape distortion of early eluting metabolites are not noticed; opt for a RP column for superior retention of highly polar species when analysis fractionation is not feasible; use ultrahigh quality grade solvents and "vintage" analytical tricks such as postcolumn organic enrichment of the mobile phase to enhance ESI efficiency. The final proposed protocol offers an example of how novel and old-fashioned analytical solutions may fruitfully cohabit in untargeted metabolomics

  19. Puerto Rico ESI/RSI: FISH (Fish Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  20. Puerto Rico ESI/RSI: MGT (Management Areas)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  1. Puerto Rico ESI/RSI: INVERT (Invertebrate Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  2. Puerto Rico ESI/RSI: INVERT (Invertebrate Lines)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  3. Puerto Rico ESI/RSI: FISHL (Fish Lines)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  4. Profiling the Oxylipin and Endocannabinoid Metabolome by UPLC-ESI-MS/MS in Human Plasma to Monitor Postprandial Inflammation.

    Science.gov (United States)

    Gouveia-Figueira, Sandra; Späth, Jana; Zivkovic, Angela M; Nording, Malin L

    2015-01-01

    Bioactive lipids, including oxylipins, endocannabinoids, and related compounds may function as specific biochemical markers of certain aspects of inflammation. However, the postprandial responsiveness of these compounds is largely unknown; therefore, changes in the circulating oxylipin and endocannabinoid metabolome in response to a challenge meal were investigated at six occasions in a subject who freely modified her usual diet. The dietary change, and especially the challenge meal itself, represented a modification of precursor fatty acid status, with expectedly subtle effects on bioactive lipid levels. To detect even the slightest alteration, highly sensitive ultra-performance liquid chromatography (UPLC) coupled to electrospray ionization (ESI) tandem mass spectrometry (MS/MS) methods for bioactive lipid profiling was employed. A previously validated UPLC-ESI-MS/MS method for profiling the endocannabinoid metabolome was used, while validation of an UPLC-ESI-MS/MS method for oxylipin analysis was performed with acceptable outcomes for a majority of the parameters according to the US Food and Drug Administration guidelines for linearity (0.9938 metabolome, caused by changes in diet and ii) responsiveness to a challenge meal for a subset of the oxylipin and endocannabinoid metabolome. To summarize, we have shown proof-of-concept of our UPLC-ESI-MS/MS bioactive lipid protocols for the purpose of monitoring subtle shifts, and thereby useful to address lipid-mediated postprandial inflammation.

  5. Prince William Sound, Alaska ESI: HYDRO (Hydrology)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  6. Prince William Sound, Alaska ESI: INVERT (Invertebrates)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  7. Investigation of glucosinolate profile and qualitative aspects in sprouts and roots of horseradish (Armoracia rusticana) using LC-ESI-hybrid linear ion trap with Fourier transform ion cyclotron resonance mass spectrometry and infrared multiphoton dissociation.

    Science.gov (United States)

    Agneta, Rosa; Rivelli, Anna Rita; Ventrella, Emanuela; Lelario, Filomena; Sarli, Giulio; Bufo, Sabino Aurelio

    2012-08-01

    Within the family of Brassicaceae, an important source of glucosinolates (GLSs) is represented by horseradish ( Armoracia rusticana P. Gaertner, B. Meyer & Scherbius), cultivated for its roots, which are grated fresh or processed into a sauce and used as a condiment. The characteristic pungent flavor of the root depends on the abundance of the bioactive GLS molecules. In crude plant extracts (sprouts and roots) of an accession of horseradish largely diffused in the Basilicata region (southern Italy), which develops many sprouts and produces white, fiery, and sharp-flavored marketable roots, we characterized the GLS profile by LC-ESI-LTQ-FTICR-MS and IRMPD. In sprouts and roots we identified 16 and 11 GLSs, respectively. We confirmed the presence of sinigrin, 4-hydroxyglucobrassicin, glucobrassicin, gluconasturtin, and 4-methoxyglucobrassicin and identified glucoiberin, gluconapin, glucocochlearin, glucoconringianin, glucosativin, glucoibarin, 5-hydroxyglucobrassicin, glucocapparilinearisin or glucobrassicanapin, glucotropaeolin, and glucoarabishirsutain, not previously characterized in horseradish. Of particular note was the presence of the putative 2-methylsulfonyl-oxo-ethyl-GLS.

  8. Puerto Rico ESI and RSI: ESI (Environmental Sensitivity Index Shoreline Types) / RSI (Reach Sensitivity Index River and Stream Types)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  9. Potential of dynamically harmonized Fourier transform ion cyclotron resonance cell for high-throughput metabolomics fingerprinting: control of data quality.

    Science.gov (United States)

    Habchi, Baninia; Alves, Sandra; Jouan-Rimbaud Bouveresse, Delphine; Appenzeller, Brice; Paris, Alain; Rutledge, Douglas N; Rathahao-Paris, Estelle

    2018-01-01

    Due to the presence of pollutants in the environment and food, the assessment of human exposure is required. This necessitates high-throughput approaches enabling large-scale analysis and, as a consequence, the use of high-performance analytical instruments to obtain highly informative metabolomic profiles. In this study, direct introduction mass spectrometry (DIMS) was performed using a Fourier transform ion cyclotron resonance (FT-ICR) instrument equipped with a dynamically harmonized cell. Data quality was evaluated based on mass resolving power (RP), mass measurement accuracy, and ion intensity drifts from the repeated injections of quality control sample (QC) along the analytical process. The large DIMS data size entails the use of bioinformatic tools for the automatic selection of common ions found in all QC injections and for robustness assessment and correction of eventual technical drifts. RP values greater than 10 6 and mass measurement accuracy of lower than 1 ppm were obtained using broadband mode resulting in the detection of isotopic fine structure. Hence, a very accurate relative isotopic mass defect (RΔm) value was calculated. This reduces significantly the number of elemental composition (EC) candidates and greatly improves compound annotation. A very satisfactory estimate of repeatability of both peak intensity and mass measurement was demonstrated. Although, a non negligible ion intensity drift was observed for negative ion mode data, a normalization procedure was easily applied to correct this phenomenon. This study illustrates the performance and robustness of the dynamically harmonized FT-ICR cell to perform large-scale high-throughput metabolomic analyses in routine conditions. Graphical abstract Analytical performance of FT-ICR instrument equipped with a dynamically harmonized cell.

  10. [Eppendorf Schizophrenia Inventory (ESI) vs. Frankfurt Complaint Questionnaire (FCQ). Direct comparison in a clinical trial].

    Science.gov (United States)

    Mass, R

    2005-09-01

    This study is the first to directly compare two clinical questionnaires which are both aimed at self-experienced cognitive dysfunctions of schizophrenia: Eppendorf Schizophrenia Inventory (ESI) and Frankfurt Complaint Questionnaire (FCQ). Evaluated were (a) diagnostic validity, (b) psychometric properties, (c) scale intercorrelations, and (d) factor analytic stability. Ad (a): schizophrenic subjects (n=36) show highly significant increases in the ESI scales and sum score when compared to other clinical groups (patients with depression, alcohol dependence, or obsessive-compulsive disorder, n>30, respectively); on the other hand, the FCQ yields no systematic group differences. Ad (b): mean of reliability coefficients (Cronbach alpha) of the ESI scales is r(tt)=0.86, mean of reliability coefficients of the FCQ scales is significantly lower. Ad (c): the mean intercorrelation between ESI and FCQ scales amounts to r(xy)=0.56 (minimum 0.29, maximum 0.73), corresponding to an average shared variance of about 31%. Ad (d): factor analysis yielded an ESI factor and a FBF factor; one-way ANOVA with the factor scores confirms the diagnostic validity of the ESI. ESI and FCQ measure essentially different aspects of schizophrenic psychopathology. Regarding reliability and diagnostic validity, the ESI is superior to the FCQ.

  11. Characterization, stoichiometry, and stability of salivary protein-tannin complexes by ESI-MS and ESI-MS/MS.

    Science.gov (United States)

    Canon, Francis; Paté, Franck; Meudec, Emmanuelle; Marlin, Thérèse; Cheynier, Véronique; Giuliani, Alexandre; Sarni-Manchado, Pascale

    2009-12-01

    Numerous protein-polyphenol interactions occur in biological and food domains particularly involving proline-rich proteins, which are representative of the intrinsically unstructured protein group (IUP). Noncovalent protein-ligand complexes are readily detected by electrospray ionization mass spectrometry (ESI-MS), which also gives access to ligand binding stoichiometry. Surprisingly, the study of interactions between polyphenolic molecules and proteins is still an area where ESI-MS has poorly benefited, whereas it has been extensively applied to the detection of noncovalent complexes. Electrospray ionization mass spectrometry has been applied to the detection and the characterization of the complexes formed between tannins and a human salivary proline-rich protein (PRP), namely IB5. The study of the complex stability was achieved by low-energy collision-induced dissociation (CID) measurements, which are commonly implemented using triple quadrupole, hybrid quadrupole time-of-flight, or ion trap instruments. Complexes composed of IB5 bound to a model polyphenol EgCG have been detected by ESI-MS and further analyzed by MS/MS. Mild ESI interface conditions allowed us to observe intact noncovalent PRP-tannin complexes with stoichiometries ranging from 1:1 to 1:5. Thus, ESI-MS shows its efficiency for (1) the study of PRP-tannin interactions, (2) the determination of stoichiometry, and (3) the study of complex stability. We were able to establish unambiguously both their stoichiometries and their overall subunit architecture via tandem mass spectrometry and solution disruption experiments. Our results prove that IB5.EgCG complexes are maintained intact in the gas phase.

  12. Metabolic profiling of roots of liquorice (Glycyrrhiza glabra) from different geographical areas by ESI/MS/MS and determination of major metabolites by LC-ESI/MS and LC-ESI/MS/MS.

    Science.gov (United States)

    Montoro, Paola; Maldini, Mariateresa; Russo, Mariateresa; Postorino, Santo; Piacente, Sonia; Pizza, Cosimo

    2011-02-20

    Liquid chromatography electrospray mass spectrometry (LC-ESI/MS) has been applied to the full characterization of saponins and phenolics in hydroalcoholic extracts of roots of liquorice (Glycyrrhiza glabra). Relative quantitative analyses of the samples with respect to the phenolic constituents and to a group of saponins related to glycyrrhizic acid were performed using LC-ESI/MS. For the saponin constituents, full scan LC-MS/MS fragmentation of the protonated (positive ion mode) or deprotonated (negative ion mode) molecular species generated diagnostic fragment ions that provided information concerning the triterpene skeleton and the number and nature of the substituents. On the basis of the specific fragmentation of glycyrrhizic acid, an LC-MS/MS method was developed in order to quantify the analyte in the liquorice root samples. Chinese G. glabra roots contained the highest levels of glycyrrhizic acid, followed by those from Italy (Calabria). Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Puerto Rico ESI/RSI: T_MAMMAL (Terrestrial Mammals)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  14. Puerto Rico ESI and RSI: SHELFBND (Shelf Boundary)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  15. Puerto Rico ESI/RSI: BENTHIC (Benthic Marine Habitats)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  16. Puerto Rico ESI/RSI: REPTILES (Reptiles and Amphibians)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  17. Esi- ja alkuopetuksen opettajien näkemyksiä inklusiivisesta kasvatuksesta

    OpenAIRE

    Kanerva, Laura

    2014-01-01

    Tutkimukseni tarkoituksena oli selvittää millaisia näkemyksiä esi- ja alkuopetuksen opettajilla oli inklusiivisesta kasvatuksesta osana esi- ja alkuopetusta. Tutkielman aihe on ajankohtainen, koska nykyään pidetään yhä tärkeämpänä, että kaikilla lapsilla on oikeus päästä päivähoitoon lähipäiväkotiin tai kouluun lähikouluun. Tämän tutkimuksen tarkoituksena oli selvittää miten esi- ja alkuopetuksen opettajat määrittelivät inkluusion osaksi esi- ja alkuopetusta, miten esi- ja alkuopetuksen o...

  18. Effect-directed analysis via hyphenated high-performance thin-layer chromatography for bioanalytical profiling of sunflower leaves.

    Science.gov (United States)

    Móricz, Ágnes M; Ott, Péter G; Yüce, Imanuel; Darcsi, András; Béni, Szabolcs; Morlock, Gertrud E

    2018-01-19

    High-performance thin-layer chromatography (HPTLC) coupled with effect-directed analysis was used for non-targeted screening of sunflower leaf extract for components exhibiting antioxidant, antibacterial and/or cholinesterase enzyme inhibitory effects. The active compounds were characterized by HPTLC-electrospray ionization-high resolution mass spectrometry (ESI-HRMS) and HPTLC-Direct Analysis in Real Time (DART)-MS/MS. The latter ambient ionization technique (less soft than ESI) resulted in oxidation and fragmentation products and characteristic fragment ions. NMR spectroscopy after targeted isolation via preparative normal phase flash chromatography and semi-preparative reversed phase high-performance liquid chromatography supported the identification of two diterpenes to be (-)-kaur-16-en-19-oic acid and 15-α-angeloyloxy-ent-kaur-16-en-19-oic acid. Both compounds found to be multi-potent as they inhibited acetylcholinesterase and butyrylcholinesterase and showed antibacterial effects against Gram-positive Bacillus subtilis and Gram-negative Aliivibrio fischeri bacteria. Kaurenoic acid was also active against the Gram-negative pepper pathogenic Xanthomonas euvesicatoria bacteria. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Golfo de Fonseca ESI; Honduras and Nicaragua: FISH

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  20. Prince William Sound, Alaska ESI: FISH (Fish Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  1. Prince William Sound, Alaska ESI: NESTS (Bird Nests)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  2. Golfo de Fonseca ESI; Honduras and Nicaragua: SALTPOND

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  3. Golfo de Fonseca ESI; Honduras and Nicaragua: BIRDS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  4. Golfo de Fonseca ESI; Honduras and Nicaragua: INDEX

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  5. Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  6. 'Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry'

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  7. Design improvements to the ESI-80 wind turbine

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, T.; Kleeman, A.; Manwell, J.; McGowan, J. [Univ. of Massachusetts, Amherst, MA (United States)

    1996-12-31

    This paper describes two investigations related to improvements to an ESI-80 wind turbine. One of them involved modeling the tip flaps during braking. The other was a study of the turbine behavior with various delta-3 angles. These topics are of interest since the turbine is a two-bladed, teetered, free-yaw machine with tip flaps and an adjustable delta-3 angle. Tip flaps are used for slowing the turbine during shutdown and as an emergency system to insure that the rotor does not go into an overspeed condition in the event of failure of other parts of the system. Upon deployment, the tip flaps are exposed to a number of varying forces including aerodynamic, damper, spring, centripetal, and gravitational forces and forces at the hinged connection to the blades. For maximum braking the angle of tip flap deployment needs to be as large as possible without striking the blades in overspeed conditions and when covered with ice. To investigate tip flap design tradeoffs, a dynamic model of the tip flaps on the modified ESI-80 turbine was developed. Results include a determination of the effect of the addition of weight to the flap, overspeed conditions, and changes in damping coefficient. Changes in the delta-3 angle can be used to couple pitching and flapping motions, affecting both teeter and yaw behavior. These effects have been investigated using a modified version of YawDyn. The effects of changes in the delta-3 angle on the teeter and yaw behavior of the modified ESI-80 wind turbine were investigated. Results show that increased teeter excursions in steady high winds can be reduced by increasing the delta-3 angle. Increasing the delta-3 angle may also increase yaw motion in low wind speeds. Results suggest that the optimum delta-3 angle for improved performance may be substantially greater than the presently used angle of zero degrees. 8 refs., 16 figs.

  8. Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI-MSMS and ESI-nozzle-skimmer-MSMS.

    Science.gov (United States)

    Siegel, Marshall M; Kong, Fangming; Feng, Xidong; Carter, Guy T

    2009-12-01

    Three lipocyclopeptide antibiotics, aspartocins A (1), B (2), and C (3), were obtained from the aspartocin complex by HPLC separation methodology. Their structures were elucidated using previously published chemical degradation results coupled with spectroscopic studies including ESI-MS, ESI-Nozzle Skimmer-MSMS and NMR. All three aspartocin compounds share the same cyclic decapeptide core of cyclo [Dab2 (Asp1-FA)-Pip3-MeAsp4-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11]. They differ only in the fatty acid side chain moiety (FA) corresponding to (Z)-13-methyltetradec-3-ene-carbonyl, (+,Z)-12-methyltetradec-3-ene-carbonyl and (Z)-12-methyltridec-3-ene-carbonyl for aspartocins A (1), B (2), and C (3), respectively. All of the sequence ions were observed by ESI-MSMS of the doubly charged parent ions. However, a number of the sequence ions observed were of low abundance. To fully sequence the lipocyclopeptide antibiotic structures, these low abundance sequence ions together with complementary sequence ions were confirmed by ESI-Nozzle-Skimmer-MSMS of the singly charged linear peptide parent fragment ions H-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11-Dab2(1+)-Asp1-FA. Cyclization of the aspartocins was demonstrated to occur via the beta-amino group of Dab2 from ions of moderate intensity in the ESI-MSMS spectra. As the fatty acid moieties do not undergo internal fragmentations under the experimental ESI mass spectral conditions used, the 14 Da mass difference between the fatty acid moieties of aspartocins A (1) and B (2) versus aspartocin C (3) was used as an internal mass tag to differentiate fragment ions containing fatty acid moieties and those not containing the fatty acid moieties. The most numerous and abundant fragment ions observed in the tandem mass spectra are due to the cleavage of the tertiary nitrogen amide of the pipecolic acid residue-3 (16 fragment ions) and the proline residue-11 (7 fragment ions). In addition, the neutral loss of ethanimine from alpha

  9. Puerto Rico ESI/RSI: M_MAMMAL (Marine Mammal Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  10. Puerto Rico ESI/RSI: SOCECON (Socioeconomic Lines and Points)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) and Reach Sensitivity Index (RSI) data for Puerto Rico. ESI data characterize estuarine...

  11. Golfo de Fonseca ESI; Honduras and Nicaragua: HYDRO (Hydrology)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  12. Golfo de Fonseca ESI; Honduras and Nicaragua: INVERT (Invertebrates)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  13. Fourier Transform Mass Spectrometry and Nuclear Magnetic Resonance Analysis for the Rapid and Accurate Characterization of Hexacosanoylceramide.

    Science.gov (United States)

    Ross, Charles W; Simonsick, William J; Bogusky, Michael J; Celikay, Recep W; Guare, James P; Newton, Randall C

    2016-06-28

    Ceramides are a central unit of all sphingolipids which have been identified as sites of biological recognition on cellular membranes mediating cell growth and differentiation. Several glycosphingolipids have been isolated, displaying immunomodulatory and anti-tumor activities. These molecules have generated considerable interest as potential vaccine adjuvants in humans. Accurate analyses of these and related sphingosine analogues are important for the characterization of structure, biological function, and metabolism. We report the complementary use of direct laser desorption ionization (DLDI), sheath flow electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and high-field nuclear magnetic resonance (NMR) analysis for the rapid, accurate identification of hexacosanoylceramide and starting materials. DLDI does not require stringent sample preparation and yields representative ions. Sheath-flow ESI yields ions of the product and byproducts and was significantly better than monospray ESI due to improved compound solubility. Negative ion sheath flow ESI provided data of starting materials and products all in one acquisition as hexacosanoic acid does not ionize efficiently when ceramides are present. NMR provided characterization of these lipid molecules complementing the results obtained from MS analyses. NMR data was able to differentiate straight chain versus branched chain alkyl groups not easily obtained from mass spectrometry.

  14. Fourier Transform Mass Spectrometry and Nuclear Magnetic Resonance Analysis for the Rapid and Accurate Characterization of Hexacosanoylceramide

    Directory of Open Access Journals (Sweden)

    Charles W. Ross

    2016-06-01

    Full Text Available Ceramides are a central unit of all sphingolipids which have been identified as sites of biological recognition on cellular membranes mediating cell growth and differentiation. Several glycosphingolipids have been isolated, displaying immunomodulatory and anti-tumor activities. These molecules have generated considerable interest as potential vaccine adjuvants in humans. Accurate analyses of these and related sphingosine analogues are important for the characterization of structure, biological function, and metabolism. We report the complementary use of direct laser desorption ionization (DLDI, sheath flow electrospray ionization (ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS and high-field nuclear magnetic resonance (NMR analysis for the rapid, accurate identification of hexacosanoylceramide and starting materials. DLDI does not require stringent sample preparation and yields representative ions. Sheath-flow ESI yields ions of the product and byproducts and was significantly better than monospray ESI due to improved compound solubility. Negative ion sheath flow ESI provided data of starting materials and products all in one acquisition as hexacosanoic acid does not ionize efficiently when ceramides are present. NMR provided characterization of these lipid molecules complementing the results obtained from MS analyses. NMR data was able to differentiate straight chain versus branched chain alkyl groups not easily obtained from mass spectrometry.

  15. Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

    Science.gov (United States)

    Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

    2016-04-01

    Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

  16. Mineralogy And Raw Material Characterization Of Esie Stone ...

    African Journals Online (AJOL)

    Electronprobe mineral data of samples of Esie statues is presented as a possible tool for provenance studies. Most of the samples contain talc, chlorite, cummingtonite and rarely tremolite. Other talc-bearing schists are prevalent in the Esie area. However talc-cummingtonite rocks, similar to the raw materials used for the ...

  17. 2002 Environmental Sustainability Index (ESI)

    Data.gov (United States)

    National Aeronautics and Space Administration — The 2002 Environmental Sustainability Index (ESI) measures overall progress toward environmental sustainability for 142 countries based on environmental systems,...

  18. Developmental validation of the PowerPlex(®) ESI 16/17 Fast and PowerPlex(®) ESX 16/17 Fast Systems.

    Science.gov (United States)

    McLaren, Robert S; Bourdeau-Heller, Jeanne; Patel, Jaynish; Thompson, Jonelle M; Pagram, Jenny; Loake, Thomas; Beesley, David; Pirttimaa, Markus; Hill, Carolyn R; Duewer, David L; Kline, Margaret C; Butler, John M; Storts, Douglas R

    2014-11-01

    The PowerPlex(®) ESI 16 Fast, ESI 17 Fast, ESX 16 Fast, and ESX 17 Fast Systems represent faster cycling versions (50min or less) of the PowerPlex(®) ESI and ESX Systems released by Promega in 2009 to accommodate the ENFSI and EDNAP groups' call for new STR multiplexes for Europe. In addition to amplification of purified DNA samples, these new faster cycling systems allow for direct amplification from single-source blood and buccal samples deposited on FTA(®) and nonFTA paper as well as from SwabSolution™ extracts of buccal swabs without the need for purification and quantitation. There are no changes to the autosomal primer pair sequences in the PowerPlex(®) ESI Fast and ESX Fast Systems compared to the original multiplexes, and full concordance at all autosomal loci and amelogenin was observed with data generated previously with the original PowerPlex(®) ESI and ESX Systems. This paper describes the developmental validation study performed on these new fast systems following guidelines issued by the Scientific Working Group on DNA Analysis Methods (SWGDAM) and those of the DNA Advisory Board (DAB). Validation data demonstrate that these systems are sensitive for detecting low levels of DNA while also being capable of generating robust profiles from the high amount of input DNA present in direct-amplification samples. These systems are also tolerant to both high concentrations of PCR inhibitors as well as to slight variations in the final concentration of master mix and primer pair present in the amplification reaction that might be encountered due to pipetting error. The results of this validation study demonstrate that these systems may be used on multiple thermal cyclers and capillary electrophoresis platforms. Copyright © 2014 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

  19. Fragmentation analysis of water-soluble atmospheric organic matter using ultrahigh-resolution FT-ICR mass spectrometry.

    Science.gov (United States)

    Leclair, Jeffrey P; Collett, Jeffrey L; Mazzoleni, Lynn R

    2012-04-17

    Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

  20. 2005 Environmental Sustainability Index (ESI)

    Data.gov (United States)

    National Aeronautics and Space Administration — The 2005 Environmental Sustainability Index (ESI) is a measure of overall progress towards environmental sustainability, developed for 146 countries. The index...

  1. Relative quantification of enantiomers of chiral amines by high-throughput LC–ESI-MS/MS using isotopic variants of light and heavy L-pyroglutamic acids as the derivatization reagents

    International Nuclear Information System (INIS)

    Mochizuki, Toshiki; Taniguchi, Sayuri; Tsutsui, Haruhito; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo’oka, Toshimasa

    2013-01-01

    Highlights: ► Development of chiral labeling reagent for a pair of amine enantiomers. ► High-throughput analysis of diastereomers by UPLC–ESI-MS/MS. ► Highly efficient separation and detection of the enantiomers. ► Differential analysis of enantiomer ratio in different sample groups using light and heavy labeling reagents. -- Abstract: L-Pyroglutamic acid (L-PGA) was evaluated as a chiral labeling reagent for the enantioseparation of chiral amines in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. Several amines and amino acid methyl esters were used as typical representatives of the chiral amines. Both enantiomers of the chiral amines were easily labeled with L-PGAs at room temperature for 60 min in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxy-1H-benzotriazole as the activation reagents. The resulting diastereomers were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs = 1.6–6.8). A highly sensitive detection at a low-fmol level (1–4 fmol) was also obtained from the multiple reaction monitoring (MRM) chromatograms. Therefore, a high-throughput determination was achieved by the present UPLC–ESI-MS/MS method. An isotope labeling strategy using light and heavy L-PGAs for the differential analysis of chiral amines in different sample groups was also proposed in this paper. As a model study, the differential analysis of the R and S ratio of 1-phenylethylamine (PEA) was performed according to the proposed procedure using light and heavy reagents, i.e., L-PGA and L-PGA-d 5 . The R/S ratio of PEA, spiked at the different concentrations in rat plasma, was almost similar to the theoretical values. Consequently, the proposed strategy using light and heavy chiral labeling reagents seems to be applicable for the differential analysis of chiral amine enantiomers in different sample groups, such as healthy persons and

  2. Quantitation of iothalamate in urine and plasma using liquid chromatography electrospray tandem mass spectrometry (HPLC-ESI-MS/MS).

    Science.gov (United States)

    Molinaro, Ross J; Ritchie, James C

    2010-01-01

    The following chapter describes a method to measure iothalamate in plasma and urine samples using high performance liquid chromatography combined with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Methanol and water are spiked with the internal standard (IS) iohexol. Iothalamate is isolated from plasma after IS spiked methanol extraction and from urine by IS spiked water addition and quick-spin filtration. The plasma extractions are dried under a stream of nitrogen. The residue is reconstituted in ammonium acetate-formic acid-water. The reconstituted plasma and filtered urine are injected into the HPLC-ESI-MS/MS. Iothalamate and iohexol show similar retention times in plasma and urine. Quantification of iothalamate in the samples is made by multiple reaction monitoring using the hydrogen adduct mass transitions, from a five-point calibration curve.

  3. Multi-Segment Direct Inject nano-ESI-LTQ-FT-ICR-MS/MS For Protein Identification

    Directory of Open Access Journals (Sweden)

    Neal Rachel E

    2011-07-01

    Full Text Available Abstract Reversed phase high performance liquid chromatography (HPLC interfaced to electrospray tandem mass spectrometry (MS/MS is commonly used for the identification of peptides from proteolytically cleaved proteins embedded in a polyacrylamide gel matrix as well as for metabolomics screening. HPLC separations are time consuming (30-60 min average, costly (columns and mobile phase reagents, and carry the risk of column carry over between samples. The use of a chip-based nano-ESI platform (Advion NanoMate based on replaceable nano-tips for sample introduction eliminates sample cross-contamination, provides unchanging sample matrix, and enhances spray stability with attendant increases in reproducibility. Recent papers have established direct infusion nano-ESI-MS/MS utilizing the NanoMate for protein identification of gel spots based on full range MS scans with data dependent MS/MS. In a full range scan, discontinuous ion suppression due to sample matrix can impair identification of putative mass features of interest in both the proteomic and metabolomic workflows. In the current study, an extension of an established direct inject nano-ESI-MS/MS method is described that utilizes the mass filtering capability of an ion-trap for ion packet separation into four narrow mass ranges (50 amu overlap with segment specific dynamic data dependent peak inclusion for MS/MS fragmentation (total acquisition time of 3 minutes. Comparison of this method with a more traditional nanoLC-MS/MS based protocol utilizing solvent/sample stream splitting to achieve nanoflow demonstrated comparable results for protein identification from polyacrylamide gel matrices. The advantages of this method include full automation, lack of cross-contamination, low cost, and high throughput.

  4. The Portuguese version of the Epilepsy Surgery Inventory (ESI-55): cross-cultural adaptation and evaluation of psychometric properties.

    Science.gov (United States)

    Alonso, Neide Barreira; Ciconelli, Rozana Mesquita; da Silva, Tatiana Indelicato; Westphal-Guitti, Ana Carolina; Azevedo, Auro Mauro; da Silva Noffs, Maria Helena; Caboclo, Luís Otávio Sales Ferreira; Sakamoto, Américo Ceiki; Targas Yacubian, Elza Márcia

    2006-08-01

    The purpose of this study was to develop a Portuguese version of the Epilepsy Surgery Inventory (ESI-55) and to assess its psychometric properties. Sixty patients with temporal lobe epilepsy related to unilateral mesial temporal sclerosis who underwent presurgical evaluation at the Universidade Federal de São Paulo (UNIFESP) formed the sample for this study. The psychometric properties of the ESI-55 included: reliability, validity, and responsiveness. Internal consistency was high in all domains (Cronbach's alpha ranging from 0.76 for Social Function to 0.88 for Physical Function) except Overall Quality of Life (alpha=0.45). Test-retest reliability after 1 week was good, with the intraclass correlation coefficient ranging from 0.79 (Energy/Fatigue) to 0.92 (Role Limitations due to Emotional Problems). Interrater reliability ranged from 0.84 (Cognitive Function) to 0.94 (Role Limitations due to Physical Problems). For construct validity, we verified a high correlation between the ESI-55 and Health Assessment Questionnaire-8 for the Physical Function domain (Pearson linear correlation=-0.84), and a moderate correlation for the Pain domain (P=-0.58), but for the other subscales no correlation was detected. Beck Depression Inventory and ESI-55 domains were highly statistically correlated (ANOVA: P0.05). With respect to demographic characteristics, a statistically significant correlation was observed for the variable educational level (Student t, PESI-55 scores. There was a high correlation between seizure frequency and ESI-55 domains for clinical variables (ANOVA, Pgroup in three domains--Health Perception (1.24), Emotional Well-Being (1.32), and Energy/Fatigue (1.48)-as reflected by the standard response mean and the effect size of the sample. Our results support the psychometric properties of the Portuguese version of the ESI-55 as a measure of health-related quality of life.

  5. High-throughput and rapid quantification of lipids by nanoflow UPLC-ESI-MS/MS: application to the hepatic lipids of rabbits with nonalcoholic fatty liver disease.

    Science.gov (United States)

    Byeon, Seul Kee; Lee, Jong Cheol; Chung, Bong Chul; Seo, Hong Seog; Moon, Myeong Hee

    2016-07-01

    A rapid and high-throughput quantification method (approximately 300 lipids within 20 min) was established using nanoflow ultrahigh-pressure liquid chromatography-tandem mass spectrometry (nUPLC-ESI-MS/MS) with selective reaction monitoring (SRM) and applied to the quantitative profiling of the hepatic lipids of rabbits with different metabolic conditions that stimulate the development of nonalcoholic fatty liver disease (NAFLD). Among the metabolic conditions of rabbits in this study [inflammation (I), high-cholesterol diet (HC), and high-cholesterol diet combined with inflammation (HCI)], significant perturbation in hepatic lipidome (>3-fold and p groups, while no single lipid showed a significant change in group I. In addition, this study revealed a dramatic increase (>2-fold) in relatively high-abundant monohexosylceramides (MHCs), sphingomyelins (SMs), and triacylglycerols (TGs) in both the HC and HCI groups, especially in MHCs as all 11 MHCs increased by larger than 3- to 12-fold. As the levels of the relatively high-abundant lipids in the above classes increased, the total lipidome level of each class increased significantly by approximately 2-fold to 5-fold. Other classes of lipids also generally increased, which was likely induced by the increase in mitogenic and nonapoptotic MHCs and SMs, as they promote cell proliferation. On the other hand, a slight decrease in the level of apoptotic ceramides (Cers) was observed, which agreed with the general increase in total lipid level. As distinct changes in hepatic lipidome were observed from HC groups, this suggests that HC or HCI is highly associated with NAFLD but not inflammation alone itself. Graphical Abstract Schematic of lipidomic analysis from hepatic tissue using nanoflow LC-ESI-MS/MS and nUPLC-ESI-MS/MS.

  6. Hyphenation of capillary high-performance ion-exchange chromatography with mass spectrometry using sheath-flow electrospray ionization.

    Science.gov (United States)

    Kochmann, Sven; Matysik, Frank-Michael

    2014-12-15

    Mass spectrometry (MS) is an attractive method for extending capillary-size ion chromatography (cHPIC) to create a valuable technique for speciation analysis. For hyphenation, the aqueous effluent of cHPIC has to be transformed into a volatile mixture for MS while preserving analytical concentrations as well as peak shapes during transfer from cHPIC to MS. Finally, the approach should technically be flexible and easy-to-use. A combination of cHPIC and sheath-flow electrospray ionization (ESI)-MS offers to solve all these challenges. cHPIC/sheath-flow-ESI-TOFMS was used in this study for the speciation analysis of various arsenic model compounds. These model compounds were analyzed with different hyphenation setups and configurations of cHPIC/MS and their respective assets and drawbacks were examined and discussed. The parameters (flow rate and composition of sheath liquid) of sheath-flow ESI and their influence on the performance of the spray and the sensitivity of the detector were investigated and compared with those of sheathless ESI. Using an injection valve to couple cHPIC and MS was found to be the best method for hyphenation, since it constitutes a flexible and dead-volume-free approach. The investigation of sheath-flow ESI revealed that the flow rate of the sheath liquid has to resemble the flow rate of the IC effluent to ensure a stable spray and that a composition of 2-propanol/water/ammonia at 50:50:0.2 (v/v/v) suits most applications without unilaterally promoting the sensitivity for either organic or inorganic compounds. The optimized setup and conditions were successfully applied to the analysis of a mixture of important arsenic species and used to determine limits of detection of organic and inorganic arsenic species (3.7 µg L(-1) elemental arsenic). A method for cHPIC/sheath-flow-ESI-MS was developed. The method was shown to be a valuable tool for speciation and trace analysis. It features no dead volume, fast transfer from IC to MS, only minimal

  7. Prince William Sound, Alaska ESI: M_MAMMAL (Marine Mammal Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  8. U.S. Virgin Islands and British Virgin Islands ESI: INDEX

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  9. U.S. Virgin Islands and British Virgin Islands ESI: HABITATS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  10. Golfo de Fonseca ESI; Honduras and Nicaragua: MGT (Management Areas)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  11. U.S. Virgin Islands and British Virgin Islands ESI: BIRDS

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  12. Exploring Biosignatures Associated with Thenardite by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (GALDI-FTICR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    C. Doc Richardson; Nancy W. Hinman; Timothy R. McJunkin; J. Michelle Kotler; Jill R. Scott

    2008-10-01

    Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) has been employed to determine how effectively bio/organic molecules associated with the mineral thenardite (Na2SO4) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C2H4NO-2 at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition ofC18H39O7Na-. Anatural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination were estimated to be 3 parts per trillion or~7 zeptomoles (10-21) per laser spot. Attempts to improve the signal-to-noise ratio by co-adding FTICR-MS data predetermined to contain the biosignatures of interest revealed problems due to a lack of phase coherence between data sets.

  13. Structural Characterization of Core Region in Erwinia amylovora Lipopolysaccharide

    Directory of Open Access Journals (Sweden)

    Angela Casillo

    2017-03-01

    Full Text Available Erwinia amylovora (E. amylovora is the first bacterial plant pathogen described and demonstrated to cause fire blight, a devastating plant disease affecting a wide range of species including a wide variety of Rosaceae. In this study, we reported the lipopolysaccharide (LPS core structure from E. amylovora strain CFBP1430, the first one for an E. amylovora highly pathogenic strain. The chemical characterization was performed on the mutants waaL (lacking only the O-antigen LPS with a complete LPS-core, wabH and wabG (outer-LPS core mutants. The LPSs were isolated from dry cells and analyzed by means of chemical and spectroscopic methods. In particular, they were subjected to a mild acid hydrolysis and/or a hydrazinolysis and investigated in detail by one and two dimensional Nuclear Magnetic Resonance (NMR spectroscopy and ElectroSpray Ionization Fourier Transform-Ion Cyclotron Resonance (ESI FT-ICR mass spectrometry.

  14. An analytical approach based on ESI-MS, LC-MS and PCA for the quali-quantitative analysis of cycloartane derivatives in Astragalus spp.

    Science.gov (United States)

    Napolitano, Assunta; Akay, Seref; Mari, Angela; Bedir, Erdal; Pizza, Cosimo; Piacente, Sonia

    2013-11-01

    Astragalus species are widely used as health foods and dietary supplements, as well as drugs in traditional medicine. To rapidly evaluate metabolite similarities and differences among the EtOH extracts of the roots of eight commercial Astragalus spp., an approach based on direct analyses by ESI-MS followed by PCA of ESI-MS data, was carried out. Successively, quali-quantitative analyses of cycloartane derivatives in the eight Astragalus spp. by LC-ESI-MS(n) and PCA of LC-ESI-MS data were performed. This approach allowed to promptly highlighting metabolite similarities and differences among the various Astragalus spp. PCA results from LC-ESI-MS data of Astragalus samples were in reasonable agreement with both PCA results of ESI-MS data and quantitative results. This study affords an analytical method for the quali-quantitative determination of cycloartane derivatives in herbal preparations used as health and food supplements. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Quantitative Determination of Bioactive Constituents in Noni Juice by High-performance Liquid Chromatography with Electrospray Ionization Triple Quadrupole Mass Spectrometry.

    Science.gov (United States)

    Yan, Yongqiu; Lu, Yu; Jiang, Shiping; Jiang, Yu; Tong, Yingpeng; Zuo, Limin; Yang, Jun; Gong, Feng; Zhang, Ling; Wang, Ping

    2018-01-01

    Noni juice has been extensively used as folk medicine for the treatment of arthritis, infections, analgesic, colds, cancers, and diabetes by Polynesians for many years. Due to the lack of standard scientific evaluation methods, various kinds of commercial Noni juice with different quality and price were available on the market. To establish a sensitive, reliable, and accurate high-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometry (HPLC-ESI-MS/MS) method for separation, identification, and simultaneous quantitative analysis of bioactive constituents in Noni juice. The analytes and eight batches of commercially available samples from different origins were separated and analyzed by the HPLC-ESI-MS/MS method on an Agilent ZORBAX SB-C 18 (150 mm × 4.6 mm i.d., 5 μm) column using a gradient elution of acetonitrile-methanol-0.05% glacial acetic acid in water (v/v) at a constant flow rate of 0.5 mL/min. Seven components were identification and all of the assay parameters were within the required limits. Components were within the correlation coefficient values ( R 2 ≥ 0.9993) at the concentration ranges tested. The precision of the assay method was high-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometryThe presented method was successfully applied to the quality control of eight batches of commercially available samples of Noni juiceThis method is simple, sensitive, reliable, accurate, and efficient method with strong specificity, good precision, and high recovery rate and provides a reliable basis for quality control of Noni juice. Abbreviations used: HPLC-ESI-MS/MS: High-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometry, LOD: Limit of detection, LOQ: Limit of quantitation, S/N: Signal-to-noise ratio, RSD: Relative standard deviations, DP: Declustering potential, CE: Collision energy, MRM: Multiple reaction monitoring, RT

  16. Potential origin and formation for molecular components of humic acids in soils

    Science.gov (United States)

    Hatcher, Patrick; DiDonato, Nicole; Waggoner, Derek

    2016-04-01

    Humification is defined as the process by which plant and microbial debris are transformed in to humic substances. Proposed pathways for the formation of humic substances, include the lignin and lignin decomposition theories, the lignin-polyphenol theory as well as the melanoidin pathway. It is generally accepted that a combination of several of these pathways with some modifications may be responsible for producing humic substances. The current study examines humic acids from numerous soil samples to demonstrate their molecular composition. In addition we provide an explanation for the formation of these molecules that introduces a new perspective of the humification process. Our work utilizes advanced analytical techniques such as ESI-FTICR-MS and solid state NMR to more completely characterize humic acids at the molecular level. Methods Humic acids were extracted from soils using 0.5 M NaOH followed by treatment with a Dowex™ ion-exchange resin to remove sodium ions. Solid State 13C NMR spectra were obtained on a Bruker 400 MHz Avance II spectrometer equipped with a 4 mm solid state MAS probe. ESI-FTICR-MS analysis was conducted in the negative ion mode on a Bruker Daltonics 12 Tesla Apex Qe FTICR-MS instrument equipped with an Apollo II ESI source. Results: Soil humic acids from numerous soils were investigated in this study. The molecular formulas calculated from ultrahigh resolution mass spectra of well humified soils fall clearly into two predominant regions consisting of condensed aromatic molecules as well as high H/C, low O/C carboxyl-containing aliphatic molecules (CCAM). In contrast, the spectral data for humic acids from a poorly humified spodosol soil show a less dramatic separation of these regions, with relatively more molecular formula plotting in the lignin-like region and relatively fewer condensed aromatic molecules. From the mass spectral observations made for the humic acids, we can readily discern a relationship based on degree of

  17. The comparison of naturally weathered oil and artificially photo-degraded oil at the molecular level by a combination of SARA fractionation and FT-ICR MS

    International Nuclear Information System (INIS)

    Islam, Ananna; Cho, Yunju; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

    2013-01-01

    Highlights: • Weathered oils from the Hebei Spirit oil spill and photo degraded oils are compared. • We investigate changes of polar species at the molecular level by 15T FT-ICR MS. • Significant reduction of sulfur class compounds in saturates fraction is observed. • The relative abundance of protonated compounds (presumably basic nitrogen compounds) increase after degradation. • Changes of polar compounds occurred by natural and photo degradation are similar. -- Abstract: Two sets of oil samples, one obtained from different weathering stages of the M/V Hebei Spirit oil spill site and the other prepared by an in vitro photo-degradation experiment, were analyzed and compared at the molecular level by atmospheric pressure photo-ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). For a more detailed comparison at the molecular level, the oil samples were separated into saturate, aromatic, resin, and asphaltene (SARA) fractions before MS analysis. Gravimetric analysis of the SARA fractions revealed a decreased weight percentage of the aromatic fraction and an increased resin fraction in both sets of samples. Molecular-level investigations of the SARA fractions showed a significant reduction in the S 1 class in the saturate fraction and increase of S 1 O 1 class compounds with high DBE values in resin fraction. Levels of N 1 and N 1 O 1 class compounds resulting in protonated ions (presumably basic nitrogen compounds) increased after degradation compared to compounds generating molecular ions (presumably non-basic nitrogen compounds). This study revealed changes occurring in heteroatom polar species of crude oils such as sulfur and nitrogen containing compounds that have not been easily detected with conventional GC based techniques

  18. Changes in the expression of N- and O-glycopeptides in patients with colorectal cancer and hepatocellular carcinoma quantified by full-MS scan FT-ICR and multiple reaction monitoring

    Czech Academy of Sciences Publication Activity Database

    Darebná, P.; Novák, Petr; Kučera, R.; Topolčan, O.; Sanda, M.; Goldman, R.; Pompach, Petr

    2017-01-01

    Roč. 153, SI (2017), s. 44-52 ISSN 1874-3919 Grant - others:Ministerstvo pro místní rozvoj(CZ) CZ2.16./3.1.00/24023 Institutional support: RVO:61388971 Keywords : Mass spectrometry * Glycomics * FT-ICR Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 3.914, year: 2016

  19. U.S. Virgin Islands and British Virgin Islands ESI: HYDRO (Hydrology)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  20. Golfo de Fonseca ESI; Honduras and Nicaragua: REPTILES (Reptiles and Amphibians)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  1. Golfo de Fonseca ESI; Honduras and Nicaragua: T_MAMMAL (Terrestrial Mammals)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  2. Golfo de Fonseca ESI; Honduras and Nicaragua: M_MAMMAL (Marine Mammals)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  3. Simultaneous determination of thirteen flavonoids from Xiaobuxin-Tang extract using high-performance liquid chromatography coupled with electrospray ionization mass spectrometry.

    Science.gov (United States)

    Cen, Meifeng; Ruan, Jinxiu; Huang, Lihua; Zhang, Zhenqing; Yu, Nengjiang; Zhang, Youzhi; Cheng, Xuange; Xiong, Xiaohong; Wang, Guixiang; Zang, Linquan; Wang, Sujun

    2015-11-10

    A simple and reliable high performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) analysis method was established to simultaneously determine thirteen flavonoids of Xiaobuxing-Tang in intestine perfusate, namely onpordin, 3'-O-methylorobol, glycitein, patuletin, genistein, luteolin, quercetin, nepitrin, quercimeritrin, daidzin, patulitrin, quercetagitrin and 3-glucosylisorhamnetin. Detection was performed on a quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source operating in negative ionization mode. Negative ion ESI was used to form deprotonated molecules at m/z 315 for onpordin, m/z 299 for 3'-O-methylorobol, m/z 283 for glycitein, m/z 331 for patuletin, m/z 269 for genistein, m/z 285 for luteolin, m/z 301 for quercetin, m/z 477 for nepitrin, m/z 463 for quercimeritrin, m/z 461 for daidzin, m/z 493 for patulitrin, m/z 479 for quercetagitrin, m/z 477 for 3-glucosylisorhamnetin and m/z 609.2 for rutin. The linearity, sensitivity, selectivity, repeatability, accuracy, precision, recovery and matrix effect of the assay were evaluated. The proposed method was successfully applied to simultaneous determination of these thirteen flavonoids, and using this method, the intestinal absorption profiles of thirteen flavonoids were preliminarily predicted. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Quantitative analysis of the major constituents of St John's wort with HPLC-ESI-MS.

    Science.gov (United States)

    Chandrasekera, Dhammitha H; Welham, Kevin J; Ashton, David; Middleton, Richard; Heinrich, Michael

    2005-12-01

    A method was developed to profile the major constituents of St John's wort extracts using high-performance liquid chromatography-electrospray mass spectrometry (HPLC-ESI-MS). The objective was to simultaneously separate, identify and quantify hyperforin, hypericin, pseudohypericin, rutin, hyperoside, isoquercetrin, quercitrin and chlorogenic acid using HPLC-MS. Quantification was performed using an external standardisation method with reference standards. The method consisted of two protocols: one for the analysis of flavonoids and glycosides and the other for the analysis of the more lipophilic hypericins and hyperforin. Both protocols used a reverse phase Luna phenyl hexyl column. The separation of the flavonoids and glycosides was achieved within 35 min and that of the hypericins and hyperforin within 9 min. The linear response range in ESI-MS was established for each compound and all had linear regression coefficient values greater than 0.97. Both protocols proved to be very specific for the constituents analysed. MS analysis showed no other signals within the analyte peaks. The method was robust and applicable to alcoholic tinctures, tablet/capsule extracts in various solvents and herb extracts. The method was applied to evaluate the phytopharmaceutical quality of St John's wort preparations available in the UK in order to test the method and investigate if they contain at least the main constituents and at what concentrations.

  5. HPLC-DAD-ESI/MS Identification of Light Harvesting and Light Screening Pigments in the Lake Sediments at Edmonson Point

    OpenAIRE

    Giovannetti, Rita; Alibabaei, Leila; Zannotti, Marco; Ferraro, Stefano; Petetta, Laura

    2013-01-01

    The composition of sedimentary pigments in the Antarctic lake at Edmonson Point has been investigated and compared with the aim to provide a useful analytical method for pigments separation and identification, providing reference data for future assessment of possible changes in environmental conditions. Reversed phase high performance liquid chromatography (HPLC) with electrospray-mass spectrometry (ESI-MS) detection and diode array detection (DAD) has been used to identify light screeni...

  6. Comprehensive list of metabolites measured by DI-FTICR mass spectrometry in thyme plants with contrasting tolerance to drought

    Directory of Open Access Journals (Sweden)

    Parviz Moradi

    2017-06-01

    Full Text Available This article contains data related to the main research entitled “Metabolomic approach reveals the biochemical mechanisms underlying drought stress tolerance in Thyme” (Moradi et al., 2017 [1]. Two thyme populations with contrasting drought tolerance were subjected to long term water deficit. Leaf samples harvested at the end of stress period and bi-phasic extraction carried out to get polar and non-polar fractions. Extracted samples were analyzed through Direct Infusion FT-ICR mass spectrometry. Date files comprise of four separate tables for all the putatively identified metabolites and their intensities in watered and droughted plants. P-values beside each m/z values indicate significances of difference between peak intensities of stressed and control conditions.

  7. 2000 Pilot Environmental Sustainability Index (ESI)

    Data.gov (United States)

    National Aeronautics and Space Administration — The 2000 Pilot Environmental Sustainability Index (ESI) is an exploratory effort to construct an index that measures the ability of a nation's economy to achieve...

  8. Unambiguous Metabolite Identification in High-Throughput Metabolomics by Hybrid 1H-NMR/ESI-MS1 Approach

    Energy Technology Data Exchange (ETDEWEB)

    2016-10-18

    The invention improves accuracy of metabolite identification by combining direct infusion ESI-MS with one-dimensional 1H-NMR spectroscopy. First, we apply a standard 1H-NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in a metabolomics reference libraries. This generates a list of candidate metabolites. The list contains both false positive and ambiguous identifications. The software tool (the invention) takes the list of candidate metabolites, generated from NMRbased metabolite identification, and then calculates, for each of the candidate metabolites, the monoisotopic mass-tocharge (m/z) ratios for each commonly observed ion, fragment and adduct feature. These are then used to assign m/z ratios in experimental ESI-MS spectra of the same sample. Detection of the signals of a given metabolite in both NMR and MS spectra resolves the ambiguities, and therefore, significantly improves the confidence of the identification.

  9. Western Alaska ESI: LAKES (Lake Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector polygons representing lakes and land masses used in the creation of the Environmental Sensitivity Index (ESI) for Western Alaska. The...

  10. Towards Discovery and Targeted Peptide Biomarker Detection Using nanoESI-TIMS-TOF MS

    Energy Technology Data Exchange (ETDEWEB)

    Garabedian, Alyssa; Benigni, Paolo; Ramirez, Cesar; Baker, Erin M.; Liu, Tao; Smith, Richard D.; Fernandez-Lima, Francisco

    2018-05-01

    Abstract. In the present work, the potential of trapped ion mobility spectrometry coupled to TOF mass spectrometry (TIMS-TOF MS) for discovery and targeted monitoring of peptide biomarkers from human-in-mouse xenograft tumor tissue was evaluated. In particular, a TIMS-MS workflow was developed for the detection and quantification of peptide biomarkers using internal heavy analogs, taking advantage of the high mobility resolution (R = 150–250) prior to mass analysis. Five peptide biomarkers were separated, identified, and quantified using offline nanoESI-TIMSCID- TOF MS; the results were in good agreement with measurements using a traditional LC-ESI-MS/MS proteomics workflow. The TIMS-TOF MS analysis permitted peptide biomarker detection based on accurate mobility, mass measurements, and high sequence coverage for concentrations in the 10–200 nM range, while simultaneously achieving discovery measurements

  11. Lanthanide and actinide inorganic complexes in natural waters. TRLFS and ESI-MS studies

    Energy Technology Data Exchange (ETDEWEB)

    Vercouter, T.; Amekraz, B.; Moulin, C.; Vitorge, P

    2004-07-01

    Aqueous complexes of M(III) f-element ions with the inorganic ligands CO{sub 3}{sup 2-} and SO{sub 4}{sup 2-} have been investigated using the highly-sensitive speciation techniques TRLFS and ESI-MS. The Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) species have been characterized by TRLFS, and the stoichiometry of the limiting complex Eu(CO{sub 3}){sub 3}{sup 3-} have been confirmed by solubility measurements of NaEu(CO{sub 3}){sub 2}(s) at high ionic strength. Temperature effect on Cm(III) carbonate complexes is evidenced by the TRLFS technique. Investigation on sulphate complexation has been done at various ionic strengths by TRLFS on Eu(III) and by ESI-MS on La(III). New thermodynamic data are obtained by both techniques, which are consistent with literature data. (authors)

  12. U.S. Virgin Islands and British Virgin Islands ESI: INVERT (Invertebrate Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  13. U.S. Virgin Islands and British Virgin Islands ESI: INVERT (Invertebrate Lines)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  14. U.S. Virgin Islands and British Virgin Islands ESI: FISH (Fish Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  15. Golfo de Fonseca ESI; Honduras and Nicaragua: SOCECON (Socioeconomic Lines and Points)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Golfo de Fonseca. ESI data characterize estuarine environments and wildlife by their...

  16. Detecting Protein-Glycolipid Interactions Using Glycomicelles and CaR-ESI-MS.

    Science.gov (United States)

    Han, Ling; Kitova, Elena N; Klassen, John S

    2016-11-01

    This study reports on the use of the catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS) assay, combined with glycomicelles, as a method for detecting specific interactions between water-soluble proteins and glycolipids (GLs) in aqueous solution. The B subunit homopentamers of cholera toxin (CTB 5 ) and Shiga toxin type 1 B (Stx1B 5 ) and the gangliosides GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2 served as model systems for this study. The CTB 5 exhibits broad specificity for gangliosides and binds to GM1, GM2, GM3, GD1a, GD1b, and GT1b; Stx1B 5 does not recognize gangliosides. The CaR-ESI-MS assay was used to analyze solutions of CTB 5 or Stx1B 5 and individual gangliosides (GM1, GM2, GM3, GD1a, GD1b, GT1b, and GD2) or mixtures thereof. The high affinity interaction of CTB 5 with GM1 was successfully detected. However, the apparent affinity, as determined from the mass spectra, is significantly lower than that of the corresponding pentasaccharide or when GM1 is presented in model membranes such as nanodiscs. Interactions between CTB 5 and the low affinity gangliosides GD1a, GD1b, and GT1b, as well as GD2, which served as a negative control, were detected; no binding of CTB 5 to GM2 or GM3 was observed. The CaR-ESI-MS results obtained for Stx1B 5 reveal that nonspecific protein-ganglioside binding can occur during the ESI process, although the extent of binding varies between gangliosides. Consequently, interactions detected for CTB 5 with GD1a, GD1b, and GT1b are likely nonspecific in origin. Taken together, these results reveal that the CaR-ESI-MS/glycomicelle approach for detecting protein-GL interactions is prone to false positives and false negatives and must be used with caution. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

  17. DIRECT INFUSION ESI-MS APPLIED IN THE DETECTION OF BYPRODUCTS DUE TO REDUCTIVE DEGRADATION OF ACETAMIPRID BY ZERO-VALENT IRON

    Directory of Open Access Journals (Sweden)

    Jean C. Cruz

    2015-09-01

    Full Text Available This study investigated the reductive degradation of acetamiprid (5 mg L-1 in aqueous medium (at pH 2.0 induced by zero-valent iron (50 mg. The process was monitored using high-performance liquid chromatography (HPLC to determine the degradation rate as a function of reaction time, and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS to search for (and potentially characterize any possible byproducts formed during degradation. The results obtained via HPLC showed that after 60 min, the degradation of the substrate reached nearly 100% in an acidic medium, whereas the mineralization rate (as determined by total organic carbon measurements was as low as 3%. Data obtained by DI-ESI-MS showed that byproducts were formed mainly by insertions of hydrogen atoms into the nitrile, imine, and pyridine ring moieties, in addition to the observation of chlorine substitution by hydrogen replacement (hydrodechlorination reactions.

  18. Analysis of iodinated quorum sensing peptides by LC–UV/ESI ion trap mass spectrometry

    Directory of Open Access Journals (Sweden)

    Yorick Janssens

    2018-02-01

    Full Text Available Five different quorum sensing peptides (QSP were iodinated using different iodination techniques. These iodinated peptides were analyzed using a C18 reversed phase HPLC system, applying a linear gradient of water and acetonitrile containing 0.1% (m/v formic acid as mobile phase. Electrospray ionization (ESI ion trap mass spectrometry was used for the identification of the modified peptides, while semi-quantification was performed using total ion current (TIC spectra. Non-iodinated peptides and mono- and di-iodinated peptides (NIP, MIP and DIP respectively were well separated and eluted in that order. Depending on the used iodination method, iodination yields varied from low (2% to high (57%.

  19. LC/PDA/ESI-MS Profiling and Radical Scavenging Activity of Anthocyanins in Various Berries

    Directory of Open Access Journals (Sweden)

    Jun-ichiro Nakajima

    2004-01-01

    Full Text Available Anthocyanin extracts of two blueberries, Vaccinium myrtillus (bilberry and Vaccinium ashei (rabbiteye blueberry, and of three other berries, Ribes nigrum (black currant, Aronia melanocarpa (chokeberry, and Sambucus nigra (elderberry, were analyzed by high-performance liquid chromatography coupled with photodiode array detection and electrospray ionization - mass spectrometry (LC/PDA/ESI-MS. Both bilberry and rabbiteye blueberry contained 15 identical anthocyanins with different distribution patterns. Black currant, chokeberry, and elderberry contained 6, 4, and 4 kinds of anthocyanins, respectively. The radical scavenging activities of these berry extracts were analyzed by using 2,2-diphenyl-1-picrylhydrazyl (DPPH. All these extracts showed potent antiradical activities.

  20. Structural Characterization of a Thrombin-Aptamer Complex by High Resolution Native Top-Down Mass Spectrometry

    Science.gov (United States)

    Zhang, Jiang; Loo, Rachel R. Ogorzalek; Loo, Joseph A.

    2017-09-01

    Native mass spectrometry (MS) with electrospray ionization (ESI) has evolved as an invaluable tool for the characterization of intact native proteins and non-covalently bound protein complexes. Here we report the structural characterization by high resolution native top-down MS of human thrombin and its complex with the Bock thrombin binding aptamer (TBA), a 15-nucleotide DNA with high specificity and affinity for thrombin. Accurate mass measurements revealed that the predominant form of native human α-thrombin contains a glycosylation mass of 2205 Da, corresponding to a sialylated symmetric biantennary oligosaccharide structure without fucosylation. Native MS showed that thrombin and TBA predominantly form a 1:1 complex under near physiological conditions (pH 6.8, 200 mM NH4OAc), but the binding stoichiometry is influenced by the solution ionic strength. In 20 mM ammonium acetate solution, up to two TBAs were bound to thrombin, whereas increasing the solution ionic strength destabilized the thrombin-TBA complex and 1 M NH4OAc nearly completely dissociated the complex. This observation is consistent with the mediation of thrombin-aptamer binding through electrostatic interactions and it is further consistent with the human thrombin structure that contains two anion binding sites on the surface. Electron capture dissociation (ECD) top-down MS of the thrombin-TBA complex performed with a high resolution 15 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer showed the primary binding site to be at exosite I located near the N-terminal sequence of the heavy chain, consistent with crystallographic data. High resolution native top-down MS is complementary to traditional structural biology methods for structurally characterizing native proteins and protein-DNA complexes. [Figure not available: see fulltext.

  1. LC/ESI-MS method applied to characterization of flavonoids glycosides in B. forficata subsp. pruinosa

    Directory of Open Access Journals (Sweden)

    Lidiane da Silveira Farias

    2014-06-01

    Full Text Available Bauhinia forficata is used in folk medicine for its hypoglycemiant effect. In the south of Brazil, the subspecies pruinosa is found in a region with the characteristic flora, pampa biome. This species has been consumed by the local population as a tea for diabetes treatment. We studied the chemical composition of hydroethanolic extracts using LC/ESI-MS. The leaf extracts were prepared by percolation with 50% (v/v ethanol. The chromatographic analyses were performed using a reverse-phase system, gradient elution with acetonitrile:phosphoric acid 0.05%, and ESI-MS in the positive ion mode. The chemical profile of the flavonoids was suggested to involve four quercetin and kaempferol glycosides.

  2. Quantification of piperazine phosphate in human plasma by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry employing precolumn derivatization with dansyl chloride.

    Science.gov (United States)

    Lin, Hui; Tian, Yuan; Zhang, Zunjian; Wu, Lili; Chen, Yun

    2010-04-01

    This paper describes a novel method that combines dansyl chloride (DNS-CL) derivatization with high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) for the sensitive and selective determination of piperazine phosphate in human plasma. After addition of ondansetron hydrochloride as internal standard (IS), piperazine phosphate was derivatized and then extracted with ethyl acetate. After being evaporated and reconstituted, the sample was analyzed using LC-ESI/MS/MS. Separation was achieved using an Agilent ZORBAX SB-C(18) (150 mm x 2.1 mm I.D., 3.5 microm) column and isocratic elution with 10 mM ammonium acetate solution (pH 3.0)-methanol (50: 50, v/v). Detection was performed on a triple-quadrupole mass spectrometer utilizing electrospray ionization (ESI) interface operating in positive ion and selected reaction monitoring (SRM) mode with the precursor to product ion transitions m/z 320-->171 for DNS-CL-piperazine phosphate and m/z 294-->170 for the IS. The method was fully validated for its selectivity, sensitivity, linearity, precision, accuracy, recovery, matrix effect and stability. The coefficient (r) of piperazine phosphate with a linear range of 0.1-15 microg mL(-1) was 0.9974-0.9995. The limit of detection and lower limit of quantification in human plasma were 0.01 and 0.1 microg mL(-1), respectively. The validated LC-ESI/MS/MS method has been successfully applied to a bioequivalence study of piperazine phosphate trochiscus in Chinese healthy male volunteers. 2010 Elsevier B.V. All rights reserved.

  3. Tandem solid-phase extraction followed by HPLC-ESI/QTOF/MS/MS for rapid screening and structural identification of trace diterpenoids in flowers of Rhododendron molle.

    Science.gov (United States)

    Zou, Hong-Yan; Luo, Jun; Xu, De-Ran; Kong, Ling-Yi

    2014-01-01

    'Naoyanghua', composed of the flowers of Rhododendron molle G. Don, is a traditional Chinese medicine that is widely known for its toxicity. Grayanane-type diterpenoids are the main active ingredients in R. molle, as well as possibly their toxicity: they are, however, difficult to isolate and analyse using common chromatographic methods, due to their small amounts and absence of conjugated groups, such as phenyl and α, β-unsaturated ketone. To establish a highly sensitive, selective and reliable method for the qualitative evaluation of trace diterpenoids in the flowers of R. molle by using tandem solid-phase extraction followed by high-performance liquid chromatography with electrospray ionisation quadrupole-time-of-flight mass spectrometry (HPLC-ESI/QTOF/MS/MS). Tandem solid phase extraction (SPE) was undertaken using a polyamide cartridge and a C18E cartridge in succession to enrich the trace diterpenoids. HPLC-ESI/QTOF/MS/MS was used to determine the fragmentation patterns of diterpenoids and to tentatively characterise their fragmentation pathways. HPLC-ESI/QTOF/MS/MS detected a total of 14 diterpenoids, eight of which were identified by comparison with literature sources and six based on fragmentation analysis. Among the latter six, rhodojaponin VI-3-glucoside was tentatively identified as a new diterpenoid glycoside and rhodojaponin VII, rhodojaponin IV and rhodojaponin I were reported from R. molle for the first time. By qualitative research of diterpenoids in this plant by HPLC-ESI/QTOF/MS/MS, a reliable methodology for the analysis of these active constituents of R. molle was established for the first time. Copyright © 2014 John Wiley & Sons, Ltd.

  4. ESI mass spectrometry applied to enantiodiscrimination of chiral systems

    International Nuclear Information System (INIS)

    Lagana, A.; Paladini, A.; Catone, D.; Giardini, A.; Filippi, A.; D'Ettole, A.; Speranze, M.

    2002-01-01

    Experiments with electrospray ionization coupled with mass spectrometric detection (ESI-MS) together with collisional induced dissociation (CID) were performed in order to study the affinity of chiral alfa-aminophosphonic acids towards first-group metals (Na, Li, K) in gaseous phase and how this can be affected by the ligands configuration. The results are discussed in the light of structure calculation performed by using an empirical force field. The CID fragmentation spectra of diastereomeric clusters containing (1-amino-2-methylpropyl)phosphonic acid enantiomers (P R , P S ), (S)-(+)-(1-aminoethyl)phosphonic acid (E S ) and a sodium ion ( [NaP R (E S ) 2 ] + and [NaP S (E S ) 2 ] + ) is given. (nevyjel)

  5. Comparison of High Performance Liquid Chromatography with Fluorescence Detector and with Tandem Mass Spectrometry methods for detection and quantification of Ochratoxin A in green and roasted coffee beans

    Directory of Open Access Journals (Sweden)

    Raquel Duarte da Costa Cunha Bandeira

    2013-12-01

    Full Text Available Two analytical methods for the determination and confirmation of ochratoxin A (OTA in green and roasted coffee samples were compared. Sample extraction and clean-up were based on liquid-liquid phase extraction and immunoaffinity column. The detection of OTA was carried out with the high performance liquid chromatography (HPLC combined either with fluorescence detection (FLD, or positive electrospray ionization (ESI+ coupled with tandem mass spectrometry (MS-MS. The results obtained with the LC-ESI-MS/MS were specific and more sensitive, with the advantages in terms of unambiguous analyte identification, when compared with the HPLC-FLD.

  6. U.S. Virgin Islands and British Virgin Islands ESI: T_MAMMAL (Terrestrial Mammals)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  7. U.S. Virgin Islands and British Virgin Islands ESI: REPTILES (Reptiles and Amphibians)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  8. Two-Step Separation of Nostotrebin 6 from Cultivated Soil Cyanobacterium (Nostoc sp. by High Performance Countercurrent Chromatography

    Directory of Open Access Journals (Sweden)

    José Cheel

    2014-06-01

    Full Text Available High performance countercurrent chromatography (HPCCC was successfully applied for the separation of nostotrebin 6 from cultivated soil cyanobacteria in a two-step operation. A two-phase solvent system composed of n-hexane–ethyl acetate–methanol–water (4:5:4:5, v/v/v/v was employed for the HPCCC separation. In the first-step operation, its neutral upper phase was used as stationary phase and its basic lower phase (1% NH3 in lower phase was employed as mobile phase at a flow rate of 1 mL/min. In the second operation step, its neutral upper phase was used as stationary phase, whereas both its neutral lower phase and basic lower phase were employed as mobile phase with a linear gradient elution at a flow rate of 0.8 mL/min. The revolution speed and temperature of the separation column were 1,000 rpm and 30 °C, respectively. Using HPCCC followed by clean-up on Sephadex LH-20 gel, 4 mg of nostotrebin 6 with a purity of 99% as determined by HPLC/DAD-ESI-HRMS was obtained from 100 mg of crude extract. The chemical identity of the isolated compound was confirmed by comparing its spectroscopic data (UV, ESI-HRMS, ESI-HRMS2 with those of an authentic standard and data available in the literature.

  9. HPLC-DAD-ESI/MS identification of light harvesting and light screening pigments in the lake sediments at Edmonson Point.

    Science.gov (United States)

    Giovannetti, Rita; Alibabaei, Leila; Zannotti, Marco; Ferraro, Stefano; Petetta, Laura

    2013-01-01

    The composition of sedimentary pigments in the Antarctic lake at Edmonson Point has been investigated and compared with the aim to provide a useful analytical method for pigments separation and identification, providing reference data for future assessment of possible changes in environmental conditions. Reversed phase high performance liquid chromatography (HPLC) with electrospray-mass spectrometry (ESI-MS) detection and diode array detection (DAD) has been used to identify light screening and light harvesting pigments. The results are discussed in terms of local environmental conditions.

  10. Towards Discovery and Targeted Peptide Biomarker Detection Using nanoESI-TIMS-TOF MS

    Science.gov (United States)

    Garabedian, Alyssa; Benigni, Paolo; Ramirez, Cesar E.; Baker, Erin S.; Liu, Tao; Smith, Richard D.; Fernandez-Lima, Francisco

    2017-09-01

    In the present work, the potential of trapped ion mobility spectrometry coupled to TOF mass spectrometry (TIMS-TOF MS) for discovery and targeted monitoring of peptide biomarkers from human-in-mouse xenograft tumor tissue was evaluated. In particular, a TIMS-MS workflow was developed for the detection and quantification of peptide biomarkers using internal heavy analogs, taking advantage of the high mobility resolution (R = 150-250) prior to mass analysis. Five peptide biomarkers were separated, identified, and quantified using offline nanoESI-TIMS-CID-TOF MS; the results were in good agreement with measurements using a traditional LC-ESI-MS/MS proteomics workflow. The TIMS-TOF MS analysis permitted peptide biomarker detection based on accurate mobility, mass measurements, and high sequence coverage for concentrations in the 10-200 nM range, while simultaneously achieving discovery measurements of not initially targeted peptides as markers from the same proteins and, eventually, other proteins. [Figure not available: see fulltext.

  11. Virginia ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for Virginia. The...

  12. Phytochemical Analysis of Pfaffia glomerata Inflorescences by LC-ESI-MS/MS

    Directory of Open Access Journals (Sweden)

    Daniele F. Felipe

    2014-09-01

    Full Text Available Pfaffia glomerata contains high levels of β-ecdysone, which has shown a range of beneficial pharmacological effects. The present study demonstrated that inflorescences of P. glomerata contain other important bioactive compounds in addition to β-ecdysone. The identification of compounds from inflorescences using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS was performed for the first time. The eight compounds identified were β-ecdysone, flavonoid glycosides such as quercetin-3-O-glucoside, kaempferol-3-O-glucoside and kaempferol-3-O-(6-p-coumaroyl-glucoside, oleanane-type triterpenoid saponins such as ginsenoside Ro and chikusetsusaponin IV, in addition to oleanonic acid and gluconic acid. This study provided information on the phytochemicals contained in P. glomerata inflorescences revealing the potential application of this plant part as raw material for the phytotherapeutic and cosmetic industries.

  13. LC coupled to ESI, MALDI and ICP MS - A multiple hyphenation for metalloproteomic studies.

    Science.gov (United States)

    Coufalíková, Kateřina; Benešová, Iva; Vaculovič, Tomáš; Kanický, Viktor; Preisler, Jan

    2017-05-22

    A new multiple detection arrangement for liquid chromatography (LC) that supplements conventional electrospray ionization (ESI) mass spectrometry (MS) detection with two complementary detection techniques, matrix-assisted laser desorption/ionization (MALDI) MS and substrate-assisted laser desorption inductively coupled plasma (SALD ICP) MS has been developed. The combination of the molecular and elemental detectors in a single separation run is accomplished by utilizing a commercial MALDI target made of conductive plastic. The proposed platform provides a number of benefits in today's metalloproteomic applications, which are demonstrated by analysis of a metallothionein mixture. To maintain metallothionein complexes, separation is carried out at a neutral pH. The effluent is split; a major portion is directed to ESI MS while the remaining 1.8% fraction is deposited onto a plastic MALDI target. Dried droplets are overlaid with MALDI matrix and analysed consecutively by MALDI MS and SALD ICP MS. In the ESI MS spectra, the MT isoform complexes with metals and their stoichiometry are determined; the apoforms are revealed in the MALDI MS spectra. Quantitative determination of metallothionein isoforms is performed via determination of metals in the complexes of the individual protein isoforms using SALD ICP MS. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Western Alaska ESI: BIOINDEX (Biological Index Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector polygons representing the boundaries of the 1:250,000 map boundaries used in the creation of the Environmental Sensitivity Index (ESI)...

  15. Identification and determination of the major constituents in traditional Chinese medicine Longdan Xiegan Pill by HPLC-DAD-ESI-MS

    Directory of Open Access Journals (Sweden)

    Hui Liu

    2011-02-01

    Full Text Available A novel and sensitive HPLC-UV method has been developed for the simultaneous determination of twelve major compounds in Longdan Xiegan Pill. The chemical profile of the twelve compounds, including geniposidic acid (1, geniposide(2, gentiopicroside(3, liquiritin(4, crocin(5, baicalin(6, wogonoside(7, baicalein(8, glycyrrhizic acid (9, wogonin (10, oroxylin A (11 and aristolochic acid A (12, was acquired using high-performance liquid chromatography-diode array detector coupled with an electrospray tandem mass spectrometer (HPLC-DAD-ESI-MS. The analysis was performed on a Dikma Platisil ODS C18 column (250 mm × 4. 6 mm, 5 μm with a gradient solvent system of acetonitrile-0. 1% aqueous formic acid. The validation was carried out and the linearities (r > 0. 9996, repeatability (RSD<1. 8%, intra- and inter-day precision (RSD< 1. 3%, and recoveries (ranging from 96. 6% to 103. 4% were acceptable. The limits of detection (LOD of these compounds ranged from 0.29 to 4. 17 ng. Aristolochic acid A, which is the toxic ingredient, was not detected in all the batches of Longdan Xiegan Pill. Furthermore, hierarchical cluster analysis was used to evaluate the variation of the herbal prescription. The proposed method is simple, effective and suitable for the quality control of this traditional Chinese medicine (TCM. Keywords: Longdan Xiegan Pill, high-performance liquid chromatography-diode array detector coupled with an electrospray tandem mass spectrometer (HPLC-DAD-ESI-MS, qualitative evaluation, aristolochic acid A, hierarchical cluster analysis

  16. Practical approaches to the ESI-MS analysis of catalytic reactions.

    Science.gov (United States)

    Yunker, Lars P E; Stoddard, Rhonda L; McIndoe, J Scott

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) is a soft ionization technique commonly coupled with liquid or gas chromatography for the identification of compounds in a one-time view of a mixture (for example, the resulting mixture generated by a synthesis). Over the past decade, Scott McIndoe and his research group at the University of Victoria have developed various methodologies to enhance the ability of ESI-MS to continuously monitor catalytic reactions as they proceed. The power, sensitivity and large dynamic range of ESI-MS have allowed for the refinement of several homogenous catalytic mechanisms and could potentially be applied to a wide range of reactions (catalytic or otherwise) for the determination of their mechanistic pathways. In this special feature article, some of the key challenges encountered and the adaptations employed to counter them are briefly reviewed. Copyright © 2014 John Wiley & Sons, Ltd.

  17. HPLC-DAD-ESI/MS Identification of Light Harvesting and Light Screening Pigments in the Lake Sediments at Edmonson Point

    Directory of Open Access Journals (Sweden)

    Rita Giovannetti

    2013-01-01

    Full Text Available The composition of sedimentary pigments in the Antarctic lake at Edmonson Point has been investigated and compared with the aim to provide a useful analytical method for pigments separation and identification, providing reference data for future assessment of possible changes in environmental conditions. Reversed phase high performance liquid chromatography (HPLC with electrospray-mass spectrometry (ESI-MS detection and diode array detection (DAD has been used to identify light screening and light harvesting pigments. The results are discussed in terms of local environmental conditions.

  18. Flavonoids from the flowers of Impatiens glandulifera Royle isolated by high performance countercurrent chromatography.

    Science.gov (United States)

    Vieira, Mariana N; Winterhalter, Peter; Jerz, Gerold

    2016-01-01

    Impatiens glandulifera Royle (Balsaminaceae) is an annual herb from the Himalaya region, currently widespread along European river systems and one of the most important neophyte invading plants in Germany. Exploring the effects of allelopathic plant chemicals is important for the understanding of its ecological impacts in the process of suppression of indigenous plant species. To investigate the chemical composition of Impatiens glandulifera flowers (IGFs) using high performance countercurrent chromatography (HPCCC). The flowers of Impatiens glandulifera were manually separated and extracted with ethanol. LC-ESI-MS/MS was used to characterise the crude extract of IGF. The various flavonoids detected were isolated by HPCCC using of methyl tert-butyl ether-acetonitrile-water (2:2:3, v/v/v). The combination of the data provided by preparative ESI-MS/MS metabolite profiling, LC-ESI-MS/MS, UV-vis and 1D/2D-NMR spectroscopic analysis was used to elucidate the structures of the isolated compounds. HPCCC runs led to the direct isolation of pure dihydromyricetin (ampelopsin), eriodictyol-7-O-glucoside, kaempferol-3-O-glucoside (astragalin) and kaempferol-3-O-6"-malonyl-glucoside, as well as the pre-purification of kaempferol-3-O-rhamno-rhamnosyldiglucoside, quercetin-3-O-galactoside (hyperoside), quercetin and kaempferol in a single step. This is the first report on the flavonoid composition of the species Impatiens glandulifera. The developed protocol was successfully used to isolate the main flavonoids from the crude extract of IGFs. This combined HPCCC and HPLC procedure could be applied to the fast fractionation and recovery of flavonoid derivatives of other plant extracts. Copyright © 2016 John Wiley & Sons, Ltd.

  19. U.S. Virgin Islands and British Virgin Islands ESI: M_MAMMAL (Marine Mammal Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  20. U.S. Virgin Islands and British Virgin Islands ESI: SOCECON (Socioeconomic Lines and Points)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  1. Simultaneous Determination of Seven Phenolic Acids in Rat Plasma Using UHPLC-ESI-MS/MS after Oral Administration of Echinacea purpurea Extract

    Directory of Open Access Journals (Sweden)

    Yan Du

    2017-09-01

    Full Text Available A rapid and sensitive Ultra High Performance Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (UHPLC-ESI-MS/MS method was developed and validated to simultaneously determine the concentration of seven phenolic acids (syringic acid, ferulic acid, caffeic acid, vanillic acid, p-coumaric acid, 3,4-dihydroxybenzoic acid and 4-hydroxybenzoic acid in rat plasma after oral administration of Echinacea purpurea extract. After mixing with the internal standard (IS, butylparaben, plasma samples were prepared by liquid–liquid extraction with ethyl acetate. The separation was performed using the Agilent Eclipse Plus C18 column (1.8 μm, 2.1 mm × 50 mm with a gradient system consisting of solution A (0.1% acetic acid in water and solution B (methanol at a flow rate of 0.3 mL/min. The detection was accomplished by a multiple reaction monitoring (MRM mode with electrospray ionization (ESI. The method was validated in terms of linearity, precision, accuracy, extraction recovery, matrix effect and stability. This method was successfully applied to study the pharmacokinetic properties of the seven compounds after oral administration of Echinacea purpurea extract in rats.

  2. High throughput HPLC-ESI(-)-MS/MS methodology for mercapturic acid metabolites of 1,3-butadiene: Biomarkers of exposure and bioactivation.

    Science.gov (United States)

    Kotapati, Srikanth; Esades, Amanda; Matter, Brock; Le, Chap; Tretyakova, Natalia

    2015-11-05

    1,3-Butadiene (BD) is an important industrial and environmental carcinogen present in cigarette smoke, automobile exhaust, and urban air. The major urinary metabolites of BD in humans are 2-(N-acetyl-L-cystein-S-yl)-1-hydroxybut-3-ene/1-(N-acetyl-L-cystein-S-yl)-2-hydroxybut-3-ene (MHBMA), 4-(N-acetyl-L-cystein-S-yl)-1,2-dihydroxybutane (DHBMA), and 4-(N-acetyl-L-cystein-S-yl)-1,2,3-trihydroxybutyl mercapturic acid (THBMA), which are formed from the electrophilic metabolites of BD, 3,4-epoxy-1-butene (EB), hydroxymethyl vinyl ketone (HMVK), and 3,4-epoxy-1,2-diol (EBD), respectively. In the present work, a sensitive high-throughput HPLC-ESI(-)-MS/MS method was developed for simultaneous quantification of MHBMA and DHBMA in small volumes of human urine (200 μl). The method employs a 96 well Oasis HLB SPE enrichment step, followed by isotope dilution HPLC-ESI(-)-MS/MS analysis on a triple quadrupole mass spectrometer. The validated method was used to quantify MHBMA and DHBMA in urine of workers from a BD monomer and styrene-butadiene rubber production facility (40 controls and 32 occupationally exposed to BD). Urinary THBMA concentrations were also determined in the same samples. The concentrations of all three BD-mercapturic acids and the metabolic ratio (MHBMA/(MHBMA+DHBMA+THBMA)) were significantly higher in the occupationally exposed group as compared to controls and correlated with BD exposure, with each other, and with BD-hemoglobin biomarkers. This improved high throughput methodology for MHBMA and DHBMA will be useful for future epidemiological studies in smokers and occupationally exposed workers. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  3. Columbia River ESI: NWI (National Wetlands Inventory - Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector polygons representing the wetlands of Columbia River classified according to the Environmental Sensitivity Index (ESI) classification...

  4. esis: un balance de los escritos publicados sobre Economía y otros temas

    Directory of Open Access Journals (Sweden)

    Myrna Limas Hernández

    2009-01-01

    Full Text Available La inquietud por presentar a los lectores(as de una Revista de Ciencias Sociales y Humanidades un balance de los escritos publicados sobre Economía a lo largo de 20 años, sugiere tomar como referencia una idea central del proyecto Nóesis (parafraseando a Ferro Gay en Nóesis, 1989 y a Pedraza, 1994: la actividad propia del intelectual se propone rastrear la causa de todas las cosas. Por ello, procede hacer uso del ejercicio de la razón. De ahí que la vinculación entre Nóesis y Economía sugiere detectar y organizar qué tipo de asuntos se han revisado e intentado compartir desde economistas y no economistas desde esta plataforma común. El formato considerado para atender esta tarea se basa en resolver algunas preguntas básicas que plantean: ¿qué se ha producido en Nóesis sobre Economía?, ¿cuánto se ha producido en Nóesis sobre Economía?, y ¿desde quién o desde dónde se han producido los artículos de Nóesis que tratan sobre Economía? Las respuestas probables a esta tercia de interrogantes nos guían a continuación.

  5. Western Alaska ESI: STREAMS (River and Stream Lines)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines representing inland linear hydrography features used in the creation of the Environmental Sensitivity Index (ESI) for Western...

  6. Columbia River ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for Columbia...

  7. Development of a chromatographic separation method hyphenated to electro-spray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS): application to the lanthanides speciation analysis

    International Nuclear Information System (INIS)

    Beuvier, Ludovic

    2015-01-01

    This work focuses on the development of a chromatographic separation method coupled to both ESI-MS and ICP-MS in order to achieve the comprehensive speciation analysis of lanthanides in aqueous phase representative of back-extraction phases of advanced spent nuclear fuel treatment processes. This analytical method allowed the separation, the characterization and the quantitation of lanthanides complexes holding poly-aminocarboxylic ligands, such as DTPA and EDTA, used as complexing agents in these processes. A HILIC separation method of lanthanides complexes has been developed with an amide bonded stationary phase. A screening of a wide range of mobile phase compositions demonstrated that the adsorption mechanism was predominant. This screening allowed also obtaining optimized separation conditions. Faster analysis conditions with shorter amide column packed with sub 2 μm particles reduced analysis time by 2.5 and 25% solvent consumption. Isotopic and structural characterization by HILIC ESI-MS was performed as well as the development of external calibration quantitation method. Analytical performances of quantitation method were determined. Finally, the development of the HILIC coupling to ESI-MS and ICP-MS was achieved. A simultaneous quantitation method by ESI-MS and ICP-MS was performed to determine the species quantitative distribution in solution. Analytical performances of quantitation method were also determined. (author) [fr

  8. Environmental Sensitivity Index (ESI) Atlas: Georgia, maps and geographic information systems data (NODC Accession 0013780)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of Georgia. ESI data characterize estuarine environments and wildlife by...

  9. Environmental Sensitivity Index (ESI) Atlas: Kodiak, maps and geographic information systems data (NODC Accession 0026418)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of Kodiak Island and Shelikof Strait, Alaska. ESI data characterize...

  10. Environmental Sensitivity Index (ESI) Atlas: Mississippi, maps and geographic information systems data (NODC Accession 0013801)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of Mississippi. ESI data characterize coastal environments and wildlife by...

  11. Environmental Sensitivity Index (ESI) Atlas: Louisiana maps and geographic information systems data (NODC Accession 0013802)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of Louisiana. ESI data characterize estuarine environments and wildlife by...

  12. Comparative analysis of Ligusticum chuanxiong and related umbelliferous medicinal plants by high performance liquid chromatography-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Yi, Tao; Leung, Kelvin Sze-Yin; Lu, Guang-Hua; Zhang, Hao

    2007-04-01

    A highly precise and accurate method, based on high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS), was developed for the qualitative and quantitative comparison of the main constituents in the rhizome of Ligusticum chuanxiong (LC) and three related umbelliferous medicinal plants. A comprehensive validation of the developed method was conducted, and the method was highly sensitive, reproducible and accurate. The unique properties of the present method were validated by analyzing 20 related herbal samples including 5 LC samples, 5 Cnidium officinale samples (CO), 5 Angelica sinensis samples (AS) and 5 Angelica acutiloba samples (AA). Twelve compounds including phenolic constituents, alkylphthalides and phthalide dimers were identified by online ESI-MS and by comparison with literature data and standard compounds, and six of them were quantified by HPLC-DAD simultaneously. The results demonstrated that identical compound types were identified as the main constituents of LC, CO, AS and AA herbs. The results also support the alternative application of these medicinal plants in Chinese and Japanese folk medicines. In the present study, it was found that the variation in the abundance of senkyunolide A was significant in these related herbs; it is therefore feasible to choose senkyunolide A as a characteristic compound for quality evaluation and chemical authentication of these herbs.

  13. Rapid Screening for Potential Epitopes Reactive with a Polycolonal Antibody by Solution-Phase H/D Exchange Monitored by FT-ICR Mass Spectrometry

    Science.gov (United States)

    Zhang, Qian; Noble, Kyle A.; Mao, Yuan; Young, Nicolas L.; Sathe, Shridhar K.; Roux, Kenneth H.; Marshall, Alan G.

    2013-07-01

    The potential epitopes of a recombinant food allergen protein, cashew Ana o 2, reactive to polyclonal antibodies, were mapped by solution-phase amide backbone H/D exchange (HDX) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Ana o 2 polyclonal antibodies were purified in the serum from a goat immunized with cashew nut extract. Antibodies were incubated with recombinant Ana o 2 (rAna o 2) to form antigen:polyclonal antibody (Ag:pAb) complexes. Complexed and uncomplexed (free) rAna o 2 were then subjected to HDX-MS analysis. Four regions protected from H/D exchange upon pAb binding are identified as potential epitopes and mapped onto a homologous model.

  14. Environmental Sensitivity Index (ESI) Atlas: Virginia, maps and geographic information systems data (NODC Accession 0014794)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Virginia from 1998 to 2004 (vs. 2 GDB). ESI data characterize estuarine environments and...

  15. Optimization of the Extraction of Anthocyanins from the Fruit Skin of Rhodomyrtus tomentosa (Ait. Hassk and Identification of Anthocyanins in the Extract Using High-Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry (HPLC-ESI-MS

    Directory of Open Access Journals (Sweden)

    Yuan-Ming Sun

    2012-05-01

    Full Text Available Anthocyanins are naturally occurring polyphenols that impart bright color to fruits, vegetables and plants. In this study, the extraction of anthocyanins from freeze-dried fruit skin of downy rose-myrtle (Rhodomyrtus tomentosa (Ait. Hassk var. Gangren was optimized using response surface methodology (RSM. Using 60% ethanol containing 0.1% (v/v hydrochloric acid as extraction solvent, the optimal conditions for maximum yields of anthocyanin (4.358 ± 0.045 mg/g were 15.7:1 (v/w liquid to solid ratio, 64.38 °C with a 116.88 min extraction time. The results showed good fits with the proposed model for the anthocyanin extraction (R2 = 0.9944. Furthermore, the results of high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS analysis of the anthocyanins extracted from the fruit skin of downy rose-myrtle revealed the presence of five anthocyanin components, which were tentatively identified as delphinidin-3-glucoside, cyanidin-3-glucoside, peonidin-3-glucoside, petunidin-3-glucoside and malvidin-3-glucoside.

  16. UFLC-ESI-MS/MS analysis of multiple mycotoxins in medicinal and edible Areca catechu.

    Science.gov (United States)

    Liu, Hongmei; Luo, Jiaoyang; Kong, Weijun; Liu, Qiutao; Hu, Yichen; Yang, Meihua

    2016-05-01

    A robust, sensitive and reliable ultra fast liquid chromatography combined with electrospray ionization tandem mass spectrometry (UFLC-ESI-MS/MS) was optimized and validated for simultaneous identification and quantification of eleven mycotoxins in medicinal and edible Areca catechu, based on one-step extraction without any further clean-up. Separation and quantification were performed in both positive and negative modes under multiple reaction monitoring (MRM) in a single run with zearalanone (ZAN) as internal standard. The chromatographic conditions and MS/MS parameters were carefully optimized. Matrix-matched calibration was recommended to reduce matrix effects and improve accuracy, showing good linearity within wide concentration ranges. Limits of quantification (LOQ) were lower than 50 μg kg(-1), while limits of detection (LOD) were in the range of 0.1-20 μg kg(-1). The accuracy of the developed method was validated for recoveries, ranging from 85% to 115% with relative standard deviation (RSD) ≤14.87% at low level, from 75% to 119% with RSD ≤ 14.43% at medium level and from 61% to 120% with RSD ≤ 13.18% at high level, respectively. Finally, the developed multi-mycotoxin method was applied for screening of these mycotoxins in 24 commercial samples. Only aflatoxin B2 and zearalenone were found in 2 samples. This is the first report on the application of UFLC-ESI(+/-)-MS/MS for multi-class mycotoxins in A. catechu. The developed method with many advantages of simple pretreatment, rapid determination and high sensitivity is a proposed candidate for large-scale detection and quantification of multiple mycotoxins in other complex matrixes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Controlling the Host-Guest Interaction Mode through a Redox Stimulus.

    Science.gov (United States)

    Szalóki, György; Croué, Vincent; Carré, Vincent; Aubriet, Frédéric; Alévêque, Olivier; Levillain, Eric; Allain, Magali; Aragó, Juan; Ortí, Enrique; Goeb, Sébastien; Sallé, Marc

    2017-12-18

    A proof-of-concept related to the redox-control of the binding/releasing process in a host-guest system is achieved by designing a neutral and robust Pt-based redox-active metallacage involving two extended-tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host-guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host-guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental data ( 1 H NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Sensitivity of GC-EI/MS, GC-EI/MS/MS, LC-ESI/MS/MS, LC-Ag(+) CIS/MS/MS, and GC-ESI/MS/MS for analysis of anabolic steroids in doping control.

    Science.gov (United States)

    Cha, Eunju; Kim, Sohee; Kim, Ho Jun; Lee, Kang Mi; Kim, Ki Hun; Kwon, Oh-Seung; Lee, Jaeick

    2015-01-01

    This study compared the sensitivity of various separation and ionization methods, including gas chromatography with an electron ionization source (GC-EI), liquid chromatography with an electrospray ionization source (LC-ESI), and liquid chromatography with a silver ion coordination ion spray source (LC-Ag(+) CIS), coupled to a mass spectrometer (MS) for steroid analysis. Chromatographic conditions, mass spectrometric transitions, and ion source parameters were optimized. The majority of steroids in GC-EI/MS/MS and LC-Ag(+) CIS/MS/MS analysis showed higher sensitivities than those obtained with other analytical methods. The limits of detection (LODs) of 65 steroids by GC-EI/MS/MS, 68 steroids by LC-Ag(+) CIS/MS/MS, 56 steroids by GC-EI/MS, 54 steroids by LC-ESI/MS/MS, and 27 steroids by GC-ESI/MS/MS were below cut-off value of 2.0 ng/mL. LODs of steroids that formed protonated ions in LC-ESI/MS/MS analysis were all lower than the cut-off value. Several steroids such as unconjugated C3-hydroxyl with C17-hydroxyl structure showed higher sensitivities in GC-EI/MS/MS analysis relative to those obtained using the LC-based methods. The steroids containing 4, 9, 11-triene structures showed relatively poor sensitivities in GC-EI/MS and GC-ESI/MS/MS analysis. The results of this study provide information that may be useful for selecting suitable analytical methods for confirmatory analysis of steroids. Copyright © 2015 John Wiley & Sons, Ltd.

  19. Simultaneous quantification of differently glycosylated, acetylated and 2,3-dihydro-2,5-dihydroxy-6-methyl-4h-pyran-4-one-conjugated soyasaponins using reversed-phase high-performance liquid chromatography with evaporative light scattering detection

    NARCIS (Netherlands)

    DeCroos, K.; Vincken, J.P.; Heng, L.; Bakker, R.; Gruppen, H.; Verstraete, W.

    2005-01-01

    A novel method utilizing high-performance liquid chromatography (HPLC) with evaporative light scattering detection (ELSD) and electrospray ionisation mass spectrometry (ESI-MS) was developed for the analysis of soyasaponins, a divers group of triterpenic compounds with one or two sugar side chains,

  20. Determination of pharmaceutical compounds in surface- and ground-water samples by solid-phase extraction and high-performance liquid chromatography-electrospray ionization mass spectrometry

    Science.gov (United States)

    Cahill, J.D.; Furlong, E.T.; Burkhardt, M.R.; Kolpin, D.; Anderson, L.G.

    2004-01-01

    Commonly used prescription and over-the-counter pharmaceuticals are possibly present in surface- and ground-water samples at ambient concentrations less than 1 μg/L. In this report, the performance characteristics of a combined solid-phase extraction isolation and high-performance liquid chromatography–electrospray ionization mass spectrometry (HPLC–ESI-MS) analytical procedure for routine determination of the presence and concentration of human-health pharmaceuticals are described. This method was developed and used in a recent national reconnaissance of pharmaceuticals in USA surface waters. The selection of pharmaceuticals evaluated for this method was based on usage estimates, resulting in a method that contains compounds from diverse chemical classes, which presents challenges and compromises when applied as a single routine analysis. The method performed well for the majority of the 22 pharmaceuticals evaluated, with recoveries greater than 60% for 12 pharmaceuticals. The recoveries of angiotensin-converting enzyme inhibitors, a histamine (H2) receptor antagonist, and antihypoglycemic compound classes were less than 50%, but were retained in the method to provide information describing the potential presence of these compounds in environmental samples and to indicate evidence of possible matrix enhancing effects. Long-term recoveries, evaluated from reagent-water fortifications processed over 2 years, were similar to initial method performance. Method detection limits averaged 0.022 μg/L, sufficient for expected ambient concentrations. Compound-dependent matrix effects on HPLC/ESI-MS analysis, including enhancement and suppression of ionization, were observed as a 20–30% increase in measured concentrations for three compounds and greater than 50% increase for two compounds. Changing internal standard and more frequent ESI source maintenance minimized matrix effects. Application of the method in the national survey demonstrates that several

  1. A new kaempferol diglycoside from Datura suaveolens Humb. & Bonpl. ex. Willd.

    Science.gov (United States)

    Sajeli Begum, A; Sahai, Mahendra; Fujimoto, Yoshinori; Asai, K; Schneider, Kathrin; Nicholson, Graeme; Suessmuth, Roderich

    2006-11-01

    A new flavonol glycoside, kaempferol 3-O-alpha-L-arabinopyranosyl-7-O-beta-D-glucopyranoside (1), has been isolated from methanol extract of leaves of Datura suaveolens (Solanaceae), along with six other known compounds, which include kaempferol 3-O-alpha-L-arabinopyranoside (2), 3-phenyl lactic acid, 3-(3-indolyl) lactic acid, and its methyl ester, physalindicanol A and physalindicanol B. The structural elucidation of 1 and characterization of the known compounds are based on detailed spectral analysis (ESI-FTICR-MS and 2D-NMR). This is the first report of isolation of these compounds from this plant.

  2. Environmental Sensitivity Index (ESI) Atlas: Cook Inlet, Alaska, maps and geographic information systems (NODC Accession 0046027)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Cook Inlet and Kenai Peninsula, Alaska. ESI data characterize estuarine environments and...

  3. Quickly Screening for Potential α-Glucosidase Inhibitors from Guava Leaves Tea by Bioaffinity Ultrafiltration Coupled with HPLC-ESI-TOF/MS Method.

    Science.gov (United States)

    Wang, Lu; Liu, Yufeng; Luo, You; Huang, Kuiying; Wu, Zhenqiang

    2018-02-14

    Guava leaves tea (GLT) has a potential antihyperglycemic effect. Nevertheless, it is unclear which compound plays a key role in reducing blood sugar. In this study, GLT extract (IC 50 = 19.37 ± 0.21 μg/mL) exhibited a stronger inhibitory potency against α-glucosidase than did acarbose (positive control) at IC 50 = 178.52 ± 1.37 μg/mL. To rapidly identify the specific α-glucosidase inhibitor components from GLT, an approach based on bioaffinity ultrafiltration combined with high performance liquid chromatography coupled to electrospray ionization-time-of-flight-mass spectrometry (BAUF-HPLC-ESI-TOF/MS) was developed. Under the optimal bioaffinity ultrafiltration conditions, 11 corresponding potential α-glucosidase inhibitors with high affinity degrees (ADs) were screened and identified from the GLT extract. Quercetin (IC 50 = 4.51 ± 0.71 μg/mL) and procyanidin B3 (IC 50 = 28.67 ± 5.81 μg/mL) were determined to be primarily responsible for the antihyperglycemic effect, which further verified the established screening method. Moreover, structure-activity relationships were discussed. In conclusion, the BAUF-HPLC-ESI-TOF/MS method could be applied to determine the potential α-glucosidase inhibitors from complex natural products quickly.

  4. High field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter from the South Atlantic Ocean

    Science.gov (United States)

    Hertkorn, N.; Harir, M.; Koch, B. P.; Michalke, B.; Grill, P.; Schmitt-Kopplin, P.

    2012-01-01

    satisfactorily explain the observed disparity in NMR transverse relaxation of the four marine DOM samples. Likewise, the presence of metal ions in isolated marine DOM remained near constant or declined from surface to depth for important paramagnetic ions like Mn, Cr, Fe, Co, Ni and Cu. Iron in particular, a strong complexing paramagnetic ion, was found most abundant by a considerable margin in surface (FISH) marine DOM for which well resolved COSY cross peaks were observed. Hence, facile relationships between metal content of isolated DOM (which does not reflect authentic marine DOM metal content) and transverse NMR relaxation were not observed. High field (12 T) negative electrospray ionization FTICR mass spectra showed at first view rather conforming mass spectra for all four DOM samples with abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing numbers of mass peaks from surface to bottom DOM and similar fractions (~50%) of assigned molecular compositions throughout all DOM samples. The average mass increased from surface to bottom DOM by about 10 Dalton. The limited variance of FTICR mass spectra probably resulted from a rather inherent conformity of marine DOM at the mandatory level of intrinsic averaging provided by FTICR mass spectrometry, when many isomers unavoidably project on single nominal mass peaks. In addition, averaging from ion suppression added to the accordance observed. The proportion of CHO and CHNO molecular series increased from surface to depth whereas CHOS and especially CHNOS molecular series markedly declined. The abundance of certain aromatic CHOS compounds declined with water depth. For future studies, COSY NMR spectra appear best suited to assess organic molecular complexity of marine DOM and to define individual DOM molecules of yet unknown structure and function. Non-target organic structural spectroscopy at the level demonstrated here covered nearly all carbon present in marine DOM. The exhaustive characterization of

  5. Environmental Sensitivity Index (ESI) Atlas: New Hampshire, maps and Geographic Information Systems data (NODC Accession 0014789)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the New Hampshire coast from 2003 to 2004. ESI data characterize estuarine environments...

  6. Environmental Sensitivity Index (ESI) Atlas: Hudson River, maps and geographic information systems data (NODC Accession 0014791)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Hudson River from 1942 to 2005. ESI data characterize estuarine environments and...

  7. Environmental Sensitivity Index (ESI) Atlas: Columbia River, maps and geographic information systems data (NODC Accession 0013951)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Columbia River from 1979 to 2004. ESI data characterize estuarine environments and...

  8. Characterization of Flavonoids and Phenolic Acids in Myrcia bella Cambess. Using FIA-ESI-IT-MSn and HPLC-PAD-ESI-IT-MS Combined with NMR

    Directory of Open Access Journals (Sweden)

    Anne L. Dokkedal

    2013-07-01

    Full Text Available The leaves of Myrcia DC. ex Guill species are used in traditional medicine and are also exploited commercially as herbal drugs for the treatment of diabetes mellitus. The present work aimed to assess the qualitative and quantitative profiles of M. bella hydroalcoholic extract, due to these uses, since the existing legislation in Brazil determines that a standard method must be developed in order to be used for quality control of raw plant materials. The current study identified eleven known flavonoid-O-glycosides and six acylated flavonoid derivatives of myricetin and quercetin, together with two kaempferol glycosides and phenolic acids such as caffeic acid, ethil galate, gallic acid and quinic acid. In total, 24 constituents were characterized, by means of extensive preparative chromatographic analyses, along with MS and NMR techniques. An HPLC-PAD-ESI-IT-MS and FIA-ESI-IT-MSn method were developed for rapid identification of acylated flavonoids, flavonoid-O-glycosides derivatives of myricetin and quercetin and phenolic acids in the hydroalcoholic M. bella leaves extract. The FIA-ESI-IT-MS techinique is a powerful tool for direct and rapid identification of the constituents after isolation and NMR characterization. Thus, it could be used as an initial method for identification of authentic samples concerning quality control of Myrcia spp extracts.

  9. Measurement of O(6)-alkylguanine-DNA alkyltransferase activity in tumour cells using stable isotope dilution HPLC-ESI-MS/MS.

    Science.gov (United States)

    Sun, Guohui; Zhao, Lijiao; Fan, Tengjiao; Ren, Ting; Zhong, Rugang

    2016-10-15

    The repair of DNA mediated by O(6)-alkylguanine-DNA alkyltransferase (AGT) provides protection against DNA damage from endogenous or exogenous alkylation of the O(6) position of guanine. However, this repair acts as a double-edged sword in cancer treatment, as it not only protects normal cells from chemotherapy-associated toxicities, but also results in cancer cell resistance to guanine O(6)-alkylating antitumour agents. Thus, AGT plays an important role in predicting the individual susceptibility to guanine O(6)-alkylating carcinogens and chemotherapies. Accordingly, it is necessary to establish a quantitative method for determining AGT activity with high accuracy, sensitivity and practicality. Here, we describe a novel nonradioactive method for measuring AGT activity using stable isotope dilution high-performance liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). This method is based on the irreversibility of the removal of the O(6)-alkyl group from guanine by AGT and on the high affinity of O(6)-benzylguanine (O(6)-BG) as an AGT substrate. HPLC-ESI-MS/MS was used to measure the AGT activities in cell protein extracts from eight tumour lines, demonstrating that AGT activity was quite variable among different cell lines, ranging from nondetectable to 1021 fmol/mg protein. The experiments performed in intact tumour cells yielded similar results but exhibited slightly higher activities than those observed in cell protein extracts. The accuracy of this method was confirmed by an examination of AGT expression levels using western blotting analysis. To our knowledge, this method is the first mass spectrometry-based AGT activity assay, and will likely provide assistance in the screening of cancer risk or the application of chemotherapies. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. North Slope, Alaska ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for the North...

  11. The mechanism of reduced IgG/IgE-binding of β-lactoglobulin by pulsed electric field pretreatment combined with glycation revealed by ECD/FTICR-MS.

    Science.gov (United States)

    Yang, Wenhua; Tu, Zongcai; Wang, Hui; Zhang, Lu; Kaltashov, Igor A; Zhao, Yunlong; Niu, Chendi; Yao, Honglin; Ye, Wenfeng

    2018-01-24

    Bovine β-lactoglobulin (β-Lg) is a major allergen existing in milk and causes about 90% of IgE-mediated cow's milk allergies. Previous studies showed that pulsed electric field (PEF) treatment could partially unfold the protein, which may contribute to the improvement of protein glycation. In this study, the effect of PEF pretreatment combined with glycation on the IgG/IgE-binding ability and the structure of β-Lg was investigated. The result showed that PEF pretreatment combined with glycation significantly reduced the IgG and IgE binding abilities, which was attributed to the changes of secondary and tertiary structure and the increase in glycation sites and degree of substitution per peptide (DSP) value determined by electron capture dissociation Fourier transform ion cyclotron resonance mass spectrometry (ECD/FTICR-MS). Unexpectedly, glycation sites (K47, K91 and K135) added by two mannose molecules were identified in glycated β-Lg with PEF pretreatment. Moreover, the results indicated that PEF pretreatment at 25 kV cm -1 for 60 μs promoted the reduction of IgG/IgE-binding capacity by increasing the glycation degree of β-Lg, whereas single PEF treatment under the same conditions markedly enhanced the IgG/IgE-binding ability by partially unfolding the structure of β-Lg. The results suggested that ECD/FTICR-MS could help us to understand the mechanism of reduction in the IgG/IgE-binding of β-Lg by structural characterization at the molecular level. Therefore, PEF pretreatment combined with glycation may provide an alternative method for β-Lg desensitization.

  12. Gulf-Wide Information System, Environmental Sensitivity Index Swamps, Geographic NAD83, LDWF (2001) [esi_swamp_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) swamps data of coastal Louisiana. The ESI is a classification and ranking system, which characterizes...

  13. Gulf-Wide Information System, Environmental Sensitivity Index Salinity, Geographic NAD83, LDWF (2001) [esi_salinity_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) salinity data of coastal Louisiana. The ESI is a classification and ranking system, which characterizes...

  14. Gulf-Wide Information System, Environmental Sensitivity Index Seagrass, Geographic NAD83, LDWF (2001) [esi_seagrass_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) seagrass data of coastal Louisiana. The ESI is a classification and ranking system, which characterizes...

  15. ESI MS/MS Study of Calix[4]arene Derivatives and their Metal Complexes

    OpenAIRE

    Benković, Tomislav; Tomišić, Vladislav; Frkanec, Leo; Galić, Nives

    2012-01-01

    The peptidocalixarenes 1–3 bearing tryptophan, phenylglycine and leucil units at the lower rim and their complexes with alkali-metal (Li+, Na+, K+, Rb+, Cs+) and selected lanthanide cations (La3+, Ce3+, Eu3+, Yb3+) were analyzed by ESI MS. The influences of the solvent (acetonitrile, methanol, addition of formic acid or sodium acetate) and the calixarene:cation molar ratio on signal intensities were investigated. Comprehensive MS/MS analyses were performed of all singly and doubly charged ion...

  16. FT-ICR MS analysis of blended pine-microalgae feedstock HTL biocrudes

    Energy Technology Data Exchange (ETDEWEB)

    Jarvis, Jacqueline M.; Billing, Justin M.; Corilo, Yuri E.; Schmidt, Andrew J.; Hallen, Richard T.; Schaub, Tanner M.

    2018-03-01

    Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is utilized for direct comparison of the chemical composition of biocrudes generated from the hydrothermal liquefaction of 100% pine, 100% algae, 75:25 pine:algae, and 50:50 pine:algae feedstocks. This analysis reveals that the of the 72:25 and 50:50 pine:algal HTL biocrudes is essentially a composite of the two parent feeds (i.e., pine and algae) with a lower relative abundance of Ox species and a higher relative abundance of nitrogen-containing species than the pine HTL biocrude. Alternatively, the biocrude blends have a lower relative abundance of nitrogen-containing species where N>2 than the algal HTL biocrude. The 75:25 pine:algal HTL biocrude has more elemental formulae in common with the pine HTL biocrude than the 50:50 blend; however, both blends have more elemental formulae in common with the algal HTL biocrude. Interestingly, >20% of the elemental formulae assigned to monoisotopic peaks within the 75:25 and 50:50 biocrude blends are species not present in either the pine or algal HTL biocrudes. The highest relative abundance of these new species belong to the N2O4-6 classes, which correspond to heteroatom classes with a moderate number of nitrogen atoms and higher number of oxygen atoms per molecules than the species within the pure algal HTL biocrude. Compositionally, the novel species have the same structural motif but are of higher DBE and carbon numbers than the species within the algal HTL biocrude. These original species are most likely generated from reactions between molecules from both feeds, which results in compounds wotj higher oxygen content than typically seen in the algal HTL biocrude but also higher nitrogen contents than observed in the pine HTL biocrude.

  17. Chemical characterisation of non-defective and defective green arabica and robusta coffees by electrospray ionization-mass spectrometry (ESI-MS).

    Science.gov (United States)

    Mendonça, Juliana C F; Franca, Adriana S; Oliveira, Leandro S; Nunes, Marcella

    2008-11-15

    The coffee roasted in Brazil is considered to be of low quality, due to the presence of defective coffee beans that depreciate the beverage quality. These beans, although being separated from the non-defective ones prior to roasting, are still commercialized in the coffee trading market. Thus, it was the aim of this work to verify the feasibility of employing ESI-MS to identify chemical characteristics that will allow the discrimination of Arabica and Robusta species and also of defective and non-defective coffees. Aqueous extracts of green (raw) defective and non-defective coffee beans were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS) and this technique provided characteristic fingerprinting mass spectra that not only allowed for discrimination of species but also between defective and non-defective coffee beans. ESI-MS profiles in the positive mode (ESI(+)-MS) provided separation between defective and non-defective coffees within a given species, whereas ESI-MS profiles in the negative mode (ESI(-)-MS) provided separation between Arabica and Robusta coffees. Copyright © 2008 Elsevier Ltd. All rights reserved.

  18. Environmental Sensitivity Index (ESI) Atlas: Aleutian Islands, Alaska, maps and geographic information systems data (NODC Accession 0014927)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the Aleutian Islands, Alaska. ESI data characterize coastal environments and wildlife by...

  19. Characterization of flavonoids and phenolic acids in Myrcia bella Cambess. using FIA-ESI-IT-MS(n) and HPLC-PAD-ESI-IT-MS combined with NMR.

    Science.gov (United States)

    Saldanha, Luiz L; Vilegas, Wagner; Dokkedal, Anne L

    2013-07-16

    The leaves of Myrcia DC. ex Guill species are used in traditional medicine and are also exploited commercially as herbal drugs for the treatment of diabetes mellitus. The present work aimed to assess the qualitative and quantitative profiles of M. bella hydroalcoholic extract, due to these uses, since the existing legislation in Brazil determines that a standard method must be developed in order to be used for quality control of raw plant materials. The current study identified eleven known flavonoid-O-glycosides and six acylated flavonoid derivatives of myricetin and quercetin, together with two kaempferol glycosides and phenolic acids such as caffeic acid, ethil galate, gallic acid and quinic acid. In total, 24 constituents were characterized, by means of extensive preparative chromatographic analyses, along with MS and NMR techniques. An HPLC-PAD-ESI-IT-MS and FIA-ESI-IT-MS(n) method were developed for rapid identification of acylated flavonoids, flavonoid-O-glycosides derivatives of myricetin and quercetin and phenolic acids in the hydroalcoholic M. bella leaves extract. The FIA-ESI-IT-MS techinique is a powerful tool for direct and rapid identification of the constituents after isolation and NMR characterization. Thus, it could be used as an initial method for identification of authentic samples concerning quality control of Myrcia spp extracts.

  20. Biochemical and Pharmacological Characterizations of ESI-09 Based EPAC Inhibitors: Defining the ESI-09 “Therapeutic Window”

    OpenAIRE

    Yingmin Zhu; Haijun Chen; Stephen Boulton; Fang Mei; Na Ye; Giuseppe Melacini; Jia Zhou; Xiaodong Cheng

    2015-01-01

    The cAMP signaling cascade is one of the most frequently targeted pathways for the development of pharmaceutics. A plethora of recent genetic and pharmacological studies suggest that exchange proteins directly activated by cAMP (EPACs) are implicated in multiple pathologies. Selective EPAC inhibitors have been recently developed. One specific inhibitor, ESI-09, has been shown to block EPAC activity and functions, as well as to recapitulate genetic phenotypes of EPAC knockout mice when applied...

  1. Comparative HPLC/ESI-MS and HPLC/DAD study of different populations of cultivated, wild and commercial Gentiana lutea L.

    Science.gov (United States)

    Mustafa, Ahmed M; Caprioli, Giovanni; Ricciutelli, Massimo; Maggi, Filippo; Marín, Rosa; Vittori, Sauro; Sagratini, Gianni

    2015-05-01

    The root of Gentiana lutea L., famous for its bitter properties, is often used in alcoholic bitter beverages, food products and traditional medicine to stimulate the appetite and improve digestion. This study presents a new, fast, and accurate HPLC method using HPLC/ESI-MS and HPLC/DAD for simultaneous analysis of iridoids (loganic acid), secoiridoids (gentiopicroside, sweroside, swertiamarin, amarogentin) and xanthones (isogentisin) in different populations of G.lutea L., cultivated in the Monti Sibillini National Park, obtained wild there, or purchased commercially. Comparison of HPLC/ESI-MS and HPLC/DAD indicated that HPLC/ESI-MS is more sensitive, reliable and selective. Analysis of twenty samples showed that gentiopicroside is the most dominant compound (1.85-3.97%), followed by loganic acid (0.11-1.30%), isogentisin (0.03-0.48%), sweroside (0.05-0.35%), swertiamarin (0.08-0.30%), and amarogentin (0.01-0.07%). The results confirmed the high quality of the G.lutea cultivated in the Monti Sibillini National Park. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Comparison and characterization of soybean and sunflower lecithins used for chocolate production by high-performance thin-layer chromatography with fluorescence detection and electrospray mass spectrometry.

    Science.gov (United States)

    Krüger, Stephanie; Bürmann, Laura; Morlock, Gertrud E

    2015-03-25

    The scarce availability of nongenetically modified soybeans on the world market represents a growing problem for food manufacturers. Hence, in this study the effects of substituting soybean with sunflower lecithin were investigated with regard to chocolate production. The glycerophospholipid pattern of the different lecithin samples was investigated by high-performance thin-layer chromatography fluorescence detection (HPTLC-FLD) and by HPTLC-positive ion electrospray ionization mass spectrometry (ESI(+)-MS) via the TLC-MS Interface and by scanning HPTLC-matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOFMS). Especially, the contents of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) were of interest due to the influencing effects of these two glycerophospholipids on the rheological parameters of chocolate production. The lecithin substitution led to only slight differences in the rheological parameters of milk and dark chocolate. Limits of detection (LODs) and limits of quantification (LOQs) of seven glycerophospholipids were studied for three detection modes. Mean LODs ranged from 8 to 40 mg/kg for HPTLC-FLD and, using a single-quadrupole MS, from 10 to 280 mg/kg for HPTLC-ESI(+)-MS as well as from 15 to 310 mg/kg for HPTLC-FLD-ESI(+)-MS recorded after derivatization with the primuline reagent.

  3. Analysis of 2-(2-Phenylethylchromones by UPLC-ESI-QTOF-MS and Multivariate Statistical Methods in Wild and Cultivated Agarwood

    Directory of Open Access Journals (Sweden)

    Yuanbin Li

    2016-05-01

    Full Text Available Agarwood is the fragrant resinous material mainly formed from species of Aquilaria. 2-(2-phenylethylchromones, especially the highly oxidized 5,6,7,8-tetrahydro-2-(2-phenylethylchromones, are the main representative compounds from agarwood. It is important to determine whether agarwood in trade is from cultivated trees or natural trees in the Convention on the International Trade in Endangered Species (CITES. We characterized the 2-(2-phenylethylchromones in agarwood by ultra-performance liquid chromatography coupled with electrospray ionization mass spectrometry (UPLC–ESI-QTOF-MS and differentiated wild from cultivated agarwood by metabolomic analysis. A total of 141 chromones including 50 potentially new compounds were evaluated as belonging to four structural classes (unoxidized 2-(2-phenylethylchromones, 5,6,7,8-tetrahydro-2-(2-phenylethyl-chromones, bi-2-(2-phenylethylchromones, and tri-2-(2-phenylethylchromones. The metabolic difference between wild and cultivated agarwood was analyzed by component analysis (PCA and orthogonal partial least squares discriminant analysis (OPLS-DA. Fourteen markers of metabolisms in wild and cultivated agarwood were constructed (e.g., 6,7-dimethoxy-2-(2-phenylethylchromone, 6,8-dihydroxy-2-(2-phenylethylchromone, 6-methoxy-2-(2-phenylethylchromone, etc.. These results indicated that UPLC–ESI-QTOF-MS-based metabonomics analysis in agarwood may be useful for distinguishing wild agarwood from cultivated agarwood.

  4. Õpetamine esi- ja algõpetuses : Alusväärtused. Ülesanded ja eesmärgid. Orientatsioonidest õppeaineteni. Metoodilised tervikud. Hindamine

    Index Scriptorium Estoniae

    2001-01-01

    Esi- ja algõpetuse alusväärtused ja eesmärgid. Esiõpetuse teadmisala-orientatsioonid ja algõpetuse õppeained. Mängu tähtsusest väikelaste õppimises, õppetunni planeerimine, integreeritud õpetus algõpetuses. Hindamine esi- ja algõpetuses

  5. Gulf-Wide Information System, Environmental Sensitivity Index Marsh, Geographic NAD83, LDWF (2001) [esi_fresh_marsh_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) fresh marsh data of coastal Louisiana. The ESI is a classification and ranking system, which...

  6. Comparative study of label and label-free techniques using shotgun proteomics for relative protein quantification.

    Science.gov (United States)

    Sjödin, Marcus O D; Wetterhall, Magnus; Kultima, Kim; Artemenko, Konstantin

    2013-06-01

    The analytical performance of three different strategies, iTRAQ (isobaric tag for relative and absolute quantification), dimethyl labeling (DML) and label free (LF) for relative protein quantification using shotgun proteomics have been evaluated. The methods have been explored using samples containing (i) Bovine proteins in known ratios and (ii) Bovine proteins in known ratios spiked into Escherichia coli. The latter case mimics the actual conditions in a typical biological sample with a few differentially expressed proteins and a bulk of proteins with unchanged ratios. Additionally, the evaluation was performed on both QStar and LTQ-FTICR mass spectrometers. LF LTQ-FTICR was found to have the highest proteome coverage while the highest accuracy based on the artificially regulated proteins was found for DML LTQ-FTICR (54%). A varying linearity (k: 0.55-1.16, r(2): 0.61-0.96) was shown for all methods within selected dynamic ranges. All methods were found to consistently underestimate Bovine protein ratios when matrix proteins were added. However, LF LTQ-FTICR was more tolerant toward a compression effect. A single peptide was demonstrated to be sufficient for a reliable quantification using iTRAQ. A ranking system utilizing several parameters important for quantitative proteomics demonstrated that the overall performance of the five different methods was; DML LTQ-FTICR>iTRAQ QStar>LF LTQ-FTICR>DML QStar>LF QStar. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Hemoglobin variants as models for investigation of dissociation of intact polypeptide chains by ESI tandem mass spectrometry

    International Nuclear Information System (INIS)

    Light, K.J.; Loo, J.A.; Edmonds, C.G.; Smith, R.D.

    1991-06-01

    Electrospray ionization mass spectroscopy (ESI-MS) is rapidly becoming a practical biochemical tool for peptide and protein sequence analysis. The utility of ESI-MS is through use of Collisionally Activated Dissociation (ESI-CAD-MS). Human hemoglobin (Hb, ∼62 kDa) consists of four polypeptide chains and a prosthetic heme group. There are over 400 Hb variants, characterized by amino acid substitutions in either the alpha or beta polypeptide chains. We investigated ESI-CAD-MS as a tool for rapidly analyzing amino acid substitutions, using eight Hb beta chain variants. The approximate location of the modification can be deduced from comparison of the CAD mass spectra and observance of the mass shifts of the fragment ion containing the substitution. Fragmentation occurs preferentially at the amino terminus of proline residues. For most substitutions, differences in CAD mass spectra were not seen. 2 figs

  8. esis: un oasis intelectual en el desierto chihuahuense

    Directory of Open Access Journals (Sweden)

    Luis Antonio Payán Alvarado

    2009-01-01

    Full Text Available Durante dos décadas, la revista académica Nóesis ha sido uno de los oasis intelectuales de la investigación científica social en el estado de Chihuahua. Su trayectoria durante estos veinte años constituye, primero, un reconocimiento de nuestro rezago en la indagación científica dentro de las ciencias sociales y, segundo, un compromiso importante para subsanar nuestras deficiencias en este terreno. El presente ensayo formula tres preguntas importantes a fin de explorar la trayectoria de Nóesis: Unde venis?, Ubi es?, y Quo vadis?, mediante las cuales se pretende explorar brevemente el pasado, el presente, y el futuro de la revista, dadas las condiciones actuales de la comunidad epistémica de la Universidad Autónoma de Ciudad Juárez, del estado de Chihuahua y de la región norte de México.

  9. Cook Inlet and Kenai Peninsula, Alaska ESI: INDEX (Index Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector polygons representing the boundaries used in the creation of the Environmental Sensitivity Index (ESI) for Cook Inlet and Kenai...

  10. Bristol Bay, Alaska Subarea ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for the Bristol...

  11. Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

    Science.gov (United States)

    Torvinen, Mika; Kalenius, Elina; Sansone, Francesco; Casnati, Alessandro; Jänis, Janne

    2012-02-01

    The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.

  12. Native MS and ECD Characterization of a Fab-Antigen Complex May Facilitate Crystallization for X-ray Diffraction

    Science.gov (United States)

    Zhang, Ying; Cui, Weidong; Wecksler, Aaron T.; Zhang, Hao; Molina, Patricia; Deperalta, Galahad; Gross, Michael L.

    2016-07-01

    Native mass spectrometry (MS) and top-down electron-capture dissociation (ECD) combine as a powerful approach for characterizing large proteins and protein assemblies. Here, we report their use to study an antibody Fab (Fab-1)-VEGF complex in its near-native state. Native ESI with analysis by FTICR mass spectrometry confirms that VEGF is a dimer in solution and that its complex with Fab-1 has a binding stoichiometry of 2:2. Applying combinations of collisionally activated dissociation (CAD), ECD, and infrared multiphoton dissociation (IRMPD) allows identification of flexible regions of the complex, potentially serving as a guide for crystallization and X-ray diffraction analysis.

  13. Non-volatile floral oils of Diascia spp. (Scrophulariaceae).

    Science.gov (United States)

    Dumri, Kanchana; Seipold, Lars; Schmidt, Jürgen; Gerlach, Günter; Dötterl, Stefan; Ellis, Allan G; Wessjohann, Ludger A

    2008-04-01

    The floral oils of Diascia purpurea, Diascia vigilis, Diascia cordata, Diascia megathura, Diascia integerrima and Diascia barberae (Scrophulariaceae) were selectively collected from trichome elaiophores. The derivatized floral oils were analyzed by gas chromatography-mass spectrometry (GC-MS), whilst the underivatized samples were analysed by electrospray ionization mass spectrometry (ESI-MS) and Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). The most common constituents of the floral oils investigated are partially acetylated acylglycerols of (3R)-acetoxy fatty acids (C(14), C(16), and C(18)), as was proven with non-racemic synthetic reference samples. The importance of these oils for Rediviva bees is discussed in a co-evolutionary context.

  14. Environmental Sensitivity Index (ESI) Atlas: San Francisco Bay - 1998, maps and geographic information systems data (NODC Accession 0036884)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of San Francisco Bay. ESI data characterize estuarine environments and...

  15. Environmental Sensitivity Index (ESI) Atlas: San Francisco Bay, California maps and geographic information systems data (NODC Accession 0013224)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of San Francisco Bay. ESI data characterize estuarine environments and...

  16. Environmental Sensitivity Index (ESI) Atlas: Puerto Rico - 2000, maps and geographic information systems data DVD (NODC Accession 0014188)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — ESI data characterize coastal environments and wildlife by their sensitivity to spilled oil. The ESI data include information for three main components: shoreline...

  17. Surfactant-free microemulsion electrokinetic chromatography (SF-MEEKC) with UV and MS detection - a novel approach for the separation and ESI-MS detection of neutral compounds.

    Science.gov (United States)

    Mohorič, Urška; Beutner, Andrea; Krickl, Sebastian; Touraud, Didier; Kunz, Werner; Matysik, Frank-Michael

    2016-12-01

    Microemulsion electrokinetic chromatography (MEEKC) is a powerful tool to separate neutral species based on differences in their hydrophobic and hydrophilic properties. However, as a major drawback the conventionally used SDS based microemulsions are not compatible with electrospray ionization mass spectrometry (ESI-MS). In this work, a surfactant-free microemulsion (SFME) consisting of water, ethanol, and 1-octanol is used for surfactant-free microemulsion electrokinetic chromatography (SF-MEEKC). Ammonium acetate was added to the SFME enabling electrophoretic separations. The stability of SFMEs containing ammonium acetate was investigated using small-angle X-ray scattering and dynamic light scattering. A method for the separation of a model system of hydrophobic and hydrophilic neutral vitamins, namely the vitamins B 2 and D 3 , and the cationic vitamin B 1 was developed using UV/VIS detection. The influence of the ammonium acetate concentration on the separation performance was studied in detail. The method was characterized concerning reproducibility of migration times and peak areas and concerning the linearity of the calibration data. Furthermore, SF-MEEKC was coupled to ESI-MS investigating the compatibility between SFMEs and the ESI process. The signal intensities of ESI-MS measurements of the model analytes were comparable for SFMEs and aqueous systems. Finally, the vitamin D 3 content of a drug treating vitamin D 3 deficiency was determined by SF-MEEKC coupled to ESI-MS using 25-hydroxycholecalciferol as an internal standard. Graphical abstract The concept of surfactant-free microemulsion electrokinetic chromatography coupled to electrospray ionization mass spectrometry.

  18. Environmental Sensitivity Index (ESI) Atlas: North Carolina and South Carolina Digital Data Re-release, 1996 (NODC Accession 0049956)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises an update of the Environmental Sensitivity Indexes (ESI) data for North and South Carolina. ESI data characterize estuarine environments and...

  19. Non-aqueous CE-MS of cinchona alkaloids - characterizationof a novel CE-ESI-MS interface

    DEFF Research Database (Denmark)

    Hansen, Frederik André; Hansen, Steen Honoré; Petersen, Nickolaj J.

    We have recently in our group at the University of Copenhagen developed a robust and simple sheatless CE-ESI-MS interface (capillary electrophoresis – electrospray ionization-mass spectrometry). In this presentation the interface is characterized and compared with HPLC-MS for studying...... a submicron fracture in the capillary close the ESI tip. The fracture provides a zero dead volume and excellent conducting properties due to the large amount of ions in the electric double layer. Electric current exceeding the upper limit of CE instrumentation of up to 300 µA can easily be obtained....... Furthermore, the increased conductivity of the buffer in the fracture generates field free pumping of the analytes towards the ESI spray tip. In this study the device was used to analyze the four major alkaloids (diastereomeric pairs of quinine/quinidine and cinchonine/cinchonidine) in Cinchona bark samples...

  20. Compendium of Environmental Sustainability Indicator Collections: 2005 Environmental Sustainability Index (ESI)

    Data.gov (United States)

    National Aeronautics and Space Administration — The 2005 Environmental Sustainability Index (ESI) portion of the Compendium of Environmental Sustainability Indicators Collection contains 103 variables for 146...

  1. Combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for qualitative analysis of drugs.

    Science.gov (United States)

    Pavlic, Marion; Libiseller, Kathrin; Oberacher, Herbert

    2006-09-01

    The potential of the combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for the identification of therapeutic and illicit drugs has been evaluated. Reserpine was used for standardizing experimental conditions and for characterization of the performance of the applied mass spectrometric system. Experiments revealed that because of the mass accuracy, the stability of calibration, and the reproducibility of fragmentation, the QqTOF mass spectrometer is an appropriate platform for establishment of a tandem-mass-spectral library. Three-hundred and nineteen substances were used as reference samples to build the spectral library. For each reference compound, product-ion spectra were acquired at ten different collision-energy values between 5 eV and 50 eV. For identification of unknown compounds, a library search algorithm was developed. The closeness of matching between a measured product-ion spectrum and a spectrum stored in the library was characterized by a value called "match probability", which took into account the number of matched fragment ions, the number of fragment ions observed in the two spectra, and the sum of the intensity differences calculated for matching fragments. A large value for the match probability indicated a close match between the measured and the reference spectrum. A unique feature of the library search algorithm-an implemented spectral purification option-enables characterization of multi-contributor fragment-ion spectra. With the aid of this software feature, substances comprising only 1.0% of the total amount of binary mixtures were unequivocally assigned, in addition to the isobaric main contributors. The spectral library was successfully applied to the characterization of 39 forensic casework samples.

  2. Metabolomic screening using ESI-FT MS identifies potential radiation-responsive molecules in mouse urine

    International Nuclear Information System (INIS)

    Iizuka, Daisuke; Yoshioka, Susumu; Kawai, Hidehiko; Izumi, Shunsuke; Suzuki, Fumio; Kamiya, Kenji

    2017-01-01

    The demand for establishment of high-throughput biodosimetric methods is increasing. Our aim in this study was to identify low-molecular-weight urinary radiation-responsive molecules using electrospray ionization Fourier transform mass spectrometry (ESI-FT MS), and our final goal was to develop a sensitive biodosimetry technique that can be applied in the early triage of a radiation emergency medical system. We identified nine metabolites by statistical comparison of mouse urine before and 8 h after irradiation. Time-course analysis showed that, of these metabolites, thymidine and either thymine or imidazoleacetic acid were significantly increased dose-dependently 8 h after radiation exposure; these molecules have already been reported as potential radiation biomarkers. Phenyl glucuronide was significantly decreased 8 h after radiation exposure, irrespective of the dose. Histamine and 1-methylhistamine were newly identified by MS/MS and showed significant, dose-dependent increases 72 h after irradiation. Quantification of 1-methylhistamine by enzyme-linked immunosorbent assay (ELISA) analysis also showed a significant increase 72 h after 4 Gy irradiation. These results suggest that urinary metabolomics screening using ESI-FT MS can be a powerful tool for identifying promising radiation-responsive molecules, and that urinary 1-methylhistamine is a potential radiation-responsive molecule for acute, high-dose exposure.

  3. Environmental Sensitivity Index (ESI) Atlas: Delaware, New Jersey, Pennsylvania, maps and geographic information systems data (NODC Accession 0014793)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Delaware, New Jersey, and Pennsylvania from 1969 to 2000(May 2002 v.3). ESI data...

  4. Gulf-Wide Information System, Environmental Sensitivity Index Brackish Marsh, Geographic NAD83, LDWF (2001) [esi_brackish_marsh_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) brackish marshes data of coastal Louisiana. The ESI is a classification and ranking system, which...

  5. Gulf-Wide Information System, Environmental Sensitivity Index Intermediate Marsh, Geographic NAD83, LDWF (2001) [esi_intermediate_marsh_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) intermediate marshes data of coastal Louisiana. The ESI is a classification and ranking system, which...

  6. Gulf-Wide Information System, Environmental Sensitivity Index Oyster Leases, Geographic NAD83, LDWF (2001) [esi_oyster_lease_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) oyster leases data of coastal Louisiana. The ESI is a classification and ranking system, which...

  7. Efficient methods for isolating five phytochemicals from Gentiana macrophylla using high-performance countercurrent chromatography.

    Science.gov (United States)

    Rho, Taewoong; Jung, Mila; Lee, Min Won; Chin, Young-Won; Yoon, Kee Dong

    2016-12-01

    Efficient high-performance countercurrent chromatography methods were developed to isolate five typical compounds from the extracts of Gentiana macrophylla. n-Butanol-soluble extract of G. macrophylla contained three hydrophilic iridoids, loganic acid (1), swertiamarin (2) and gentiopicroside (3), and a chromene derivative, macrophylloside D (4) which were successfully isolated by flow rate gradient (1.5 mL/min in 0-60 min, 5.0 mL/min in 60-120 min), and consecutive flow rate gradient HPCCC using n-butanol/0.1% aqueous trifluoroacetic acid (1:1, v/v, normal phase mode) system. The yields of 1-4 were 22, 16, 122, and 6 mg, respectively, with purities over 97% in a flow rate gradient high-performance countercurrent chromatography, and consecutive flow rate gradient high-performance countercurrent chromatography gave 1, 2, 3 (54, 41, 348 mg, respectively, purities over 97%) and 4 (13 mg, purity at 95%) from 750 mg of sample. The main compound in methylene chloride soluble extract, 2-methoxyanofinic acid, was successfully separated by n-hexane/ethyl acetate/methanol/water (4:6:4:6, v/v/v/v, flow-rate: 4 mL/min, reversed phase mode) condition. The structures of five isolates were elucidated by 1 H, 13 C NMR and ESI-Q-TOF-MS spectroscopic data which were compared with previously reported values. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A highly sensitive method for quantification of iohexol

    DEFF Research Database (Denmark)

    Schulz, A.; Boeringer, F.; Swifka, J.

    2014-01-01

    -chromatography-electrospray-massspectrometry (LC-ESI-MS) approach using the multiple reaction monitoring mode for iohexol quantification. In order to test whether a significantly decreased amount of iohexol is sufficient for reliable quantification, a LC-ESI-MS approach was assessed. We analyzed the kinetics of iohexol in rats after application...... of different amounts of iohexol (15 mg to 150 1.tg per rat). Blood sampling was conducted at four time points, at 15, 30, 60, and 90 min, after iohexol injection. The analyte (iohexol) and the internal standard (iotha(amic acid) were separated from serum proteins using a centrifugal filtration device...... with a cut-off of 3 kDa. The chromatographic separation was achieved on an analytical Zorbax SB C18 column. The detection and quantification were performed on a high capacity trap mass spectrometer using positive ion ESI in the multiple reaction monitoring (MRM) mode. Furthermore, using real-time polymerase...

  9. Environmental Sensitivity Index (ESI) Atlas: Northwest Arctic, Alaska, volume 2, maps and geographic information systems data (NODC Accession 0046028)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Northwest Arctic, Alaska. ESI data characterize estuarine environments and wildlife by...

  10. Environmental Sensitivity Index (ESI) Atlas: US and British Virgin Islands, maps and geographic information systems data (NODC Accession 0002069)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife by their...

  11. A fast and sensitive method for the separation of carotenoids using ultra-high performance supercritical fluid chromatography-mass spectrometry.

    Science.gov (United States)

    Jumaah, Firas; Plaza, Merichel; Abrahamsson, Victor; Turner, Charlotta; Sandahl, Margareta

    2016-08-01

    In this study, a rapid and sensitive ultra-high performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS) method has been developed and partially validated for the separation of carotenoids within less than 6 min. Six columns of orthogonal selectivity were examined, and the best separation was obtained by using a 1-aminoanthracene (1-AA) column. The length of polyene chain as well as the number of hydroxyl groups in the structure of the studied carotenoids determines their differences in the physiochemical properties and thus the separation that is achieved on this column. All of the investigated carotenoids were baseline separated with resolution values greater than 1.5. The effects of gradient program, back pressure, and column temperature were studied with respect to chromatographic properties such as retention and selectivity. Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were compared in both positive and negative mode, using both direct infusion and hyphenated with UHPSFC. The ESI in positive mode provided the highest response. The coefficient of determination (R (2)) for all calibration curves were greater than 0.998. Limit of detection (LOD) was in the range of 2.6 and 25.2 ng/mL for α-carotene and astaxanthin, respectively, whereas limit of quantification (LOQ) was in the range of 7.8 and 58.0 ng/mL for α-carotene and astaxanthin, respectively. Repeatability and intermediate precision of the developed UHPSFC-MS method were determined and found to be RSD supercritical fluid extracts of microalgae and rosehip. Graphical Abstract Ultra-high performance supercritical fluid chromatography-a rapid separation method for the analysis of carotenoids in rosehip and microalgae samples.

  12. Environmental Sensitivity Index (ESI) Atlas: American Samoa, 2004 (NODC Accession 0002827)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Currently, the most widely used approach to sensitive environment mapping in the United States is the NOAA Environmental Sensitivity Index (ESI). This approach...

  13. Environmental Sensitivity Index (ESI) Atlas: Upper Texas Coast (NODC Accession 0046089)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This CD-ROM product from the NOAA National Ocean Service Hazardous Materials Response and Assessment Division contains the Environmental Sensitivity Index (ESI) data...

  14. Gulf-Wide Information System, Environmental Sensitivity Index Classification of the Outer Coast, Geographic NAD83, LDWF (2001) [esi_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains arcs representing the Environmental Sensitivity Index (ESI) classification of the outer coast of Louisiana. The ESI is a classification and...

  15. Horizontal Transfer of the Salmonella enterica Serovar Infantis Resistance and Virulence Plasmid pESI to the Gut Microbiota of Warm-Blooded Hosts

    Directory of Open Access Journals (Sweden)

    Gili Aviv

    2016-09-01

    Full Text Available Salmonella enterica serovar Infantis is one of the prevalent salmonellae worldwide. Recently, we showed that the emergence of S. Infantis in Israel was facilitated by the acquisition of a unique megaplasmid (pESI conferring multidrug resistance and increased virulence phenotypes. Here we elucidate the ecology, transmission properties, and regulation of pESI. We show that despite its large size (~280 kb, pESI does not impose a significant metabolic burden in vitro and that it has been recently fixed in the domestic S. Infantis population. pESI conjugation and the transcription of its pilus (pil genes are inhibited at the ambient temperature (27°C and by ≥1% bile but increased under temperatures of 37 to 41°C, oxidative stress, moderate osmolarity, and the microaerobic conditions characterizing the intestinal environment of warm-blooded animals. The pESI-encoded protein TraB and the oxygen homeostasis regulator Fnr were identified as transcriptional regulators of pESI conjugation. Using the mouse model, we show that following S. Infantis infection, pESI can be horizontally transferred to the gut microbiota, including to commensal Escherichia coli strains. Possible transfer, but not persistence, of pESI was also observed into Gram-positive mouse microbiota species, especially Lactobacillus reuteri. Moreover, pESI was demonstrated to further disseminate from gut microbiota to S. enterica serovar Typhimurium, in the context of gastrointestinal infection. These findings exhibit the ability of a selfish clinically relevant megaplasmid to distribute to and from the microbiota and suggest an overlooked role of the microbiota as a reservoir of mobile genetic elements and intermediator in the spread of resistance and virulence genes between commensals and pathogenic bacteria.

  16. Tandem mass spectrometry approach for the investigation of the steroidal metabolism: structure-fragmentation relationship (SFR) in anabolic steroids and their metabolites by ESI-MS/MS analysis.

    Science.gov (United States)

    Musharraf, Syed Ghulam; Ali, Arslan; Khan, Naik Tameem; Yousuf, Maria; Choudhary, Muhammad Iqbal; Atta-ur-Rahman

    2013-02-01

    Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to investigate the effect of different substitutions introduced during metabolism on fragmentation patterns of four anabolic steroids including methyltestosterone, methandrostenolone, cis-androsterone and adrenosterone, along with their metabolites. Collision-induced dissociation (CID) analysis was performed to correlate the major product ions of 19 steroids with structural features. The analysis is done to portray metabolic alteration, such as incorporation or reduction of double bonds, hydroxylations, and/or oxidation of hydroxyl moieties to keto functional group on steroidal skeleton which leads to drastically changed product ion spectra from the respective classes of steroids, therefore, making them difficult to identify. The comparative ESI-MS/MS study also revealed some characteristic peaks to differentiate different steroidal metabolites and can be useful for the unambiguous identification of anabolic steroids in biological fluid. Moreover, LC-ESI-MS/MS analysis of fermented extract of methyltestosterone, obtained by Macrophomina phaseolina was also investigated. Copyright © 2012 Elsevier Inc. All rights reserved.

  17. ESI-07 Rose Atoll, American Samoa 2003 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  18. ESI-PR21, Ciales, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  19. ESI-PR22, Corozal, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  20. ESI-PR64, Guayama, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  1. ESI-PR41 Naguabo, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  2. ESI-PR29, Mayaguez, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  3. ESI-PR30, Rosario, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-PR20, Florida, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-PR09, Manati, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-PR46, Yauco, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-PR11, Bayamon, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. ESI-PR18 Bayaney, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  9. ESI-PR56, Parguera, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  10. ESI-PR07, Arecibo, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  11. ESI-08,Swains Island, American Samoa 2003 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  12. ESI-PR13, Carolina, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  13. ESI-PR39 Juncos, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. ESI-PR35, Orocovis, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  15. ESI-PR06, Camuy, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  16. ESI-PR02, Aguadilla, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  17. Ultrahigh-performance liquid chromatography electrospray ionization Q-Orbitrap mass spectrometry for the analysis of 451 pesticide residues in fruits and vegetables: method development and validation.

    Science.gov (United States)

    Wang, Jian; Chow, Willis; Chang, James; Wong, Jon W

    2014-10-22

    This paper presents an application of ultrahigh-performance liquid chromatography electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap MS) for the determination of 451 pesticide residues in fruits and vegetables. Pesticides were extracted from samples using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure. UHPLC/ESI Q-Orbitrap MS in full MS scan mode acquired full MS data for quantification, and UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) (i.e., data-dependent scan mode) obtained product ion spectra for identification. UHPLC/ESI Q-Orbitrap MS quantification was achieved using matrix-matched standard calibration curves along with the use of isotopically labeled standards or a chemical analogue as internal standards to achieve optimal method accuracy. The method performance characteristics include overall recovery, intermediate precision, and measurement uncertainty evaluated according to a nested experimental design. For the 10 matrices studied, 94.5% of the pesticides in fruits and 90.7% in vegetables had recoveries between 81 and 110%; 99.3% of the pesticides in fruits and 99.1% of the pesticides in vegetables had an intermediate precision of ≤20%; and 97.8% of the pesticides in fruits and 96.4% of the pesticides in vegetables showed measurement uncertainty of ≤50%. Overall, the UHPLC/ESI Q-Orbitrap MS demonstrated acceptable performance for the quantification of pesticide residues in fruits and vegetables. The UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) along with library matching showed great potential for identification and is being investigated further for routine practice.

  18. New methodology for capillary electrophoresis with ESI-MS detection: Electrophoretic focusing on inverse electromigration dispersion gradient. High-sensitivity analysis of sulfonamides in waters

    Czech Academy of Sciences Publication Activity Database

    Malá, Zdeňka; Gebauer, Petr; Boček, Petr

    2016-01-01

    Roč. 935, SEP (2016), s. 249-257 ISSN 0003-2670 R&D Projects: GA ČR(CZ) GA16-09135S Institutional support: RVO:68081715 Keywords : electrophoretic focusing * CE-ESI-MS * capillary electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.950, year: 2016

  19. Novel molecular-level evidence of iodine binding to natural organic matter from Fourier transform ion cyclotron resonance mass spectrometry

    International Nuclear Information System (INIS)

    Xu, Chen; Chen, Hongmei; Sugiyama, Yuko; Zhang, Saijin; Li, Hsiu-Ping; Ho, Yi-Fang; Chuang, Chia-ying; Schwehr, Kathleen A.; Kaplan, Daniel I.; Yeager, Chris; Roberts, Kimberly A.; Hatcher, Patrick G.; Santschi, Peter H.

    2013-01-01

    Major fractions of radioiodine ( 129 I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios ( 2 or -HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on 129 I migration. Highlights: ► IO 3 − reduced by lignin-, tannin-like compounds/carboxylic-rich alicyclic molecules ► Condensed aromatic and lignin-like compounds generated after iodate-iodination ► Aliphatic and less aromatic compounds formed after iodide-iodination ► Organo-iodine identified as unsaturated hydrocarbons, lignin and protein ► Organo-iodine with low O/C ratios imply less environmental mobility

  20. Molecular diagnosis of bloodstream infections in onco-haematology patients with PCR/ESI-MS technology.

    Science.gov (United States)

    Jordana-Lluch, Elena; Rivaya, Belén; Marcó, Clara; Giménez, Montserrat; Quesada, Mª Dolores; Escobedo, Agustín; Batlle, Montserrat; Martró, Elisa; Ausina, Vicente

    2017-02-01

    Onco-haematological patients are prone to develop infections, and antibiotic prophylaxis may lead to negative blood cultures. Thus, the microbiological diagnosis and subsequent administration of a targeted antimicrobial therapy is often difficult. The goal of this study was to evaluate the usefulness of IRIDICA (PCR/ESI-MS technology) for the molecular diagnosis of bloodstream infections in this patient group. A total of 463 whole blood specimens from different sepsis episodes in 429 patients were analysed using the PCR/ESI-MS platform, comparing the results with those of blood culture and other clinically relevant information. The sensitivity of PCR/ESI-MS by specimen (excluding polymicrobial infections, n = 25) in comparison with blood culture was 64.3% overall, 69.0% in oncological patients, and 59.3% in haematological patients. When comparing with a clinical infection criterion, overall sensitivity rose to 74.7%, being higher in oncological patients (80.0%) than in haematological patients (67.7%). Thirty-one microorganisms isolated by culture were not detected by IRIDICA, whereas 42 clinically relevant pathogens not isolated by culture were detected moleculary. PCR/ESI-MS offers a reliable identification of pathogens directly from whole blood. While additional studies are needed to confirm our findings, the system showed a lower sensitivity in onco-haematological patients in comparison with previously reported results in patients from the Intensive Care Unit. Copyright © 2016 The British Infection Association. Published by Elsevier Ltd. All rights reserved.

  1. An UPLC-ESI-MS/MS Assay Using 6-Aminoquinolyl-N-Hydroxysuccinimidyl Carbamate Derivatization for Targeted Amino Acid Analysis: Application to Screening of Arabidopsis thaliana Mutants

    Directory of Open Access Journals (Sweden)

    Carolina Salazar

    2012-07-01

    Full Text Available In spite of the large arsenal of methodologies developed for amino acid assessment in complex matrices, their implementation in metabolomics studies involving wide-ranging mutant screening is hampered by their lack of high-throughput, sensitivity, reproducibility, and/or wide dynamic range. In response to the challenge of developing amino acid analysis methods that satisfy the criteria required for metabolomic studies, improved reverse-phase high-performance liquid chromatography-mass spectrometry (RPHPLC-MS methods have been recently reported for large-scale screening of metabolic phenotypes. However, these methods focus on the direct analysis of underivatized amino acids and, therefore, problems associated with insufficient retention and resolution are observed due to the hydrophilic nature of amino acids. It is well known that derivatization methods render amino acids more amenable for reverse phase chromatographic analysis by introducing highly-hydrophobic tags in their carboxylic acid or amino functional group. Therefore, an analytical platform that combines the 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC pre-column derivatization method with ultra performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS is presented in this article. For numerous reasons typical amino acid derivatization methods would be inadequate for large scale metabolic projects. However, AQC derivatization is a simple, rapid and reproducible way of obtaining stable amino acid adducts amenable for UPLC-ESI-MS/MS and the applicability of the method for high-throughput metabolomic analysis in Arabidopsis thaliana is demonstrated in this study. Overall, the major advantages offered by this amino acid analysis method include high-throughput, enhanced sensitivity and selectivity; characteristics that showcase its utility for the rapid screening of the preselected plant metabolites without compromising the quality of the

  2. An UPLC-ESI-MS/MS Assay Using 6-Aminoquinolyl-N-Hydroxysuccinimidyl Carbamate Derivatization for Targeted Amino Acid Analysis: Application to Screening of Arabidopsis thaliana Mutants.

    Science.gov (United States)

    Salazar, Carolina; Armenta, Jenny M; Shulaev, Vladimir

    2012-07-06

    In spite of the large arsenal of methodologies developed for amino acid assessment in complex matrices, their implementation in metabolomics studies involving wide-ranging mutant screening is hampered by their lack of high-throughput, sensitivity, reproducibility, and/or wide dynamic range. In response to the challenge of developing amino acid analysis methods that satisfy the criteria required for metabolomic studies, improved reverse-phase high-performance liquid chromatography-mass spectrometry (RPHPLC-MS) methods have been recently reported for large-scale screening of metabolic phenotypes. However, these methods focus on the direct analysis of underivatized amino acids and, therefore, problems associated with insufficient retention and resolution are observed due to the hydrophilic nature of amino acids. It is well known that derivatization methods render amino acids more amenable for reverse phase chromatographic analysis by introducing highly-hydrophobic tags in their carboxylic acid or amino functional group. Therefore, an analytical platform that combines the 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) pre-column derivatization method with ultra performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS) is presented in this article. For numerous reasons typical amino acid derivatization methods would be inadequate for large scale metabolic projects. However, AQC derivatization is a simple, rapid and reproducible way of obtaining stable amino acid adducts amenable for UPLC-ESI-MS/MS and the applicability of the method for high-throughput metabolomic analysis in Arabidopsis thaliana is demonstrated in this study. Overall, the major advantages offered by this amino acid analysis method include high-throughput, enhanced sensitivity and selectivity; characteristics that showcase its utility for the rapid screening of the preselected plant metabolites without compromising the quality of the metabolic data. The

  3. Environmental Sensitivity Index (ESI) Atlas: Prince William Sound, Alaska, Volumes 1 and 2, geographic information systems data (NODC Accession 0019218)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Prince William Sound, Alaska. ESI data characterize estuarine environments and wildlife by...

  4. Sample handling and contamination encountered when coupling offline normal phase high performance liquid chromatography fraction collection of petroleum samples to Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Oro, Nicole E; Whittal, Randy M; Lucy, Charles A

    2012-09-05

    Normal phase high performance liquid chromatography (HPLC) is used to separate a gas oil petroleum sample, and the fractions are collected offline and analyzed on a high resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FT-ICR MS). The separation prior to MS analysis dilutes the sample significantly; therefore the fractions need to be prepared properly to achieve the best signal possible. The methods used to prepare the HPLC fractions for MS analysis are described, with emphasis placed on increasing the concentration of analyte species. The dilution effect also means that contamination in the MS spectra needs to be minimized. The contamination from molecular sieves, plastics, soap, etc. and interferences encountered during the offline fraction collection process are described and eliminated. A previously unreported MS contamination of iron formate clusters with a 0.8 mass defect in positive mode electrospray is also described. This interference resulted from the stainless steel tubing in the HPLC system. Contamination resulting from what has tentatively been assigned as palmitoylglycerol and stearoylglycerol was also observed; these compounds have not previously been reported as contaminant peaks. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Verification of propofol sulfate as a further human propofol metabolite using LC-ESI-QQQ-MS and LC-ESI-QTOF-MS analysis.

    Science.gov (United States)

    Maas, Alexandra; Maier, Christoph; Michel-Lauter, Beate; Broecker, Sebastian; Madea, Burkhard; Hess, Cornelius

    2017-03-01

    Propofol (2,6-diisopropylphenol) is a water-insoluble, intravenous anesthetic that is widely used for the induction and maintenance of anesthesia as well as for endoscopic and pediatric sedation. After admission, propofol undergoes extensive hepatic and extrahepatic metabolism, including direct conjugation to propofol glucuronide and hydroxylation to 2,6-diisopropyl-1,4-quinol. The latter substance subsequently undergoes phase II metabolism, resulting in the formation of further metabolites (1quinolglucuronide, 4quinolglucuronide and 4quinol-sulfate). Further minor phase I propofol metabolites (2-(ω-propanol)-6-isopropylphenol and 2-(ω-propanol)-6-isopropyl-1,4-quinol)) are also described. Due to its chemical structure with the phenolic hydroxyl group, propofol is also an appropriate substrate for sulfation by sulfotransferases. The existence of propofol sulfate was investigated by liquid chromatography electrospray ionization triple quadrupole mass spectrometry (LCESIQQQ-MS) and liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LCESI-QTOF-MS). A propofol sulfate reference standard was used for identification and method development, yielding a precursor at m/z 257 (deprotonated propofol sulfate) and product ions at m/z 177 (deprotonated propofol) and m/z 80 ([SO3]-). Propofol sulfate - a further phase II metabolite of propofol - was verified in urine samples by LC-ESI-QQQ-MS and LC-ESI-QTOF-MS. Analyses of urine samples from five volunteers collected before and after propofol-induced sedation verified the presence of propofol sulfate in urine following propofol administration, whereas ascertained concentrations of this metabolite were significantly lower compared with detected propofol glucuronide concentrations. The existence of propofol sulfate as a further phase II propofol metabolite in humans could be verified by two different detection techniques (LCESIQQQ-MS and LC-ESI-QTOFMS) on the basis of a propofol sulfate

  6. HepG2 cells biospecific extraction and HPLC-ESI-MS analysis for screening potential antiatherosclerotic active components in Bupeuri radix.

    Science.gov (United States)

    Liu, Shuqiang; Tan, Zhibin; Li, Pingting; Gao, Xiaoling; Zeng, Yuaner; Wang, Shuling

    2016-03-20

    HepG2 cells biospecific extraction method and high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) analysis was proposed for screening of potential antiatherosclerotic active components in Bupeuri radix, a well-known Traditional Chinese Medicine (TCM). The hypothesis suggested that when cells are incubated together with the extracts of TCM, the potential bioactive components in the TCM should selectively combine with the receptor or channel of HepG2 cells, then the eluate which contained biospecific component binding to HepG2 cells was identified using HPLC-ESI-MS analysis. The potential bioactive components of Bupeuri radix were investigated using the proposed approach. Five compounds in the saikosaponins of Bupeuri radix were detected as these components selectively combined with HepG2 cells, among these compounds, two potentially bioactive compounds namely saikosaponin b1 and saikosaponin b2 (SSb2) were identified by comparing with the chromatography of the standard sample and analysis of the structural clearance characterization of MS. Then SSb2 was used to assess the uptake of DiI-high density lipoprotein (HDL) in HepG2 cells for antiatherosclerotic activity. The results have showed that SSb2, with indicated concentrations (5, 15, 25, and 40 μM) could remarkably uptake dioctadecylindocarbocyanine labeled- (DiI) -HDL in HepG2 cells (Vs control group, *PESI-MS analysis is a rapid, convenient, and reliable method for screening potential bioactive components in TCM and SSb2 may be a valuable novel drug agent for the treatment of atherosclerosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Environmental Sensitivity Index (ESI) Atlas: U.S. and British Virgin Islands maps and geographic information systems data (NODC Accession 0049955)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises an update of the Environmental Sensitivity Index (ESI) data for the Virgin Islands. ESI data characterize estuarine environments and wildlife...

  8. Simultaneous Determination of Fifteen Constituents of Jitai Tablet Using Ultra High-Performance Liquid Chromatography Coupled with Triple Quadrupole Electrospray Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Shuping Wang

    2014-01-01

    Full Text Available An ultra-high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS method was developed for simultaneous determination of fifteen constituents in Jitai tablet (JTT, a complex Traditional Chinese Medicine prescription (TCMP used in treating opiate addiction. Benefitting from a small particle size (1.8 µm C18 column, accelerated analysis with satisfactory resolution, sensitivity and selectivity were achieved in a single run within 7 min with linear gradient elution of acetonitrile-0.1% (v/v formic acid in water. The analytical signal was obtained by multiple reaction monitoring transitions via electrospray ionization source operating in both positive and negative ionization mode. The approach was validated for linearity, sensitivity, precision, repeatability, stability and recovery. All analytes showed good linearity over a wide concentration range (r > 0.99. The method limits ranged from 0.03 ng/mL to 19.35 ng/mL which are sensitive enough for quality control studies. The developed method was successfully applied to the simultaneous determination of fifteen constituents in JTT. In conclusion, our experimental results demonstrate that UHPLC-ESI-MS/MS is a useful approach for the overall quality assessment of complex TCMPs.

  9. Qualitative and Quantitative Analysis of Rhizoma Smilacis glabrae by Ultra High Performance Liquid Chromatography Coupled with LTQ OrbitrapXL Hybrid Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Shao-Dan Chen

    2014-07-01

    Full Text Available Rhizoma Smilacis glabrae, a traditional Chinese medicine (TCM as well as a functional food, has been commonly used for detoxification treatments, relieving dampness and as a diuretic. In order to quickly define the chemical profiles and control the quality of Smilacis glabrae, ultra high performance liquid chromatography coupled with electrospray ionization hybrid linear trap quadrupole orbitrap mass spectrometry (UHPLC-ESI/LTQ-Orbitrap-MS was applied for simultaneous identification and quantification of its bioactive constituents. A total of 56 compounds, including six new compounds, were identified or tentatively deduced on the basis of their retention behaviors, mass spectra, or by comparison with reference substances and literature data. The identified compounds belonged to flavonoids, phenolic acids and phenylpropanoid glycosides. In addition, an optimized UHPLC-ESI/LTQ-Orbitrap-MS method was established for quantitative determination of six marker compounds from five batches. The validation of the method, including linearity, sensitivity (LOQ, precision, repeatability and spike recoveries, was carried out and demonstrated to be satisfied the requirements of quantitative analysis. The results suggested that the established method would be a powerful and reliable analytical tool for the characterization of multi-constituent in complex chemical system and quality control of TCM.

  10. Comparison of different tandem mass spectrometric techniques (ESI-IT, ESI- and IP-MALDI-QRTOF and vMALDI-TOF/RTOF) for the analysis of crocins and picrocrocin from the stigmas of Crocus sativus L.

    Science.gov (United States)

    Koulakiotis, Nikolaos Stavros; Pittenauer, Ernst; Halabalaki, Maria; Tsarbopoulos, Anthony; Allmaier, Günter

    2012-03-30

    The expensive spice saffron originating from the stigmas of Crocus sativus L. and also applied in traditional Chinese medicine (TCM) constitutes a complex mixture of glycoconjugates varying not only in the aglycon structure, but also in glycosylation pattern. Therefore, various tandem mass spectrometric techniques were evaluated for their usefulness in structural elucidation. Three selected constituents of the stigmas of Crocus sativus L., trans- and cis-crocin-4 as well as picrocrocin, were isolated and purified by HPLC and finally analyzed by ESI-MS (ion trap, QqRTOF), IP-MALDI-MS (QqRTOF) and vMALDI-MS (TOF/RTOF) in combination with tandem mass spectrometry in collision energy regimes ranging from a few eV (LE) to 20 keV (HE) collisions for the first time. These data aid in structurally elucidating minor, unknown glycoconjugates originating from this plant-derived spice. LE-CID of isomeric crocins on either an ion trap with ESI or a QqRTOF-instrument with ESI or IP-MALDI as desorption/ionization technique only yielded a limited number of structurally diagnostic sodiated product ions related to the carbohydrate moiety as well as to the intact aglycon in contrast to true HE-CID. The low MW constituent picrocrocin did not yield useful LE-CID spectra, but showed a high number of structurally diagnostic product ions by HE-CID utilizing a vMALDI TOF/RTOF-instrument. The highest number of structurally diagnostic product ions allowing also determination of the carbohydrate linkage of the gentiobiose-moiety of isomeric crocins ((0,4)A(2), (3,5)A(2) product ions indicating a 1→6 carbohydrate linkage) was only achievable by HE-CID. Fragmentation of the aglycon was not observed by any collision energy regime applied. Copyright © 2012 John Wiley & Sons, Ltd.

  11. Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

    Science.gov (United States)

    Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-08-28

    The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.

  12. Determining the degradation efficiency and mechanisms of ethyl violet using HPLC-PDA-ESI-MS and GC-MS

    Directory of Open Access Journals (Sweden)

    Chung Wen-Hsin

    2012-06-01

    Full Text Available Abstract Background The discharge of wastewater that contains high concentrations of reactive dyes is a well-known problem associated with dyestuff activities. In recent years, semiconductor photocatalysis has become more and more attractive and important since it has a great potential to contribute to such environmental problems. One of the most important aspects of environmental photocatalysis is in the selection of semiconductor materials like ZnO and TiO2, which are close to being two of the ideal photocatalysts in several respects. For example, they are relatively inexpensive, and they provide photo-generated holes with high oxidizing power due to their wide band gap energy. In this work, nanostructural ZnO film on the Zn foil of the Alkaline-Manganese Dioxide-Zinc Cell was fabricated to degrade EV dye. The major innovation of this paper is to obtain the degradation mechanism of ethyl violet dyes resulting from the HPLC-PDA-ESI-MS analyses. Results The fabrication of ZnO nanostructures on zinc foils with a simple solution-based corrosion strategy and the synthesis, characterization, application, and implication of Zn would be reported in this study. Other objectives of this research are to identify the reaction intermediates and to understand the detailed degradation mechanism of EV dye, as model compound of triphenylmethane dye, with active Zn metal, by HPLC-ESI-MS and GC-MS. Conclusions ZnO nanostructure/Zn-foils had an excellent potential for future applications on the photocatalytic degradation of the organic dye in the environmental remediation. The intermediates of the degradation process were separated and characterized by the HPLC-PDA-ESI-MS and GC-MS, and twenty-six intermediates were characterized in this study. Based on the variation of the amount of intermediates, possible degradation pathways for the decolorization of dyes are also proposed and discussed.

  13. Simultaneous detection of six urinary pteridines and creatinine by high-performance liquid chromatography-tandem mass spectrometry for clinical breast cancer detection.

    Science.gov (United States)

    Burton, Casey; Shi, Honglan; Ma, Yinfa

    2013-11-19

    Recent preliminary studies have implicated urinary pteridines as candidate biomarkers in a growing number of malignancies including breast cancer. While the developments of capillary electrophoresis-laser induced fluorescence (CE-LIF), high performance liquid chromatography (HPLC), and liquid chromatography-mass spectroscopy (LC-MS) pteridine urinalyses among others have helped to enable these findings, limitations including poor pteridine specificity, asynchronous or nonexistent renal dilution normalization, and a lack of information regarding adduct formation in mass spectrometry techniques utilizing electrospray ionization (ESI) have prevented application of these techniques to a larger clinical setting. In this study, a simple, rapid, specific, and sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method has been developed and optimized for simultaneous detection of six pteridines previously implicated in breast cancer and creatinine as a renal dilution factor in urine. In addition, this study reports cationic adduct formation of urinary pteridines under ESI-positive ionization for the first time. This newly developed technique separates and detects the following six urinary pteridines: 6-biopterin, 6-hydroxymethylpterin, d-neopterin, pterin, isoxanthopterin, and xanthopterin, as well as creatinine. The method detection limit for the pteridines is between 0.025 and 0.5 μg/L, and for creatinine, it is 0.15 μg/L. The method was also validated by spiked recoveries (81-105%), reproducibility (RSD: 1-6%), and application to 25 real urine samples from breast cancer positive and negative samples through a double-blind study. The proposed technique was finally compared directly with a previously reported CE-LIF technique, concluding that additional or alternative renal dilution factors are needed for proper investigation of urinary pteridines as breast cancer biomarkers.

  14. ESI-MSn and LC-ESI-MS studies to characterize forced degradation products of bosentan and a validated stability-indicating LC-UV method.

    Science.gov (United States)

    Bansal, Gulshan; Singh, Ranjit; Saini, Balraj; Bansal, Yogita

    2013-01-01

    The present study reports the characterization of forced degradation products of bosentan and a validated stability-indicating HPLC method for the stability testing of bosentan tablets. The forced degradation was carried out under the conditions of hydrolysis, oxidation, dry heat and photolysis. The drug was found unstable in acid, alkali and oxidative media whereas stable to the hydrolysis in water, to dry heat and to photolysis. In total, six degradation products were formed in all conditions which were resolved in a single run on a C-18 column with gradient elution using ammonium acetate buffer (pH 4.5, 5.0mM), methanol and acetonitrile. Structures of all the degradation products were characterized through +ESI-MS(n) and LC-ESI-MS spectral data of bosentan as well as LC-ESI-MS spectral data of the products. The products II-VI were characterized as 6-amino-[2,2']bipyrimidinyl-4,5-diol, 6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-ol, 2-[6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yloxy]-ethanol, 4-tert-butyl-N-[6-(1-methoxyethoxy)-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yl]-benzenesulfonamide and 4-tert-butyl-N-[6-hydroxy-5-(2-methoxyphenoxy)-[2,2']bipyrimidinyl-4-yl]-benzenesulfonamide, respectively. The peak of the product I was found to be due to two secondary degradation products which co-eluted and were characterized as β-hydroxyethyl p-tert-butylphenylsulfonate (Ia) and 2-[2-(2-hydroxyethoxy)-phenoxy]-ethanol (Ib). These products were formed due to hydrolysis of sulfonamide and alkylaryl ether and the diaryl ether linkages as well as dehydration of the primary alcohol group. The most probable degradation mechanisms were proposed. The HPLC method was found to be stability-indicating, linear (2-100 μg ml(-1)), accurate, precise, sensitive, specific, rugged and robust for quantitation of the drug. The method was applied to the stability testing of the commercially available bosentan tablets successfully. Copyright © 2012 Elsevier B.V. All

  15. Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

    Science.gov (United States)

    Stinson, Craig A.; Xia, Yu

    2014-07-01

    In biological systems, carbon-centered small molecule radicals are primarily formed via external radiation or internal radical reactions. These radical species can react with a variety of biomolecules, most notably nucleic acids, the consequence of which has possible links to gene mutation and cancer. Sulfur-containing peptides and proteins are reactive toward a variety of radical species and many of them behave as radical scavengers. In this study, the reactions between alkyl alcohol carbon-centered radicals (e.g., •CH2OH for methanol) and cysteinyl peptides within a nanoelectrospray ionization (nanoESI) plume were explored. The reaction system involved ultraviolet (UV) irradiation of a nanoESI plume using a low pressure mercury lamp consisting of 185 and 254 nm emission bands. The alkyl alcohol was added as solvent into the nanoESI solution and served as the precursor of hydroxyalkyl radicals upon UV irradiation. The hydroxyalkyl radicals subsequently reacted with cysteinyl peptides either containing a disulfide linkage or free thiol, which led to the formation of peptide- S-hydroxyalkyl product. This radical reaction coupled with subsequent MS/MS was shown to have analytical potential by cleaving intrachain disulfide linked peptides prior to CID to enhance sequence information. Tandem mass spectrometry via collision-induced dissociation (CID), stable isotope labeling, and accurate mass measurement were employed to verify the identities of the reaction products.

  16. Environmental Sensitivity Index (ESI) Atlas: South Florida, July 1996 (NODC Accession 0006539)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps in Portable Document Format (.PDF) for the shoreline of South Florida (to encompass the...

  17. Cook Inlet and Kenai Peninsula, Alaska ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for Cook Inlet...

  18. Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures - Application to the petroleomic analysis of bio-oils.

    Science.gov (United States)

    Hertzog, Jasmine; Carré, Vincent; Le Brech, Yann; Mackay, Colin Logan; Dufour, Anthony; Mašek, Ondřej; Aubriet, Frédéric

    2017-05-29

    The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C x H y O z with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. HPLC-DAD-ESI-MS Analysis of Flavonoids from Leaves of Different Cultivars of Sweet Osmanthus.

    Science.gov (United States)

    Wang, Yiguang; Fu, Jianxin; Zhang, Chao; Zhao, Hongbo

    2016-09-14

    Osmanthus fragrans Lour. has traditionally been a popular ornamental plant in China. In this study, ethanol extracts of the leaves of four cultivar groups of O. fragrans were analyzed by high-performance liquid chromatography coupled with diode array detection (HPLC-DAD) and high-performance liquid chromatography with electrospray ionization and mass spectrometry (HPLC-ESI-MS). The results suggest that variation in flavonoids among O. fragrans cultivars is quantitative, rather than qualitative. Fifteen components were detected and separated, among which, the structures of 11 flavonoids and two coumarins were identified or tentatively identified. According to principal component analysis (PCA) and hierarchical cluster analysis (HCA) based on the abundance of these components (expressed as rutin equivalents), 22 selected cultivars were classified into four clusters. The seven cultivars from Cluster III ('Xiaoye Sugui', 'Boye Jingui', 'Wuyi Dangui', 'Yingye Dangui', 'Danzhuang', 'Foding Zhu', and 'Tianxiang Taige'), which are enriched in rutin and total flavonoids, and 'Sijigui' from Cluster II which contained the highest amounts of kaempferol glycosides and apigenin 7-O-glucoside, could be selected as potential pharmaceutical resources. However, the chemotaxonomy in this paper does not correlate with the distribution of the existing cultivar groups, demonstrating that the distribution of flavonoids in O. fragrans leaves does not provide an effective means of classification for O. fragrans cultivars based on flower color.

  20. Analysis of antioxidants in insulation cladding of copper wire: a comparison of different mass spectrometric techniques (ESI-IT, MALDI-RTOF and RTOF-SIMS).

    Science.gov (United States)

    Schnöller, Johannes; Pittenauer, Ernst; Hutter, Herbert; Allmaier, Günter

    2009-12-01

    Commercial copper wire and its polymer insulation cladding was investigated for the presence of three synthetic antioxidants (ADK STAB AO412S, Irganox 1010 and Irganox MD 1024) by three different mass spectrometric techniques including electrospray ionization-ion trap-mass spectrometry (ESI-IT-MS), matrix-assisted laser desorption/ionization reflectron time-of-flight (TOF) mass spectrometry (MALDI-RTOF-MS) and reflectron TOF secondary ion mass spectrometry (RTOF-SIMS). The samples were analyzed either directly without any treatment (RTOF-SIMS) or after a simple liquid/liquid extraction step (ESI-IT-MS, MALDI-RTOF-MS and RTOF-SIMS). Direct analysis of the copper wire itself or of the insulation cladding by RTOF-SIMS allowed the detection of at least two of the three antioxidants but at rather low sensitivity as molecular radical cations and with fairly strong fragmentation (due to the highly energetic ion beam of the primary ion gun). ESI-IT- and MALDI-RTOF-MS-generated abundant protonated and/or cationized molecules (ammoniated or sodiated) from the liquid/liquid extract. Only ESI-IT-MS allowed simultaneous detection of all three analytes in the extract of insulation claddings. The latter two so-called 'soft' desorption/ionization techniques exhibited intense fragmentation only by applying low-energy collision-induced dissociation (CID) tandem MS on a multistage ion trap-instrument and high-energy CID on a tandem TOF-instrument (TOF/RTOF), respectively. Strong differences in the fragmentation behavior of the three analytes could be observed between the different CID spectra obtained from either the IT-instrument (collision energy in the very low eV range) or the TOF/RTOF-instrument (collision energy 20 keV), but both delivered important structural information. Copyright 2009 John Wiley & Sons, Ltd.

  1. ESI-05, Ofu & Olosega Islands, American Samoa 2003 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  2. ESI-PR61, Santa Isabel, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  3. ESI-PR26, El Yunque, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-HI95 Midway Islands, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-PR12, San Juan, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-PR65, Punta Tuna, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-HI90 Gardner Pinnacles, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. ESI-HI92 Laysan Island, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  9. ESI-HI91 Maro Reef, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  10. ESI-03, Tutuila Island - South, American Samoa 2003 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  11. ESI-PR43, Puerto Real, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  12. ESI-PR59, Punta Cuchara , Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  13. ESI-HI93 Lisianski Island, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. ESI-PR24, Aguas Buenas, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  15. ESI-PR55, Cabo Rojo, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  16. ESI-PR49, Rio Descalabrado, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  17. Environmental Sensitivity Index (ESI) Atlas: Great Lakes, 1995-1998 (NODC Accession 0013820)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps in .PDF format for the following Great Lakes and associated waterways: north, east, and west...

  18. Guam and the Northern Mariana Islands ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for Guam and the...

  19. Relationships between Molecular Composition and Optical Properties of Dissolved Organic Matter

    Science.gov (United States)

    Cooper, W. T.; Tfaily, M.; Osborne, D.; Paul, A.; Podgorski, D. C.; Corbett, J.; Chanton, J.

    2009-12-01

    Our focus is on the relationships between the optical properties of dissolved organic matter (DOM) and its molecular composition. For example, we demonstrated that changes in the absorption and fluorescence characteristics of DOM in outwelling from Brazilian mangrove forests correlated with decreases in highly unsaturated organic compounds as DOM was transported from mangrove porewaters to the continental shelf. In that work we combined ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) that provided detailed compositional information with absorption and Excitation/Emission Matrix (EEM) spectroscopy This presentation will highlight new results utilizing the combination of optical spectroscopy and FT-ICR mass spectrometry to illuminate the processes which control DOM cycling. Our focus will be on the contributions of the heteroatom components of DOM (i.e. organic sulfur and organic nitrogen) to its optical properties and how changes in optical properties correlate with important environmental processes like humification and bioavailability. Figure 1 below includes a narrow 0.20 Dalton window from a mass spectrum which demonstrates the ability of ultrahigh resolution mass spectrometry to resolve and identify nitrogen heteroatom compounds in DOM. Our study sites include the Glacial Lake Agassiz Peatlands (GLAP) in northern Minnesota and wetlands in the Caloosahatchee River basin in South Florida. Figure 1. Isolated 0.20 Da window of an ESI-FT-ICR mass spectrum of DOM from a GLAP bog. Labels identify N1 (d,e,f) and N3 classes of nitrogen heteroatoms. The 0.0031 Da mass spacing is used to confirm the N3 class.

  20. Gulf-Wide Information System, Environmental Sensitivity Index Scrub-Shrub and Wetlands, Geographic NAD83, LDWF (2001) [esi_scrub-shrub_wetland_LDWF_2001

    Data.gov (United States)

    Louisiana Geographic Information Center — This data set contains Environmental Sensitivity Index (ESI) scrub-shrub and wetlands data of coastal Louisiana. The ESI is a classification and ranking system,...

  1. LC-ESI/MS/MS method for rapid screening and confirmation of 44 exogenous anabolic steroids in human urine.

    Science.gov (United States)

    Jeon, Byoung Wook; Yoo, Hye Hyun; Jeong, Eun Sook; Kim, Ho Jun; Jin, Changbae; Kim, Dong Hyun; Lee, Jaeick

    2011-09-01

    A sensitive and rapid method based on liquid chromatography-triple-quadrupole tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) has been developed and validated for the screening and confirmation of 44 exogenous anabolic steroids (29 parent steroids and 15 metabolites) in human urine. The method involves an enzymatic hydrolysis, liquid-liquid extraction, and detection by LC-MS/MS. A triple-quadrupole mass spectrometer was operated in positive ESI mode with selected reaction monitoring (SRM) mode for the screening and product ion scan mode for the confirmation. The protonated molecular ions were used as precursor ions for the SRM analysis and product ion scan. The intraday and interday precisions of the target analytes at concentrations of the minimum required performance levels for the screening were 2-14% and 2-15%, respectively. The limits of detection for the screening and confirmation method were 0.1-10 ng/mL and 0.2-10 ng/mL, respectively, for 44 steroids. This method was successfully applied to analysis of urine samples from suspected anabolic steroid abusers.

  2. History and General Introduction

    International Nuclear Information System (INIS)

    Dunbar, R.C.

    1991-01-01

    In the domain of analytical mass spectrometry (MS), FT-ICR's place is established as combining particular advantages of extraordinary mass resolution and accuracy, a wide array of sample-ionization techniques, and a uniquely wide range of methods for structure characterization of the primary sample ions. Costs are already attractive compared with other high-performance alternatives, and as both magnets and computers (which comprise much of the expense of FT-ICR hardware) become cheaper and more powerful, the performance/cost ratio for the technique will continue to improve. This paper will provide an introduction to those who have little previous knowledge of the technique; provide an overview of the technique's outstanding areas of scientific and analytical application; and provide some historical perspective on how we reached the present state of the art

  3. Determination of Ten Corticosteroids in Illegal Cosmetic Products by a Simple, Rapid, and High-Performance LC-MS/MS Method

    Directory of Open Access Journals (Sweden)

    Vita Giaccone

    2017-01-01

    Full Text Available The aim of our present work was the development of a rapid high-performance liquid chromatography method with electrospray ionization and tandem mass spectrometry detection (LC-ESI-MS/MS for the determination of several corticosteroids in cosmetic products. Corticosteroids are suspected to be illegally added in cosmetic preparations in order to enhance the curative effect against some skin diseases. Sample preparation step consists in a single extraction with acetonitrile followed by centrifugation and filtration. The compounds were separated by reversed-phase chromatography with water and acetonitrile (both with 0.1% formic acid gradient elution and detected by ESI-MS positive and negative ionization mode. The method was validated at the validation level of 0.1 mg kg−1. Linearity was studied in the 5–250 μg L−1 range and linear coefficients (r2 were all over 0.99. The accuracy and precision of the method were satisfactory. The LOD ranged from 0.085 to 0.109 mg kg−1 and the LOQ from 0.102 to 0.121 mg kg−1. Mean recoveries for all the analytes were within the range 91.9–99.2%. The developed method is sensitive and useful for detection, quantification, and confirmation of these corticosteroids in cosmetic preparations and can be applied in the analysis of the suspected samples under investigation.

  4. Establish an automated flow injection ESI-MS method for the screening of fragment based libraries: Application to Hsp90.

    Science.gov (United States)

    Riccardi Sirtori, Federico; Caronni, Dannica; Colombo, Maristella; Dalvit, Claudio; Paolucci, Mauro; Regazzoni, Luca; Visco, Carlo; Fogliatto, Gianpaolo

    2015-08-30

    ESI-MS is a well established technique for the study of biopolymers (nucleic acids, proteins) and their non covalent adducts, due to its capacity to detect ligand-target complexes in the gas phase and allows inference of ligand-target binding in solution. In this article we used this approach to investigate the interaction of ligands to the Heat Shock Protein 90 (Hsp90). This enzyme is a molecular chaperone involved in the folding and maturation of several proteins which has been subjected in the last years to intensive drug discovery efforts due to its key role in cancer. In particular, reference compounds, with a broad range of dissociation constants from 40pM to 100μM, were tested to assess the reliability of ESI-MS for the study of protein-ligand complexes. A good agreement was found between the values measured with a fluorescence polarization displacement assay and those determined by mass spectrometry. After this validation step we describe the setup of a medium throughput screening method, based on ESI-MS, suitable to explore interactions of therapeutic relevance biopolymers with chemical libraries. Our approach is based on an automated flow injection ESI-MS method (AFI-MS) and has been applied to screen the Nerviano Medical Sciences proprietary fragment library of about 2000 fragments against Hsp90. In order to discard false positive hits and to discriminate those of them interacting with the N-terminal ATP binding site, competition experiments were performed using a reference inhibitor. Gratifyingly, this group of hits matches with the ligands previously identified by NMR FAXS techniques and confirmed by X-ray co-crystallization experiments. These results support the use of AFI-MS for the screening of medium size libraries, including libraries of small molecules with low affinity typically used in fragment based drug discovery. AFI-MS is a valid alternative to other techniques with the additional opportunities to identify compounds interacting with

  5. Chemical Differentiation of Dendrobium officinale and Dendrobium devonianum by Using HPLC Fingerprints, HPLC-ESI-MS, and HPTLC Analyses

    Science.gov (United States)

    Ye, Zi; Dai, Jia-Rong; Zhang, Cheng-Gang; Lu, Ye; Wu, Lei-Lei; Gong, Amy G. W.; Wang, Zheng-Tao

    2017-01-01

    The stems of Dendrobium officinale Kimura et Migo (Dendrobii Officinalis Caulis) have a high medicinal value as a traditional Chinese medicine (TCM). Because of the limited supply, D. officinale is a high priced TCM, and therefore adulterants are commonly found in the herbal market. The dried stems of a closely related Dendrobium species, Dendrobium devonianum Paxt., are commonly used as the substitute; however, there is no effective method to distinguish the two Dendrobium species. Here, a high performance liquid chromatography (HPLC) method was successfully developed and applied to differentiate D. officinale and D. devonianum by comparing the chromatograms according to the characteristic peaks. A HPLC coupled with electrospray ionization multistage mass spectrometry (HPLC-ESI-MS) method was further applied for structural elucidation of 15 flavonoids, 5 phenolic acids, and 1 lignan in D. officinale. Among these flavonoids, 4 flavonoid C-glycosides were firstly reported in D. officinale, and violanthin and isoviolanthin were identified to be specific for D. officinale compared with D. devonianum. Then, two representative components were used as chemical markers. A rapid and reliable high performance thin layer chromatography (HPTLC) method was applied in distinguishing D. officinale from D. devonianum. The results of this work have demonstrated that these developed analytical methods can be used to discriminate D. officinale and D. devonianum effectively and conveniently. PMID:28769988

  6. Cook Inlet and Kenai Peninsula, Alaska ESI: ROAD_MRK (Road Number Points)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector points used in plotting the road numbers on the summary maps. It comprises a portion of the Environmental Sensitivity Index (ESI) data...

  7. Improved ultra-performance liquid chromatography with electrospray ionization quadrupole-time-of-flight high-definition mass spectrometry method for the rapid analysis of the chemical constituents of a typical medical formula: Liuwei Dihuang Wan.

    Science.gov (United States)

    Wang, Ping; Lv, Hai tao; Zhang, Ai hua; Sun, Hui; Yan, Guang li; Han, Ying; Wu, Xiu hong; Wang, Xi jun

    2013-11-01

    Liuwei Dihuang Wan (LDW), a classic Chinese medicinal formula, has been used to improve or restore declined functions related to aging and geriatric diseases, such as impaired mobility, vision, hearing, cognition, and memory. It has attracted increasing attention as one of the most popular and valuable herbal medicines. However, the systematic analysis of the chemical constituents of LDW is difficult and thus has not been well established. In this paper, a rapid, sensitive, and reliable ultra-performance LC with ESI quadrupole TOF high-definition MS method with automated MetaboLynx analysis in positive and negative ion mode was established to characterize the chemical constituents of LDW. The analysis was performed on a Waters UPLC™ HSS T3 using a gradient elution system. MS/MS fragmentation behavior was proposed for aiding the structural identification of the components. Under the optimized conditions, a total of 50 peaks were tentatively characterized by comparing the retention time and MS data. It is concluded that a rapid and robust platform based on ultra-performance LC with ESI quadrupole TOF high-definition MS has been successfully developed for globally identifying multiple constituents of traditional Chinese medicine prescriptions. This is the first report on the systematic analysis of the chemical constituents of LDW. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The 4-pyridylmethyl ester as a protecting group for glutamic and aspartic acids: 'flipping' peptide charge states for characterization by positive ion mode ESI-MS.

    Science.gov (United States)

    Garapati, Sriramya; Burns, Colin S

    2014-03-01

    Use of the 4-pyridylmethyl ester group for side-chain protection of glutamic acid residues in solid-phase peptide synthesis enables switching of the charge state of a peptide from negative to positive, thus making detection by positive ion mode ESI-MS possible. The pyridylmethyl ester moiety is readily removed from peptides in high yield by hydrogenation. Combining the 4-pyridylmethyl ester protecting group with benzyl ester protection reduces the number of the former needed to produce a net positive charge and allows for purification by RP HPLC. This protecting group is useful in the synthesis of highly acidic peptide sequences, which are often beset by problems with purification by standard RP HPLC and characterization by ESI-MS. Copyright © 2014 European Peptide Society and John Wiley & Sons, Ltd.

  9. Environmental Sensitivity Index (ESI) Atlas: Florida 1995-1997 maps in portable document format (pdf) and geographic information systems data (NODC Accession 0014187)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — ESI data characterize coastal environments and wildlife by their sensitivity to spilled oil. The ESI data include information for three main components: shoreline...

  10. Chemical profiling analysis of Maca using UHPLC-ESI-Orbitrap MS coupled with UHPLC-ESI-QqQ MS and the neuroprotective study on its active ingredients

    Science.gov (United States)

    Zhou, Yanyan; Li, Peng; Brantner, Adelheid; Wang, Hongjie; Shu, Xinbin; Yang, Jian; Si, Nan; Han, Lingyu; Zhao, Haiyu; Bian, Baolin

    2017-03-01

    Lepidium meyenii (Maca), originated from Peru, has been cultivated widely in China as a popular health care food. However, the chemical and effective studies of Maca were less in-depth, which restricted its application seriously. To ensure the quality of Maca, a feasible and accurate strategy was established. One hundred and sixty compounds including 30 reference standards were identified in 6 fractions of methanol extract of Maca by UHPLC-ESI-Orbitrap MS. Among them, 15 representative active compounds were simultaneously determined in 17 samples by UHPLC-ESI-QqQ MS. The results suggested that Maca from Yunnan province was the potential substitute for the one from Peru. Meanwhile, the neuroprotective effects of Maca were investigated. Three fractions and two pure compounds showed strong activities in the 1-methyl-4-phenyl-1, 2, 3, 6-tetrahydropyridine (MPTP)-induced zebrafish model. Among them, 80% methanol elution fraction (Fr5) showed significant neuroprotective activity, followed by 100% part (Fr6). The inhibition of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) was a possible mechanism of its neuroprotective effect.

  11. Isolation by pressurised fluid extraction (PFE) and identification using CPC and HPLC/ESI/MS of phenolic compounds from Brazilian cherry seeds (Eugenia uniflora L.).

    Science.gov (United States)

    Oliveira, Alessandra L; Destandau, Emilie; Fougère, Laëtitia; Lafosse, Michel

    2014-02-15

    Brazilian cherry seeds are a waste product from juice and frozen pulp production and, the seeds composition was investigated to valorize this by-product. Compounds separation was performed with ethanol by pressurised fluid extraction (PFE). Here we determine the effect of temperature (T), static time (ST), number of cycles (C), and flush volume (VF) on the yield, composition and total phenolic content (TPC) of the seed extracts. T, ST and their interaction positively influenced yield and TPC. Extracts were fractionated by high performance liquid chromatography (HPLC) and centrifugal partition chromatography (CPC). The collected fractions characterizations were made by electrospray ionisation mass spectrometry (ESI/MS) and high resolution mass spectrometry (HRMS) indicated the presence of ellagic acid pentoside and deoxyhexose, quercitrin and kaempferol pentoside. All of these compounds have antioxidant properties and normally are found in plant extracts. These results confirm that Brazilian cherry seed extract is a potentially valuable source of antioxidants. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Few-layered CoHPO4.3H2O ultrathin nanosheets for high performance of electrode materials for supercapacitors

    Science.gov (United States)

    Pang, Huan; Wang, Shaomei; Shao, Weifang; Zhao, Shanshan; Yan, Bo; Li, Xinran; Li, Sujuan; Chen, Jing; Du, Weimin

    2013-06-01

    Ultrathin cobalt phosphate (CoHPO4.3H2O) nanosheets are successfully synthesized by a one pot hydrothermal method. Novel CoHPO4.3H2O ultrathin nanosheets are assembled for constructing the electrodes of supercapacitors. Benefiting from the nanostructures, the as-prepared electrode shows a specific capacitance of 413 F g-1, and no obvious decay even after 3000 charge-discharge cycles. Such a quasi-two-dimensional material is a new kind of supercapacitor electrode material with high performance.Ultrathin cobalt phosphate (CoHPO4.3H2O) nanosheets are successfully synthesized by a one pot hydrothermal method. Novel CoHPO4.3H2O ultrathin nanosheets are assembled for constructing the electrodes of supercapacitors. Benefiting from the nanostructures, the as-prepared electrode shows a specific capacitance of 413 F g-1, and no obvious decay even after 3000 charge-discharge cycles. Such a quasi-two-dimensional material is a new kind of supercapacitor electrode material with high performance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01460f

  13. Phenolic Profiling of Duchesnea indica Combining Macroporous Resin Chromatography (MRC with HPLC-ESI-MS/MS and ESI-IT-MS

    Directory of Open Access Journals (Sweden)

    Mingzhi Zhu

    2015-12-01

    Full Text Available Duchesnea indica (D. indica is an important traditional Chinese medicine, and has long been clinically used to treat cancer in Asian countries. It has been described previously as a rich source of phenolic compounds with a broad array of diversified structures, which are the major active ingredients. However, an accurate and complete phenolic profiling has not been determined yet. In the present work, the total phenolic compounds in crude extracts from D. indica were enriched and fractionated over a macroporous resin column, then identified by HPLC-ESI-MS/MS and ESI-IT-MS (ion trap MS. A total of 27 phenolic compounds were identified in D. indica, of which 21 compounds were identified for the first time. These 27 phenolic compounds encompassing four phenolic groups, including ellagitannins, ellagic acid and ellagic acid glycosides, hydroxybenzoic acid and hydroxycinnamic acid derivatives, and flavonols, were then successfully quantified using peak areas against those of the corresponding standards with good linearity (R2 > 0.998 in the range of the tested concentrations. As a result, the contents of individual phenolic compounds varied from 6.69 mg per 100 g dry weight (DW for ellagic acid to 71.36 mg per 100 g DW for brevifolin carboxylate. Not only did this study provide the first phenolic profiling of D. indica, but both the qualitative identification and the subsequent quantitative analysis of 27 phenolic compounds from D. indica should provide a good basis for future exploration of this valuable medicinal plant.

  14. Characterization and identification of iridoid glucosides, flavonoids and anthraquinones in Hedyotis diffusa by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Liu, E-Hu; Zhou, Ting; Li, Guo-Bin; Li, Jing; Huang, Xiu-Ning; Pan, Feng; Gao, Ning

    2012-01-01

    The multiple bioactive constituents in Hedyotis diffusa Willd. (H. diffusa) were extracted and characterized by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-ESI-MS(n)). The optimized separation condition was obtained using an Agilent ZorBax SB-C18 column (4.6×150 mm, 5 μm) and gradient elution with water (containing 0.1% formic acid) and acetonitrile (containing 0.1% formic acid), under which baseline separation for the majority of compounds was achieved. Among the compounds detected, 14 iridoid glucosides, 10 flavonoids, 7 anthraquinones, 1 coumarin and 1 triterpene were unambiguously identified or tentatively characterized based on their retention times and mass spectra in comparison with the data from standards or references. The fragmentation behavior for different types of constituents was also investigated, which could contribute to the elucidation of these constituents in H. diffusa. The present study reveals that even more iridoid glycosides were found in H. diffusa than hitherto assumed. The occurrence of two iridoid glucosides and five flavonoids in particular has not yet been described. This paper marks the first report on the structural characterization of chemical compounds in H. diffusa by a developed HPLC-ESI-MS(n) method. Copyright © 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Environmental Sensitivity Index (ESI) Atlas: Puget Sound and Strait of Juan de Fuca, maps and geographic information systems data (NODC Accession 0013952)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for the Puget Sound and Strait of Juan de Fuca from 1978 to 2006. ESI data characterize...

  16. Environmental Sensitivity Index (ESI) Atlas: West Peninsular Florida Volume 1 (NODC Accession 0006377)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps in Portable Document Format (.PDF) for the shoreline of West Peninsular Florida (to encompass...

  17. Environmental Sensitivity Index (ESI) Atlas: Alaska - 2, Northwest Arctic - 2002, North Slope - 2005, Western - 2003, maps and geographic systems data (NODC Accession 0049913)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Northwest Arctic, North Slope, and Western Alaska. ESI data characterize estuarine...

  18. Porous hollow Co3O4 with rhombic dodecahedral structures for high-performance supercapacitors

    Science.gov (United States)

    Zhang, Yi-Zhou; Wang, Yang; Xie, Ye-Lei; Cheng, Tao; Lai, Wen-Yong; Pang, Huan; Huang, Wei

    2014-11-01

    Porous hollow Co3O4 with rhombic dodecahedral structures were prepared by the calcination of ZIF-67 ([Co(mim)2; mim = 2-methylimidazolate]) rhombic dodecahedral microcrystals. A supercapacitor was successfully constructed by adopting the resulting porous hollow Co3O4 rhombic dodecahedral structure as the electrode material, which showed a large specific capacitance of 1100 F g-1 and retained more than 95.1% of the specific capacitance after 6000 continuous charge-discharge cycles. The excellent capacitive properties and stability mark the porous hollow Co3O4 with the rhombic dodecahedral structure as one of the most promising electrode materials for high-performance supercapacitors.Porous hollow Co3O4 with rhombic dodecahedral structures were prepared by the calcination of ZIF-67 ([Co(mim)2; mim = 2-methylimidazolate]) rhombic dodecahedral microcrystals. A supercapacitor was successfully constructed by adopting the resulting porous hollow Co3O4 rhombic dodecahedral structure as the electrode material, which showed a large specific capacitance of 1100 F g-1 and retained more than 95.1% of the specific capacitance after 6000 continuous charge-discharge cycles. The excellent capacitive properties and stability mark the porous hollow Co3O4 with the rhombic dodecahedral structure as one of the most promising electrode materials for high-performance supercapacitors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04782f

  19. ESI-HI27 Kawaihae, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  20. ESI-HI23 Makalawena, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  1. ESI-HI49 Paia, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  2. ESI-HI45 Lahaina, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  3. ESI-PR67, Isla De Vieques, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-HI65 Ewa, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-HI73 Kaneohe, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-HI69 Waimea, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-HI01 Hilo, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. ESI-HI33 Honokaa, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  9. ESI-HI71 Hauula, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  10. ESI-HI82 Hanalei, Island of Kauai, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  11. ESI-HI10 Pahala, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  12. ESI-VI14, Anegada U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  13. ESI-VI11, Tortola, U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. ESI-HI63 Waipahu, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  15. ESI-HI29 Mahukona, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  16. ESI-HI11 Punaluu, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  17. ESI-HI21 Kailua, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  18. ESI-HI74 Mokapu, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  19. ESI-HI46 Napili, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  20. ESI-HI17 Milolii, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  1. ESI-HI38 Kipahulu, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  2. ESI-HI67 Kaena, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  3. ESI-HI43 Maalaea, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-HI76 Lihue, Island of Kauai, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-HI72 Kahana, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-HI06 Kalapana, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-HI44 Olowalu, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. ESI-HI19 Honaunau, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  9. ESI-PR16, Central La Plata, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  10. ESI-HI66 Waianae, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  11. ESI-HI37 Hana, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  12. ESI-HI47 Kahakuloa, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  13. ESI-HI48 Wailuku, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. ESI-HI68 Haleiwa, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  15. Quantification of underivatised amino acids on dry blood spot, plasma, and urine by HPLC-ESI-MS/MS.

    Science.gov (United States)

    Giordano, Giuseppe; Di Gangi, Iole Maria; Gucciardi, Antonina; Naturale, Mauro

    2012-01-01

    Enzyme deficiencies in amino acid (AA) metabolism affecting the levels of amino acids and their derivatives in physiological fluids may serve as diagnostically significant biomarkers for one or a group of metabolic disorders. Therefore, it is important to monitor a wide range of free amino acids simultaneously and to quantify them. This is time consuming if we use the classical methods and more than ever now that many laboratories have introduced Newborn Screening Programs for the semiquantitative analysis, detection, and quantification of some amino acids needed to be performed in a short time to reduce the rate of false positives.We have modified the stable isotope dilution HPLC-electrospray ionization (ESI)-MS/MS method previously described by Qu et al. (Anal Chem 74: 2034-2040, 2002) for a more rapid, robust, sensitive, and specific detection and quantification of underivatised amino acids. The modified method reduces the time of analysis to 10 min with very good reproducibility of retention times and a better separation of the metabolites and their isomers.The omission of the derivatization step allowed us to achieve some important advantages: fast and simple sample preparation and exclusion of artefacts and interferences. The use of this technique is highly sensitive, specific, and allows monitoring of 40 underivatized amino acids, including the key isomers and quantification of some of them, in order to cover many diagnostically important intermediates of metabolic pathways.We propose this HPLC-ESI-MS/MS method for underivatized amino acids as a support for the Newborn Screening as secondary test using the same dried blood spots for a more accurate and specific examination in case of suspected metabolic diseases. In this way, we avoid plasma collection from the patient as it normally occurs, reducing anxiety for the parents and further costs for analysis.The same method was validated and applied also to plasma and urine samples with good reproducibility

  16. Determination and Pharmacokinetic Study of Three Diterpenes in Rat Plasma by UHPLC-ESI-MS/MS after Oral Administration of Rosmarinus officinalis L. Extract

    Directory of Open Access Journals (Sweden)

    Liqian Wang

    2017-06-01

    Full Text Available Rosmarinus officinalis L. is commonly used as a spice and flavoring agent. Diterpenes are the main active compounds of R. officinalis. An Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry (UHPLC-ESI-MS/MS method was developed for the determination of carnosol, rosmanol, and carnosic acid isolated from R. officinalis in rat plasma, and applied to a pharmacokinetic study after oral administration of R. officinalis extract. Sample preparation involved a liquid-liquid extraction of the analytes with ethyl acetate. Butylparaben was employed as an internal standard (I.S.. Chromatographic separation was carried out on a C18 column (ACQUITY UPLC® HSS T3, 1.8 μm, 2.1 mm × 100 mm with a gradient system consisting of the mobile phase solution A (0.1% formic acid in water and solution B (acetonitrile at the flow rate of 0.3 mL/min. The quantification was obtained using multiple reaction monitoring (MRM mode with electrospray ionization (ESI. The UHPLC-MS/MS assay was validated for linearity, accuracy, precision, extraction recovery, matrix effect and stability. This study described a simple, sensitive and validated UHPLC-MS/MS method for the simultaneous determination of three diterpene compounds in rat plasma after oral administration of R. officinalis extract, and investigated on their pharmacokinetic studies as well.

  17. High-performance thin-layer chromatography analysis of steviol glycosides in Stevia formulations and sugar-free food products, and benchmarking with (ultra) high-performance liquid chromatography.

    Science.gov (United States)

    Morlock, Gertrud E; Meyer, Stephanie; Zimmermann, Benno F; Roussel, Jean-Marc

    2014-07-11

    A high-performance TLC (HPTLC) method was newly developed and validated for analysis of 7 steviol glycosides in 6 different types of food and Stevia formulations. After a minimized one-step sample preparation, 21 samples were developed in parallel, allowing an effective food screening. Depending on the sample application volume, the method was suited to analyze food sample concentrations in the mg/kg range. LOQs of stevioside in natural yoghurt matrix spiked at 0.02, 0.13 and 0.2% were determined by the calibration curve method to be 12ng/band (peak height). ANOVA was successfully passed to prove data homogeneity in the working range (30-600ng/band). The accuracy (recovery tolerance limit, 92-120%), repeatability (3.1-5.4%) and intermediate precision (4.0-8.4%) were determined for stevioside in milk-based matrix including sample preparation and recovery rates at 3 different concentration levels. For the first time, the recording of HPTLC-ESI-MS spectra via the TLC-MS Interface was demonstrated for rebaudioside A. HPTLC contents for rebaudioside A were compared with results of two (U)HPLC methods. The running costs and analysis time of the three different methods were discussed in detail with regard to screening of food products. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Contribution to the development of new analytical methods by the coupling between capillary electrophoresis and mass spectrometry (ICP-MS and ESI-MS): applications to the nuclear and biological fields; Contribution au developpement de nouvelles methodes analytiques par le couplage entre l'electrophorese capillaire et la spectrometrie de masse (ICP-MS et ESI-MS): applications dans les domaines nucleaires et biologiques

    Energy Technology Data Exchange (ETDEWEB)

    Pitois, A

    2006-04-15

    The coupling between chromatographic and electrophoretic separation techniques and mass spectrometry is used to combine the efficiency of the separation technique to the selectivity and sensitivity of the detectors. In this work, the number of applications of the CE-MS couplings has been increased. New analytical methods have been set up in the nuclear and biological fields. New analytical methods for the determination of fission products (cesium and lanthanides) have been developed by CE-ICP-MS. They enable to determine both concentration and isotopic composition of the fission products for very low detection limits (ng/mL by CE-Q-ICPMS, pg/mL by CE-HR-ICP-MS), since all the isobaric interferences are resolved. Moreover, only some nano-liters of sample are necessary to perform the analysis. These method have been applied with success to a simulated sample of spent fuel, to a nuclear sample from PUREX process and to a leaching of MOX fuel. Then, lanthanides have been analysed by CE-ESI-MS and the capability of ESI-MS to provide structural information has been studied. Elementary information has been obtained for strong potentials. Structural information has been obtained for low potentials. Finally, a new analytical method by CE-ESI-MS for the determination of 10B-boronophenylalanine (10B-BPA) has been developed for Boron Neutron Capture Therapy (BNCT). It has been applied to the cellular lines F98 and HUVEC. This CE-ESI-MS method has been validated by HR-ICP-MS. It enables a direct quantification of the chemical form 10B-BPA in samples of limited size (some nano-liters) and for low concentrations (ng/mL). As a consequence, this CE-ESI-MS method has enabled the study of the kinetics of 10B-BPA release and uptake for the F98 cells. (author)

  19. Simultaneous qualification and quantification of baccharane glycosides in Impatientis Semen by HPLC-ESI-MSD and HPLC-ELSD.

    Science.gov (United States)

    Li, Hui-Jun; Yu, Jun-Jie; Li, Ping

    2011-03-25

    This study presents a high performance liquid chromatography (HPLC) with electrospray ionization mass spectrometric detection (ESI-MSD) and evaporative light scattering detection (ELSD) method for the simultaneous qualification and quantification of eight major baccharane glycosides, namely hosenlosides A, B, C, F, G, K, L, and M in Impatientis Semen, a Chinese herbal medicine derived from the seeds of Impatiens balsamina L. In order to achieve optimum performance, several extraction parameters (including extraction solvent, extraction mode, extraction time) were optimized. The baccharane glycosides were separated on a Shim-pack CLC-ODS column with gradient elution of water and methanol. Temperature for the ELSD drift tube was set at 98°C and the nitrogen flow rate was 2.7l/min. The unambiguous identities of the analytes were realized by comparing retention times and mass data with those of reference compounds. The developed method was fully validated in terms of linearity, sensitivity, precision, repeatability, recovery as well as robustness, and subsequently applied to evaluate the quality of 14 batches of Impatientis Semen commercial samples from different collections. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. Profiling and identification of (-)-epicatechin metabolites in rats using ultra-high performance liquid chromatography coupled with linear trap-Orbitrap mass spectrometer.

    Science.gov (United States)

    Shang, Zhanpeng; Wang, Fei; Dai, Shengyun; Lu, Jianqiu; Wu, Xiaodan; Zhang, Jiayu

    2017-08-01

    (-)-Epicatechin (EC), an optical antipode of (+)-catechin (C), possesses many potential significant health benefits. However, the in vivo metabolic pathway of EC has not been clarified yet. In this study, an efficient strategy based on ultra-high performance liquid chromatography coupled with a linear ion trap-Orbitrap mass spectrometer was developed to profile and characterize EC metabolites in rat urine, faeces, plasma, and various tissues. Meanwhile, post-acquisition data-mining methods including high-resolution extracted ion chromatogram (HREIC), multiple mass defect filters (MMDFs), and diagnostic product ions (DPIs) were utilized to screen and identify EC metabolites from HR-ESI-MS 1 to ESI-MS n stage. Finally, a total of 67 metabolites (including parent drug) were tentatively identified based on standard substances, chromatographic retention times, accurate mass measurement, and relevant drug biotransformation knowledge. The results demonstrated that EC underwent multiple in vivo metabolic reactions including methylation, dehydration, hydrogenation, glucosylation, sulfonation, glucuronidation, ring-cleavage, and their composite reactions. Among them, methylation, dehydration, glucosylation, and their composite reactions were observed only occurring on EC when compared with C. Meanwhile, the distribution of these detected metabolites in various tissues including heart, liver, spleen, lung, kidney, and brain were respectively studied. The results demonstrated that liver and kidney were the most important organs for EC and its metabolites elimination. In conclusion, the newly discovered EC metabolites significantly expanded the understanding on its pharmacological effects and built the foundation for further toxicity and safety studies. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  1. Environmental Sensitivity Index (ESI) Atlas: Southeast Alaska - volume 1, geographic information systems data and volume 2, maps in portable document format (NODC Accession 0046029)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Northwest Arctic, Alaska. ESI data characterize estuarine environments and wildlife by...

  2. Environmental Sensitivity Index (ESI) Atlas: Alaska, Prince William Sound-2000, Aleutians-2001, Bristol Bay-2004, maps and geographic information systems data (NODC Accession 0014162)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Alaska; Prince William Sound (2000), Aleutians (2001), and Bristol Bay (2004). ESI data...

  3. Environmental Sensitivity Index (ESI) Atlas: North Slope, Alaska, Volume 1, geographic information systems data, Volume 2, maps in portable document format (NODC Accession 0014928)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — ESI data characterize the marine and coastal environments and wildlife by their sensitivity to spilled oil. The ESI data include information for three main...

  4. Effect-directed fingerprints of 77 botanical extracts via a generic high-performance thin-layer chromatography method combined with assays and mass spectrometry.

    Science.gov (United States)

    Krüger, S; Hüsken, L; Fornasari, R; Scainelli, I; Morlock, G E

    2017-12-22

    Quantitative effect-directed profiles of 77 industrially and freshly extracted botanicals like herbs, spices, vegetables and fruits, widely used as food ingredients, dietary supplements or traditional medicine, gave relevant information on their quality. It allows the assessment of food, dietary supplements and phytomedicines with regard to potential health-promoting activities. In contrary to sum parameter assays and targeted analysis, chromatography combined with effect-directed analysis allows fast assignment of single active compounds and evaluation of their contribution to the overall activity, originating from a food or botanical sample. High-performance thin-layer chromatography was hyphenated with UV/Vis/FLD detection and effect-directed analysis, using the 2,2-diphenyl-1-picrylhydrazyl radical, Gram-negative Aliivibrio fischeri, Gram-positive Bacillus subtilis, acetylcholinesterase and tyrosinase assays. Bioactive compounds of interest were eluted using an elution head-based interface and further characterized by electrospray ionization (high-resolution) mass spectrometry. This highly streamlined workflow resulted in a hyphenated HPTLC-UV/Vis/FLD-EDA-ESI + /ESI - -(HR)MS method. The excellent quantification power of the method was shown on three compounds. For rosmarinic acid, contents ranged from 4.5mg/g (rooibos) to 32.6mg/g (rosemary), for kaempferol-3-glucoside from 0.6mg/g (caraway) to 4.4mg/g (wine leaves), and for quercetin-3-glucoside from 1.1mg/g (hawthorn leaves) to 17.7mg/g (thyme). Three mean repeatabilities (%RSD) over 18 quantifications for the three compounds were ≤2.2% and the mean intermediate precision over three different days (%RSD, n=3) was 5.2%. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Polyphenolic compounds in date fruit seed (Phoenix dactylifera): characterisation and quantification by using UPLC-DAD-ESI-MS.

    Science.gov (United States)

    Habib, Hosam M; Platat, Carine; Meudec, Emmanuelle; Cheynier, Veronique; Ibrahim, Wissam H

    2014-04-01

    Date fruit seeds have been demonstrated to possess high antioxidant activities due to their high content of flavonoids and phenolic compounds. The objective of this work was to identify and quantify the phenolic composition of date seeds. Two UPLC-DAD-ESI-MS analyses were performed on the seed of the Khalas variety as follows: (1) an analysis of simple phenolic compounds [phenolic acids, hydroxycinnamic acids, flavonols, flavones, flavan-3-ols (monomers, dimers and trimers)]; and (2) an analysis of all flavan-3-ols (monomers, and proanthocyanidin oligomers and polymers) after depolymerisation. The amount of total phenolic compounds before depolymerisation was found to be 2.194 ± 0.040 g kg(-1) date seed. The analysis of flavan-3-ol monomers and constitutive units of proanthocyanidins after depolymerisation revealed 50.180 ± 1.360 g kg(-1) flavan-3-ols with 46.800 ± 1.012 g kg(-1) epicatechin and 3.380 ± 0.349 g kg(-1) catechin. The results indicate that date seeds are a very rich source of bioactive compounds, thus constituting strong candidates for functional food additives and nutraceuticals. © 2013 Society of Chemical Industry.

  6. Permeability Study of Polyphenols Derived from a Phenolic-Enriched Hibiscus sabdariffa Extract by UHPLC-ESI-UHR-Qq-TOF-MS

    Science.gov (United States)

    Borrás-Linares, Isabel; Herranz-López, María; Barrajón-Catalán, Enrique; Arráez-Román, David; González-Álvarez, Isabel; Bermejo, Marival; Gutiérrez, Alberto Fernández; Micol, Vicente; Segura-Carretero, Antonio

    2015-01-01

    Previous findings on the capacity of Hibiscus sabdariffa (HS) polyphenols to ameliorate metabolic disturbances justify the necessity of studies oriented to find the potential metabolites responsible for such an effect. The present study examined the intestinal epithelial membrane permeability of polyphenols present in a phenolic-enriched Hibiscus sabdariffa extract (PEHS), free and encapsulated, using the Caco-2 cell line. Additionally, selected polyphenols (quercetin, quercetin-3-glucoside, quercetin-3-glucuronide, and N-feruloyltyramine) were also studied in the same absorption model. The powerful analytical platform used ultra-high-performance liquid chromatography coupled with ultra-high-resolution quadrupole time-of-flight mass spectrometry (UHPLC-ESI-UHR-Qq-TOF-MS), and enabled the characterization of seven new compounds in PEHS. In the permeation study, only a few compounds were able to cross the cell monolayer and the permeability was lower when the extract was in an encapsulated form. Pure compounds showed a moderate absorption in all cases. Nevertheless, these preliminary results may need further research to understand the complete absorption mechanism of Hibiscus polyphenols. PMID:26262611

  7. Permeability Study of Polyphenols Derived from a Phenolic-Enriched Hibiscus sabdariffa Extract by UHPLC-ESI-UHR-Qq-TOF-MS

    Directory of Open Access Journals (Sweden)

    Isabel Borrás-Linares

    2015-08-01

    Full Text Available Previous findings on the capacity of Hibiscus sabdariffa (HS polyphenols to ameliorate metabolic disturbances justify the necessity of studies oriented to find the potential metabolites responsible for such an effect. The present study examined the intestinal epithelial membrane permeability of polyphenols present in a phenolic-enriched Hibiscus sabdariffa extract (PEHS, free and encapsulated, using the Caco-2 cell line. Additionally, selected polyphenols (quercetin, quercetin-3-glucoside, quercetin-3-glucuronide, and N-feruloyltyramine were also studied in the same absorption model. The powerful analytical platform used ultra-high-performance liquid chromatography coupled with ultra-high-resolution quadrupole time-of-flight mass spectrometry (UHPLC-ESI-UHR-Qq-TOF-MS, and enabled the characterization of seven new compounds in PEHS. In the permeation study, only a few compounds were able to cross the cell monolayer and the permeability was lower when the extract was in an encapsulated form. Pure compounds showed a moderate absorption in all cases. Nevertheless, these preliminary results may need further research to understand the complete absorption mechanism of Hibiscus polyphenols.

  8. Permeability Study of Polyphenols Derived from a Phenolic-Enriched Hibiscus sabdariffa Extract by UHPLC-ESI-UHR-Qq-TOF-MS.

    Science.gov (United States)

    Borrás-Linares, Isabel; Herranz-López, María; Barrajón-Catalán, Enrique; Arráez-Román, David; González-Álvarez, Isabel; Bermejo, Marival; Fernández Gutiérrez, Alberto; Micol, Vicente; Segura-Carretero, Antonio

    2015-08-07

    Previous findings on the capacity of Hibiscus sabdariffa (HS) polyphenols to ameliorate metabolic disturbances justify the necessity of studies oriented to find the potential metabolites responsible for such an effect. The present study examined the intestinal epithelial membrane permeability of polyphenols present in a phenolic-enriched Hibiscus sabdariffa extract (PEHS), free and encapsulated, using the Caco-2 cell line. Additionally, selected polyphenols (quercetin, quercetin-3-glucoside, quercetin-3-glucuronide, and N-feruloyltyramine) were also studied in the same absorption model. The powerful analytical platform used ultra-high-performance liquid chromatography coupled with ultra-high-resolution quadrupole time-of-flight mass spectrometry (UHPLC-ESI-UHR-Qq-TOF-MS), and enabled the characterization of seven new compounds in PEHS. In the permeation study, only a few compounds were able to cross the cell monolayer and the permeability was lower when the extract was in an encapsulated form. Pure compounds showed a moderate absorption in all cases. Nevertheless, these preliminary results may need further research to understand the complete absorption mechanism of Hibiscus polyphenols.

  9. Rhode Island, Connecticut, New York, and New Jersey ESI: HYDRO (Hydrography Lines and Polygons)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set contains vector lines and polygons representing coastal hydrography used in the creation of the Environmental Sensitivity Index (ESI) for Rhode Island,...

  10. Contribution to the development of new analytical methods by the coupling between capillary electrophoresis and mass spectrometry (ICP-MS and ESI-MS): applications to the nuclear and biological fields

    International Nuclear Information System (INIS)

    Pitois, A.

    2006-04-01

    The coupling between chromatographic and electrophoretic separation techniques and mass spectrometry is used to combine the efficiency of the separation technique to the selectivity and sensitivity of the detectors. In this work, the number of applications of the CE-MS couplings has been increased. New analytical methods have been set up in the nuclear and biological fields. New analytical methods for the determination of fission products (cesium and lanthanides) have been developed by CE-ICP-MS. They enable to determine both concentration and isotopic composition of the fission products for very low detection limits (ng/mL by CE-Q-ICPMS, pg/mL by CE-HR-ICP-MS), since all the isobaric interferences are resolved. Moreover, only some nano-liters of sample are necessary to perform the analysis. These method have been applied with success to a simulated sample of spent fuel, to a nuclear sample from PUREX process and to a leaching of MOX fuel. Then, lanthanides have been analysed by CE-ESI-MS and the capability of ESI-MS to provide structural information has been studied. Elementary information has been obtained for strong potentials. Structural information has been obtained for low potentials. Finally, a new analytical method by CE-ESI-MS for the determination of 10B-boronophenylalanine (10B-BPA) has been developed for Boron Neutron Capture Therapy (BNCT). It has been applied to the cellular lines F98 and HUVEC. This CE-ESI-MS method has been validated by HR-ICP-MS. It enables a direct quantification of the chemical form 10B-BPA in samples of limited size (some nano-liters) and for low concentrations (ng/mL). As a consequence, this CE-ESI-MS method has enabled the study of the kinetics of 10B-BPA release and uptake for the F98 cells. (author)

  11. Stability and oxidation products of hydrolysable tannins in basic conditions detected by HPLC/DAD-ESI/QTOF/MS.

    Science.gov (United States)

    Tuominen, Anu; Sundman, Terhi

    2013-01-01

    Hydrolysable tannins occur in plants that are used for food or medicine by humans or herbivores. Basic conditions can alter the structures of tannins, that is, the oxidation of phenolic groups can lead to the formation of toxic quinones. Previously, these labile quinones and other oxidation products have been studied with colorimetric or electron paramagnetic resonance methods, which give limited information about products. To study the stability and oxidation products of hydrolysable tannins in basic conditions using HPLC with a diode-array detector (DAD) combined with electrospray ionisation (ESI) and quadrupole time-of-flight (QTOF) MS. Three galloyl glucoses, four galloyl derivatives with different polyols and three ellagitannins were purified from plants. The incubation reactions of tannins were monitored by HPLC/DAD at five pH values and in reduced oxygen conditions. Reaction products were identified based on UV spectra and mass spectral fragmentation obtained with the high-resolution HPLC/DAD-ESI/QTOF/MS. The use of a base-resistant HPLC column enabled injections without the sample pre-treatment and thus detection of short-lived products. Hydrolysable tannins were unstable in basic conditions and half-lives were mostly less than 10 min at pH 10. Degradation rates were faster at pH 11 but slower at milder pH. The HPLC analyses revealed that various products were formed and identified to be the result of hydrolysis, deprotonation and oxidation. Interestingly, the main hydrolysis product was ellagic acid; it was also formed from galloyl glucoses that do not contain oxidatively coupled galloyl groups in their initial structures. HPLD/DAD-ESI/QTOF/MS was an efficient method for the identification of polyphenol oxidation products and showed how different pH conditions determine the fate of hydrolysable tannins. Copyright © 2013 John Wiley & Sons, Ltd.

  12. Separation and identification of Se-methylselenogalactosamine - a new metabolite in basal human urine - by HPLC-ICP-MS and CE-nano-ESI-(MS)(2)

    DEFF Research Database (Denmark)

    Bendahl, L.; Gammelgaard, Bente

    2004-01-01

    Three minor metabolites were isolated from human urine. Two of these were identified by nano electrospray ionisation mass spectrometry (nESI-MS) as Se-methylseleno-N-acetylglucosamine and Se-methylselenogalactosamine, respectively. A human urine pool was lyophilised and reconstituted in methanol......-chromatographed in the reversed phase system and further purified in different separation systems before analysis by nESI-MS. By CE-nESI-MS analysis of one of the fractions, the characteristic selenium pattern was recognized around m/z 285 and ( MS) 2 fragmentation resulted in a fragments at m/z 267, 173 and 155, respectively....... It was not possible to identify this selenium compound on basis of the available data. The selenium compound in the second fraction showed co-elution with a Se-methylseleno-N-acetylglucosamine standard. The identity of this compound was verified by nESI-MS after further purification by size exclusion chromatography...

  13. ESI-HI54 Lanai South, Island of Lanai, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. ESI-HI26 Puu Hinai, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  15. ESI-HI57 Molokai Airport, Island of Molokai, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  16. ESI-HI02 Keaau Ranch, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  17. ESI-HI28 Keawanui Bay, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  18. ESI-HI09 Naliikakani Point, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  19. ESI-HI60 Molokai East, Island of Molokai, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  20. ESI-HI75 Koko head, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  1. ESI-HI62 Pearl Harbor, Island of Oahu, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  2. ESI-HI94 Pearl and Hermes Atoll, NWHI, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  3. ESI-VI12 Beef Island, U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-HI08 Kau Desert, Island of Hawaii, Hawaii 2001 ( Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-VI9, Peter Island, U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-VI13, Virgin Gorda, U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-HI07 Makaopuhi Crater, Island of Hawaii, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. Sunlight creates oxygenated species in water-soluble fractions of Deepwater horizon oil

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Phoebe Z. [Department of Chemistry, University of New Orleans, New Orleans, LA 70148 (United States); Chen, Huan [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Podgorski, David C. [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Future Fuels Institute, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); McKenna, Amy M. [National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005 (United States); Tarr, Matthew A., E-mail: mtarr@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, LA 70148 (United States)

    2014-09-15

    Graphical abstract: Sunlight oxygenates petroleum. - Highlights: • Oxidation seen in water-soluble oil fraction after exposure to simulated sunlight. • Oxygen addition occurred across a wide range of carbon number and DBE. • Oil compounds were susceptible to addition of multiple oxygens to each molecule. • Results provide understanding of fate of oil on water after exposure to sunlight. - Abstract: In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid–liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O{sub 5}), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O{sub 2}). Higher-order oxygen classes (O{sub 5}–O{sub 9}) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N{sub 1}) concurrent with an increased abundance of N{sub 1}O{sub x} classes after irradiation. The predominance of higher

  9. Environmental Sensitivity Index (ESI) Atlas: South Carolina - Volume 1, geographic information systems data, Volume 2, maps and data in portable document format (NODC Accession 0013822)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of South Carolina. ESI data characterize coastal environments and wildlife...

  10. Environmental Sensitivity Index (ESI) Atlas: North Carolina - Volume 1, geographic information systems data, Volume 2, maps and data in portable document format (NODC Accession 0013821)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of North Carolina. ESI data characterize coastal environments and wildlife...

  11. Aberrant Lipid Metabolism in Hepatocellular Carcinoma Revealed by Liver Lipidomics

    Directory of Open Access Journals (Sweden)

    Zhao Li

    2017-11-01

    Full Text Available Background: The aim of this study was to characterize the disorder of lipid metabolism in hepatocellular carcinoma (HCC. HCC is a worldwide disease. The research into the disorder of lipid metabolism in HCC is very limited. Study of lipid metabolism in liver cancer tissue may have the potential to provide new insight into HCC mechanisms. Methods: A lipidomics study of HCC based on Ultra high performance liquid chromatography-electronic spray ionization-QTOF mass spectrometer (UPLC-ESI-QTOF MS and Matrix assisted laser desorption ionization-fourier transform ion cyclotron resonance mass spectrometer (MALDI-FTICR MS was performed. Results: Triacylglycerols (TAGs with the number of double bond (DB > 2 (except 56:5 and 56:4 TAG were significantly down-regulated; conversely, others (except 52:2 TAG were greatly up-regulated in HCC tissues. Moreover, the more serious the disease was, the higher the saturated TAG concentration and the lower the polyunsaturated TAG concentration were in HCC tissues. The phosphatidylcholine (PC, phosphatidylethanolamine (PE and phosphatidylinositol (PI were altered in a certain way. Sphingomyelin (SM was up-regulated and ceramide (Cer were down-regulated in HCC tissues. Conclusions: To our knowledge, this is the first such report showing a unique trend of TAG, PC, PE and PI. The use of polyunsaturated fatty acids, like eicosapentanoic and docosahexanoic acid, as supplementation, proposed for the treatment of Non-alcoholic steatohepatitis (NASH, may also be effective for the treatment of HCC.

  12. ANALYSIS OF SULFONATES IN AQUEOUS SAMPLES BY ION-PAIR LC/ESI-MS/MS WITH IN-SOURCE CID FOR ADDUCT PEAK ELIMINATION

    Energy Technology Data Exchange (ETDEWEB)

    OUYANG,S.; VAIRAVAMURTHY,M.A.

    1999-06-13

    Determination of low-molecular-weight organic sulfonates (e.g. taurine and cysteic acid) in aqueous solutions is important in many applications of biological, environmental and pharmaceutical sciences. These compounds are difficult to be determined by commonly used reversed-phase liquid chromatographic separation combined with UV-Visible detection because of their high solubility and the lack chromophoric moieties. Here the authors report a method combining ion-pair liquid chromatography and electrospray ionization tandem mass spectrometry (IPLC/ESI-MS/MS)for determining sulfonates. The ability of low-molecular-weight sulfonates to form ion-pairs with quaternary ammonium cations in aqueous solutions allowed LC separation with a C{sub 18} column. Detection of the sulfonates was accomplished with ESI-MS that lends a universal mode of mass detection for polar, water soluble compounds. An in-source collision induced dissociation (CID) was applied to eliminate the adduct peaks in mass spectra. Characteristic marker ions showed in the second stage mass spectra lent a method for identifying sulfonates.

  13. The diagnostic utility of 3D-ESI rotating and moving dipole methodology in the pre-surgical evaluation of MRI-negative childhood epilepsy due to focal cortical dysplasia.

    Science.gov (United States)

    Russo, Angelo; Lallas, Matt; Jayakar, Prasanna; Miller, Ian; Hyslop, Ann; Dunoyer, Catalina; Resnick, Trevor; Duchowny, Michael

    2016-09-01

    This study investigates whether a combined rotating dipole (RD) and moving dipole (MD) solution enhances three-dimensional electroencephalography (EEG) source imaging (3D-ESI) localization in magnetic resonance imaging (MRI)-negative pediatric patients with focal cortical dysplasia (FCD). We retrospectively selected 14 MRI-negative patients with FCD from a cohort of 60 pediatric patients previously used to evaluate the diagnostic utility of 3D-ESI in epilepsy surgery. Patients were younger than 18 years at time of surgery and had at least 1 year of outcome data. RD and MD models were constructed for each interictal spike or sharp wave, and it was determined whether each inverse algorithm localized within the surgical resection cavity (SRC). We also compared the 3D-ESI findings and surgical outcome with positron emission tomography (PET) and ictal single photon emission computed tomography (iSPECT). RD analyses revealed a high concordance with the SRC (78.6%), particularly for temporal lobe resection (100.0%), and showed superior localization compared to PET and iSPECT, with the highest correlation in FCD type I and temporal lobe resection. Furthermore, the RD method was superior to iSPECT in FCD type II cases and to PET in extratemporal resections. RD and MD results were comparable, but in 18.2% of patients with FCD type I with localizing RDs, the MD solution was only partially within the SRC; in all of these patients 3D-ESI also correlated with superior surgical outcome compared to PET and iSPECT, especially when RD and MD solutions were analyzed together. 3D-ESI in MRI-negative cases showed superior localization compared to iSPECT or PET, especially in FCD type I and temporal lobe epilepsy, and correlated with superior surgical outcome compared to iSPECT and PET at 1 year and 2 years postoperatively, especially when RD and MD solutions were analyzed together. These findings suggest that 3D-ESI based on a combined RD-MD solution improves surgical accuracy in

  14. CMPO-functionalized C{sub 3}-symmetric tripodal ligands in liquid/liquid extractions : efficient, selective recognition of Pu(IV) with low affinity for 3+ metal ions.

    Energy Technology Data Exchange (ETDEWEB)

    Matloka, K.; Sah, A. K.; Peters, M. W.; Srinivasan, P.; Gelis, A. V.; Regalbuto, M.; Scott, M. J.; Univ. of Florida

    2007-12-10

    Structural modifications of carbamoylmethylphosphine oxide (CPMO)-functionalized triphenoxymethane platforms are described, and the influence of these changes on the ability of the ligand to extract actinides from simulated acidic nuclear waste streams has been evaluated. The ligand system has been shown to have excellent binding efficiency and a selectivity for An(IV) in comparison to the a simple monomeric CMPO ligand under analogous conditions. Both the extraction efficiency and selectivity are strongly dependent on the flexibility and electronic properties of the ligating units in the triphenoxymethane construct. The Tb(III) and Bi(III) nitrate complexes of tris-CMPO derivatives have been isolated, and their structures were elucidated by NMR, ESI FT-ICR MS, and X-ray analysis, providing information on the interactions between metal ions and the tris-CMPO molecules.

  15. Analysis of the monosaccharide composition of water-soluble polysaccharides from Sargassum fusiforme by high performance liquid chromatography/electrospray ionisation mass spectrometry.

    Science.gov (United States)

    Wu, Xiaodan; Jiang, Wei; Lu, Jiajia; Yu, Ying; Wu, Bin

    2014-02-15

    Sargassum fusiforme (hijiki) is the well-known edible algae, whose polysaccharides have been proved to possess interesting bioactivities like antitumor, antioxidant, antimicrobial and immunomodulatory activities. A facile and sensitive method based on high-performance liquid chromatography method of pre-column derivatization with 1-phenyl-3-methyl-5-pyrazolone (PMP) coupled with electrospray ionisation mass spectrometry (HPLC/ESI-MS) has been established for the analysis of the monosaccharide composition of polysaccharides in S. fusiforme. Monosaccharides have been converted into PMP-labelled derivatives with aqueous ammonia as a catalyst at 70 °C for 30 min. The optimisation of the pre-column derivatization process was studied. The LODs of the monosaccharides were in the range from 0.01 to 0.02 nmol. PMP-labelled mixture of monosaccharides has been well separated by a reverse-phase HPLC and detected by on-line ESI-MS method under optimised conditions. The mobile phase of elution system was chosen as acetonitrile (solvent A) and 20mM aqueous ammonium acetate (solvent B) (pH 3.0) with Zorbax XDB-C18 column at 30 °C for the separation of the monosaccharide derivatives. Identification of the monosaccharides composition was carried out by analysis with mass spectral behaviour and chromatography characteristics of 1-phenyl-3-methyl-5-pyrazolone (PMP) labelled monosaccharides. All PMP-labelled derivatives display high chemical stabilities, whose regular MS fragmentation is specific for reducing labelled sugars. The result showed that the S. fusiforme polysaccharide consisted of mannose, glucose, galactose, xylose, fucose and glucuronic acid or galacturonic acid, or both uronic acids. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Multi-detection of corticosteroids in sports doping and veterinary control using high-resolution liquid chromatography/time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Touber, M.E.; Engelen, M.C.; Georgakopoulus, C.; Rhijn, van J.A.; Nielen, M.W.F.

    2007-01-01

    A liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) method was developed using the latest high-resolution LC column technology, the ultra performance liquid chromatography (UPLC (TM)), and electrospray ionization (ESI) in the positive ion mode. Gradient UPLC separation conditions

  17. Interaction of pyrrolobenzodiazepine (PBD ligands with parallel intermolecular G-quadruplex complex using spectroscopy and ESI-MS.

    Directory of Open Access Journals (Sweden)

    Gajjela Raju

    Full Text Available Studies on ligand interaction with quadruplex DNA, and their role in stabilizing the complex at concentration prevailing under physiological condition, has attained high interest. Electrospray ionization mass spectrometry (ESI-MS and spectroscopic studies in solution were used to evaluate the interaction of PBD and TMPyP4 ligands, stoichiometry and selectivity to G-quadruplex DNA. Two synthetic ligands from PBD family, namely pyrene-linked pyrrolo[2,1-c][1,4]benzodiazepine hybrid (PBD1, mixed imine-amide pyrrolobenzodiazepine dimer (PBD2 and 5,10,15,20-tetrakis(N-methyl-4-pyridylporphyrin (TMPyP4 were studied. G-rich single-stranded oligonucleotide d(5'GGGGTTGGGG3' designated as d(T(2G(8, from the telomeric region of Tetrahymena Glaucoma, was considered for the interaction with ligands. ESI-MS and spectroscopic methods viz., circular dichroism (CD, UV-Visible, and fluorescence were employed to investigate the G-quadruplex structures formed by d(T(2G(8 sequence and its interaction with PBD and TMPyP4 ligands. From ESI-MS spectra, it is evident that the majority of quadruplexes exist as d(T(2G(8(2 and d(T(2G(8(4 forms possessing two to ten cations in the centre, thereby stabilizing the complex. CD band of PBD1 and PBD2 showed hypo and hyperchromicity, on interaction with quadruplex DNA, indicating unfolding and stabilization of quadruplex DNA complex, respectively. UV-Visible and fluorescence experiments suggest that PBD1 bind externally where as PBD2 intercalate moderately and bind externally to G-quadruplex DNA. Further, melting experiments using SYBR Green indicate that PBD1 unfolds and PBD2 stabilizes the G-quadruplex complex. ITC experiments using d(T(2G(8 quadruplex with PBD ligands reveal that PBD1 and PBD2 prefer external/loop binding and external/intercalative binding to quadruplex DNA, respectively. From experimental results it is clear that the interaction of PBD2 and TMPyP4 impart higher stability to the quadruplex complex.

  18. Interaction of Pyrrolobenzodiazepine (PBD) Ligands with Parallel Intermolecular G-Quadruplex Complex Using Spectroscopy and ESI-MS

    Science.gov (United States)

    Raju, Gajjela; Srinivas, Ragampeta; Santhosh Reddy, Vangala; Idris, Mohammed M.; Kamal, Ahmed; Nagesh, Narayana

    2012-01-01

    Studies on ligand interaction with quadruplex DNA, and their role in stabilizing the complex at concentration prevailing under physiological condition, has attained high interest. Electrospray ionization mass spectrometry (ESI-MS) and spectroscopic studies in solution were used to evaluate the interaction of PBD and TMPyP4 ligands, stoichiometry and selectivity to G-quadruplex DNA. Two synthetic ligands from PBD family, namely pyrene-linked pyrrolo[2,1-c][1,4]benzodiazepine hybrid (PBD1), mixed imine-amide pyrrolobenzodiazepine dimer (PBD2) and 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP4) were studied. G-rich single-stranded oligonucleotide d(5′GGGGTTGGGG3′) designated as d(T2G8), from the telomeric region of Tetrahymena Glaucoma, was considered for the interaction with ligands. ESI-MS and spectroscopic methods viz., circular dichroism (CD), UV-Visible, and fluorescence were employed to investigate the G-quadruplex structures formed by d(T2G8) sequence and its interaction with PBD and TMPyP4 ligands. From ESI-MS spectra, it is evident that the majority of quadruplexes exist as d(T2G8)2 and d(T2G8)4 forms possessing two to ten cations in the centre, thereby stabilizing the complex. CD band of PBD1 and PBD2 showed hypo and hyperchromicity, on interaction with quadruplex DNA, indicating unfolding and stabilization of quadruplex DNA complex, respectively. UV-Visible and fluorescence experiments suggest that PBD1 bind externally where as PBD2 intercalate moderately and bind externally to G-quadruplex DNA. Further, melting experiments using SYBR Green indicate that PBD1 unfolds and PBD2 stabilizes the G-quadruplex complex. ITC experiments using d(T2G8) quadruplex with PBD ligands reveal that PBD1 and PBD2 prefer external/loop binding and external/intercalative binding to quadruplex DNA, respectively. From experimental results it is clear that the interaction of PBD2 and TMPyP4 impart higher stability to the quadruplex complex. PMID:22558271

  19. Free-standing 3D polyaniline-CNT/Ni-fiber hybrid electrodes for high-performance supercapacitors

    Science.gov (United States)

    Li, Yuan; Fang, Yuzhu; Liu, Hong; Wu, Xiaoming; Lu, Yong

    2012-04-01

    Free-standing 3D macroscopic polyaniline (PANi)-carbon nanotube (CNT)-nickel fiber hybrids have been developed, and they deliver high specific capacitance (725 F g-1 at 0.5 A g-1) and high energy density at high rates (~22 W h kg-1 at 2000 W kg-1, based on total electrode mass) with good cyclability.Free-standing 3D macroscopic polyaniline (PANi)-carbon nanotube (CNT)-nickel fiber hybrids have been developed, and they deliver high specific capacitance (725 F g-1 at 0.5 A g-1) and high energy density at high rates (~22 W h kg-1 at 2000 W kg-1, based on total electrode mass) with good cyclability. Electronic supplementary information (ESI) available: Experimental details on preparation, characterization, and electrochemical testing; Fig. S1-S8, Schemes S1 and S2. See DOI: 10.1039/c2nr30252g

  20. Nano-aggregates of cobalt nickel oxysulfide as a high-performance electrode material for supercapacitors

    Science.gov (United States)

    Liu, Lifeng

    2013-11-01

    Nano-aggregates of cobalt nickel oxysulfide (CoNi)OxSy have been synthesized by hydrothermal processing and exhibited specific and areal capacitance as high as 592 F g-1 and 1628 mF cm-2, respectively, at a current density of 0.5 A g-1/1.375 mA cm-2. They also show high capacitance retention upon extended cycling at high rates.Nano-aggregates of cobalt nickel oxysulfide (CoNi)OxSy have been synthesized by hydrothermal processing and exhibited specific and areal capacitance as high as 592 F g-1 and 1628 mF cm-2, respectively, at a current density of 0.5 A g-1/1.375 mA cm-2. They also show high capacitance retention upon extended cycling at high rates. Electronic supplementary information (ESI) available: Experimental details; supplementary tables. See DOI: 10.1039/c3nr03533f

  1. Quantum-chemical, NMR, FT IR, and ESI MS studies of complexes of colchicine with Zn(II).

    Science.gov (United States)

    Jankowski, Wojciech; Kurek, Joanna; Barczyński, Piotr; Hoffmann, Marcin

    2017-04-01

    Colchicine is a tropolone alkaloid from Colchicinum autumnale. It shows antifibrotic, antimitotic, and anti-inflammatory activities, and is used to treat gout and Mediterranean fever. In this work, complexes of colchicine with zinc(II) nitrate were synthesized and investigated using DFT, 1 H and 13 C NMR, FT IR, and ESI MS. The counterpoise-corrected and uncorrected interaction energies of these complexes were calculated. We also calculated their 1 H, 13 C NMR, and IR spectra and compared them with the corresponding experimentally obtained data. According to the ESI MS mass spectra, colchicine forms stable complexes with zinc(II) nitrate that have various stoichiometries: 2:1, 1:1:1, and 2:1:1 with respect to colchichine, Zn(II), and nitrate ion. All of the complexes were investigated using the quantum theory of atoms in molecules (QTAIM). The calculated and the measured spectra showed differences before and after the complexation process. Calculated electron densities and bond critical points indicated the presence of bonds between the ligands and the central cation in the investigated complexes that satisfied the quantum theory of atoms in molecules. Graphical Abstract DFT, NMR, FT IR, ESI MS, QTAIM and puckering studies of complexes of colchicine with Zn(II).

  2. Chemical profiling analysis of Maca using UHPLC-ESI-Orbitrap MS coupled with UHPLC-ESI-QqQ MS and the neuroprotective study on its active ingredients

    OpenAIRE

    Zhou, Yanyan; Li, Peng; Brantner, Adelheid; Wang, Hongjie; Shu, Xinbin; Yang, Jian; Si, Nan; Han, Lingyu; Zhao, Haiyu; Bian, Baolin

    2017-01-01

    Lepidium meyenii (Maca), originated from Peru, has been cultivated widely in China as a popular health care food. However, the chemical and effective studies of Maca were less in-depth, which restricted its application seriously. To ensure the quality of Maca, a feasible and accurate strategy was established. One hundred and sixty compounds including 30 reference standards were identified in 6 fractions of methanol extract of Maca by UHPLC-ESI-Orbitrap MS. Among them, 15 representative active...

  3. ESI-HI42 Puu O Kali, Island of Maui, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  4. ESI-VI6, Eastern St Thomas, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  5. ESI-PR1 Isla Mona and Isla Desecheo, Puerto Rico 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  6. ESI-VI10 Jost Van Dyke, U.K. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  7. ESI-VI5, Central St Thomas, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  8. ESI-VI4 Western St.Thomas, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  9. ESI-VI7, Western St John, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  10. ESI-VI2, Christiansted, St. Croix, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  11. ESI-V1 Frederiksted, St. Croix., U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  12. Hierarchically structured MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors

    Science.gov (United States)

    Sun, Zhipeng; Firdoz, Shaik; Ying-Xuan Yap, Esther; Li, Lan; Lu, Xianmao

    2013-05-01

    We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly conductive pathway for electron transport, and efficient material utilization.We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly

  13. Simultaneous Release and Labeling of O- and N-Glycans Allowing for Rapid Glycomic Analysis by Online LC-UV-ESI-MS/MS.

    Science.gov (United States)

    Wang, Chengjian; Lu, Yu; Han, Jianli; Jin, Wanjun; Li, Lingmei; Zhang, Ying; Song, Xuezheng; Huang, Linjuan; Wang, Zhongfu

    2018-05-24

    Most glycoproteins and biological protein samples undergo both O- and N-glycosylation, making characterization of their structures very complicated and time-consuming. Nevertheless, to fully understand the biological functions of glycosylation, both the glycosylation forms need to be analyzed. Herein we report a versatile, convenient one-pot method in which O- and N-glycans are simultaneously released from glycoproteins and chromogenically labeled in situ and thus available for further characterization. In this procedure, glycoproteins are incubated with 1-phenyl-3-methyl-5-pyrazolone (PMP) in aqueous ammonium hydroxide, making O-glycans released from protein backbones by β-elimination and N-glycans liberated by alkaline hydrolysis. The released glycans are promptly derivatized with PMP in situ by Knoevenagel condensation and Michael addition, with peeling degradation almost completely prevented. The recovered mixture of O- and N-glycans as bis-PMP derivatives features strong ultraviolet (UV) absorbing ability and hydrophobicity, allowing for high-resolution chromatographic separation and high-sensitivity spectrometric detection. Using this technique, O- and N-glycans were simultaneously prepared from some model glycoproteins and complex biological samples, without significant peeling, desialylation, deacetylation, desulfation or other side-reactions, and then comprehensively analyzed by online HILIC-UV-ESI-MS/MS and RP-HPLC-UV-ESI-MS/MS, with which some novel O- and N-glycan structures were first found. This method provides a simple, versatile strategy for high-throughput glycomics analysis.

  14. HPLC-ESI-MS Characterization of Certain Polyphenolic Compounds of Carica papaya L. Fruit Extracts and Evaluation of Their Potential Against Murine Schistosomiasis mansoni.

    Science.gov (United States)

    Abdel-Lateef, Ezzat El-Sayed; Rabia, Ibrahim Aly; El-Sayed, Mortada Mohamed; Abdel-Hameed, El-Sayed Saleh

    2018-04-10

    The in vivo antischistosomal activities of Carica papaya L. extracts were evaluated and the characterization of the active secondary metabolites of the defatted methanolic extract was performed using HPLC-ESI-MS. The plant fruit powders were extracted with 85% methanol and fractionated using organic solvents. The in vivo antischistosomal effects of the methanolic extracts and its fractions, as well as the assessment of the relationship between the antischistosomal activity of these plant extracts and oxidative stress, was determined. In addition, the defatted methanolic extract was characterized by HPLC-ESI-MS analysis. The number of worms, ova, and the Oogram pattern displayed typical Schistosoma mansoni pathology 8 weeks after infection in mice. Treatment of the infected group with the defatted methanolic extracts significantly decreased worm burden, immature ova and mature ova, while increasing the percentage of dead ova in vivo. The butanol fraction was the most effective fraction reducing worm burden by 77%, ova count in the intestine by 76% and in the liver by 80%, and significantly decreased immature and mature ova ( P group. Additionally, the defatted methanolic extracts improved the reduced glutathione and malondialdehyde levels in hepatic tissues in the treated groups compared to the infected group. The HPLC-ESI-MS analysis of the Carica papaya defatted methanolic extract revealed the presence of several polyphenolic compounds. Carica papaya fruit extracts are rich with phenolic acids and flavonoids and show a significant effect against S. mansoni infections which may be used alternative to PZQ as anti-schistosomal drug against schistosomiasis. © Georg Thieme Verlag KG Stuttgart · New York.

  15. A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

    Science.gov (United States)

    Stinson, Craig A; Xia, Yu

    2016-06-21

    Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

  16. Detection, characterization and quantification of salicylic acid conjugates in plant extracts by ESI tandem mass spectrometric techniques.

    Science.gov (United States)

    Pastor, Victoria; Vicent, Cristian; Cerezo, Miguel; Mauch-Mani, Brigitte; Dean, John; Flors, Victor

    2012-04-01

    An approach for the detection and characterization of SA derivatives in plant samples is presented based on liquid chromatography coupled to electrospray ionization (ESI) tandem mass spectrometric techniques. Precursor ion scan methods using an ESI triple quadrupole spectrometer for samples from plants challenged with the virulent Pseudomonas syringae pv tomato DC3000 allowed us to detect two potential SA derivatives. The criterion used to consider a potential SA derivative is based on the detection of analytes in the precursor ion scan chromatogram upon selecting m/z 137 and m/z 93 that correspond to the salicylate and its main product ion, respectively. Product ion spectra of the newly-detected analytes as well as accurate m/z determinations using an ESI Q-time-of-flight instrument were registered as means of characterization and strongly suggest that glucosylated forms of SA at the carboxylic and at the phenol functional groups are present in plant samples. The specific synthesis and subsequent chromatography of salicylic glucosyl ester (SGE) and glucosyl salicylate (SAG) standards confirmed the chemical identity of both peaks that were obtained applying different tandem mass spectrometric techniques and accurate m/z determinations. A multiple reaction monitoring method has been developed and applied to plant samples. The advantages of this LC-ESI-MS/MS methods with respect to the traditional analysis of glucosyl conjugates are also discussed. Preliminary results revealed that SA and the glucosyl conjugates are accumulated in Arabidopsis thaliana in a time dependent manner, accordingly to the up-regulation of SA-dependent defenses following P. syringae infection. This technique applied to plant hormones or fragment ions may be useful to obtain chemical family members of plant metabolites and help identify their contribution in the signaling of plant defenses. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  17. [Study on the analytical methods of catechins in tea and green tea polyphenol samples by high performance liquid chromatography].

    Science.gov (United States)

    Dai, J; Wang, H X; Chen, S W; Tang, J

    2001-09-01

    Hypersil BDS C18 and Zorbax SB C18, suitable to separate simultaneously seven kinds of catechins and caffeine, were screened out from seven brands of reversed-phase columns. Mobile phase was a solution of methanol-water-acetic acid (or trifluoro acetic acid). Seven kinds of catechins in tea samples from six places in China and three green tea polyphenol(GTP) samples from different producers were separated and determined in 30 min by isocratic and gradient elutions. The effects of mobile phase components and temperature of column on retention parameters of catechins and caffeine are reviewed. Chromatographic conditions and pretreatment methods of samples were optimized. Gallocatechin gallate(GCG) and (-)-catechin gallate(CG) were identified by electrospray ionization mass spectrometry(ESI-MS) and prepared by high performance liquid chromatography for quantitative analysis. The other catechins, (-)-epigallocatechin (EGC), (+)-catechin (D-C), (-)-epicatechin(EC), (-)-epigallocatechin gallate(EGCG), (-)-epicatechin gallate(ECG) were identified with standards.

  18. Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

    Science.gov (United States)

    Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

    2012-03-01

    A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

  19. Highly Sensitive and High-Throughput Analysis of Plant Hormones Using MS-Probe Modification and Liquid Chromatography–Tandem Mass Spectrometry: An Application for Hormone Profiling in Oryza sativa

    Science.gov (United States)

    Kojima, Mikiko; Kamada-Nobusada, Tomoe; Komatsu, Hirokazu; Takei, Kentaro; Kuroha, Takeshi; Mizutani, Masaharu; Ashikari, Motoyuki; Ueguchi-Tanaka, Miyako; Matsuoka, Makoto; Suzuki, Koji; Sakakibara, Hitoshi

    2009-01-01

    We have developed a highly sensitive and high-throughput method for the simultaneous analysis of 43 molecular species of cytokinins, auxins, ABA and gibberellins. This method consists of an automatic liquid handling system for solid phase extraction and ultra-performance liquid chromatography (UPLC) coupled with a tandem quadrupole mass spectrometer (qMS/MS) equipped with an electrospray interface (ESI; UPLC-ESI-qMS/MS). In order to improve the detection limit of negatively charged compounds, such as gibberellins, we chemically derivatized fractions containing auxin, ABA and gibberellins with bromocholine that has a quaternary ammonium functional group. This modification, that we call ‘MS-probe’, makes these hormone derivatives have a positive ion charge and permits all compounds to be measured in the positive ion mode with UPLC-ESI-qMS/MS in a single run. Consequently, quantification limits of gibberellins increased up to 50-fold. Our current method needs 180 plant samples simultaneously. Application of this method to plant hormone profiling enabled us to draw organ distribution maps of hormone species in rice and also to identify interactions among the four major hormones in the rice gibberellin signaling mutants, gid1-3, gid2-1 and slr1. Combining the results of hormone profiling data with transcriptome data in the gibberellin signaling mutants allows us to analyze relationships between changes in gene expression and hormone metabolism. PMID:19369275

  20. Environmental Sensitivity Index (ESI) Atlas: Guam - 2005 maps and geographic information systems data (NODC Accession 0033616)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The most widely used approach to sensitive environment mapping in the U.S. is NOAA's Environmental Sensitivity Index (ESI). This approach systematically complies...

  1. Environmental Sensitivity Index (ESI) Atlas: Hawaii - 2001, maps and geographic information systems data (NODC Accession 0033632)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The most widely used approach to sensitive environment mapping in the U.S. is NOAA's Environmental Sensitivity Index (ESI). This approach systematically complies...

  2. Determination of linsidomine in human plasma by tandem LC-MS with ESI.

    Science.gov (United States)

    Sutherland, F C; de Jager, A D; Swart, K J; Hundt, H K; Scanes, T; Hundt, A F

    2000-04-01

    A sensitive method for the determination of linsidomine in plasma was developed, using high-performance liquid chromatographic (HPLC) separation with tandem mass spectrometric detection. Linsidomine was derivatised with propyl chloroformate and extracted with tert-butyl methyl ether/1,2-dichloroethane (55:45, v/v), back-extracted into HCl (0.01 M) followed by alkalinisation and back-extraction into ether; the final ether extract evaporated, reconstituted in mobile phase and then separated on a Phenomenex Luna C18 (2) 5 micron 2.1 x 150 mm column with a mobile phase consisting of methanol water formic acid (98/100%) (400:600:0.05, v/v/v) at a flow-rate of 0.4 ml min(-1). Detection was achieved by a Finnigan MAT mass spectrometer (LCQ) at unit resolution in the selected reaction monitoring (SRM) mode monitoring the transition of the protonated molecular ion m/z 257.0 to the product ion m/z 86.0. The mean recovery for linsidomine was 51% with a lower limit of quantification of 0.70 ng/ml using 1 ml plasma for extraction. This LC-MS/MS method for the determination of linsidomine in human plasma allows for better specificity and a higher sample throughput than the traditional LC-UV methods. It also demonstrates the profound effect that the composition of acidic modifiers and matrix constituents can have on the electrospray ionisation (ESI) of the analyte.

  3. Environmental Sensitivity Index (ESI) Atlas: Western Alaska - volume 1, geographic information systems data and data tables and volume 2, maps in portable document format (PDF) (NODC Accession 0046030)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Western Alaska. ESI data characterize estuarine environments and wildlife by their...

  4. A high-performance, flexible and robust metal nanotrough-embedded transparent conducting film for wearable touch screen panels

    Science.gov (United States)

    Im, Hyeon-Gyun; An, Byeong Wan; Jin, Jungho; Jang, Junho; Park, Young-Geun; Park, Jang-Ung; Bae, Byeong-Soo

    2016-02-01

    We report a high-performance, flexible and robust metal nanotrough-embedded transparent conducting hybrid film (metal nanotrough-GFRHybrimer). Using an electro-spun polymer nanofiber web as a template and vacuum-deposited gold as a conductor, a junction resistance-free continuous metal nanotrough network is formed. Subsequently, the metal nanotrough is embedded on the surface of a glass-fabric reinforced composite substrate (GFRHybrimer). The monolithic composite structure of our transparent conducting film allows simultaneously high thermal stability (24 h at 250 °C in air), a smooth surface topography (Rrms touch screen panel (TSP) is fabricated using the transparent conducting films. The flexible TSP device stably operates on the back of a human hand and on a wristband.We report a high-performance, flexible and robust metal nanotrough-embedded transparent conducting hybrid film (metal nanotrough-GFRHybrimer). Using an electro-spun polymer nanofiber web as a template and vacuum-deposited gold as a conductor, a junction resistance-free continuous metal nanotrough network is formed. Subsequently, the metal nanotrough is embedded on the surface of a glass-fabric reinforced composite substrate (GFRHybrimer). The monolithic composite structure of our transparent conducting film allows simultaneously high thermal stability (24 h at 250 °C in air), a smooth surface topography (Rrms touch screen panel (TSP) is fabricated using the transparent conducting films. The flexible TSP device stably operates on the back of a human hand and on a wristband. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07657a

  5. Determination of the glycation sites of Bacillus anthracis neoglycoconjugate vaccine by MALDI-TOF/TOF-CID-MS/MS and LC-ESI-QqTOF-tandem mass spectrometry

    Science.gov (United States)

    Jahouh, Farid; Hou, Shu-jie; Kováč, Pavol; Banoub, Joseph H.

    2012-01-01

    We present herein an efficient mass spectrometric method for the localization of the glycation sites of a model neoglycoconjugate vaccine formed by a construct of the tetrasaccharide side chain of the Bacillus anthracis exosporium and the protein carrier bovine serum albumin. The glycoconjugate was digested with both trypsin and GluC V8 endoproteinases, and the digests were then analyzed by MALDI-TOF/TOF-CID-MS/MS and nano-LC-ESI-QqTOF-CID-MS/MS. The sequences of the unknown peptides analyzed by MALDI-TOF/TOF-CID-MS/MS, following digestion with the GluC V8 endoproteinase, allowed us to recognize three glycopeptides whose glycation occupancies were, respectively, on Lys 235, Lys 420, and Lys 498. Similarly, the same analysis was performed on the tryptic digests, which permitted us to recognize two glycation sites on Lys 100 and Lys 374. In addition, we have also used LC-ESI-QqTOF-CID-MS/MS analysis for the identification of the tryptic digests. However, this analysis identified a higher number of glycopeptides than would be expected from a glycoconjugate composed of a carbohydrate–protein ratio of 5.4:1, which would have resulted in glycation occupancies of 18 specific sites. This discrepancy was due to the large number of glycoforms formed during the synthetic carbohydrate–spacer–carrier protein conjugation. Likewise, the LC-ESI-QqTOF-MS/MS analysis of the GluC V8 digest also identified 17 different glycation sites on the synthetic glycoconjugate. PMID:22012665

  6. Electricity system performance: options and opportunities for developing countries. Synthesis report of the cooperative programme on energy and development

    International Nuclear Information System (INIS)

    Adilson de Oliveira

    1992-01-01

    This report focuses on the crisis in the performance of the Electricity Supply Industries (ESI) of Africa, Asia and Latin America, and is based on the research of the Network Centres during 1990-91. It provides a review of the performance of the ESI that ranges widely from the issues of technical efficiency, through the more controversial aspects of financial and economic efficiency, to the more diffuse aspects of the social and environmental measures of performance.47 refs., 3 figs., 10 tabs., 2 appendices

  7. Proanthocyanidin screening by LC-ESI-MS of Portuguese red wines made with teinturier grapes.

    Science.gov (United States)

    Teixeira, Natércia; Azevedo, Joana; Mateus, Nuno; de Freitas, Victor

    2016-01-01

    Proanthocyanidins (PAs) are one of the most important polyphenolic compounds in wine. Among PAs, prodelphinidin (PD) dimers and trimers have not been widely detected in wines due to the lack of available commercial standards and the difficulty to detect and isolate them from natural sources. LC-ESI-MS (liquid chromatography-electrospray ionization-mass spectrometry) with the right chromatographic conditions has proven to be a powerful tool for PAs detection and identification in complex samples. This technique has been applied to an exhaustive study of PA composition of two Portuguese red wines made with teinturier grapes, especially for the identification of PD dimers and trimers. Tandem mass spectrometry (MS/MS) with ion trap provided additional information about the structures of these compounds through the fragmentation patterns of the pseudomolecular ions. A LC-ESI-MS method was optimized and 41 different compounds were found. Among them are included 8 PD dimers and 13 PD trimers. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Comparison of LC-ESI-MS and GC-MS for the Analysis of a Synthetic Tabun Sample

    National Research Council Canada - National Science Library

    D'Agostino, Paul

    2003-01-01

    Packed capillary LC-ESI-MS and capillary column GC-MS were compared for the analysis of a synthetic tabun sample as each method has advantages for the analysis of samples containing chemical warfare...

  9. Environmental Sensitivity Index (ESI) Atlas: Hawaii, December 2001, 2002, Volume 1 and 2 (NODC Accession 0002828)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Currently, the most widely used approach to sensitive environment mapping in the United States is the NOAA Environmental Sensitivity Index or ESI. This approach...

  10. First characterisation of flavonoid- and diarylheptanoid-type antioxidant phenolics in Corylus maxima by HPLC-DAD-ESI-MS.

    Science.gov (United States)

    Riethmüller, Eszter; Tóth, Gergő; Alberti, Ágnes; Végh, Krisztina; Burlini, Ilaria; Könczöl, Árpád; Balogh, György Tibor; Kéry, Ágnes

    2015-03-25

    Corylus maxima Mill. (Betulaceae) leaves have been used in traditional medicine both internally and externally, nevertheless phytochemical exploration of the plant remains incomplete. In this study, the in vitro antioxidant activity and polyphenolic composition of the ethyl acetate and methanolic extracts of C. maxima leaves and bark are reported for the first time. The radical scavenging activities of the extracts were investigated by the ABTS and DPPH assays. All the extracts of C. maxima possessed notable antioxidant activity. By mean of a HPLC-DAD-ESI-TOF and a HPLC-DAD-ESI-MS/MS method, altogether twenty-two phenolics were tentatively characterised: one flavan derivative (1), seven flavonol derivatives (4, 6, 12, 13, 16, 20 and 21) and fourteen diarylheptanoids (2, 3, 5, 7-11, 14, 15, 17-19 and 22). The amount of the two main flavonoids - myricetin-3-O-rhamnoside (6) and quercetin-3-O-rhamnoside (13) - and two diarylheptanoids - oregonin (3) and hirsutenone (15) - in the extracts were determined by a validated HPLC-ESI-MS/MS method in multiple reaction monitoring (MRM) mode. Our results showed that C. maxima could be considered as a valuable source of pharmacologically important natural products that might contribute to the revaluation of the phytotherapeutical potential of the plant. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Medicinal cannabis: Principal cannabinoids concentration and their stability evaluated by a high performance liquid chromatography coupled to diode array and quadrupole time of flight mass spectrometry method.

    Science.gov (United States)

    Citti, Cinzia; Ciccarella, Giuseppe; Braghiroli, Daniela; Parenti, Carlo; Vandelli, Maria Angela; Cannazza, Giuseppe

    2016-09-05

    In the last few years, there has been a boost in the use of cannabis-based extracts for medicinal purposes, although their preparation procedure has not been standardized but rather decided by the individual pharmacists. The present work describes the development of a simple and rapid high performance liquid chromatography method with UV detection (HPLC-UV) for the qualitative and quantitative determination of the principal cannabinoids (CBD-A, CBD, CBN, THC and THC-A) that could be applied to all cannabis-based medicinal extracts (CMEs) and easily performed by a pharmacist. In order to evaluate the identity and purity of the analytes, a high-resolution mass spectrometry (HPLC-ESI-QTOF) analysis was also carried out. Full method validation has been performed in terms of specificity, selectivity, linearity, recovery, dilution integrity and thermal stability. Moreover, the influence of the solvent (ethyl alcohol and olive oil) was evaluated on cannabinoids degradation rate. An alternative extraction method has then been proposed in order to preserve cannabis monoterpene component in final CMEs. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Identification of some chemical constituents of Indigofera hirsuta Linn. (Fabaceae) by HPLC-ESI-MS (TOF) and evaluation of the anti radical activity

    International Nuclear Information System (INIS)

    Moura, Adriana Candido da Silva; Vilegas, Wagner; Santos, Lourdes Campaner dos

    2011-01-01

    A rapid analytical approach, suitable to characterize the compounds present in the aqueous and methanol extracts prepared from the aerial parts of Indigofera hirsute, was developed. The method based on high-performance liquid chromatography coupled to mass spectrometry, electrospray positive ionization and detection by time of flight (HPLC-ESI-MS-TOF) identified, tryptophan, uracil, rutin, kempferol-3-Oβ - -D-glucopyranoside, gallic acid and methyl gallate. The antiradical activity of this extract was evaluated using DPPH assay, with gallic acid as antiradical pattern. The study revealed the antiradical activity of methyl galatte (EC 50 = 5 ± 0.3 μg mL -1 ) gallic acid (EC 50 = 5 ± 0.2 μg mL -1 ) and rutin (EC 50 = 21.6 ± 0.6 μg m L -1 ), isolated from methanol extract (EC 50 = 67.7 ± 0.9 μg mL -1 ), which showed strong antiradical activity. (author)

  13. Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors

    Science.gov (United States)

    Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

    2013-08-01

    indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage. Electronic supplementary information (ESI) available: Detailed methods of preparation of GOBINPPA, SEM images, IR spectra, TGA, nitrogen adsorption-desorption isotherms, pore size distribution, gravimetric hydrogen adsorption, carbon dioxide adsorption isotherms, and virial analysis of the adsorption data for GOBIN materials. See DOI: 10.1039/c3nr01480k

  14. Environmental Sensitivity Index (ESI) Atlas: Northern California maps and geographic information systems data (NODC Accession 0013175)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps for the shoreline of northern California which were designed to be utilized in desktop GIS...

  15. ESI-VI3 East Point, St. Croix, U.S. Virgin Islands 2000 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  16. Environmental Sensitivity Index (ESI) Atlas: West Florida, maps and geographic information systems data (NODC Accession 0006249)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) maps in Portable Document Format (.PDF) for the shoreline of West Florida (to encompass the coastal...

  17. High-Performance Liquid Chromatography with Diode Array Detector and Electrospray Ionization Ion Trap Time-of-Flight Tandem Mass Spectrometry to Evaluate Ginseng Roots and Rhizomes from Different Regions.

    Science.gov (United States)

    Wang, Hong-Ping; Zhang, You-Bo; Yang, Xiu-Wei; Yang, Xin-Bao; Xu, Wei; Xu, Feng; Cai, Shao-Qing; Wang, Ying-Ping; Xu, Yong-Hua; Zhang, Lian-Xue

    2016-05-09

    Ginseng, Panax ginseng C. A. Meyer, is an industrial crop in China and Korea. The functional components in ginseng roots and rhizomes are characteristic ginsenosides. This work developed a new high-performance liquid chromatography coupled with electrospray ionization ion trap time-of-flight multistage mass spectrometry (LC-ESI-IT-TOF-MS(n)) method to identify the triterpenoids. Sixty compounds (1-60) including 58 triterpenoids were identified from the ginseng cultivated in China. Substances 1, 2, 7, 15-20, 35, 39, 45-47, 49, 55-57, 59, and 60 were identified for the first time. To evaluate the quality of ginseng cultivated in Northeast China, this paper developed a practical liquid chromatography-diode array detection (LC-DAD) method to simultaneously quantify 14 interesting ginsenosides in ginseng collected from 66 different producing areas for the first time. The results showed the quality of ginseng roots and rhizomes from different sources was different due to growing environment, cultivation technology, and so on. The developed LC-ESI-IT-TOF-MS(n) method can be used to identify many more ginsenosides and the LC-DAD method can be used not only to assess the quality of ginseng, but also to optimize the cultivation conditions for the production of ginsenosides.

  18. Sequencing Lys-N Proteolytic Peptides by ESI and MALDI Tandem Mass Spectrometry

    Science.gov (United States)

    Dupré, Mathieu; Cantel, Sonia; Verdié, Pascal; Martinez, Jean; Enjalbal, Christine

    2011-02-01

    In this study, we explored the MS/MS behavior of various synthetic peptides that possess a lysine residue at the N-terminal position. These peptides were designed to mimic peptides produced upon proteolysis by the Lys-N enzyme, a metalloendopeptidase issued from a Japanese fungus Grifola frondosa that was recently investigated in proteomic studies as an alternative to trypsin digestion, as a specific cleavage at the amide X-Lys chain is obtained that provides N-terminal lysine peptide fragments. In contrast to tryptic peptides exhibiting a lysine or arginine residue solely at the C-terminal position, and are thus devoid of such basic amino acids within the sequence, these Lys-N proteolytic peptides can contain the highly basic arginine residue anywhere within the peptide chain. The fragmentation patterns of such sequences with the ESI-QqTOF and MALDI-TOF/TOF mass spectrometers commonly used in proteomic bottom-up experiments were investigated.

  19. Randomized double-blinded pilot clinical study of the antidiabetic activity of Balanites aegyptiaca and UPLC-ESI-MS/MS identification of its metabolites.

    Science.gov (United States)

    Rashad, Hend; Metwally, Fateheya M; Ezzat, Shahira M; Salama, Maha M; Hasheesh, Adel; Abdel Motaal, Amira

    2017-12-01

    Balanites aegyptiaca Del. (Zygophyllaceae) fruits are traditionally known for the treatment of hyperglycaemia. Several in vitro and in vivo studies proposed some mechanisms of action. However, clinical trials in human beings were never reported to date. To investigate the antidiabetic efficacy of the 70% ethanol extract of the pericarps of B. aegyptiaca (BE) within a nutritional intervention in elderly people. Ultra-performance electrospray ionization-mass spectroscopy (UPLC-ESI-MS/MS) analysis was used for metabolic profiling of BE which was incorporated in hard gelatine capsules (400 mg/day) and tested on 30 type 2 diabetes (T2D) Egyptian patients for 8 weeks. According to sex, age and body mass index participants were divided into two equivalent groups, placebo and treatment. Thirteen compounds were identified in BE using UPLC-ESI-MS/MS analysis among which five steroidal saponins, seven phenolic compounds and a sterol glucoside. At the end of the 8-week treatment, the treated group showed 26.88% decrease in 2 h postprandial plasma glucose relative to 2.6% increase in the placebo group, while fasting plasma glucose was reduced to 10.3%. Treatment with BE capsules for 8 weeks produced significant reduction in the plasma triglyceride, total cholesterol and low-density lipoprotein cholesterol by 9.0, 12.76 and 21.35%, respectively, with 29.8% increase in the high-density lipoprotein cholesterol. Plasma alanine transaminase and aspartate transaminase were reduced by 42.6 and 43.3%, respectively. Administration of the BE capsules to T2D resulted in significant improvements in the glycaemic markers and the lipid profile, without adverse effects or hypoglycaemia.

  20. Identification of Iridoids in Edible Honeysuckle Berries (Lonicera caerulea L. var. kamtschatica Sevast. by UPLC-ESI-qTOF-MS/MS

    Directory of Open Access Journals (Sweden)

    Alicja Z. Kucharska

    2016-09-01

    Full Text Available Iridoid profiles of honeysuckle berry were studied. Compounds were identified by ultra-performance liquid chromatography coupled with electrospray ionization mass spectrometry UPLC-ESI-qTOF-MS/MS in positive and negative ions mode. The MS fragmentation pathways of detected iridoid glycosides were also studied in both modes. In the negative ESI mass spectra, iridoids with a methyl ester or lactone structure have preferentially produced adduct [M + HCOOH − H]− ions. However, protonated ions of molecular fragments, which were released by glycosidic bond cleavage and following fragmentation of aglycone rings, were more usable for iridoid structure analysis. In addition, the neutral losses of H2O, CO, CO2, CH3OH, acetylene, ethenone and cyclopropynone have provided data confirming the presence of functional substituents in the aglycone. Among the 13 iridoids, 11 were identified in honeysuckle berries for the first time: pentosides of loganic acid (two isomers, pentosides of loganin (three isomers, pentosyl sweroside, and additionally 7-epi-loganic acid, 7-epi-loganin, sweroside, secologanin, and secoxyloganin. The five pentoside derivatives of loganic acid and loganin have not been previously detected in the analyzed species. Honeysuckle berries are a source of iridoids with different structures, compounds that are rarely present in fruits.

  1. Structural Feature Ions for Distinguishing N- and O-Linked Glycan Isomers by LC-ESI-IT MS/MS

    Science.gov (United States)

    Everest-Dass, Arun V.; Abrahams, Jodie L.; Kolarich, Daniel; Packer, Nicolle H.; Campbell, Matthew P.

    2013-06-01

    Glycomics is the comprehensive study of glycan expression in an organism, cell, or tissue that relies on effective analytical technologies to understand glycan structure-function relationships. Owing to the macro- and micro-heterogeneity of oligosaccharides, detailed structure characterization has required an orthogonal approach, such as a combination of specific exoglycosidase digestions, LC-MS/MS, and the development of bioinformatic resources to comprehensively profile a complex biological sample. Liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS/MS) has emerged as a key tool in the structural analysis of oligosaccharides because of its high sensitivity, resolution, and robustness. Here, we present a strategy that uses LC-ESI-MS/MS to characterize over 200 N- and O-glycans from human saliva glycoproteins, complemented by sequential exoglycosidase treatment, to further verify the annotated glycan structures. Fragment-specific substructure diagnostic ions were collated from an extensive screen of the literature available on the detailed structural characterization of oligosaccharides and, together with other specific glycan structure feature ions derived from cross-ring and glycosidic-linkage fragmentation, were used to characterize the glycans and differentiate isomers. The availability of such annotated mass spectrometric fragmentation spectral libraries of glycan structures, together with such substructure diagnostic ions, will be key inputs for the future development of the automated elucidation of oligosaccharide structures from MS/MS data.

  2. Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

    Science.gov (United States)

    Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana

    2018-01-01

    Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

  3. Simultaneous quantification of the organophosphorus pesticides dimethoate and omethoate in porcine plasma and urine by LC-ESI-MS/MS and flow-injection-ESI-MS/MS.

    Science.gov (United States)

    John, Harald; Eddleston, Michael; Clutton, R Eddie; Worek, Franz; Thiermann, Horst

    2010-05-15

    Dimethoate is an organophosphorus toxicant used in agri- and horticulture as a systemic broad-spectrum insecticide. It also exhibits toxic activity towards mammalian organism provoked by catalytic desulfuration in the liver producing its oxon-derivative omethoate thus inhibiting acetylcholinesterase, initiating cholinergic crisis and ultimately leading to death by respiratory paralysis and cardiovascular collapse. Pharmaco- and toxicokinetic studies in animal models help to broaden basic understanding of medical intervention by antidotes and supportive care. Therefore, we developed and validated a LC-ESI-MS/MS method suitable for the simultaneous, selective, precise (RSD(intra-day) 1-8%; RSD(inter-day) 5-14%), accurate (intra-day: 95-107%; inter-day: 90-115%), and robust quantification of both pesticides from porcine urine and plasma after deproteinization by precipitation and extensive dilution (1:11,250 for plasma and 1:40,000 for urine). Accordingly, lower limits of quantification (0.24-0.49 microg/ml plasma and 0.78-1.56 microg/ml urine) and lower limits of detection (0.12-0.24 microg/ml plasma and 0.39-0.78 microg/ml urine) were equivalent to quite low absolute on-column amounts (1.1-2.1 pg for plasma and 2.0-3.9 pg for urine). The calibration range (0.24-250 microg/ml plasma and 0.78-200 microg/ml urine) was subdivided into two linear ranges (r(2)>or=0.998) each covering nearly two orders of magnitude. The lack of any interfering peak in 6 individual blank specimens from plasma and urine demonstrated the high selectivity of the method. Furthermore, extensive sample dilution causing lowest concentration of potentially interfering matrix ingredients prompted us to develop and validate an additional flow-injection method (FI-ESI-MS/MS). Validation characteristics were as good as for the chromatographic method but sample throughput was enhanced by a factor of 6. Effects on ionization provoked by plasma and urine matrix from 6 individuals as well as in the

  4. Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures – Application to the petroleomic analysis of bio-oils

    Energy Technology Data Exchange (ETDEWEB)

    Hertzog, Jasmine [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Carré, Vincent, E-mail: vincent.carre@univ-lorraine.fr [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Le Brech, Yann [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mackay, Colin Logan [SIRCAMS, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, Scotland (United Kingdom); Dufour, Anthony [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mašek, Ondřej [UK Biochar Research Center, School of Geosciences, University of Edinburgh, Kings Buildings, Edinburgh, EH9 3JN (United Kingdom); and others

    2017-05-29

    The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C{sub x}H{sub y}O{sub z} with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. - Highlights: • Non-targeted mass spectrometry by combining electrospray ionization, atmospheric pressure photoionization and laser/desorption ionization. • Exhaustive description of pyrolytic bio-oil components. • Distinction of sugaric derivatives, lignin derivatives and lipids contained in a woody-based pyrolytic bio-oil.

  5. Characterization and quantification of racemic and meso-ethylenediamine-N,N'-bis(2-hydroxy-5-sulfophenylacetic) acid/iron (III) by ion-pair ultra-high performance liquid chromatography coupled with diode array detector and electrospray tandem mass spectrometry.

    Science.gov (United States)

    Biasone, Alessandro; Cianci, Giusto; Di Tommaso, Donata; Piaggesi, Alberto; Tagliavini, Emilio; Galletti, Paola; Moretti, Fabio

    2013-03-22

    EDDHSA/Fe is a promising substitute of EDDHA/Fe to fight iron chlorosis. o,o-EDDHSA structure contains two chiral carbons giving the racemic and meso couples of stereoisomers. Ion-pair HPLC and UHPLC-UV/Vis-ESI-MS/MS methods were developed for the determination of racemic and meso-o,o-EDDHSA/Fe in commercial samples of chelates. The lack of a commercial EDDHSA standard was overcome by sulfonation of a commercial available o,o-EDDHA standard and subsequent quantification by (1)H-NMR. Assignment of configurations was carried out starting from racemic and meso-o,o-EDDHA/Fe by direct sulfonation to give the corresponding o,o-EDDHSA/Fe isomers. The performances of these methods were assessed in terms of intra and inter-day precision, linearity and selectivity. The high selectivity and lower detection limit (nanomolar) of the UHPLC-ESI-MS/MS method could allow to deepen the knowledge relative to meso and rac-o,o-EDDHSA/Fe interactions with plants, its fate in different soil conditions, its mobility and other environmental aspects. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. High performance homes

    DEFF Research Database (Denmark)

    Beim, Anne; Vibæk, Kasper Sánchez

    2014-01-01

    Can prefabrication contribute to the development of high performance homes? To answer this question, this chapter defines high performance in more broadly inclusive terms, acknowledging the technical, architectural, social and economic conditions under which energy consumption and production occur....... Consideration of all these factors is a precondition for a truly integrated practice and as this chapter demonstrates, innovative project delivery methods founded on the manufacturing of prefabricated buildings contribute to the production of high performance homes that are cost effective to construct, energy...

  7. Sulphur fertilization influences the sulphur species composition in Allium sativum: sulphomics using HPLC-ICPMS/MS-ESI-MS/MS.

    Science.gov (United States)

    Raab, Andrea; Ronzan, Marilena; Feldmann, Joerg

    2017-10-18

    Garlic (A. sativum) contains a large number of small sulphur (S)-containing metabolites, which are important for its taste and smell and vary with A. sativum variety and growth conditions. This study was designed to investigate the influence of different sulphur-fertilization regimes on low molecular weight S-species by attempting the first sulphur mass balance in A. sativum roots and bulbs using HPLC-ICPMS/MS-ESI-MS/MS. Species unspecific quantification of acid soluble S-containing metabolites was achieved using HPLC-ICP-MS/MS. For identification of the compounds, high resolution ESI-MS (Orbitrap LTQ and q-TOF) was used. The plants contained up to 54 separated sulphur-containing compounds, which constitute about 80% of the total sulphur present in A. sativum. The roots and bulbs of A. sativum contained the same compounds, but not necessarily the same amounts and proportions. The S-containing metabolites in the roots reacted more sensitively to manipulations of sulphur fertilization than those compounds in the bulbs. In addition to known compounds (e.g. γ-glutamyl-S-1-propenylcysteine) we were able to identify and partially quantify 31 compounds. Three as yet undescribed S-containing compounds were also identified and quantified for the first time. Putative structures were assigned to the oxidised forms of S-1-propenylmercaptoglutathione, S-2-propenylmercaptoglutathione, S-allyl/propenyl-containing PC-2 and 2-amino-3-[(2-carboxypropyl)sulfanyl]propanoic acid. The parallel use of ICP-MS/MS as a sulphur-specific detector and ESI-MS as a molecular detector simplifies the identification and quantification of sulphur containing metabolites without species specific standards. This non-target analysis approach enables a mass balance approach and identifies the occurrence of the so far unidentified organosulphur compounds. The experiments showed that the sulphur-fertilization regime does not influence sulphur-speciation, but the concentration of some S

  8. Coupling of gas chromatography and electrospray ionization high resolution mass spectrometry for the analysis of anabolic steroids as trimethylsilyl derivatives in human urine.

    Science.gov (United States)

    Cha, Eunju; Jeong, Eun Sook; Cha, Sangwon; Lee, Jaeick

    2017-04-29

    In this study, gas chromatography (GC) was interfaced with high resolution mass spectrometry (HRMS) with electrospray ionization source (ESI) and the relevant parameters were investigated to enhance the ionization efficiency. In GC-ESI, the distances (x-, y- and z) and angle between the ESI needle, GC capillary column and MS orifice were set to 7 (x-distance), 4 (y-distance), and 1 mm (z-distance). The ESI spray solvent, acid modifier and nebulizer gas flow were methanol, 0.1% formic acid and 5 arbitrary units, respectively. Based on these results, analytical conditions for GC-ESI/HRMS were established. In particular, the results of spray solvent flow indicated a concentration-dependent mechanism (peak dilution effect), and other parameters also greatly influenced the ionization performance. The developed GC-ESI/HRMS was then applied to the analysis of anabolic steroids as trimethylsilyl (TMS) derivatives in human urine to demonstrate its application. The ionization profiles of TMS-derivatized steroids were investigated and compared with those of underivatized steroids obtained from gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS). The steroids exhibited ionization profiles based on their structural characteristics, regardless of the analyte phase or derivatization. Groups I and II with conjugated or unconjugated keto functional groups at C3 generated the [M+H] + and [M+H-TMS] + ions, respectively. On the other hand, Groups III and IV gave rise to the characteristic fragment ions [M+H-TMS-H 2 O] + and [M+H-2TMS-H 2 O] + , corresponding to loss of a neutral TMS·H 2 O moiety from the protonated molecular ion by in-source dissociation. To the best of our knowledge, this is the first study to successfully ionize and analyze steroids as TMS derivatives using ESI coupled with GC. The present system has enabled the ionization of TMS derivatives under ESI conditions

  9. Environmental Sensitivity Index (ESI) Atlas: Bristol Bay, Alaska, maps and geographic information systems data (NODC Accession 0033382)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The most widely used approach to sensitive environment mapping in the United States is the NOAA Environmental Sensitivity Index (ESI). This approach systematically...

  10. Instrument evaluation no. 11. ESI nuclear model 271 C contamination monitor

    International Nuclear Information System (INIS)

    Burgess, P.H.; Iles, W.J.

    1978-06-01

    The various radiations encountered in radiological protection cover a wide range of energies and radiation measurements have to he carried out under an equally broad spectrum of environmental conditions. This report is one of a series intended to give information on the performance characteristics of radiological protection instruments, to assist in the selection of appropriate instruments for a given purpose, to interpret the results obtained with such instruments, and, in particular, to know the likely sources and magnitude of errors that might be associated with measurements in the field. The radiation, electrical and environmental characteristics of radiation protection instruments are considered together with those aspects of the construction which make an instrument convenient for routine use. To provide consistent criteria for instrument performance, the range of tests performed on any particular class of instrument, the test methods and the criteria of acceptable performance are based broadly on the appropriate Recommendations of the International Electrotechnical Commission. The radiations in the tests are, in general, selected from the range of reference radiations for instrument calibration being drawn up by the International Standards Organisation. Normally, each report deals with the capabilities and limitations of one model of instrument and no direct comparison with other instruments intended for similar purposes is made, since the significance of particular performance characteristics largely depends on the radiations and environmental conditions in which the instrument is to be used. The results quoted here have all been obtained from tests on instruments in routine production, with the appropriate measurements being made by the NRPB. This report deals with the ESI Nuclear Model 271 C; a general purpose contamination monitor, comprising a GM tube connected by a coiled extensible cable to a ratemeter

  11. Ultra high performance supercritical fluid chromatography coupled with tandem mass spectrometry for screening of doping agents. I: Investigation of mobile phase and MS conditions.

    Science.gov (United States)

    Nováková, Lucie; Grand-Guillaume Perrenoud, Alexandre; Nicoli, Raul; Saugy, Martial; Veuthey, Jean-Luc; Guillarme, Davy

    2015-01-01

    The conditions for the analysis of selected doping substances by UHPSFC-MS/MS were optimized to ensure suitable peak shapes and maximized MS responses. A representative mixture of 31 acidic and basic doping agents was analyzed, in both ESI+ and ESI- modes. The best compromise for all compounds in terms of MS sensitivity and chromatographic performance was obtained when adding 2% water and 10mM ammonium formate in the CO2/MeOH mobile phase. Beside mobile phase, the nature of the make-up solvent added for interfacing UHPSFC with MS was also evaluated. Ethanol was found to be the best candidate as it was able to compensate for the negative effect of 2% water addition in ESI- mode and provided a suitable MS response for all doping agents. Sensitivity of the optimized UHPSFC-MS/MS method was finally assessed and compared to the results obtained in conventional UHPLC-MS/MS. Sensitivity was improved by 5-100-fold in UHPSFC-MS/MS vs. UHPLC-MS/MS for 56% of compounds, while only one compound (bumetanide) offered a significantly higher MS response (4-fold) under UHPLC-MS/MS conditions. In the second paper of this series, the optimal conditions for UHPSFC-MS/MS analysis will be employed to screen >100 doping agents in urine matrix and results will be compared to those obtained by conventional UHPLC-MS/MS. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. [Qualitative and quantitative analysis of amygdalin and its metabolite prunasin in plasma by ultra-high performance liquid chromatography-tandem quadrupole time of flight mass spectrometry and ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry].

    Science.gov (United States)

    Gao, Meng; Wang, Yuesheng; Wei, Huizhen; Ouyang, Hui; He, Mingzhen; Zeng, Lianqing; Shen, Fengyun; Guo, Qiang; Rao, Yi

    2014-06-01

    A method was developed for the determination of amygdalin and its metabolite prunasin in rat plasma after intragastric administration of Maxing shigan decoction. The analytes were identified by ultra-high performance liquid chromatography-tandem quadrupole time of flight mass spectrometry and quantitatively determined by ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry. After purified by liquid-liquid extraction, the qualitative analysis of amygdalin and prunasin in the plasma sample was performed on a Shim-pack XR-ODS III HPLC column (75 mm x 2.0 mm, 1.6 microm), using acetonitrile-0.1% (v/v) formic acid aqueous solution. The detection was performed on a Triple TOF 5600 quadrupole time of flight mass spectrometer. The quantitative analysis of amygdalin and prunasin in the plasma sample was performed by separation on an Agilent C18 HPLC column (50 mm x 2.1 mm, 1.7 microm), using acetonitrile-0.1% (v/v) formic acid aqueous solution. The detection was performed on an AB Q-TRAP 4500 triple quadrupole mass spectrometer utilizing electrospray ionization (ESI) interface operated in negative ion mode and multiple-reaction monitoring (MRM) mode. The qualitative analysis results showed that amygdalin and its metabolite prunasin were detected in the plasma sample. The quantitative analysis results showed that the linear range of amygdalin was 1.05-4 200 ng/mL with the correlation coefficient of 0.999 0 and the linear range of prunasin was 1.25-2 490 ng/mL with the correlation coefficient of 0.997 0. The method had a good precision with the relative standard deviations (RSDs) lower than 9.20% and the overall recoveries varied from 82.33% to 95.25%. The limits of detection (LODs) of amygdalin and prunasin were 0.50 ng/mL. With good reproducibility, the method is simple, fast and effective for the qualitative and quantitative analysis of the amygdalin and prunasin in plasma sample of rats which were administered by Maxing shigan decoction.

  13. ESI-HI85 Niihau South and Kaula Island, Island of Niihau, Hawaii 2001 (Environmental Sensitivity Index Map)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Environmental Sensitivity Index (ESI) maps are an integral component in oil-spill contingency planning and assessment. They serve as a source of information in the...

  14. Simultaneous detection of water-soluble vitamins using the High Performance Liquid Chromatography (HPLC - a review

    Directory of Open Access Journals (Sweden)

    Rosemond Godbless Dadzie

    2014-01-01

    Full Text Available The water-soluble vitamins (WSV: ascorbic acid (vitamin C, thiamine (B1, riboflavin (B2, niacin (B3, panthothenic acid (B5, pyridoxine, and pyridoxal (B6, folic acid (B9, biotin(B8 , and B12 are very essential in the diet of humankind. As a result of ever increasing pressures from both consumers and legal enforcers, to specify accurately nutritive compositions of WSV that are present in food materials, many researchers have attempted to fill this niche through the provision of highly sensitive and rapid high performance liquid chromatography (HPLC procedures. In view of the health benefits of WSV, a replete of HPLC methods have been developed for simultaneous determination of their contents in nature and fortified food samples, nutritional supplements, as well as blood plasmas. The rate of losses of these vitamins during food processing and analysis, in addition to their transient dynamics, presents complexities in developing a highly sensitive HPLC procedure for their simultaneous separations and assays. This review critically assesses the different HPLC procedures developed by researchers and available in the open literature for simultaneous determination of water-soluble vitamins (WSV in dried tropical fruits materials. The study revealed that not a single chromatographic run developed by researchers can simultaneously elute all the WSV at a time. However, the HPLC procedures that are capable of determining all the WSV were coupled with electrospray ionization mass spectroscopy (ESI-MS, thus making the set-up expensive.

  15. Hydroponic isotope labeling of entire plants and high-performance mass spectrometry for quantitative plant proteomics.

    Science.gov (United States)

    Bindschedler, Laurence V; Mills, Davinia J S; Cramer, Rainer

    2012-01-01

    Hydroponic isotope labeling of entire plants (HILEP) combines hydroponic plant cultivation and metabolic labeling with stable isotopes using (15)N-containing inorganic salts to label whole and mature plants. Employing (15)N salts as the sole nitrogen source for HILEP leads to the production of healthy-looking plants which contain (15)N proteins labeled to nearly 100%. Therefore, HILEP is suitable for quantitative plant proteomic analysis, where plants are grown in either (14)N- or (15)N-hydroponic media and pooled when the biological samples are collected for relative proteome quantitation. The pooled (14)N-/(15)N-protein extracts can be fractionated in any suitable way and digested with a protease for shotgun proteomics, using typically reverse phase liquid chromatography nanoelectrospray ionization tandem mass spectrometry (RPLC-nESI-MS/MS). Best results were obtained with a hybrid ion trap/FT-MS mass spectrometer, combining high mass accuracy and sensitivity for the MS data acquisition with speed and high-throughput MS/MS data acquisition, increasing the number of proteins identified and quantified and improving protein quantitation. Peak processing and picking from raw MS data files, protein identification, and quantitation were performed in a highly automated way using integrated MS data analysis software with minimum manual intervention, thus easing the analytical workflow. In this methodology paper, we describe how to grow Arabidopsis plants hydroponically for isotope labeling using (15)N salts and how to quantitate the resulting proteomes using a convenient workflow that does not require extensive bioinformatics skills.

  16. Characterisation of tryptic peptides of phosphorylated tyrosine hydroxylase by high-pressure liquid chromatography electrospray ionisation mass spectrometry

    International Nuclear Information System (INIS)

    Graham, Mark E.; Dickson, Phillip W.; Dunkley, Peter R.; Nagy-Felsobuki, Ellak I. von

    2005-01-01

    Tyrosine hydroxylase (TH) is involved in the biosynthesis of catecholamines and is activated by phosphorylation. Phosphorylated TH was analysed using high-pressure liquid chromatography combined with electrospray mass spectrometry (HPLC ESI-MS). Two mass scanning methods were used to detect tryptic cleavage products of TH. In the positive electrospray ionisation mode (ESI+), the peptides that contain the phosphorylation sites of TH were identified. In the alternative method, a phosphopeptide was detected in the negative electrospray ionisation mode (ESI-) using single ion monitoring in combination with a sequential ESI+ switching experiment. A raised baseline interfered with detection of hydrophilic peptides in ESI-, with the signal-to-noise ratio indicating that the method was operating near the limit of detection for a conventional electrospray source. The switching method improved the certainty of identification of phosphopeptides

  17. Sensitive determination of thiols in wine samples by a stable isotope-coded derivatization reagent d0/d4-acridone-10-ethyl-N-maleimide coupled with high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry analysis.

    Science.gov (United States)

    Lv, Zhengxian; You, Jinmao; Lu, Shuaimin; Sun, Weidi; Ji, Zhongyin; Sun, Zhiwei; Song, Cuihua; Chen, Guang; Li, Guoliang; Hu, Na; Zhou, Wu; Suo, Yourui

    2017-03-31

    As the key aroma compounds, varietal thiols are the crucial odorants responsible for the flavor of wines. Quantitative analysis of thiols can provide crucial information for the aroma profiles of different wine styles. In this study, a rapid and sensitive method for the simultaneous determination of six thiols in wine using d 0 /d 4 -acridone-10-ethyl-N-maleimide (d 0 /d 4 -AENM) as stable isotope-coded derivatization reagent (SICD) by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) has been developed. Quantification of thiols was performed by using d 4 -AENM labeled thiols as the internal standards (IS), followed by stable isotope dilution HPLC-ESI-MS/MS analysis. The AENM derivatization combined with multiple reactions monitoring (MRM) not only allowed trace analysis of thiols due to the extremely high sensitivity, but also efficiently corrected the matrix effects during HPLC-MS/MS and the fluctuation in MS/MS signal intensity due to instrument. The obtained internal standard calibration curves for six thiols were linear over the range of 25-10,000pmol/L (R 2 ≥0.9961). Detection limits (LODs) for most of analytes were below 6.3pmol/L. The proposed method was successfully applied for the simultaneous determination of six kinds of thiols in wine samples with precisions ≤3.5% and recoveries ≥78.1%. In conclusion, the developed method is expected to be a promising tool for detection of trace thiols in wine and also in other complex matrix. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Analysis of triglyceride degradation products in drying oils and oil paints using LC–ESI-MS

    NARCIS (Netherlands)

    van Dam, E.P.; van den Berg, K.J.; Proaño Gaibor, A.N.; van Bommel, M.

    An LC–ESI-MS method is presented as a novel approach for the study of aged drying oils and oil paints invarious stages of oxidation and hydrolysis. The method involves separation and detection of glyceridesand fatty acids on a reversed phase column using a polar gradient ranging from methanol/water

  19. Novel molecular-level evidence of iodine binding to natural organic matter from Fourier transform ion cyclotron resonance mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Chen, E-mail: xuchen66@tamu.edu [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States); Chen, Hongmei [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); Sugiyama, Yuko [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); University of Hyogo, 1-1-12, Shinzaike-honcho, Himeji, Hyogo 670-0092 (Japan); Zhang, Saijin; Li, Hsiu-Ping; Ho, Yi-Fang; Chuang, Chia-ying; Schwehr, Kathleen A. [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States); Kaplan, Daniel I. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Yeager, Chris [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Roberts, Kimberly A. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Hatcher, Patrick G. [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); Santschi, Peter H. [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States)

    2013-04-01

    Major fractions of radioiodine ({sup 129}I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios (< 0.2 or < 0.4) and yet some degree of un-saturation close to that of lignin, have multiple important environmental implications concerning possibly less sterically-hindered aromatic ring system for iodine to get access to and a lower hydrophilicity of the molecules thus to retard their migration in the natural aquatic systems. Lastly, ∼ 69% of the identified organo-iodine species contains nitrogen, which is presumably present as -NH{sub 2} or -HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on {sup 129}I migration. Highlights: ► IO{sub 3}{sup

  20. Environmental Sensitivity Index (ESI) Atlas: Massachusetts - Volume 1, geographic information systems data and Volume 2, maps and data in portable document format maps and geographic information systems data (NODC Accession 0014790)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set comprises the Environmental Sensitivity Index (ESI) data for Massachusetts from 1980 to 2000. ESI data characterize estuarine environments and wildlife...

  1. Identification and quantification of phenolic compounds of selected fruits from Madeira Island by HPLC-DAD-ESI-MS(n) and screening for their antioxidant activity.

    Science.gov (United States)

    Spínola, Vítor; Pinto, Joana; Castilho, Paula C

    2015-04-15

    Five fruits species commonly cultivated and consumed in Madeira Island (Portugal) were investigated for their phenolic profile by means of reversed phase high-performance liquid chromatography coupled to diode array detection and electrospray ionisation mass spectrometry (HPLC-DAD-ESI/MS(n)) and antioxidant potential. A large number of compounds were characterised, flavonoids and phenolic acids being the major components found in target samples, 39 compounds (flavonoids, phenolic acids, terpenoids, cyanogenic glycosides and organic acids) were identified in cherimoyas, lemons, papayas, passion-fruits and strawberries for the first time. Furthermore, all samples were systematically analysed for their total phenolic and flavonoid contents along with two radical scavenging methods (ABTS and ORAC) for antioxidant activity measurement. Target fruits presented high phenolic contents which is responsible for most of the antioxidant activity against radical reactive species (R(2)>0.80). Quantitative data showed that anthocyanins, in particular pelargonidin-3-O-hexoside (>300 mg/100 mL), present only in strawberries were the compounds in largest amounts but are the ones which contribute less to the antioxidant activity. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Concordance and population studies along with stutter and peak height ratio analysis for the PowerPlex ® ESX 17 and ESI 17 Systems.

    Science.gov (United States)

    Hill, Carolyn R; Duewer, David L; Kline, Margaret C; Sprecher, Cynthia J; McLaren, Robert S; Rabbach, Dawn R; Krenke, Benjamin E; Ensenberger, Martin G; Fulmer, Patricia M; Storts, Douglas R; Butler, John M

    2011-08-01

    The PowerPlex(®) ESX 17 and ESI 17 Systems for short tandem repeat (STR) amplification were developed by the Promega Corporation to meet the European Network of Forensic Science Institutes (ENFSI) and the European DNA Profiling (EDNAP) Group recommendations for increasing the number of STR loci included in the European Standard Set (ESS). The PowerPlex ESX 17 and ESI 17 Systems utilize different PCR primer combinations to co-amplify the following 17 loci: D1S1656, D2S441, D2S1338, D3S1358, D8S1179, D10S1248, D12S391, D16S539, D18S51, D19S433, D21S11, D22S1045, FGA, TH01, vWA, SE33, and the sex-typing locus amelogenin. A total of 1443 U.S. population samples were evaluated with pre-commercialization versions of both kits. Stutter and heterozygote peak height ratios have been used to characterize kit performance. Typing results have been used to estimate the match probabilities provided by the chosen loci as well as in concordance studies. Full concordance between the typing results for the two kits was observed in 99.994% (49,055 out of 49,062) STR allele calls compared. All genotyping discrepancies were confirmed by DNA sequence analysis. As a result of these comparisons, a second forward primer for the D22S1045 locus has been added to the PowerPlex ESX 17 System to address a primer binding site mutation and the D1S1656 locus reverse primer in the PowerPlex ESI 17 System was modified to eliminate an amplification-efficiency reducing primer dimer. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  3. Profiling of Glucosinolates and Flavonoids in Rorippa indica (Linn.) Hiern. (Cruciferae) by UHPLC-PDA-ESI/HRMSn.

    Science.gov (United States)

    An UHPLC-DAD-ESI/HRMSn profiling method was used to identify the glucosinolates and flavonoids of Rorippa montana (Cruciferae), a Chinese herb used to treat cough, diarrhea and rheumatoid arthritis. Thirty three glucosinolates, over 40 flavonol glycosides, and more than 20 other phenolic and common ...

  4. Fragmentation characteristics of hydroxycinnamic acids in ESI-MSn by density functional theory.

    Science.gov (United States)

    Yin, Zhi-Hui; Sun, Chang-Hai; Fang, Hong-Zhuang

    2017-07-01

    This work aims to analyze the electrospray ionization multistage mass spectrometry (ESI-MS n ) fragmentation characteristics of hydroxycinnamic acids (HCAs) in negative ion mode. The geometric parameters, energies, natural bond orbitals and frontier orbitals of fragments were calculated by density functional theory (DFT) to investigate mass spectral fragmentation mechanisms. The results showed that proton transfer always occurred during fragmentation of HCAs; their quasi-molecular ions ([M - H] - ) existed in more than one form and were mainly with the lowest energy. The fragmentation characteristics included the followings: (1) according to the different substitution position of phenolic hydroxyl group, the ring contraction reaction by CO elimination from benzene was in an increasingly difficult order: m-phenolic hydroxyl > p-phenolic hydroxyl > o-phenolic hydroxyl; and (2) ortho effect always occurred in o-dihydroxycinnamic acids (o-diHCAs), i.e. one phenolic hydroxyl group offered H + , which combined with the other one to lose H 2 O. In addition, there was a nucleophilic reaction during ring contraction in diHCAs that oxygen atom attacked the carbon atom binding with the other phenolic hydroxyl to lose CO 2 . The fragmentation characteristics and mechanism of HCAs could be used for analysis and identification of such compounds quickly and effectively, and as reference for structural analogues by ESI-MS. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  5. Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine

    DEFF Research Database (Denmark)

    Madsen, Henrik Tækker; Søgaard, Erik Gydesen

    2012-01-01

    To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)- hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry...... the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution...

  6. Analysis of peptide mixtures for proteomics research using LC–ESI-MS with a simple microgradient device

    Czech Academy of Sciences Publication Activity Database

    Lenobel, R.; Řehulková, H.; Šebela, M.; Franc, V.; Kahle, Vladislav; Moravcová, Dana; Řehulka, P.

    2015-01-01

    Roč. 33, č. 6 (2015), s. 420-428 ISSN 1527-5949 R&D Projects: GA MV VG20112015021 Institutional support: RVO:68081715 Keywords : LC-ESI-MS * proteomics * peptide Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 0.519, year: 2014 http://hdl.handle.net/11104/0249120

  7. High Performance Marine Vessels

    CERN Document Server

    Yun, Liang

    2012-01-01

    High Performance Marine Vessels (HPMVs) range from the Fast Ferries to the latest high speed Navy Craft, including competition power boats and hydroplanes, hydrofoils, hovercraft, catamarans and other multi-hull craft. High Performance Marine Vessels covers the main concepts of HPMVs and discusses historical background, design features, services that have been successful and not so successful, and some sample data of the range of HPMVs to date. Included is a comparison of all HPMVs craft and the differences between them and descriptions of performance (hydrodynamics and aerodynamics). Readers will find a comprehensive overview of the design, development and building of HPMVs. In summary, this book: Focuses on technology at the aero-marine interface Covers the full range of high performance marine vessel concepts Explains the historical development of various HPMVs Discusses ferries, racing and pleasure craft, as well as utility and military missions High Performance Marine Vessels is an ideal book for student...

  8. Qualitative and quantitative two-dimensional thin-layer chromatography/high performance liquid chromatography/diode-array/electrospray-ionization-time-of-flight mass spectrometry of cholinesterase inhibitors.

    Science.gov (United States)

    Mroczek, Tomasz

    2016-09-10

    Recently launched thin-layer chromatography-mass spectrometry (TLC-MS) interface enabling extraction of compounds directly from TLC plates into MS ion source was unusually extended into two-dimensional thin-layer chromatography/high performance liquid chromatography (2D, TLC/HPLC) system by its a direct connection to a rapid resolution 50×2.1mm, I.D. C18 column compartment followed by detection by diode array (DAD) and electrospray ionisation time-of-flight mass spectrometry (ESI-TOF-MS). In this way, even not separated bands of complicated mixtures of natural compounds could be analysed structurally, only within 1-2min after development of TLC plates. In comparison to typically applied TLC-MS interface, no ion suppression for acidic mobile phases was observed. Also, substantial increase in ESI-TOF-MS sensitivities and quality of spectra, were noticed. It has been utilised in combination with TLC- based bioautographic approaches of acetylcholinesterase (AChE) inhibitors, However, it can be also applied in any other procedures related to bioactivity (e.g. 2,2-Diphenyl-1-picryl-hydrazyl-DPPH screen test for radicals). This system has been also used for determination of half maximal inhibitory concentration (IC50 values) of the active inhibitor-galanthamine, as an example. Moreover, AChE inhibitory potencies of some of purified plant extracts, never studied before, have been quantitatively measured. This is first report of usage such the 2D TLC/HPLC/MS system both for qualitative and quantitative evaluation of cholinesterase inhibitors in biological matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Box-Behnken design for optimum extraction of biogenetic chemicals from P. lanceolata with an energy audit (thermal × microwave × acoustic): a case study of HPTLC determination with additional specificity using on-line/off-line coupling with DAD/NIR/ESI-MS.

    Science.gov (United States)

    Srivastava, Pooja; Ajayakumar, P V; Shanker, Karuna

    2014-01-01

    The genus Pluchea comprises about 80 species distributed worldwide, out of them, only Pluchea lanceolata (DC.) Oliv. & Hiern, is used extensively in the traditional system of India. No chromatographic method is available for its quality. To perform the energy audit for the extraction of biogenetic pentacyclic triterpene, its acetate and sterol from P. lanceolata utilising organic and four alternative solvents. Additionally to resolve the uncertainty of TLC determination, on-line/off-line coupling with a diode-array detector (DAD), and near-infrared (NIR) and electrospray ionisation (ESI) MS was introduced. The extraction of taraxasterol (Tx), taraxasterol acetate (TxAc) and stigmasterol (St) from P. lanceolata was performed using three energy modes. The effects of different operating parameters were studied for optimum extraction yield using the design of experiments, that is, the central composite design and Box-Behnken design. In addition to the retention factor (Rf ) and visible spectral matching, two additional optical spectroscopic techniques, that is, NIR and ESI-MS, were applied for extended specificity. The method was developed for Tx, TxAc and St determination using HPTLC at 645 nm. The optimum extraction yield of targeted compounds was found to be higher with organic solvents than eco-friendly surfactants. The pulse ultrasonic assisted extraction (PUAE) has resulted in optimum extraction of compounds comparable to hot extraction. Both NIR and ESI-MS provided extended specificity in determination. The 5/1-PUAE was determined to be effective, reproducible, simple and energy efficient for the determination of Tx, TxAc and St in P. lanceolata. The offline coupling of NIR and ESI-MS with HPTLC led to considerable improvement in specificity. Copyright © 2014 John Wiley & Sons, Ltd.

  10. In vivo Phosphoproteome of Human Skeletal Muscle Revealed by Phosphopeptide Enrichment and HPLC-ESI-MS/MS

    DEFF Research Database (Denmark)

    Højlund, Kurt; Bowen, Benjamin P; Hwang, Hyonson

    2009-01-01

    volunteers. Trypsin digestion of 3-5 mg human skeletal muscle protein was followed by phosphopeptide enrichment using SCX and TiO2. The resulting phosphopeptides were analyzed by HPLC-ESI-MS/MS. Using this unbiased approach, we identified 306 distinct in vivo phosphorylation sites in 127 proteins, including...

  11. Comprehensive characterization of natural organic matter by MALDI- and ESI-Fourier transform ion cyclotron resonance mass spectrometry

    International Nuclear Information System (INIS)

    Cao, Dong; Huang, Huogao; Hu, Ming; Cui, Lin; Geng, Fanglan; Rao, Ziyu; Niu, Hongyun; Cai, Yaqi; Kang, Yuehui

    2015-01-01

    Highlights: • MALDI-FT-ICR-MS was firstly employed for molecular characterization of NOM. • 1,8-Bis(dimethyl-amino)-naphthalene (DMAN) was used as matrix. • Mass spectra of NOM generated by MALDI and ESI methods were compared. • Complementary molecular information of NOM was provided by MALDI. - Abstract: Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200–800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio < 0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7 > O/C ratio > 0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM

  12. Rapid and high-throughput detection of highly pathogenic bacteria by Ibis PLEX-ID technology.

    Directory of Open Access Journals (Sweden)

    Daniela Jacob

    Full Text Available In this manuscript, we describe the identification of highly pathogenic bacteria using an assay coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS run on an Ibis PLEX-ID high-throughput platform. The biothreat cluster assay identifies most of the potential bioterrorism-relevant microorganisms including Bacillus anthracis, Francisella tularensis, Yersinia pestis, Burkholderia mallei and pseudomallei, Brucella species, and Coxiella burnetii. DNA from 45 different reference materials with different formulations and different concentrations were chosen and sent to a service screening laboratory that uses the PCR/ESI-MS platform to provide a microbial identification service. The standard reference materials were produced out of a repository built up in the framework of the EU funded project "Establishment of Quality Assurances for Detection of Highly Pathogenic Bacteria of Potential Bioterrorism Risk" (EQADeBa. All samples were correctly identified at least to the genus level.

  13. Detecting Protein-Glycolipid Interactions Using CaR-ESI-MS and Model Membranes: Comparison of Pre-loaded and Passively Loaded Picodiscs

    Science.gov (United States)

    Li, Jun; Han, Ling; Li, Jianing; Kitova, Elena N.; Xiong, Zi Jian; Privé, Gilbert G.; Klassen, John S.

    2018-04-01

    Catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS), implemented using model membranes (MMs), is a promising approach for the discovery of glycolipid ligands of glycan-binding proteins (GBPs). Picodiscs (PDs), which are lipid-transporting complexes composed of the human sphingolipid activator protein saposin A and phospholipids, have proven to be useful MMs for such studies. The present work compares the use of conventional (pre-loaded) PDs with passively loaded PDs (PLPDs) for CaR-ESI-MS screening of glycolipids against cholera toxin B subunit homopentamer (CTB5). The pre-loaded PDs were prepared from a mixture of purified glycolipid and phospholipid or a mixture of lipids extracted from tissue, while the PLPDs were prepared by incubating PDs containing only phospholipid with glycolipid-containing lipid mixtures in aqueous solution. Time-dependent changes in the composition of the PLPDs produced by incubation with glycomicelles of the ganglioside GM1 were monitored using collision-induced dissociation of the gaseous PD ions and from the extent of ganglioside binding to CTB5 measured by ESI-MS. GM1 incorporation into PDs was evident within a few hours of incubation. At incubation times ≥ 10 days, GM1 binding to CTB5 was indistinguishable from that observed with pre-loaded PDs produced directly from GM1 at the same concentration. Comparison of ganglioside binding to CTB5 measured for pre-loaded PDs and PLPDs prepared from glycolipids extracted from pig and mouse brain revealed that the PLPDs allow for the detection of a greater number of ganglioside ligands. Together, the results of this study suggest PLPDs may have advantages over conventionally prepared PDs for screening glycolipids against GBPs using CaR-ESI-MS. [Figure not available: see fulltext.

  14. Simultaneous quantitation of sphingoid bases by UPLC-ESI-MS/MS with identical (13)C-encoded internal standards

    NARCIS (Netherlands)

    Mirzaian, M.; Wisse, P.; Ferraz, M. J.; Marques, A. R. A.; Gaspar, P.; Oussoren, S. V.; Kytidou, K.; Codée, J. D. C.; van der Marel, G.; Overkleeft, H. S.; Aerts, J. M.

    2017-01-01

    Free sphingoid bases (lysosphingolipids) of primary storage sphingolipids are increased in tissues and plasma of several sphingolipidoses. As shown earlier by us, sphingoid bases can be accurately quantified using UPLC-ESI-MS/MS, particularly in combination with identical (13)C-encoded internal

  15. Major signal suppression from metal ion clusters in SFC/ESI-MS - Cause and effects.

    Science.gov (United States)

    Haglind, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Pettersson, Curt E

    2018-05-01

    The widening application area of SFC-MS with polar analytes and water-containing samples facilitates the use of quick and simple sample preparation techniques such as "dilute and shoot" and protein precipitation. This has also introduced new polar interfering components such as alkali metal ions naturally abundant in e.g. blood plasma and urine, which have shown to be retained using screening conditions in SFC/ESI-TOF-MS and causing areas of major ion suppression. Analytes co-eluting with these clusters will have a decreased signal intensity, which might have a major effect on both quantification and identification. When investigating the composition of the alkali metal clusters using accurate mass and isotopic pattern, it could be concluded that they were previously not described in the literature. Using NaCl and KCl standards and different chromatographic conditions, varying e.g. column and modifier, the clusters proved to be formed from the alkali metal ions in combination with the alcohol modifier and make-up solvent. Their compositions were [(XOCH 3 ) n  + X] + , [(XOH) n  + X] + , [(X 2 CO 3 ) n  + X] + and [(XOOCOCH 3 ) n  + X] + for X = Na + or K + in ESI+. In ESI-, the clusters depended more on modifier, with [(XCl) n  + Cl] - and [(XOCH 3 ) n  + OCH 3 ] - mainly formed in pure methanol and [(XOOCH) n  + OOCH] - when 20 mM NH 4 Fa was added. To prevent the formation of the clusters by avoiding methanol as modifier might be difficult, as this is a widely used modifier providing good solubility when analyzing polar compounds in SFC. A sample preparation with e.g. LLE would remove the alkali ions, however also introducing a time consuming and discriminating step into the method. Since the alkali metal ions were retained and affected by chromatographic adjustments as e.g. mobile phase modifications, a way to avoid them could therefore be chromatographic tuning, when analyzing samples containing them. Copyright © 2018 Elsevier

  16. The integrated quality assessment of Chinese commercial dry red wine based on a method of online HPLC-DAD-CL combined with HPLC-ESI-MS.

    Science.gov (United States)

    Yu, Hai-Xiang; Sun, Li-Qiong; Qi, Jin

    2014-07-01

    To apply an integrated quality assessment strategy to investigate the quality of multiple Chinese commercial dry red wine samples. A comprehensive method was developed by combining a high performance liquid chromatography-diode array detector-chemiluminescence (HPLC-DAD-CL) online hyphenated system with an HPLC-ESI-MS technique. Chromatographic and H2O2-scavenging active fingerprints of thirteen batches of different, commercially available Chinese dry red wine samples were obtained and analyzed. Twenty-five compounds, including eighteen antioxidants were identified and evaluated. The dominant and characteristic antioxidants in the samples were identified. The relationships between antioxidant potency and the cultivated variety of grape, producing area, cellaring period, and trade mark are also discussed. The results provide the feasibility for an integrated quality assessment strategy to be efficiently and objectively used in quality (especially antioxidant activity) assessment and identification of dry red wine. Copyright © 2014 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

  17. Application of CE-ICP-MS and CE-ESI-MS/MS for identification of Zn-binding ligands in Goji berries extracts.

    Science.gov (United States)

    Ruzik, Lena; Kwiatkowski, Piotr

    2018-06-01

    The identification of groups of ligands binding metals is a crucial issue for the better understanding of their bioaccessibility. In the current study, we have intended an approach for identification of Zn-binding ligands based on using capillary electrophoresis combined with inductively coupled plasma mass spectrometry (CE-ICP-MS) and tandem electrospray ionization mass spectrometry (CE-ESI-MS/MS). The approach, which featured the use of the coupling of capillary electrophoresis with inductively coupled plasma mass spectrometry allows to separate and observe zinc ions present in complexes with respect to their size and charge and to identify nine compounds with zinc isotopic profile. CE-ICP-MS provides us with information about presence of zinc species and elemental information about zinc distribution. CE-ESI-MS/MS provide us with information about the most favorable Zn binding ligands: amino acids, flavonols, stilbenoids, fenolic acids and carotenoids. The presented work is the continuation of previous studies based on using LC-ESI-MS/MS, though, now we presented a new solutions with the possibility of changing detectors without changing the separation techniques, what is important without re-optimizing the method. The new presented method allows to identify the zinc-binding ligands in shorter time. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. First signal from a broadband cryogenic preamplifier cooled by circulating liquid nitrogen in a 7 T Fourier transform ion cyclotron resonance mass spectrometer.

    Science.gov (United States)

    Choi, Myoung Choul; Lee, Jeong Min; Lee, Se Gyu; Choi, Sang Hwan; Choi, Yeon Suk; Lee, Kyung Jae; Kim, SeungYong; Kim, Hyun Sik; Stahl, Stefan

    2012-12-18

    Despite the outstanding performance of Fourier transform ion cyclotron/mass spectrometry (FTICR/MS), the complexity of the cellular proteome or natural compounds presents considerable challenges. Sensitivity is a key performance parameter of a FTICR mass spectrometer. By improving this parameter, the dynamic range of the instrument can be increased to improve the detection signal of low-abundance compounds or fragment ion peaks. In order to improve sensitivity, a cryogenic detection system was developed by the KBSI (Korean Basic Science Institute) in collaboration with Stahl-Electronics (Mettenheim, Germany). A simple, efficient liquid circulation cooling system was designed and a cryogenic preamplifier implemented inside a FTICR mass spectrometer. This cooling system circulates a cryoliquid from a Dewar to the "liquid circulation unit" through a CF flange to cool a copper block and a cryopreamplifier; the cooling medium is subsequently exhausted into the air. The cryopreamplifier can be operated over a very wide temperature range, from room temperature to low temperature environments (4.2 K). First, ion signals detected by the cryopreamplifier using a circulating liquid nitrogen cooling system were observed and showed a signal-to-noise ratio (S/N) about 130% better than that obtained at room temperature.

  19. Perspectivas mecanisticas de reações organicas catalisadas por paladio : Heck, oxa-Heck e acoplamento de Buchwald-Hartwig por ESI-MS/MS

    OpenAIRE

    Boniek Gontijo Vaz

    2009-01-01

    Resumo: A espectrometria de Massas por eletronspray (ESI-MS) tornou-se um método prático para o estudo de mecanismos reacionais em solução. Neste trabalho importantes reações catalisadas por paládio: reação de Heck-Mizoroki, oxa-Heck e o acoplamento de Buchwald-Hartwig foram monitoradas por ESI-MS visando interceptar espécies que comprovam as atuais propostas mecanísticas ou que abram caminho para novas propostas para estas reações. O monitoramento das reações foi realizado no modo off-line, ...

  20. NACE-ESI-TOF MS to reveal phenolic compounds from olive oil: introducing enriched olive oil directly inside capillary.

    Science.gov (United States)

    Gómez-Caravaca, Ana María; Carrasco-Pancorbo, Alegría; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

    2009-09-01

    Most CE methods for the analysis of phenols from olive oil use an aqueous electrolyte separation medium, although the importance of NACE is obvious, as this kind of CE seems to be more compatible with the hydrophobic olive oil matrix and could facilitate its direct injection. In the current work we develop a method involving SPE and NACE coupled to ESI-TOF MS. All the CE and ESI-TOF MS parameters were optimized in order to maximize the number of phenolic compounds detected and the sensitivity in their determination. Electrophoretic separation was carried out using a CE buffer system consisting of 25 mM NH(4)OAc/AcH in methanol/ACN (1/1 v/v) at an apparent pH value of 5.0. We studied in depth the effect of the nature and concentration of different electrolytes dissolved in different organic solvents and other experimental and instrumental CE variables. The results were compared with those obtained by CZE (with aqueous buffers) coupled to ESI-TOF MS; both methods offered to the analyst the chance to study phenolic compounds of different families (such as phenolic alcohols, lignans, complex phenols, flavonoids, etc.) from virgin olive oil by injecting methanolic extracts with efficient and fast CE separations. In the case of NACE method, we also studied the direct injection of the investigated matrix introducing a plug of olive oil directly into the capillary.