POWERFUL NEW TOOLS FOR ANALYZING ENVIRONMENTAL CONTAMINATION: MASS PEAK PROFILING FROM SELECTED-ION RECORDING DATA AND A PROFILE GENERATION MODEL

EPA Science Inventory

Capillary gas chromatography with mass spectrometric detection is the most commonly used technique for analyzing samples from Superfund sites. While the U.S. EPA has developed target lists of compounds for which library mass spectra are available on most mass spectrometer data s...

Selective ion accumulation in an ICP/ITMS using a filtered noise field

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

Eiden, G.C.; Barinaga, C.J.; Koppenaal, D.W.

1995-12-31

Selective accumulation of ions in an ion trap mass spectrometer (ITMS) has been characterized using both single frequency and broadband resonant excitation. The goal of this work is to enhance selective accumulation of ions from plasmas and other external ion sources. The charge capacity of the ITMS is 10{sup 6} to 10{sup 7} ions, although the mass spectrum is distorted at much lower space charge. Detection of trace ions necessitates selective detection schemes such as selective trapping or optical detection. The authors report results of selective trapping studies for Sr, Y, and Zr solutions (100 ppb Y and 1 ppbmore » each Sr, Zr). {open_quotes}Background{close_quotes} ions in mass channels adjacent to the channel of interest is a worst case situation with respect to selective ejection and abundance sensitivity. Real samples will often have matrix ion m/z values much further removed from the m/z of the ions of interest. Thus, the authors also give results for a multielement solution. Ions from an inductively coupled plasma ion source are endcap injected into the ITMS. Broadband waveforms were generated by an HST-1000 (Teledyne MEC) instrument, using the filtered noise field (FNF) method. The experiment is controlled by the ITMS electronics and ICMS software. The sequence of experimental events is: ion injection at q{sub z} = 0.4 (typical), collisionally cool ions, set trapping potential for resonant excitation (q{sub z} = 0.2 to 0.6), analysis rf ramp.« less

Supersonic molecular beam-hyperthermal surface ionisation coupled with time-of-flight mass spectrometry applied to trace level detection of polynuclear aromatic hydrocarbons in drinking water for reduced sample preparation and analysis time.

PubMed

Davis, S C; Makarov, A A; Hughes, J D

1999-01-01

Analysis of sub-ppb levels of polynuclear aromatic hydrocarbons (PAHs) in drinking water by high performance liquid chromatography (HPLC) fluorescence detection typically requires large water samples and lengthy extraction procedures. The detection itself, although selective, does not give compound identity confirmation. Benchtop gas chromatography/mass spectrometry (GC/MS) systems operating in the more sensitive selected ion monitoring (SIM) acquisition mode discard spectral information and, when operating in scanning mode, are less sensitive and scan too slowly. The selectivity of hyperthermal surface ionisation (HSI), the high column flow rate capacity of the supersonic molecular beam (SMB) GC/MS interface, and the high acquisition rate of time-of-flight (TOF) mass analysis, are combined here to facilitate a rapid, specific and sensitive technique for the analysis of trace levels of PAHs in water. This work reports the advantages gained by using the GC/HSI-TOF system over the HPLC fluorescence method, and discusses in some detail the nature of the instrumentation used.

State-of-the art of selective detection and identification of I-, Br-, Cl-, and F-containing compounds in gas chromatography and liquid chromatography.

PubMed

Brede, Cato; Pedersen-Bjergaard, Stig

2004-09-24

This review article presents an overview of halogen-specific detection in gas chromatography (GC) and liquid chromatography (LC). Attention is primarily focused on the use of plasma emission spectroscopy and plasma mass spectrometry as detectors, but other halogen-selective detection principles are also mentioned. Different instrumental configurations are discussed both with respect to technical set-up and performance, the principal reasons for halogen-selective detection are highlighted, and recent applications are reviewed from areas such as environmental chemistry, petroleum characterization, and drug analysis.

Critical comparison of mass analyzers for forensic hair analysis by ambient ionization mass spectrometry.

PubMed

Duvivier, Wilco F; van Beek, Teris A; Nielen, Michel W F

2016-11-15

Recently, several direct and/or ambient mass spectrometry (MS) approaches have been suggested for drugs of abuse imaging in hair. The use of mass spectrometers with insufficient selectivity could result in false-positive measurements due to isobaric interferences. Different mass analyzers have been evaluated regarding their selectivity and sensitivity for the detection of Δ9-tetrahydrocannabinol (THC) from intact hair samples using direct analysis in real time (DART) ionization. Four different mass analyzers, namely (1) an orbitrap, (2) a quadrupole orbitrap, (3) a triple quadrupole, and (4) a quadrupole time-of-flight (QTOF), were evaluated. Selectivity and sensitivity were assessed by analyzing secondary THC standard dilutions on stainless steel mesh screens and blank hair samples, and by the analysis of authentic cannabis user hair samples. Additionally, separation of isobaric ions by use of travelling wave ion mobility (TWIM) was investigated. The use of a triple quadrupole instrument resulted in the highest sensitivity; however, transitions used for multiple reaction monitoring were only found to be specific when using high mass resolution product ion measurements. A mass resolution of at least 30,000 FWHM at m/z 315 was necessary to avoid overlap of THC with isobaric ions originating from the hair matrix. Even though selectivity was enhanced by use of TWIM, the QTOF instrument in resolution mode could not indisputably differentiate THC from endogenous isobaric ions in drug user hair samples. Only the high resolution of the (quadrupole) orbitrap instruments and the QTOF instrument in high-resolution mode distinguished THC in hair samples from endogenous isobaric interferences. As expected, enhanced selectivity compromises sensitivity and THC was only detectable in hair from heavy users. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Mass-tag enhanced immuno-laser desorption/ionization mass spectrometry for sensitive detection of intact protein antigens.

PubMed

Lorey, Martina; Adler, Belinda; Yan, Hong; Soliymani, Rabah; Ekström, Simon; Yli-Kauhaluoma, Jari; Laurell, Thomas; Baumann, Marc

2015-05-19

A new read-out method for antibody arrays using laser desorption/ionization-mass spectrometry (LDI-MS) is presented. Small, photocleavable reporter molecules with a defined mass called "mass-tags" are used for detection of immunocaptured proteins from human plasma. Using prostate specific antigen (PSA), a biomarker for prostate cancer, as a model antigen, a high sensitivity generic detection methodology based immunocapture with a primary antibody and with a biotin labeled secondary antibody coupled to mass-tagged avidin is demonstrated. As each secondary antibody can bind several avidin molecules, each having a large number of mass-tags, signal amplification can be achieved. The developed PSA sandwich mass-tag analysis method provided a limit of detection below 200 pg/mL (6 pM) for a 10 μL plasma sample, well below the clinically relevant cutoff value of 3-4 ng/mL. This brings the limit of detection (LOD) for detection of intact antigens with matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) down to levels comparable to capture by anti-peptide antibodies selected reaction monitoring (SISCAPA SRM) and enzyme linked immunosorbent assay (ELISA), as 6 pM corresponds to a maximal amount of 60 amol PSA captured on-spot. We propose the potential use of LDI (laser desorption/ionization) with mass-tag read-out implemented in a sandwich assay format for low abundant and/or early disease biomarker detection.

Method for selective detection of explosives in mass spectrometer or ion mobility spectrometer at parts-per-quadrillion level

DOEpatents

Ewing, Robert G.; Atkinson, David A.; Clowers, Brian H.

2015-09-01

A method for selective detection of volatile and non-volatile explosives in a mass spectrometer or ion mobility spectrometer at a parts-per-quadrillion level without preconcentration is disclosed. The method comprises the steps of ionizing a carrier gas with an ionization source to form reactant ions or reactant adduct ions comprising nitrate ions (NO.sub.3.sup.-); selectively reacting the reactant ions or reactant adduct ions with at least one volatile or non-volatile explosive analyte at a carrier gas pressure of at least about 100 Ton in a reaction region disposed between the ionization source and an ion detector, the reaction region having a length which provides a residence time (tr) for reactant ions therein of at least about 0.10 seconds, wherein the selective reaction yields product ions comprising reactant ions or reactant adduct ions that are selectively bound to the at least one explosive analyte when present therein; and detecting product ions with the ion detector to determine presence or absence of the at least one explosive analyte.

Advancing Explosives Detection Capabilities: Vapor Detection

ScienceCinema

Atkinson, David

2018-05-11

A new, PNNL-developed method provides direct, real-time detection of trace amounts of explosives such as RDX, PETN and C-4. The method selectively ionizes a sample before passing the sample through a mass spectrometer to detect explosive vapors. The method could be used at airports to improve aviation security.

Advancing Explosives Detection Capabilities: Vapor Detection

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

Atkinson, David

2012-10-15

A new, PNNL-developed method provides direct, real-time detection of trace amounts of explosives such as RDX, PETN and C-4. The method selectively ionizes a sample before passing the sample through a mass spectrometer to detect explosive vapors. The method could be used at airports to improve aviation security.

Mass-Selective Chiral Analysis

NASA Astrophysics Data System (ADS)

Boesl, Ulrich; Kartouzian, Aras

2016-06-01

Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

Halobacterium salinarum NRC-1 PeptideAtlas: strategies for targeted proteomics

PubMed Central

Van, Phu T.; Schmid, Amy K.; King, Nichole L.; Kaur, Amardeep; Pan, Min; Whitehead, Kenia; Koide, Tie; Facciotti, Marc T.; Goo, Young-Ah; Deutsch, Eric W.; Reiss, David J.; Mallick, Parag; Baliga, Nitin S.

2009-01-01

The relatively small numbers of proteins and fewer possible posttranslational modifications in microbes provides a unique opportunity to comprehensively characterize their dynamic proteomes. We have constructed a Peptide Atlas (PA) for 62.7% of the predicted proteome of the extremely halophilic archaeon Halobacterium salinarum NRC-1 by compiling approximately 636,000 tandem mass spectra from 497 mass spectrometry runs in 88 experiments. Analysis of the PA with respect to biophysical properties of constituent peptides, functional properties of parent proteins of detected peptides, and performance of different mass spectrometry approaches has helped highlight plausible strategies for improving proteome coverage and selecting signature peptides for targeted proteomics. Notably, discovery of a significant correlation between absolute abundances of mRNAs and proteins has helped identify low abundance of proteins as the major limitation in peptide detection. Furthermore we have discovered that iTRAQ labeling for quantitative proteomic analysis introduces a significant bias in peptide detection by mass spectrometry. Therefore, despite identifying at least one proteotypic peptide for almost all proteins in the PA, a context-dependent selection of proteotypic peptides appears to be the most effective approach for targeted proteomics. PMID:18652504

A microcantilever-based silver ion sensor using DNA-functionalized gold nanoparticles as a mass amplifier

NASA Astrophysics Data System (ADS)

You, Juneseok; Song, Yeongjin; Park, Chanho; Jang, Kuewhan; Na, Sungsoo

2017-06-01

Silver ions have been used to sterilize many products, however, it has recently been demonstrated that silver ions can be toxic. This toxicity has been studied over many years with the lethal concentration at 10 μM. Silver ions can accumulate through the food chain, causing serious health problems in many species. Hence, there is a need for a commercially available silver ion sensor, with high detection sensitivity. In this work, we develop an ultra-sensitive silver ion sensor platform, using cytosine based DNA and gold nanoparticles as the mass amplifier. We achieve a lower detection limit for silver ions of 10 pM; this detection limit is one million times lower than the toxic concentration. Using our sensor platform we examine highly selective characteristics of other typical ions in water from natural sources. Furthermore, our sensor platform is able to detect silver ions in a real practical sample of commercially available drinking water. Our sensor platform, which we have termed a ‘MAIS’ (mass amplifier ion sensor), with a simple detection procedure, high sensitivity, selectivity and real practical applicability has shown potential as an early toxicity assessment of silver ions in the environment.

Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane.

PubMed

Kim, Yushin; Amemiya, Shigeru

2008-08-01

A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.

Quantitative genetics and sex-specific selection on sexually dimorphic traits in bighorn sheep

PubMed Central

Poissant, Jocelyn; Wilson, Alastair J; Festa-Bianchet, Marco; Hogg, John T; Coltman, David W

2008-01-01

Sexual conflict at loci influencing traits shared between the sexes occurs when sex-specific selection pressures are antagonistic relative to the genetic correlation between the sexes. To assess whether there is sexual conflict over shared traits, we estimated heritability and intersexual genetic correlations for highly sexually dimorphic traits (horn volume and body mass) in a wild population of bighorn sheep (Ovis canadensis) and quantified sex-specific selection using estimates of longevity and lifetime reproductive success. Body mass and horn volume showed significant additive genetic variance in both sexes, and intersexual genetic correlations were 0.24±0.28 for horn volume and 0.63±0.30 for body mass. For horn volume, selection coefficients did not significantly differ from zero in either sex. For body weight, selection coefficients were positive in females but did not differ from zero in males. The absence of detectable sexually antagonistic selection suggests that currently there are no sexual conflicts at loci influencing horn volume and body mass. PMID:18211870

Improved Steroids Detection and Evidence for Their Regiospecific Decompositions Using Anion Attachment Mass Spectrometry.

PubMed

Dumont, Quentin; Bárcenas, Mariana; Dossmann, Héloïse; Bailloux, Isabelle; Buisson, Corinne; Mechin, Nathalie; Molina, Adeline; Lasne, Françoise; Rannulu, Nalaka S; Cole, Richard B

2016-04-05

Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification.

Properties of an H I-selected galaxy sample

NASA Technical Reports Server (NTRS)

Szomoru, Arpad; Guhathakurta, Puragra; Van Gorkom, Jacqueline H.; Knapen, Johan H.; Weinberg, David H.; Fruchter, Andrew S.

1994-01-01

We analyze the properties of a sample of galaxies identified in a 21cm, H I-line survey of selected areas in the Perseus-Pisces supercluster and its foreground void. Twelve fields were observed in the supercluster, five of them (target fields) centered on optically bright galaxies, and the other seven (blank fields) selected to contain no bright galaxies within 45 min. of their centers. We detected nine previously uncatalogued, gas-rich galaxies, six of them in the target fields. We also detected H I from seven previously catalogued galaxies in these fields. Observations in the void covered the same volume as the 12 supercluster fields at the same H I-mass sensitivity, but no objects were detected. Combining out H I data with optical broadband and H alpha imaging, we conclude that the properties of H I-selected galaxies do not differ substantially from those of late-type galaxies found in optical surveys. In particular, the galaxies in our sample do not appear to be unusually faint for their H I mass, or for their circular velocity. We find tentative evidence for a connection between optical surface brightness and degree of isolation, in the sense that low surface brightness galaxies tend to be more isolated. The previously catalogued, optically bright galaxies in our survey volume dominate the total H I mass density and cross section; the uncatalogued galaxies contribute only approximately 19 percent of the mass and approximately 12 percent of the cross section. Thus, existing estimates of the density and cross section of neutral hydrogen, most of which are based on optically selected galaxy samples, are probably accurate. Such estimates can be used to compare the nearby universe to the high-redshift universe probed by quasar absorption lines.

Infrared Detection of Very Low Mass Stars.

NASA Astrophysics Data System (ADS)

Probst, Ronald George

We present in this thesis a review of very-low -mass ((TURN)0.1 M(,0)) star research, and results of two observational programs directed at the photometric detection of low mass binary companions in the infrared. Present theoretical desiderata are model atmospheres for very cool dwarf stars and determination of the minimum protostellar mass with all relevant physics included. Luminosities for these stars are well determined, but the effective temperature scale is uncertain and abundance analyses are lacking. Masses are known for very few, and with large relative errors. The luminosity function for M(,v) > 13 is very uncertain. Astrometric methods provide at present the only means of detecting very low mass objects in significant numbers. Completion of the near-star parallax catalogue and measurement of additional low-mass binaries are important observational programs. The potential of photometric selection of red dwarf binaries is explored in Chapter II. Separation of binaries from single stars by color anomalies alone is found impractical. Detection by overluminosity in the HR diagram is hampered by the intrinsic spread of the field star population. However, we find that application of both kinematic and photometric criteria allows binaries to be detected with only moderate contamination by single stars; we discuss several binary suspects selected in this way. Our approach uses an infrared bandpass to provide temperature resolution in the color baseline, and we present JHK photometry for 60 stars, including recent parallax stars with M(,v)>14. We examine the status of the least luminous stars; there is no conclusive evidence that they are not hydrogen-burning objects. Chapter III presents a survey of (TURN)100 white dwarfs at 2 (mu) for infrared excess indicative of low -luminosity cool companions. White dwarf-red dwarf composites are detectable by infared color anomalies down to M(,v)(TURN)21 for the red dwarf component, and our survey is complete to absolute magnitudes on this level. Candidates for astrometric mass determination are suggested. Several stars are found to be composites containing an accretion disk or a hot subdwarf + dK secondary. We find very few new low-luminosity companions to normal white dwarfs. This does not appear to be a selection effect, nor is there reason to believe that all parent systems have been altered or destroyed in the mass loss phase. Our strongly negative result constrains the luminosity function for red dwarf companions to decline steeply past M(,v) (DBLTURN) 13. This may reflect a general decline in the initial mass function for star formation, or a failure of systems with large mass ratios to form or remain bound in the parent star-forming regions.

Improving mass candidate detection in mammograms via feature maxima propagation and local feature selection.

PubMed

Melendez, Jaime; Sánchez, Clara I; van Ginneken, Bram; Karssemeijer, Nico

2014-08-01

Mass candidate detection is a crucial component of multistep computer-aided detection (CAD) systems. It is usually performed by combining several local features by means of a classifier. When these features are processed on a per-image-location basis (e.g., for each pixel), mismatching problems may arise while constructing feature vectors for classification, which is especially true when the behavior expected from the evaluated features is a peaked response due to the presence of a mass. In this study, two of these problems, consisting of maxima misalignment and differences of maxima spread, are identified and two solutions are proposed. The first proposed method, feature maxima propagation, reproduces feature maxima through their neighboring locations. The second method, local feature selection, combines different subsets of features for different feature vectors associated with image locations. Both methods are applied independently and together. The proposed methods are included in a mammogram-based CAD system intended for mass detection in screening. Experiments are carried out with a database of 382 digital cases. Sensitivity is assessed at two sets of operating points. The first one is the interval of 3.5-15 false positives per image (FPs/image), which is typical for mass candidate detection. The second one is 1 FP/image, which allows to estimate the quality of the mass candidate detector's output for use in subsequent steps of the CAD system. The best results are obtained when the proposed methods are applied together. In that case, the mean sensitivity in the interval of 3.5-15 FPs/image significantly increases from 0.926 to 0.958 (p < 0.0002). At the lower rate of 1 FP/image, the mean sensitivity improves from 0.628 to 0.734 (p < 0.0002). Given the improved detection performance, the authors believe that the strategies proposed in this paper can render mass candidate detection approaches based on image location classification more robust to feature discrepancies and prove advantageous not only at the candidate detection level, but also at subsequent steps of a CAD system.

Analysis of Urinary Metabolites of Nerve and Blister Chemical Warfare Agents

DTIC Science & Technology

2014-08-01

of CWAs. The analysis methods use UHPLC-MS/MS in Multiple Reaction Monitoring ( MRM ) mode to enhance the selectivity and sensitivity of the method...Chromatography Mass Spectrometry LOD Limit Of Detection LOQ Limit of Quantitation MRM Multiple Reaction Monitoring MSMS Tandem mass...urine [1]. Those analysis methods use UHPLC- MS/MS in Multiple Reaction Monitoring ( MRM ) mode to enhance the selectivity and sensitivity of the method

Rapid analysis of N-linked oligosaccharides in glycoproteins (ovalbumin, ribonuclease B and fetuin) by reversed-phase ultra-performance liquid chromatography with fluorescence detection and electrospray ionization time-of-flight mass spectrometry.

PubMed

Kurihara, Takamasa; Min, Jun Zhe; Hirata, Asuka; Toyo'oka, Toshimasa; Inagaki, Shinsuke

2009-05-01

Rapid, selective and sensitive determination of N-linked oligosaccharides in glycoproteins (ovalbumin, ribonuclease B and fetuin) was performed by ultra-performance liquid chromatography (UPLC) with fluorescence (FL) and electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS). The asparaginyl-oligosaccharide moiety was first liberated from each glycoprotein by pronase E (a proteolitic enzyme). The oligosaccharide fractions separated by gel-permeation chromatography were labeled with 1-pyrenesulfonyl chloride (PSC, a fluorescence reagent), separated by UPLC in a short run time, and then detected by FL and TOF-MS. The PSC-labeled oligosaccharides were selectively identified from the FL detection and then sensitively determined by ESI-TOF-MS. As the results, 15, eight and four kinds of N-linked oligosaccharides were detected from ovalbumin, ribonuclease B and fetuin, respectively. Because the present method is rapid (within 9 min), selective and sensitive (approximate 60 fmol, S/N = 5), the determination of N-linked oligosaccharides in various glycoproteins seems to be possible.

Detection, characterization and identification of crucifer phytoalexins using high-performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry.

PubMed

Pedras, M Soledade C; Adio, Adewale M; Suchy, Mojmir; Okinyo, Denis P O; Zheng, Qing-An; Jha, Mukund; Sarwar, Mohammed G

2006-11-10

We have analyzed 23 crucifer phytoalexins (e.g. brassinin, dioxibrassinin, cyclobrassinin, brassicanals A and C) by HPLC with diode array detection and electrospray ionization mass spectrometry (HPLC-DAD-ESI-MS) using both negative and positive ion modes. Positive ion mode ESI-MS appeared more sensitive than negative ion mode ESI-MS in detecting this group of compounds. A new HPLC separation method, new LC-MS and LC-MS(2) data and proposed fragmentation pathways, LC retention times, and UV spectra for selected compounds are reported.

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

PubMed

Santa, Tomofumi

2011-01-01

Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

SELECTIVITY AND SPECIFICITY OF SMALL MOLECULE FLUORESCENT DYES/PROBES USED FOR THE DETECTION OF Zn2+ AND Ca2+ IN CELLS

PubMed Central

Landero-Figueroa, Julio A.; Vignesh, Kavitha Subramanian; Deepe, George; Caruso, Joseph

2014-01-01

Fluorescent dyes are widely used in the detection of labile (free or exchangeable) Zn2+ and Ca2+ in living cells. However, their specificity over other cations and selectivity for detection of labile vs. protein-bound metal in cells remains unclear. We characterized these important properties for commonly used Zn2+ and Ca2+ dyes in a cellular environment. By tracing the fluorescence emission signal along with UV-Vis and size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS) in tandem, we demonstrated that among the dyes used for Zn2+, Zinpyr-1 fluoresces in the low molecular mass (LMM) region containing labile Zn2+, but also fluoresces in different molecular mass regions where zinc ion is detected. However, FluoZin™-3 AM, Newport Green™ DCF and Zinquin ethyl ester display weak fluorescence, lack of metal specificity and respond strongly in the high molecular mass (HMM) region. Four Ca2+ dyes were studied in an unperturbed cellular environment, and two of these were tested for binding behavior under an intracellular Ca2+ release stimulus. A majority of Ca2+ was in the labile form as tested by SEC-ICP-MS, but the fluorescence from Calcium Green-1™ AM, Oregon Green® 488 BAPTA-1, Fura red™ AM and Fluo-4 NW dyes in cells did not correspond to free Ca2+ detection. Instead, the dyes showed non-specific fluorescence in the mid- and high-molecular mass regions containing Zn, Fe and Cu. Proteomic analysis of one of the commonly seen fluorescing regions showed the possibility for some dyes to recognize Zn and Cu bound to metallothionein-2. These studies indicate that Zn2+ and Ca2+ binding dyes manifest fluorescence responses that are not unique to recognition of labile metals and bind other metals, leading to suboptimal specificity and selectivity. PMID:24356796

Planar chromatography mediated screening of tetracycline and fluoroquinolone antibiotics in milk by fluorescence and mass selective detection.

PubMed

Chen, Yisheng; Schwack, Wolfgang

2013-10-18

A rapid and efficient method for preliminary screening of four tetracyclines (tetracycline, chlortetracycline, oxytetracycline, doxycline) and three fluoroquinolones (enrofloxacin, ciprofloxacin, marbofloxacin), mostly detected in milk, by high-performance thin-layer chromatography-fluorescence detection and electrospray ionization mass spectrometry (HPTLC-FLD-ESI/MS) is highlighted. The optimized separation of the target antibiotics on ethylenediamine tetraacetic acid modified silica gel plates showed marked benefits for screening purposes. Besides, selective and sensitive densitometry in fluorescence mode was established with excitation at 366nm for the tetracyclines, 300nm for enrofloxacin and ciprofloxacin, and 280nm for marbofloxacin. Limits of detection (LOD) and quantitation (LOQ) with 95% confidence were in the range of 12-25 and 45-95μg/kg, respectively, in milk samples. Recoveries of target antibiotics from milk samples spiked at three critical levels (50, 100 and 150μg/kg) ranged from 76% to 105%. More importantly, a mass selective detection (MSD) was established as additional tool for confirmatory purposes. Using the elution-head based TLC-MS interface, the optimized elution flow consisting of acetonitrile/ammonium formate buffer (9/1, v/v) at a rate of 0.3mL/min enabled time-dependent resolution of analytes from the major interfering compounds, thus circumventing serious ion suppression effects. The established MSD assay also offered high sensitivity (25μg/kg) for confirmation, meeting Commission Regulation (EU) No. 37/2010. Copyright © 2013 Elsevier B.V. All rights reserved.

A deep learning approach for the analysis of masses in mammograms with minimal user intervention.

PubMed

Dhungel, Neeraj; Carneiro, Gustavo; Bradley, Andrew P

2017-04-01

We present an integrated methodology for detecting, segmenting and classifying breast masses from mammograms with minimal user intervention. This is a long standing problem due to low signal-to-noise ratio in the visualisation of breast masses, combined with their large variability in terms of shape, size, appearance and location. We break the problem down into three stages: mass detection, mass segmentation, and mass classification. For the detection, we propose a cascade of deep learning methods to select hypotheses that are refined based on Bayesian optimisation. For the segmentation, we propose the use of deep structured output learning that is subsequently refined by a level set method. Finally, for the classification, we propose the use of a deep learning classifier, which is pre-trained with a regression to hand-crafted feature values and fine-tuned based on the annotations of the breast mass classification dataset. We test our proposed system on the publicly available INbreast dataset and compare the results with the current state-of-the-art methodologies. This evaluation shows that our system detects 90% of masses at 1 false positive per image, has a segmentation accuracy of around 0.85 (Dice index) on the correctly detected masses, and overall classifies masses as malignant or benign with sensitivity (Se) of 0.98 and specificity (Sp) of 0.7. Copyright © 2017 Elsevier B.V. All rights reserved.

Decoration of silicon nanostructures with copper particles for simultaneous selective capture and mass spectrometry detection of His-tagged model peptide.

PubMed

Coffinier, Yannick; Kurylo, Ievgen; Drobecq, Hervé; Szunerits, Sabine; Melnyk, Oleg; Zaitsev, Vladimir N; Boukherroub, Rabah

2014-10-21

We present in this work a simple and fast preparation method of a new affinity surface-assisted laser/desorption ionization mass spectrometry (SALDI-MS) substrate based on silicon nanostructures decorated with copper particles. The silicon nanostructures were fabricated by the metal-assisted chemical etching (MACE) method. Then, superhydrophilic areas surrounded by superhydrophobic regions were formed through hydrosilylation reaction of 1-octadecene, followed by local degradation of the octadecyl layer. After that, copper particles were deposited in the hydrophilic areas by using the electroless method. We have demonstrated that these surfaces were able to perform high selective capture of model His-tag peptide even in a complex mixture such as serum solution. Then, the captured peptide was detected by mass spectrometry at a femtomolar level without the need of organic matrix.

Diagnosing Prion Diseases: Mass Spectrometry-Based Approaches

USDA-ARS?s Scientific Manuscript database

Mass spectrometry is an established means of quantitating the prions present in infected hamsters. Calibration curves relating the area ratios of the selected analyte peptides and their oxidized analogs to stable isotope labeled internal standards were prepared. The limit of detection (LOD) and limi...

Galaxy And Mass Assembly (GAMA): bivariate functions of Hα star-forming galaxies

NASA Astrophysics Data System (ADS)

Gunawardhana, M. L. P.; Hopkins, A. M.; Taylor, E. N.; Bland-Hawthorn, J.; Norberg, P.; Baldry, I. K.; Loveday, J.; Owers, M. S.; Wilkins, S. M.; Colless, M.; Brown, M. J. I.; Driver, S. P.; Alpaslan, M.; Brough, S.; Cluver, M.; Croom, S.; Kelvin, L.; Lara-López, M. A.; Liske, J.; López-Sánchez, A. R.; Robotham, A. S. G.

2015-02-01

We present bivariate luminosity and stellar mass functions of Hα star-forming galaxies drawn from the Galaxy And Mass Assembly (GAMA) survey. While optically deep spectroscopic observations of GAMA over a wide sky area enable the detection of a large number of 0.001 < SFRHα (M⊙ yr-1) < 100 galaxies, the requirement for an Hα detection in targets selected from an r-band magnitude-limited survey leads to an incompleteness due to missing optically faint star-forming galaxies. Using z < 0.1 bivariate distributions as a reference we model the higher-z distributions, thereby approximating a correction for the missing optically faint star-forming galaxies to the local star formation rate (SFR) and M densities. Furthermore, we obtain the r-band luminosity functions (LFs) and stellar mass functions of Hα star-forming galaxies from the bivariate LFs. As our sample is selected on the basis of detected Hα emission, a direct tracer of ongoing star formation, this sample represents a true star-forming galaxy sample, and is drawn from both photometrically classified blue and red subpopulations, though mostly from the blue population. On average 20-30 per cent of red galaxies at all stellar masses are star forming, implying that these galaxies may be dusty star-forming systems.

Halobacterium salinarum NRC-1 PeptideAtlas: toward strategies for targeted proteomics and improved proteome coverage.

PubMed

Van, Phu T; Schmid, Amy K; King, Nichole L; Kaur, Amardeep; Pan, Min; Whitehead, Kenia; Koide, Tie; Facciotti, Marc T; Goo, Young Ah; Deutsch, Eric W; Reiss, David J; Mallick, Parag; Baliga, Nitin S

2008-09-01

The relatively small numbers of proteins and fewer possible post-translational modifications in microbes provide a unique opportunity to comprehensively characterize their dynamic proteomes. We have constructed a PeptideAtlas (PA) covering 62.7% of the predicted proteome of the extremely halophilic archaeon Halobacterium salinarum NRC-1 by compiling approximately 636 000 tandem mass spectra from 497 mass spectrometry runs in 88 experiments. Analysis of the PA with respect to biophysical properties of constituent peptides, functional properties of parent proteins of detected peptides, and performance of different mass spectrometry approaches has highlighted plausible strategies for improving proteome coverage and selecting signature peptides for targeted proteomics. Notably, discovery of a significant correlation between absolute abundances of mRNAs and proteins has helped identify low abundance of proteins as the major limitation in peptide detection. Furthermore, we have discovered that iTRAQ labeling for quantitative proteomic analysis introduces a significant bias in peptide detection by mass spectrometry. Therefore, despite identifying at least one proteotypic peptide for almost all proteins in the PA, a context-dependent selection of proteotypic peptides appears to be the most effective approach for targeted proteomics.

Determination of formetanate hydrochloride in fruit samples using liquid chromatography-mass selective detection or -tandem mass spectrometry.

PubMed

Podhorniak, Lynda V; Kamel, Alaa; Rains, Diane M

2010-05-26

A rapid multiresidue method that captures residues of the insecticide formetanate hydrochloride (FHCl) in selected fruits is described. The method was used to provide residue data for dietary exposure determinations of FHCl. Using an acetonitrile extraction with a dispersive cleanup based on AOAC International method 2007.01, also known as QuEChERS, which was further modified and streamlined, thousands of samples were successfully analyzed for FHCl residues. FHCl levels were determined both by liquid chromatography-single-stage mass spectrometry (LC-MS) and ultraperformance liquid chromatography (UPLC)-tandem mass spectrometry (LC-MS/MS). The target limit of detection (LOD) and the limit of quantitation (LOQ) achieved for FHCl were 3.33 and 10 ng/g, respectively, with LC-MS and 0.1 and 0.3 ng/g, respectively, with LC-MS/MS. Recoveries at these previously unpublished levels ranged from 95 to 109%. A set of 20-40 samples can be prepared in one working day by two chemists.

Analysis of selected herbicide metabolites in surface and ground water of the United States

USGS Publications Warehouse

Scribner, E.A.; Thurman, E.M.; Zimmerman, L.R.

2000-01-01

One of the primary goals of the US Geological Survey (USGS) Laboratory in Lawrence, Kansas, is to develop analytical methods for the analysis of herbicide metabolites in surface and ground water that are vital to the study of herbicide fate and degradation pathways in the environment. Methods to measure metabolite concentrations from three major classes of herbicides - triazine, chloroacetanilide and phenyl-urea - have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatography/mass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatography/mass spectrometry. Two metabolites of the chloroacetanilide herbicides - ethane sulfonic acid and oxanilic acid - are detected by high-performance liquid chromatography with diode-array detection and liquid chromatography/mass spectrometry. Alachlor ethane sulfonic acid also has been detected by solid-phase extraction and enzyme-linked immunosorbent assay. Six phenylurea metabolites are all detected by liquid chromatography/mass spectrometry; four of the six metabolites also are detected by gas chromatography/mass spectrometry. Additionally, surveys of herbicides and their metabolites in surface water, ground water, lakes, reservoirs, and rainfall have been conducted through the USGS laboratory in Lawrence. These surveys have been useful in determining herbicide and metabolite occurrence and temporal distribution and have shown that metabolites may be useful in evaluation of non-point-source contamination. Copyright (C) 2000 Elsevier Science B.V.

Comprehensive comparison of liquid chromatography selectivity as provided by two types of liquid chromatography detectors (high resolution mass spectrometry and tandem mass spectrometry): "where is the crossover point?".

PubMed

Kaufmann, A; Butcher, P; Maden, K; Walker, S; Widmer, M

2010-07-12

The selectivity of mass traces obtained by monitoring liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was compared. A number of blank extracts (fish, pork kidney, pork liver and honey) were separated by ultra performance liquid chromatography (UPLC). Detected were some 100 dummy transitions respectively dummy exact masses (traces). These dummy masses were the product of a random generator. The range of the permitted masses corresponded to those which are typical for analytes (e.g. veterinary drugs). The large number of monitored dummy traces ensured that endogenous compounds present in the matrix extract, produced a significant number of detectable chromatographic peaks. All obtained chromatographic peaks were integrated and standardized. Standardisation was done by dividing these absolute peak areas by the average response of a set of 7 different veterinary drugs. This permitted a direct comparison between the LC-HRMS and LC-MS/MS data. The data indicated that the selectivity of LC-HRMS exceeds LC-MS/MS, if high resolution mass spectrometry (HRMS) data is recorded with a resolution of 50,000 full width at half maximum (FWHM) and a corresponding mass window. This conclusion was further supported by experimental data (MS/MS based trace analysis), where a false positive finding was observed. An endogenous matrix compound present in honey matrix behaved like a banned nitroimidazole drug. This included identical retention time and two MRM traces, producing an MRM ratio between them, which perfectly matched the ratio observed in the external standard. HRMS measurement clearly resolved the interfering matrix compound and unmasked the false positive MS/MS finding. Copyright 2010 Elsevier B.V. All rights reserved.

The selective determination of sulfates, sulfonates, and phosphates in urine by capillary electrophoresis/mass spectrometry.

PubMed

Bunz, Svenja-Catharina; Neusüß, Christian

2013-01-01

Metabolite identification and metabolite profiling are of major importance in the pharmaceutical and clinical context. However, anions of biological relevance such as sulfates, sulfonates, and phosphates are rarely included in common techniques for metabolite studies. In this protocol, we demonstrate a unique method to selectively determine these anions. The method comprises a capillary electrophoresis separation using an acidic background electrolyte (pH ≤ 2) and anodic detection by mass spectrometry via negative electrospray ionization. In this way, only anions of strong acids like sulfates are determined. The selectivity for sulfur-containing species is proved based on the specific isotopic ratios. In conjunction with the accurate mass from the time-of-flight mass spectrometer, the presented method is well suited for clinical and pharmaceutical applications to identify possible metabolites and to quantify known metabolites.

Computer-aided detection of bladder mass within non-contrast-enhanced region of CT Urography (CTU)

NASA Astrophysics Data System (ADS)

Cha, Kenny H.; Hadjiiski, Lubomir M.; Chan, Heang-Ping; Caoili, Elaine M.; Cohan, Richard H.; Weizer, Alon; Zhou, Chuan

2016-03-01

We are developing a computer-aided detection system for bladder cancer in CT urography (CTU). We have previously developed methods for detection of bladder masses within the contrast-enhanced region of the bladder. In this study, we investigated methods for detection of bladder masses within the non-contrast enhanced region. The bladder was first segmented using a newly developed deep-learning convolutional neural network in combination with level sets. The non-contrast-enhanced region was separated from the contrast-enhanced region with a maximum-intensityprojection- based method. The non-contrast region was smoothed and a gray level threshold was employed to segment the bladder wall and potential masses. The bladder wall was transformed into a straightened thickness profile, which was analyzed to identify lesion candidates as a prescreening step. The lesion candidates were segmented using our autoinitialized cascaded level set (AI-CALS) segmentation method, and 27 morphological features were extracted for each candidate. Stepwise feature selection with simplex optimization and leave-one-case-out resampling were used for training and validation of a false positive (FP) classifier. In each leave-one-case-out cycle, features were selected from the training cases and a linear discriminant analysis (LDA) classifier was designed to merge the selected features into a single score for classification of the left-out test case. A data set of 33 cases with 42 biopsy-proven lesions in the noncontrast enhanced region was collected. During prescreening, the system obtained 83.3% sensitivity at an average of 2.4 FPs/case. After feature extraction and FP reduction by LDA, the system achieved 81.0% sensitivity at 2.0 FPs/case, and 73.8% sensitivity at 1.5 FPs/case.

Simultaneous detection and quantification of select nitromusks, antimicrobial agent, and antihistamine in fish of grocery stores by gas chromatography-mass spectrometry.

PubMed

Foltz, James; Abdul Mottaleb, M; Meziani, Mohammed J; Rafiq Islam, M

2014-07-01

Continually detected biologically persistent nitromusks; galaxolide (HHCB), tonalide (AHTN) and musk ketone (MK), antimicrobial triclosan (TCS), and antihistamine diphenhydramine (DPH) were examined for the first time in edible fillets originating from eight fish species grown in salt- and fresh-water. The sampled fish collected from local grocery stores were homogenized, extracted, pre-concentrated and analyzed by gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring (SIM). The presence of the target compounds in fish extracts was confirmed based on similar mass spectral features and retention behavior with standards. Internal standard based calibration plots were used for quantification. The HHCB, AHTN, TCS and DPH were consistently observed with concentration of 0.163-0.892, 0.068-0.904, 0.189-1.182, and 0.942-7.472 ng g(-1), respectively. These values are at least 1-3 orders of magnitude lower than those obtained in environmental fish specimens. The MK was not detected in any fish. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fast, low-level detection of strontium-90 and strontium-89 in environmental samples by collinear resonance ionization spectroscopy

NASA Astrophysics Data System (ADS)

Monz, L.; Hohmann, R.; Kluge, H.-J.; Kunze, S.; Lantzsch, J.; Otten, E. W.; Passler, G.; Senne, P.; Stenner, J.; Stratmann, K.; Swendt, K.; Zimmer, K.; Herrmann, G.; Trautmann, N.; Walter, K.

1993-12-01

Environmental assessment in the wake of a nuclear accident requires the rapid determination of the radiotoxic isotopes 89Sr and 90Sr. Useful measurements must be able to detect 10 8 atoms in the presence of about 10 18 atoms of the stable, naturally occurring isotopes. This paper describes a new approach to this problem using resonance ionization spectroscopy in collinear geometry, combined with classical mass separation. After collection and chemical separation, the strontium from a sample is surface-ionized and the ions are accelerated to an energy of about 30 keV. Initially, a magnetic mass separator provides an isotopic selectivity of about 10 6. The ions are then neutralized by charge exchange and the resulting fast strontium atoms are selectively excited into high-lying atomic Rydberg states by narrow-band cw laser light in collinear geometry. The Rydberg atoms are then field-ionized and detected. Thus far, a total isotopic selectivity of S > 10 10 and an overall efficiency of ξ = 5 × 10 -6 have been achieved. The desired detection limit of 10 8 atoms 90Sr has been demonstrated with synthetic samples.

Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

NASA Astrophysics Data System (ADS)

Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

2017-05-01

Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio ( m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- ( m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones.

Chemical microsensors

DOEpatents

Li, DeQuan; Swanson, Basil I.

1995-01-01

An article of manufacture is provided including a substrate having an oxide surface layer and a selective thin film of a cyclodextrin derivative chemically bound upon said substrate, said film is adapted for the inclusion of a selected organic compound therewith. Such an article can be either a chemical sensor capable of detecting a resultant mass change from inclusion of the selected organic compound or a chemical separator capable of reversibly selectively separating a selected organic compound.

Strategy to improve the quantitative LC-MS analysis of molecular ions resistant to gas-phase collision induced dissociation: application to disulfide-rich cyclic peptides.

PubMed

Ciccimaro, Eugene; Ranasinghe, Asoka; D'Arienzo, Celia; Xu, Carrie; Onorato, Joelle; Drexler, Dieter M; Josephs, Jonathan L; Poss, Michael; Olah, Timothy

2014-12-02

Due to observed collision induced dissociation (CID) fragmentation inefficiency, developing sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) assays for CID resistant compounds is especially challenging. As an alternative to traditional LC-MS/MS, we present here a methodology that preserves the intact analyte ion for quantification by selectively filtering ions while reducing chemical noise. Utilizing a quadrupole-Orbitrap MS, the target ion is selectively isolated while interfering matrix components undergo MS/MS fragmentation by CID, allowing noise-free detection of the analyte's surviving molecular ion. In this manner, CID affords additional selectivity during high resolution accurate mass analysis by elimination of isobaric interferences, a fundamentally different concept than the traditional approach of monitoring a target analyte's unique fragment following CID. This survivor-selected ion monitoring (survivor-SIM) approach has allowed sensitive and specific detection of disulfide-rich cyclic peptides extracted from plasma.

In house validation of a high resolution mass spectrometry Orbitrap-based method for multiple allergen detection in a processed model food.

PubMed

Pilolli, Rosa; De Angelis, Elisabetta; Monaci, Linda

2018-02-13

In recent years, mass spectrometry (MS) has been establishing its role in the development of analytical methods for multiple allergen detection, but most analyses are being carried out on low-resolution mass spectrometers such as triple quadrupole or ion traps. In this investigation, performance provided by a high resolution (HR) hybrid quadrupole-Orbitrap™ MS platform for the multiple allergens detection in processed food matrix is presented. In particular, three different acquisition modes were compared: full-MS, targeted-selected ion monitoring with data-dependent fragmentation (t-SIM/dd2), and parallel reaction monitoring. In order to challenge the HR-MS platform, the sample preparation was kept as simple as possible, limited to a 30-min ultrasound-aided protein extraction followed by clean-up with disposable size exclusion cartridges. Selected peptide markers tracing for five allergenic ingredients namely skim milk, whole egg, soy flour, ground hazelnut, and ground peanut were monitored in home-made cookies chosen as model processed matrix. Timed t-SIM/dd2 was found the best choice as a good compromise between sensitivity and accuracy, accomplishing the detection of 17 peptides originating from the five allergens in the same run. The optimized method was validated in-house through the evaluation of matrix and processing effects, recoveries, and precision. The selected quantitative markers for each allergenic ingredient provided quantification of 60-100 μg ingred /g allergenic ingredient/matrix in incurred cookies.

Disk mass determination through CO isotopologues

NASA Astrophysics Data System (ADS)

Miotello, Anna; Kama, Mihkel; van Dishoeck, Ewine

2015-08-01

One of the key properties for understanding how disks evolve to planetary systems is their overall mass, combined with their surface density distribution. So far, virtually all disk mass determinations are based on observations of the millimeter continuum dust emission.To derive the total gas + dust disk mass from these data involves however several big assumptions. The alternative method is to directly derive the gas mass through the detection of carbon monoxide (CO) and its less abundant isotopologues. CO chemistry is well studied and easily implemented in chemical models, provided that isotope-selective processes are properly accounted for.CO isotope-selective photodissociation was implemented for the first time in a full physical-chemical code in Miotello et al. (2014). The main result is that if isotope-selective effects are not considered in the data analysis, disk masses can be underestimated by an order of magnitude or more. For example, the mass discrepancy found for the renowned TW Hya disk may be explained or at least mitigated by this implementation. In this poster, we present new results for a large grid of disk models. We derive mass correction factors for different disk, stellar and grain properties in order to account for isotope-selective effects in analyzing ALMA data of CO isotopologues (Miotello et al., in prep.).

Planetary mass function and planetary systems

NASA Astrophysics Data System (ADS)

Dominik, M.

2011-02-01

With planets orbiting stars, a planetary mass function should not be seen as a low-mass extension of the stellar mass function, but a proper formalism needs to take care of the fact that the statistical properties of planet populations are linked to the properties of their respective host stars. This can be accounted for by describing planet populations by means of a differential planetary mass-radius-orbit function, which together with the fraction of stars with given properties that are orbited by planets and the stellar mass function allows the derivation of all statistics for any considered sample. These fundamental functions provide a framework for comparing statistics that result from different observing techniques and campaigns which all have their very specific selection procedures and detection efficiencies. Moreover, recent results both from gravitational microlensing campaigns and radial-velocity surveys of stars indicate that planets tend to cluster in systems rather than being the lonely child of their respective parent star. While planetary multiplicity in an observed system becomes obvious with the detection of several planets, its quantitative assessment however comes with the challenge to exclude the presence of further planets. Current exoplanet samples begin to give us first hints at the population statistics, whereas pictures of planet parameter space in its full complexity call for samples that are 2-4 orders of magnitude larger. In order to derive meaningful statistics, however, planet detection campaigns need to be designed in such a way that well-defined fully deterministic target selection, monitoring and detection criteria are applied. The probabilistic nature of gravitational microlensing makes this technique an illustrative example of all the encountered challenges and uncertainties.

Recent developments in cyanide detection: A review

PubMed Central

Ma, Jian; Dasgupta, Purnendu K.

2010-01-01

The extreme toxicity of cyanide and environmental concerns from its continued industrial use continue to generate interest in facile and sensitive methods for cyanide detection. In recent years there is also additional recognition of HCN toxicity from smoke inhalation and potential use of cyanide as a weapon of terrorism. This review summarizes the literature since 2005 on cyanide measurement in different matrices ranging from drinking water and wastewater, to cigarette smoke and exhaled breath to biological fluids like blood, urine and saliva. The dramatic increase in the number of publications on cyanide measurement is indicative of the great interest in this field not only from analytical chemists, but also researchers from diverse environmental, medical, forensic and clinical arena. The recent methods cover both established and emerging analytical disciplines and include naked eye visual detection, spectrophotometry/colorimetry, capillary electrophoresis with optical absorbance detection, fluorometry, chemiluminescence, near-infrared cavity ring down spectroscopy, atomic absorption spectrometry, electrochemical methods (potentiometry/amperometry/ion chromatography-pulsed amperometry), mass spectrometry (selected ion flow tube mass spectrometry, electrospray ionization mass spectrometry, gas chromatography-mass spectrometry), gas chromatography (nitrogen phosphorus detector, electron capture detector) and quartz crystal mass monitors. PMID:20599024

[The use of the deuterated internal standard for morphine quantitation for the purpose of doping control by gas chromatography with mass-selective detection].

PubMed

Savel'eva, N B; Bykovskaia, N Iu; Dikunets, M A; Bolotov, S L; Rodchenkov, G M

2010-01-01

The objective of this study was to demonstrate the possibility to use deuterated compounds as internal standards for the quantitative analysis of morphine by gas chromatography with mass-selective detection for the purpose of doping control. The paper is focused on the problems associated with the use of deuterated morphine-D3 as the internal standard. Quantitative characteristics of the calibration dependence thus documented are presented along with uncertainty values obtained in the measurements with the use of deuterated morphine-D6. An approach to the assessment of method bias associated with the application of morphine-D6 as the deuterated internal standard is described.

Detection of enhancement in number densities of background galaxies due to magnification by massive galaxy clusters

DOE PAGES

Chiu, I.; Dietrich, J. P.; Mohr, J.; ...

2016-02-18

We present a detection of the enhancement in the number densities of background galaxies induced from lensing magnification and use it to test the Sunyaev-Zel'dovich effect (SZE) inferred masses in a sample of 19 galaxy clusters with median redshift z≃0.42 selected from the South Pole Telescope SPT-SZ survey. Two background galaxy populations are selected for this study through their photometric colours; they have median redshifts z median≃0.9 (low-z background) and z median≃1.8 (high-z background). Stacking these populations, we detect the magnification bias effect at 3.3σ and 1.3σ for the low- and high-z backgrounds, respectively. We fit NFW models simultaneously tomore » all observed magnification bias profiles to estimate the multiplicative factor η that describes the ratio of the weak lensing mass to the mass inferred from the SZE observable-mass relation. We further quantify systematic uncertainties in η resulting from the photometric noise and bias, the cluster galaxy contamination and the estimations of the background properties. The resulting η for the combined background populations with 1σ uncertainties is 0.83 ± 0.24(stat) ± 0.074(sys), indicating good consistency between the lensing and the SZE-inferred masses. We also use our best-fit η to predict the weak lensing shear profiles and compare these predictions with observations, showing agreement between the magnification and shear mass constraints. Our work demonstrates the promise of using the magnification as a complementary method to estimate cluster masses in large surveys.« less

Rapid detection of cocaine, benzoylecgonine and methylecgonine in fingerprints using surface mass spectrometry.

PubMed

Bailey, Melanie J; Bradshaw, Robert; Francese, Simona; Salter, Tara L; Costa, Catia; Ismail, Mahado; P Webb, Roger; Bosman, Ingrid; Wolff, Kim; de Puit, Marcel

2015-09-21

Latent fingerprints provide a potential route to the secure, high throughput and non-invasive detection of drugs of abuse. In this study we show for the first time that the excreted metabolites of drugs of abuse can be detected in fingerprints using ambient mass spectrometry. Fingerprints and oral fluid were taken from patients attending a drug and alcohol treatment service. Gas chromatography mass spectrometry (GC-MS) was used to test the oral fluid of patients for the presence of cocaine and benzoylecgonine. The corresponding fingerprints were analysed using Desorption Electrospray Ionization (DESI) which operates under ambient conditions and Ion Mobility Tandem Mass Spectrometry Matrix Assisted Laser Desorption Ionization (MALDI-IMS-MS/MS) and Secondary Ion Mass Spectrometry (SIMS). The detection of cocaine, benzoylecgonine (BZE) and methylecgonine (EME) in latent fingerprints using both DESI and MALDI showed good correlation with oral fluid testing. The sensitivity of SIMS was found to be insufficient for this application. These results provide exciting opportunities for the use of fingerprints as a new sampling medium for secure, non-invasive drug detection. The mass spectrometry techniques used here offer a high level of selectivity and consume only a small area of a single fingerprint, allowing repeat and high throughput analyses of a single sample.

Application of targeted quantitative proteomics analysis in human cerebrospinal fluid using a liquid chromatography matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometer (LC MALDI TOF/TOF) platform.

PubMed

Pan, Sheng; Rush, John; Peskind, Elaine R; Galasko, Douglas; Chung, Kathryn; Quinn, Joseph; Jankovic, Joseph; Leverenz, James B; Zabetian, Cyrus; Pan, Catherine; Wang, Yan; Oh, Jung Hun; Gao, Jean; Zhang, Jianpeng; Montine, Thomas; Zhang, Jing

2008-02-01

Targeted quantitative proteomics by mass spectrometry aims to selectively detect one or a panel of peptides/proteins in a complex sample and is particularly appealing for novel biomarker verification/validation because it does not require specific antibodies. Here, we demonstrated the application of targeted quantitative proteomics in searching, identifying, and quantifying selected peptides in human cerebrospinal spinal fluid (CSF) using a matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometer (MALDI TOF/TOF)-based platform. The approach involved two major components: the use of isotopic-labeled synthetic peptides as references for targeted identification and quantification and a highly selective mass spectrometric analysis based on the unique characteristics of the MALDI instrument. The platform provides high confidence for targeted peptide detection in a complex system and can potentially be developed into a high-throughput system. Using the liquid chromatography (LC) MALDI TOF/TOF platform and the complementary identification strategy, we were able to selectively identify and quantify a panel of targeted peptides in the whole proteome of CSF without prior depletion of abundant proteins. The effectiveness and robustness of the approach associated with different sample complexity, sample preparation strategies, as well as mass spectrometric quantification were evaluated. Other issues related to chromatography separation and the feasibility for high-throughput analysis were also discussed. Finally, we applied targeted quantitative proteomics to analyze a subset of previously identified candidate markers in CSF samples of patients with Parkinson's disease (PD) at different stages and Alzheimer's disease (AD) along with normal controls.

Identifying the site of spin trapping in proteins by a combination of liquid chromatography, ELISA, and off-line tandem mass spectrometry.

PubMed

Lardinois, Olivier M; Detweiler, Charles D; Tomer, Kenneth B; Mason, Ronald P; Deterding, Leesa J

2008-03-01

An off-line mass spectrometry method that combines immuno-spin trapping and chromatographic procedures has been developed for selective detection of the nitrone spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) covalently attached to proteins, an attachment which occurs only subsequent to DMPO trapping of free radicals. In this technique, the protein-DMPO nitrone adducts are digested to peptides with proteolytic agents, peptides from the enzymatic digest are separated by HPLC, and enzyme-linked immunosorbent assays (ELISA) using polyclonal anti-DMPO nitrone antiserum are used to detect the eluted HPLC fractions that contain DMPO nitrone adducts. The fractions showing positive ELISA signals are then concentrated and characterized by tandem mass spectrometry (MS/MS). This method, which constitutes the first liquid chromatography-ELISA-mass spectrometry (LC-ELISA-MS)-based strategy for selective identification of DMPO-trapped protein residues in complex peptide mixtures, facilitates location and preparative fractionation of DMPO nitrone adducts for further structural characterization. The strategy is demonstrated for human hemoglobin, horse heart myoglobin, and sperm whale myoglobin, three globin proteins known to form DMPO-trappable protein radicals on treatment with H(2)O(2). The results demonstrate the power of the new experimental strategy to select DMPO-labeled peptides and identify sites of DMPO covalent attachments.

Detection of nicotine as an indicator of tobacco smoke by direct analysis in real time (DART) tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Kuki, Ákos; Nagy, Lajos; Nagy, Tibor; Zsuga, Miklós; Kéki, Sándor

2015-01-01

The residual tobacco smoke contamination (thirdhand smoke, THS) on the clothes of a smoker was examined by direct analysis in real time (DART) mass spectrometry. DART-MS enabled sensitive and selective analysis of nicotine as the indicator of tobacco smoke pollution. Tandem mass spectrometric (MS/MS) experiments were also performed to confirm the identification of nicotine. Transferred thirdhand smoke originated from the fingers of a smoker onto other objects was also detected by DART mass spectrometry. DART-MS/MS was utilized for monitoring the secondhand tobacco smoke (SHS) in the air of the laboratory using nicotine as an indicator. To the best of our knowledge, this is the first report on the application of DART-MS and DART-MS/MS to the detection of thirdhand smoke and to the monitoring of secondhand smoke.

Chemosensors for detection of nitroaromatic compounds (explosives)

NASA Astrophysics Data System (ADS)

Zyryanov, G. V.; Kopchuk, D. S.; Kovalev, I. S.; Nosova, E. V.; Rusinov, V. L.; Chupakhin, O. N.

2014-09-01

The key types of low-molecular-mass chemosensors for the detection of nitroaromatic compounds representing energetic substances (explosives) are analyzed. The coordination and chemical properties of these chemosensors and structural features of their complexes with nitroaromatic compounds are considered. The causes and methods for attaining high selectivity of recognition are demonstrated. The primary attention is paid to the use of low-molecular-mass chemosensors for visual detection of explosives of this class by colorimetric and photometric methods. Examples of using photo- and chemiluminescence for this purpose are described. A separate section is devoted to electrochemical methods of detection of nitroaromatic compounds. Data published from 2000 to 2014 are mainly covered. The bibliography includes 245 references.

New Polymer Coatings for Chemically Selective Mass Sensors

NASA Technical Reports Server (NTRS)

Sims, S. C.; Wright, Cassandra; Cobb, J.; McCalla, T.; Revelle, R.; Morris, V. R.; Pollack, S. K.

1997-01-01

There is a current need to develop sensitive and chemically specific sensors for the detection of nitric acid for in-situ measurements in the atmosphere. Polymer coatings have been synthesized and tested for their sensitivity and selectivity to nitric acid. A primary requirement for these polymers is detectability down to the parts per trillion range. The results of studies using these polymers as coatings for quartz crystal microbalances (QCM) and surface acoustic wave (SAW) devices will be presented.

A DUAL PLATFORM FOR SELECTIVE ANALYTE ENRICHMENT AND IONIZATION IN MASS SPECTROMETRY USING APTAMER-CONJUGATED GRAPHENE OXIDE

PubMed Central

Gulbakan, Basri; Yasun, Emir; Shukoor, M. Ibrahim; Zhu, Zhi; You, Mingxu; Tan, Xiaohong; Sanchez, Hernan; Powell, David H.; Dai, Hongjie; Tan, Weihong

2010-01-01

This study demonstrates the use of aptamer-conjugated graphene oxide as an affinity extraction and detection platform for analytes from complex biological media. We have shown that cocaine and adenosine can be selectively enriched from plasma samples and that direct mass spectrometric readout can be obtained without a matrix and with greatly improved signal-to-noise ratios. The aptamer conjugated graphene oxide has clear advantages in target enrichment and in generating highly efficient ionization of target molecules for mass spectrometry. These results demonstrate the utility of the approach for analysis of small molecules in real biological samples. PMID:21090719

Internal calibration on adjacent samples (InCAS) with Fourier transform mass spectrometry.

PubMed

O'Connor, P B; Costello, C E

2000-12-15

Using matrix-assisted laser desorption/ionization (MAL DI) on a trapped ion mass spectrometer such as a Fourier transform mass spectrometer (FTMS) allows accumulation of ions in the cell from multiple laser shots prior to detection. If ions from separate MALDI samples are accumulated simultaneously in the cell, ions from one sample can be used to calibrate ions from the other sample. Since the ions are detected simultaneously in the cell, this is, in effect, internal calibration, but there are no selective desorption effects in the MALDI source. This method of internal calibration with adjacent samples is demonstrated here on cesium iodide clusters, peptides, oligosaccharides, poly(propylene glycol), and fullerenes and provides typical FTMS internal calibration mass accuracy of < 1 ppm.

A matrix-assisted laser desorption/ionization mass spectroscopy method for the analysis of small molecules by integrating chemical labeling with the supramolecular chemistry of cucurbituril.

PubMed

Ding, Jun; Xiao, Hua-Ming; Liu, Simin; Wang, Chang; Liu, Xin; Feng, Yu-Qi

2018-10-05

Although several methods have realized the analysis of low molecular weight (LMW) compounds using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) by overcoming the problem of interference with MS signals in the low mass region derived from conventional organic matrices, this emerging field still requires strategies to address the issue of analyzing complex samples containing LMW components in addition to the LMW compounds of interest, and solve the problem of lack of universality. The present study proposes an integrated strategy that combines chemical labeling with the supramolecular chemistry of cucurbit [n]uril (CB [n]) for the MALDI MS analysis of LMW compounds in complex samples. In this strategy, the target LMW compounds are first labeled by introducing a series of bifunctional reagents that selectively react with the target analytes and also form stable inclusion complexes with CB [n]. Then, the labeled products act as guest molecules that readily and selectively form stable inclusion complexes with CB [n]. This strategy relocates the MS signals of the LMW compounds of interest from the low mass region suffering high interference to the high mass region where interference with low mass components is absent. Experimental results demonstrate that a wide range of LMW compounds, including carboxylic acids, aldehydes, amines, thiol, and cis-diols, can be successfully detected using the proposed strategy, and the limits of detection were in the range of 0.01-1.76 nmol/mL. In addition, the high selectivity of the labeling reagents for the target analytes in conjunction with the high selectivity of the binding between the labeled products and CB [n] ensures an absence of signal interference with the non-targeted LMW components of complex samples. Finally, the feasibility of the proposed strategy for complex sample analysis is demonstrated by the accurate and rapid quantitative analysis of aldehydes in saliva and herbal medicines. As such, this work not only provides an alternative method for the detection of various LMW compounds using MALDI MS, but also can be applied to the selective and high-throughput analysis of LMW analytes in complex samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Matrix effect on the determination of synthetic corticosteroids and diuretics by liquid chromatography-tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Dikunets, M. A.; Appolonova, S. A.; Rodchenkov, G. M.

2009-04-01

This work presents a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) procedure for selective and reliable screening of corticosteroids and diuretics in human urine. Sample preparation included the extraction, evaporation of the organic extract under nitrogen, and solution of the dry residue. The extract was analyzed by HPLC combined with tandem mass spectrometry using electro-spraying ionization at atmospheric pressure with negative ion recording. The mass spectra of all compounds were recorded, and the characteristic ions, retention times, and detection limits were determined. The procedure was validated by evaluating the degree of the matrix suppression of ionization, extraction of analytes from human biological liquid, and the selectivity and specificity of determination.

Quasi-dynamic mode of nanomembranes for time-of-flight mass spectrometry of proteins.

PubMed

Park, Jonghoo; Kim, Hyunseok; Blick, Robert H

2012-04-21

Mechanical resonators realized on the nano-scale by now offer applications in mass-sensing of biomolecules with extraordinary sensitivity. The general idea is that perfect mechanical biosensors should be of extremely small size to achieve zeptogram sensitivity in weighing single molecules similar to a balance. However, the small scale and long response time of weighing biomolecules with a cantilever restrict their usefulness as a high-throughput method. Commercial mass spectrometry (MS) such as electro-spray ionization (ESI)-MS and matrix-assisted laser desorption/ionization (MALDI)-time of flight (TOF)-MS are the gold standards to which nanomechanical resonators have to live up to. These two methods rely on the ionization and acceleration of biomolecules and the following ion detection after a mass selection step, such as time-of-flight (TOF). Hence, the spectrum is typically represented in m/z, i.e. the mass to ionization charge ratio. Here, we describe the feasibility and mass range of detection of a new mechanical approach for ion detection in time-of-flight mass spectrometry, the principle of which is that the impinging ion packets excite mechanical oscillations in a silicon nitride nanomembrane. These mechanical oscillations are henceforth detected via field emission of electrons from the nanomembrane. Ion detection is demonstrated in MALDI-TOF analysis over a broad range with angiotensin, bovine serum albumin (BSA), and an equimolar protein mixture of insulin, BSA, and immunoglobulin G (IgG). We find an unprecedented mass range of operation of the nanomembrane detector.

EPA Method 538: Determination of Selected Organic Contaminants in Drinking Water by Direct Aqueous Injection-Liquid Chromatography/Tandem Mass Spectrometry (DAI-LC/MS/MS)

EPA Pesticide Factsheets

EPA’s Selected Analytical Methods for Environmental Remediation and Recovery (SAM) lists this method for preparation and analysis of drinking water samples to detect and measure acephate, diisopropyl methylphosphonate (DIMP), methamidophos and thiofanox.

Selective Detection of Peptide-Oligonucleotide Heteroconjugates Utilizing Capillary HPLC-ICPMS

NASA Astrophysics Data System (ADS)

Catron, Brittany; Caruso, Joseph A.; Limbach, Patrick A.

2012-06-01

A method for the selective detection and quantification of peptide:oligonucleotide heteroconjugates, such as those generated by protein:nucleic acid cross-links, using capillary reversed-phase high performance liquid chromatography (cap-RPHPLC) coupled with inductively coupled plasma mass spectrometry detection (ICPMS) is described. The selective detection of phosphorus as 31P+, the only natural isotope, in peptide-oligonucleotide heteroconjugates is enabled by the elemental detection capabilities of the ICPMS. Mobile phase conditions that allow separation of heteroconjugates while maintaining ICPMS compatibility were investigated. We found that trifluoroacetic acid (TFA) mobile phases, used in conventional peptide separations, and hexafluoroisopropanol/triethylamine (HFIP/TEA) mobile phases, used in conventional oligonucleotide separations, both are compatible with ICPMS and enable heteroconjugate separation. The TFA-based separations yielded limits of detection (LOD) of ~40 ppb phosphorus, which is nearly seven times lower than the LOD for HFIP/TEA-based separations. Using the TFA mobile phase, 1-2 pmol of a model heteroconjugate were routinely separated and detected by this optimized capLC-ICPMS method.

The Frequency of Low-Mass Exoplanets

NASA Astrophysics Data System (ADS)

O'Toole, S. J.; Jones, H. R. A.; Tinney, C. G.; Butler, R. P.; Marcy, G. W.; Carter, B.; Bailey, J.; Wittenmyer, R. A.

2009-08-01

We report first results from the Anglo-Australian Telescope Rocky Planet Search—an intensive, high-precision Doppler planet search targeting low-mass exoplanets in contiguous 48 night observing blocks. On this run, we targeted 24 bright, nearby and intrinsically stable Sun-like stars selected from the Anglo-Australian Planet Search's main sample. These observations have already detected one low-mass planet reported elsewhere (HD 16417b), and here we reconfirm the detection of HD 4308b. Further, we have Monte Carlo simulated data from this run on a star-by-star basis to produce robust detection constraints. These simulations demonstrate clear differences in the exoplanet detectability functions from star to star due to differences in sampling, data quality and intrinsic stellar stability. They reinforce the importance of star-by-star simulation when interpreting the data from Doppler planet searches. These simulations indicate that for some of our target stars we are sensitive to close-orbiting planets as small as a few Earth masses. The two low-mass planets present in our 24-star sample indicate that the exoplanet minimum mass function at low masses is likely to be a flat α ~ -1 (for dN/dM vprop M α) and that between 15% ± 10% (at α = -0.3) and 48% ± 34% (at α = -1.3) of stars host planets with orbital periods of less than 16 days and minimum masses greater than 3 M ⊕.

Investigation of heavy-metal accumulation in selected plant samples using laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Galiová, M.; Kaiser, J.; Novotný, K.; Novotný, J.; Vaculovič, T.; Liška, M.; Malina, R.; Stejskal, K.; Adam, V.; Kizek, R.

2008-12-01

Single-pulse Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass-Spectrometry (LA-ICP-MS) were applied for mapping the silver and copper distribution in Helianthus Annuus L. samples treated with contaminant in controlled conditions. For Ag and Cu detection the 328.07 nm Ag(I) and 324.75 nm Cu(I) lines were used, respectively. The LIBS experimental conditions (mainly the laser energy and the observation window) were optimized in order to avoid self-absorption effect in the measured spectra. In the LA-ICP-MS analysis the Ag 107 and Cu 63 isotopes were detected. The capability of these two analytical techniques for high-resolution mapping of selected trace chemical elements was demonstrated.

Detection of enhancement in number densities of background galaxies due to magnification by massive galaxy clusters

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

Chiu, I.; Dietrich, J. P.; Mohr, J.

2016-02-18

We present a detection of the enhancement in the number densities of background galaxies induced from lensing magnification and use it to test the Sunyaev-Zel'dovich effect (SZE-) inferred masses in a sample of 19 galaxy clusters with median redshift z similar or equal to 0.42 selected from the South Pole Telescope SPT-SZ survey. These clusters are observed by the Megacam on the Magellan Clay Telescope though gri filters. Two background galaxy populations are selected for this study through their photometric colours; they have median redshifts zmedian similar or equal to 0.9 (low-z background) and z(median) similar or equal to 1.8more » (high-z background). Stacking these populations, we detect the magnification bias effect at 3.3 sigma and 1.3 sigma for the low-and high-z backgrounds, respectively. We fit Navarro, Frenk and White models simultaneously to all observed magnification bias profiles to estimate the multiplicative factor. that describes the ratio of the weak lensing mass to the mass inferred from the SZE observable-mass relation. We further quantify systematic uncertainties in. resulting from the photometric noise and bias, the cluster galaxy contamination and the estimations of the background properties. The resulting. for the combined background populations with 1 sigma uncertainties is 0.83 +/- 0.24(stat) +/- 0.074(sys), indicating good consistency between the lensing and the SZE-inferred masses. We use our best-fitting eta to predict the weak lensing shear profiles and compare these predictions with observations, showing agreement between the magnification and shear mass constraints. This work demonstrates the promise of using the magnification as a complementary method to estimate cluster masses in large surveys.« less

Methods of analysis by the U. S. Geological Survey National Water Quality Laboratory - determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring

USGS Publications Warehouse

Sandstrom, Mark W.; Wydoski, Duane S.; Schroeder, Michael P.; Zamboni, Jana L.; Foreman, William T.

1992-01-01

A method for the isolation of organonitrogen herbicides from natural water samples using solid-phase extraction and analysis by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase extraction cartridges containing octadecyl-bonded porous silica to remove the herbicides. The cartridges are dried using carbon dioxide, and adsorbed herbicides are removed from the cartridges by elution with 1.8 milliliters of hexaneisopropanol (3:1). Extracts of the eluants are analyzed by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring of at least three characteristic ions. The method detection limits are dependent on sample matrix and each particular herbicide. The method detection limits, based on a 100-milliliter sample size, range from 0.02 to 0.25 microgram per liter. Recoveries averaged 80 to 115 percent for the 23 herbicides and 2 metabolites in 1 reagent-water and 2 natural-water samples fortified at levels of 0.2 and 2.0 micrograms per liter.

Optimization of breast mass classification using sequential forward floating selection (SFFS) and a support vector machine (SVM) model

PubMed Central

Tan, Maxine; Pu, Jiantao; Zheng, Bin

2014-01-01

Purpose: Improving radiologists’ performance in classification between malignant and benign breast lesions is important to increase cancer detection sensitivity and reduce false-positive recalls. For this purpose, developing computer-aided diagnosis (CAD) schemes has been attracting research interest in recent years. In this study, we investigated a new feature selection method for the task of breast mass classification. Methods: We initially computed 181 image features based on mass shape, spiculation, contrast, presence of fat or calcifications, texture, isodensity, and other morphological features. From this large image feature pool, we used a sequential forward floating selection (SFFS)-based feature selection method to select relevant features, and analyzed their performance using a support vector machine (SVM) model trained for the classification task. On a database of 600 benign and 600 malignant mass regions of interest (ROIs), we performed the study using a ten-fold cross-validation method. Feature selection and optimization of the SVM parameters were conducted on the training subsets only. Results: The area under the receiver operating characteristic curve (AUC) = 0.805±0.012 was obtained for the classification task. The results also showed that the most frequently-selected features by the SFFS-based algorithm in 10-fold iterations were those related to mass shape, isodensity and presence of fat, which are consistent with the image features frequently used by radiologists in the clinical environment for mass classification. The study also indicated that accurately computing mass spiculation features from the projection mammograms was difficult, and failed to perform well for the mass classification task due to tissue overlap within the benign mass regions. Conclusions: In conclusion, this comprehensive feature analysis study provided new and valuable information for optimizing computerized mass classification schemes that may have potential to be useful as a “second reader” in future clinical practice. PMID:24664267

Comparison of statistical methods for detection of serum lipid biomarkers for mesothelioma and asbestos exposure.

PubMed

Xu, Rengyi; Mesaros, Clementina; Weng, Liwei; Snyder, Nathaniel W; Vachani, Anil; Blair, Ian A; Hwang, Wei-Ting

2017-07-01

We compared three statistical methods in selecting a panel of serum lipid biomarkers for mesothelioma and asbestos exposure. Serum samples from mesothelioma, asbestos-exposed subjects and controls (40 per group) were analyzed. Three variable selection methods were considered: top-ranked predictors from univariate model, stepwise and least absolute shrinkage and selection operator. Crossed-validated area under the receiver operating characteristic curve was used to compare the prediction performance. Lipids with high crossed-validated area under the curve were identified. Lipid with mass-to-charge ratio of 372.31 was selected by all three methods comparing mesothelioma versus control. Lipids with mass-to-charge ratio of 1464.80 and 329.21 were selected by two models for asbestos exposure versus control. Different methods selected a similar set of serum lipids. Combining candidate biomarkers can improve prediction.

Automated detection of masses on whole breast volume ultrasound scanner: false positive reduction using deep convolutional neural network

NASA Astrophysics Data System (ADS)

Hiramatsu, Yuya; Muramatsu, Chisako; Kobayashi, Hironobu; Hara, Takeshi; Fujita, Hiroshi

2017-03-01

Breast cancer screening with mammography and ultrasonography is expected to improve sensitivity compared with mammography alone, especially for women with dense breast. An automated breast volume scanner (ABVS) provides the operator-independent whole breast data which facilitate double reading and comparison with past exams, contralateral breast, and multimodality images. However, large volumetric data in screening practice increase radiologists' workload. Therefore, our goal is to develop a computer-aided detection scheme of breast masses in ABVS data for assisting radiologists' diagnosis and comparison with mammographic findings. In this study, false positive (FP) reduction scheme using deep convolutional neural network (DCNN) was investigated. For training DCNN, true positive and FP samples were obtained from the result of our initial mass detection scheme using the vector convergence filter. Regions of interest including the detected regions were extracted from the multiplanar reconstraction slices. We investigated methods to select effective FP samples for training the DCNN. Based on the free response receiver operating characteristic analysis, simple random sampling from the entire candidates was most effective in this study. Using DCNN, the number of FPs could be reduced by 60%, while retaining 90% of true masses. The result indicates the potential usefulness of DCNN for FP reduction in automated mass detection on ABVS images.

Organic chemical analysis on a microscopic scale using two-step laser desorption/laser ionization mass spectrometry

NASA Technical Reports Server (NTRS)

Kovalenko, L. J.; Philippoz, J.-M.; Bucenell, J. R.; Zenobi, R.; Zare, R. N.

1991-01-01

The distribution of PAHs in the Allende meteorite has been measured using two-step laser desorption and laser multiphoton-ionization mass spectrometry. This method enables in situ analysis (with a spatial resolution of 1 mm or better) of selected organic molecules. Results show that PAH concentrations are locally high compared to the average concentration found by analysis of pulverized samples, and are found primarily in the fine-grained matrix; no PAHs were detected in the interiors of individual chondrules at the detection limit (about 0.05 ppm).

DMS-prefiltered mass spectrometry for the detection of biomarkers

NASA Astrophysics Data System (ADS)

Coy, Stephen L.; Krylov, Evgeny V.; Nazarov, Erkinjon G.

2008-04-01

Technologies based on Differential Mobility Spectrometry (DMS) are ideally matched to rapid, sensitive, and selective detection of chemicals like biomarkers. Biomarkers linked to exposure to radiation, exposure to CWA's, exposure to toxic materials (TICs and TIMs) and to specific diseases are being examined in a number of laboratories. Screening for these types of exposure can be improved in accuracy and greatly speeded up by using DMS-MS instead of slower techniques like LC-MS and GC-MS. We have performed an extensive series of tests with nanospray-DMS-mass spectroscopy and standalone nanospray-DMS obtaining extensive information on chemistry and detectivity. DMS-MS systems implemented with low-resolution, low-cost, portable mass-spectrometry systems are very promising. Lowresolution mass spectrometry alone would be inadequate for the task, but with DMS pre-filtration to suppress interferences, can be quite effective, even for quantitative measurement. Bio-fluids and digests are well suited to ionization by electrospray and detection by mass-spectrometry, but signals from critical markers are overwhelmed by chemical noise from unrelated species, making essential quantitative analysis impossible. Sionex and collaborators have presented data using DMS to suppress chemical noise, allowing detection of cancer biomarkers in 10,000-fold excess of normal products 1,2. In addition, a linear dynamic range of approximately 2,000 has been demonstrated with accurate quantitation 3. We will review the range of possible applications and present new data on DMS-MS biomarker detection.

Amonia gas: an improved reagent for chemical ionization mass spectrometry of bile acid methyl ester acetates

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

DeMark, B.R.; Klein, P.D.

1981-01-01

The ammonia chemical ionization mass spectra of 28 methyl ester acetate derivatives of bile acids and related compounds have been determined by gas-liquid chromatography-mass spectrometry. Advantages of ammonia ionization over the previously studied isobutane ionization include a 130 to 270% enhancement in the sensitivity of base peak monitoring, and direct determination of molecular weight from the base peak (M + NH/sub 4//sup +/) in the mass spectrum of any of the derivatives. Minor ions in the ammonia spectra also allow selective detection of 3-keto compounds and can indicate unsaturation or double bond conjugation in the molecule. The significance of thesemore » studies for the detection and quantitation of bile acids is discussed. 2 tables.« less

Mass Spectrometric Detection of Botulinum Neurotoxin by Measuring its Activity in Serum and Milk

NASA Astrophysics Data System (ADS)

Kalb, Suzanne R.; Pirkle, James L.; Barr, John R.

Botulinum neurotoxins (BoNTs) are bacterial protein toxins which are considered likely agents for bioterrorism due to their extreme toxicity and high availability. A new mass spectrometry based assay called Endopep MS detects and defines the toxin serotype in clinical and food matrices via toxin activity upon a peptide substrate which mimics the toxin's natural target. Furthermore, the subtype of the toxin is differentiated by employing mass spectrometry based proteomic techniques on the same sample. The Endopep-MS assay selectively detects active BoNT and defines the serotype faster and with sensitivity greater than the mouse bioassay. One 96-well plate can be analyzed in under 7 h. On higher level or "hot" samples, the subtype can then be differentiated in less than 2 h with no need for DNA.

Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

PubMed

Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

2015-02-01

Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

Metal cation detection in positive ion mode electrospray ionization mass spectrometry using a tetracationic salt as a gas-phase ion-pairing agent: evaluation of the effect of chelating agents on detection sensitivity.

PubMed

Xu, Chengdong; Dodbiba, Edra; Padivitage, Nilusha L T; Breitbach, Zachary S; Armstrong, Daniel W

2012-12-30

The detection of metal cations continues to be essential in many scientific and industrial areas of interest. The most common electrospray ionization mass spectrometry (ESI-MS) approach involves chelating the metal ions and detecting the organometallic complex in the negative ion mode. However, it is well known that negative ion mode ESI-MS is generally less sensitive than the positive ion mode. To achieve greater sensitivity, it is necessary to examine the feasibility of detecting the chelated metal cations in positive ion mode ESI-MS. Since highly solvated native metal cations have relatively low ionization efficiency in ESI-MS, and can be difficult to detect in the positive ion mode, a tetracationic ion-pairing agent was added to form a complex with the negatively charged metal chelate. The use of the ion-pairing agent leads to the generation of an overall positively charged complex, which can be detected at higher m/z values in the positive ion mode by electrospray ionization linear quadrupole ion trap mass spectrometry. Thirteen chelating agents with diverse structures were evaluated in this study. The nature of the chelating agent played as important a role as was previously determined for cationic pairing agents. The detection limits of six metal cations reached sub-picogram levels and significant improvements were observed when compared to negative ion mode detection where the metal-chelates were monitored without adding the ion-pairing reagent (IPR). Also, selective reaction monitoring (SRM) analyses were performed on the ternary complexes, which improved detection limits by one to three orders of magnitude. With this method it was possible to analyze the metal cations in the positive ion mode ESI-MS with the advantage of speed, sensitivity and selectivity. The optimum solution pH for this type of analysis is 5-7. Tandem mass spectrometry (MS/MS) further increases the sensitivity. Speciation is straightforward making this a broadly useful approach for the analysis of metal ions. Copyright © 2012 John Wiley & Sons, Ltd.

The Bivariate Luminosity--HI Mass Distribution Function of Galaxies based on the NIBLES Survey

NASA Astrophysics Data System (ADS)

Butcher, Zhon; Schneider, Stephen E.; van Driel, Wim; Lehnert, Matt

2016-01-01

We use 21cm HI line observations for 2610 galaxies from the Nançay Interstellar Baryons Legacy Extragalactic Survey (NIBLES) to derive a bivariate luminosity--HI mass distribution function. Our HI survey was selected to randomly probe the local (900 < cz < 12,000 km/s) galaxy population in each 0.5 mag wide bin for the absolute z-band magnitude range of -13.5 < Mz < -24 without regard to morphology or color. This targeted survey allowed more on-source integration time for weak and non-detected sources, enabling us to probe lower HI mass fractions and apply lower upper limits for non-detections than would be possible with the larger blind HI surveys. Additionally, we obtained a factor of four higher sensitivity follow-up observations at Arecibo of 90 galaxies from our non-detected and marginally detected categories to quantify the underlying HI distribution of sources not detected at Nançay. Using the optical luminosity function and our higher sensitivity follow up observations as priors, we use a 2D stepwise maximum likelihood technique to derive the two dimensional volume density distribution of luminosity and HI mass in each SDSS band.

Liquid Microjunction Surface Sampling Probe Electrospray Mass Spectrometry for Detection of Drugs and Metabolites in Thin Tissue Sections

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

Van Berkel, Gary J; Kertesz, Vilmos; Koeplinger, Kenneth A.

2008-01-01

A self-aspirating, liquid micro-junction surface sampling probe/electrospray emitter mass spectrometry system was demonstrated for use in the direct analysis of spotted and dosed drugs and their metabolites in thin tissue sections. Proof-of-principle sampling and analysis directly from tissue without the need for sample preparation was demonstrated first by raster scanning a region on a section of rat liver onto which reserpine was spotted. The mass spectral signal from selected reaction monitoring was used to develop a chemical image of the spotted drug on the tissue. The probe was also used to selectively spot sample areas of sagittal whole mouse bodymore » tissue sections that had been dosed orally (90 mg/kg) with R,S-sulforaphane 3 hrs prior to sacrifice. Sulforaphane and its glutathione and N-acetyl cysteine conjugates were monitored with selected reaction monitoring and detected in the stomach and various other tissues from the dosed mouse. No signal for these species was observed in the tissue from a control mouse. The same dosed tissue section was used to illustrate the possibility of obtaining a line scan across the whole body section. In total these results illustrate the potential for rapid screening of the distribution of drugs and metabolites in tissue sections with the micro-liquid junction surface sampling probe/electrospray mass spectrometry approach.« less

Gallium metal affinity capture tandem mass spectrometry for the selective detection of phosphopeptides in complex mixtures

PubMed Central

Blacken, Grady R.; Sadílek, Martin; Tureček, František

2008-01-01

Metal affinity capture tandem mass spectrometry (MAC-MSMS) is evaluated in a comparative study of a lysine-derived nitrilotriacetic acid (Nα, Nα-bis-(carboxymethyl)lysine, LysNTA) and an aspartic-acid-related iminodiacetic acid (N-(4-aminobutyl)aspartic acid, AspIDA) as selective phosphopeptide detection reagents. Both LysNTA and AspIDA spontaneously form ternary complexes with GaIII and phosphorylated amino acids and phosphopeptides upon mixing in solution. Collision-induced dissociation of positive complex ions produced by electrospray produces common fragments (LysNTA + H)+ or (AspIDA + H)+ at m/z 263 and 205, respectively. MSMS precursor scans using these fragments as reporter ions allow one to selectively detect multiple charge states of phosphopeptides in mixtures. It follows from this comparative study that LysNTA is superior to AspIDA in detecting phosphopeptides, possibly because of the higher coordination number and greater stability constant for GaIII – phosphopeptide complexation of the former reagent. In a continuing development of MAC-MSMS for proteomics applications, we demonstrate its utility in a post-column reaction format. Using a simple post-column-reaction ‘T’ and syringe pump to deliver our chelating reagents, α-casein tryptic phosphopeptides can be selectively analyzed from a solution containing a twofold molar excess of bovine serum albumin. The MAC-MSMS method is shown to be superior to the commonly used neutral loss scan for the common loss of phosphoric acid. PMID:18265438

GASPS—A Herschel Survey of Gas and Dust in Protoplanetary Disks: Summary and Initial Statistics

NASA Astrophysics Data System (ADS)

Dent, W. R. F.; Thi, W. F.; Kamp, I.; Williams, J. P.; Menard, F.; Andrews, S.; Ardila, D.; Aresu, G.; Augereau, J.-C.; Barrado y Navascues, D.; Brittain, S.; Carmona, A.; Ciardi, D.; Danchi, W.; Donaldson, J.; Duchene, G.; Eiroa, C.; Fedele, D.; Grady, C.; de Gregorio-Molsalvo, I.; Howard, C.; Huélamo, N.; Krivov, A.; Lebreton, J.; Liseau, R.; Martin-Zaidi, C.; Mathews, G.; Meeus, G.; Mendigutía, I.; Montesinos, B.; Morales-Calderon, M.; Mora, A.; Nomura, H.; Pantin, E.; Pascucci, I.; Phillips, N.; Pinte, C.; Podio, L.; Ramsay, S. K.; Riaz, B.; Riviere-Marichalar, P.; Roberge, A.; Sandell, G.; Solano, E.; Tilling, I.; Torrelles, J. M.; Vandenbusche, B.; Vicente, S.; White, G. J.; Woitke, P.

2013-05-01

We describe a large-scale far-infrared line and continuum survey of protoplanetary disk through to young debris disk systems carried out using the ACS instrument on the Herschel Space Observatory. This Open Time Key program, known as GASPS (Gas Survey of Protoplanetary Systems), targeted ~250 young stars in narrow wavelength regions covering the [OI] fine structure line at 63 μm the brightest far-infrared line in such objects. A subset of the brightest targets were also surveyed in [OI]145 μm, [CII] at 157 μm, as well as several transitions of H2O and high-excitation CO lines at selected wavelengths between 78 and 180 μm. Additionally, GASPS included continuum photometry at 70, 100 and 160 μm, around the peak of the dust emission. The targets were SED Class II-III T Tauri stars and debris disks from seven nearby young associations, along with a comparable sample of isolated Herbig AeBe stars. The aim was to study the global gas and dust content in a wide sample of circumstellar disks, combining the results with models in a systematic way. In this overview paper we review the scientific aims, target selection and observing strategy of the program. We summarise some of the initial results, showing line identifications, listing the detections, and giving a first statistical study of line detectability. The [OI] line at 63 μm was the brightest line seen in almost all objects, by a factor of ~10. Overall [OI]63 μm detection rates were 49%, with 100% of HAeBe stars and 43% of T Tauri stars detected. A comparison with published disk dust masses (derived mainly from sub-mm continuum, assuming standard values of the mm mass opacity) shows a dust mass threshold for [OI]63 μm detection of ~10-5 Msolar. Normalising to a distance of 140 pc, 84% of objects with dust masses >=10-5 Msolar can be detected in this line in the present survey; 32% of those of mass 10-6-10-5 Msolar, and only a very small number of unusual objects with lower masses can be detected. This is consistent with models with a moderate UV excess and disk flaring. For a given disk mass, [OI] detectability is lower for M stars compared with earlier spectral types. Both the continuum and line emission was, in most systems, spatially and spectrally unresolved and centred on the star, suggesting that emission in most cases was from the disk. Approximately 10 objects showed resolved emission, most likely from outflows. In the GASPS sample, [OI] detection rates in T Tauri associations in the 0.3-4 Myr age range were ~50%. For each association in the 5-20 Myr age range, ~2 stars remain detectable in [OI]63 μm, and no systems were detected in associations with age >20 Myr. Comparing with the total number of young stars in each association, and assuming a ISM-like gas/dust ratio, this indicates that ~18% of stars retain a gas-rich disk of total mass ~1 MJupiter for 1-4 Myr, 1-7% keep such disks for 5-10 Myr, but none are detected beyond 10-20 Myr. The brightest [OI] objects from GASPS were also observed in [OI]145 μm, [CII]157 μm and CO J = 18 - 17, with detection rates of 20-40%. Detection of the [CII] line was not correlated with disk mass, suggesting it arises more commonly from a compact remnant envelope.

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

NASA Technical Reports Server (NTRS)

Getty, Stephanie; Brickerhoff, William; Cornish, Timothy; Ecelberger, Scott; Floyd, Melissa

2012-01-01

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Analytical performance of the various acquisition modes in Orbitrap MS and MS/MS.

PubMed

Kaufmann, Anton

2018-04-30

Quadrupole Orbitrap instruments (Q Orbitrap) permit high-resolution mass spectrometry (HRMS)-based full scan acquisitions and have a number of acquisition modes where the quadrupole isolates a particular mass range prior to a possible fragmentation and HRMS-based acquisition. Selecting the proper acquisition mode(s) is essential if trace analytes are to be quantified in complex matrix extracts. Depending on the particular requirements, such as sensitivity, selectivity of detection, linear dynamic range, and speed of analysis, different acquisition modes may have to be chosen. This is particularly important in the field of multi-residue analysis (e.g., pesticides or veterinary drugs in food samples) where a large number of analytes within a complex matrix have to be detected and reliably quantified. Meeting the specific detection and quantification performance criteria for every targeted compound may be challenging. It is the aim of this paper to describe the strengths and the limitations of the currently available Q Orbitrap acquisition modes. In addition, the incorporation of targeted acquisitions between full scan experiments is discussed. This approach is intended to integrate compounds that require an additional degree of sensitivity or selectivity into multi-residue methods. This article is protected by copyright. All rights reserved.

Double-observer approach to estimating egg mass abundance of vernal pool breeding amphibians

USGS Publications Warehouse

Grant, E.H.C.; Jung, R.E.; Nichols, J.D.; Hines, J.E.

2005-01-01

Interest in seasonally flooded pools, and the status of associated amphibian populations, has initiated programs in the northeastern United States to document and monitor these habitats. Counting egg masses is an effective way to determine the population size of pool-breeding amphibians, such as wood frogs (Rana sylvatica) and spotted salamanders (Ambystoma maculatum). However, bias is associated with counts if egg masses are missed. Counts unadjusted for the proportion missed (i.e., without adjustment for detection probability) could lead to false assessments of population trends. We used a dependent double-observer method in 2002-2003 to estimate numbers of wood frog and spotted salamander egg masses at seasonal forest pools in 13 National Wildlife Refuges, 1 National Park, 1 National Seashore, and 1 State Park in the northeastern United States. We calculated detection probabilities for egg masses and examined whether detection probabilities varied by species, observers, pools, and in relation to pool characteristics (pool area, pool maximum depth, within-pool vegetation). For the 2 years, model selection indicated that no consistent set of variables explained the variation in data sets from individual Refuges and Parks. Because our results indicated that egg mass detection probabilities vary spatially and temporally, we conclude that it is essential to use estimation procedures, such as double-observer methods with egg mass surveys, to determine population sizes and trends of these species.

Application of capillary gas chromatography-reaction interface/mass spectrometry to the selective detection of sup 13 C-, sup 15 N-, sup 2 H-, and sup 14 C-labeled drugs and their metabolites

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

Chace, D.H.

1989-01-01

A novel reaction interface/mass spectrometer (RIMS) technique has been applied to the selective detection of {sup 13}C-, {sup 15}N-, {sup 2}H-, and {sup 14}C-labeled phenytoin and its metabolites in urine following separation by capillary gas chromatography. The microwave-powered reaction interface converts materials from their original forms into small molecules whose mass spectra serve to identify and quantify the nuclides. The presence of each element is followed by monitoring the isotopic variants of CO{sub 2}, NO, H{sub 2}, or CH{sub 4} that are produced by the reaction interface. Chromatograms showing only enriched {sup 13}C and {sup 15}N were produced using themore » net {sup 13}CO{sub 2} or {sup 15}NO signal derived by subtracting the abundance of naturally occurring isotopes from the observed M + 1 signal. When hydrogen was used as a reactant gas, a selective chromatogram of {sup 2}H (D) was obtained by measuring HD at m/Z 3.0219, and a chromatogram showing {sup 14}C was obtained by measuring {sup 14}CH{sub 4} at m/Z 18.034 with a high resolution. For a stable isotope detection, metabolites representing less than 1.5% of the total labeled compounds could be detected in the chromatogram. Detection limits of 170 pCi/mL (34 pCi on column that is equivalent to 187 pg) of a {sup 14}C- labeled metabolite was detected. To identify many of these labeled peaks (metabolites), the chromatographic analysis was repeated with the reaction interface turned off and mass spectra obtained at the retention times found in the RIMS experiment. In addition to the ability of GC-RIMS to detect the presence of {sup 13}C-, {sup 15}N-, and {sup 2}H- (D), it can also quantify the level of enrichment. Enrichment of {sup 13}C and {sup 15}N is quantified by measuring the ratio of excess {sup 13}CO{sub 2} to total {sup 12}CO{sub 2} or excess {sup 15}NO to total {sup 14}NO.« less

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

DOE PAGES

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; ...

2016-04-05

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

Resonant micro and nanoelectromechanical systems: Actuation and biological sensing studies

NASA Astrophysics Data System (ADS)

Ilic, Bojan

This thesis explores various actuation mechanisms of resonant nanoelectro-mechanical systems (NEMS) with emphasis directed towards detection of biomolecules. Arrays of bulk and surface micromachined devices, made using conventional thin film fabrication methods, are used to explore the mass loading effects of selective molecular immobilization on the surface of the NEMS resonators. Experimentally measured shift in the first eigenfrequency is correlated to the amount of mass loading from the binding events and verified using theoretical constructs. Under ambient conditions where considerable damping occurs, immunospecific detection of single Escherichia coli O157:H7 cells is demonstrated by measuring the out of plane vibrational resonant mode using an optical deflection system with thermal noise as an excitation mechanism. Further sensitivity enhancement utilizing vacuum encapsulation in conjunction with piezoelectric actuation and tailoring of the cantilever dimensions is demonstrated by measuring mass loading of a nonpathogenic insect baculovirus, single Aminopropyltriethoxysilane (APTS), Hexamethyldisilazane (HMDS) and Octade-cyltrichlorosilane (OTS) monolayers. To highlight the lower detectable mass limit, surface machined NEMS oscillators with integrated circular Au contacts and sub-attogram mass detection sensitivity are used for selective immobilization of dinitrophenyl poly(ethylene glycol) undecanthiol based molecules. Experimental and theoretical elucidation of optical actuation of NEMS cantilevers at large distances from the clamped end is presented. These observations are considered within the theoretical framework of heat transfer and used to measure binding events of single double-stranded deoxyribonucleic acid (dsDNA) molecules to localized gold nanodots near the free end of a NEMS oscillator. Because this method allows direct coupling of energy into the device layer, several modes of in-plane vibrations are observed and employed in shaking off spherical latex particles. Finally, this thesis describes studies of dynamic detection of vibrational characteristics of suspended NEMS oscillators through direct coupling with a micromechanical probe. Changes in the dynamic amplitude and phase of the probe allow the measurement of the mechanical quality factor. Measured spectral response of the NEMS is in good agreement with optical characterization and modelling results.

Fast detection of narcotics by single photon ionization mass spectrometry and laser ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Laudien, Robert; Schultze, Rainer; Wieser, Jochen

2010-10-01

In this contribution two analytical devices for the fast detection of security-relevant substances like narcotics and explosives are presented. One system is based on an ion trap mass spectrometer (ITMS) with single photon ionization (SPI). This soft ionization technique, unlike electron impact ionization (EI), reduces unwanted fragment ions in the mass spectra allowing the clear determination of characteristic (usually molecular) ions. Their enrichment in the ion trap and identification by tandem MS investigations (MS/MS) enables the detection of the target substances in complex matrices at low concentrations without time-consuming sample preparation. For SPI an electron beam pumped excimer light source of own fabrication (E-Lux) is used. The SPI-ITMS system was characterized by the analytical study of different drugs like cannabis, heroin, cocaine, amphetamines, and some precursors. Additionally, it was successfully tested on-site in a closed illegal drug laboratory, where low quantities of MDMA could be directly detected in samples from floors, walls and lab equipments. The second analytical system is based on an ion mobility (IM) spectrometer with resonant multiphoton ionization (REMPI). With the frequency quadrupled Nd:YAG laser (266 nm), used for ionization, a selective and sensitive detection of aromatic compounds is possible. By application of suited aromatic dopants, in addition, also non-aromatic polar compounds are accessible by ion molecule reactions like proton transfer or complex formation. Selected drug precursors could be successfully detected with this device as well, qualifying it to a lower-priced alternative or useful supplement of the SPI-ITMS system for security analysis.

Selective detection of carbon-13, nitrogen-15, and deuterium labeled metabolites by capillary gas chromatography-chemical reaction interface/mass spectrometry

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

Chace, D.H.; Abramson, F.P.

1989-12-15

We have applied a new chemical reaction interface/mass spectrometer technique (CRIMS) to the selective detection of 13C-, 15N-, and 2H-labeled phenytoin and its metabolites in urine following separation by capillary gas chromatography. The microwave-powered chemical reaction interface converts materials from their original forms into small molecules whose mass spectra serve to identify and quantify the nuclides that make up each analyte. The presence of each element is followed by monitoring the isotopic variants of CO2, NO, or H2 that are produced by the chemical reaction interface. Chromatograms showing only enriched 13C and 15N were produced by subtracting the abundance ofmore » naturally occurring isotopes from the observed M + 1 signal. A selective chromatogram of 2H (D) was obtained by measuring HD at m/z 3.0219 with a resolution of 2000. Metabolites representing less than 1.5% of the total labeled compounds could be identified in the chromatogram. Detection limits from urine of 380 pg/mL of a 15N-labeled metabolite, 7 ng/mL of a 13C-labeled metabolite, and 16 ng/mL of a deuterium labeled metabolite were determined at a signal to noise ratio of 2. Depending on the isotope examined, a linear dynamic range of 250-1000 was observed using CRIMS. To identify many of these labeled peaks (metabolites), the chromatographic analysis was repeated with the chemical reaction interface turned off and mass spectra obtained at the retention times found in the CRIMS experiment. CRIMS is a new analytical method that appears to be particularly useful for metabolism studies.« less

A NEW APPROACH TO IDENTIFYING THE MOST POWERFUL GRAVITATIONAL LENSING TELESCOPES

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

Wong, Kenneth C.; Zabludoff, Ann I.; Ammons, S. Mark

2013-05-20

The best gravitational lenses for detecting distant galaxies are those with the largest mass concentrations and the most advantageous configurations of that mass along the line of sight. Our new method for finding such gravitational telescopes uses optical data to identify projected concentrations of luminous red galaxies (LRGs). LRGs are biased tracers of the underlying mass distribution, so lines of sight with the highest total luminosity in LRGs are likely to contain the largest total mass. We apply this selection technique to the Sloan Digital Sky Survey and identify the 200 fields with the highest total LRG luminosities projected withinmore » a 3.'5 radius over the redshift range 0.1 {<=} z {<=} 0.7. The redshift and angular distributions of LRGs in these fields trace the concentrations of non-LRG galaxies. These fields are diverse; 22.5% contain one known galaxy cluster and 56.0% contain multiple known clusters previously identified in the literature. Thus, our results confirm that these LRGs trace massive structures and that our selection technique identifies fields with large total masses. These fields contain two to three times higher total LRG luminosities than most known strong-lensing clusters and will be among the best gravitational lensing fields for the purpose of detecting the highest redshift galaxies.« less

ON THE STAR FORMATION PROPERTIES OF VOID GALAXIES

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

Moorman, Crystal M.; Moreno, Jackeline; White, Amanda

2016-11-10

We measure the star formation properties of two large samples of galaxies from the SDSS in large-scale cosmic voids on timescales of 10 and 100 Myr, using H α emission line strengths and GALEX FUV fluxes, respectively. The first sample consists of 109,818 optically selected galaxies. We find that void galaxies in this sample have higher specific star formation rates (SSFRs; star formation rates per unit stellar mass) than similar stellar mass galaxies in denser regions. The second sample is a subset of the optically selected sample containing 8070 galaxies with reliable H i detections from ALFALFA. For the fullmore » H i detected sample, SSFRs do not vary systematically with large-scale environment. However, investigating only the H i detected dwarf galaxies reveals a trend toward higher SSFRs in voids. Furthermore, we estimate the star formation rate per unit H i mass (known as the star formation efficiency; SFE) of a galaxy, as a function of environment. For the overall H i detected population, we notice no environmental dependence. Limiting the sample to dwarf galaxies still does not reveal a statistically significant difference between SFEs in voids versus walls. These results suggest that void environments, on average, provide a nurturing environment for dwarf galaxy evolution allowing for higher specific star formation rates while forming stars with similar efficiencies to those in walls.« less

Piezoelectric cantilever sensors

NASA Technical Reports Server (NTRS)

Shih, Wan Y. (Inventor); Shih, Wei-Heng (Inventor); Shen, Zuyan (Inventor)

2008-01-01

A piezoelectric cantilever with a non-piezoelectric, or piezoelectric tip useful as mass and viscosity sensors. The change in the cantilever mass can be accurately quantified by monitoring a resonance frequency shift of the cantilever. For bio-detection, antibodies or other specific receptors of target antigens may be immobilized on the cantilever surface, preferably on the non-piezoelectric tip. For chemical detection, high surface-area selective absorbent materials are coated on the cantilever tip. Binding of the target antigens or analytes to the cantilever surface increases the cantilever mass. Detection of target antigens or analytes is achieved by monitoring the cantilever's resonance frequency and determining the resonance frequency shift that is due to the mass of the adsorbed target antigens on the cantilever surface. The use of a piezoelectric unimorph cantilever allows both electrical actuation and electrical sensing. Incorporating a non-piezoelectric tip (14) enhances the sensitivity of the sensor. In addition, the piezoelectric cantilever can withstand damping in highly viscous liquids and can be used as a viscosity sensor in wide viscosity range.

Method for quantitative determination and separation of trace amounts of chemical elements in the presence of large quantities of other elements having the same atomic mass

DOEpatents

Miller, C.M.; Nogar, N.S.

1982-09-02

Photoionization via autoionizing atomic levels combined with conventional mass spectroscopy provides a technique for quantitative analysis of trace quantities of chemical elements in the presence of much larger amounts of other elements with substantially the same atomic mass. Ytterbium samples smaller than 10 ng have been detected using an ArF* excimer laser which provides the atomic ions for a time-of-flight mass spectrometer. Elemental selectivity of greater than 5:1 with respect to lutetium impurity has been obtained. Autoionization via a single photon process permits greater photon utilization efficiency because of its greater absorption cross section than bound-free transitions, while maintaining sufficient spectroscopic structure to allow significant photoionization selectivity between different atomic species. Separation of atomic species from others of substantially the same atomic mass is also described.

A tandem mass spectrometer for crossed-beam irradiation of mass-selected molecular systems by keV atomic ions

NASA Astrophysics Data System (ADS)

Schwob, Lucas; Lalande, Mathieu; Chesnel, Jean-Yves; Domaracka, Alicja; Huber, Bernd A.; Maclot, Sylvain; Poully, Jean-Christophe; Rangama, Jimmy; Rousseau, Patrick; Vizcaino, Violaine; Adoui, Lamri; Méry, Alain

2018-04-01

In the present paper, we describe a new home-built crossed-beam apparatus devoted to ion-induced ionization and fragmentation of isolated biologically relevant molecular systems. The biomolecular ions are produced by an electrospray ionization source, mass-over-charge selected, accumulated in a 3D ion trap, and then guided to the extraction region of an orthogonal time-of-flight mass spectrometer. Here, the target molecular ions interact with a keV atomic ion beam produced by an electron cyclotron resonance ion source. Cationic products from the collision are detected on a position sensitive detector and analyzed by time-of-flight mass spectrometry. A detailed description of the operation of the setup is given, and early results from irradiation of a protonated pentapeptide (leucine-enkephalin) by a 7 keV He+ ion beam are presented as a proof-of-principle.

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

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

Determination of Low Concentrations of Acetochlor in Water by Automated Solid-Phase Extraction and Gas Chromatography with Mass-Selective Detection

USGS Publications Warehouse

Lindley, C.E.; Stewart, J.T.; Sandstrom, M.W.

1996-01-01

A sensitive and reliable gas chromatographic/mass spectrometric (GC/MS) method for determining acetochlor in environmental water samples was developed. The method involves automated extraction of the herbicide from a filtered 1 L water sample through a C18 solid-phase extraction column, elution from the column with hexane-isopropyl alcohol (3 + 1), and concentration of the extract with nitrogen gas. The herbicide is quantitated by capillary/column GC/MS with selected-ion monitoring of 3 characteristic ions. The single-operator method detection limit for reagent water samples is 0.0015 ??g/L. Mean recoveries ranged from about 92 to 115% for 3 water matrixes fortified at 0.05 and 0.5 ??g/L. Average single-operator precision, over the course of 1 week, was better than 5%.

Current role of liquid chromatography-mass spectrometry in clinical and forensic toxicology.

PubMed

Maurer, Hans H

2007-08-01

This paper reviews multi-analyte single-stage and tandem liquid chromatography-mass spectrometry (LC-MS) procedures using different mass analyzers (quadrupole, ion trap, time-of-flight) for screening, identification, and/or quantification of drugs, poisons, and/or their metabolites in blood, plasma, serum, or urine published after 2004. Basic information about the biosample assayed, work-up, LC column, mobile phase, ionization type, mass spectral detection mode, and validation data of each procedure is summarized in tables. The following analytes are covered: drugs of abuse, analgesics, opioids, sedative-hypnotics, benzodiazepines, antidepressants including selective-serotonin reuptake inhibitors (SSRIs), herbal phenalkylamines (ephedrines), oral antidiabetics, antiarrhythmics and other cardiovascular drugs, antiretroviral drugs, toxic alkaloids, quaternary ammonium drugs and herbicides, and dialkylphosphate pesticides. The pros and cons of the reviewed procedures are critically discussed, particularly, the need for studies on matrix effects, selectivity, analyte stability, and the use of stable-isotope labeled internal standards instead of unlabeled therapeutic drugs. In conclusion, LC-MS will probably become a gold standard for detection of very low concentrations particularly in alternative matrices and for quantification in clinical and forensic toxicology. However, some drawbacks still need to be addressed and finally overcome.

High-resolution mass spectrometry method for the detection, characterization and quantitation of pharmaceuticals in water.

PubMed

Pinhancos, Rebeca; Maass, Sara; Ramanathan, Dil M

2011-11-01

The presence of pharmaceuticals in drinking water is an emerging environmental concern. In most environmental testing laboratories, LC-MS/MS assays based on selected reaction monitoring are used as part of a battery of tests used to assure water quality. Although LC-MS/MS continues to be the best tool for detecting pharmaceuticals in water, the combined use of hybrid high-resolution mass spectrometry (HRMS) and ultrahigh pressure liquid chromatography (UHPLC) is starting to become a practical tool to study emerging environmental contaminants. The hybrid LTQ-orbitrap mass spectrometer is suitable for integrated quantitative and qualitative bioanalysis because of the following reasons: (1) the ability to collect full-scan HRMS spectra with scan speeds suitable for UHPLC separations, (2) routine measurement of mass with less than 5 ppm mass accuracy, (3) high mass resolving power, and (4) ability to perform on-the-fly polarity switching in the linear ion trap (LTQ). In the present work, we provide data demonstrating the application of UHPLC-LTQ-orbitrap for the detection, characterization and quantification of pharmaceuticals and their metabolites in drinking water. Copyright © 2011 John Wiley & Sons, Ltd.

Liquid extraction surface analysis (LESA) of food surfaces employing chip-based nano-electrospray mass spectrometry.

PubMed

Eikel, Daniel; Henion, Jack

2011-08-30

An automated surface-sampling technique called liquid extraction surface analysis (LESA), coupled with infusion nano-electrospray high-resolution mass spectrometry and tandem mass spectrometry (MS/MS), is described and applied to the qualitative determination of surface chemical residues resulting from the artificial spraying of selected fresh fruits and vegetables with representative pesticides. Each of the targeted pesticides was readily detected with both high-resolution and full-scan collision-induced dissociation (CID) mass spectra. In the case of simazine and sevin, a mass resolution of 100,000 was insufficient to distinguish the isobaric protonated molecules for these compounds. When the surface of a spinach leaf was analyzed by LESA, trace levels of diazinon were readily detected on the spinach purchased directly from a supermarket before they were sprayed with the five-pesticide mixture. A 30 s rinse under hot running tap water appeared to quantitatively remove all remaining residues of this pesticide. Diazinon was readily detected by LESA analysis on the skin of the artificially sprayed spinach. Finally, incurred pyrimethanil at a level of 169 ppb in a batch slurry of homogenized apples was analyzed by LESA and this pesticide was readily detected by both high-resolution mass spectrometry and full-scan CID mass spectrometry, thus showing that pesticides may also be detected in whole fruit homogenized samples. This report shows that representative pesticides on fruit and vegetable surfaces present at levels 20-fold below generally allowed EPA tolerance levels are readily detected and confirmed by the title technologies making LESA-MS as interesting screening method for food safety purposes. Copyright © 2011 John Wiley & Sons, Ltd.

Ultrananocrystalline Diamond Membranes for Detection of High-Mass Proteins

NASA Astrophysics Data System (ADS)

Kim, H.; Park, J.; Aksamija, Z.; Arbulu, M.; Blick, R. H.

2016-12-01

Mechanical resonators realized on the nanoscale by now offer applications in mass sensing of biomolecules with extraordinary sensitivity. The general idea is that perfect mechanical mass sensors should be of extremely small size to achieve zepto- or yoctogram sensitivity in weighing single molecules similar to a classical scale. However, the small effective size and long response time for weighing biomolecules with a cantilever restricts their usefulness as a high-throughput method. Commercial mass spectrometry (MS), on the other hand, such as electrospray ionization and matrix-assisted laser desorption and ionization (MALDI) time of flight (TOF) and their charge-amplifying detectors are the gold standards to which nanomechanical resonators have to live up to. These two methods rely on the ionization and acceleration of biomolecules and the following ion detection after a mass selection step, such as TOF. The principle we describe here for ion detection is based on the conversion of kinetic energy of the biomolecules into thermal excitation of chemical vapor deposition diamond nanomembranes via phonons followed by phonon-mediated detection via field emission of thermally emitted electrons. We fabricate ultrathin diamond membranes with large lateral dimensions for MALDI TOF MS of high-mass proteins. These diamond membranes are realized by straightforward etching methods based on semiconductor processing. With a minimal thickness of 100 nm and cross sections of up to 400 ×400 μ m2 , the membranes offer extreme aspect ratios. Ion detection is demonstrated in MALDI TOF analysis over a broad range from insulin to albumin. The resulting data in detection show much enhanced resolution as compared to existing detectors, which can offer better sensitivity and overall performance in resolving protein masses.

Efficient Enrichment and Analysis of Vicinal-Diol-Containing Flavonoid Molecules Using Boronic-Acid-Functionalized Particles and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.

PubMed

Kim, Eunjin; Kang, Hyunook; Choi, Insung; Song, Jihyeon; Mok, Hyejung; Jung, Woong; Yeo, Woon-Seok

2018-05-09

Detection and quantitation of flavonoids are relatively difficult compared to those of other small-molecule analytes because flavonoids undergo rapid metabolic processes, resulting in their elimination from the body. Here, we report an efficient enrichment method for facilitating the analysis of vicinal-diol-containing flavonoid molecules using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In our strategy, boronic-acid-functionalized polyacrylamide particles were used, where boronic acids bound to vicinal diols to form boronate monoesters at basic pH. This complex remained intact during the enrichment processes, and the vicinal-diol-containing flavonoids were easily separated by centrifugation and subsequent acidic treatments. The selectivity and limit of detection of our strategy were confirmed by mass spectrometry analysis, and the validity was assessed by performing the detection and quantitation of quercetin in mouse organs.

Rapid detection of undesired cosmetic ingredients by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

PubMed

Ouyang, Jie; An, Dongli; Chen, Tengteng; Lin, Zhiwei

2017-10-01

In recent years, cosmetic industry profits soared due to the widespread use of cosmetics, which resulted in illicit manufacturers and products of poor quality. Therefore, the rapid and accurate detection of the composition of cosmetics has become crucial. At present, numerous methods, such as gas chromatography and liquid chromatography-mass spectrometry, were available for the analysis of cosmetic ingredients. However, these methods present several limitations, such as failure to perform comprehensive and rapid analysis of the samples. Compared with other techniques, matrix-assisted laser desorption ionization time-of-flight mass spectrometry offered the advantages of wide detection range, fast speed and high accuracy. In this article, we briefly summarized how to select a suitable matrix and adjust the appropriate laser energy. We also discussed the rapid identification of undesired ingredients, focusing on antibiotics and hormones in cosmetics.

A Chandra Survey of low-mass clusters at 0.8 < z < 0.9 selected in the 100 deg^2 SPT-Pol Deep Field

NASA Astrophysics Data System (ADS)

Kraft, Ralph

2016-09-01

We propose to observe a complete sample of 4 galaxy clusters at 1e14 < M500 < 3e14 and 0.8 < z < 0.9. These systems were selected from the 100 deg^2 deep field of the SPT-Pol SZ survey. This survey are has significant complementary data, including uniform depth ATCA, Herschel, Spitzer, and DES imaging, enabling a wide variety of astrophysical and cosmological studies. This sample complements the successful SPT-XVP survey, which has a broad redshift range and a narrow mass range, by including clusters over a narrow redshift range and broad mass range. These systems are such low mass and high redshift that they will not be detected in the eRosita all-sky survey.

A Chandra Survey of low-mass clusters at 0.7 < z < 0.8 selected in the 100 deg^2 SPT-Pol Deep Field

NASA Astrophysics Data System (ADS)

Kraft, Ralph

2016-09-01

We propose to observe a complete sample of 4 galaxy clusters at 1e14 < M500 < 3e14 and 0.7 < z < 0.8. These systems were selected from the 100 deg^2 deep field of the SPT-Pol SZ survey. This survey are has significant complementary data, including uniform depth ATCA, Herschel, Spitzer, and DES imaging, enabling a wide variety of astrophysical and cosmological studies. This sample complements the successful SPT-XVP survey, which has a broad redshift range and a narrow mass range, by including clusters over a narrow redshift range and broad mass range. These systems are such low mass and high redshift that they will not be detected in the eRosita all-sky survey.

Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

2016-07-01

An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m3 to 6.3 μg/m3. Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection.

Sub-millimetre properties of massive star-forming galaxies at z ~ 2 in SHADES/SXDF

NASA Astrophysics Data System (ADS)

Takagi, T.; Mortier, A. M. J.; Shimasaku, K.; Coppin, K.; Pope, A.; Ivison, R. J.; Hanami, H.; Serjeant, S.; Dunlop, J. S.

2007-05-01

We study the submillimetre (submm) properties of the following NIR-selected massive galaxies at high redshifts: BzK-selected star-forming galaxies (BzKs), distant red galaxies (DRGs) and extremely red objects (EROs). We used the SCUBA HAlf Degree Extragalactic Survey (SHADES), the largest uniform submm survey to date. We detected 6 NIR-selected galaxies in our SCUBA map. Four submm-detected galaxies out of six are found to be detected both at 24 micron and in radio (1.4 GHz), and therefore confirmed as genuine submm-bright galaxies. We identify two submm-bright NIR-selected galaxies are the BzK-DRG-ERO overlapping population. Although this overlapping population is rare, about 12% of this population could be submm galaxies. With a stacking analysis, we detected the 850-micron flux of submm-faint BzKs and EROs in our SCUBA maps. While the contribution from BzKs at z˜2 to submm background is about 10 - 15 % and similar to that from EROs typically at z˜1, BzKs have a higher fraction (˜30%) of flux in resolved sources than EROs do. Therefore, submm flux of BzKs seems to be biased high. From the SED fitting using an evolutionary model of starbursts with radiative transfer, submm-bright NIR-selected galaxies, mostly BzKs, are found to have the stellar mass of >5x1010M[sun] with the bolometric luminosity of >3x1012L[sun]. On the other hand, an average SED of submm-faint BzKs indicates the typical stellar mass of <6x1010M[sun] and therefore less massive.

Galaxy And Mass Assembly (GAMA): Improved emission lines measurements in four representative samples at 0.07

NASA Astrophysics Data System (ADS)

Rodrigues, M.; Foster, C.; Taylor, E. N.; Wright, A. H.; Hopkins, A. M.; Baldry, I.; Brough, S.; Bland-Hawthorn, J.; Cluver, M. E.; Lara-López, M. A.; Liske, J.; López-Sánchez, Á. R.; Pimbblet, K. A.

2016-05-01

This paper presents a new catalog of emission lines based on the GAMA II data for galaxies between 0.07 9.4 at z ~ 0.1 and log M∗> 10.6 at z ~ 0.30. We have developed a dedicated code called MARVIN that automates the main steps of the data analysis, but imposes visual individual quality control of each measurement. We use this catalog to investigate how the sample selection influences the shape of the stellar mass - metallicity relation. We find that commonly used selection criteria on line detections and by AGN rejection could affect the shape and dispersion of the high-mass end of the M - Z relation. For log M∗> 10.6, common selection criteria reject about 65% of the emission-line galaxies. We also find that the relation does not evolve significantly from z = 0.07 to z = 0.34 in the range of stellar mass for which the samples are representative (log M∗> 10.6). For lower stellar masses (log M∗< 10.2) we are able to show that the observed 0.15 dex metallicity decrease in the same redshift range is a consequence of a color bias arising from selecting targets in the r-band. We highlight that this color selection bias affects all samples selected in r-band (e.g., GAMA and SDSS), even those drawn from volume-limited samples. Previously reported evolution of the M - Z relation at various redshifts may need to be revised to evaluate the effect of this selection bias.

A Measurement of the Millimeter Emission and the Sunyaev-Zel'dovich Effect Associated with Low-Frequency Radio Sources

NASA Technical Reports Server (NTRS)

Gralla, Megan B.; Crichton, Devin; Marriage, Tobias; Mo, Wenli; Aguirre, Paula; Addison, Graeme E.; Asboth, V.; Battaglia, Nick; Bock, James; Bond, J. Richard;

Use of a least absolute shrinkage and selection operator (LASSO) model to selected ion flow tube mass spectrometry (SIFT-MS) analysis of exhaled breath to predict the efficacy of dialysis: a pilot study.

PubMed

Wang, Maggie Haitian; Chong, Ka Chun; Storer, Malina; Pickering, John W; Endre, Zoltan H; Lau, Steven Yf; Kwok, Chloe; Lai, Maria; Chung, Hau Yin; Ying Zee, Benny Chung

2016-09-28

Selected ion flow tube-mass spectrometry (SIFT-MS) provides rapid, non-invasive measurements of a full-mass scan of volatile compounds in exhaled breath. Although various studies have suggested that breath metabolites may be indicators of human disease status, many of these studies have included few breath samples and large numbers of compounds, limiting their power to detect significant metabolites. This study employed a least absolute shrinkage and selective operator (LASSO) approach to SIFT-MS data of breath samples to preliminarily evaluate the ability of exhaled breath findings to monitor the efficacy of dialysis in hemodialysis patients. A process of model building and validation showed that blood creatinine and urea concentrations could be accurately predicted by LASSO-selected masses. Using various precursors, the LASSO models were able to predict creatinine and urea concentrations with high adjusted R-square (>80%) values. The correlation between actual concentrations and concentrations predicted by the LASSO model (using precursor H 3 O + ) was high (Pearson correlation coefficient  =  0.96). Moreover, use of full mass scan data provided a better prediction than compounds from selected ion mode. These findings warrant further investigations in larger patient cohorts. By employing a more powerful statistical approach to predict disease outcomes, breath analysis using SIFT-MS technology could be applicable in future to daily medical diagnoses.

Optically detected, single nanoparticle mass spectrometer with pre-filtered electrospray nanoparticle source

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

Howder, Collin R.; Bell, David M.; Anderson, Scott L.

2014-01-15

An instrument designed for non-destructive mass analysis of single trapped nanoparticles is described. The heart of the instrument is a 3D quadrupole (Paul) trap constructed to give optical access to the trap center along ten directions, allowing passage of lasers for particle heating and detection, particle injection, collection of scattered or fluorescent photons for particle detection and mass analysis, and collection of particles on TEM grids for analysis, as needed. Nanoparticles are injected using an electrospray ionization (ESI) source, and conditions are described for spraying and trapping polymer particles, bare metal particles, and ligand stabilized particles with masses ranging frommore » 200 kDa to >3 GDa. Conditions appropriate to ESI and injection of different types of particles are described. The instrument is equipped with two ion guides separating the ESI source and nanoparticle trap. The first ion guide is mostly to allow desolvation and differential pumping before the particles enter the trap section of the instrument. The second is a linear quadrupole guide, which can be operated in mass selective or mass band-pass modes to limit transmission to species with mass-to-charge ratios in the range of interest. With a little experience, the design allows injection of single particles into the trap upon demand.« less

Detection and identification of drugs and toxicants in human body fluids by liquid chromatography-tandem mass spectrometry under data-dependent acquisition control and automated database search.

PubMed

Oberacher, Herbert; Schubert, Birthe; Libiseller, Kathrin; Schweissgut, Anna

2013-04-03

Systematic toxicological analysis (STA) is aimed at detecting and identifying all substances of toxicological relevance (i.e. drugs, drugs of abuse, poisons and/or their metabolites) in biological material. Particularly, gas chromatography-mass spectrometry (GC/MS) represents a competent and commonly applied screening and confirmation tool. Herein, we present an untargeted liquid chromatography-tandem mass spectrometry (LC/MS/MS) assay aimed to complement existing GC/MS screening for the detection and identification of drugs in blood, plasma and urine samples. Solid-phase extraction was accomplished on mixed-mode cartridges. LC was based on gradient elution in a miniaturized C18 column. High resolution electrospray ionization-MS/MS in positive ion mode with data-dependent acquisition control was used to generate tandem mass spectral information that enabled compound identification via automated library search in the "Wiley Registry of Tandem Mass Spectral Data, MSforID". Fitness of the developed LC/MS/MS method for application in STA in terms of selectivity, detection capability and reliability of identification (sensitivity/specificity) was demonstrated with blank samples, certified reference materials, proficiency test samples, and authentic casework samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Air Monitoring for Hazardous Gas Detection

NASA Technical Reports Server (NTRS)

Arkin, C. Richard; Griffin, Timothy P.; Adams, Frederick W.; Naylor, Guy; Haskell, William; Floyd, David; Curley, Charles; Follistein, Duke W.

2004-01-01

The Hazardous Gas Detection Lab (HGDL) at Kennedy Space Center is involved in the design and development of instrumentation that can detect and quantify various hazardous gases. Traditionally these systems are designed for leak detection of the cryogenic gases used for the propulsion of the Shuttle and other vehicles. Mass spectrometers are the basis of these systems, which provide excellent quantitation, sensitivity, selectivity, response times and detection limits. A Table lists common gases monitored for aerospace applications. The first five gases, hydrogen, helium, nitrogen, oxygen, and argon are historically the focus of the HGDL.

An effective selection method for low-mass active black holes and first spectroscopic identification

NASA Astrophysics Data System (ADS)

Morokuma, Tomoki; Tominaga, Nozomu; Tanaka, Masaomi; Yasuda, Naoki; Furusawa, Hisanori; Taniguchi, Yuki; Kato, Takahiro; Jiang, Ji-an; Nagao, Tohru; Kuncarayakti, Hanindyo; Morokuma-Matsui, Kana; Ikeda, Hiroyuki; Blinnikov, Sergei; Nomoto, Ken'ichi; Kokubo, Mitsuru; Doi, Mamoru

2016-06-01

We present a new method for effectively selecting objects which may be low-mass active black holes (BHs) at galaxy centers using high-cadence optical imaging data, and our first spectroscopic identification of an active 2.7 × 106 M⊙ BH at z = 0.164. This active BH was originally selected due to its rapid optical variability, from a few hours to a day, based on Subaru Hyper Suprime-Cam g-band imaging data taken with a 1 hr cadence. Broad and narrow Hα lines and many other emission ones are detected in our optical spectra taken with Subaru FOCAS, and the BH mass is measured via the broad Hα emission line width (1880 km s-1) and luminosity (4.2 × 1040 erg s-1) after careful correction to the atmospheric absorption around 7580-7720 Å. We measure the Eddington ratio and find it to be as low as 0.05, considerably smaller than those in a previous SDSS sample with similar BH mass and redshift, which indicates one of the special potentials of our Subaru survey. The g - r color and morphology of the extended component indicate that the host galaxy is a star-forming galaxy. We also show the effectiveness of our variability selection for low-mass active BHs.

Quantification of proteins in urine samples using targeted mass spectrometry methods.

PubMed

Khristenko, Nina; Domon, Bruno

2015-01-01

Numerous clinical proteomics studies are focused on the development of biomarkers to improve either diagnostics for early disease detection or the monitoring of the response to the treatment. Although, a wealth of biomarker candidates are available, their evaluation and validation in a true clinical setup remains challenging. In biomarkers evaluation studies, a panel of proteins of interest are systematically analyzed in a large cohort of samples. However, in spite of the latest progresses in mass spectrometry, the consistent detection of pertinent proteins in high complex biological samples is still a challenging task. Thus, targeted LC-MS/MS methods are better suited for the systematic analysis of biomarkers rather than shotgun approaches. This chapter describes the workflow used to perform targeted quantitative analyses of proteins in urinary samples. The peptides, as surrogates of the protein of interest, are commonly measured using a triple quadrupole mass spectrometers operated in selected reaction monitoring (SRM) mode. More recently, the advances in targeted LC-MS/MS analysis based on parallel reaction monitoring (PRM) performed on a quadrupole-orbitrap instrument have allowed to increase the specificity and selectivity of the measurements.

Analysis of multiple quaternary ammonium compounds in the brain using tandem capillary column separation and high resolution mass spectrometric detection.

PubMed

Falasca, Sara; Petruzziello, Filomena; Kretz, Robert; Rainer, Gregor; Zhang, Xiaozhe

2012-06-08

Endogenous quaternary ammonium compounds are involved in various physiological processes in the central nervous system. In the present study, eleven quaternary ammonium compounds, including acetylcholine, choline, carnitine, acetylcarnitine and seven other acylcarnitines of low polarity, were analyzed from brain extracts using a two dimension capillary liquid chromatography-Fourier transform mass spectrometry method. To deal with their large difference in hydrophobicities, tandem coupling between reversed phase and hydrophilic interaction chromatography columns was used to separate all the targeted quaternary ammonium compounds. Using high accuracy mass spectrometry in selected ion monitoring mode, all the compounds could be detected from each brain sample with high selectivity. The developed method was applied for the relative quantification of these quaternary ammonium compounds in three different brain regions of tree shrews: prefrontal cortex, striatum, and hippocampus. The comparative analysis showed that quaternary ammonium compounds were differentially distributed across the three brain areas. The analytical method proved to be highly sensitive and reliable for simultaneous determination of all the targeted analytes from brain samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Integrated Droplet-Based Microextraction with ESI-MS for Removal of Matrix Interference in Single-Cell Analysis.

PubMed

Zhang, Xiao-Chao; Wei, Zhen-Wei; Gong, Xiao-Yun; Si, Xing-Yu; Zhao, Yao-Yao; Yang, Cheng-Dui; Zhang, Si-Chun; Zhang, Xin-Rong

2016-04-29

Integrating droplet-based microfluidics with mass spectrometry is essential to high-throughput and multiple analysis of single cells. Nevertheless, matrix effects such as the interference of culture medium and intracellular components influence the sensitivity and the accuracy of results in single-cell analysis. To resolve this problem, we developed a method that integrated droplet-based microextraction with single-cell mass spectrometry. Specific extraction solvent was used to selectively obtain intracellular components of interest and remove interference of other components. Using this method, UDP-Glc-NAc, GSH, GSSG, AMP, ADP and ATP were successfully detected in single MCF-7 cells. We also applied the method to study the change of unicellular metabolites in the biological process of dysfunctional oxidative phosphorylation. The method could not only realize matrix-free, selective and sensitive detection of metabolites in single cells, but also have the capability for reliable and high-throughput single-cell analysis.

Isolation and recovery of selected polybrominated diphenyl ethers from human serum and sheep serum: coupling reversed-phase solid-phase disk extraction and liquid-liquid extraction techniques with a capillary gas chromatographic electron capture negative ion mass spectrometric determinative technique.

PubMed

Loconto, Paul R; Isenga, David; O'Keefe, Michael; Knottnerus, Mark

2008-01-01

Polybrominated diphenyl ethers (PBDEs) are isolated and recovered with acceptable percent recoveries from human serum via liquid-liquid extraction and column chromatographic cleanup and fractionation with quantitation using capillary gas chromatography-mass spectrometry with electron capture negative ion and selected ion monitoring. PBDEs are found in unspiked serum. An alternative sample preparation approach is developed using sheep serum that utilizes a formic acid pre-treatment followed by reversed-phase solid-phase disk extraction and normal-phase solid-phase cleanup using acidified silica gel that yields>50% recoveries. When these percent recoveries are combined with a minimized phase ratio for human serum and very low instrument detection limits, method detection limits below 500 parts-per-trillion are realized.

The impact of selection on population genetic structure in the clam Meretrix petechialis revealed by microsatellite markers.

PubMed

Lu, Xia; Wang, Hongxia; Li, Yan; Liu, Baozhong

2016-02-01

The aim of our work is to evaluate the impact of mass selection on genetic structure in artificially closed populations of the clam Meretrix petechialis. In the present study, we performed mass selection over four generations (from 2004 to 2010) on two clam populations [shell features of purple lines (SP) and black dots (SB)] and analyzed their temporal genetic variation and structure using microsatellite makers. The two closed populations originated from the natural Shandong population (SD); thus, a natural SD population (10SD) was used to detect the current genetic structure after 6 years of natural selection. The results showed that the genetic diversity of the four generations of SB and SP was gradually reduced but remained at relatively high levels (SB, A = 18.9.4-16.8, Ho = 0.7389-0.6971, and He = 0.8897-0.8591; SP, A = 20.0-17.8, Ho = 0.7512-0.7043, and He = 0.8938-0.8625), which has not been reduced compared with that of the 10SD population (A = 17.8, Ho = 0.6803, and He = 0.8302). The Ne estimates for the two populations were almost at the same levels as the actual numbers of parental individuals. In addition, a low inbreeding coefficient was detected in the two populations (SB, 0.00201-0.00639; SP, 0.00176-0.00541). Based on the results, the present mass selection has not made a large impact on the population genetic structure of the closed populations. The present investigation provides important information for the development of management strategies for genetic breeding of the clam.

Computer-aided detection of bladder masses in CT urography (CTU)

NASA Astrophysics Data System (ADS)

Cha, Kenny H.; Hadjiiski, Lubomir M.; Chan, Heang-Ping; Caoili, Elaine M.; Cohan, Richard H.; Weizer, Alon; Samala, Ravi K.

2017-03-01

We are developing a computer-aided detection system for bladder cancer in CT urography (CTU). We have previously developed methods for detection of bladder masses within the contrast-enhanced and the non-contrastenhanced regions of the bladder individually. In this study, we investigated methods for detection of bladder masses within the entire bladder. The bladder was segmented using our method that combined deep-learning convolutional neural network with level sets. The non-contrast-enhanced region was separated from the contrast-enhanced region with a maximum-intensity-projection-based method. The non-contrast region was smoothed and gray level threshold was applied to the contrast and non-contrast regions separately to extract the bladder wall and potential masses. The bladder wall was transformed into a straightened thickness profile, which was analyzed to identify lesion candidates in a prescreening step. The candidates were mapped back to the 3D CT volume and segmented using our auto-initialized cascaded level set (AI-CALS) segmentation method. Twenty-seven morphological features were extracted for each candidate. A data set of 57 patients with 71 biopsy-proven bladder lesions was used, which was split into independent training and test sets: 42 training cases with 52 lesions, and 15 test cases with 19 lesions. Using the training set, feature selection was performed and a linear discriminant (LDA) classifier was designed to merge the selected features for classification of bladder lesions and false positives. The trained classifier was evaluated with the test set. FROC analysis showed that the system achieved a sensitivity of 86.5% at 3.3 FPs/case for the training set, and 84.2% at 3.7 FPs/case for the test set.

Detection of Radiation-Exposure Biomarkers by Differential Mobility Prefiltered Mass Spectrometry (DMS-MS)

PubMed Central

Coy, Stephen L.; Krylov, Evgeny V.; Schneider, Bradley B.; Covey, Thomas R.; Brenner, David J.; Tyburski, John B.; Patterson, Andrew D.; Krausz, Kris W.; Fornace, Albert J.; Nazarov, Erkinjon G.

2010-01-01

Technology to enable rapid screening for radiation exposure has been identified as an important need, and, as a part of a NIH / NIAD effort in this direction, metabolomic biomarkers for radiation exposure have been identified in a recent series of papers. To reduce the time necessary to detect and measure these biomarkers, differential mobility spectrometry – mass spectrometry (DMS-MS) systems have been developed and tested. Differential mobility ion filters preselect specific ions and also suppress chemical noise created in typical atmospheric-pressure ionization sources (ESI, MALDI, and others). Differential-mobility-based ion selection is based on the field dependence of ion mobility, which, in turn, depends on ion characteristics that include conformation, charge distribution, molecular polarizability, and other properties, and on the transport gas composition which can be modified to enhance resolution. DMS-MS is able to resolve small-molecule biomarkers from nearly-isobaric interferences, and suppresses chemical noise generated in the ion source and in the mass spectrometer, improving selectivity and quantitative accuracy. Our planar DMS design is rapid, operating in a few milliseconds, and analyzes ions before fragmentation. Depending on MS inlet conditions, DMS-selected ions can be dissociated in the MS inlet expansion, before mass analysis, providing a capability similar to MS/MS with simpler instrumentation. This report presents selected DMS-MS experimental results, including resolution of complex test mixtures of isobaric compounds, separation of charge states, separation of isobaric biomarkers (citrate and isocitrate), and separation of nearly-isobaric biomarker anions in direct analysis of a bio-fluid sample from the radiation-treated group of a mouse-model study. These uses of DMS combined with moderate resolution MS instrumentation indicate the feasibility of field-deployable instrumentation for biomarker evaluation. PMID:20305793

An isotope dilution ultra high performance liquid chromatography-tandem mass spectrometry method for the simultaneous determination of sugars and humectants in tobacco products.

PubMed

Wang, Liqun; Cardenas, Roberto Bravo; Watson, Clifford

2017-09-08

CDC's Division of Laboratory Sciences developed and validated a new method for the simultaneous detection and measurement of 11 sugars, alditols and humectants in tobacco products. The method uses isotope dilution ultra high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and has demonstrated high sensitivity, selectivity, throughput and accuracy, with recoveries ranging from 90% to 113%, limits of detection ranging from 0.0002 to 0.0045μg/mL and coefficients of variation (CV%) ranging from 1.4 to 14%. Calibration curves for all analytes were linear with linearity R 2 values greater than 0.995. Quantification of tobacco components is necessary to characterize tobacco product components and their potential effects on consumer appeal, smoke chemistry and toxicology, and to potentially help distinguish tobacco product categories. The researchers analyzed a variety of tobacco products (e.g., cigarettes, little cigars, cigarillos) using the new method and documented differences in the abundance of selected analytes among product categories. Specifically, differences were detected in levels of selected sugars found in little cigars and cigarettes, which could help address appeal potential and have utility when product category is unknown, unclear, or miscategorized. Copyright © 2017. Published by Elsevier B.V.

Use of a bisphenol-A imprinted polymer as a selective sorbent for the determination of phenols and phenoxyacids in honey by liquid chromatography with diode array and tandem mass spectrometric detection.

PubMed

Herrero-Hernández, E; Carabias-Martínez, R; Rodríguez-Gonzalo, E

2009-09-21

An extraction-preconcentration procedure based on the use of a molecularly imprinted polymer (MIP) as selective sorbent has been developed for the determination of several phenolic compounds (bisphenol-A, bisphenol-F and 4-nitrophenol) and phenoxyacid herbicides (2,4-D, 2,4,5-T and 2,4,5-TP) in honey samples. Liquid chromatography with diode array detection (LC-DAD) and electrospray ionisation-ion trap mass spectrometry (LC-IT-MS) were used for the separation, identification and quantification of these analytes. The molecularly imprinted polymer was obtained by precipitation polymerisation with bisphenol-A (BPA) as template and 4-vinylpyridine as the functional monomer. The behaviour of this sorbent was compared with those of other materials frequently used in SPE. The selectivity of the BPA-MIP for the target analytes was tested in samples containing other pesticides in common use. The recoveries achieved for all six compounds were in the 81-96% range. By applying the proposed procedure prior to LC-IT-MS, the limits of detection achieved in commercial honey samples were in the 0.1-3.8 ng g(-1) range, with relative standard deviations of 12-24%.

Detection of chlorinated and brominated byproducts of drinking water disinfection using electrospray ionization-high-field asymmetric waveform ion mobility spectrometry-mass spectrometry.

PubMed

Ells, B; Barnett, D A; Froese, K; Purves, R W; Hrudey, S; Guevremont, R

1999-10-15

The lower limit of detection for low molecular weight polar and ionic analytes using electrospray ionization-mass spectrometry (ESI-MS) is often severely compromised by an intense background that obscures ions of trace components in solution. Recently, a new technique, referred to as high-field asymmetric waveform ion mobility spectrometry (FAIMS), has been shown to separate gas-phase ions at atmospheric pressure and room temperature. A FAIMS instrument is an ion filter that may be tuned, by control of electrical voltages, to continuously transmit selected ions from a complex mixture. This capability offers significant advantages when FAIMS is coupled with ESI, a source that generates a wide variety of ions, including solvent clusters and salt adducts. In this report, the tandem arrangement of ESI-FAIMS-MS is used for the analysis of haloacetic acids, a class of disinfection byproducts regulated by the US EPA. FAIMS is shown to effectively discriminate against background ions resulting from the electrospray of tap water solutions containing the haloacetic acids. Consequently, mass spectra are simplified, the selectivity of the method is improved, and the limits of detection are lowered compared with conventional ESI-MS. The detection limits of ESI-FAIMS-MS for six haloacetic acids ranged between 0.5 and 4 ng/mL in 9:1 methanol/tap water (5 and 40 ng/mL in the original tap water samples) with no preconcentration, derivatization, or chromatographic separation prior to analysis.

Selective extraction of halogenated compounds from data measured by comprehensive multidimensional gas chromatography/high resolution time-of-flight mass spectrometry for non-target analysis of environmental and biological samples.

PubMed

Hashimoto, Shunji; Zushi, Yasuyuki; Fushimi, Akihiro; Takazawa, Yoshikatsu; Tanabe, Kiyoshi; Shibata, Yasuyuki

2013-03-22

We developed a method that selectively extracts a subset from comprehensive 2D gas chromatography (GC×GC) and high-resolution time-of-flight mass spectrometry (HRTOFMS) data to detect and identify trace levels of organohalogens. The data were obtained by measuring several environmental and biological samples, namely fly ash, soil, sediment, the atmosphere, and human urine. For global analysis, some samples were measured without purification. By using our novel software, the mass spectra of organochlorines or organobromines were then extracted into a data subset under high mass accuracy conditions that were approximately equivalent to a mass resolution of 6000 for some samples. Mass defect filtering as pre-screening for the data extraction was very effective in removing the mass spectra of hydrocarbons. Those results showed that data obtained with HRTOFMS are valuable for global analysis of organohalogens, and probably of other compounds if specific data extraction methods can be devised. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of vitamins D2 and D3 in selected food matrices by online high-performance liquid chromatography-gas chromatography-mass spectrometry (HPLC-GC-MS).

PubMed

Nestola, Marco; Thellmann, Andrea

2015-01-01

An online normal-phase liquid chromatography-gas chromatography-mass spectrometry (HPLC-GC-MS) method was developed for the determination of vitamins D2 and D3 in selected food matrices. Transfer of the sample from HPLC to GC was realized by large volume on-column injection; detection was performed with a time-of-flight mass spectrometer (TOF-MS). Typical GC problems in the determination of vitamin D such as sample degradation or sensitivity issues, previously reported in the literature, were not observed. Determination of total vitamin D content was done by quantitation of its pyro isomer based on an isotopically labelled internal standard (ISTD). Extracted ion traces of analyte and ISTD showed cross-contribution, but non-linearity of the calibration curve was not determined inside the chosen calibration range by selection of appropriate quantifier ions. Absolute limits of detection (LOD) and quantitation (LOQ) for vitamins D2 and D3 were calculated as approximately 50 and 150 pg, respectively. Repeatability with internal standard correction was below 2 %. Good agreement between quantitative results of an established high-performance liquid chromatography with UV detection (HPLC-UV) method and HPLC-GC-MS was found. Sterol-enriched margarine was subjected to HPLC-GC-MS and HPLC-MS/MS for comparison, because HPLC-UV showed strong matrix interferences. HPLC-GC-MS produced comparable results with less manual sample cleanup. In summary, online hyphenation of HPLC and GC allowed a minimization in manual sample preparation with an increase of sample throughput.

Microfluidics-to-Mass Spectrometry: A review of coupling methods and applications

PubMed Central

Wang, Xue; Yi, Lian; Mukhitov, Nikita; Schrell, Adrian M.; Dhumpa, Raghuram; Roper, Michael G.

2014-01-01

Microfluidic devices offer great advantages in integrating sample processes, minimizing sample and reagent volumes, and increasing analysis speed, while mass spectrometry detection provides high information content, is sensitive, and can be used in quantitative analyses. The coupling of microfluidic devices to mass spectrometers is becoming more common with the strengths of both systems being combined to analyze precious and complex samples. This review summarizes select achievements published between 2010 – July 2014 in novel coupling between microfluidic devices and mass spectrometers. The review is subdivided by the types of ionization sources employed, and the different microfluidic systems used. PMID:25458901

13CO Survey of Northern Intermediate-Mass Star-Forming Regions

NASA Astrophysics Data System (ADS)

Lundquist, Michael J.; Kobulnicky, H. A.; Kerton, C. R.

2014-01-01

We conducted a survey of 13CO with the OSO 20-m telescope toward 68 intermediate-mass star-forming regions (IM SFRs) visible in the northern hemisphere. These regions have mostly been excluded from previous CO surveys and were selected from IRAS colors that specify cool dust and large PAH contribution. These regions are known to host stars up to, but not exceeding, about 8 solar masses. We detect 13CO in 57 of the 68 IM SFRs down to a typical RMS of ~50 mK. We present kinematic distances, minimum column densities, and minimum masses for these IM SFRs.

High mass accuracy assay for trimethylamine N-oxide using stable-isotope dilution with liquid chromatography coupled to orthogonal acceleration time of flight mass spectrometry with multiple reaction monitoring.

PubMed

Heaney, Liam M; Jones, Donald J L; Mbasu, Richard J; Ng, Leong L; Suzuki, Toru

2016-01-01

Trimethylamine N-oxide (TMAO) has attracted interest as circulating levels have reported prognostic value in patients with cardiovascular conditions, such as heart failure. With continual advances in accurate mass measurements, robust methods that can employ the capabilities of time of flight mass spectrometers would offer additional utility in the analysis of complex clinical samples. A Waters Acquity UPLC was coupled to a Waters Synapt G2-S high-resolution mass spectrometer. TMAO was measured in plasma by stable-isotope dilution-hydrophilic interaction liquid chromatography-time of flight mass spectrometry with multiple reaction monitoring (LC-ToF-MRM). Two transitions were monitored: m/z 76.1 to 58.066/59.073 and m/z 85.1 to 66.116/68.130. The method was assessed for linearity, lower limits of detection and quantitation, and reproducibility. A selected cohort of patients with systolic heart failure (SHF; n = 43) and healthy controls (n = 42) were measured to verify the assay is suitable for the analysis of clinical samples. Quantitative analysis of TMAO using LC-ToF-MRM enabled linearity to be established between 0.1 and 75 μmol/L, with a lower limit of detection of 0.05 μmol/L. Relative standard deviations reported an inter-day variation of ≤20.8% and an intra-day variation of ≤11.4% with an intra-study quality control variation of 2.7%. Run times were 2.5 min. Clinical application of the method reported that TMAO in SHF was elevated compared to that of healthy controls (p < 0.0005). LC-ToF-MRM offers a highly selective method for accurate mass measurement of TMAO with rapid and reproducible results. Applicability of the method was shown in a selected cohort of patient samples.

Luminance level of a monitor: influence on detectability and detection rate of breast cancer in 2D mammography

NASA Astrophysics Data System (ADS)

Bemelmans, Frédéric; Rashidnasab, Alaleh; Chesterman, Frédérique; Kimpe, Tom; Bosmans, Hilde

2016-03-01

Purpose: To evaluate lesion detectability and reading time as a function of luminance level of the monitor. Material and Methods: 3D mass models and microcalcification clusters were simulated into ROIs of for processing mammograms. Randomly selected ROIs were subdivided in three groups according to their background glandularity: high (>30%), medium (15-30%) and low (<15%). 6 non-spiculated masses (9 - 11mm), 6 spiculated masses (5 - 7mm) and 6 microcalcification clusters (2 - 4mm) were scaled in 3D to create a range of sizes. The linear attenuation coefficient (AC) of the masses was adjusted from 100% glandular tissue to 90%, 80%, 70%, to create different contrasts. Six physicists read the full database on Barco's Coronis Uniti monitor for four different luminance levels (300, 800, 1000 and 1200 Cd/m2), using a 4-AFC tool. Percentage correct (PC) and time were computed for all different conditions. A paired t-test was performed to evaluate the effect of luminance on PC and time. A multi-factorial analysis was performed using MANOVA.. Results: Paired t-test indicated a statistically significant difference for the average time per session between 300 and 1200; 800 and 1200; 1000 and 1200 Cd/m2, for all participants combined. There was no effect on PC. MANOVA denoted significantly lower reading times for high glandularity images at 1200 Cd/m2. Both types of masses were significantly faster detected at 1200 Cd/m2, for the contrast study. In the size study, microcalcification clusters and spiculated masses had a significantly higher detection rate at 1200 Cd/m2. Conclusion: These results demonstrate a significant decrease in reading time, while detectability remained constant.

A selective and sensitive method for quantitation of lysergic acid diethylamide (LSD) in whole blood by gas chromatography-ion trap tandem mass spectrometry.

PubMed

Libong, Danielle; Bouchonnet, Stéphane; Ricordel, Ivan

2003-01-01

A gas chromatography-ion trap tandem mass spectrometry (GC-ion trap MS-MS) method for detection and quantitation of LSD in whole blood is presented. The sample preparation process, including a solid-phase extraction step with Bond Elut cartridges, was performed with 2 mL of whole blood. Eight microliters of the purified extract was injected with a cold on-column injection method. Positive chemical ionization was performed using acetonitrile as reagent gas; LSD was detected in the MS-MS mode. The chromatograms obtained from blood extracts showed the great selectivity of the method. GC-MS quantitation was performed using lysergic acid methylpropylamide as the internal standard. The response of the MS was linear for concentrations ranging from 0.02 ng/mL (detection threshold) to 10.0 ng/mL. Several parameters such as the choice of the capillary column, the choice of the internal standard and that of the ionization mode (positive CI vs. EI) were rationalized. Decomposition pathways under both ionization modes were studied. Within-day and between-day stability were evaluated.

Assessment of strobilurin fungicides' content in soya-based drinks by liquid micro-extraction and liquid chromatography with tandem mass spectrometry.

PubMed

Campillo, Natalia; Iniesta, María Jesús; Viñas, Pilar; Hernández-Córdoba, Manuel

2015-01-01

Seven strobilurin fungicides were pre-concentrated from soya-based drinks using dispersive liquid-liquid micro-extraction (DLLME) with a prior protein precipitation step in acid medium. The enriched phase was analysed by liquid chromatography (LC) with dual detection, using diode array detection (DAD) and electrospray-ion trap tandem mass spectrometry (ESI-IT-MS/MS). After selecting 1-undecanol and methanol as the extractant and disperser solvents, respectively, for DLLME, the Taguchi experimental method, an orthogonal array design, was applied to select the optimal solvent volumes and salt concentration in the aqueous phase. The matrix effect was evaluated and quantification was carried out using external aqueous calibration for DAD and matrix-matched calibration method for MS/MS. Detection limits in the 4-130 and 0.8-4.5 ng g(-1) ranges were obtained for DAD and MS/MS, respectively. The DLLME-LC-DAD-MS method was applied to the analysis of 10 different samples, none of which was found to contain residues of the studied fungicides.

Selective detection of carbohydrates and their peptide conjugates by ESI-MS using synthetic quaternary ammonium salt derivatives of phenylboronic acids.

PubMed

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Selective Detection of Carbohydrates and Their Peptide Conjugates by ESI-MS Using Synthetic Quaternary Ammonium Salt Derivatives of Phenylboronic Acids

NASA Astrophysics Data System (ADS)

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Simultaneous determination of sulfonamides, tetracyclines and tiamulin in swine wastewater by solid-phase extraction and liquid chromatography-mass spectrometry.

PubMed

Ben, Weiwei; Qiang, Zhimin; Adams, Craig; Zhang, Heqing; Chen, Liping

2008-08-22

Little is known about the contamination level of antibiotics in swine wastewater in China. The highly complex matrix of swine wastewater, which generally has a chemical oxygen demand (COD) concentration as high as 15,000 mg/L, makes it difficult to detect antibiotics at trace levels. In this work, a highly selective and sensitive analytical method was developed for simultaneous determination of three classes of commonly used veterinary antibiotics including five sulfonamides, three tetracyclines and one macrolide in swine wastewater using solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS). The method detection limits (MDL) in the swine wastewater were determined to be between 5 and 91 ng/L, depending on specific antibiotics. Except sulfamethizole, all the other eight antibiotics were detected in the swine wastewaters collected from three concentrated swine feeding plants located in the Beijing (China) area, showing a concentration range of 0.62-32.67 microg/L. These results reveal the representative concentration levels of selected antibiotics in the swine wastewaters of Beijing area.

Evaluation of the Botanical Authenticity and Phytochemical Profile of Black Cohosh Products by High-Performance Liquid Chromatography with Selected Ion Monitoring Liquid Chromatography–Mass Spectrometry

PubMed Central

Jiang, Bei; Kronenberg, Fredi; Nuntanakorn, Paiboon; Qiu, Ming-Hua; Kennelly, Edward J.

2011-01-01

Black cohosh (Actaea racemosa L., syn. Cimicifuga racemosa L.) has become increasingly popular as a dietary supplement in the United States for the treatment of symptoms related to menopause, but the botanical authenticity of most products containing black cohosh has not been evaluated, nor is manufacturing highly regulated in the United States. In this study, 11 black cohosh products were analyzed for triterpene glycosides, phenolic constituents, and formononetin by high-performance liquid chromatography–photodiode array detection and a new selected ion monitoring liquid chromatography–mass spectrometry method. Three of the 11 products were found to contain the marker compound cimifugin and not cimiracemoside C, thereby indicating that these plants contain Asian Actaea instead of black cohosh. One product contained both black cohosh and an Asian Actaea species. For the products containing only black cohosh, there was significant product-to-product variability in the amounts of the selected triterpene glycosides and phenolic constituents, and as expected, no formononetin was detected. PMID:16637680

A liquid chromatography-mass spectrometric method for the determination of oak moss allergens atranol and chloroatranol in perfumes.

PubMed

Bossi, Rossana; Rastogi, Suresh C; Bernard, Guillaume; Gimenez-Arnau, Elena; Johansen, Jeanne D; Lepoittevin, Jean-Pierre; Menné, Torkil

2004-05-01

This paper describes a validated liquid chromatographic-tandem mass spectrometric method for quantitative analysis of the potential oak moss allergens atranol and chloroatranol in perfumes and similar products. The method employs LC-MS-MS with electrospray ionization (ESI) in negative mode. The compounds are analysed by selective reaction monitoring (SRM) of 2 or 3 ions for each compound in order to obtain high selectivity and sensitivity. The method has been validated for the following parameters: linearity; repeatability; recovery; limit of detection; and limit of quantification. The limits of detection, 5.0 ng/mL and 2.4 ng/mL, respectively, for atranol and chloroatranol, achieved by this method allowed identification of these compounds at concentrations below those causing allergic skin reactions in oak-moss-sensitive patients. The recovery of chloratranol from spiked perfumes was 96+/-4%. Low recoveries (49+/-5%) were observed for atranol in spiked perfumes, indicating ion suppression caused by matrix components. The method has been applied to the analysis of 10 randomly selected perfumes and similar products.

Selective detection of carbon-13-labeled compounds by gas chromatography/emission spectroscopy

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

Quimby, B.D.; Dryden, P.C.; Sullivan, J.J.

1990-11-15

This paper describes a technique which also provides selective GC detection of compounds with excess {sup 13}C content. Molecular emission from CO bands in the vacuum ultraviolet region is monitored with an atomic emission detector (AED) (4,5). Samples can also be analyzed for C, H, O, N, S, P, Cl, F, etc. by changing the reagent and makeup gas flows. This combination of {sup 13}C specificity with atomic information is useful in the identification of unknown compounds, especially when combined with mass spectral data, as shown by Hooker and DeZwaan (6).

Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

PubMed

Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

2013-09-01

From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). Copyright © 2012 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

A completely automated CAD system for mass detection in a large mammographic database.

PubMed

Bellotti, R; De Carlo, F; Tangaro, S; Gargano, G; Maggipinto, G; Castellano, M; Massafra, R; Cascio, D; Fauci, F; Magro, R; Raso, G; Lauria, A; Forni, G; Bagnasco, S; Cerello, P; Zanon, E; Cheran, S C; Lopez Torres, E; Bottigli, U; Masala, G L; Oliva, P; Retico, A; Fantacci, M E; Cataldo, R; De Mitri, I; De Nunzio, G

2006-08-01

Mass localization plays a crucial role in computer-aided detection (CAD) systems for the classification of suspicious regions in mammograms. In this article we present a completely automated classification system for the detection of masses in digitized mammographic images. The tool system we discuss consists in three processing levels: (a) Image segmentation for the localization of regions of interest (ROIs). This step relies on an iterative dynamical threshold algorithm able to select iso-intensity closed contours around gray level maxima of the mammogram. (b) ROI characterization by means of textural features computed from the gray tone spatial dependence matrix (GTSDM), containing second-order spatial statistics information on the pixel gray level intensity. As the images under study were recorded in different centers and with different machine settings, eight GTSDM features were selected so as to be invariant under monotonic transformation. In this way, the images do not need to be normalized, as the adopted features depend on the texture only, rather than on the gray tone levels, too. (c) ROI classification by means of a neural network, with supervision provided by the radiologist's diagnosis. The CAD system was evaluated on a large database of 3369 mammographic images [2307 negative, 1062 pathological (or positive), containing at least one confirmed mass, as diagnosed by an expert radiologist]. To assess the performance of the system, receiver operating characteristic (ROC) and free-response ROC analysis were employed. The area under the ROC curve was found to be Az = 0.783 +/- 0.008 for the ROI-based classification. When evaluating the accuracy of the CAD against the radiologist-drawn boundaries, 4.23 false positives per image are found at 80% of mass sensitivity.

Detection of volatile compounds emitted by Pseudomonas aeruginosa using selected ion flow tube mass spectrometry.

PubMed

Carroll, Will; Lenney, Warren; Wang, Tianshu; Spanel, Patrik; Alcock, Alice; Smith, David

2005-05-01

Pseudomonas aeruginosa (PA) is associated with a distinctive smell produced by a combination of volatile compounds (VCs). Selected ion flow tube mass spectrometry (SIFT-MS) provides a novel and rapid methodology for rapid, accurate detection of trace quantities (parts per billion; ppb) of VCs in air. We studied the VCs produced by different isolates of PA cultures in vitro from patients with cystic fibrosis. Twenty-one patients with cystic fibrosis provided sputum and cough swab samples for culture. These were used to inoculate blood agar (BA) and Pseudomonas-selective media (PSM). These plates were incubated for 48 hr at 37 degrees C inside sealed plastic bags. The air surrounding the samples after 48 hr (headspace) was analyzed using SIFT-MS. PA growth was commonly associated with the production of significant quantities of VCs, notably hydrogen cyanide gas (HCN). This was detectable in the headspace of 15/22 of PA-positive samples. In contrast, it was only seen in the headspace of 1/13 control samples (6 sterile plates and 7 plates with only mixed upper respiratory tract flora). The concentration of HCN was significantly higher above PA-positive samples than above other bacterial growth (P < 0.01), and in our study, levels of HCN greater than 100 ppb were a sensitive (68%) and highly specific (100%) biomarker of PA. SIFT-MS can detect a range of VCs from PA in vitro. HCN may be a specific indicator of PA infection in vivo, and offers promise as a biomarker for noninvasive detection of PA infection by breath analysis. Copyright 2005 Wiley-Liss, Inc

Binary Cepheids: Separations and Mass Ratios in 5 Solar Mass Binaries

DTIC Science & Technology

2013-10-01

astrometry, photometry , direct imaging), each with selection biases. However, Cepheids—cool, evolved stars of∼5M—are a special case because ultraviolet...detected velocity variability. In an imaging survey with the Hubble Space Telescope Wide Field Camera 3, we resolved three of the companions (those...1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and

Derivatization of beta-dicarbonyl compound with 2,4-dinitrophenylhydrazine to enhance mass spectrometric detection: application in quantitative analysis of houttuynin in human plasma.

PubMed

Duan, Xiaotao; Zhong, Dafang; Chen, Xiaoyan

2008-06-01

Houttuynin (decanoyl acetaldehyde), a beta-dicarbonyl compound, is the major antibacterial constituent in the volatile oil of Houttuynina cordata Thunb. In the present work, detection of houttuynin in human plasma based on the chemical derivatization with 2,4-dinitrophenylhydrazine (DNPH) coupled with liquid chromatography/tandem mass spectrometry was described. The primary reaction products between the beta-dicarbonyl compound and DNPH in aqueous phase were identified as heterocyclic structures, of which the mass spectrometric ionization and fragmentation behavior were characterized with the aid of high-resolution multistage mass spectral analysis. For quantification, houttuynin and internal standard (IS, benzophenone) in plasma were firstly converted to their DNPH derivatives without sample purification, then extracted from human plasma with n-hexane and detected by liquid chromatography tandem mass spectrometry performed in selected reaction monitoring (SRM) mode. This method allowed for a lower limit of quantification (LLOQ) of 1.0 ng/ml using 100-microl plasma. The validation results showed high accuracy (%bias < 2.1) and precision (%CV < 7.2) at broad linear dynamic range (1.0-5000 ng/ml). The simple and quantitative derivatization coupled with tandem mass spectrometric analysis facilitates a sensitive and robust method for the determination of plasma houttuynin in pharmacokinetic studies.

Comparison of different mass spectrometric approaches coupled to gas chromatography for the analysis of organochlorine pesticides in serum samples.

PubMed

Fang, Jing; Wu, Qian; Zhao, Yun; Zhao, Hongzhi; Xu, Shunqing; Cai, Zongwei

2017-01-01

Gas chromatography-triple quadrupole mass spectrometry (GC-QqQMS) was applied for the determination of eight organochlorine pesticides (OCPs) in human serum. OCPs were extracted from the serum sample by solid phase extraction (SPE) and analyzed by gas chromatography mass spectrometry (GC-MS) or gas chromatography tandem mass spectrometry (GC-MS/MS). Electron ionization (EI) and negative chemical ionization (NCI) under two data acquisition modes, namely selected ion monitoring (SIM) and multiple reaction monitoring (MRM), were compared. The use of MRM generally provided higher selectivity and sensitivity because less interference from the sample matrix existed. The EI mode is more suitable for less electronegative compounds such as dichlorodiphenyldichloroethanes (DDDs) with detection limits ranging from 0.0060 to 0.060ng/mL. In the NCI mode, MRM analysis provided good and lower detection limits (0.0011-0.0030ng/mL) for pesticides containing more chlorines. The methods were validated by analyzing the pesticides in spiked serum at different levels with recoveries ranged from 83% to 116% and relative standard deviations of less than 10%. The developed method was applied for the determination of the OCPs in real human serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of limonin glucoside metabolites from human prostate cell culture medium using high-performance liquid chromatography/electrospray ionization mass spectrometry and tandem mass spectrometry.

PubMed

Tian, Qingguo; Kent, Kyle D; Bomser, Joshua A; Schwartz, Steven J

2004-01-01

The metabolism of limonin 17-beta-D-glucopyranoside (LG) by non-cancerous (RWPE-1) and cancerous (PC-3) human prostate epithelial cells was investigated using high-performance liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) with in-source fragmentation and tandem mass spectrometry (MS/MS). During positive ion LC/ESI-MS, LG formed an abundant sodiated species ([M+Na]+) while the protonated molecule was barely observable. [M+Na]+ further fragmented into the less abundant [LARL+H]+ and a predominantly protonated aglycone molecule (limonin) due to in-source fragmentation. The major metabolite, limonin A-ring lactone (LARL), formed an abundant protonated molecule that was fragmented into a protonated molecule of limonin by loss of one molecule of water. In MS/MS by collisionally activated dissociation (CAD), LG produced the sodiated aglycone, [aglycone+Na]+, while LARL fragmented into [M+H]+ of limonin and fragment ions resulted by further loss of water, carbon monoxide and carbon dioxide, indicating the presence of oxygenated-ring structures. The limits of detection of LG were 0.4 and 20 fmol in selected-ion monitoring (SIM) and selected-reaction monitoring (SRM) detection, respectively. Copyright 2004 John Wiley & Sons, Ltd.

A Chandra Survey of high-redshift (0.7 < z < 0.8) clusters selected in the 100 deg^2 SPT-Pol Deep Field

NASA Astrophysics Data System (ADS)

Garmire, Gordon

2016-09-01

We propose to observe a complete sample of 10 galaxy clusters at 1e14 < M500 < 5e14 and 0.7 < z < 0.8. These systems were selected from the 100 deg^2 deep field of the SPT-Pol SZ survey. This survey are has significant complementary data, including uniform depth ATCA, Herschel, Spitzer, and DES imaging, enabling a wide variety of astrophysical and cosmological studies. This sample complements the successful SPT-XVP survey, which has a broad redshift range and a narrow mass range, by including clusters over a narrow redshift range and broad mass range. These systems are such low mass and high redshift that they will not be detected in the eRosita all-sky survey.

EVIDENCE FOR THE UNIVERSALITY OF PROPERTIES OF RED-SEQUENCE GALAXIES IN X-RAY- AND RED-SEQUENCE-SELECTED CLUSTERS AT z ∼ 1

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

Foltz, R.; Wilson, G.; DeGroot, A.

We study the slope, intercept, and scatter of the color–magnitude and color–mass relations for a sample of 10 infrared red-sequence-selected clusters at z ∼ 1. The quiescent galaxies in these clusters formed the bulk of their stars above z ≳ 3 with an age spread Δt ≳ 1 Gyr. We compare UVJ color–color and spectroscopic-based galaxy selection techniques, and find a 15% difference in the galaxy populations classified as quiescent by these methods. We compare the color–magnitude relations from our red-sequence selected sample with X-ray- and photometric-redshift-selected cluster samples of similar mass and redshift. Within uncertainties, we are unable tomore » detect any difference in the ages and star formation histories of quiescent cluster members in clusters selected by different methods, suggesting that the dominant quenching mechanism is insensitive to cluster baryon partitioning at z ∼ 1.« less

Raman and photothermal spectroscopies for explosive detection

NASA Astrophysics Data System (ADS)

Finot, Eric; Brulé, Thibault; Rai, Padmnabh; Griffart, Aurélien; Bouhélier, Alexandre; Thundat, Thomas

2013-06-01

Detection of explosive residues using portable devices for locating landmine and terrorist weapons must sat- isfy the application criteria of high reproducibility, specificity, sensitivity and fast response time. Vibrational spectroscopies such as Raman and infrared spectroscopies have demonstrated their potential to distinguish the members of the chemical family of more than 30 explosive materials. The characteristic chemical fingerprints in the spectra of these explosives stem from the unique bond structure of each compound. However, these spectroscopies, developed in the early sixties, suffer from a poor sensitivity. On the contrary, MEMS-based chemical sensors have shown to have very high sensitivity lowering the detection limit down to less than 1 picogram, (namely 10 part per trillion) using sensor platforms based on microcantilevers, plasmonics, or surface acoustic waves. The minimum amount of molecules that can be detected depends actually on the transducer size. The selectivity in MEMS sensors is usually realized using chemical modification of the active surface. However, the lack of sufficiently selective receptors that can be immobilized on MEMS sensors remains one of the most critical issues. Microcantilever based sensors offer an excellent opportunity to combine both the infrared photothermal spectroscopy in their static mode and the unique mass sensitivity in their dynamic mode. Optical sensors based on localized plasmon resonance can also take up the challenge of addressing the selectivity by monitoring the Surface Enhanced Raman spectrum down to few molecules. The operating conditions of these promising localized spectroscopies will be discussed in terms of reliability, compactness, data analysis and potential for mass deployment.

Determination of secondary and tertiary amines as N-nitrosamine precursors in drinking water system using ultra-fast liquid chromatography-tandem mass spectrometry.

PubMed

Wu, Qihua; Shi, Honglan; Ma, Yinfa; Adams, Craig; Eichholz, Todd; Timmons, Terry; Jiang, Hua

2015-01-01

N-Nitrosamines are potent mutagenic and carcinogenic emerging water disinfection by-products (DBPs). The most effective strategy to control the formation of these DBPs is minimizing their precursors from source water. Secondary and tertiary amines are dominating precursors of N-nitrosamines formation during drinking water disinfection process. Therefore, the screening and removal of these amines in source water are very essential for preventing the formation of N-nitrosamines. A rapid, simple, and sensitive ultrafast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) method has been developed in this study to determine seven amines, including dimethylamine, ethylmethylamine, diethylamine, dipropylamine, trimethylamine, 3-(dimethylaminomethyl)indole, and 4-dimethylaminoantipyrine, as major precursors of N-nitrosamines in drinking water system. No sample preparation process is needed except a simple filtration. Separation and detection can be achieved in 11 min per sample. The method detection limits of selected amines are ranging from 0.02 μg/L to 1 μg/L except EMA (5 μg/L), and good calibration linearity was achieved. The developed method was applied to determine the selected precursors in source water and drinking water samples collected from Midwest area of the United States. In most of water samples, the concentrations of selected precursors of N-nitrosamines were below their method detection limits. Dimethylamine was detected in some of water samples at the concentration up to 25.4 μg/L. Copyright © 2014 Elsevier B.V. All rights reserved.

Three-step HPLC-ESI-MS/MS procedure for screening and identifying non-target flavonoid derivatives

NASA Astrophysics Data System (ADS)

Rak, Gábor; Fodor, Péter; Abrankó, László

2010-02-01

A three-step HPLC-ESI-MS/MS procedure is designed for screening and identification of non-target flavonoid derivatives of selected flavonoid aglycones. In this method the five commonly appearing aglycones (apigenin, luteolin, myricetin, naringenin and quercetin) were selected. The method consists of three individual mass spectrometric experiments of which the first two were implemented within a single chromatographic acquisition. The third step was carried out during a replicate chromatographic run using the same RP-HPLC conditions. The first step, a multiple reaction monitoring (MRM) scan of the aglycones was performed to define the number of derivatives relating to the selected aglycones. For this purpose the characteristic aglycone parts of the unknowns were used as specific tags of the molecules, which were generated as in-source fragments. Secondly, a full scan MS experiment is performed to identify the masses of the potential derivatives of the selected aglycones. Finally, the third step had the capability to confirm the supposed derivatives. The developed method was applied to a commercially available black currant juice to demonstrate its capability to detect and identify various flavonoid glycosides without any preliminary information about their presence in the sample. As a result 13 compounds were detected and identified in total. Namely, 3 different myricetin glycosides and the myricetin aglycone 2 luteolin glycosides plus the aglycone and 3 quercetin glycosides plus the aglycone could be identified from the tested black currant sample. In the case of apigenin and naringenin only the aglycones could be detected.

GASPS--A Herschel Survey of Gas and Dust in Protoplanetary Disks: Summary and Initial Statistics

NASA Technical Reports Server (NTRS)

Dent, W.R.F.; Thi, W. F.; Kamp, I.; Williams, J. P.; Menard, F.; Andrews, S.; Ardila, D.; Aresu, G.; Augereau, J.-C.; Barrado y Navascues, D.;

Cluster richness-mass calibration with cosmic microwave background lensing

NASA Astrophysics Data System (ADS)

Geach, James E.; Peacock, John A.

2017-11-01

Identifying galaxy clusters through overdensities of galaxies in photometric surveys is the oldest1,2 and arguably the most economical and mass-sensitive detection method3,4, compared with X-ray5-7 and Sunyaev-Zel'dovich effect8 surveys that detect the hot intracluster medium. However, a perennial problem has been the mapping of optical `richness' measurements onto total cluster mass3,9-12. Emitted at a conformal distance of 14 gigaparsecs, the cosmic microwave background acts as a backlight to all intervening mass in the Universe, and therefore has been gravitationally lensed13-15. Experiments such as the Atacama Cosmology Telescope16, South Pole Telescope17-19 and the Planck20 satellite have now detected gravitational lensing of the cosmic microwave background and produced large-area maps of the foreground deflecting structures. Here we present a calibration of cluster optical richness at the 10% level by measuring the average cosmic microwave background lensing measured by Planck towards the positions of large numbers of optically selected clusters, detecting the deflection of photons by structures of total mass of order 1014 M⊙. Although mainly aimed at the study of larger-scale structures, the Planck estimate of the cosmic microwave background lensing field can be used to recover a nearly unbiased lensing signal for stacked clusters on arcminute scales15,21. This approach offers a clean measure of total cluster masses over most of cosmic history, largely independent of baryon physics.

Mobility-Resolved Ion Selection in Uniform Drift Field Ion Mobility Spectrometry/Mass Spectrometry: Dynamic Switching in Structures for Lossless Ion Manipulations

DOE PAGES

Webb, Ian K.; Garimella, Sandilya V. B.; Tolmachev, Aleksey V.; ...

2014-09-15

A Structures for Lossless Ion Manipulations (SLIM) module that allows ion mobility separations and the switching of ions between alternative drift paths is described. The SLIM switch component has a “Tee” configuration and allows switching of ions between a linear path and a 90-degree bend. By controlling switching times, ions can be deflected to an alternative channel as a function of their mobilities. In the initial evaluation the switch is used in a static mode and shown compatible with high performance ion mobility separations at 4 torr. In the “dynamic mode” we show that mobility-selected ions can be switched intomore » the alternative channel, and that various ion species can be independently selected based on their mobilities for time-of-flight mass spectrometer (TOF MS) IMS detection and mass analysis. Ultimately, this development also provides the basis for e.g. the selection of specific mobilities for storage and accumulation, and key modules for the assembly of SLIM devices enabling much more complex sequences of ion manipulations.« less

Assessment of groundwater, soil-gas, and soil contamination at the Vietnam Armor Training Facility, Fort Gordon, Georgia, 2009-2010

USGS Publications Warehouse

Guimaraes, Wladmir B.; Falls, W. Fred; Caldwell, Andral W.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.

2011-01-01

The U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, Georgia, assessed the groundwater, soil gas, and soil for contaminants at the Vietnam Armor Training Facility (VATF) at Fort Gordon, from October 2009 to September 2010. The assessment included the detection of organic compounds in the groundwater and soil gas, and inorganic compounds in the soil. In addition, organic contaminant assessment included organic compounds classified as explosives and chemical agents in selected areas. The assessment was conducted to provide environmental contamination data to the U.S. Army at Fort Gordon pursuant to requirements of the Resource Conservation and Recovery Act Part B Hazardous Waste Permit process. Four passive samplers were deployed in groundwater wells at the VATF in Fort Gordon. Total petroleum hydrocarbons were detected above the method detection level at all four wells. The only other volatile organic compounds detected above their method detection level were undecane and pentadecane, which were detected in two of the four wells sampled. Soil-gas samplers were deployed at 72 locations in a grid pattern across the VATF. Total petroleum hydrocarbons were detected in 71 of the 72 samplers (one sampler was destroyed in the field and not analyzed) at levels above the method detection level, and the combined mass of benzene, toluene, ethylbenzene, and total xylene was detected above the detection level in 31 of the 71 samplers that were analyzed. Other volatile organic compounds detected above their respective method detection levels were naphthalene, 2-methyl-naphthalene, tridecane, 1,2,4-trimethylbenzene, and perchloroethene. Subsequent to the soil-gas survey, four areas determined to have elevated contaminant mass were selected and sampled for explosives and chemical agents. No detections of explosives or chemical agents above their respective method detection levels were found at any of the sampling locations. The same four locations that were sampled for explosives and chemical agents were selected for the collection of soil samples. A fifth location also was selected on the basis of the elevated contaminant mass of the soil-gas survey. No metals that exceeded the Regional Screening Levels for Industrial Soils as classified by the U.S. Environmental Protection Agency were detected at any of the five VATF locations. The soil samples also were compared to values from the ambient, uncontaminated (background) levels for soils in South Carolina, as classified by the South Carolina Department of Health and Environmental Control. Because South Carolina is adjacent to Georgia and the soils in the coastal plain are similar, these comparisons are valid. No similar values are available for Georgia to use for comparison purposes. The metals that were detected above the ambient background levels for South Carolina, as classified by the South Carolina Department of Health and Environmental Control, include aluminum, arsenic, barium, beryllium, calcium, chromium, copper, iron, lead, magnesium, manganese, nickel, potassium, sodium, and zinc.

Detection of Metastatic Breast and Thyroid Cancer in Lymph Nodes by Desorption Electrospray Ionization Mass Spectrometry Imaging

NASA Astrophysics Data System (ADS)

Zhang, Jialing; Feider, Clara L.; Nagi, Chandandeep; Yu, Wendong; Carter, Stacey A.; Suliburk, James; Cao, Hop S. Tran; Eberlin, Livia S.

2017-06-01

Ambient ionization mass spectrometry has been widely applied to image lipids and metabolites in primary cancer tissues with the purpose of detecting and understanding metabolic changes associated with cancer development and progression. Here, we report the use of desorption electrospray ionization mass spectrometry (DESI-MS) to image metastatic breast and thyroid cancer in human lymph node tissues. Our results show clear alterations in lipid and metabolite distributions detected in the mass spectra profiles from 42 samples of metastatic thyroid tumors, metastatic breast tumors, and normal lymph node tissues. 2D DESI-MS ion images of selected molecular species allowed discrimination and visualization of specific histologic features within tissue sections, including regions of metastatic cancer, adjacent normal lymph node, and fibrosis or adipose tissues, which strongly correlated with pathologic findings. In thyroid cancer metastasis, increased relative abundances of ceramides and glycerophosphoinisitols were observed. In breast cancer metastasis, increased relative abundances of various fatty acids and specific glycerophospholipids were seen. Trends in the alterations in fatty acyl chain composition of lipid species were also observed through detailed mass spectra evaluation and chemical identification of molecular species. The results obtained demonstrate DESI-MSI as a potential clinical tool for the detection of breast and thyroid cancer metastasis in lymph nodes, although further validation is needed. [Figure not available: see fulltext.

Simultaneous Proteomic Discovery and Targeted Monitoring using Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry

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

Burnum-Johnson, Kristin E.; Nie, Song; Casey, Cameron P.

Current proteomics approaches are comprised of both broad discovery measurements as well as more quantitative targeted measurements. These two different measurement types are used to initially identify potentially important proteins (e.g., candidate biomarkers) and then enable improved quantification for a limited number of selected proteins. However, both approaches suffer from limitations, particularly the lower sensitivity, accuracy, and quantitation precision for discovery approaches compared to targeted approaches, and the limited proteome coverage provided by targeted approaches. Herein, we describe a new proteomics approach that allows both discovery and targeted monitoring (DTM) in a single analysis using liquid chromatography, ion mobility spectrometrymore » and mass spectrometry (LC-IMS-MS). In DTM, heavy labeled peptides for target ions are spiked into tryptic digests and both the labeled and unlabeled peptides are broadly detected using LC-IMS-MS instrumentation, allowing the benefits of discovery and targeted approaches. To understand the possible improvement of the DTM approach, it was compared to LC-MS broad measurements using an accurate mass and time tag database and selected reaction monitoring (SRM) targeted measurements. The DTM results yielded greater peptide/protein coverage and a significant improvement in the detection of lower abundance species compared to LC-MS discovery measurements. DTM was also observed to have similar detection limits as SRM for the targeted measurements indicating its potential for combining the discovery and targeted approaches.« less

Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

PubMed

Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

2014-03-01

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

Detection of Gunshot Residues Using Mass Spectrometry

PubMed Central

Blanes, Lucas; Cole, Nerida; Doble, Philip; Roux, Claude

2014-01-01

In recent years, forensic scientists have become increasingly interested in the detection and interpretation of organic gunshot residues (OGSR) due to the increasing use of lead- and heavy metal-free ammunition. This has also been prompted by the identification of gunshot residue- (GSR-) like particles in environmental and occupational samples. Various techniques have been investigated for their ability to detect OGSR. Mass spectrometry (MS) coupled to a chromatographic system is a powerful tool due to its high selectivity and sensitivity. Further, modern MS instruments can detect and identify a number of explosives and additives which may require different ionization techniques. Finally, MS has been applied to the analysis of both OGSR and inorganic gunshot residue (IGSR), although the “gold standard” for analysis is scanning electron microscopy with energy dispersive X-ray microscopy (SEM-EDX). This review presents an overview of the technical attributes of currently available MS and ionization techniques and their reported applications to GSR analysis. PMID:24977168

Development of a nucleotide sugar purification method using a mixed mode column & mass spectrometry detection.

PubMed

Eastwood, Heather; Xia, Fang; Lo, Mei-Chu; Zhou, Jing; Jordan, John B; McCarter, John; Barnhart, Wesley W; Gahm, Kyung-Hyun

2015-11-10

Analysis of nucleotide sugars, nucleoside di- and triphosphates and sugar-phosphates is an essential step in the process of understanding enzymatic pathways. A facile and rapid separation method was developed to analyze these compounds present in an enzymatic reaction mixture utilized to produce nucleotide sugars. The Primesep SB column explored in this study utilizes hydrophobic interactions as well as electrostatic interactions with the phosphoric portion of the nucleotide sugars. Ammonium formate buffer was selected due to its compatibility with mass spectrometry. Negative ion mode mass spectrometry was adopted for detection of the sugar phosphate (fucose-1-phophate), as the compound is not amenable to UV detection. Various mobile phase conditions such as pH, buffer concentration and organic modifier were explored. The semi-preparative separation method was developed to prepare 30mg of the nucleotide sugar. (19)F NMR was utilized to determine purity of the purified fluorinated nucleotide sugar. The collected nucleotide sugar was found to be 99% pure. Published by Elsevier B.V.

Validation of a liquid chromatography-tandem mass spectrometry method for the identification and quantification of 5-nitroimidazole drugs and their corresponding hydroxy metabolites in lyophilised pork meat.

PubMed

Zeleny, Reinhard; Harbeck, Stefan; Schimmel, Heinz

2009-01-09

A liquid chromatography-electrospray ionisation tandem mass spectrometry method for the simultaneous detection and quantitation of 5-nitroimidazole veterinary drugs in lyophilised pork meat, the chosen format of a candidate certified reference material, has been developed and validated. Six analytes have been included in the scope of validation, i.e. dimetridazole (DMZ), metronidazole (MNZ), ronidazole (RNZ), hydroxymetronidazole (MNZOH), hydroxyipronidazole (IPZOH), and 2-hydroxymethyl-1-methyl-5-nitroimidazole (HMMNI). The analytes were extracted from the sample with ethyl acetate, chromatographically separated on a C(18) column, and finally identified and quantified by tandem mass spectrometry in the multiple reaction monitoring mode (MRM) using matrix-matched calibration and (2)H(3)-labelled analogues of the analytes (except for MNZOH, where [(2)H(3)]MNZ was used). The method was validated in accordance with Commission Decision 2002/657/EC, by determining selectivity, linearity, matrix effect, apparent recovery, repeatability and intermediate precision, decision limits and detection capabilities, robustness of sample preparation method, and stability of extracts. Recovery at 1 microg/kg level was at 100% (estimates in the range of 101-107%) for all analytes, repeatabilities and intermediate precisions at this level were in the range of 4-12% and 2-9%, respectively. Linearity of calibration curves in the working range 0.5-10 microg/kg was confirmed, with r values typically >0.99. Decision limits (CCalpha) and detection capabilities (CCbeta) according to ISO 11843-2 (calibration curve approach) were 0.29-0.44 and 0.36-0.54 microg/kg, respectively. The method reliably identifies and quantifies the selected nitroimidazoles in the reconstituted pork meat in the low and sub-microg/kg range and will be applied in an interlaboratory comparison for determining the mass fraction of the selected nitroimidazoles in the candidate reference material currently developed at IRMM.

Assessment of meat authenticity using bioinformatics, targeted peptide biomarkers and high-resolution mass spectrometry.

PubMed

Ruiz Orduna, Alberto; Husby, Erik; Yang, Charles T; Ghosh, Dipankar; Beaudry, Francis

2015-01-01

In recent years a significant increase of food fraud has been observed, ranging from false label claims to the use of additives and fillers to increase profitability. Recently in 2013 horse and pig DNAs were detected in beef products sold from several retailers. Mass spectrometry (MS) has become the workhorse in protein research, and the detection of marker proteins could serve for both animal species and tissue authentication. Meat species authenticity is performed in this paper using a well-defined proteogenomic annotation, carefully chosen surrogate tryptic peptides and analysis using a hybrid quadrupole-Orbitrap MS. Selected mammalian meat samples were homogenised and proteins were extracted and digested with trypsin. The samples were analysed using a high-resolution MS. Chromatography was achieved using a 30-min linear gradient along with a BioBasic C8 100 × 1 mm column at a flow rate of 75 µl min(-1). The MS was operated in full-scan high resolution and accurate mass. MS/MS spectra were collected for selected proteotypic peptides. Muscular proteins were methodically analysed in silico in order to generate tryptic peptide mass lists and theoretical MS/MS spectra. Following a comprehensive bottom-up proteomic analysis, we detected and identified a proteotypic myoglobin tryptic peptide (120-134) for each species with observed m/z below 1.3 ppm compared with theoretical values. Moreover, proteotypic peptides from myosin-1, myosin-2 and β-haemoglobin were also identified. This targeted method allowed comprehensive meat speciation down to 1% (w/w) of undesired product.

Comparison of Quantitative Mass Spectrometry Platforms for Monitoring Kinase ATP Probe Uptake in Lung Cancer.

PubMed

Hoffman, Melissa A; Fang, Bin; Haura, Eric B; Rix, Uwe; Koomen, John M

2018-01-05

Recent developments in instrumentation and bioinformatics have led to new quantitative mass spectrometry platforms including LC-MS/MS with data-independent acquisition (DIA) and targeted analysis using parallel reaction monitoring mass spectrometry (LC-PRM), which provide alternatives to well-established methods, such as LC-MS/MS with data-dependent acquisition (DDA) and targeted analysis using multiple reaction monitoring mass spectrometry (LC-MRM). These tools have been used to identify signaling perturbations in lung cancers and other malignancies, supporting the development of effective kinase inhibitors and, more recently, providing insights into therapeutic resistance mechanisms and drug repurposing opportunities. However, detection of kinases in biological matrices can be challenging; therefore, activity-based protein profiling enrichment of ATP-utilizing proteins was selected as a test case for exploring the limits of detection of low-abundance analytes in complex biological samples. To examine the impact of different MS acquisition platforms, quantification of kinase ATP uptake following kinase inhibitor treatment was analyzed by four different methods: LC-MS/MS with DDA and DIA, LC-MRM, and LC-PRM. For discovery data sets, DIA increased the number of identified kinases by 21% and reduced missingness when compared with DDA. In this context, MRM and PRM were most effective at identifying global kinome responses to inhibitor treatment, highlighting the value of a priori target identification and manual evaluation of quantitative proteomics data sets. We compare results for a selected set of desthiobiotinylated peptides from PRM, MRM, and DIA and identify considerations for selecting a quantification method and postprocessing steps that should be used for each data acquisition strategy.

Use of specific peptide biomarkers for quantitative confirmation of hidden allergenic peanut proteins Ara h 2 and Ara h 3/4 for food control by liquid chromatography-tandem mass spectrometry.

PubMed

Careri, M; Costa, A; Elviri, L; Lagos, J-B; Mangia, A; Terenghi, M; Cereti, A; Garoffo, L Perono

2007-11-01

A liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS-MS) method based on the detection of biomarker peptides from allergenic proteins was devised for confirming and quantifying peanut allergens in foods. Peptides obtained from tryptic digestion of Ara h 2 and Ara h 3/4 proteins were identified and characterized by LC-MS and LC-MS-MS with a quadrupole-time of flight mass analyzer. Four peptides were chosen and investigated as biomarkers taking into account their selectivity, the absence of missed cleavages, the uniform distribution in the Ara h 2 and Ara h 3/4 protein isoforms together with their spectral features under ESI-MS-MS conditions, and good repeatability of LC retention time. Because of the different expression levels, the selection of two different allergenic proteins was proved to be useful in the identification and univocal confirmation of the presence of peanuts in foodstuffs. Using rice crisp and chocolate-based snacks as model food matrix, an LC-MS-MS method with triple quadrupole mass analyzer allowed good detection limits to be obtained for Ara h 2 (5 microg protein g(-1) matrix) and Ara h 3/4 (1 microg protein g(-1) matrix). Linearity of the method was established in the 10-200 microg g(-1) range of peanut proteins in the food matrix investigated. Method selectivity was demonstrated by analyzing tree nuts (almonds, pecan nuts, hazelnuts, walnuts) and food ingredients such as milk, soy beans, chocolate, cornflakes, and rice crisp.

Spectroscopic follow-up of variability-selected active galactic nuclei in the Chandra Deep Field South

NASA Astrophysics Data System (ADS)

Boutsia, K.; Leibundgut, B.; Trevese, D.; Vagnetti, F.

2009-04-01

Context: Supermassive black holes with masses of 10^5-109 M⊙ are believed to inhabit most, if not all, nuclear regions of galaxies, and both observational evidence and theoretical models suggest a scenario where galaxy and black hole evolution are tightly related. Luminous AGNs are usually selected by their non-stellar colours or their X-ray emission. Colour selection cannot be used to select low-luminosity AGNs, since their emission is dominated by the host galaxy. Objects with low X-ray to optical ratio escape even the deepest X-ray surveys performed so far. In a previous study we presented a sample of candidates selected through optical variability in the Chandra Deep Field South, where repeated optical observations were performed in the framework of the STRESS supernova survey. Aims: The analysis is devoted to breaking down the sample in AGNs, starburst galaxies, and low-ionisation narrow-emission line objects, to providing new information about the possible dependence of the emission mechanisms on nuclear luminosity and black-hole mass, and eventually studying the evolution in cosmic time of the different populations. Methods: We obtained new optical spectroscopy for a sample of variability selected candidates with the ESO NTT telescope. We analysed the new spectra, together with those existing in the literature and studied the distribution of the objects in U-B and B-V colours, optical and X-ray luminosity, and variability amplitude. Results: A large fraction (17/27) of the observed candidates are broad-line luminous AGNs, confirming the efficiency of variability in detecting quasars. We detect: i) extended objects which would have escaped the colour selection and ii) objects of very low X-ray to optical ratio, in a few cases without any X-ray detection at all. Several objects resulted to be narrow-emission line galaxies where variability indicates nuclear activity, while no emission lines were detected in others. Some of these galaxies have variability and X-ray to optical ratio close to active galactic nuclei, while others have much lower variability and X-ray to optical ratio. This result can be explained by the dilution of the nuclear light due to the host galaxy. Conclusions: Our results demonstrate the effectiveness of supernova search programmes to detect large samples of low-luminosity AGNs. A sizable fraction of the AGN in our variability sample had escaped X-ray detection (5/47) and/or colour selection (9/48). Spectroscopic follow-up to fainter flux limits is strongly encouraged. Based on observations collected at the European Southern Observatory, Chile, 080.B-0187(A).

THE MOST LUMINOUS GALAXIES DISCOVERED BY WISE

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

Tsai, Chao-Wei; Eisenhardt, Peter R. M.; Stern, Daniel

2015-06-01

We present 20 Wide-field Infrared Survey Explorer (WISE)-selected galaxies with bolometric luminosities L{sub bol} > 10{sup 14} L{sub ☉}, including five with infrared luminosities L{sub IR} ≡ L{sub (rest} {sub 8–1000} {sub μm)} > 10{sup 14} L{sub ☉}. These “extremely luminous infrared galaxies,” or ELIRGs, were discovered using the “W1W2-dropout” selection criteria which requires marginal or non-detections at 3.4 and 4.6 μm (W1 and W2, respectively) but strong detections at 12 and 22 μm in the WISE survey. Their spectral energy distributions are dominated by emission at rest-frame 4–10 μm, suggesting that hot dust with T{sub d} ∼ 450 Kmore » is responsible for the high luminosities. These galaxies are likely powered by highly obscured active galactic nuclei (AGNs), and there is no evidence suggesting these systems are beamed or lensed. We compare this WISE-selected sample with 116 optically selected quasars that reach the same L{sub bol} level, corresponding to the most luminous unobscured quasars in the literature. We find that the rest-frame 5.8 and 7.8 μm luminosities of the WISE-selected ELIRGs can be 30%–80% higher than that of the unobscured quasars. The existence of AGNs with L{sub bol} > 10{sup 14} L{sub ☉} at z > 3 suggests that these supermassive black holes are born with large mass, or have very rapid mass assembly. For black hole seed masses ∼10{sup 3} M{sub ☉}, either sustained super-Eddington accretion is needed, or the radiative efficiency must be <15%, implying a black hole with slow spin, possibly due to chaotic accretion.« less

Molecular classification of liver cirrhosis in a rat model by proteomics and bioinformatics.

PubMed

Xu, Xiu-Qin; Leow, Chon K; Lu, Xin; Zhang, Xuegong; Liu, Jun S; Wong, Wing-Hung; Asperger, Arndt; Deininger, Sören; Eastwood Leung, Hon-Chiu

2004-10-01

Liver cirrhosis is a worldwide health problem. Reliable, noninvasive methods for early detection of liver cirrhosis are not available. Using a three-step approach, we classified sera from rats with liver cirrhosis following different treatment insults. The approach consisted of: (i) protein profiling using surface-enhanced laser desorption/ionization (SELDI) technology; (ii) selection of a statistically significant serum biomarker set using machine learning algorithms; and (iii) identification of selected serum biomarkers by peptide sequencing. We generated serum protein profiles from three groups of rats: (i) normal (n=8), (ii) thioacetamide-induced liver cirrhosis (n=22), and (iii) bile duct ligation-induced liver fibrosis (n=5) using a weak cation exchanger surface. Profiling data were further analyzed by a recursive support vector machine algorithm to select a panel of statistically significant biomarkers for class prediction. Sensitivity and specificity of classification using the selected protein marker set were higher than 92%. A consistently down-regulated 3495 Da protein in cirrhosis samples was one of the selected significant biomarkers. This 3495 Da protein was purified on-chip and trypsin digested. Further structural characterization of this biomarkers candidate was done by using cross-platform matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) peptide mass fingerprinting (PMF) and matrix-assisted laser desorption/ionization time of flight/time of flight (MALDI-TOF/TOF) tandem mass spectrometry (MS/MS). Combined data from PMF and MS/MS spectra of two tryptic peptides suggested that this 3495 Da protein shared homology to a histidine-rich glycoprotein. These results demonstrated a novel approach to discovery of new biomarkers for early detection of liver cirrhosis and classification of liver diseases.

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.

PubMed

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.

EPA Method 200.8: Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry

EPA Pesticide Factsheets

\\tEPA’s Selected Analytical Methods for Environmental Remediation and Recovery (SAM) lists this method for preparation and analysis of drinking water samples to detect and measure compounds containing arsenic, thallium and vanadium.

Hybrid quadrupole mass filter/quadrupole ion trap/time-of-flight-mass spectrometer for infrared multiple photon dissociation spectroscopy of mass-selected ions

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

Gulyuz, Kerim; Stedwell, Corey N.; Wang Da

2011-05-15

We present a laboratory-constructed mass spectrometer optimized for recording infrared multiple photon dissociation (IRMPD) spectra of mass-selected ions using a benchtop tunable infrared optical parametric oscillator/amplifier (OPO/A). The instrument is equipped with two ionization sources, an electrospray ionization source, as well as an electron ionization source for troubleshooting. This hybrid mass spectrometer is composed of a quadrupole mass filter for mass selection, a reduced pressure ({approx}10{sup -5} Torr) quadrupole ion trap (QIT) for OPO irradiation, and a reflectron time-of-flight drift tube for detecting the remaining precursor and photofragment ions. A helium gas pulse is introduced into the QIT to temporarilymore » increase the pressure and hence enhance the trapping efficiency of axially injected ions. After a brief pump-down delay, the compact ion cloud is subjected to the focused output from the continuous wave OPO. In a recent study, we implemented this setup in the study of protonated tryptophan, TrpH{sup +}, as well as collision-induced dissociation products of this protonated amino acid [W. K. Mino, Jr., K. Gulyuz, D. Wang, C. N. Stedwell, and N. C. Polfer, J. Phys. Chem. Lett. 2, 299 (2011)]. Here, we give a more detailed account on the figures of merit of such IRMPD experiments. The appreciable photodissociation yields in these measurements demonstrate that IRMPD spectroscopy of covalently bound ions can be routinely carried out using benchtop OPO setups.« less

Metallocarbohedrenes: Transmission Electron Microscopy of Mass Gated Deposits

NASA Astrophysics Data System (ADS)

Castleman, M. E. Lyn, Jr.

2002-03-01

Titanium and zirconium Met-Car cluster ions have been detected from the direct laser vaporization of metal-graphite mixtures using time-of-flight mass spectrometry. Optimization of the production conditions enabled sufficient intensities to mass select and deposit Met-Cars on surfaces. High-resolution transmission electron microscopy images of mass gated Met-Car species reveals deposited nanocrystals 2 nm in diameter. Diffraction patterns indicate the presence of multiple species and shows that the deposits have spatial orientation. Lattice parameters have been extracted. The implication of the findings will be discussed. Support for the work has been from the AFOSR F49620-01-1-0122.

Simultaneous detection of perchlorate and bromate using rapid high-performance ion exchange chromatography-tandem mass spectrometry and perchlorate removal in drinking water.

PubMed

West, Danielle M; Mu, Ruipu; Gamagedara, Sanjeewa; Ma, Yinfa; Adams, Craig; Eichholz, Todd; Burken, Joel G; Shi, Honglan

2015-06-01

Perchlorate and bromate occurrence in drinking water causes health concerns due to their effects on thyroid function and carcinogenicity, respectively. The purpose of this study was threefold: (1) to advance a sensitive method for simultaneous rapid detection of perchlorate and bromate in drinking water system, (2) to systematically study the occurrence of these two contaminants in Missouri drinking water treatment systems, and (3) to examine effective sorbents for minimizing perchlorate in drinking water. A rapid high-performance ion exchange chromatography-tandem mass spectrometry (HPIC-MS/MS) method was advanced for simultaneous detection of perchlorate and bromate in drinking water. The HPIC-MS/MS method was rapid, required no preconcentration of the water samples, and had detection limits for perchlorate and bromate of 0.04 and 0.01 μg/L, respectively. The method was applied to determine perchlorate and bromate concentrations in total of 23 selected Missouri drinking water treatment systems during differing seasons. The water systems selected include different source waters: groundwater, lake water, river water, and groundwater influenced by surface water. The concentrations of perchlorate and bromate were lower than or near to method detection limits in most of the drinking water samples monitored. The removal of perchlorate by various adsorbents was studied. A cationic organoclay (TC-99) exhibited effective removal of perchlorate from drinking water matrices.

Mass amplifying probe for sensitive fluorescence anisotropy detection of small molecules in complex biological samples.

PubMed

Cui, Liang; Zou, Yuan; Lin, Ninghang; Zhu, Zhi; Jenkins, Gareth; Yang, Chaoyong James

2012-07-03

Fluorescence anisotropy (FA) is a reliable and excellent choice for fluorescence sensing. One of the key factors influencing the FA value for any molecule is the molar mass of the molecule being measured. As a result, the FA method with functional nucleic acid aptamers has been limited to macromolecules such as proteins and is generally not applicable for the analysis of small molecules because their molecular masses are relatively too small to produce observable FA value changes. We report here a molecular mass amplifying strategy to construct anisotropy aptamer probes for small molecules. The probe is designed in such a way that only when a target molecule binds to the probe does it activate its binding ability to an anisotropy amplifier (a high molecular mass molecule such as protein), thus significantly increasing the molecular mass and FA value of the probe/target complex. Specifically, a mass amplifying probe (MAP) consists of a targeting aptamer domain against a target molecule and molecular mass amplifying aptamer domain for the amplifier protein. The probe is initially rendered inactive by a small blocking strand partially complementary to both target aptamer and amplifier protein aptamer so that the mass amplifying aptamer domain would not bind to the amplifier protein unless the probe has been activated by the target. In this way, we prepared two probes that constitute a target (ATP and cocaine respectively) aptamer, a thrombin (as the mass amplifier) aptamer, and a fluorophore. Both probes worked well against their corresponding small molecule targets, and the detection limits for ATP and cocaine were 0.5 μM and 0.8 μM, respectively. More importantly, because FA is less affected by environmental interferences, ATP in cell media and cocaine in urine were directly detected without any tedious sample pretreatment. Our results established that our molecular mass amplifying strategy can be used to design aptamer probes for rapid, sensitive, and selective detection of small molecules by means of FA in complex biological samples.

Chemical Microsensors For Detection Of Explosives And Chemical Warfare Agents

DOEpatents

Yang, Xiaoguang; Swanson, Basil I.

2001-11-13

An article of manufacture is provided including a substrate having an oxide surface layer and a layer of a cyclodextrin derivative chemically bonded to said substrate, said layer of a cyclodextrin derivative adapted for the inclusion of selected compounds, e.g., nitro-containing organic compounds, therewith. Such an article can be a chemical microsensor capable of detecting a resultant mass change from inclusion of the nitro-containing organic compound.

Chemotaxonomic differentiation of legionellae by detection and characterization of aminodideoxyhexoses and other unique sugars using gas chromatography-mass spectrometry.

PubMed Central

Fox, A; Rogers, J C; Fox, K F; Schnitzer, G; Morgan, S L; Brown, A; Aono, R

1990-01-01

Legionellae have been differentiated previously by analyzing their carbohydrate contents by gas chromatography with flame ionization detection. In the present study, total ion mode gas chromatography-mass spectrometry (GC-MS) was used to detect a number of unusual sugars, including one that is structurally related to O-methyldideoxyheptoses. Increased sensitivity and selectivity for carbohydrate detection was achieved by selected ion-monitoring GC-MS. Two of the uncommon sugars previously discovered in the legionellae (X1 and X2) were identified as quinovosamine and fucosamine, respectively. Legionella pneumophila contained rhamnose and quinovosamine but not the quinovosamine isomer fucosamine. Tatlockia micdadei and Legionella maceachernii contained large amounts of rhamnose, fucose, and fucosamine but not quinovosamine. These two species were the only legionellae studied that contained another unusual sugar that is referred to as X3, pending determination of its structure. Fluoribacter dumoffi, Fluoribacter bozemanae, and Legionella anisa were varied in their carbohydrate contents, both within and between species, but could be distinguished from L. pneumophila and the T. micdadei and L. maceachernii group. Fluoribacter gormanii was unique among the legionellae in that it lacked both quinovosamine and fucosamine. Legionella jordanis contained other unusual carbohydrates in addition to quinovosamine. GC-MS may have wide application in the differentiation of bacterial species. PMID:2324276

Fast quantitative analysis of boric acid by gas chromatography-mass spectrometry coupled with a simple and selective derivatization reaction using triethanolamine.

PubMed

Zeng, Li-Min; Wang, Hao-Yang; Guo, Yin-Long

2010-03-01

A fast, selective, and sensitive GC-MS method has been developed and validated for the determination of boric acid in the drinking water by derivatization with triethanolamine. This analytic strategy successfully converts the inorganic, nonvolatile boric acid B(OH)(3) present in the drinking water to a volatile triethanolamine borate B(OCH(2)CH(2))(3)N in a quantitative manner, which facilitates the GC measurement. The SIM mode was applied in the analysis and showed high accuracy, specificity, and reproducibility, as well as reducing the matrix effect effectively. The calibration curve was obtained from 0.01 microg/mL to 10.0 microg/mL with a satisfactory correlation coefficient of 0.9988. The limit of detection for boric acid was 0.04 microg/L. Then the method was applied for detection of the amount of boric acid in bottled drinking water and the results are in accordance with the reported concentration value of boric acid. This study offers a perspective into the utility of GC-MS as an alternate quantitative tool for detection of B(OH)(3), even for detection of boron in various other samples by digesting the boron compounds to boric acid. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.

PubMed

Viidanoja, Jyrki

2015-02-27

A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. Copyright © 2015 Elsevier B.V. All rights reserved.

Targeted Selected Reaction Monitoring Mass Spectrometric Immunoassay for Insulin-like Growth Factor 1

PubMed Central

Niederkofler, Eric E.; Phillips, David A.; Krastins, Bryan; Kulasingam, Vathany; Kiernan, Urban A.; Tubbs, Kemmons A.; Peterman, Scott M.; Prakash, Amol; Diamandis, Eleftherios P.; Lopez, Mary F.; Nedelkov, Dobrin

2013-01-01

Insulin-like growth factor 1 (IGF1) is an important biomarker of human growth disorders that is routinely analyzed in clinical laboratories. Mass spectrometry-based workflows offer a viable alternative to standard IGF1 immunoassays, which utilize various pre-analytical preparation strategies. In this work we developed an assay that incorporates a novel sample preparation method for dissociating IGF1 from its binding proteins. The workflow also includes an immunoaffinity step using antibody-derivatized pipette tips, followed by elution, trypsin digestion, and LC-MS/MS separation and detection of the signature peptides in a selected reaction monitoring (SRM) mode. The resulting quantitative mass spectrometric immunoassay (MSIA) exhibited good linearity in the range of 1 to 1,500 ng/mL IGF1, intra- and inter-assay precision with CVs of less than 10%, and lowest limits of detection of 1 ng/mL. The linearity and recovery characteristics of the assay were also established, and the new method compared to a commercially available immunoassay using a large cohort of human serum samples. The IGF1 SRM MSIA is well suited for use in clinical laboratories. PMID:24278387

Range of protein detection by selected/multiple reaction monitoring mass spectrometry in an unfractionated human cell culture lysate.

PubMed

Ebhardt, H Alexander; Sabidó, Eduard; Hüttenhain, Ruth; Collins, Ben; Aebersold, Ruedi

2012-04-01

Selected or multiple reaction monitoring is a targeted mass spectrometry method (S/MRM-MS), in which many peptides are simultaneously and consistently analyzed during a single liquid chromatography-mass spectrometry (LC-S/MRM-MS) measurement. These capabilities make S/MRM-MS an attractive method to monitor a consistent set of proteins over various experimental conditions. To increase throughput for S/MRM-MS it is advantageous to use scheduled methods and unfractionated protein extracts. Here, we established the practically measurable dynamic range of proteins reliably detectable and quantifiable in an unfractionated protein extract from a human cell line using LC-S/MRM-MS. Initially, we analyzed S/MRM transition peak groups in terms of interfering signals and compared S/MRM transition peak groups to MS1-triggered MS2 spectra using dot-product analysis. Finally, using unfractionated protein extract from human cell lysate, we quantified the upper boundary of copies per cell to be 35 million copies per cell, while 7500 copies per cell represents a lower boundary using a single 35 min linear gradient LC-S/MRM-MS measurement on a current, standard commercial instrument. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A hybrid approach to urine drug testing using high-resolution mass spectrometry and select immunoassays.

PubMed

McMillin, Gwendolyn A; Marin, Stephanie J; Johnson-Davis, Kamisha L; Lawlor, Bryan G; Strathmann, Frederick G

2015-02-01

The major objective of this research was to propose a simplified approach for the evaluation of medication adherence in chronic pain management patients, using liquid chromatography time-of-flight (TOF) mass spectrometry, performed in parallel with select homogeneous enzyme immunoassays (HEIAs). We called it a "hybrid" approach to urine drug testing. The hybrid approach was defined based on anticipated positivity rates, availability of commercial reagents for HEIAs, and assay performance, particularly analytical sensitivity and specificity for drug(s) of interest. Subsequent to implementation of the hybrid approach, time to result was compared with that observed with other urine drug testing approaches. Opioids, benzodiazepines, zolpidem, amphetamine-like stimulants, and methylphenidate metabolite were detected by TOF mass spectrometry to maximize specificity and sensitivity of these 37 drug analytes. Barbiturates, cannabinoid metabolite, carisoprodol, cocaine metabolite, ethyl glucuronide, methadone, phencyclidine, propoxyphene, and tramadol were detected by HEIAs that performed adequately and/or for which positivity rates were very low. Time to result was significantly reduced compared with the traditional approach. The hybrid approach to urine drug testing provides a simplified and analytically specific testing process that minimizes the need for secondary confirmation. Copyright© by the American Society for Clinical Pathology.

HICOSMO - cosmology with a complete sample of galaxy clusters - I. Data analysis, sample selection and luminosity-mass scaling relation

NASA Astrophysics Data System (ADS)

Schellenberger, G.; Reiprich, T. H.

2017-08-01

The X-ray regime, where the most massive visible component of galaxy clusters, the intracluster medium, is visible, offers directly measured quantities, like the luminosity, and derived quantities, like the total mass, to characterize these objects. The aim of this project is to analyse a complete sample of galaxy clusters in detail and constrain cosmological parameters, like the matter density, Ωm, or the amplitude of initial density fluctuations, σ8. The purely X-ray flux-limited sample (HIFLUGCS) consists of the 64 X-ray brightest galaxy clusters, which are excellent targets to study the systematic effects, that can bias results. We analysed in total 196 Chandra observations of the 64 HIFLUGCS clusters, with a total exposure time of 7.7 Ms. Here, we present our data analysis procedure (including an automated substructure detection and an energy band optimization for surface brightness profile analysis) that gives individually determined, robust total mass estimates. These masses are tested against dynamical and Planck Sunyaev-Zeldovich (SZ) derived masses of the same clusters, where good overall agreement is found with the dynamical masses. The Planck SZ masses seem to show a mass-dependent bias to our hydrostatic masses; possible biases in this mass-mass comparison are discussed including the Planck selection function. Furthermore, we show the results for the (0.1-2.4) keV luminosity versus mass scaling relation. The overall slope of the sample (1.34) is in agreement with expectations and values from literature. Splitting the sample into galaxy groups and clusters reveals, even after a selection bias correction, that galaxy groups exhibit a significantly steeper slope (1.88) compared to clusters (1.06).

Sensitive ionization of non-volatile analytes using protein solutions as spray liquid in desorption electrospray ionization mass spectrometry.

PubMed

Zhu, Zhiqiang; Han, Jing; Zhang, Yan; Zhou, Yafei; Xu, Ning; Zhang, Bo; Gu, Haiwei; Chen, Huanwen

2012-12-15

Desorption electrospray ionization (DESI) is the most popular ambient ionization technique for direct analysis of complex samples without sample pretreatment. However, for many applications, especially for trace analysis, it is of interest to improve the sensitivity of DESI-mass spectrometry (MS). In traditional DESI-MS, a mixture of methanol/water/acetic acid is usually used to generate the primary ions. In this article, dilute protein solutions were electrosprayed in the DESI method to create multiply charged primary ions for the desorption ionization of trace analytes on various surfaces (e.g., filter paper, glass, Al-foil) without any sample pretreatment. The analyte ions were then detected and structurally characterized using a LTQ XL mass spectrometer. Compared with the methanol/water/acetic acid (49:49:2, v/v/v) solution, protein solutions significantly increased the signal levels of non-volatile compounds such as benzoic acid, TNT, o-toluidine, peptide and insulin in either positive or negative ion detection mode. For all the analytes tested, the limits of detection (LODs) were reduced to about half of the original values which were obtained using traditional DESI. The results showed that the signal enhancement is highly correlated with the molecular weight of the proteins and the selected solid surfaces. The proposed DESI method is a universal strategy for rapid and sensitive detection of trace amounts of strongly bound and/or non-volatile analytes, including explosives, peptides, and proteins. The results indicate that the sensitivity of DESI can be further improved by selecting larger proteins and appropriate solid surfaces. Copyright © 2012 John Wiley & Sons, Ltd.

Peak tree: a new tool for multiscale hierarchical representation and peak detection of mass spectrometry data.

PubMed

Zhang, Peng; Li, Houqiang; Wang, Honghui; Wong, Stephen T C; Zhou, Xiaobo

2011-01-01

Peak detection is one of the most important steps in mass spectrometry (MS) analysis. However, the detection result is greatly affected by severe spectrum variations. Unfortunately, most current peak detection methods are neither flexible enough to revise false detection results nor robust enough to resist spectrum variations. To improve flexibility, we introduce peak tree to represent the peak information in MS spectra. Each tree node is a peak judgment on a range of scales, and each tree decomposition, as a set of nodes, is a candidate peak detection result. To improve robustness, we combine peak detection and common peak alignment into a closed-loop framework, which finds the optimal decomposition via both peak intensity and common peak information. The common peak information is derived and loopily refined from the density clustering of the latest peak detection result. Finally, we present an improved ant colony optimization biomarker selection method to build a whole MS analysis system. Experiment shows that our peak detection method can better resist spectrum variations and provide higher sensitivity and lower false detection rates than conventional methods. The benefits from our peak-tree-based system for MS disease analysis are also proved on real SELDI data.

Detection of Listeria monocytogenes from selective enrichment broth using MALDI-TOF Mass Spectrometry.

PubMed

Jadhav, Snehal; Sevior, Danielle; Bhave, Mrinal; Palombo, Enzo A

2014-01-31

Conventional methods used for primary detection of Listeria monocytogenes from foods and subsequent confirmation of presumptive positive samples involve prolonged incubation and biochemical testing which generally require four to five days to obtain a result. In the current study, a simple and rapid proteomics-based MALDI-TOF MS approach was developed to detect L. monocytogenes directly from selective enrichment broths. Milk samples spiked with single species and multiple species cultures were incubated in a selective enrichment broth for 24h, followed by an additional 6h secondary enrichment. As few as 1 colony-forming unit (cfu) of L. monocytogenes per mL of initial selective broth culture could be detected within 30h. On applying the same approach to solid foods previously implicated in listeriosis, namely chicken pâté, cantaloupe and Camembert cheese, detection was achieved within the same time interval at inoculation levels of 10cfu/mL. Unlike the routine application of MALDI-TOF MS for identification of bacteria from solid media, this study proposes a cost-effective and time-saving detection scheme for direct identification of L. monocytogenes from broth cultures.This article is part of a Special Issue entitled: Trends in Microbial Proteomics. Globally, foodborne diseases are major causes of illness and fatalities in humans. Hence, there is a continual need for reliable and rapid means for pathogen detection from food samples. Recent applications of MALDI-TOF MS for diagnostic microbiology focused on detection of microbes from clinical specimens. However, the current study has emphasized its use as a tool for detecting the major foodborne pathogen, Listeria monocytogenes, directly from selective enrichment broths. This proof-of-concept study proposes a detection scheme that is more rapid and simple compared to conventional methods of Listeria detection. Very low levels of the pathogen could be identified from different food samples post-enrichment in selective enrichment broths. Use of this scheme will facilitate rapid and cost-effective testing for this important foodborne pathogen. © 2013.

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

Sharma, Seema; Simpson, David C.; Tolic, Nikola

We investigated the combination of weak anion exchange (WAX) fractionation and on-line reversed phase liquid chromatography (RPLC) separation using a 12 T FTICR mass spectrometer for the detection of intact proteins from a Shewanella oneidensis MR-1 cell lysate. 715 intact proteins were detected and the combined results from the WAX fractions and the unfractionated cell lysate were aligned using LC-MS features to facilitate protein abundance measurements. Protein identifications and post translational modifications were assigned for ~10% of the detected proteins by comparing intact protein mass measurements to proteins identified in peptide MS/MS analysis of an aliquot of the same fraction.more » Intact proteins were also detected for S. oneidensis lysates obtained from cells grown on 13C, 15N depleted media under aerobic and sub-oxic conditions. This work aimed at optimizing intact protein detection for profiling proteins at a level that incorporates their modification complement. The strategy can be readily applied for measuring differential protein abundances, and provides a platform for high-throughput selection of biologically relevant targets for further characterization.« less

Source selection for cluster weak lensing measurements in the Hyper Suprime-Cam survey

NASA Astrophysics Data System (ADS)

Medezinski, Elinor; Oguri, Masamune; Nishizawa, Atsushi J.; Speagle, Joshua S.; Miyatake, Hironao; Umetsu, Keiichi; Leauthaud, Alexie; Murata, Ryoma; Mandelbaum, Rachel; Sifón, Cristóbal; Strauss, Michael A.; Huang, Song; Simet, Melanie; Okabe, Nobuhiro; Tanaka, Masayuki; Komiyama, Yutaka

2018-03-01

We present optimized source galaxy selection schemes for measuring cluster weak lensing (WL) mass profiles unaffected by cluster member dilution from the Subaru Hyper Suprime-Cam Strategic Survey Program (HSC-SSP). The ongoing HSC-SSP survey will uncover thousands of galaxy clusters to z ≲ 1.5. In deriving cluster masses via WL, a critical source of systematics is contamination and dilution of the lensing signal by cluster members, and by foreground galaxies whose photometric redshifts are biased. Using the first-year CAMIRA catalog of ˜900 clusters with richness larger than 20 found in ˜140 deg2 of HSC-SSP data, we devise and compare several source selection methods, including selection in color-color space (CC-cut), and selection of robust photometric redshifts by applying constraints on their cumulative probability distribution function (P-cut). We examine the dependence of the contamination on the chosen limits adopted for each method. Using the proper limits, these methods give mass profiles with minimal dilution in agreement with one another. We find that not adopting either the CC-cut or P-cut methods results in an underestimation of the total cluster mass (13% ± 4%) and the concentration of the profile (24% ± 11%). The level of cluster contamination can reach as high as ˜10% at R ≈ 0.24 Mpc/h for low-z clusters without cuts, while employing either the P-cut or CC-cut results in cluster contamination consistent with zero to within the 0.5% uncertainties. Our robust methods yield a ˜60 σ detection of the stacked CAMIRA surface mass density profile, with a mean mass of M200c = [1.67 ± 0.05(stat)] × 1014 M⊙/h.

The masses of retired A stars with asteroseismology: Kepler and K2 observations of exoplanet hosts

NASA Astrophysics Data System (ADS)

North, Thomas S. H.; Campante, Tiago L.; Miglio, Andxsrea; Davies, Guy R.; Grunblatt, Samuel K.; Huber, Daniel; Kuszlewicz, James S.; Lund, Mikkel N.; Cooke, Benjamin F.; Chaplin, William J.

2017-12-01

We investigate the masses of 'retired A stars' using asteroseismic detections on seven low-luminosity red-giant and sub-giant stars observed by the NASA Kepler and K2 missions. Our aim is to explore whether masses derived from spectroscopy and isochrone fitting may have been systematically overestimated. Our targets have all previously been subject to long-term radial velocity observations to detect orbiting bodies, and satisfy the criteria used by Johnson et al. to select survey stars which may have had A-type (or early F-type) main-sequence progenitors. The sample actually spans a somewhat wider range in mass, from ≈ 1 M⊙ up to ≈ 1.7 M⊙. Whilst for five of the seven stars the reported discovery mass from spectroscopy exceeds the mass estimated using asteroseismology, there is no strong evidence for a significant, systematic bias across the sample. Moreover, comparisons with other masses from the literature show that the absolute scale of any differences is highly sensitive to the chosen reference literature mass, with the scatter between different literature masses significantly larger than reported error bars. We find that any mass difference can be explained through use of different constraints during the recovery process. We also conclude that underestimated uncertainties on the input parameters can significantly bias the recovered stellar masses, which may have contributed to the controversy on the mass scale for retired A stars.

Identification of the nitrogen-based blister agents bis(2-chloroethyl)methylamine (HN-2) and tris(2-chloroethyl)amine (HN-3) and their hydrolysis products on soil using ion trap secondary ion mass spectrometry.

PubMed

Gresham, G L; Groenewold, G S; Olson, J E

2000-12-01

The nitrogen blister agents HN-2 (bis(2-chloroethyl)methylamine) and HN-3 (tris(2-chloroethyl)amine) were directly analyzed on the surface of soil samples using ion trap secondary ion mass spectrometry (SIMS). In the presence of water, HN-1 (bis(2-choroethyl)ethylamine), HN-2 and HN-3 undergo hydrolysis to form N-ethyldiethanolamine, N-methyldiethanolamine and triethanolamine (TEA), respectively; these compounds can be readily detected as adsorbed species on soil particles. When soil samples spiked with HN-3 in alcohol were analyzed, 2-alkoxyethylamine derivatives were observed on the sample surfaces. This result shows that nitrogen blister agents will undergo condensation reactions with nucleophilic compounds and emphasizes the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of ion trap SIMS to isolate and accumulate ions, and then perform tandem mass spectrometric analysis improves the detection of low-abundance surface contaminants and the selectivity of the technique. Utilizing these techniques, the limits of detection for HN-3 were studied as a function of surface coverage. It was found that HN-3 could be detected at a surface coverage of 0.01 monolayer, which corresponds to 20 ppm (mass/mass) for a soil having a surface area of 2.2 m(2) g(-1). TEA, the exhaustive hydrolysis product of HN-3, was detected at a surface coverage of 0.001 monolayer, which corresponds to 0.86 ppm. Copyright 2000 John Wiley & Sons, Ltd.

Planck/SDSS Cluster Mass and Gas Scaling Relations for a Volume-Complete redMaPPer Sample

NASA Astrophysics Data System (ADS)

Jimeno, Pablo; Diego, Jose M.; Broadhurst, Tom; De Martino, I.; Lazkoz, Ruth

2018-04-01

Using Planck satellite data, we construct Sunyaev-Zel'dovich (SZ) gas pressure profiles for a large, volume-complete sample of optically selected clusters. We have defined a sample of over 8,000 redMaPPer clusters from the Sloan Digital Sky Survey (SDSS), within the volume-complete redshift region 0.100 < z < 0.325, for which we construct SZ effect maps by stacking Planck data over the full range of richness. Dividing the sample into richness bins we simultaneously solve for the mean cluster mass in each bin together with the corresponding radial pressure profile parameters, employing an MCMC analysis. These profiles are well detected over a much wider range of cluster mass and radius than previous work, showing a clear trend towards larger break radius with increasing cluster mass. Our SZ-based masses fall ˜16% below the mass-richness relations from weak lensing, in a similar fashion as the "hydrostatic bias" related with X-ray derived masses. Finally, we derive a tight Y500-M500 relation over a wide range of cluster mass, with a power law slope equal to 1.70 ± 0.07, that agrees well with the independent slope obtained by the Planck team with an SZ-selected cluster sample, but extends to lower masses with higher precision.

Mammogram segmentation using maximal cell strength updation in cellular automata.

PubMed

Anitha, J; Peter, J Dinesh

2015-08-01

Breast cancer is the most frequently diagnosed type of cancer among women. Mammogram is one of the most effective tools for early detection of the breast cancer. Various computer-aided systems have been introduced to detect the breast cancer from mammogram images. In a computer-aided diagnosis system, detection and segmentation of breast masses from the background tissues is an important issue. In this paper, an automatic segmentation method is proposed to identify and segment the suspicious mass regions of mammogram using a modified transition rule named maximal cell strength updation in cellular automata (CA). In coarse-level segmentation, the proposed method performs an adaptive global thresholding based on the histogram peak analysis to obtain the rough region of interest. An automatic seed point selection is proposed using gray-level co-occurrence matrix-based sum average feature in the coarse segmented image. Finally, the method utilizes CA with the identified initial seed point and the modified transition rule to segment the mass region. The proposed approach is evaluated over the dataset of 70 mammograms with mass from mini-MIAS database. Experimental results show that the proposed approach yields promising results to segment the mass region in the mammograms with the sensitivity of 92.25% and accuracy of 93.48%.

Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

NASA Astrophysics Data System (ADS)

Graichen, Adam M.; Vachet, Richard W.

2013-06-01

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

Rapid quantification of iodopropynyl butylcarbamate as the preservative in cosmetic formulations using high-performance liquid chromatography-electrospray mass spectrometry.

PubMed

Frauen, M; Steinhart, H; Rapp, C; Hintze, U

2001-07-01

A simple, rapid and reproducible method for identification and quantification of iodopropynyl butylcarbamate (IPBC) in different cosmetic formulations is presented. The determination was carried out using a high-performance liquid chromatography (HPLC) procedure on a reversed phase column coupled to a single quadrupole mass spectrometer (MS) via an electrospray ionization (ESI) interface. Detection was performed in the positive selected ion-monitoring mode. In methanol/water extracts from different cosmetic formulations a detection limit between 50 and 100 ng/g could be achieved. A routine analytical procedure could be set up with good quantification reliability (relative standard deviation between 0.9 and 2.9%).

Recent Advances in Bacteria Identification by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Using Nanomaterials as Affinity Probes

PubMed Central

Chiu, Tai-Chia

2014-01-01

Identifying trace amounts of bacteria rapidly, accurately, selectively, and with high sensitivity is important to ensuring the safety of food and diagnosing infectious bacterial diseases. Microbial diseases constitute the major cause of death in many developing and developed countries of the world. The early detection of pathogenic bacteria is crucial in preventing, treating, and containing the spread of infections, and there is an urgent requirement for sensitive, specific, and accurate diagnostic tests. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is an extremely selective and sensitive analytical tool that can be used to characterize different species of pathogenic bacteria. Various functionalized or unmodified nanomaterials can be used as affinity probes to capture and concentrate microorganisms. Recent developments in bacterial detection using nanomaterials-assisted MALDI-MS approaches are highlighted in this article. A comprehensive table listing MALDI-MS approaches for identifying pathogenic bacteria, categorized by the nanomaterials used, is provided. PMID:24786089

Evaluation of gas chromatography-tandem quadrupole mass spectrometry for the determination of organochlorine pesticides in fats and oils.

PubMed

Patel, Katan; Fussell, Richard J; Hetmanski, Mike; Goodall, David M; Keely, Brendan J

2005-03-18

A gas chromatography-tandem quadrupole mass spectrometry multi-residue method for the analysis of 19 organochlorine pesticides in fats and oils has been developed. Gel permeation chromatography was employed to remove lipid material prior to GC-MS/MS analysis. Average recoveries of the pesticides spiked at 10 and 50 microg kg(-1) into fish oil, pork fat, olive oil and hydrogenated vegetable oil were typically in the range 70-110% with relative standard deviations generally less than 10%. Calculated limits of detection are between 0.1 and 2.0 microg kg(-1) and results obtained for the analysis of proficiency test materials are in good agreement with assigned values. The higher selectivity of the GC-MS/MS compared to electron capture detection and GC-MS in selective ion monitoring mode allowed unambiguous identification and confirmation of all the target pesticides at low microg kg(-1) levels in fats and oils in a single analysis.

Recent advances in bacteria identification by matrix-assisted laser desorption/ionization mass spectrometry using nanomaterials as affinity probes.

PubMed

Chiu, Tai-Chia

2014-04-28

Identifying trace amounts of bacteria rapidly, accurately, selectively, and with high sensitivity is important to ensuring the safety of food and diagnosing infectious bacterial diseases. Microbial diseases constitute the major cause of death in many developing and developed countries of the world. The early detection of pathogenic bacteria is crucial in preventing, treating, and containing the spread of infections, and there is an urgent requirement for sensitive, specific, and accurate diagnostic tests. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is an extremely selective and sensitive analytical tool that can be used to characterize different species of pathogenic bacteria. Various functionalized or unmodified nanomaterials can be used as affinity probes to capture and concentrate microorganisms. Recent developments in bacterial detection using nanomaterials-assisted MALDI-MS approaches are highlighted in this article. A comprehensive table listing MALDI-MS approaches for identifying pathogenic bacteria, categorized by the nanomaterials used, is provided.

Rapid determination of organochlorine pesticides and polychlorinated biphenyls, using selected ion monitoring mass spectrometry

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

Hargesheimer, E.E.

Methane chemical ionization (CI)-selected ion monitoring (SIM) mass spectrometry was used to identify and conclusively distinguish 19 organochlorine pesticides from polychlorinated biphenyls (PCBs) at parts-per-trillion to parts-per-billion levels in environmental water sample extracts with minimal sample cleanup. Two CI-SIM screens were developed. One set of ions scanned specifically for the presence of 4 classes of pesticides; diphenylmethane derivatives, bridged polycyclic chlorinated benzenes, and acetanilide pesticides. The second set of ions responded exclusively to PCBs with biphenyl moieties containing from 1 to 8 chlorine atoms. Eight commercial Aroclor mixtures were analyzed and distinguished from the pesticides groups. The detection limit formore » pesticides and PCBs by CI-SIM screening was 0.005 and 0.1 ppB, respectively. CI-SIM can be used as an alternative method for the analysis of biological or environmental samples containing interferences that complicate the detection of PCBs and chlorinated pesticides. 8 references, 6 figures, 6 tables.« less

Mass spectrometry of selective androgen receptor modulators.

PubMed

Thevis, Mario; Schänzer, Wilhelm

2008-07-01

Nonsteroidal selective androgen receptor modulators (SARMs) are an emerging class of drugs for treatment of various diseases including osteoporosis and muscle wasting as well as the correction of age-related functional decline such as muscle strength and power. Several SARMs, which have advanced to preclinical and clinical trials, are composed of diverse chemical structures including arylpropionamide-, bicyclic hydantoin-, quinoline-, and tetrahydroquinoline-derived nuclei. Since January 2008, SARMs have been categorized as anabolic agents and prohibited by the World Anti-Doping Agency (WADA). Suitable detection methods for these low-molecular weight drugs were based on mass spectrometric approaches, which necessitated the elucidation of dissociation pathways in order to characterize and identify the target analytes in doping control samples as well as potential metabolic products and synthetic analogs. Fragmentation patterns of representatives of each category of SARMs after electrospray ionization (ESI) and collision-induced dissociation (CID) as well as electron ionization (EI) are summarized. The complexity and structural heterogeneity of these drugs is a daunting challenge for detection methods. Copyright 2008 John Wiley & Sons, Ltd.

Multidimensional gas chromatography in combination with accurate mass, tandem mass spectrometry, and element-specific detection for identification of sulfur compounds in tobacco smoke.

PubMed

Ochiai, Nobuo; Mitsui, Kazuhisa; Sasamoto, Kikuo; Yoshimura, Yuta; David, Frank; Sandra, Pat

2014-09-05

A method is developed for identification of sulfur compounds in tobacco smoke extract. The method is based on large volume injection (LVI) of 10μL of tobacco smoke extract followed by selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography (GC) coupled to a hybrid quadrupole time-of-flight mass spectrometer (Q-TOF-MS) using electron ionization (EI) and positive chemical ionization (PCI), with parallel sulfur chemiluminescence detection (SCD). In order to identify each individual sulfur compound, sequential heart-cuts of 28 sulfur fractions from (1)D GC to (2)D GC were performed with the three MS detection modes (SCD/EI-TOF-MS, SCD/PCI-TOF-MS, and SCD/PCI-Q-TOF-MS). Thirty sulfur compounds were positively identified by MS library search, linear retention indices (LRI), molecular mass determination using PCI accurate mass spectra, formula calculation using EI and PCI accurate mass spectra, and structure elucidation using collision activated dissociation (CAD) of the protonated molecule. Additionally, 11 molecular formulas were obtained for unknown sulfur compounds. The determined values of the identified and unknown sulfur compounds were in the range of 10-740ngmg total particulate matter (TPM) (RSD: 1.2-12%, n=3). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

High-field modulated ion-selective field-effect-transistor (FET) sensors with sensitivity higher than the ideal Nernst sensitivity.

PubMed

Chen, Yi-Ting; Sarangadharan, Indu; Sukesan, Revathi; Hseih, Ching-Yen; Lee, Geng-Yen; Chyi, Jen-Inn; Wang, Yu-Lin

2018-05-29

Lead ion selective membrane (Pb-ISM) coated AlGaN/GaN high electron mobility transistors (HEMT) was used to demonstrate a whole new methodology for ion-selective FET sensors, which can create ultra-high sensitivity (-36 mV/log [Pb 2+ ]) surpassing the limit of ideal sensitivity (-29.58 mV/log [Pb 2+ ]) in a typical Nernst equation for lead ion. The largely improved sensitivity has tremendously reduced the detection limit (10 -10  M) for several orders of magnitude of lead ion concentration compared to typical ion-selective electrode (ISE) (10 -7  M). The high sensitivity was obtained by creating a strong filed between the gate electrode and the HEMT channel. Systematical investigation was done by measuring different design of the sensor and gate bias, indicating ultra-high sensitivity and ultra-low detection limit obtained only in sufficiently strong field. Theoretical study in the sensitivity consistently agrees with the experimental finding and predicts the maximum and minimum sensitivity. The detection limit of our sensor is comparable to that of Inductively-Coupled-Plasma Mass Spectrum (ICP-MS), which also has detection limit near 10 -10  M.

Monitoring/Verification using DMS: TATP Example

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

Stephan Weeks, Kevin Kyle, Manuel Manard

Field-rugged and field-programmable differential mobility spectrometry (DMS) networks provide highly selective, universal monitoring of vapors and aerosols at detectable levels from persons or areas involved with illicit chemical/biological/explosives (CBE) production. CBE sensor motes used in conjunction with automated fast gas chromatography with DMS detection (GC/DMS) verification instrumentation integrated into situational operations-management systems can be readily deployed and optimized for changing application scenarios. The feasibility of developing selective DMS motes for a “smart dust” sampling approach with guided, highly selective, fast GC/DMS verification analysis is a compelling approach to minimize or prevent the illegal use of explosives or chemical and biologicalmore » materials. DMS is currently one of the foremost emerging technologies for field separation and detection of gas-phase chemical species. This is due to trace-level detection limits, high selectivity, and small size. Fast GC is the leading field analytical method for gas phase separation of chemical species in complex mixtures. Low-thermal-mass GC columns have led to compact, low-power field systems capable of complete analyses in 15–300 seconds. A collaborative effort optimized a handheld, fast GC/DMS, equipped with a non-rad ionization source, for peroxide-based explosive measurements.« less

Monitoring/Verification Using DMS: TATP Example

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

Kevin Kyle; Stephan Weeks

Field-rugged and field-programmable differential mobility spectrometry (DMS) networks provide highly selective, universal monitoring of vapors and aerosols at detectable levels from persons or areas involved with illicit chemical/biological/explosives (CBE) production. CBE sensor motes used in conjunction with automated fast gas chromatography with DMS detection (GC/DMS) verification instrumentation integrated into situational operationsmanagement systems can be readily deployed and optimized for changing application scenarios. The feasibility of developing selective DMS motes for a “smart dust” sampling approach with guided, highly selective, fast GC/DMS verification analysis is a compelling approach to minimize or prevent the illegal use of explosives or chemical and biologicalmore » materials. DMS is currently one of the foremost emerging technologies for field separation and detection of gas-phase chemical species. This is due to trace-level detection limits, high selectivity, and small size. GC is the leading analytical method for the separation of chemical species in complex mixtures. Low-thermal-mass GC columns have led to compact, low-power field systems capable of complete analyses in 15–300 seconds. A collaborative effort optimized a handheld, fast GC/DMS, equipped with a non-rad ionization source, for peroxide-based explosive measurements.« less

Two-dimensional on-line detection of brominated and iodinated volatile organic compounds by ECD and ICP-MS after GC separation.

PubMed

Schwarz, A; Heumann, K G

2002-09-01

Inductively coupled plasma-mass spectrometry (ICP-MS) was coupled to a gas chromatographic (GC) system with electron capture detector (ECD), which enables relatively easy characterization and quantification of brominated and iodinated (halogenated) volatile organic compounds (HVOCs) in aquatic and air samples. The GC-ECD system is connected in series with an ICP-MS by a directly heated transfer line and an outlet port-hole for elimination of the ECD make-up gas during ignition of the plasma. The hyphenated GC-ECD/ICP-MS system provides high selectivity and sensitivity for monitoring individual HVOCs under fast chromatographic conditions. The ECD is most sensitive for the detection of chlorinated and brominated but the ICP-MS for iodinated compounds. The greatest advantage of the use of an ICP-MS is its element-specific detection, which allows clear identification of compounds in most cases. The absolute detection limits for ICP-MS are 0.5 pg for iodinated, 10 pg for brominated, and 50 pg for chlorinated HVOCs with the additional advantage that calibration is almost independent on different compounds of the same halogen. In contrast to that detection limits for ECD vary for the different halogenated compounds and lie in the range of 0.03-11 pg. The two-dimensional GC-ECD/ICP-MS instrumentation is compared with electron impact mass spectrometry (EI-MS) and microwave induced plasma atomic emission detection (MIP-AED). Even if EI-MS has additional power in identifying unknown peaks by its scan mode, the detection limits are much higher compared with GC-ECD/ICP-MS, whereas the selective ion monitoring mode (SIM) reaches similar detection limits. The MIP-AED detection limits are at the same level as EI-MS in the scan mode.

Environment-based selection effects of Planck clusters

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

Kosyra, R.; Gruen, D.; Seitz, S.

2015-07-24

We investigate whether the large-scale structure environment of galaxy clusters imprints a selection bias on Sunyaev–Zel'dovich (SZ) catalogues. Such a selection effect might be caused by line of sight (LoS) structures that add to the SZ signal or contain point sources that disturb the signal extraction in the SZ survey. We use the Planck PSZ1 union catalogue in the Sloan Digital Sky Survey (SDSS) region as our sample of SZ-selected clusters. We calculate the angular two-point correlation function (2pcf) for physically correlated, foreground and background structure in the RedMaPPer SDSS DR8 catalogue with respect to each cluster. We compare ourmore » results with an optically selected comparison cluster sample and with theoretical predictions. In contrast to the hypothesis of no environment-based selection, we find a mean 2pcf for background structures of -0.049 on scales of ≲40 arcmin, significantly non-zero at ~4σ, which means that Planck clusters are more likely to be detected in regions of low background density. We hypothesize this effect arises either from background estimation in the SZ survey or from radio sources in the background. We estimate the defect in SZ signal caused by this effect to be negligibly small, of the order of ~10 -4 of the signal of a typical Planck detection. Analogously, there are no implications on X-ray mass measurements. However, the environmental dependence has important consequences for weak lensing follow up of Planck galaxy clusters: we predict that projection effects account for half of the mass contained within a 15 arcmin radius of Planck galaxy clusters. We did not detect a background underdensity of CMASS LRGs, which also leaves a spatially varying redshift dependence of the Planck SZ selection function as a possible cause for our findings.« less

Real-Time Ozone Detection Based on a Microfabricated Quartz Crystal Tuning Fork Sensor

PubMed Central

Wang, Rui; Tsow, Francis; Zhang, Xuezhi; Peng, Jhih-Hong; Forzani, Erica S.; Chen, Yongsheng; Crittenden, John C.; Destaillats, Hugo; Tao, Nongjian

2009-01-01

A chemical sensor for ozone based on an array of microfabricated tuning forks is described. The tuning forks are highly sensitive and stable, with low power consumption and cost. The selective detection is based on the specific reaction of the polymer with ozone. With a mass detection limit of ∼2 pg/mm2 and response time of 1 second, the sensor coated with a polymer sensing material can detect ppb-level ozone in air. The sensor is integrated into a miniaturized wearable device containing a detection circuit, filtration, battery and wireless communication chip, which is ideal for personal and microenvironmental chemical exposure monitoring. PMID:22346720

Simultaneous Proteomic Discovery and Targeted Monitoring using Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry*

PubMed Central

Burnum-Johnson, Kristin E.; Nie, Song; Casey, Cameron P.; Monroe, Matthew E.; Orton, Daniel J.; Ibrahim, Yehia M.; Gritsenko, Marina A.; Clauss, Therese R. W.; Shukla, Anil K.; Moore, Ronald J.; Purvine, Samuel O.; Shi, Tujin; Qian, Weijun; Liu, Tao; Baker, Erin S.; Smith, Richard D.

2016-01-01

Current proteomic approaches include both broad discovery measurements and quantitative targeted analyses. In many cases, discovery measurements are initially used to identify potentially important proteins (e.g. candidate biomarkers) and then targeted studies are employed to quantify a limited number of selected proteins. Both approaches, however, suffer from limitations. Discovery measurements aim to sample the whole proteome but have lower sensitivity, accuracy, and quantitation precision than targeted approaches, whereas targeted measurements are significantly more sensitive but only sample a limited portion of the proteome. Herein, we describe a new approach that performs both discovery and targeted monitoring (DTM) in a single analysis by combining liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS). In DTM, heavy labeled target peptides are spiked into tryptic digests and both the labeled and unlabeled peptides are detected using LC-IMS-MS instrumentation. Compared with the broad LC-MS discovery measurements, DTM yields greater peptide/protein coverage and detects lower abundance species. DTM also achieved detection limits similar to selected reaction monitoring (SRM) indicating its potential for combined high quality discovery and targeted analyses, which is a significant step toward the convergence of discovery and targeted approaches. PMID:27670688

Rapid and selective determination of multi-sulfonamides by high-performance thin layer chromatography coupled to fluorescent densitometry and electrospray ionization mass detection.

PubMed

Chen, Yisheng; Schwack, Wolfgang

2014-02-28

In the European Union (EU), sulfonamides are among the most widely administrated groups of antibiotics in animal husbandry. Therefore, monitoring their residues in edible animal tissues plays an important role in the EU food safety framework. In this work, a simple and efficient method for the rapid screening of twelve prior sulfonamides frequently prescribed as veterinary drugs by high-performance thin-layer chromatography (HPTLC) was established. Sample extracts obtained with acetonitrile were tenfold concentrated and applied to HPTLC without any further cleanup. Following separation and fluram derivatization, sensitive and selective quantitation of the analytes can readily be accomplished with fluorescent densitometry. Limits of detection and quantitation were 15-40 and 35-70μg/kg, respectively. Additionally, a confirmative detection by HPTLC-electrospray ionization mass spectrometry (HPTLC-ESI/MS) was optimized, offering straightforward identification of target zones. Therefore, the risk of potential false positive findings can efficiently be reduced. The method was validated to meet the enforced commission regulation (EU) No. 37/2010, regarding different matrix complexities (bovine milk, porcine liver and kidney). Copyright © 2014 Elsevier B.V. All rights reserved.

Application of Targeted Mass Spectrometry for the Quantification of Sirtuins in the Central Nervous System

NASA Astrophysics Data System (ADS)

Jayasena, T.; Poljak, A.; Braidy, N.; Zhong, L.; Rowlands, B.; Muenchhoff, J.; Grant, R.; Smythe, G.; Teo, C.; Raftery, M.; Sachdev, P.

2016-10-01

Sirtuin proteins have a variety of intracellular targets, thereby regulating multiple biological pathways including neurodegeneration. However, relatively little is currently known about the role or expression of the 7 mammalian sirtuins in the central nervous system. Western blotting, PCR and ELISA are the main techniques currently used to measure sirtuin levels. To achieve sufficient sensitivity and selectivity in a multiplex-format, a targeted mass spectrometric assay was developed and validated for the quantification of all seven mammalian sirtuins (SIRT1-7). Quantification of all peptides was by multiple reaction monitoring (MRM) using three mass transitions per protein-specific peptide, two specific peptides for each sirtuin and a stable isotope labelled internal standard. The assay was applied to a variety of samples including cultured brain cells, mammalian brain tissue, CSF and plasma. All sirtuin peptides were detected in the human brain, with SIRT2 being the most abundant. Sirtuins were also detected in human CSF and plasma, and guinea pig and mouse tissues. In conclusion, we have successfully applied MRM mass spectrometry for the detection and quantification of sirtuin proteins in the central nervous system, paving the way for more quantitative and functional studies.

Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas.

PubMed

Benham, Kevin; Hodyss, Robert; Fernández, Facundo M; Orlando, Thomas M

2016-11-01

We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation. Graphical Abstract ᅟ.

Development of a fiber coating based on molecular sol-gel imprinting technology for selective solid-phase micro extraction of caffeine from human serum and determination by gas chromatography/mass spectrometry.

PubMed

Rajabi Khorrami, Afshin; Rashidpur, Amene

2012-05-21

In this work, a molecular sol-gel imprinting approach has been introduced to produce a fiber coating for selective direct immersion solid-phase microextraction (SPME) of caffeine. The polymerization mixture was composed of vinyl trimethoxysilane and methacrylic acid as vinyl sol-gel precursor and functional monomer, respectively. Caffeine was used as template molecule during polymerization process. The prepared fibers could be coupled directly to gas chromatography/mass spectrometry (GC/MS) and used for trace analysis of caffeine in a complex sample such as human serum. The parameters influencing SPME such as time, temperature and stirring speed were optimized. The prepared coating showed good selectivity towards caffeine in the presence of some structurally related compounds. Also, it offered high imprinting capability in comparison to bare fiber and non-imprinted coating. Linear range for caffeine detection was 1-80 μg mL(-1) and the limit of detection was 0.1 μg mL(-1). The intra-day and inter-day precisions of the peak areas for five replicates were 10 and 16%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Highly sensitive and selective detection of Al(III) ions in aqueous buffered solution with fluorescent peptide-based sensor.

PubMed

In, Byunggyu; Hwang, Gi Won; Lee, Keun-Hyeung

2016-09-15

A fluorescent sensor based on a tripeptide (SerGluGlu) with a dansyl fluorophore detected selectively Al(III) among 16 metal ions in aqueous buffered solutions without any organic cosolvent. The peptide-based sensor showed a highly sensitive turn on response to aluminium ion with high binding affinity (1.84×10(4)M(-1)) in aqueous buffered solutions. The detection limit (230nM, 5.98ppb) of the peptide-based sensor was much lower than the maximum allowable level (7.41μM) of aluminium ions in drinking water demanded by EPA. The binding mode of the peptide sensor with aluminium ions was characterized using ESI mass spectrometry, NMR titration, and pH titration experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Material radioassay and selection for the XENON1T dark matter experiment

NASA Astrophysics Data System (ADS)

Aprile, E.; Aalbers, J.; Agostini, F.; Alfonsi, M.; Amaro, F. D.; Anthony, M.; Arneodo, F.; Barrow, P.; Baudis, L.; Bauermeister, B.; Benabderrahmane, M. L.; Berger, T.; Breur, P. A.; Brown, A.; Brown, E.; Bruenner, S.; Bruno, G.; Budnik, R.; Bütikofer, L.; Calvén, J.; Cardoso, J. M. R.; Cervantes, M.; Cichon, D.; Coderre, D.; Colijn, A. P.; Conrad, J.; Cussonneau, J. P.; Decowski, M. P.; de Perio, P.; Di Gangi, P.; Di Giovanni, A.; Diglio, S.; Eurin, G.; Fei, J.; Ferella, A. D.; Fieguth, A.; Franco, D.; Fulgione, W.; Gallo Rosso, A.; Galloway, M.; Gao, F.; Garbini, M.; Geis, C.; Goetzke, L. W.; Grandi, L.; Greene, Z.; Grignon, C.; Hasterok, C.; Hogenbirk, E.; Itay, R.; Kaminsky, B.; Kessler, G.; Kish, A.; Landsman, H.; Lang, R. F.; Lellouch, D.; Levinson, L.; Le Calloch, M.; Lin, Q.; Lindemann, S.; Lindner, M.; Lopes, J. A. M.; Manfredini, A.; Maris, I.; Marrodán Undagoitia, T.; Masbou, J.; Massoli, F. V.; Masson, D.; Mayani, D.; Messina, M.; Micheneau, K.; Miguez, B.; Molinario, A.; Murra, M.; Naganoma, J.; Ni, K.; Oberlack, U.; Pakarha, P.; Pelssers, B.; Persiani, R.; Piastra, F.; Pienaar, J.; Piro, M.-C.; Pizzella, V.; Plante, G.; Priel, N.; Rauch, L.; Reichard, S.; Reuter, C.; Rizzo, A.; Rosendahl, S.; Rupp, N.; Saldanha, R.; dos Santos, J. M. F.; Sartorelli, G.; Scheibelhut, M.; Schindler, S.; Schreiner, J.; Schumann, M.; Scotto Lavina, L.; Selvi, M.; Shagin, P.; Shockley, E.; Silva, M.; Simgen, H.; Sivers, M. v.; Stein, A.; Thers, D.; Tiseni, A.; Trinchero, G.; Tunnell, C.; Upole, N.; Wang, H.; Wei, Y.; Weinheimer, C.; Wulf, J.; Ye, J.; Zhang, Y.; Laubenstein, M.; Nisi, S.

2017-12-01

The XENON1T dark matter experiment aims to detect weakly interacting massive particles (WIMPs) through low-energy interactions with xenon atoms. To detect such a rare event necessitates the use of radiopure materials to minimize the number of background events within the expected WIMP signal region. In this paper we report the results of an extensive material radioassay campaign for the XENON1T experiment. Using gamma-ray spectroscopy and mass spectrometry techniques, systematic measurements of trace radioactive impurities in over one hundred samples within a wide range of materials were performed. The measured activities allowed for stringent selection and placement of materials during the detector construction phase and provided the input for XENON1T detection sensitivity estimates through Monte Carlo simulations.

Highly selective and sensitive detection of Cu2+ with lysine enhancing bovine serum albumin modified-carbon dots fluorescent probe.

PubMed

Liu, Jia-Ming; Lin, Li-ping; Wang, Xin-Xing; Lin, Shao-Qin; Cai, Wen-Lian; Zhang, Li-Hong; Zheng, Zhi-Yong

2012-06-07

Based on the ability of lysine (Lys) to enhance the fluorescence intensity of bovine serum albumin modified-carbon dots (CDs-BSA) to decrease surface defects and quench fluorescence of the CDs-BSA-Lys system in the presence of Cu(2+) under conditions of phosphate buffer (PBS, pH = 5.0) at 45 °C for 10 min, a sensitive Lys enhancing CDs-BSA fluorescent probe was designed. The environment-friendly, simple, rapid, selective and sensitive fluorescent probe has been utilized to detect Cu(2+) in hair and tap water samples and it achieved consistent results with those obtained by inductively coupled plasma mass spectroscopy (ICP-MS). The mechanism of the proposed assay for the detection of Cu(2+) is discussed.

Naphthaldimine-based simple glucose derivative as a highly selective sensor for colorimetric detection of Cu2+ ion in aqueous media

NASA Astrophysics Data System (ADS)

Dolai, Bholanath; Bhaumik, Atanu; Pramanik, Nabakumar; Ghosh, Kalyan Sundar; Atta, Ananta Kumar

2018-07-01

Naphthaldimine-based glucose derivatives 1 and 3 have been designed, synthesized and characterized. In aqueous media, glucose derivative 1, exhibited high selectivity and sensitivity towards Cu2+ ion in comparison with various cations and anions. In presence of Cu2+, sensor 1 has provided significant naked-eye detectable color change. The formation of 1-Cu2+ complex has been analyzed by UV-vis spectroscopy, 1H NMR titration experiments, mass spectrometry and DFT (density functional theory) calculations. Limit of detection of 1 as a colorimetric sensor for Cu2+ ion is found to be 0.23 μM, much lower than recommended value of World Health Organization (WHO), which makes to Cu2+ sensor 1 more effective and useful.

[Determination of Heavy Metal Elements in Diatomite Filter Aid by Inductively Coupled Plasma Mass Spectrometry].

PubMed

Nie, Xi-du; Fu, Liang

2015-11-01

This study established a method for determining Be, Cr, Ni, As, Cd, Sb, Sn, Tl, Hg and Pb, total 10 heavy metals in diatomite filter aid. The diatomite filter aid was digested by using the mixture acid of HNO₃ + HF+ H₃PO₄ in microwave system, 10 heavy metals elements were determined by inductively coupled plasma mass spectrometry (ICP-MS). The interferences of mass spectrometry caused by the high silicon substrate were optimized, first the equipment parameters and isotopes of test metals were selected to eliminate these interferences, the methane was selected as reactant gas, and the mass spectral interferences were eliminated by dynamic reaction cell (DRC). Li, Sc, Y, In and Bi were selected as the internal standard elements to correct the interferences caused by matrix and the drift of sensitivity. The results show that the detection limits for analyte is in the range of 3.29-15.68 ng · L⁻¹, relative standard deviations (RSD) is less than 4.62%, and the recovery is in the range of 90.71%-107.22%. The current method has some advantages such as, high sensitivity, accurate, and precision, which can be used in diatomite filter aid quality control and safety estimations.

Quantitative thin-layer chromatography/mass spectrometry analysis of caffeine using a surface sampling probe electrospray ionization tandem mass spectrometry system.

PubMed

Ford, Michael J; Deibel, Michael A; Tomkins, Bruce A; Van Berkel, Gary J

2005-07-15

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 mum/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 muL) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by approximately 8% or more) than the literature values.

Capillary moving-boundary isotachophoresis with electrospray ionization mass-spectrometric detection and hydrogen ion used as essential terminator: Methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides in waters.

PubMed

Malá, Zdena; Gebauer, Petr

2017-10-06

Capillary isotachophoresis (ITP) is an electrophoretic technique offering high sensitivity due to permanent stacking of the migrating analytes. Its combination with electrospray-ionization mass-spectrometric (ESI-MS) detection is limited by the narrow spectrum of ESI-compatible components but can be compensated by experienced system architecture. This work describes a methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides, based on implementation of the concepts of moving-boundary isotachophoresis and of H + as essential terminating component into cationic ITP with ESI-MS detection. Theoretical description of such kind of system is given and equations for zone-related boundary mobilities are derived, resulting in a much more general definition of the effective mobility of the terminating H + zone than used so far. Explicit equations allowing direct calculation for selected simple systems are derived. The presented theory allows prediction of stacking properties of particular systems and easy selection of suitable electrolyte setups. A simple ESI-compatible system composed of acetic acid and ammonium with H + and ammonium as a mixed terminator was selected for the analysis of 2-hydroxyatrazine and 2-hydroxyterbutylazine, degradation products of s-triazine herbicides. The proposed method was tested with direct injection without any sample pretreatment and provided excellent linearity and high sensitivity with limits of detection below 100ng/L (0.5nM). Example analyses of unspiked and spiked drinking and river water are shown. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Profiles for Lung Cancer Pathogenesis and Detection in US Veterans

DTIC Science & Technology

2012-10-01

will be further strengthened via Multiple Reaction Monitoring ( MRM ) performed on the remaining samples by the Vanderbilt group. MRM using mass...proteomics detects all protein changes in the sample in an unfocused fashion, MRM is targeted and highly selective, allowing us to specifically look for...proteins of interest. To this end, we have generated a list of candidate proteins for MRM utilizing shotgun proteomic, mRNA array, and miRNA array

Design and development of a fast ion mass spectrometer

NASA Technical Reports Server (NTRS)

Burch, J. L.

1983-01-01

Two Fast Ion Mass Spectrometers (FIMS A and FIMS B) were developed. The design, development, construction, calibration, integration, and flight of these instruments, along with early results from the data analysis efforts are summarized. A medium energy ion mass spectrometer that covers mass velocity space with significantly higher time resolution, improved mass resolution, (particularly for heavier ions), and wider energy range than existing instruments had achieved was completed. The initial design consisted of a dual channel cylindrical electrostatic analyzer followed by a dual channel cylindrical velocity filter. The gain versus count rate characteristics of the high current channel electron multipliers (CEM's), which were chosen for ion detection, revealed a systematic behavior that can be used as a criterion for selection of CEM's for long counting lifetimes.

A New Catalog of Contact Binary Stars from ROTSE-I Sky Patrols

NASA Astrophysics Data System (ADS)

Gettel, S. J.; McKay, T. A.; Geske, M. T.

2005-05-01

Over 65,000 variable stars have been detected in the data from the ROTSE-I Sky Patrols. Using period-color and light curve selection techniques, about 5000 objects have been identified as contact binaries. This selection is tested for completeness against EW objects in the GCVS. By utilizing infrared color data from 2MASS, we fit a period-color-luminosity relation to these stars and estimate their distances.

IDENTIFICATION OF COMPOUNDS IN SOUTH AFRICAN STREAM SAMPLES USING ION COMPOSITION ELUCIDATION (ICE)

EPA Science Inventory

Analytical methods for target compounds usually employ clean-up procedures to remove potential mass interferences and utilize selected ion recording (SIR) to provide low detection limits. Such an approach, however, could overlook non-target compounds that might be present and tha...

The Atacama Cosmology Telescope: Sunyaev-Zel'dovich-Selected Galaxy Clusters AT 148 GHz in the 2008 Survey

NASA Technical Reports Server (NTRS)

Marriage, Tobias A.; Acquaviva, Viviana; Ade, Peter A. R.; Aguirre, Paula; Amiri, Mandana; Appel, John William; Barrientos, L. Felipe; Battistelli, Elia S.; Bond, J. Richard; Brown, Ben;

Novel pollutants in the Moscow atmosphere in winter period: Gas chromatography-high resolution time-of-flight mass spectrometry study.

PubMed

Mazur, D M; Polyakova, O V; Artaev, V B; Lebedev, A T

2017-03-01

The most common mass spectrometry approach analyzing contamination of the environment deals with targeted analysis, i.e. detection and quantification of the selected (priority) pollutants. However non-targeted analysis is becoming more often the method of choice for environmental chemists. It involves implementation of modern analytical instrumentation allowing for comprehensive detection and identification of the wide variety of compounds of the environmental interest present in the sample, such as pharmaceuticals and their metabolites, musks, nanomaterials, perfluorinated compounds, hormones, disinfection by-products, flame retardants, personal care products, and many others emerging contaminants. The paper presents the results of detection and identification of previously unreported organic compounds in snow samples collected in Moscow in March 2016. The snow analysis allows evaluation of long-term air pollution in the winter period. Gas chromatography coupled to a high resolution time-of-flight mass spectrometer has enabled us with capability to detect and identify such novel analytes as iodinated compounds, polychlorinated anisoles and even Ni-containing organic complex, which are unexpected in environmental samples. Some considerations concerning the possible sources of origin of these compounds in the environment are discussed. Copyright © 2017 LECO. Published by Elsevier Ltd.. All rights reserved.

Anti-theft device staining on banknotes detected by mass spectrometry imaging.

PubMed

Correa, Deleon Nascimento; Zacca, Jorge Jardim; Rocha, Werickson Fortunato de Carvalho; Borges, Rodrigo; de Souza, Wanderley; Augusti, Rodinei; Eberlin, Marcos Nogueira; Vendramini, Pedro Henrique

2016-03-01

We describe the identification and limits of detection of ink staining by mass spectrometry imaging (MSI), as used in anti-theft devices (ATDs). Such ink staining is applied to banknotes during automated teller machine (ATM) explosions. Desorption electrospray ionization (DESI) coupled with high-resolution and high-accuracy orbitrap mass spectrometry (MS) and a moving stage device were applied to obtain 2D molecular images of the major dyes used for staining, that is, 1-methylaminoanthraquinone (MAAQ), rhodamine B (RB) and rhodamine 6G (R6G). MAAQ could not be detected because of its inefficient desorption by DESI from the banknote cellulose surface. By contrast, ATD staining on banknotes is perceptible by the human naked eye only at concentrations higher than 0.2 μg cm(-2), whereas both RB and R6G at concentrations 200 times lower (as low as 0.001 μg cm(-2)) could be easily detected and imaged by DESI-MSI, with selective and specific identification of each analyte and their spatial distribution on samples from suspects. This technique is non-destructive, and no sample preparation is required, which ensures sample preservation for further forensic investigations. Copyright © 2016. Published by Elsevier Ireland Ltd.

A liquid chromatography-tandem mass spectrometry assay for the detection and quantification of trehalose in biological samples.

PubMed

Kretschmer, Philip M; Bannister, Austin M; O Brien, Molly K; MacManus-Spencer, Laura A; Paulick, Margot G

2016-10-15

Trehalose is an important disaccharide that is used as a cellular protectant by many different organisms, helping these organisms better survive extreme conditions, such as dehydration, oxidative stress, and freezing temperatures. Methods to detect and accurately measure trehalose from different organisms will help us gain a better understanding of the mechanisms behind trehalose's ability to act as a cellular protectant. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay using selected reaction monitoring mode for the detection and quantification of trehalose using maltose as an internal standard has been developed. This assay uses a commercially available LC column for trehalose separation and a standard triple quadrupole mass spectrometer, thus allowing many scientists to take advantage of this simple assay. The calibration curve from 3 to 100μM trehalose was fit best by a single polynomial. This LC-MS/MS assay directly detects and accurately quantifies trehalose, with an instrument limit of detection (LOD) that is 2-1000 times more sensitive than the most commonly-used assays for trehalose detection and quantification. Furthermore, this assay was used to detect and quantify endogenous trehalose produced by Escherichia coli (E. coli) cells, which were found to have an intracellular concentration of 8.5±0.9mM trehalose. This method thus shows promise for the reliable detection and quantification of trehalose from different biological sources. Copyright © 2016 Elsevier B.V. All rights reserved.

Chloride interference in the determination of bromate in drinking water by reagent free ion chromatography with mass spectrometry detection.

PubMed

Cavalli, Silvano; Polesello, Stefano; Valsecchi, Sara

2005-08-26

Bromate, a well known by-product of the ozonation of drinking water, has been included among the substances which have to be monitored in the drinking water according to the last EC Directive 251/98 on potable water with a regulated limit of 10 microg l(-1). The need of performing routine analysis at this limit is a driving force for the developing of new simple and sensitive methods of detection, which should be also able to overcome the effect of matrix composition. This work explored the use of mass spectrometry detection with electrospray ionisation hyphenated to a reagent free ion chromatograph with hydroxide gradient elution for the determination of bromate in drinking water. The use of a high capacity hydroxide selective column operated in gradient mode allowed to avoid the interference by carbonate peak, which moved to longer retention times. The effect of increasing chloride concentrations from 0 to 250 mg l(-1), which is the guideline limit for drinking water in Directive 251/98/EC, was to decrease absolute mass spectrometric response and chromatographic efficiency and, on the consequence, to increase the effective detection limits. The effect of the chloride concentration on the detection of bromate is discussed.

Galaxy And Mass Assembly (GAMA): detection of low-surface-brightness galaxies from SDSS data

NASA Astrophysics Data System (ADS)

Williams, Richard P.; Baldry, I. K.; Kelvin, L. S.; James, P. A.; Driver, S. P.; Prescott, M.; Brough, S.; Brown, M. J. I.; Davies, L. J. M.; Holwerda, B. W.; Liske, J.; Norberg, P.; Moffett, A. J.; Wright, A. H.

2016-12-01

We report on a search for new low-surface-brightness galaxies (LSBGs) using Sloan Digital Sky Survey (SDSS) data within the Galaxy And Mass Assembly (GAMA) equatorial fields. The search method consisted of masking objects detected with SDSS PHOTO, combining gri images weighted to maximize the expected signal-to-noise ratio, and smoothing the images. The processed images were then run through a detection algorithm that finds all pixels above a set threshold and groups them based on their proximity to one another. The list of detections was cleaned of contaminants such as diffraction spikes and the faint wings of masked objects. From these, selecting potentially the brightest in terms of total flux, a list of 343 LSBGs was produced having been confirmed using VISTA Kilo-degree Infrared Galaxy Survey (VIKING) imaging. The photometry of this sample was refined using the deeper VIKING Z band as the aperture-defining band. Measuring their g - I and J - K colours shows that most are consistent with being at redshifts less than 0.2. The photometry is carried out using an AUTO aperture for each detection giving surface brightnesses of μr ≳ 25 mag arcsec-2 and magnitudes of r > 19.8 mag. None of these galaxies are bright enough to be within the GAMA main survey limit but could be part of future deeper surveys to measure the low-mass end of the galaxy stellar mass function.

Sensitive and selective liquid chromatography-tandem mass spectrometry method for the determination of five ganoderic acids in Ganoderma lucidum and its related species.

PubMed

Liu, Yongli; Liu, Youping; Qiu, Feng; Di, Xin

2011-03-25

The present paper describes a novel, sensitive and selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous analysis of ganoderic acids C(2), B, A, H, D in Ganoderma lucidum and its related species. Ganoderma samples were prepared using simple ultrasonic extraction. Chromatographic separation was carried out on an Agilent Zorbax XDB C(18) column (250 mm × 4.6 mm i.d., 5μm) with an isocratic mobile phase consisting of acetonitrile, water and formic acid (42:58:0.5, v/v/v). Mass spectrometric detection was achieved by a triple-quadrupole mass spectrometer equipped with an atmospheric pressure chemical ionization (APCI) interface operating in negative and positive ionization mode via a single within-run polarity switching. Quantitation of five ganoderic acids was performed using selective reaction monitoring (SRM) mode. The intra- and inter-day precision was less than 6.2% and the accuracy ranged from 90.0% to 105.7%. The limit of quantification (LOQ) was 20.0-40.0 ng/mL and the limit of detection (LOD) was 3.0-25.0 ng/mL. With this method, low levels of ganoderic acids in the fruiting bodies of Ganoderma sinense and Ganoderma applanatum were accurately quantified for the first time. Importantly, the method allows unequivocal quantification of the five ganoderic acids in the spores and fruiting bodies of Ganoderma lucidum, whereas the previously published methods have lacked the capability. The method presented will be a powerful tool for quality control of Ganoderma lucidum and its related species. Copyright © 2010 Elsevier B.V. All rights reserved.

Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis.

PubMed

Kleeblatt, Juliane; Schubert, Jochen K; Zimmermann, Ralf

2015-02-03

A fast detection method to analyze gaseous organic compounds in complex gas mixtures was developed, using a needle trap device (NTD) in conjunction with thermal-desorption photoionization time-of-flight mass spectrometry (TD-PI-TOFMS). The mass spectrometer was coupled via a deactivated fused silica capillary to an injector of a gas chromatograph. In the hot injector, the analytes collected on the NTD were thermally desorbed and directly transferred to the PI-TOFMS ion source. The molecules are softly ionized either by single photon ionization (SPI, 118 nm) or by resonance enhanced multiphoton ionization (REMPI, 266 nm), and the molecular ion signals are detected in the TOF mass analyzer. Analyte desorption and the subsequent PI-TOFMS detection step only lasts ten seconds. The specific selectivity of REMPI (i.e., aromatic compounds) and universal ionization characteristics render PI-MS as a promising detection system. As a first demonstrative application, the alveolar phase breath gas of healthy, nonsmoking subjects was sampled on NTDs. While smaller organic compounds such as acetone, acetaldehyde, isoprene, or cysteamine can be detected in the breath gas with SPI, REMPI depicts the aromatic substances phenol and indole at 266 nm. In the breath gas of a healthy, smoking male subject, several xenobiotic substances such as benzene, toluene, styrene, and ethylbenzene can be found as well. Furthermore, the NTD-REMPI-TOFMS setup was tested for breath gas taken from a mechanically ventilated pig under continuous intravenous propofol (2,6-diisopropylphenol, narcotic drug) infusion.

Single-cell MALDI-MS as an analytical tool for studying intrapopulation metabolic heterogeneity of unicellular organisms.

PubMed

Amantonico, Andrea; Urban, Pawel L; Fagerer, Stephan R; Balabin, Roman M; Zenobi, Renato

2010-09-01

Heterogeneity is a characteristic feature of all populations of living organisms. Here we make an attempt to validate a single-cell mass spectrometric method for detection of changes in metabolite levels occurring in populations of unicellular organisms. Selected metabolites involved in central metabolism (ADP, ATP, GTP, and UDP-Glucose) could readily be detected in single cells of Closterium acerosum by means of negative-mode matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). The analytical capabilities of this approach were characterized using standard compounds. The method was then used to study populations of individual cells with different levels of the chosen metabolites. With principal component analysis and support vector machine algorithms, it was possible to achieve a clear separation of individual C. acerosum cells in different metabolic states. This study demonstrates the suitability of mass spectrometric analysis of metabolites in single cells to measure cell-population heterogeneity.

Low-mass dark matter search using ionization signals in XENON100

NASA Astrophysics Data System (ADS)

Aprile, E.; Aalbers, J.; Agostini, F.; Alfonsi, M.; Amaro, F. D.; Anthony, M.; Arneodo, F.; Barrow, P.; Baudis, L.; Bauermeister, B.; Benabderrahmane, M. L.; Berger, T.; Breur, P. A.; Brown, A.; Brown, E.; Bruenner, S.; Bruno, G.; Budnik, R.; Buss, A.; Bütikofer, L.; Cardoso, J. M. R.; Cervantes, M.; Cichon, D.; Coderre, D.; Colijn, A. P.; Conrad, J.; Cussonneau, J. P.; Decowski, M. P.; de Perio, P.; di Gangi, P.; di Giovanni, A.; Duchovni, E.; Ferella, A. D.; Fieguth, A.; Franco, D.; Fulgione, W.; Galloway, M.; Garbini, M.; Geis, C.; Goetzke, L. W.; Greene, Z.; Grignon, C.; Gross, E.; Hasterok, C.; Hogenbirk, E.; Itay, R.; Kaminsky, B.; Kessler, G.; Kish, A.; Landsman, H.; Lang, R. F.; Levinson, L.; Le Calloch, M.; Levy, C.; Linde, F.; Lindemann, S.; Lindner, M.; Lopes, J. A. M.; Lyashenko, A.; Manfredini, A.; Marrodán Undagoitia, T.; Masbou, J.; Massoli, F. V.; Masson, D.; Mayani, D.; Melgarejo Fernandez, A. J.; Meng, Y.; Messina, M.; Micheneau, K.; Miguez, B.; Molinario, A.; Murra, M.; Naganoma, J.; Oberlack, U.; Orrigo, S. E. A.; Pakarha, P.; Pelssers, B.; Persiani, R.; Piastra, F.; Pienaar, J.; Plante, G.; Priel, N.; Rauch, L.; Reichard, S.; Reuter, C.; Rizzo, A.; Rosendahl, S.; Rupp, N.; Dos Santos, J. M. F.; Sartorelli, G.; Scheibelhut, M.; Schindler, S.; Schreiner, J.; Schumann, M.; Scotto Lavina, L.; Selvi, M.; Shagin, P.; Simgen, H.; Stein, A.; Thers, D.; Tiseni, A.; Trinchero, G.; Tunnell, C. D.; von Sivers, M.; Wall, R.; Wang, H.; Weber, M.; Wei, Y.; Weinheimer, C.; Wulf, J.; Zhang, Y.; Xenon Collaboration

2016-11-01

We perform a low-mass dark matter search using an exposure of 30 kg ×yr with the XENON100 detector. By dropping the requirement of a scintillation signal and using only the ionization signal to determine the interaction energy, we lowered the energy threshold for detection to 0.7 keV for nuclear recoils. No dark matter detection can be claimed because a complete background model cannot be constructed without a primary scintillation signal. Instead, we compute an upper limit on the WIMP-nucleon scattering cross section under the assumption that every event passing our selection criteria could be a signal event. Using an energy interval from 0.7 keV to 9.1 keV, we derive a limit on the spin-independent WIMP-nucleon cross section that excludes WIMPs with a mass of 6 GeV /c2 above 1.4 ×10-41 cm2 at 90% confidence level.

An ensemble-based approach for breast mass classification in mammography images

NASA Astrophysics Data System (ADS)

Ribeiro, Patricia B.; Papa, João. P.; Romero, Roseli A. F.

2017-03-01

Mammography analysis is an important tool that helps detecting breast cancer at the very early stages of the disease, thus increasing the quality of life of hundreds of thousands of patients worldwide. In Computer-Aided Detection systems, the identification of mammograms with and without masses (without clinical findings) is highly needed to reduce the false positive rates regarding the automatic selection of regions of interest that may contain some suspicious content. In this work, the introduce a variant of the Optimum-Path Forest (OPF) classifier for breast mass identification, as well as we employed an ensemble-based approach that can enhance the effectiveness of individual classifiers aiming at dealing with the aforementioned purpose. The experimental results also comprise the naïve OPF and a traditional neural network, being the most accurate results obtained through the ensemble of classifiers, with an accuracy nearly to 86%.

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

Belov, Mikhail E.; Anderson, Gordon A.; Smith, Richard D.

Data-dependent selective external ion ejection with improved resolution is demonstrated with a 3.5 tesla FTICR instrument employing DREAMS (Dynamic Range Enhancement Applied to Mass Spectrometry) technology. To correct for the fringing rf-field aberrations each rod of the selection quadrupole has been segmented into three sections, so that ion excitation and ejection was performed by applying auxiliary rf-only waveforms in the region of the middle segments. Two different modes of external ion trapping and ejection were studied with the mixtures of model peptides and a tryptic digest of bovine serum albumin. A mass resolution of about 100 has been attained formore » rf-only dipolar ejection in a quadrupole operating at a Mathieu parameter q of{approx} 0.45. LC-ESI-DREAMS-FTICR analysis of a 0.1 mg/mL solution of bovine serum albumin digest resulted in detection of 82 unique tryptic peptides with mass measurement errors lower than 5 ppm, providing 100% sequence coverage of the protein.« less

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

Belov, Mikhail E.; Anderson, Gordon A.; Smith, Richard D.

Data-dependent selective external ion ejection with improved resolution is demonstrated with a 3.5 tesla FTICR instrument employing DREAMS (Dynamic Range Enhancement Applied to Mass Spectrometry) technology. To correct for the fringing rf-field aberrations each rod of the selection quadrupole has been segmented into three sections, so that ion excitation and ejection was performed by applying auxiliary rf-only waveforms in the region of the middle segments. Two different modes of external ion trapping and ejection were studied with the mixtures of model peptides and a tryptic digest of bovine serum albumin. A mass resolution of about 100 had been attained formore » rf-only dipolar ejection in a quadrupole operating at a Mathieu parameter q of ~0.45. LC-ESI-DREAMS-FTICR analysis of a 0.1 mg/mL solution of bovine serum albumin digest resulted in detection of 82 unique tryptic peptides with mass measurement errors lower than 5 ppm, providing 100 % sequence coverage of the protein.« less

Enantioselective supercritical fluid chromatography-tandem mass spectrometry method for simultaneous estimation of risperidone and its 9-hydroxyl metabolites in rat plasma.

PubMed

Prasad, Thatipamula R; Joseph, Siji; Kole, Prashant; Kumar, Anoop; Subramanian, Murali; Rajagopalan, Sudha; Kr, Prabhakar

2017-11-01

Objective of the current work was to develop a 'green chemistry' compliant selective and sensitive supercritical fluid chromatography-tandem mass spectrometry method for simultaneous estimation of risperidone (RIS) and its chiral metabolites in rat plasma. Methodology & results: Agilent 1260 Infinity analytical supercritical fluid chromatography system resolved RIS and its chiral metabolites within runtime of 6 min using a gradient chromatography method. Using a simple protein precipitation sample preparation followed by mass spectrometric detection achieved a sensitivity of 0.92 nM (lower limit of quantification). With linearity over four log units (0.91-7500 nM), the method was found to be selective, accurate, precise and robust. The method was validated and was successfully applied for simultaneous estimation of RIS and 9-hydroxyrisperidone metabolites (R & S individually) after intravenous and per oral administration to rats.

Synthesis and Mass Spectrometric Characterization of Organic Nitrates

NASA Astrophysics Data System (ADS)

Grünert, A.; Woidich, S.; Ballschmiter, K.

2003-04-01

Organic nitrates, as trace constituents in urban air, can be analyzed by adsorptive low volume sampling (LVS) as well as by adsorptive high volume sampling (HVS). Air samples ranging from 25 L to 100 L for the LVS and 100 m3 to 500 m3 for the (HVS) were collected, respectively. Analysis is performed by thermodesorption (LVS) or solvent elution combined with group separation (HVS) using normal-phase HPLC and high resolution capillary gas chromatography with electron capture detection (HRGC-ECD) and mass selective detection (HRGC-MSD). For identification and quantification available reference compounds are required for both methods (1;2). Following numbers of congeners of organic nitrate have been synthesized: 77 monoalkyl nitrates (C1-C16), 43 dialkyl nitrates (C2-C10), 37 hydroxy alkyl nitrates (C2-C8) and 41 carbonyl alkyl nitrates (C3-C12). Alkanes, alkenes, alcohols, ketones and halocarbons have been used as precursors. Characterisation of the reference compounds by retention-data and mass-spectra was performed by high resolution capillary gas chromatography with mass selective detection in the EI- and the NCI (CH4) mode (1-3). EI-ionization leads to the dominating indicator ion NO2+ for organic nitrates with m/z = 46 u. The characteristic fragments with NCI (CH4) show ions at m/z = 46 u and m/z = 62 u, corresponding to NO2- and NO3-. The use of flame ionisation detection (HRGC-FID) and the principle of the molar response for carbon allows the quantitation of reference solutions as the final tool for the determination of the levels and patterns of organic nitrates in urban air samples. (1) J. Kastler: "Analytik, Massenspektrometrie und Vorkommen multifunktioneller Alkylnitrate in belasteter und unbelasteter Atmosphäre" Dr.rer.nat.-Thesis, University of Ulm (1999) (2) G. Werner, J. Kastler, R. Looser, K. Ballschmiter: "Organic Nitrates of Isoprenes as Atmospheric Trace Compounds" Angew. Chem. Int. Ed. (1999) 38(11): 1634-1637 (3) S.Woidich, O. Froscheis, O. Luxenhofer, K. Ballschmiter: "EI- and NCI-mass spectrometry of aryl-alkyl nitrates and their occurrence in urban air" Fresenius J Anal Chem (1999) 364: 91-99

Research and Development of Non-Spectroscopic MEMS-Based Sensor Arrays for Targeted Gas Detection

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

Loui, A; McCall, S K

2011-10-24

The ability to monitor the integrity of gas volumes is of interest to the stockpile surveillance community. Specifically, the leak detection of noble gases, at relevant concentration ranges and distinguished from other chemical species that may be simultaneously present, is particularly challenging. Aside from the laboratory-based method of gas chromatography-mass spectrometry (GC-MS), where samples may be collected by solid-phase microextraction (SPME) or cryofocusing, the other major approaches for gas-phase detection employ lasers typically operating in the mid-infrared wavelength region. While mass spectrometry can readily detect noble gases - the helium leak detector is an obvious example - laser-based methods suchmore » as infrared (IR) or Raman spectroscopy are completely insensitive to them as their monatomic nature precludes a non-zero dipole moment or changes in polarizability upon excitation. Therefore, noble gases can only be detected by one of two methods: (1) atomic emission spectroscopies which require the generation of plasmas through laser-induced breakdown, electrical arcing, or similar means; (2) non-spectroscopic methods which measure one or more physical properties (e.g., mass, thermal conductivity, density). In this report, we present our progress during Fiscal Year 2011 (FY11) in the research and development of a non-spectroscopic method for noble gas detection. During Fiscal Year 2010 (FY10), we demonstrated via proof-of-concept experiments that the combination of thermal conductivity detection (TCD) and coating-free damped resonance detection (CFDRD) using micro-electromechanical systems (MEMS) could provide selective sensing of these inert species. Since the MEMS-based TCD technology was directly adapted from a brassboard prototype commissioned by a previous chemical sensing project, FY11 efforts focused on advancing the state of the newer CFDRD method. This work, guided by observations previously reported in the open literature, has not only resulted in a substantially measureable increase in selectivity but has also revealed a potential method for mitigating or eliminating thermal drift that does not require a secondary reference sensor. The design of an apparatus to test this drift compensation scheme will be described. We will conclude this report with a discussion of planned efforts in Fiscal Year 2012 (FY12).« less

Applicability of hybrid linear ion trap-high resolution mass spectrometry and quadrupole-linear ion trap-mass spectrometry for mycotoxin analysis in baby food.

PubMed

Rubert, Josep; James, Kevin J; Mañes, Jordi; Soler, Carla

2012-02-03

Recent developments in mass spectrometers have created a paradoxical situation; different mass spectrometers are available, each of them with their specific strengths and drawbacks. Hybrid instruments try to unify several advantages in one instrument. In this study two of wide-used hybrid instruments were compared: hybrid quadrupole-linear ion trap-mass spectrometry (QTRAP®) and the hybrid linear ion trap-high resolution mass spectrometry (LTQ-Orbitrap®). Both instruments were applied to detect the presence of 18 selected mycotoxins in baby food. Analytical parameters were validated according to 2002/657/CE. Limits of quantification (LOQs) obtained by QTRAP® instrument ranged from 0.45 to 45 μg kg⁻¹ while lower limits of quantification (LLOQs) values were obtained by LTQ-Orbitrap®: 7-70 μg kg⁻¹. The correlation coefficients (r) in both cases were upper than 0.989. These values highlighted that both instruments were complementary for the analysis of mycotoxin in baby food; while QTRAP® reached best sensitivity and selectivity, LTQ-Orbitrap® allowed the identification of non-target and unknowns compounds. Copyright © 2011 Elsevier B.V. All rights reserved.

Analytical strategies for controlling polysorbate-based nanomicelles in fruit juice.

PubMed

Krtkova, Veronika; Schulzova, Vera; Lacina, Ondrej; Hrbek, Vojtech; Tomaniova, Monika; Hajslova, Jana

2014-06-01

This study focused on the detection and quantification of organic micelle-type nanoparticles (NPs) with polysorbate components (polysorbate 20 and polysorbate 80) in their micelle shells that could be used to load biologically active compounds into fruit juice. Several advanced analytical techniques were applied in the stepwise method development strategy used. In the first phase, a system consisting of ultrahigh-performance liquid chromatography employing a size exclusion column coupled with an evaporative light scattering detector (UHPLC-SEC-ELSD) was used for the fractionation of micelle assemblies from other, lower molecular weight sample components. The limit of detection (LoD) of these polysorbate micelles in spiked apple juice was 500 μg mL(-1). After this screening step, mass spectrometric (MS) detection was utilized to confirm the presence of polysorbates in the detected micelles. Two alternative MS techniques were tested: (i) ambient high-resolution mass spectrometry employing a direct analysis in real time ion source coupled with an Orbitrap MS analyzer (DART-Orbitrap MS) enabled fast and simple detection of the polysorbates present in the samples, with a lowest calibration level (LCL) of 1000 μg mL(-1); (ii) ultrahigh-performance reversed-phase liquid chromatography coupled with high-resolution time-of-flight mass spectrometry (UHPLC-HRTOF-MS) provided highly selective and sensitive detection and quantification of polysorbates with an LCL of 0.5 μg mL(-1).

Microfluidic cantilever detects bacteria and measures their susceptibility to antibiotics in small confined volumes

NASA Astrophysics Data System (ADS)

Etayash, Hashem; Khan, M. F.; Kaur, Kamaljit; Thundat, Thomas

2016-10-01

In the fight against drug-resistant bacteria, accurate and high-throughput detection is essential. Here, a bimaterial microcantilever with an embedded microfluidic channel with internal surfaces chemically or physically functionalized with receptors selectively captures the bacteria passing through the channel. Bacterial adsorption inside the cantilever results in changes in the resonance frequency (mass) and cantilever deflection (adsorption stress). The excitation of trapped bacteria using infrared radiation (IR) causes the cantilever to deflect in proportion to the infrared absorption of the bacteria, providing a nanomechanical infrared spectrum for selective identification. We demonstrate the in situ detection and discrimination of Listeria monocytogenes at a concentration of single cell per μl. Trapped Escherichia coli in the microchannel shows a distinct nanomechanical response when exposed to antibiotics. This approach, which combines enrichment with three different modes of detection, can serve as a platform for the development of a portable, high-throughput device for use in the real-time detection of bacteria and their response to antibiotics.

The use of gas chromatographic-mass spectrometric-computer systems in pharmacokinetic studies.

PubMed

Horning, M G; Nowlin, J; Stafford, M; Lertratanangkoon, K; Sommer, K R; Hill, R M; Stillwell, R N

1975-10-29

Pharmacokinetic studies involving plasma, urine, breast milk, saliva and liver homogenates have been carried out by selective ion detection with a gas chromatographic-mass spectrometric-computer system operated in the chemical ionization mode. Stable isotope labeled drugs were used as internal standards for quantification. The half-lives, the concentration at zero time, the slope (regression coefficient), the maximum velocity of the reaction and the apparent Michaelis constant of the reaction were determined by regression analysis, and also by graphic means.

Screening of agrochemicals in foodstuffs using low-temperature plasma (LTP) ambient ionization mass spectrometry.

PubMed

Wiley, Joshua S; García-Reyes, Juan F; Harper, Jason D; Charipar, Nicholas A; Ouyang, Zheng; Cooks, R Graham

2010-05-01

Low-temperature plasma (LTP) permits direct ambient ionization and mass analysis of samples in their native environment with minimal or no prior preparation. LTP utilizes dielectric barrier discharges (DBDs) to create a low power plasma which is guided by gas flow onto the sample from which analytes are desorbed and ionized. In this study, the potential of LTP-MS for the detection of pesticide residues in food is demonstrated. Thirteen multi-class agricultural chemicals were studied (ametryn, amitraz, atrazine, buprofezin, DEET, diphenylamine, ethoxyquin, imazalil, isofenphos-methyl, isoproturon, malathion, parathion-ethyl and terbuthylazine). To evaluate the potential of the proposed approach, LTP-MS experiments were performed directly on fruit peels as well as on fruit/vegetable extracts. Most of the agrochemicals examined displayed remarkable sensitivity in the positive ion mode, giving limits of detection (LOD) for the direct measurement in the low picogram range. Tandem mass spectrometry (MS/MS) was used to confirm identification of selected pesticides by using for these experiments spiked fruit/vegetable extracts (QuEChERS, a standard sample treatment protocol) at levels as low as 1 pg, absolute, for some of the analytes. Comparisons of the data obtained by direct LTP-MS were made with the slower but more accurate conventional LC-MS/MS procedure. Herbicides spiked in aqueous solutions were detectable at LODs as low as 0.5 microg L(-1) without the need for any sample preparation. The results demonstrate that ambient LTP-MS can be applied for the detection and confirmation of traces of agrochemicals in actual market-purchased produce and in natural water samples. Quantitative analysis was also performed in a few selected cases and displayed a relatively high degree of linearity over four orders of magnitude.

CONNECTING GRBs AND ULIRGs: A SENSITIVE, UNBIASED SURVEY FOR RADIO EMISSION FROM GAMMA-RAY BURST HOST GALAXIES AT 0 < z < 2.5

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

Perley, D. A.; Perley, R. A.; Hjorth, J.

2015-03-10

Luminous infrared galaxies and submillimeter galaxies contribute significantly to stellar mass assembly and provide an important test of the connection between the gamma-ray burst (GRB) rate and that of overall cosmic star formation. We present sensitive 3 GHz radio observations using the Karl G. Jansky Very Large Array of 32 uniformly selected GRB host galaxies spanning a redshift range from 0 < z < 2.5, providing the first fully dust- and sample-unbiased measurement of the fraction of GRBs originating from the universe's most bolometrically luminous galaxies. Four galaxies are detected, with inferred radio star formation rates (SFRs) ranging between 50 and 300 Mmore » {sub ☉} yr{sup –1}. Three of the four detections correspond to events consistent with being optically obscured 'dark' bursts. Our overall detection fraction implies that between 9% and 23% of GRBs between 0.5 < z < 2.5 occur in galaxies with S {sub 3GHz} > 10 μJy, corresponding to SFR > 50 M {sub ☉} yr{sup –1} at z ∼ 1 or >250 M {sub ☉} yr{sup –1} at z ∼ 2. Similar galaxies contribute approximately 10%-30% of all cosmic star formation, so our results are consistent with a GRB rate that is not strongly biased with respect to the total SFR of a galaxy. However, all four radio-detected hosts have stellar masses significantly lower than IR/submillimeter-selected field galaxies of similar luminosities. We suggest that the GRB rate may be suppressed in metal-rich environments but independently enhanced in intense starbursts, producing a strong efficiency dependence on mass but little net dependence on bulk galaxy SFR.« less

Intact mass detection, interpretation, and visualization to automate Top-Down proteomics on a large scale

PubMed Central

Durbin, Kenneth R.; Tran, John C.; Zamdborg, Leonid; Sweet, Steve M. M.; Catherman, Adam D.; Lee, Ji Eun; Li, Mingxi; Kellie, John F.; Kelleher, Neil L.

2011-01-01

Applying high-throughput Top-Down MS to an entire proteome requires a yet-to-be-established model for data processing. Since Top-Down is becoming possible on a large scale, we report our latest software pipeline dedicated to capturing the full value of intact protein data in automated fashion. For intact mass detection, we combine algorithms for processing MS1 data from both isotopically resolved (FT) and charge-state resolved (ion trap) LC-MS data, which are then linked to their fragment ions for database searching using ProSight. Automated determination of human keratin and tubulin isoforms is one result. Optimized for the intricacies of whole proteins, new software modules visualize proteome-scale data based on the LC retention time and intensity of intact masses and enable selective detection of PTMs to automatically screen for acetylation, phosphorylation, and methylation. Software functionality was demonstrated using comparative LC-MS data from yeast strains in addition to human cells undergoing chemical stress. We further these advances as a key aspect of realizing Top-Down MS on a proteomic scale. PMID:20848673

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-07-16

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas andmore » particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-02-18

We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gasmore » and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25–50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas–particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Unique capabilities of AC frequency scanning and its implementation on a Mars Organic Molecule Analyzer linear ion trap.

PubMed

Snyder, Dalton T; Kaplan, Desmond A; Danell, Ryan M; van Amerom, Friso H W; Pinnick, Veronica T; Brinckerhoff, William B; Mahaffy, Paul R; Cooks, R Graham

2017-06-21

A limitation of conventional quadrupole ion trap scan modes which use rf amplitude control for mass scanning is that, in order to detect a subset of an ion population, the rest of the ion population must also be interrogated. That is, ions cannot be detected out of order; they must be detected in order of either increasing or decreasing mass-to-charge (m/z). However, an ion trap operated in the ac frequency scan mode, where the rf amplitude is kept constant and instead the ac frequency is used for mass-selective operations, has no such limitation because any variation in the ac frequency affects only the subset of ions whose secular frequencies match the perturbation frequency. Hence, an ion trap operated in the ac frequency scan mode can perform any arbitrary mass scan, as well as a sequence of scans, using a single ion injection; we demonstrate both capabilities here. Combining these two capabilities, we demonstrate the acquisition of a full mass spectrum, a product ion spectrum, and a second generation product ion spectrum using a single ion injection event. We further demonstrate a "segmented scan" in which different mass ranges are interrogated at different rf amplitudes in order to improve resolution over a portion of the mass range, and a "periodic scan" in which ions are continuously introduced into the ion trap to achieve a nearly 100% duty cycle. These unique scan modes, along with other characteristics of ac frequency scanning, are particularly appropriate for miniature ion trap mass spectrometers. Hence, implementation of ac frequency scanning on a prototype of the Mars Organic Molecule Analyzer mass spectrometer is also described.

Quantitation of cocaine and cocaethylene in small volumes of rat whole blood using gas chromatography-mass spectrometry.

PubMed

Burdick, J D; Boni, R L; Fochtman, F W

1997-05-01

A simple solid phase extraction (SPE) technique combined with gas chromatography-mass spectrometry (GC/MS) operated in selected ion monitoring (SIM) mode is described for quantitation of cocaine and cocaethylene in small samples (250 microliters) of rat whole blood. Use of (N-[2H3C])-cocaine and (N-[2H3C])-cocaethylene internal standards resulted in high sensitivity and selectivity for this analytical method. Analysis was performed using a Hewlett-Packard 5890 GC equipped with a 7673A Automatic Liquid Sampler linked to a Hewlett-Packard 5972 Mass Selective Detector. Separation of analytes was accomplished on a cross-linked methyl silicone gum capillary column (Ultra 1: 12m x 0.2mm (i.d.) x 0.33 microns). Linearity was established over a wide range of concentrations (5.0-2000.0 ng ml-1) with good precision. Limits of detection (LOD) were 1.0 and 2.0 ng ml-1 for cocaine and cocaethylene, respectively. This analytical method was designed for use in pharmacokinetic experiments studying the formation of cocaethylene following ethanol pretreatment in rats administered cocaine.

The stellar masses of ˜ 40 000 UV selected Galaxies from the WiggleZ survey at 0.3

NASA Astrophysics Data System (ADS)

Banerji, Manda; Glazebrook, Karl; Blake, Chris; Brough, Sarah; Colless, Matthew; Contreras, Carlos; Couch, Warrick; Croton, Darren J.; Croom, Scott; Davis, Tamara M.; Drinkwater, Michael J.; Forster, Karl; Gilbank, David; Gladders, Mike; Jelliffe, Ben; Jurek, Russell J.; Li, I.-hui; Madore, Barry; Martin, D. Christopher; Pimbblet, Kevin; Poole, Gregory B.; Pracy, Michael; Sharp, Rob; Wisnioski, Emily; Woods, David; Wyder, Ted K.; Yee, H. K. C.

2013-05-01

We characterize the stellar masses and star formation rates in a sample of ˜40 000 spectroscopically confirmed UV-luminous galaxies at 0.3 < z < 1.0 selected from within the WiggleZ Dark Energy Survey. In particular, we match this UV bright population to wide-field infrared surveys such as the near-infrared (NIR) UKIDSS Large Area Survey (LAS) and the mid-infrared Wide-Field Infrared Survey Explorer (WISE) All-Sky Survey. We find that ˜30 per cent of the UV-luminous WiggleZ galaxies, corresponding to the brightest and reddest subset, are detected at >5σ in the UKIDSS-LAS at all redshifts. An even more luminous subset of 15 per cent are also detected in the WISE 3.4 and 4.6 μm bands. In addition, 22 of the WiggleZ galaxies are extremely luminous at 12 and 22 μm and have colours consistent with being star formation dominated. We compute stellar masses for this very large sample of extremely blue galaxies and quantify the sensitivity of the stellar mass estimates to various assumptions made during the spectral energy distribution (SED) fitting. The median stellar masses are log10(M*/M⊙) = 9.6 ± 0.7, 10.2 ± 0.5 and 10.4 ± 0.4 for the IR undetected, UKIDSS detected and UKIDSS+WISE detected galaxies, respectively. We demonstrate that the inclusion of NIR photometry can lead to tighter constraints on the stellar masses by bringing down the upper bound on the stellar mass estimate. The mass estimates are found to be most sensitive to the inclusion of secondary bursts of star formation as well as changes in the stellar population synthesis models, both of which can lead to median discrepancies of the order of 0.3 dex in the stellar masses. We conclude that even for these extremely blue galaxies, different SED fitting codes therefore produce extremely robust stellar mass estimates. We find, however, that the best-fitting M/LK is significantly lower than that predicted by simple optical colour-based estimators for many of the WiggleZ galaxies. The simple colour-based estimator overpredicts M/LK by ˜0.4 dex on average. The effect is more pronounced for bluer galaxies with younger best-fitting ages. The WiggleZ galaxies have star formation rates of 3-10 M⊙ yr-1 and mostly lie at the upper end of the main sequence of star-forming galaxies at these redshifts. Their rest-frame UV luminosities and stellar masses are comparable to both local compact UV-luminous galaxies as well as Lyman break galaxies at z ˜ 2-3. The stellar masses from this paper will be made publicly available with the next WiggleZ data release.

Infrared Luminosities and Dust Properties of z ≈ 2 Dust-obscured Galaxies

NASA Astrophysics Data System (ADS)

Bussmann, R. S.; Dey, Arjun; Borys, C.; Desai, V.; Jannuzi, B. T.; Le Floc'h, E.; Melbourne, J.; Sheth, K.; Soifer, B. T.

2009-11-01

We present SHARC-II 350 μm imaging of twelve 24 μm bright (F 24 μm > 0.8 mJy) Dust-Obscured Galaxies (DOGs) and Combined Array for Research in Millimeter-wave Astronomy (CARMA) 1 mm imaging of a subset of two DOGs. These objects are selected from the Boötes field of the NOAO Deep Wide-Field Survey. Detections of four DOGs at 350 μm imply infrared (IR) luminosities which are consistent to within a factor of 2 of expectations based on a warm-dust spectral energy distribution (SED) scaled to the observed 24 μm flux density. The 350 μm upper limits for the 8 non-detected DOGs are consistent with both Mrk 231 and M82 (warm-dust SEDs), but exclude cold dust (Arp 220) SEDs. The two DOGs targeted at 1 mm were not detected in our CARMA observations, placing strong constraints on the dust temperature: T dust > 35-60 K. Assuming these dust properties apply to the entire sample, we find dust masses of ≈3 × 108 M sun. In comparison to other dusty z ~ 2 galaxy populations such as submillimeter galaxies (SMGs) and other Spitzer-selected high-redshift sources, this sample of DOGs has higher IR luminosities (2 × 1013 L sun versus 6 × 1012 L sun for the other galaxy populations) that are driven by warmer dust temperatures (>35-60 K versus ~30 K) and lower inferred dust masses (3 × 108 M sun versus 3 × 109 M sun). Wide-field Herschel and Submillimeter Common-User Bolometer Array-2 surveys should be able to detect hundreds of these power-law-dominated DOGs. We use the existing Hubble Space Telescope and Spitzer/InfraRed Array Camera data to estimate stellar masses of these sources and find that the stellar to gas mass ratio may be higher in our 24 μm bright sample of DOGs than in SMGs and other Spitzer-selected sources. Although much larger sample sizes are needed to provide a definitive conclusion, the data are consistent with an evolutionary trend in which the formation of massive galaxies at z ~ 2 involves a submillimeter bright, cold-dust, and star-formation-dominated phase followed by a 24 μm bright, warm-dust and AGN-dominated phase.

A liquid-phase microextraction method, combining a dual gauge microsyringe with a hollow fiber membrane, for the determination of organochlorine pesticides in aqueous solution by gas chromatography/ion trap mass spectrometry.

PubMed

Yan, Chih-Hao; Wu, Hui-Fen

2004-01-01

A liquid-phase microextraction (LPME) method has been demonstrated for the extraction and determination of organochlorine pesticides (OCPs) in aqueous solution. The method combines a dual gauge microsyringe with a hollow fiber membrane (LPME/DGM-HF) followed by detection by gas chromatography/ion trap mass spectrometry (GC/ITMS). The advantages include speed, low solvent and sample consumption, simplicity and ease of use. The extraction time, solvent selection, salt concentration and sample stirring rate have been investigated in order to optimize extraction efficiency. The viability is evaluated by measuring the linearity and detection limit of the five OCPs in aqueous solution. Detection linearity for the OCPs has been achieved over a range of concentrations between 1 and 500 microg/L (r2 > 0.930), with a detection limit of 0.1 microg/L for each OCP. Copyright 2004 John Wiley & Sons, Ltd.

THE CLUSTERING OF ALFALFA GALAXIES: DEPENDENCE ON H I MASS, RELATIONSHIP WITH OPTICAL SAMPLES, AND CLUES OF HOST HALO PROPERTIES

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

Papastergis, Emmanouil; Giovanelli, Riccardo; Haynes, Martha P.

We use a sample of ≈6000 galaxies detected by the Arecibo Legacy Fast ALFA (ALFALFA) 21 cm survey to measure the clustering properties of H I-selected galaxies. We find no convincing evidence for a dependence of clustering on galactic atomic hydrogen (H I) mass, over the range M{sub H{sub I}} ≈ 10{sup 8.5}-10{sup 10.5} M{sub ☉}. We show that previously reported results of weaker clustering for low H I mass galaxies are probably due to finite-volume effects. In addition, we compare the clustering of ALFALFA galaxies with optically selected samples drawn from the Sloan Digital Sky Survey (SDSS). We findmore » that H I-selected galaxies cluster more weakly than even relatively optically faint galaxies, when no color selection is applied. Conversely, when SDSS galaxies are split based on their color, we find that the correlation function of blue optical galaxies is practically indistinguishable from that of H I-selected galaxies. At the same time, SDSS galaxies with red colors are found to cluster significantly more than H I-selected galaxies, a fact that is evident in both the projected as well as the full two-dimensional correlation function. A cross-correlation analysis further reveals that gas-rich galaxies 'avoid' being located within ≈3 Mpc of optical galaxies with red colors. Next, we consider the clustering properties of halo samples selected from the Bolshoi ΛCDM simulation. A comparison with the clustering of ALFALFA galaxies suggests that galactic H I mass is not tightly related to host halo mass and that a sizable fraction of subhalos do not host H I galaxies. Lastly, we find that we can recover fairly well the correlation function of H I galaxies by just excluding halos with low spin parameter. This finding lends support to the hypothesis that halo spin plays a key role in determining the gas content of galaxies.« less

Looking for Galaxies in All the Right Places: A Search for Stellar Populations in ALFALFA’s Ultra-compact High Velocity Clouds

NASA Astrophysics Data System (ADS)

Janesh, William; Rhode, Katherine L.; Salzer, John J.; Janowiecki, Steven; Adams, Elizabeth; Haynes, Martha P.; Giovanelli, Riccardo; Cannon, John M.

2018-01-01

Nearby gas-rich dwarf galaxies are excellent laboratories for investigating the baryonic feedback processes that govern star formation and galaxy evolution in galaxies at the extreme end of the mass function. Detecting and studying such objects may help resolve the well-known tension between cosmological model predictions for low-mass dark matter halos and observations. The ALFALFA neutral hydrogen (Hi) survey has detected a sample of isolated ultra-compact high-velocity Hi clouds (UCHVCs) with kinematic properties that make them likely members of the Local Volume, but that have no optical counterparts in existing optical surveys. This UCHVC sample possesses Hi properties (at 1 Mpc, Hi masses of ~105-106 M⊙, Hi diameters of ~2-3 kpc, and dynamical masses of ~107-108 M⊙) similar to other known ultra-faint dwarf galaxies like Leo T. Following the discovery of Leo P, an extremely metal-poor, gas-rich star-forming dwarf galaxy associated with an ALFALFA UCHVC, we have initiated a campaign to obtain deep optical imaging of 56 UCHVCs using the wide field-of-view, high-resolution ODI camera on the WIYN 3.5-m telescope. Here we present a brief overview of our campaign to search for resolved stellar populations associated with the UCHVCs in our optical images, and initial results from our survey.After creating a stellar catalog from the pipeline-reduced and stacked ODI g- and i-band images, we apply a color-magnitude filter tuned for old, metal-poor stellar populations to select red giant branch stars at distances between 250 kpc and 2 Mpc. The spatial distribution of the stars selected by the filter is then smoothed, and overdensities in the fields are identified. Of the 22 targets analyzed to date, seven have associated stellar populations detected at a high confidence (92% to 99.9% significance). The detected objects have a range of distances (from 350 kpc to 1.6 Mpc) and have optical properties similar to those of ultra-faint dwarf galaxies. These objects have extreme Hi-to-stellar mass ratios, and given their isolation, may represent a progenitor population to the ultra-faint dwarfs. They also help constrain the conditions needed for star formation in the lowest-mass galaxies.

Meat Authentication via Multiple Reaction Monitoring Mass Spectrometry of Myoglobin Peptides.

PubMed

Watson, Andrew D; Gunning, Yvonne; Rigby, Neil M; Philo, Mark; Kemsley, E Kate

2015-10-20

A rapid multiple reaction monitoring (MRM) mass spectrometric method for the detection and relative quantitation of the adulteration of meat with that of an undeclared species is presented. Our approach uses corresponding proteins from the different species under investigation and corresponding peptides from those proteins, or CPCP. Selected peptide markers can be used for species detection. The use of ratios of MRM transition peak areas for corresponding peptides is proposed for relative quantitation. The approach is introduced by use of myoglobin from four meats: beef, pork, horse and lamb. Focusing in the present work on species identification, by use of predictive tools, we determine peptide markers that allow the identification of all four meats and detection of one meat added to another at levels of 1% (w/w). Candidate corresponding peptide pairs to be used for the relative quantification of one meat added to another have been observed. Preliminary quantitation data presented here are encouraging.

Development of multi-membrane near-infrared diode mass spectrometer for field analysis of aromatic hydrocarbons.

PubMed

Mach, Phillip M; Wright, Kenneth C; Verbeck, Guido F

2015-02-01

Membrane Inlet Mass Spectrometry (MIMS) is a technique that incorporates a semi-permeable membrane selective for differing organic molecules and chemistries. This eliminates the need for time-consuming sample preparation and facilitates near instantaneous analysis. This study will examine how the front end of MIMS incorporates three dual inlet ports, allowing for differing MIMS materials and selectivity for specific environments. Polydimethylsiloxane (PDMS) membranes have proven to be selective of benzene, toluene, and xylene (BTX) as well as aromatic hydrocarbons that are common in petroleum products while remaining selective against the aliphatic chains. PDMS has proven to be a successful choice of membrane with high permeability in atmospheric environments. In addition, polycyclic aromatic hydrocarbons (PAHs) such as acenaphthene, acenapthylene, naphthalene, and fluorene have recently been detected to the 5 ppb level in a nitrogen atmosphere with our current configuration. This preliminary work provides proof of concept using near-infrared laser diodes that act upon the membrane to increase its permeability and provide higher sensitivity of aromatic samples.

Planck/SDSS cluster mass and gas scaling relations for a volume-complete redMaPPer sample

NASA Astrophysics Data System (ADS)

Jimeno, Pablo; Diego, Jose M.; Broadhurst, Tom; De Martino, I.; Lazkoz, Ruth

2018-07-01

Using Planck satellite data, we construct Sunyaev-Zel'dovich (SZ) gas pressure profiles for a large, volume-complete sample of optically selected clusters. We have defined a sample of over 8000 redMaPPer clusters from the Sloan Digital Sky Survey, within the volume-complete redshift region 0.100

Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

NASA Technical Reports Server (NTRS)

Getty, Stephanie A.; Cook, Jamie E.; Balvin, Manuel; Brinckerhoff, William B.; Li, Xiang; Grubisic, Andrej; Cornish, Timothy; Ferrance, Jerome; Southard, Adrian

2017-01-01

The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

Capillary isoelectric focusing of probiotic bacteria from cow's milk in tapered fused silica capillary with off-line matrix-assisted laser desorption/ionization time-of-flight mass spectrometry identification.

PubMed

Horká, Marie; Karásek, Pavel; Salplachta, Jiří; Růžička, Filip; Vykydalová, Marie; Kubesová, Anna; Dráb, Vladimír; Roth, Michal; Slais, Karel

2013-07-25

In this study, combination of capillary isoelectric focusing (CIEF) in tapered fused silica (FS) capillary with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is presented as an efficient approach for unambiguous identification of probiotic bacteria in real sample. For this purpose, bacteria within genus Lactobacillus were selected as model bioanalytes and cow's milk was selected as a biological sample. CIEF analysis of both the cultivated bacteria and the bacteria in the milk was optimized and isoelectric points characterizing the examined bacteria were subsequently determined independently of the bacterial sample origin. The use of tapered FS capillary significantly enhanced the separation capacity and efficiency of the CIEF analyses performed. In addition, the cell number injected into the tapered FS capillary was quantified and an excellent linearity of the calibration curves was achieved which enabled quantitative analysis of the bacteria by CIEF with UV detection. The minimum detectable number of bacterial cells was 2×10(6) mL(-1). Finally, cow's milk spiked with the selected bacterium was analyzed by CIEF in tapered FS capillary, the focused and detected bacterial cells were collected from the capillary, deposited onto the cultivation medium, and identified using MALDI-TOF MS afterward. Our results have revealed that the proposed procedure can be advantageously used for unambiguous identification of probiotic bacteria in a real sample. Copyright © 2013 Elsevier B.V. All rights reserved.

Validated semiquantitative/quantitative screening of 51 drugs in whole blood as silylated derivatives by gas chromatography-selected ion monitoring mass spectrometry and gas chromatography electron capture detection.

PubMed

Gunnar, Teemu; Mykkänen, Sirpa; Ariniemi, Kari; Lillsunde, Pirjo

2004-07-05

A comprehensively validated procedure is presented for simultaneous semiquantitative/quantitative screening of 51 drugs of abuse or drugs potentially hazardous for traffic safety in serum, plasma or whole blood. Benzodiazepines (12), cannabinoids (3), opioids (8), cocaine, antidepressants (13), antipsychotics (5) and antiepileptics (2) as well as zolpidem, zaleplon, zopiclone, meprobamate, carisoprodol, tizanidine and orphenadrine and internal standard flurazepam, were isolated by high-yield liquid-liquid extraction (LLE). The dried extracts were derivatized by two-step silylation and analyzed by the combination of two different gas chromatographic (GC) separations with both electron capture detection (ECD) and mass spectrometry (MS) operating in a selected ion-monitoring (SIM) mode. Quantitative or semiquantitative results were obtained for each substance based on four-point calibration. In the validation tests, accuracy, reproducibility, linearity, limit of detection (LOD) and limit of quantitation (LOQ), selectivity, as well as extraction efficiency and stability of standard stock solutions were tested, and derivatization was optimized in detail. Intra- and inter-day precisions were within 2.5-21.8 and 6.0-22.5%, and square of correlation coefficients of linearity ranged from 0.9896 to 0.9999. The limit of quantitation (LOQ) varied from 2 to 2000 ng/ml due to a variety of the relevant concentrations of the analyzed substances in blood. The method is feasible for highly sensitive, reliable and possibly routinely performed clinical and forensic toxicological analyses.

Exploring the Chemical Link Between Local Ellipticals and Their High-Redshift Progenitors

NASA Technical Reports Server (NTRS)

Leja, Joel; Van Dokkum, Pieter G.; Momcheva, Ivelina; Brammer, Gabriel; Skelton, Rosalind E.; Whitaker, Katherine E.; Andrews, Brett H.; Franx, Marijn; Kriek, Mariska; Van Der Wel, Arjen;

The Detection and Statistics of Giant Arcs behind CLASH Clusters

NASA Astrophysics Data System (ADS)

Xu, Bingxiao; Postman, Marc; Meneghetti, Massimo; Seitz, Stella; Zitrin, Adi; Merten, Julian; Maoz, Dani; Frye, Brenda; Umetsu, Keiichi; Zheng, Wei; Bradley, Larry; Vega, Jesus; Koekemoer, Anton

2016-02-01

We developed an algorithm to find and characterize gravitationally lensed galaxies (arcs) to perform a comparison of the observed and simulated arc abundance. Observations are from the Cluster Lensing And Supernova survey with Hubble (CLASH). Simulated CLASH images are created using the MOKA package and also clusters selected from the high-resolution, hydrodynamical simulations, MUSIC, over the same mass and redshift range as the CLASH sample. The algorithm's arc elongation accuracy, completeness, and false positive rate are determined and used to compute an estimate of the true arc abundance. We derive a lensing efficiency of 4 ± 1 arcs (with length ≥6″ and length-to-width ratio ≥7) per cluster for the X-ray-selected CLASH sample, 4 ± 1 arcs per cluster for the MOKA-simulated sample, and 3 ± 1 arcs per cluster for the MUSIC-simulated sample. The observed and simulated arc statistics are in full agreement. We measure the photometric redshifts of all detected arcs and find a median redshift zs = 1.9 with 33% of the detected arcs having zs > 3. We find that the arc abundance does not depend strongly on the source redshift distribution but is sensitive to the mass distribution of the dark matter halos (e.g., the c-M relation). Our results show that consistency between the observed and simulated distributions of lensed arc sizes and axial ratios can be achieved by using cluster-lensing simulations that are carefully matched to the selection criteria used in the observations.

Quantitative Caffeine Analysis Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

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

Ford, Michael J; Deibel, Michael A.; Tomkins, Bruce A

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methodsmore » determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.« less

The quantitation of 2-oxo-3-hydroxy lysergic acid diethylamide (O-H-LSD) in human urine specimens, a metabolite of LSD: comparative analysis using liquid chromatography-selected ion monitoring mass spectrometry and liquid chromatography-ion trap mass spectrometry.

PubMed

Poch, G K; Klette, K L; Anderson, C

2000-04-01

This paper compares the potential forensic application of two sensitive and rapid procedures (liquid chromatography-mass spectrometry and liquid chromatography-ion trap mass spectrometry) for the detection and quantitation of 2-oxo-3-hydroxy lysergic acid diethylamide (O-H-LSD) a major LSD metabolite. O-H-LSD calibration curves for both procedures were linear over the concentration range 0-8,000 pg/mL with correlation coefficients (r2) greater than 0.99. The observed limit of detection (LOD) and limit of quantitation (LOQ) for O-H-LSD in both procedures was 400 pg/mL. Sixty-eight human urine specimens that had previously been found to contain LSD by gas chromatography-mass spectrometry were reanalyzed by both procedures for LSD and O-H-LSD. These specimens contained a mean concentration of O-H-LSD approximately 16 times higher than the LSD concentration. Because both LC methods produce similar results, either procedure can be readily adapted to O-H-LSD analysis for use in high-volume drug-testing laboratories. In addition, the possibility of significantly increasing the LSD detection time window by targeting this major LSD metabolite for analysis may influence other drug-free workplace programs to test for LSD.

A SEARCH FOR STELLAR-MASS BLACK HOLES VIA ASTROMETRIC MICROLENSING

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

Lu, J. R.; Sinukoff, E.; Ofek, E. O.

While dozens of stellar-mass black holes (BHs) have been discovered in binary systems, isolated BHs have eluded detection. Their presence can be inferred when they lens light from a background star. We attempt to detect the astrometric lensing signatures of three photometrically identified microlensing events, OGLE-2011-BLG-0022, OGLE-2011-BLG-0125, and OGLE-2012-BLG-0169 (OB110022, OB110125, and OB120169), located toward the Galactic Bulge. These events were selected because of their long durations, which statistically favors more massive lenses. Astrometric measurements were made over one to two years using laser-guided adaptive optics observations from the W. M. Keck Observatory. Lens model parameters were first constrained bymore » the photometric light curves. The OB120169 light curve is well fit by a single-lens model, while both OB110022 and OB110125 light curves favor binary lens models. Using the photometric fits as prior information, no significant astrometric lensing signal was detected and all targets were consistent with linear motion. The significant lack of astrometric signal constrains the lens mass of OB110022 to 0.05–1.79 M {sub ⊙} in a 99.7% confidence interval, which disfavors a BH lens. Fits to OB110125 yielded a reduced Einstein crossing time and insufficient observations during the peak, so no mass limits were obtained. Two degenerate solutions exist for OB120169, which have a lens mass between 0.2–38.8 M {sub ⊙} and 0.4–39.8 M {sub ⊙} for a 99.7% confidence interval. Follow-up observations of OB120169 will further constrain the lens mass. Based on our experience, we use simulations to design optimal astrometric observing strategies and show that with more typical observing conditions the detection of BHs is feasible.« less

High-throughput matrix-assisted laser desorption ionization-time of flight mass spectrometry as an alternative approach to monitoring drug resistance of hepatitis B virus.

PubMed

Rybicka, Magda; Stalke, Piotr; Dreczewski, Marcin; Smiatacz, Tomasz; Bielawski, Krzysztof Piotr

2014-01-01

Long-term antiviral therapy of chronic hepatitis B virus (HBV) infection can lead to the selection of drug-resistant HBV variants and treatment failure. Moreover, these HBV strains are possibly present in treatment-naive patients. Currently available assays for the detection of HBV drug resistance can identify mutants that constitute ≥5% of the viral population. Furthermore, drug-resistant HBV variants can be detected when a viral load is >10(4) copies/ml (1,718 IU/ml). The aim of this study was to compare matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) and multitemperature single-strand conformation polymorphism (MSSCP) with commercially available assays for the detection of drug-resistant HBV strains. HBV DNA was extracted from 87 serum samples acquired from 45 chronic hepatitis B (CHB) patients. The 37 selected HBV variants were analyzed in 4 separate primer extension reactions on the MALDI-TOF MS. Moreover, MSSCP for identifying drug-resistant HBV YMDD variants was developed and turned out to be more sensitive than INNOLiPA HBV DR and direct sequencing. MALDI-TOF MS had the capability to detect mutant strains within a mixed viral population occurring with an allelic frequency of approximately 1% (with a specific value of ≥10(2) copies/ml, also expressed as ≥17.18 IU/ml). In our study, MSSCP detected 98% of the HBV YMDD variants among strains detected by the MALDI-TOF MS assay. The routine tests revealed results of 40% and 11%, respectively, for INNOLiPA and direct sequencing. The commonly available HBV tests are less sensitive than MALDI-TOF MS in the detection of HBV-resistant variants, including quasispecies.

Quantitative Thin-Layer Chromatography/Mass Spectrometry Analysis of Caffeine Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

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

Ford, Michael J; Deibel, Michael A.; Tomkins, Bruce A

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methodsmore » determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.« less

A Compact Tandem Two-Step Laser Time-of-Flight Mass Spectrometer for In Situ Analysis of Non-Volatile Organics on Planetary Surfaces

NASA Technical Reports Server (NTRS)

Getty, Stephanie A.; Brinckerhoff, William B.; Li, Xiang; Elsila, Jamie; Cornish, Timothy; Ecelberger, Scott; Wu, Qinghao; Zare, Richard

2014-01-01

Two-step laser desorption mass spectrometry is a well suited technique to the analysis of high priority classes of organics, such as polycyclic aromatic hydrocarbons, present in complex samples. The use of decoupled desorption and ionization laser pulses allows for sensitive and selective detection of structurally intact organic species. We have recently demonstrated the implementation of this advancement in laser mass spectrometry in a compact, flight-compatible instrument that could feasibly be the centerpiece of an analytical science payload as part of a future spaceflight mission to a small body or icy moon.

The sensitivity of benzene cluster cation chemical ionization mass spectrometry to select biogenic terpenes

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael P.; Novak, Gordon A.; Bertram, Timothy H.

2018-06-01

Benzene cluster cations are a sensitive and selective reagent ion for chemical ionization of select biogenic volatile organic compounds. We have previously reported the sensitivity of a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), using benzene cluster cation ion chemistry, for detection of dimethyl sulfide, isoprene and α-pinene. Here, we present laboratory measurements of the sensitivity of the same instrument to a series of terpenes, including isoprene, α-pinene, β-pinene, D-limonene, ocimene, β-myrcene, farnesene, α-humulene, β-caryophyllene, and isolongifolene at atmospherically relevant mixing ratios (< 100 pptv). In addition, we determine the dependence of CI-ToFMS sensitivity on the reagent ion neutral delivery concentration and water vapor concentration. We show that isoprene is primarily detected as an adduct (C5H8 ṡ C6H6+) with a sensitivity ranging between 4 and 10 ncps ppt-1, which depends strongly on the reagent ion precursor concentration, de-clustering voltages, and specific humidity (SH). Monoterpenes are detected primarily as the molecular ion (C10H16+) with an average sensitivity, across the five measured compounds, of 14 ± 3 ncps ppt-1 for SH between 7 and 14 g kg-1, typical of the boreal forest during summer. Sesquiterpenes are detected primarily as the molecular ion (C15H24+) with an average sensitivity, across the four measured compounds, of 9.6 ± 2.3 ncps ppt-1, that is also independent of specific humidity. Comparable sensitivities across broad classes of terpenes (e.g., monoterpenes and sesquiterpenes), coupled to the limited dependence on specific humidity, suggest that benzene cluster cation CI-ToFMS is suitable for field studies of biosphere-atmosphere interactions.

Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry.

PubMed

Raina, Renata; Sun, Lina

2008-05-01

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).

Fluorescence calibration method for single-particle aerosol fluorescence instruments

NASA Astrophysics Data System (ADS)

Shipley Robinson, Ellis; Gao, Ru-Shan; Schwarz, Joshua P.; Fahey, David W.; Perring, Anne E.

2017-05-01

Real-time, single-particle fluorescence instruments used to detect atmospheric bioaerosol particles are increasingly common, yet no standard fluorescence calibration method exists for this technique. This gap limits the utility of these instruments as quantitative tools and complicates comparisons between different measurement campaigns. To address this need, we have developed a method to produce size-selected particles with a known mass of fluorophore, which we use to calibrate the fluorescence detection of a Wideband Integrated Bioaerosol Sensor (WIBS-4A). We use mixed tryptophan-ammonium sulfate particles to calibrate one detector (FL1; excitation = 280 nm, emission = 310-400 nm) and pure quinine particles to calibrate the other (FL2; excitation = 280 nm, emission = 420-650 nm). The relationship between fluorescence and mass for the mixed tryptophan-ammonium sulfate particles is linear, while that for the pure quinine particles is nonlinear, likely indicating that not all of the quinine mass contributes to the observed fluorescence. Nonetheless, both materials produce a repeatable response between observed fluorescence and particle mass. This procedure allows users to set the detector gains to achieve a known absolute response, calculate the limits of detection for a given instrument, improve the repeatability of the instrumental setup, and facilitate intercomparisons between different instruments. We recommend calibration of single-particle fluorescence instruments using these methods.

Integrated HI emission in galaxy groups and clusters

NASA Astrophysics Data System (ADS)

Ai, Mei; Zhu, Ming; Fu, Jian

2017-09-01

The integrated HI emission from hierarchical structures such as groups and clusters of galaxies can be detected by FAST at intermediate redshifts. Here we propose to use FAST to study the evolution of the global HI content of clusters and groups over cosmic time by measuring their integrated HI emissions. We use the Virgo Cluster as an example to estimate the detection limit of FAST, and have estimated the integration time to detect a Virgo type cluster at different redshifts (from z = 0.1 to z = 1.5).We have also employed a semi-analytic model (SAM) to simulate the evolution of HI contents in galaxy clusters. Our simulations suggest that the HI mass of a Virgo-like cluster could be 2-3 times higher and the physical size could be more than 50% smaller when redshift increases from z = 0.3 to z = 1. Thus the integration time could be reduced significantly and gas rich clusters at intermediate redshifts can be detected by FAST in less than 2 hours of integration time. For the local Universe, we have also used SAM simulations to create mock catalogs of clusters to predict the outcomes from FAST all sky surveys. Comparing with the optically selected catalogs derived by cross matching the galaxy catalogs from the SDSS survey and the ALFALFA survey, we find that the HI mass distribution of the mock catalog with 20 s of integration time agrees well with that of observations. However, the mock catalog with 120 s of integration time predicts many more groups and clusters that contain a population of low mass HI galaxies not detected by the ALFALFA survey. A future deep HI blind sky survey with FAST would be able to test such prediction and set constraints on the numerical simulation models. The observational strategy and sample selections for future FAST observations of galaxy clusters at high redshifts are also discussed.

Comparison of Different IMAC Techniques Used for Enrichment of Phosphorylated Peptides

PubMed Central

Kånge, Rikard; Selditz, Ulrike; Granberg, Maria; Lindberg, Ulrika; Ekstrand, Gunnar; Ek, Bo; Gustafsson, Magnus

2005-01-01

Four commercially available immobilized metal ion affinity chromatography (IMAC) methods for phosphopeptide enrichment were compared using small volumes and concentrations of phosphopeptide mixtures with or without extra-added bovine serum albumin (BSA) nonphosphorylated peptides. Addition of abundant tryptic BSA peptides to the phosphopeptide mixture increases the demand for selective IMAC capture. While SwellGel gallium Discs, IPAC Metal Chelating Resin, and ZipTipMC Pipette Tips allow for the possibility of enriching phosphopeptides, the Gyrolab MALDI IMAC1 also presents the possibility of verifying existing phosphopeptides after a dephosphorylation step. Phosphate-containing peptides are identified through a mass shift between phosphorylated and dephosphorylated spectra of 80 Da (or multiples of 80 Da). This verification is useful if the degree of phosphorylation is low in the sample or if the ionization is unfavorable, which often is the case for phosphopeptides. A peptide mixture in which phosphorylated serine, threonine, and tyrosine were represented was diluted in steps and thereafter enriched using the four different IMAC methods prior to analyses with matrix assisted laser desorption/ionization mass spectrometry. The enrichment of phosphopeptides using SwellGel Gallium Discs or Gyrolab MALDI IMAC1 was not significantly affected by the addition of abundant BSA peptides added to the sample mixture, and the achieved detection limits using these techniques were also the lowest. All four of the included phosphopeptides were detected by MALDI-MS only after enrichment using the Gyrolab MALDI IMAC1 compact disc (CD) and detection down to low femtomole levels was possible. Furthermore, selectivity, reproducibility, and detection for a number of other phosphopeptides using the IMAC CD are reported herein. For example, two phosphopeptides sent out in a worldwide survey performed by the Proteomics Research Group (PRG03) of the Association of Biomolecular Resource Facilities (ABRF) were detected and verified by means of the 80 Da mass shift achieved by on-column dephosphorylation. PMID:16030316

An Ultra-Trace Analysis Technique for SF6 Using Gas Chromatography with Negative Ion Chemical Ionization Mass Spectrometry.

PubMed

Jong, Edmund C; Macek, Paul V; Perera, Inoka E; Luxbacher, Kray D; McNair, Harold M

2015-07-01

Sulfur hexafluoride (SF6) is widely used as a tracer gas because of its detectability at low concentrations. This attribute of SF6 allows the quantification of both small-scale flows, such as leakage, and large-scale flows, such as atmospheric currents. SF6's high detection sensitivity also facilitates greater usage efficiency and lower operating cost for tracer deployments by reducing quantity requirements. The detectability of SF6 is produced by its high molecular electronegativity. This property provides a high potential for negative ion formation through electron capture thus naturally translating to selective detection using negative ion chemical ionization mass spectrometry (NCI-MS). This paper investigates the potential of using gas chromatography (GC) with NCI-MS for the detection of SF6. The experimental parameters for an ultra-trace SF6 detection method utilizing minimal customizations of the analytical instrument are detailed. A method for the detection of parts per trillion (ppt) level concentrations of SF6 for the purpose of underground ventilation tracer gas analysis was successfully developed in this study. The method utilized a Shimadzu gas chromatography with negative ion chemical ionization mass spectrometry system equipped with an Agilent J&W HP-porous layer open tubular column coated with an alumina oxide (Al2O3) S column. The method detection limit (MDL) analysis as defined by the Environmental Protection Agency of the tracer data showed the method MDL to be 5.2 ppt. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Simultaneous Proteomic Discovery and Targeted Monitoring using Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry.

PubMed

Burnum-Johnson, Kristin E; Nie, Song; Casey, Cameron P; Monroe, Matthew E; Orton, Daniel J; Ibrahim, Yehia M; Gritsenko, Marina A; Clauss, Therese R W; Shukla, Anil K; Moore, Ronald J; Purvine, Samuel O; Shi, Tujin; Qian, Weijun; Liu, Tao; Baker, Erin S; Smith, Richard D

2016-12-01

Current proteomic approaches include both broad discovery measurements and quantitative targeted analyses. In many cases, discovery measurements are initially used to identify potentially important proteins (e.g. candidate biomarkers) and then targeted studies are employed to quantify a limited number of selected proteins. Both approaches, however, suffer from limitations. Discovery measurements aim to sample the whole proteome but have lower sensitivity, accuracy, and quantitation precision than targeted approaches, whereas targeted measurements are significantly more sensitive but only sample a limited portion of the proteome. Herein, we describe a new approach that performs both discovery and targeted monitoring (DTM) in a single analysis by combining liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS). In DTM, heavy labeled target peptides are spiked into tryptic digests and both the labeled and unlabeled peptides are detected using LC-IMS-MS instrumentation. Compared with the broad LC-MS discovery measurements, DTM yields greater peptide/protein coverage and detects lower abundance species. DTM also achieved detection limits similar to selected reaction monitoring (SRM) indicating its potential for combined high quality discovery and targeted analyses, which is a significant step toward the convergence of discovery and targeted approaches. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Comprehensive Biothreat Cluster Identification by PCR/Electrospray-Ionization Mass Spectrometry

PubMed Central

Sampath, Rangarajan; Mulholland, Niveen; Blyn, Lawrence B.; Massire, Christian; Whitehouse, Chris A.; Waybright, Nicole; Harter, Courtney; Bogan, Joseph; Miranda, Mary Sue; Smith, David; Baldwin, Carson; Wolcott, Mark; Norwood, David; Kreft, Rachael; Frinder, Mark; Lovari, Robert; Yasuda, Irene; Matthews, Heather; Toleno, Donna; Housley, Roberta; Duncan, David; Li, Feng; Warren, Robin; Eshoo, Mark W.; Hall, Thomas A.; Hofstadler, Steven A.; Ecker, David J.

2012-01-01

Technology for comprehensive identification of biothreats in environmental and clinical specimens is needed to protect citizens in the case of a biological attack. This is a challenge because there are dozens of bacterial and viral species that might be used in a biological attack and many have closely related near-neighbor organisms that are harmless. The biothreat agent, along with its near neighbors, can be thought of as a biothreat cluster or a biocluster for short. The ability to comprehensively detect the important biothreat clusters with resolution sufficient to distinguish the near neighbors with an extremely low false positive rate is required. A technological solution to this problem can be achieved by coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS). The biothreat assay described here detects ten bacterial and four viral biothreat clusters on the NIAID priority pathogen and HHS/USDA select agent lists. Detection of each of the biothreat clusters was validated by analysis of a broad collection of biothreat organisms and near neighbors prepared by spiking biothreat nucleic acids into nucleic acids extracted from filtered environmental air. Analytical experiments were carried out to determine breadth of coverage, limits of detection, linearity, sensitivity, and specificity. Further, the assay breadth was demonstrated by testing a diverse collection of organisms from each biothreat cluster. The biothreat assay as configured was able to detect all the target organism clusters and did not misidentify any of the near-neighbor organisms as threats. Coupling biothreat cluster-specific PCR to electrospray ionization mass spectrometry simultaneously provides the breadth of coverage, discrimination of near neighbors, and an extremely low false positive rate due to the requirement that an amplicon with a precise base composition of a biothreat agent be detected by mass spectrometry. PMID:22768032

Sensitive Detection of Neonicotinoid Insecticides and Other Selected Pesticides in Pollen and Nectar Using Nanoflow Liquid Chromatography Orbitrap Tandem Mass Spectrometry.

PubMed

Moreno-González, David; Alcántara-Durán, Jaime; Gilbert-López, Bienvenida; Beneito-Cambra, Miriam; Cutillas, Víctor M; Rajski, Łukasz; Molina-Díaz, Antonio; García-Reyes, Juan F

2018-03-01

In this work, a new method based on nanoflow LC with high-resolution MS was developed for the determination of eight pesticides in pollen and nectar samples, including neonicotinoid insecticides and other selected pesticides commonly found in bees and beeswax. Detection was undertaken with a hybrid quadrupole-Orbitrap mass spectrometer (Q Exactive™) equipped with a commercial nanospray ion source. The extraction of pesticides from pollen samples was performed by a modified micro-QuEChERS method scaled down to Eppendorf tubes, whereas nectar samples were simply diluted with a water-methanol (95 + 5, v/v) solution. Good linearity (>0.999 in all cases) was obtained between 0.05 and 500 µg/kg and between 0.04 and 400 µg/kg for pollen and nectar, respectively. Recovery rates in pollen ranged from 85 to 97%, with RSDs <12%. Matrix effect was evaluated and showed negligible effects for all studied pesticides. The lowest concentration levels tested and validated were 0.5 and 0.4 µg/kg for pollen and nectar matrixes, respectively. In addition, selected incurred samples were studied, obtaining several positive findings in pollen and nectar samples, demonstrating the sensitivity and applicability of the proposed method.

An adaptive incremental approach to constructing ensemble classifiers: application in an information-theoretic computer-aided decision system for detection of masses in mammograms.

PubMed

Mazurowski, Maciej A; Zurada, Jacek M; Tourassi, Georgia D

2009-07-01

Ensemble classifiers have been shown efficient in multiple applications. In this article, the authors explore the effectiveness of ensemble classifiers in a case-based computer-aided diagnosis system for detection of masses in mammograms. They evaluate two general ways of constructing subclassifiers by resampling of the available development dataset: Random division and random selection. Furthermore, they discuss the problem of selecting the ensemble size and propose two adaptive incremental techniques that automatically select the size for the problem at hand. All the techniques are evaluated with respect to a previously proposed information-theoretic CAD system (IT-CAD). The experimental results show that the examined ensemble techniques provide a statistically significant improvement (AUC = 0.905 +/- 0.024) in performance as compared to the original IT-CAD system (AUC = 0.865 +/- 0.029). Some of the techniques allow for a notable reduction in the total number of examples stored in the case base (to 1.3% of the original size), which, in turn, results in lower storage requirements and a shorter response time of the system. Among the methods examined in this article, the two proposed adaptive techniques are by far the most effective for this purpose. Furthermore, the authors provide some discussion and guidance for choosing the ensemble parameters.

Oxidation of selected organophosphate pesticides during chlorination of simulated drinking water.

PubMed

Kamel, Alaa; Byrne, Christian; Vigo, Craig; Ferrario, Joseph; Stafford, Charles; Verdin, Gregory; Siegelman, Frederic; Knizner, Steven; Hetrick, James

2009-02-01

Ten organophosphate (OP) pesticides: phorate, disulfoton, terbufos, methidathion, bensulide, chlorethoxyfos, phosmet, methyl parathion, phostebupirim, and temephos were evaluated for their potential to undergo oxidation to their respective oxons and/or other oxidation analogues in laboratory water. Samples were collected at time intervals up to 72h of chlorination and analyzed by both gas chromatography-mass selective detection (GC-MSD) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results show that methidathion and methyl parathion were stable in unchlorinated water, while all other OP pesticides were not stable over the 72h exposure period. In chlorinated water, phorate and disulfoton formed stable sulfone oxons. Temephos formed stable dioxon sulfoxide and dioxon sulfone. Methidathion, bensulide, chlorethyoxyfos, methyl parathion, and phostebupirim formed stable oxons over the 72h exposure period. Terbufos, phorate, disulfoton and temephos oxon sulfoxides; temephos sulfoxide; and phosmet oxon were initially formed but were not detected after 24h. The data illustrate that organothiophosphate pesticides may form oxons and/or other oxidation analogues during chlorination in water treatment plants, which are persistent for at least 72h.

Rapid screening of selective serotonin re-uptake inhibitors in urine samples using solid-phase microextraction gas chromatography-mass spectrometry.

PubMed

Salgado-Petinal, Carmen; Lamas, J Pablo; Garcia-Jares, Carmen; Llompart, Maria; Cela, Rafael

2005-07-01

In this paper a solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)-venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline-in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL(-1) urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified.

A multifunctional fluorescence sensor for Cd2+, PO43- and Cr3+ in different system and the practical application.

PubMed

Wang, Qingming; Tan, Yingzi; Wang, Nianhua; Lu, Zhixiang; Wang, Wenling

2018-05-07

A fluorescence probe based on thiosemicarbazide has been synthesized and well characterized by 1 H NMR, 13 C NMR, Elemental analysis, Electrospray ionization mass spectra. The probe 1 functions as a multitarget ion sensor, detect biologically and ecologically important Cd 2+ , PO 4 3- and Cr 3+ . Meanwhile, probe 1 displays selectivity for Cd 2+ over other metal ions and anions in DMF by emission spectrum. Interestingly, probe 1 has been explored to recognize PO 4 3- in CH 3 OH-H 2 O (v:v = 1:9). The binding stoichiometry of probe 1 with Cd 2+ and PO 4 3- are 2:1 and 1:1, respectively, which are confirmed by Electrospray ionization mass spectra. Probe 1 is selective, sensitive and reversibility/reusability to Cd 2+ and PO 4 3- with the detection limit as low as 0.035 μM and 0.011 μM respectively. Besides, the designed probe 1 has shown potential applications in the area of photo-printing. Copyright © 2018. Published by Elsevier B.V.

Determination of flubendiamide in honey at trace levels by using solid phase extraction and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

PubMed

Ares, Ana M; Valverde, Silvia; Bernal, José L; Toribio, Laura; Nozal, María J; Bernal, José

2017-10-01

In this study, a new method has been developed to determine flubendiamide in honey using liquid chromatography coupled to a selective mass spectrometry detector (quadrupole-time-of-flight). An efficient sample treatment involving a solid phase extraction with a C 18 sorbent was proposed (average analyte recoveries were between 94 and 104%). Chromatographic analysis (9min) was performed on a C 18 column (Gemini C 18 , 50×2.0mm, 3µm, 110Å). The mobile phase consisted of water and acetonitrile, with a flow rate of 0.5mL/min in gradient elution mode. The method was fully validated in terms of selectivity, limits of detection and quantification, matrix effect, linearity, trueness and precision. Low limits of detection and quantification were obtained, ranging from 0.1 to 0.2µg/kg and 0.4 to 0.6µg/kg, respectively. The method was applied to analyze flubendiamide in honey from different botanic origins (multifloral, rosemary and heather). Copyright © 2017 Elsevier Ltd. All rights reserved.

The Local Universe as Seen in the Far-Infrared and Far-Ultraviolet: A Global Point of View of the Local Recent Star Formation

NASA Astrophysics Data System (ADS)

Buat, V.; Takeuchi, T. T.; Iglesias-Páramo, J.; Xu, C. K.; Burgarella, D.; Boselli, A.; Barlow, T.; Bianchi, L.; Donas, J.; Forster, K.; Friedman, P. G.; Heckman, T. M.; Lee, Y.-W.; Madore, B. F.; Martin, D. C.; Milliard, B.; Morissey, P.; Neff, S.; Rich, M.; Schiminovich, D.; Seibert, M.; Small, T.; Szalay, A. S.; Welsh, B.; Wyder, T.; Yi, S. K.

2007-12-01

We select far-infrared (FIR: 60 μm) and far-ultraviolet (FUV: 530 Å) samples of nearby galaxies in order to discuss the biases encountered by monochromatic surveys (FIR or FUV). Very different volumes are sampled by each selection, and much care is taken to apply volume corrections to all the analyses. The distributions of the bolometric luminosity of young stars are compared for both samples: they are found to be consistent with each other for galaxies of intermediate luminosities, but some differences are found for high (>5×1010 Lsolar) luminosities. The shallowness of the IRAS survey prevents us from securing a comparison at low luminosities (<2×109 Lsolar). The ratio of the total infrared (TIR) luminosity to the FUV luminosity is found to increase with the bolometric luminosity in a similar way for both samples up to 5×1010 Lsolar. Brighter galaxies are found to have a different behavior according to their selection: the LTIR/LFUV ratio of the FUV-selected galaxies brighter than 5×1010 Lsolar reaches a plateau, whereas LTIR/LFUV continues to increase with the luminosity of bright galaxies selected in FIR. The volume-averaged specific star formation rate (SFR per unit galaxy stellar mass, SSFR) is found to decrease toward massive galaxies within each selection. The mean values of the SSFR are found to be larger than those measured for optical and NIR-selected samples over the whole mass range for the FIR selection, and for masses larger than 1010 Msolar for the FUV selection. Luminous and massive galaxies selected in FIR appear as active as galaxies with similar characteristics detected at z~0.7.

Method and apparatus for noble gas atom detection with isotopic selectivity

DOEpatents

Hurst, G. Samuel; Payne, Marvin G.; Chen, Chung-Hsuan; Parks, James E.

1984-01-01

Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noble gas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noble gas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noble gas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noble gas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noble gas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noble gas isotope analyses are described.

Biodegradation of carbamazepine and clarithromycin by Trichoderma harzianum and Pleurotus ostreatus investigated by liquid chromatography - high-resolution tandem mass spectrometry (FTICR MS-IRMPD).

PubMed

Buchicchio, Alessandro; Bianco, Giuliana; Sofo, Adriano; Masi, Salvatore; Caniani, Donatella

2016-07-01

In this study, the capability of pharmaceutical biodegradation of fungus Trichoderma harzianum was evaluated through the comparison with the well-known biodegradation capability of white-rot fungus Pleurotus ostreatus. The study was performed in aqueous phase under aerobic conditions, using two of the most frequently detected drugs in water bodies: carbamazepine and clarithromycin, with concentrations commonly found in treated wastewater (4μg/l and 0.03μg/l respectively). For the first time, we demonstrated that T. harzianum is able to remove carbamazepine and clarithromycin. The analyses were performed by reversed-phase liquid chromatography/mass spectrometry, using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry upon electrospray ionization in positive ion mode. The high selectivity and mass accuracy provided by high-resolution mass spectrometry, allowed us to identify some unknown metabolites. On the basis of our study, the major metabolites detected in liquid culture treated by T. harzianum were: 14-hydroxy-descladinosyl- and descladinosyl-clarithromycin, which are pharmacologically inactive products not dangerous for the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Validation of a method to detect cocaine and its metabolites in nails by gas chromatography-mass spectrometry.

PubMed

Valente-Campos, Simone; Yonamine, Mauricio; de Moraes Moreau, Regina Lucia; Silva, Ovandir Alves

2006-06-02

The objective of the present work was to compare previously published methods and provide validation data to detect simultaneously cocaine (COC), benzoylecgonine (BE) and norcocaine (NCOC) in nail. Finger and toenail samples (5mg) were cut in very small pieces and submitted to an initial procedure for external decontamination. Methanol (3 ml) was used to release analytes from the matrix. A cleanup step was performed simultaneously by solid-phase extraction (SPE) and the residue was derivatized with pentafluoropropionic anhydride/pentafluoropropanol (PFPA/PFP). Gas chromatography-mass spectrometry (GC-MS) was used to detect the analytes in selected ion monitoring mode (SIM). Confidence parameters of validation of the method were: recovery, intra- and inter-assay precision, as well as limit of detection (LOD) of the analytes. The limits of detection were: 3.5 ng/mg for NCOC and 3.0 ng/mg for COC and BE. Good intra-assay precision was observed for all detected substances (coefficient of variation (CV)<11%). The inter-assay precision for norcocaine and benzoylecgonine were <4%. For intra- and inter-assay precision deuterated internal standards were used. Toenail and fingernail samples from eight declared cocaine users were submitted to the validated method.

Residual Agar Determination in Bacterial Spores by Electrospray Ionization Mass Spectrometry

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

Wahl, Karen L.; Colburn, Heather A.; Wunschel, David S.

2010-02-15

Presented here is an analytical method to detect residual agar from a bacterial spore sample as an indication of culturing on an agar plate. This method is based on the resolubilization of agar polysaccharide from a bacterial spore sample, enzymatic digestion, followed by electrospray ionization tandem mass spectrometry (ESI-MSn) analysis for detection of a specific agar fragment ion. A range of Bacillus species and strains were selected to demonstrate the effectiveness of this approach. The characteristic agar fragment ion was detected in the spores grown on agar that were washed from 1 to 5 times, irradiated or non-irradiated and notmore » in the spores grown in broth. A sample containing approximately 108 spores is currently needed for confident detection of residual agar from culture on agar plates in the presence of bacterial spores with a limit of detection of approximately 1 ppm agar spiked into a broth-grown spore sample. The results of a proficiency test with 42 blinded samples are presented demonstrating the utility of this method with no false positives and only 3 false negatives for samples that were below the detection level of the method as documented.« less

Determination of doping peptides via solid-phase microelution and accurate-mass quadrupole time-of-flight LC-MS.

PubMed

Cuervo, Darío; Loli, Cynthia; Fernández-Álvarez, María; Muñoz, Gloria; Carreras, Daniel

2017-10-15

A complete analytical protocol for the determination of 25 doping-related peptidic drugs and 3 metabolites in urine was developed by means of accurate-mass quadrupole time-of-flight (Q-TOF) LC-MS analysis following solid-phase extraction (SPE) on microplates and conventional SPE pre-treatment for initial testing and confirmation, respectively. These substances included growth hormone releasing factors, gonadotropin releasing factors and anti-diuretic hormones, with molecular weights ranging from 540 to 1320Da. Optimal experimental conditions were stablished after investigation of different parameters concerning sample preparation and instrumental analysis. Weak cation exchange SPE followed by C18 HPLC chromatography and accurate mass detection provided the required sensitivity and selectivity for all the target peptides under study. 2mg SPE on 96-well microplates can be used in combination with full scan MS detection for the initial testing, thus providing a fast, cost-effective and high-throughput protocol for the processing of a large batch of samples simultaneously. On the other hand, extraction on 30mg SPE cartridges and subsequent target MS/MS determination was the protocol of choice for confirmatory purposes. The methodology was validated in terms of selectivity, recovery, matrix effect, precision, sensitivity (limit of detection, LOD), cross contamination, carryover, robustness and stability. Recoveries ranged from 6 to 70% (microplates) and 17-95% (cartridges), with LODs from 0.1 to 1ng/mL. The suitability of the method was assessed by analyzing different spiked or excreted urines containing some of the target substances. Copyright © 2017 Elsevier B.V. All rights reserved.

Semi-automated solid phase extraction method for the mass spectrometric quantification of 12 specific metabolites of organophosphorus pesticides, synthetic pyrethroids, and select herbicides in human urine.

PubMed

Davis, Mark D; Wade, Erin L; Restrepo, Paula R; Roman-Esteva, William; Bravo, Roberto; Kuklenyik, Peter; Calafat, Antonia M

2013-06-15

Organophosphate and pyrethroid insecticides and phenoxyacetic acid herbicides represent important classes of pesticides applied in commercial and residential settings. Interest in assessing the extent of human exposure to these pesticides exists because of their widespread use and their potential adverse health effects. An analytical method for measuring 12 biomarkers of several of these pesticides in urine has been developed. The target analytes were extracted from one milliliter of urine by a semi-automated solid phase extraction technique, separated from each other and from other urinary biomolecules by reversed-phase high performance liquid chromatography, and detected using tandem mass spectrometry with isotope dilution quantitation. This method can be used to measure all the target analytes in one injection with similar repeatability and detection limits of previous methods which required more than one injection. Each step of the procedure was optimized to produce a robust, reproducible, accurate, precise and efficient method. The required selectivity and sensitivity for trace-level analysis (e.g., limits of detection below 0.5ng/mL) was achieved using a narrow diameter analytical column, higher than unit mass resolution for certain analytes, and stable isotope labeled internal standards. The method was applied to the analysis of 55 samples collected from adult anonymous donors with no known exposure to the target pesticides. This efficient and cost-effective method is adequate to handle the large number of samples required for national biomonitoring surveys. Published by Elsevier B.V.

Detection and quantification of proteins and cells by use of elemental mass spectrometry: progress and challenges.

PubMed

Yan, Xiaowen; Yang, Limin; Wang, Qiuquan

2013-07-01

Much progress has been made in identification of the proteins in proteomes, and quantification of these proteins has attracted much interest. In addition to popular tandem mass spectrometric methods based on soft ionization, inductively coupled plasma mass spectrometry (ICPMS), a typical example of mass spectrometry based on hard ionization, usually used for analysis of elements, has unique advantages in absolute quantification of proteins by determination of an element with a definite stoichiometry in a protein or attached to the protein. In this Trends article, we briefly describe state-of-the-art ICPMS-based methods for quantification of proteins, emphasizing protein-labeling and element-tagging strategies developed on the basis of chemically selective reactions and/or biospecific interactions. Recent progress from protein to cell quantification by use of ICPMS is also discussed, and the possibilities and challenges of ICPMS-based protein quantification for universal, selective, or targeted quantification of proteins and cells in a biological sample are also discussed critically. We believe ICPMS-based protein quantification will become ever more important in targeted quantitative proteomics and bioanalysis in the near future.

Comparison of the Detection Characteristics of Trace Species Using Laser-Induced Breakdown Spectroscopy and Laser Breakdown Time-of-Flight Mass Spectrometry

PubMed Central

Wang, Zhenzhen; Deguchi, Yoshihiro; Yan, Junjie; Liu, Jiping

2015-01-01

The rapid and precise element measurement of trace species, such as mercury, iodine, strontium, cesium, etc. is imperative for various applications, especially for industrial needs. The elements mercury and iodine were measured by two detection methods for comparison of the corresponding detection features. A laser beam was focused to induce plasma. Emission and ion signals were detected using laser-induced breakdown spectroscopy (LIBS) and laser breakdown time-of-flight mass spectrometry (LB-TOFMS). Multi-photon ionization and electron impact ionization in the plasma generation process can be controlled by the pressure and pulse width. The effect of electron impact ionization on continuum emission, coexisting molecular and atomic emissions became weakened in low pressure condition. When the pressure was less than 1 Pa, the plasma was induced by laser dissociation and multi-photon ionization in LB-TOFMS. According to the experimental results, the detection limits of mercury and iodine in N2 were 3.5 ppb and 60 ppb using low pressure LIBS. The mercury and iodine detection limits using LB-TOFMS were 1.2 ppb and 9.0 ppb, which were enhanced due to different detection features. The detection systems of LIBS and LB-TOFMS can be selected depending on the condition of each application. PMID:25769051

Comparison of capillary electrophoresis-mass spectrometry and hydrophilic interaction chromatography-mass spectrometry for anionic metabolic profiling of urine.

PubMed

Kok, Miranda G M; Somsen, Govert W; de Jong, Gerhardus J

2015-01-01

In order to assess the utility of a recently developed capillary electrophoresis-mass spectrometry (CE-MS) method for the study of anionic metabolites in urine, a comparison was made with hydrophilic interaction chromatography-MS (HILIC-MS) using negative electrospray ionization. After optimization of the HILIC conditions, a gradient employing 10mM ammonium acetate (pH 6.8) in acetonitrile-water (5 min 90% acetonitrile followed by 90%-50% acetonitrile in 10 min) was selected, providing baseline separation of five representative anionic test metabolites. Relative standard deviations (RSDs) for HILIC retention times and peak areas were below 0.2% and 7.7%, respectively, and detection limits were in the range 0.04-2.21 μM. Metabolites in rat urine could also be analysed in a reproducible way with retention time and peak area RSDs below 0.6% and 13.6%, respectively. The CE-MS and HILIC-MS methods were compared in terms of reproducibility, sensitivity, selectivity and coverage of the anionic urinary metabolome. In general, peak area RSDs were similar whereas HILIC-MS yielded better retention-time repeatability and up to 80 times lower detection limits (expressed in injected concentration) for test metabolites as compared to CE-MS. Rat urine analysis by HILIC-MS provided detection of 1360 molecular features compared to 347 molecular features revealed with CE-MS. Of these, a number of 144 molecular features were found with both HILIC-MS and CE-MS, which showed on average 10 times higher peak areas in HILIC-MS. The HILIC retention and CE migration times of the common features were clearly not correlated. The HILIC and CE behavior of the test metabolites and 16 putatively identified common features were evaluated involving their physicochemical properties, indicating a markedly different separation selectivity, and thus significant degree of orthogonality of HILIC and CE. Copyright © 2014 Elsevier B.V. All rights reserved.

A new high selective and sensitive turn-on fluorescent and ratiometric absorption chemosensor for Cu2+ based on benzimidazole in aqueous solution and its application in live cell.

PubMed

Bing, Qijing; Wang, Lin; Li, Donglin; Wang, Guang

2018-09-05

A new benzimidazole base turn-on fluorescent and ratiometric absorption chemosensor (L) bearing bidentate ligand for detection of Cu 2+ was designed and synthesized. Fluorescence and UV-vis spectra studies demonstrated that L can detect Cu 2+ ions in aqueous solution using fluorescence enhancement and ratiometric absorption sensing over a wide pH range. Both fluorescent and ratiometric absorption sensing of L for Cu 2+ possessed high selectivity and sensitivity over other competitive metal ions and had low detection limit. Job's plot, mass spectra and DFT calculation indicated the sensing mechanism is the complex formation between L and Cu 2+ with 1:2 stoichiometry. Fluorescence images of HepG2 in the absence and presence of Cu 2+ displayed L had cell permeability and detection ability for Cu 2+ in live cells. Copyright © 2018 Elsevier B.V. All rights reserved.

Measuring Low Mass Galaxies In The WFC3 Infrared Spectroscopic Parallels Survey

NASA Astrophysics Data System (ADS)

Colbert, James; Teplitz, Harry; Scarlata, Claudia; Siana, Brian; Malkan, Matt; McCarthy, Patrick; Henry, Alaina; Atek, Hakim; Fosbury, Robert; Ross, Nathanial; Hathi, Nimish; Bridge, Carrie; Bunker, Andrew; Dressler, Alan; Shim, Hyunjin; Bedregal, Alejandro; Dominguez, Alberto; Rafelski, Marc; Masters, Dan; Martin, Crystal; Dai, Sophia

2015-10-01

The WFC3 Infrared Spectroscopic Parallel (WISP) Survey uses over 1800 HST orbits to study galaxy evolution over a majority of cosmic history. Its slitless grism spectroscopy over a wide, continuous spectral range (0.8-1.7 micron) provides an unbiased selection of thousands of emission line galaxies over 0.5 < z < 2.5. Hundreds of these galaxies are detected in multiple emission lines, allowing for important diagnostics of metallicity and dust extinction. We propose deep 3.6 micron imaging (5 sigma, 0.9 micro-Jy) of 60 of the deepest WISP fields observed with the combination of G102+G141 grisms, in order to detect emission-line galaxies down to 0.1 L* and masses below 10^8 Mo. Combined with our HST optical and near-IR photometry, these IRAC data will be critical to determining accurate stellar masses for both passive and active galaxies in our survey. We will determine the evolution of the faint end slope of the stellar mass function and the mass-metallicity relation down to low-mass galaxies. The addition of the IRAC photometry will also provide much stronger constraints on dust extinction and star formation history, especially when combined with information available from the emission lines themselves.

Characterization of crude oil biomarkers using comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry.

PubMed

Mogollón, Noroska Gabriela Salazar; Prata, Paloma Santana; Dos Reis, Jadson Zeni; Neto, Eugênio Vaz Dos Santos; Augusto, Fabio

2016-09-01

Oil samples from Recôncavo basin (NE Brazil), previously analyzed by traditional techniques such as gas chromatography coupled to tandem mass spectrometry, were evaluated using comprehensive two-dimensional gas chromatography coupled to quadrupole mass spectrometry and comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry along with simplified methods of samples preparation to evaluate the differences and advantages of these analytical techniques to better understand the development of the organic matter in this basin without altering the normal distribution of the compounds in the samples. As a result, the geochemical parameters calculated by comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry described better the origin, maturity, and biodegradation of both samples probably by increased selectivity, resolution, and sensitivity inherent of the multidimensional technique. Additionally, the detection of the compounds such as, the C(14α-) homo-26-nor-17α-hopane series, diamoretanes, nor-spergulanes, C19 -C26 A-nor-steranes and 4α-methylsteranes resolved and detected by comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry were key to classify and differentiate these lacustrine samples according to their maturity and deposition conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas chromatographic quadrupole time-of-flight full scan high resolution mass spectrometric screening of human urine in antidoping analysis.

PubMed

Abushareeda, Wadha; Lyris, Emmanouil; Kraiem, Suhail; Wahaibi, Aisha Al; Alyazidi, Sameera; Dbes, Najib; Lommen, Arjen; Nielen, Michel; Horvatovich, Peter L; Alsayrafi, Mohammed; Georgakopoulos, Costas

2017-09-15

This paper presents the development and validation of a high-resolution full scan (FS) electron impact ionization (EI) gas chromatography coupled to quadrupole Time-of-Flight mass spectrometry (GC/QTOF) platform for screening anabolic androgenic steroids (AAS) in human urine samples. The World Antidoping Agency (WADA) enlists AAS as prohibited doping agents in sports, and our method has been developed to comply with the qualitative specifications of WADA to be applied for the detection of sports antidoping prohibited substances, mainly for AAS. The method also comprises of the quantitative analysis of the WADA's Athlete Biological Passport (ABP) endogenous steroidal parameters. The applied preparation of urine samples includes enzymatic hydrolysis for the cleavage of the Phase II glucuronide conjugates, generic liquid-liquid extraction and trimethylsilyl (TMS) derivatization steps. Tandem mass spectrometry (MS/MS) acquisition was applied on few selected ions to enhance the specificity and sensitivity of GC/TOF signal of few compounds. The full scan high resolution acquisition of analytical signal, for known and unknown TMS derivatives of AAS provides the antidoping system with a new analytical tool for the detection designer drugs and novel metabolites, which prolongs the AAS detection, after electronic data files' reprocessing. The current method is complementary to the respective liquid chromatography coupled to mass spectrometry (LC/MS) methodology widely used to detect prohibited molecules in sport, which cannot be efficiently ionized with atmospheric pressure ionization interface. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of various liquid chromatographic methods involving UV and atmospheric pressure chemical ionization mass spectrometric detection for the efficient trace analysis of phenylurea herbicides in various types of water samples.

PubMed

van der Heeft, E; Dijkman, E; Baumann, R A; Hogendoorn, E A

2000-05-19

The performance of mass spectrometric (MS) detection and UV detection in combination with reversed-phase liquid chromatography without and with the use of coupled column RPLC (LC-LC) has been compared for the trace analysis of phenylurea herbicides in environmental waters. The selected samples of this comparative study originated from an inter-laboratory study. For both detection modes, a 50 mm x 4.6 mm I.D. column and a 100 mm x 4.6 mm I.D. column packed with 3 microm C18 were used as the first (C-1) and second (C-2) column, respectively. Atmospheric pressure chemical ionization mass spectrometry was performed on a magnetic sector instrument. The LC-LC-MS analysis was carried out on-line by means of direct large volume (11.7 ml) injection (LVI). The performance of both on-line (LVI, 4 ml of sample) and off-line LC-LC-UV (244 nm) analysis was investigated. The latter procedure consisted of a solid-phase extraction (SPE) of 250 ml of water sample on a 500 mg C18 cartridge. The comparative study showed that LC-LC-MS is more selective then LC-LC-UV and, in most cases, more sensitive. The LVI-LC-LC-MS approach combines direct quantification and confirmation of most of the analytes down to a level of 0.01 microg/l in water samples in less then 30 min. As regards LC-LC-UV, the off-line method appeared to be a more viable approach in comparison with the on-line procedure. This method allows the screening of phenylurea's in various types of water samples down to a level of at least 0.05 microg/l. On-line analysis with LVI provided marginal sensitivity (limits of detection of about 0.1 microg/l) and selectivity was sometimes less in case of surface water samples. Both the on-line LVI-LC-LC-MS method and the LC-LC-UV method using off-line SPE were validated by analysing a series of real-life reference samples. These samples were part of an inter-laboratory test and contained residues of herbicides ranging from 0.02 to 0.8 microg/l. Beside good correlation between the methods the data agreed very well with the true values of the samples.

Breath analysis using external cavity diode lasers: a review

NASA Astrophysics Data System (ADS)

Bayrakli, Ismail

2017-04-01

Most techniques that are used for diagnosis and therapy of diseases are invasive. Reliable noninvasive methods are always needed for the comfort of patients. Owing to its noninvasiveness, ease of use, and easy repeatability, exhaled breath analysis is a very good candidate for this purpose. Breath analysis can be performed using different techniques, such as gas chromatography mass spectrometry (MS), proton transfer reaction-MS, and selected ion flow tube-MS. However, these devices are bulky and require complicated procedures for sample collection and preconcentration. Therefore, these are not practical for routine applications in hospitals. Laser-based techniques with small size, robustness, low cost, low response time, accuracy, precision, high sensitivity, selectivity, low detection limit, real-time, and point-of-care detection have a great potential for routine use in hospitals. In this review paper, the recent advances in the fields of external cavity lasers and breath analysis for detection of diseases are presented.

Environmental applications for the analysis of chlorinated dibenzo-p-dioxins and dibenzofurans using mass spectrometry/mass spectrometry

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

Reiner, E.J.; Schellenberg, D.H.; Taguchi, V.Y.

1991-01-01

A mass spectrometry/mass spectrometry-multiple reaction monitoring (MS/MS-MRM) technique for the analysis of all tetra- through octachlorinated dibenzo-p-dioxins (Cl{sub x}DD, x = 4-8) and dibenzofurans (Cl{sub x}DF, x = 4-8) has been developed at the Ministry of the Environment (MOE) utilizing a triple quadrupole mass spectrometer. Optimization of instrumental parameters using the analyte of interest in a direct insertion probe (DIP) resulted in sensitivities approaching those obtainable by high-resolution mass spectrometric (HRMS) methods. All congeners of dioxins and furans were detected in the femtogram range. Results on selected samples indicated that for some matrices, fewer chemical interferences were observed by MS/MSmore » than by HRMS. The technique used to optimize the instrument for chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs) analysis is adaptable to other analytes.« less

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

NASA Technical Reports Server (NTRS)

Yu, Anthony W.; Li, Steven X.; Fahey, Molly E.; Grubisic, Andrej; Farcy, Benjamin J.; Uckert, Kyle; Li, Xiang; Getty, Stephanie

2017-01-01

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 µm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Potentialities of mass spectrometry (ICP-MS) for actinides determination in urine.

PubMed

Bouvier-Capely, C; Ritt, J; Baglan, N; Cossonnet, C

2004-05-01

The applicability of inductively coupled plasma-mass spectrometry (ICP-MS) for determining actinides in urine was investigated. Performances of ICP-MS including detection limit and analysis time were studied and compared with alpha spectrometry performances. In the field of individual monitoring of workers, the comparison chart obtained in this study can be used as a guide for medical laboratories to select the most adequate procedure to be carried out depending on the case in question (the radioisotope to be measured, the required sensitivity, and the desired response time).

Simultaneous determination of three major lignans in rat plasma by LC-MS/MS and its application to a pharmacokinetic study after oral administration of Diphylleia sinensis extract.

PubMed

Zhao, Chengliang; Zhang, Nan; He, Weiyan; Li, Rui; Shi, Dan; Pang, Li; Dong, Ning; Xu, Hong; Ji, Honglei

2014-04-01

A sensitive and selective liquid chromatography tandem mass spectrometry was developed and validated for the simultaneous determination of three major lignans (podophyllotoxin, epipodophyllotoxin, and 4'-demethylpodophyllotoxin) in rat plasma using diphenhydramine as the internal standard. The analytes were detected using a triple quadrupole mass spectrometer that was equipped with an electrospray ionization source in the positive ion and selected reaction monitoring modes. The linearity of the calibration curve was good, with coefficients of determination (r(2) ) >0.9914 for all of the analytes. The developed method was successfully applied for the simultaneous determination of the three lignans in rat plasma following oral administration of Diphylleia sinensis extract to rats. Copyright © 2013 John Wiley & Sons, Ltd.

Search for X-ray Emission from AGB Stars in the Coronal Graveyard

NASA Astrophysics Data System (ADS)

Montez, Rodolfo

2013-10-01

Maser observations demonstrate the existence of magnetic fields in the circumstellar envelopes of AGB stars. However, thus far, only 2-3 AGB stars have exhibited evidence for coronal X-ray emission. We have demonstrated that only the sensitivity of modern X-ray telescopes can detect magnetically-induced coronal emission and have identified a sample of AGB stars which are ideal candidates to search for such emission. Specifically, we have selected a sample of AGB stars with SiO maser emission, UV emission in at least one of the GALEX bandpasses, and low mass loss rates. The four selected AGB stars provide a pilot sample that optimally probes for coronal activity beyond the giant phase and that provides valuable tests for the launching and shaping of AGB mass loss.

The Atacama Cosmology Telescope: The Two-season ACTPol Sunyaev–Zel’dovich Effect Selected Cluster Catalog

NASA Astrophysics Data System (ADS)

Hilton, Matt; Hasselfield, Matthew; Sifón, Cristóbal; Battaglia, Nicholas; Aiola, Simone; Bharadwaj, V.; Bond, J. Richard; Choi, Steve K.; Crichton, Devin; Datta, Rahul; Devlin, Mark J.; Dunkley, Joanna; Dünner, Rolando; Gallardo, Patricio A.; Gralla, Megan; Hincks, Adam D.; Ho, Shuay-Pwu P.; Hubmayr, Johannes; Huffenberger, Kevin M.; Hughes, John P.; Koopman, Brian J.; Kosowsky, Arthur; Louis, Thibaut; Madhavacheril, Mathew S.; Marriage, Tobias A.; Maurin, Loïc; McMahon, Jeff; Miyatake, Hironao; Moodley, Kavilan; Næss, Sigurd; Nati, Federico; Newburgh, Laura; Niemack, Michael D.; Oguri, Masamune; Page, Lyman A.; Partridge, Bruce; Schmitt, Benjamin L.; Sievers, Jon; Spergel, David N.; Staggs, Suzanne T.; Trac, Hy; van Engelen, Alexander; Vavagiakis, Eve M.; Wollack, Edward J.

2018-03-01

We present a catalog of 182 galaxy clusters detected through the Sunyaev–Zel’dovich (SZ) effect by the Atacama Cosmology Telescope in a contiguous 987.5 deg2 field. The clusters were detected as SZ decrements by applying a matched filter to 148 GHz maps that combine the original ACT equatorial survey with data from the first two observing seasons using the ACTPol receiver. Optical/IR confirmation and redshift measurements come from a combination of large public surveys and our own follow-up observations. Where necessary, we measured photometric redshifts for clusters using a pipeline that achieves accuracy Δz/(1 + z) = 0.015 when tested on Sloan Digital Sky Survey data. Under the assumption that clusters can be described by the so-called universal pressure profile (UPP) and its associated mass scaling law, the full signal-to-noise ratio > 4 sample spans the mass range 1.6< {M}500{{c}}UPP}/{10}14 {M}ȯ < 9.1, with median {M}500{{c}}UPP}=3.1× {10}14 {M}ȯ . The sample covers the redshift range 0.1 < z < 1.4 (median z = 0.49), and 28 clusters are new discoveries (median z = 0.80). We compare our catalog with other overlapping cluster samples selected using the SZ, optical, and X-ray wavelengths. We find that the ratio of the UPP-based SZ mass to richness-based weak-lensing mass is < {M}500{{c}}UPP}> /< {M}500{{c}}λ {WL}> =0.68+/- 0.11. After applying this calibration, the mass distribution for clusters with M 500c > 4 × 1014 M ⊙ is consistent with the number of such clusters found in the South Pole Telescope SZ survey.

Panchromatic properties of 99000 galaxies detected by SDSS, and (some by) ROSAT, GALEX, 2MASS, IRAS, GB6, FIRST, NVSS and WENSS surveys

NASA Astrophysics Data System (ADS)

Obrić, M.; Ivezić, Ž.; Best, P. N.; Lupton, R. H.; Tremonti, C.; Brinchmann, J.; Agüeros, M. A.; Knapp, G. R.; Gunn, J. E.; Rockosi, C. M.; Schlegel, D.; Finkbeiner, D.; Gaćeša, M.; Smolčić, V.; Anderson, S. F.; Voges, W.; Jurić, M.; Siverd, R. J.; Steinhardt, W.; Jagoda, A. S.; Blanton, M. R.; Schneider, D. P.

2006-08-01

We discuss the panchromatic properties of 99088 galaxies selected from the Sloan Digital Sky Survey (SDSS) Data Release 1 `main' spectroscopic sample (a flux-limited sample for 1360deg2). These galaxies are positionally matched to sources detected by ROSAT, Galaxy Evolution Explorer (GALEX), two-Micron All-Sky Survey (2MASS), Infrared Astronomical Satellite (IRAS), Green Bank GB6 survey (GB6), Faint Images of the Radio Sky at Twenty-centimetres (FIRST), NRAO VLA Sky Survey (NVSS) and Westerbork Northern Sky Survey (WENSS). The matching fraction varies from <1 per cent for ROSAT and GB6 to ~40 per cent for GALEX and 2MASS. In addition to its size, the advantages of this sample are well-controlled selection effects, faint flux limits and the wealth of measured parameters, including accurate X-ray to radio photometry, angular sizes and optical spectra. We find strong correlations between the detection fraction at other wavelengths and optical properties such as flux, colours and emission-line strengths. For example, ~2/3 of SDSS `main' galaxies classified as active galactic nucleus (AGN) using emission-line strengths are detected by 2MASS, while the corresponding fraction for star-forming galaxies (SFs) is only ~1/10. Similarly, over 90 per cent of galaxies detected by IRAS display strong emission lines in their optical spectra, compared to ~50 per cent for the whole SDSS sample. Using GALEX, SDSS and 2MASS data, we construct the ultraviolet-infrared (UV-IR) broad-band spectral energy distributions for various types of galaxies, and find that they form a nearly one-parameter family. For example, the SDSS u- and r-band data, supplemented with redshift, can be used to `predict' K-band magnitudes measured by 2MASS with an rms scatter of only 0.2mag. When a dust content estimate determined from SDSS spectra with the aid of models is also utilized, this scatter decreases to 0.1mag and can be fully accounted for by measurement uncertainties. We demonstrate that this interstellar dust content, inferred from optical SDSS spectra by Kauffmann et al., is indeed higher for galaxies detected by IRAS and that it can be used to `predict' measured IRAS 60μm flux density within a factor of 2 using only SDSS data. We also show that the position of a galaxy in the emission-line-based Baldwin-Phillips-Terlevich diagram is correlated with the optical light concentration index and u - r colour determined from the SDSS broad-band imaging data, and discuss changes in the morphology of this diagram induced by requiring detections at other wavelengths. Notably, we find that SDSS `main' galaxies detected by GALEX include a non-negligible fraction (10-30 per cent) of AGNs, and hence do not represent a clean sample of starburst galaxies. We study the IR-radio correlation and find evidence that its slope may be different for AGN and SFs and related to the Hα/Hβ line-strength ratio.

Relationships between HI Gas Mass, Stellar Mass and Star Formation Rate of HICAT+WISE Galaxies

NASA Astrophysics Data System (ADS)

Parkash, Vaishali; Brown, Michael J. I.

2018-01-01

Galaxies grow via a combination of star formation and mergers. In this thesis, I have studied what drives star formation in nearby galaxies. Using archival WISE, Galex, 21-cm data and new IFU observations, I examine the HI content, Hα emission, stellar kinematics, and gas kinematics of three sub-classes of galaxies: spiral galaxies, shell galaxies and HI galaxies with unusually low star formation rates (SFR). In this dissertation talk, I will focus on the scaling relations between atomic (HI) gas, stellar mass and SFR of spiral galaxies. Star formation is fuelled by HI and molecular hydrogen, therefore we expect correlations between HI mass, stellar mass and SFR. However, the measured scaling relationships vary in the prior literature due to sample selection or low completeness. I will discuss new scaling relationships determined using HI Parkes All Sky-Survey Catalogue (HICAT) and the Wide-field Infrared Survey Explorer (WISE). The combination of the local HICAT survey with sensitive WISE mid-infrared imaging improves the stellar masses, SFRs and completeness relative to previous literature. Of the 3,513 HICAT sources, we find 3.4 μm counterparts for 2,824 sources (80%), and provide new WISE matched aperture photometry for these galaxies. For a stellar mass selected sample of z ≤ 0.01 spiral galaxies, we find HI detections for 94% of the galaxies, enabling us to accurately measure HI mass as a function of stellar mass. In contrast to HI-selected galaxy samples, we find that star formation efficiency of spiral galaxies is constant at 10-9.5 yr‑1 with a scatter of 0.5 dex for stellar masses above 109.5 solar masses. We find HI mass increases with stellar mass for spiral galaxies, but the scatter is 1.7 dex for all spiral galaxies and 0.6 dex for galaxies with the T-type 5 to 7. We find an upper limit on HI mass that depends on stellar mass, which is consistent with this limit being dictated by the halo spin parameter.

The expanding role of mass spectrometry in the field of vaccine development.

PubMed

Sharma, Vaneet Kumar; Sharma, Ity; Glick, James

2018-05-31

Biological mass spectrometry has evolved as a core analytical technology in the last decade mainly because of its unparalleled ability to perform qualitative as well as quantitative profiling of enormously complex biological samples with high mass accuracy, sensitivity, selectivity and specificity. Mass spectrometry-based techniques are also routinely used to assess glycosylation and other post-translational modifications, disulfide bond linkage, and scrambling as well as for the detection of host cell protein contaminants in the field of biopharmaceuticals. The role of mass spectrometry in vaccine development has been very limited but is now expanding as the landscape of global vaccine development is shifting towards the development of recombinant vaccines. In this review, the role of mass spectrometry in vaccine development is presented, some of the ongoing efforts to develop vaccines for diseases with global unmet medical need are discussed and the regulatory challenges of implementing mass spectrometry techniques in a quality control laboratory setting are highlighted. © 2018 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc.

Selective and comprehensive analysis of organohalogen compounds by GC × GC-HRTofMS and MS/MS.

PubMed

Hashimoto, Shunji; Zushi, Yasuyuki; Takazawa, Yoshikatsu; Ieda, Teruyo; Fushimi, Akihiro; Tanabe, Kiyoshi; Shibata, Yasuyuki

2018-03-01

Thousands of organohalogen compounds, including hazardous chemicals such as polychlorinated biphenyls (PCBs) and other persistent organic pollutants (POPs), were selectively and simultaneously detected and identified with simple, or no, purification from environmental sample extracts by using several advanced methods. The methods used were software extraction from two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (GC × GC-HRTofMS) data, measurement by negative chemical ionization with HRTofMS, and neutral loss scanning (NLS) with GC × GC-MS/MS. Global and selective detection of organochlorines and bromines in environmental samples such as sediments and fly ash was achieved by NLS using GC × GC-MS/MS (QQQ), with the expected losses of 35 Cl and 79 Br. We confirmed that negative chemical ionization was effective for sensitive and selective ionization of organohalogens, even using GC × GC-HRTofMS. The 2D total ion chromatograms obtained by using negative chemical ionization and selective extraction of organohalogens using original software from data measured by electron impact ionization were very similar; the software thus functioned well to extract organohalogens. Combining measurements made by using these different methods will help to detect organohalogens selectively and globally. However, to compare the data obtained by individual measurements, the retention times of the peaks on the 2D chromatograms need to match.

Analysis of non-steroidal anti-inflammatory drugs in milk using QuEChERS and liquid chromatography coupled to mass spectrometry: triple quadrupole versus Q-Orbitrap mass analyzers.

PubMed

Rúbies, Antoni; Guo, Lili; Centrich, Francesc; Granados, Mercè

2016-08-01

We developed a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method for the high throughput determination of 10 non-steroidal anti-inflammatory drugs (NSAIDs) in milk samples using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) with a triple quadrupole (QqQ) instrument and an electrospray ionization (ESI) source. The new extraction procedure is highly efficient, and we obtained absolute recoveries in the range 78.1-97.1 % for the extraction and clean-up steps. Chromatographic separation is performed in the gradient mode with a biphenyl column and acidic mobile phases consisting of water and acetonitrile containing formic acid. The chromatographic run time was about 12 min, and NSAID peaks showed a good symmetry factor. For MS/MS detection, we used multiple reaction monitoring (MRM) mode, using ESI in both positive and negative modes. Our method has been validated in compliance with the European Commission Decision 657/2002/EC, and we obtained very satisfactory results in inter-laboratory testing. Furthermore, we explored the use of a hybrid high resolution mass spectrometer, combining a quadrupole and an Orbitrap mass analyzer, for high resolution (HR) MS/MS detection of NSAIDs. We achieved lower NSAID quantification limits with Q-Orbitrap high resolution mass spectrometry (HRMS/MS) detection than those achieved with the QqQ instrument; however, its main feature is its very high selectivity, which makes HRMS/MS particularly suitable for confirmatory analysis.

Results of the first continuous meteor head echo survey at polar latitudes

NASA Astrophysics Data System (ADS)

Schult, Carsten; Stober, Gunter; Janches, Diego; Chau, Jorge L.

2017-11-01

We present the first quasi continuous meteor head echo measurements obtained during a period of over two years using the Middle Atmosphere ALOMAR Radar System (MAARSY). The measurements yield information on the altitude, trajectory, vector velocity, radar cross section, deceleration and dynamical mass of every single event. The large statistical amount of nearly one million meteor head detections provide an excellent overview of the elevation, altitude, velocity and daily count rate distributions during different times of the year at polar latitudes. Only 40% of the meteors were detected within the full width half maximum of the specific sporadic meteor sources. Our observation of the sporadic meteors are compared to the observations with other radar systems and a meteor input function (MIF). The best way to compare different radar systems is by comparing the radar cross section (RCS), which is the main detection criterion for each system. In this study we aim to compare our observations with a MIF, which provides information only about the meteoroid mass. Thus, we are using a statistical approach for the elevation and velocity dependent visibility and a specific mass selection. The predicted absolute count rates from the MIF are in a good agreement with the observation when it is assumed that the radar system is only sensitive to meteoroids with masses higher than one microgram. The analysis of the dynamic masses seems to be consistent with this assumption since the count rate of events with smaller masses are low and decrease even more by using events with relatively small errors.

Chemical vapor detection using a capacitive micromachined ultrasonic transducer.

PubMed

Lee, Hyunjoo J; Park, Kwan Kyu; Kupnik, Mario; Oralkan, O; Khuri-Yakub, Butrus T

2011-12-15

Distributed sensing of gas-phase chemicals using highly sensitive and inexpensive sensors is of great interest for many defense and consumer applications. In this paper we present ppb-level detection of dimethyl methylphosphonate (DMMP), a common simulant for sarin gas, with a ppt-level resolution using an improved capacitive micromachined ultrasonic transducer (CMUT) as a resonant chemical sensor. The improved CMUT operates at a higher resonant frequency of 47.7 MHz and offers an improved mass sensitivity of 48.8 zg/Hz/μm(2) by a factor of 2.7 compared to the previous CMUT sensors developed. A low-noise oscillator using the CMUT resonant sensor as the frequency-selective device was developed for real-time sensing, which exhibits an Allan deviation of 1.65 Hz (3σ) in the presence of a gas flow; this translates into a mass resolution of 80.5 zg/μm(2). The CMUT resonant sensor is functionalized with a 50-nm thick DKAP polymer developed at Sandia National Laboratory for dimethyl methylphosphonate (DMMP) detection. To demonstrate ppb-level detection of the improved chemical sensor system, the sensor performance was tested at a certified lab (MIT Lincoln Laboratory), which is equipped with an experimental chemical setup that reliably and accurately delivers a wide range of low concentrations down to 10 ppb. We report a high volume sensitivity of 34.5 ± 0.79 pptv/Hz to DMMP and a good selectivity of the polymer to DMMP with respect to dodecane and 1-octanol.

Simultaneous determination of estrogenic odorant alkylphenols, chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry.

PubMed

Yuan, Su-Fen; Liu, Ze-Hua; Lian, Hai-Xian; Yang, Chuangtao; Lin, Qing; Yin, Hua; Dang, Zhi

2016-10-01

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R (2) > 0.989), low limit of detection (LOD, 0.002-0.5 μg/L), and excellent recoveries (76-126 %) with low relative standard deviation (RSD, 0.7-12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.

EVOLUTION IN THE H I GAS CONTENT OF GALAXY GROUPS: PRE-PROCESSING AND MASS ASSEMBLY IN THE CURRENT EPOCH

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

Hess, Kelley M.; Wilcots, Eric M., E-mail: hess@ast.uct.ac.za, E-mail: ewilcots@astro.wisc.edu

We present an analysis of the neutral hydrogen (H I) content and distribution of galaxies in groups as a function of their parent dark matter halo mass. The Arecibo Legacy Fast ALFA survey α.40 data release allows us, for the first time, to study the H I properties of over 740 galaxy groups in the volume of sky common to the Sloan Digital Sky Survey (SDSS) and ALFALFA surveys. We assigned ALFALFA H I detections a group membership based on an existing magnitude/volume-limited SDSS Data Release 7 group/cluster catalog. Additionally, we assigned group ''proximity' membership to H I detected objectsmore » whose optical counterpart falls below the limiting optical magnitude—thereby not contributing substantially to the estimate of the group stellar mass, but significantly to the total group H I mass. We find that only 25% of the H I detected galaxies reside in groups or clusters, in contrast to approximately half of all optically detected galaxies. Further, we plot the relative positions of optical and H I detections in groups as a function of parent dark matter halo mass to reveal strong evidence that H I is being processed in galaxies as a result of the group environment: as optical membership increases, groups become increasingly deficient of H I rich galaxies at their center and the H I distribution of galaxies in the most massive groups starts to resemble the distribution observed in comparatively more extreme cluster environments. We find that the lowest H I mass objects lose their gas first as they are processed in the group environment, and it is evident that the infall of gas rich objects is important to the continuing growth of large scale structure at the present epoch, replenishing the neutral gas supply of groups. Finally, we compare our results to those of cosmological simulations and find that current models cannot simultaneously predict the H I selected halo occupation distribution for both low and high mass halos.« less

Selective-Reagent-Ionization Mass Spectrometry: New Prospects for Atmospheric Research

NASA Astrophysics Data System (ADS)

Sulzer, Philipp; Jordan, Alfons; Hartungen, Eugen; Hanel, Gernot; Jürschik, Simone; Herbig, Jens; Märk, Lukas; Märk, Tilmann D.

2014-05-01

Proton-Transfer-Reaction Mass Spectrometry (PTR-MS), which was introduced to the scientific community in the 1990's, has quickly evolved into a well-established technology for atmospheric research and environmental chemistry [1]. Advantages of PTR-MS are i) high sensitivities of several hundred cps/ppbv, ii) detection limits at or below the pptv level, iii) direct injection sampling (i.e. no sample preparation), iv) response times in the 100 ms regime and v) online quantification. However, one drawback is a somehow limited selectivity, as in case of quadrupole mass filter based instruments only information about nominal m/z are available. In Time-Of-Flight (TOF) mass analyzer based instruments selectivity is drastically increased by a high mass resolution of up to 8000 m/Δm, but e.g. isomers still cannot be separated. In 2009 we introduced an advanced version of PTR-MS, which permits switching the reagent ions from H3O+ to NO+ and O2+, respectively [2]. This novel type of instrumentation was called Selective-Reagent-Ionization Mass Spectrometry (SRI-MS) and has been successfully used to separate isomers, e.g. the biogenic compounds isoprene and 2-methyl-3-buten-2-ol as shown by Karl et al. [3]. Switching the reagent ions dramatically increases selectivity and thus applicability of SRI-MS in atmospheric research. Here we report on the latest results utilizing an even more advanced embodiment of SRI-MS enabling the use of the additional reagent ions Kr+ and Xe+ [4]. With this technology important atmospheric compounds, such as CO2, CO, CH4, O2, etc. can be quantified and selectivity is increased even further. We present comparison data between diesel and gasoline car exhaust gases and quantitative data on indoor air for these compounds, which are not detectable with classical PTR-MS. Additionally, we show very recent examples of isomers which cannot be separated with PTR-MS but can clearly be distinguished with SRI-MS. Finally, we give an overview of ongoing SRI-MS developments, which include TOF based instruments with increased sensitivity of one order of magnitude (i.e. in the 103 cps/ppbv regime) by means of using a quadrupole ion guide between the drift tube and the TOF analyzer. It is expected that these developments will have a serious impact in atmospheric research, because increased sensitivity implies reduced measurement times and thus, e.g. even more accurate flux measurements. References [1] J. de Gouw, C. Warneke, T. Karl, G. Eerdekens, C. van der Veen, R. Fall, Mass Spectrometry Reviews, 26 (2007), 223-257. [2] A. Jordan, S. Haidacher, G. Hanel, E. Hartungen, J. Herbig, L. Märk, R. Schottkowsky, H. Seehauser, P. Sulzer, T.D. Märk, International Journal of Mass Spectrometry, 286 (2009), 32 - 38. [3] T. Karl, A. Hansel, L. Cappellin, L. Kaser, I. Herdlinger-Blatt, W. Jud, Atmospheric Chemistry and Physics, 12/24 (2012), 11877-11884. [4] P. Sulzer, A. Edtbauer, E. Hartungen, S. Juerschik, A. Jordan, G. Hanel, S. Feil, S. Jaksch, L. Märk, T.D. Märk, International Journal of Mass Spectrometry, 321 (2012), 66-70. Acknowledgement We acknowledge financial support by the Austrian Research Promotion Agency (FFG), Wien.

The POKEMON Speckle Survey of Nearby M-Dwarfs

NASA Astrophysics Data System (ADS)

van Belle, Gerard; von Braun, Kaspar; Horch, Elliott; Clark, Catherine; DSSI Speckle Team

2018-01-01

The POKEMON (Pervasive Overview of Kompanions of Every M-dwarf in Our Neighborhood) survey of nearby M-dwarfs intends to inspect, at diffraction-limited resolution, every low-mass star out to 15pc, along with selected additional objects to 25pc. The primary emphasis of the survey is detection of low-mass companions to these M-dwarfs for refinement of the low-mass star multiplicity rate. The resultant catalog of M-dwarf companions will also guide immediate refinement of transit planet detection results from surveys such as TESS. POKEMON is using Lowell Observatory's 4.3-m Discovery Channel Telescope (DCT) with the Differential Speckle Survey Instrument (DSSI) speckle camera, along with the NN-Explore Exoplanet Stellar Speckle Imager (NESSI) speckle imager on 3.5-m WIYN; the survey takes advantage of the extremely rapid observing cadence rates possible with WIYN and (especially) DCT. The current status and preliminary results from the first 20+ nights of observing will be presented. Gotta observe them all!

Pharmaceuticals in grocery market fish fillets by gas chromatography-mass spectrometry.

PubMed

Mottaleb, Musavvir Arafat; Stowe, Carly; Johnson, Daniel R; Meziani, Mohammed J; Mottaleb, M Abdul

2016-01-01

Occurrences of pharmaceuticals are evident in aquatic organisms. A reproducible gas chromatography-mass spectrometry (GC-MS) method using selected ion monitoring (SIM) has been used to determine the anti-histamine diphenhydramine (DPH), anti-anxiety diazepam (DZP), anti-seizure carbamazepine (CZP) drugs and their metabolites in grocery stores fish that were homogenized, extracted, pre-concentrated, cleaned up, and examined. Identifications of the compounds in extracts were obtained by comparing similar mass spectral features and retention properties with standards. Among nine frequently detected drugs, only DPH and DZP were observed and ranged from 0.61 to 6.21 and 1.99 to 16.57 ng/g, respectively, in fourteen fish species. These concentration values were lower than the environmental fish. Mean spike recoveries of analytes exceeded 75% with relative standard deviations (RSD)<10%. The statistically-derived method detection limits (MDLs) for nine compounds ranged from 0.13 to 5.56 ng/g. Average surrogate recoveries were 80-85% with 4-9% RSD. Copyright © 2015 Elsevier Ltd. All rights reserved.

The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

PubMed

Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail А; Pod'yachev, Sergey P

2014-06-01

A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide. Copyright © 2014 Elsevier B.V. All rights reserved.

Simultaneous screening for 238 drugs in blood by liquid chromatography-ion spray tandem mass spectrometry with multiple-reaction monitoring.

PubMed

Gergov, M; Ojanperä, I; Vuori, E

2003-09-25

A liquid chromatography-tandem mass spectrometry (LC-MS-MS) method is presented for the qualitative screening for 238 drugs in blood samples, which is considerably more than in previous methods. After a two-step liquid-liquid extraction and C(18) chromatography, the compounds were introduced into a triple quadrupole mass spectrometer equipped with a turbo ion spray ion source operating in the positive ionization mode. Identification was based on the compound's absolute retention time, protonated molecular ion, and one representative fragment ion obtained by multiple reaction monitoring (MRM) at an individually selected collision energy of 20, 35, or 50 eV. The limit of detection (LOD) for the majority of the compounds (80%) was < or = 0.05 mg/l, ranging from 0.002 mg/l (e.g., antihistamines) to 5 mg/l (acidic compounds), and for malathion it was 10 mg/l. The LOD values were sufficiently low to allow the majority of compounds to be detected at therapeutic concentrations in the blood.

Mass Spectrometer Containing Multiple Fixed Collectors

NASA Technical Reports Server (NTRS)

Moskala, Robert; Celo, Alan; Voss, Guenter; Shaffer, Tom

2008-01-01

A miniature mass spectrometer that incorporates features not typically found in prior mass spectrometers is undergoing development. This mass spectrometer is designed to simultaneously measure the relative concentrations of five gases (H2, He, N2, O2, and Ar) in air, over the relative-concentration range from 10(exp -6) to 1, during a sampling time as short as 1 second. It is intended to serve as a prototype of a product line of easy-to-use, portable, lightweight, highspeed, relatively inexpensive instruments for measuring concentrations of multiple chemical species in such diverse applications as detecting explosive or toxic chemicals in air, monitoring and controlling industrial processes, measuring concentrations of deliberately introduced isotopes in medical and biological investigations, and general environmental monitoring. The heart of this mass spectrometer is an integral combination of a circular cycloidal mass analyzer, multiple fixed ion collectors, and two mass-selective ion sources. By circular cycloidal mass analyzer is meant an analyzer that includes (1) two concentric circular cylindrical electrodes for applying a radial electric field and (2) a magnet arranged to impose a magnetic flux aligned predominantly along the cylindrical axis, so that ions, once accelerated into the annulus between the electrodes, move along circular cycloidal trajectories. As in other mass analyzers, trajectory of each ion is determined by its mass-to-charge ratio, and so ions of different species can be collected simultaneously by collectors (Faraday cups) at different locations intersected by the corresponding trajectories (see figure). Unlike in other mass analyzers, the installation of additional collectors to detect additional species does not necessitate increasing the overall size of the analyzer assembly.

Total cyanide mass measurement with micro-ion selective electrode for determination of specific activity of carbon-11 cyanide.

PubMed

Shea, Colleen; Alexoff, David L; Kim, Dohyun; Hoque, Ruma; Schueller, Michael J; Fowler, Joanna S; Qu, Wenchao

2015-08-01

In this research, we aim to directly measure the specific activity (SA) of the carbon-11 cyanide ([(11)C]CN¯) produced by our in-house built automated [(11)C]HCN production system and to identify the major sources of (12)C-cyanide ((12)CN¯). The [(11)C]CN¯ is produced from [(11)C]CO2, which is generated by the (14)N(p,α)(11)C nuclear reaction using a cyclotron. Direct measurement of cyanide concentrations was accomplished using a relatively inexpensive, and easy to use ion selective electrode (ISE) which offered an appropriate range of sensitivity for detecting mass. Multiple components of the [(11)C]HCN production system were isolated in order to determine their relative contributions to (12)CN¯ mass. It was determined that the system gases were responsible for approximately 30% of the mass, and that the molecular sieve/nickel furnace unit contributed approximately 70% of the mass. Beam on target (33µA for 1 and 10min) did not contribute significantly to the mass. Additionally, we compared the SA of our [(11)C]HCN precursor determined using the ISE to the SA of our current [(11)C]CN¯ derived radiotracers determined by HPLC to assure there was no significant difference between the two methods. These results are the first reported use of an ion selective electrode to determine the SA of no-carrier-added cyanide ion, and clearly show that it is a valuable, inexpensive and readily available tool suitable for this purpose. Copyright © 2015 Elsevier Ltd. All rights reserved.

A cytochrome P450 regulates a domestication trait in cultivated tomato

PubMed Central

Chakrabarti, Manohar; Zhang, Na; Sauvage, Christopher; Muños, Stéphane; Blanca, Jose; Cañizares, Joaquin; Diez, Maria Jose; Schneider, Rhiannon; Mazourek, Michael; McClead, Jammi; Causse, Mathilde; van der Knaap, Esther

2013-01-01

Domestication of crop plants had effects on human lifestyle and agriculture. However, little is known about the underlying molecular mechanisms accompanying the changes in fruit appearance as a consequence of selection by early farmers. We report the fine mapping and cloning of a tomato (Solanum lycopersicum) fruit mass gene encoding the ortholog of KLUH, SlKLUH, a P450 enzyme of the CYP78A subfamily. The increase in fruit mass is predominantly the result of enlarged pericarp and septum tissues caused by increased cell number in the large fruited lines. SlKLUH also modulates plant architecture by regulating number and length of the side shoots, and ripening time, and these effects are particularly strong in plants that transgenically down-regulate SlKLUH expression carrying fruits of a dramatically reduced mass. Association mapping followed by segregation analyses revealed that a single nucleotide polymorphism in the promoter of the gene is highly associated with fruit mass. This single polymorphism may potentially underlie a regulatory mutation resulting in increased SlKLUH expression concomitant with increased fruit mass. Our findings suggest that the allele giving rise to large fruit arose in the early domesticates of tomato and becoming progressively more abundant upon further selections. We also detected association of fruit weight with CaKLUH in chile pepper (Capsicum annuum) suggesting that selection of the orthologous gene may have occurred independently in a separate domestication event. Altogether, our findings shed light on the molecular basis of fruit mass, a key domestication trait in tomato and other fruit and vegetable crops. PMID:24082112

Total cyanide mass measurement with micro-ion selective electrode for determination of specific activity of carbon-11 cyanide

DOE PAGES

Shea, Colleen; Alexoff, David L.; Kim, Dohyun; ...

2015-04-25

In this study, we aim to directly measure the specific activity (SA) of the carbon-11 cyanide ([ 11C]CN¯) produced by our in-house built automated [ 11C]HCN production system and to identify the major sources of 12C-cyanide ( 12CN¯). The [ 11C]CN¯ is produced from [ 11C]CO 2, which is generated by the 14N(p,α) 11C nuclear reaction using a cyclotron. Direct measurement of cyanide concentrations was accomplished using a relatively inexpensive, and easy to use ion selective electrode (ISE) which offered an appropriate range of sensitivity for detecting mass. Multiple components of the [ 11C]HCN production system were isolated in ordermore » to determine their relative contributions to 12CN¯ mass. It was determined that the system gases were responsible for approximately 30% of the mass, and that the molecular sieve/nickel furnace unit contributed approximately 70% of the mass. Beam on target (33 µA for 1 and 10 min) did not contribute significantly to the mass. Additionally, we compared the SA of our [ 11C]HCN precursor determined using the ISE to the SA of our current [ 11C]CN¯ derived radiotracers determined by HPLC to assure there was no significant difference between the two methods. These results are the first reported use of an ion selective electrode to determine the SA of no-carrier-added cyanide ion, and clearly show that it is a valuable, inexpensive and readily available tool suitable for this purpose.« less

Total cyanide mass measurement with micro-ion selective electrode for determination of specific activity of carbon-11 cyanide

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

Shea, Colleen; Alexoff, David L.; Kim, Dohyun

In this study, we aim to directly measure the specific activity (SA) of the carbon-11 cyanide ([ 11C]CN¯) produced by our in-house built automated [ 11C]HCN production system and to identify the major sources of 12C-cyanide ( 12CN¯). The [ 11C]CN¯ is produced from [ 11C]CO 2, which is generated by the 14N(p,α) 11C nuclear reaction using a cyclotron. Direct measurement of cyanide concentrations was accomplished using a relatively inexpensive, and easy to use ion selective electrode (ISE) which offered an appropriate range of sensitivity for detecting mass. Multiple components of the [ 11C]HCN production system were isolated in ordermore » to determine their relative contributions to 12CN¯ mass. It was determined that the system gases were responsible for approximately 30% of the mass, and that the molecular sieve/nickel furnace unit contributed approximately 70% of the mass. Beam on target (33 µA for 1 and 10 min) did not contribute significantly to the mass. Additionally, we compared the SA of our [ 11C]HCN precursor determined using the ISE to the SA of our current [ 11C]CN¯ derived radiotracers determined by HPLC to assure there was no significant difference between the two methods. These results are the first reported use of an ion selective electrode to determine the SA of no-carrier-added cyanide ion, and clearly show that it is a valuable, inexpensive and readily available tool suitable for this purpose.« less

Determination of trichloroanisole and trichlorophenol in wineries' ambient air by passive sampling and thermal desorption-gas chromatography coupled to tandem mass spectrometry.

PubMed

Camino-Sánchez, F J; Bermúdez-Peinado, R; Zafra-Gómez, A; Ruíz-García, J; Vílchez-Quero, J L

2015-02-06

The present paper describes the calibration of selected passive samplers used in the quantitation of trichlorophenol and trichloroanisole in wineries' ambient air, by calculating the corresponding sampling rates. The method is based on passive sampling with sorbent tubes and involves thermal desorption-gas chromatography-triple quadrupole mass spectrometry analysis. Three commercially available sorbents were tested using sampling cartridges with a radial design instead of axial ones. The best results were found for Tenax TA™. Sampling rates (R-values) for the selected sorbents were determined. Passive sampling was also used for accurately determining the amount of compounds present in the air. Adequate correlation coefficients between the mass of the target analytes and exposure time were obtained. The proposed validated method is a useful tool for the early detection of trichloroanisole and its precursor trichlorophenol in wineries' ambient air while avoiding contamination of wine or winery facilities. Copyright © 2015 Elsevier B.V. All rights reserved.

Novel Selectivity-Based Forensic Toxicological Validation of a Paper Spray Mass Spectrometry Method for the Quantitative Determination of Eight Amphetamines in Whole Blood.

PubMed

Teunissen, Sebastiaan F; Fedick, Patrick W; Berendsen, Bjorn J A; Nielen, Michel W F; Eberlin, Marcos N; Graham Cooks, R; van Asten, Arian C

2017-12-01

Paper spray tandem mass spectrometry is used to identify and quantify eight individual amphetamines in whole blood in 1.3 min. The method has been optimized and fully validated according to forensic toxicology guidelines, for the quantification of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA), 3,4-methylenedioxy-N-ethylamphetamine (MDEA), para-methoxyamphetamine (PMA), para-methoxymethamphetamine (PMMA), and 4-fluoroamphetamine (4-FA). Additionally, a new concept of intrinsic and application-based selectivity is discussed, featuring increased confidence in the power to discriminate the amphetamines from other chemically similar compounds when applying an ambient mass spectrometric method without chromatographic separation. Accuracy was within ±15% and average precision was better than 15%, and better than 20% at the LLOQ. Detection limits between 15 and 50 ng/mL were obtained using only 12 μL of whole blood. Graphical abstract ᅟ.

Novel Selectivity-Based Forensic Toxicological Validation of a Paper Spray Mass Spectrometry Method for the Quantitative Determination of Eight Amphetamines in Whole Blood

NASA Astrophysics Data System (ADS)

Teunissen, Sebastiaan F.; Fedick, Patrick W.; Berendsen, Bjorn J. A.; Nielen, Michel W. F.; Eberlin, Marcos N.; Graham Cooks, R.; van Asten, Arian C.

2017-12-01

Paper spray tandem mass spectrometry is used to identify and quantify eight individual amphetamines in whole blood in 1.3 min. The method has been optimized and fully validated according to forensic toxicology guidelines, for the quantification of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy- N-methylamphetamine (MDMA), 3,4-methylenedioxy- N-ethylamphetamine (MDEA), para-methoxyamphetamine (PMA), para-methoxymethamphetamine (PMMA), and 4-fluoroamphetamine (4-FA). Additionally, a new concept of intrinsic and application-based selectivity is discussed, featuring increased confidence in the power to discriminate the amphetamines from other chemically similar compounds when applying an ambient mass spectrometric method without chromatographic separation. Accuracy was within ±15% and average precision was better than 15%, and better than 20% at the LLOQ. Detection limits between 15 and 50 ng/mL were obtained using only 12 μL of whole blood. [Figure not available: see fulltext.

Electronic Absorption Spectra of Mass-Selected Hydrocarbon Cations in Solid Neon: C_nH_4+ (n=5-8,10,12)

NASA Astrophysics Data System (ADS)

Nagy, A.; Fulara, J.; Garkusha, I.; Maier, J. P.

2011-05-01

Small, unsaturated hydrocarbons, C_nH_m (n,m≤6), play an important role in astrochemical models as they have been detected in various space objects such as the interstellar medium or envelopes of carbon-rich stars. Although identification of most of these species was based on rotational studies, they are candidate carriers of the infamous diffuse interstellar bands. It has been proposed that corresponding cationic species formed upon UV radiation may also be of astrophysical relevance; therefore, their optical spectra need to be determined. In this contribution, electronic absorption spectra of mass-selected C_nH_4+ (n=5-8,10,12) ions trapped in neon matrices are presented. The cations were produced in a hot-cathode discharge source, guided through a series of electrostatic lenses, mass filtered and co-deposited with excess of neon onto a rhodium-coated sapphire plate held at 6 K. In the same experiments, neutral species were generated from the cations by a photobleaching procedure.

Herschel and ALMA Observations of Massive SZE-selected Clusters

NASA Astrophysics Data System (ADS)

Wu, John F.; Aguirre, Paula; Baker, Andrew J.; Devlin, Mark J.; Hilton, Matt; Hughes, John P.; Infante, Leopoldo; Lindner, Robert R.; Sifón, Cristóbal

2018-02-01

We present new Herschel observations of four massive, Sunyaev–Zel’dovich effect–selected clusters at 0.3≤slant z≤slant 1.1, two of which have also been observed with the Atacama Large Millimeter/submillimeter Array (ALMA). We detect 19 Herschel/Photoconductor Array Camera and Spectrometer (PACS) counterparts to spectroscopically confirmed cluster members, five of which have redshifts determined via CO (4–3) and [C I] ({}3{P}1{--}{}3{P}0) lines. The mean [C I]/CO line ratio is 0.19 ± 0.07 in brightness temperature units, consistent with previous results for field samples. We do not detect significant stacked ALMA dust continuum or spectral-line emission, implying upper limits on mean interstellar medium (H2 + H I) and molecular gas masses. An apparent anticorrelation of {L}{IR} with clustercentric radius is driven by the tight relation between star formation rate and stellar mass. We find an average specific star formation rate of log(sSFR/yr‑1) = ‑10.36, which is below the {SFR}{--}{M}* correlation measured for field galaxies at similar redshifts. The fraction of infrared-bright galaxies (IRBGs; {log}({L}{IR}/{L}ȯ )> 10.6) per cluster and average sSFR rise significantly with redshift. For CO detections, we find {f}{gas}∼ 0.2, comparable to those of field galaxies, and gas depletion timescales of about 2 Gyr. We use radio observations to distinguish active galactic nuclei (AGNs) from star-forming galaxies. At least four of our 19 Herschel cluster members have {q}{IR}< 1.8, implying an AGN fraction {f}{AGN}≳ 0.2 for our PACS-selected sample.

THE DETECTION AND STATISTICS OF GIANT ARCS BEHIND CLASH CLUSTERS

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

Xu, Bingxiao; Zheng, Wei; Postman, Marc

We developed an algorithm to find and characterize gravitationally lensed galaxies (arcs) to perform a comparison of the observed and simulated arc abundance. Observations are from the Cluster Lensing And Supernova survey with Hubble (CLASH). Simulated CLASH images are created using the MOKA package and also clusters selected from the high-resolution, hydrodynamical simulations, MUSIC, over the same mass and redshift range as the CLASH sample. The algorithm's arc elongation accuracy, completeness, and false positive rate are determined and used to compute an estimate of the true arc abundance. We derive a lensing efficiency of 4 ± 1 arcs (with length ≥6″ andmore » length-to-width ratio ≥7) per cluster for the X-ray-selected CLASH sample, 4 ± 1 arcs per cluster for the MOKA-simulated sample, and 3 ± 1 arcs per cluster for the MUSIC-simulated sample. The observed and simulated arc statistics are in full agreement. We measure the photometric redshifts of all detected arcs and find a median redshift z{sub s} = 1.9 with 33% of the detected arcs having z{sub s} > 3. We find that the arc abundance does not depend strongly on the source redshift distribution but is sensitive to the mass distribution of the dark matter halos (e.g., the c–M relation). Our results show that consistency between the observed and simulated distributions of lensed arc sizes and axial ratios can be achieved by using cluster-lensing simulations that are carefully matched to the selection criteria used in the observations.« less

Analysis of Androgenic Steroids in Environmental Waters by Large-volume Injection Liquid Chromatography Tandem Mass Spectrometry

PubMed Central

Backe, Will J.; Ort, Christoph; Brewer, Alex J.; Field, Jennifer A.

2014-01-01

A new method was developed for the analysis of natural and synthetic androgenic steroids and their selected metabolites in aquatic environmental matrices using direct large-volume injection (LVI) high performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). Method accuracy ranged from 88 to 108% for analytes with well-matched internal standards. Precision, quantified by relative standard deviation (RSD), was less than 12%. Detection limits for the method ranged from 1.2 to 360 ng/L. The method was demonstrated on a series of 1-hr composite wastewater influent samples collected over a day with the purpose of assessing temporal profiles of androgen loads in wastewater. Testosterone, androstenedione, boldenone, and nandrolone were detected in the sample series at concentrations up to 290 ng/L and loads up to 535 mg. Boldenone, a synthetic androgen, had a temporal profile that was strongly correlated to testosterone, a natural human androgen, suggesting its source may be endogenous. An analysis of the sample particulate fraction revealed detectable amounts of sorbed testosterone and androstenedione. Androstenedione sorbed to the particulate fraction accounted for an estimated five to seven percent of the total androstenedione mass. PMID:21391574

Analysis of androgenic steroids in environmental waters by large-volume injection liquid chromatography tandem mass spectrometry.

PubMed

Backe, Will J; Ort, Christoph; Brewer, Alex J; Field, Jennifer A

2011-04-01

A new method was developed for the analysis of natural and synthetic androgenic steroids and their selected metabolites in aquatic environmental matrixes using direct large-volume injection (LVI) high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). Method accuracy ranged from 87.6 to 108% for analytes with well-matched internal standards. Precision, quantified by relative standard deviation (RSD), was less than 12%. Detection limits for the method ranged from 1.2 to 360 ng/L. The method was demonstrated on a series of 1 h composite wastewater influent samples collected over a day with the purpose of assessing temporal profiles of androgen loads in wastewater. Testosterone, androstenedione, boldenone, and nandrolone were detected in the sample series at concentrations up to 290 ng/L and loads up to 535 mg/h. Boldenone, a synthetic androgen, had a temporal profile that was strongly correlated to testosterone, a natural human androgen, suggesting its source may be endogenous. An analysis of the sample particulate fraction revealed detectable amounts of sorbed testosterone and androstenedione. Androstenedione sorbed to the particulate fraction accounted for an estimated 5 to 7% of the total androstenedione mass.

A Uniformly Selected Sample of Low-mass Black Holes in Seyfert 1 Galaxies. II. The SDSS DR7 Sample

NASA Astrophysics Data System (ADS)

Liu, He-Yang; Yuan, Weimin; Dong, Xiao-Bo; Zhou, Hongyan; Liu, Wen-Juan

2018-04-01

A new sample of 204 low-mass black holes (LMBHs) in active galactic nuclei (AGNs) is presented with black hole masses in the range of (1–20) × 105 M ⊙. The AGNs are selected through a systematic search among galaxies in the Seventh Data Release (DR7) of the Sloan Digital Sky Survey (SDSS), and careful analyses of their optical spectra and precise measurement of spectral parameters. Combining them with our previous sample selected from SDSS DR4 makes it the largest LMBH sample so far, totaling over 500 objects. Some of the statistical properties of the combined LMBH AGN sample are briefly discussed in the context of exploring the low-mass end of the AGN population. Their X-ray luminosities follow the extension of the previously known correlation with the [O III] luminosity. The effective optical-to-X-ray spectral indices α OX, albeit with a large scatter, are broadly consistent with the extension of the relation with the near-UV luminosity L 2500 Å. Interestingly, a correlation of α OX with black hole mass is also found, with α OX being statistically flatter (stronger X-ray relative to optical) for lower black hole masses. Only 26 objects, mostly radio loud, were detected in radio at 20 cm in the FIRST survey, giving a radio-loud fraction of 4%. The host galaxies of LMBHs have stellar masses in the range of 108.8–1012.4 M ⊙ and optical colors typical of Sbc spirals. They are dominated by young stellar populations that seem to have undergone continuous star formation history.

The invisible AGN catalogue: a mid-infrared-radio selection method for optically faint active galactic nuclei

NASA Astrophysics Data System (ADS)

Truebenbach, Alexandra E.; Darling, Jeremy

2017-06-01

A large fraction of active galactic nuclei (AGN) are 'invisible' in extant optical surveys due to either distance or dust-obscuration. The existence of this large population of dust-obscured, infrared (IR)-bright AGN is predicted by models of galaxy-supermassive black hole coevolution and is required to explain the observed X-ray and IR backgrounds. Recently, IR colour cuts with Wide-field Infrared Survey Explorer have identified a portion of this missing population. However, as the host galaxy brightness relative to that of the AGN increases, it becomes increasingly difficult to differentiate between IR emission originating from the AGN and from its host galaxy. As a solution, we have developed a new method to select obscured AGN using their 20-cm continuum emission to identify the objects as AGN. We created the resulting invisible AGN catalogue by selecting objects that are detected in AllWISE (mid-IR) and FIRST (20 cm), but are not detected in SDSS (optical) or 2MASS (near-IR), producing a final catalogue of 46 258 objects. 30 per cent of the objects are selected by existing selection methods, while the remaining 70 per cent represent a potential previously unidentified population of candidate AGN that are missed by mid-IR colour cuts. Additionally, by relying on a radio continuum detection, this technique is efficient at detecting radio-loud AGN at z ≥ 0.29, regardless of their level of dust obscuration or their host galaxy's relative brightness.

Supercritical-fluid extraction and chromatography-mass spectrometry for analysis of mycotoxins

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

Smith, R.D.; Udseth, H.R.

1982-07-01

The use of direct supercritical-fluid injection-mass spectrometry for the rapid analysis of mycotoxins of the tricothecene group is demonstrated. A solution containing diacetoxyscirpenol or T-2 toxin is injected into a fluid consisting primarily of pentane or carbon dioxide and is rapidly brought to supercritical conditions. Direct injection of the fluid stream into a chemical ionization source allows thermally labile compounds to be analyzed. Under these conditions trichothecene mass spectra showing significant (M + 1)/sup +/ ions and distinctive fragmentation patterns are obtained. Detection limits are in the subnanogram range. Direct analysis from complex substrates using selective supercritical-fluid extraction is proposed.more » 4 figures.« less

UPLC-MS/MS determination of ephedrine, methylephedrine, amygdalin and glycyrrhizic acid in Beagle plasma and its application to a pharmacokinetic study after oral administration of Ma Huang Tang.

PubMed

Yan, Tianhua; Fu, Qiang; Wang, Jing; Ma, Shiping

2015-02-01

An ultra performance liquid chromatography-mass spectrometric (UPLC-MS) method was developed to investigate the pharmacokinetic properties of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid after oral gavage of Ma Huang Tang (MHT) in Beagles. Beagle plasma samples were pretreated using liquid-liquid extraction, and chromatographic separation was performed on a C18 column using a linear gradient of water-formic acid mixture (0.1%). The pharmacokinetic parameters of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid from MHT in Beagles were quantitatively determined by UPLC with tandem mass detector. The qualitative detection of the four compounds was accomplished by selected ion monitoring in negative/positive ion modes electrospray ionization-mass spectrometry (ESI-MS). Detection was based on multiple reaction monitoring with the precursor-to-product ion transitions m/z 166.096-116.983 (ephedrine), m/z 179.034-146.087 (methylephedrine), m/z 456.351-323.074 (amygdalin), and m/z 821.606-351.062 (glycyrrhizic acid). The selectivity, sensitivity, linearity, accuracy, precision, extraction recovery, ion suppression, and stability were within the acceptable ranges. The method described was successfully applied to reveal the pharmacokinetic properties of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid after oral gavage of MHT in Beagles. Copyright © 2014 John Wiley & Sons, Ltd.

P39-T Analysis of Oligosaccharides by Capillary-Scale High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection (CHPAEC-PAD) and On-Line Electrospray-Ionization Ion-Trap Mass Spectrometry (CHPAEC-ITMS)

PubMed Central

Bruggink, C.; Koeleman, C.; Barreto, V.; Lui, Y.; Pohl, C.; Ingendoh, A.; Wuhrer, M.; Hokke, C.; Deelder, A.

2007-01-01

High-pH anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD) is an established technique for selective separation and analysis of underivatized carbohydrates. The miniaturization of chromatographic techniques by means of capillary columns, and on-line coupling to mass spectrometry are critical to the further development of glycan analysis methods that are compatible with the current requirements in clinical settings. A system has been developed based on the Dionex BioLC equipped with a microbore gradient pump with PEEK flow splitter, a FAMOS micro autosampler, a modified electrochemical cell for on-line capillary PAD, and a capillary column (380 μm i.d.) packed with a new type of anion-exchange resin. This system operates with sensitivity in the low femtomol range. In addition, an on-line capillary desalter has been developed to allow direct coupling to the Bruker Esquire 3000 ion-trap mass spectrometer with electrospray ionization interface (ESI-IT-MS). Both systems have been evaluated using oligosaccharide standards as well as urine samples exhibiting various lysosomal oligosaccharide storage diseases. Initial data indicate that the robust and selective anion-exchange system, in combination with ESI-IT-MS for structure confirmation and analysis, provides a powerful platform that complements existing nano/capillary LC-MS methods for analytical determination of oligosaccharides in biological matrices.

Mono-isotope Prediction for Mass Spectra Using Bayes Network.

PubMed

Li, Hui; Liu, Chunmei; Rwebangira, Mugizi Robert; Burge, Legand

2014-12-01

Mass spectrometry is one of the widely utilized important methods to study protein functions and components. The challenge of mono-isotope pattern recognition from large scale protein mass spectral data needs computational algorithms and tools to speed up the analysis and improve the analytic results. We utilized naïve Bayes network as the classifier with the assumption that the selected features are independent to predict mono-isotope pattern from mass spectrometry. Mono-isotopes detected from validated theoretical spectra were used as prior information in the Bayes method. Three main features extracted from the dataset were employed as independent variables in our model. The application of the proposed algorithm to publicMo dataset demonstrates that our naïve Bayes classifier is advantageous over existing methods in both accuracy and sensitivity.

The first detection of neutral hydrogen in emission in a strong spiral lens

NASA Astrophysics Data System (ADS)

Lipnicky, Andrew; Chakrabarti, Sukanya; Wright, Melvyn C. H.; Blitz, Leo; Heiles, Carl; Cotton, William; Frayer, David; Blandford, Roger; Shu, Yiping; Bolton, Adam S.

2018-05-01

We report H I observations of eight spiral galaxies that are strongly lensing background sources. Our targets were selected from the Sloan WFC (Wide Field Camera) Edge-on Late-type Lens Survey (SWELLS) using the Arecibo, Karl G. Jansky Very Large Array, and Green Bank telescopes. We securely detect J1703+2451 at z = 0.063 with a signal-to-noise ratio of 6.7 and W50 = 79 ± 13 km s-1, obtaining the first detection of H I emission in a strong spiral lens. We measure a mass of M_{H I} = (1.77± 0.06^{+0.35}_{-0.75})× 10^9 M_{⊙} for this source. We find that this lens is a normal spiral, with observable properties that are fairly typical of spiral galaxies. For three other sources, we did not secure a detection; however, we are able to place strong constraints on the H I masses of those galaxies. The observations for four of our sources were rendered unusable due to strong radio frequency interference.

Comprehensive thin-layer chromatography mass spectrometry of flavanols from Juniperus communis L. and Punica granatum L.

PubMed

Smrke, Samo; Vovk, Irena

2013-05-10

The coupling of thin-layer chromatography with mass spectrometry (TLC-MS) for the analysis of monomeric flavanols and proanthocyanidins in samples presented as complex matrices has been studied. The elution conditions for TLC-MS were optimised and full scans were compared with selected reaction monitoring for the MS detection of compounds. The performance of silica gel and cellulose plates with different developing solvents in TLC-MS was assessed. Cellulose plates provided superior sensitivity while ionisation suppression was encountered with silica plates. The use of a HILIC guard column beyond the elution head was found to facilitate detection of monomer compounds on silica plates. A new comprehensive TLC×MS procedure for screening flavanols in the entire chromatogram was developed as an alternative to the use of 4-dimethylaminocinnamaldehyde to determine the locations of compounds on the plate. This new procedure was applied to detect flavanols in the peel of Punica granatum L. fruits and in seeds of Juniperus communis L., in which flavanols and proanthocyanidin dimers and trimers were detected for the first time. Copyright © 2013 Elsevier B.V. All rights reserved.

Analysis of carbohydrates by anion exchange chromatography and mass spectrometry.

PubMed

Bruggink, Cees; Maurer, Rolf; Herrmann, Heiko; Cavalli, Silvano; Hoefler, Frank

2005-08-26

A versatile liquid chromatographic platform has been developed for analysing underivatized carbohydrates using high performance anion exchange chromatography (HPAEC) followed by an inert PEEK splitter that splits the effluent to the integrated pulsed amperometric detector (IPAD) and to an on-line single quadrupole mass spectrometer (MS). Common eluents for HPAEC such as sodium hydroxide and sodium acetate are beneficial for the amperometric detection but not compatible with electrospray ionisation (ESI). Therefore a membrane-desalting device was installed after the splitter and prior to the ESI interface converting sodium hydroxide into water and sodium acetate into acetic acid. To enhance the sensitivity for the MS detection, 0.5 mmol/l lithium chloride was added after the membrane desalter to form lithium adducts of the carbohydrates. To compare sensitivity of IPAD and MS detection glucose, fructose, and sucrose were used as analytes. A calibration with external standards from 2.5 to 1000 pmole was performed showing a linear range over three orders of magnitude. Minimum detection limits (MDL) with IPAD were determined at 5 pmole levels for glucose to be 0.12 pmole, fructose 0.22 pmole and sucrose 0.11 pmole. With MS detection in the selected ion mode (SIM) the lithium adducts of the carbohydrates were detected obtaining MDL's for glucose of 1.49 pmole, fructose 1.19 pmole, and sucrose 0.36 pmole showing that under these conditions IPAD is 3-10 times more sensitive for those carbohydrates. The applicability of the method was demonstrated analysing carbohydrates in real world samples such as chicory inulin where polyfructans up to a molecular mass of 7000 g/mol were detected as quadrupoly charged lithium adducts. Furthermore mono-, di-, tri-, and oligosaccharides were detected in chicory coffee, honey and beer samples.

Antidepressants detection and quantification in whole blood samples by GC-MS/MS, for forensic purposes.

PubMed

Truta, Liliana; Castro, André L; Tarelho, Sónia; Costa, Pedro; Sales, M Goreti F; Teixeira, Helena M

2016-09-05

Depression is among the most prevalent psychiatric disorders of our society, leading to an increase in antidepressant drug consumption that needs to be accurately determined in whole blood samples in Forensic Toxicology Laboratories. For this purpose, this work presents a new gas chromatography tandem mass spectrometry (GC-MS/MS) method targeting the simultaneous and rapid determination of 14 common Antidepressants in whole blood: 13 Antidepressants (amitriptyline, citalopram, clomipramine, dothiepin, fluoxetine, imipramine, mianserin, mirtazapine, nortryptiline, paroxetine, sertraline, trimipramine and venlafaxine) and 1 Metabolite (N-desmethylclomipramine). Solid-phase extraction was used prior to chromatographic separation. Chromatographic and MS/MS parameters were selected to improve sensitivity, peak resolution and unequivocal identification of the eluted analyte. The detection was performed on a triple quadrupole tandem MS in selected ion monitoring (SIM) mode in tandem, using electronic impact ionization. Clomipramine-D3 and trimipramine-D3 were used as deutered internal standards. The validation parameters included linearity, limits of detection, lower limit of quantification, selectivity/specificity, extraction efficiency, carry-over, precision and robustness, and followed internationally accepted guidelines. Limits of quantification and detection were lower than therapeutic and sub-therapeutic concentration ranges. Overall, the method offered good selectivity, robustness and quick response (<16min) for typical concentration ranges, both for therapeutic and lethal levels. Copyright © 2016 Elsevier B.V. All rights reserved.

Automated Peak Detection and Matching Algorithm for Gas Chromatography–Differential Mobility Spectrometry

PubMed Central

Fong, Sim S.; Rearden, Preshious; Kanchagar, Chitra; Sassetti, Christopher; Trevejo, Jose; Brereton, Richard G.

2013-01-01

A gas chromatography–differential mobility spectrometer (GC-DMS) involves a portable and selective mass analyzer that may be applied to chemical detection in the field. Existing approaches examine whole profiles and do not attempt to resolve peaks. A new approach for peak detection in the 2D GC-DMS chromatograms is reported. This method is demonstrated on three case studies: a simulated case study; a case study of headspace gas analysis of Mycobacterium tuberculosis (MTb) cultures consisting of three matching GC-DMS and GC-MS chromatograms; a case study consisting of 41 GC-DMS chromatograms of headspace gas analysis of MTb culture and media. PMID:21204557

Direct and label-free detection of the human growth hormone in urine by an ultrasensitive bimodal waveguide biosensor.

PubMed

González-Guerrero, Ana Belén; Maldonado, Jesús; Dante, Stefania; Grajales, Daniel; Lechuga, Laura M

2017-01-01

A label-free interferometric transducer showing a theoretical detection limit for homogeneous sensing of 5 × 10 -8 RIU, being equivalent to a protein mass coverage resolution of 2.8 fg mm -2 , is used to develop a high sensitive biosensor for protein detection. The extreme sensitivity of this transducer combined with a selective bioreceptor layer enables the direct evaluation of the human growth hormone (hGH) in undiluted urine matrix in the 10 pg mL -1 range. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of BMAA and three alkaloid cyanotoxins in lake water using dansyl chloride derivatization and high-resolution mass spectrometry.

PubMed

Roy-Lachapelle, Audrey; Solliec, Morgan; Sauvé, Sébastien

2015-07-01

A new analytical method was developed for the detection of alkaloid cyanotoxins in harmful algal blooms. The detection of the nonproteinogenic amino acid β-N-methylamino-L-alanine (BMAA) and two of its conformation isomers, 2,4-diaminobutyric acid (DAB) and N-(2-aminoethyl) glycine (AEG), as well as three alkaloid cyanotoxins, anatoxin-a (ANA-a), cylindrospermopsin (CYN), and saxitoxin (STX), is presented. The use of a chemical derivatization with dansyl chloride (DNS) allows easier separation with reversed phase liquid chromatography. Detection with high-resolution mass spectrometry (HRMS) with the Q-Exactive enables high selectivity with specific fragmentation as well as exact mass detection, reducing considerably the possibilities of isobaric interferences. Previous to analysis, a solid phase extraction (SPE) step is used for purification and preconcentration. After DNS derivatization, samples are submitted to ultra high-performance liquid chromatography coupled with heated electrospray ionisation and the Q-Exactive mass spectrometer (UHPLC-HESI-HRMS). With an internal calibration using isotopically-labeled DAB-D3, the method was validated with good linearity (R (2)  > 0.998), and method limits of detection and quantification (MLD and MLQ) for target compounds ranged from 0.007 to 0.01 μg L(-1) and from 0.02 to 0.04 μg L(-1), respectively. Accuracy and within-day/between-days variation coefficients were below 15%. SPE recovery values ranged between 86 and 103%, and matrix effects recovery values ranged between 75 and 96%. The developed analytical method was successfully validated with 12 different lakes samples, and concentrations were found ranging between 0.009 and 0.3 μg L(-1) except for STX which was not found in any sample.

ALMA 26 arcmin2 Survey of GOODS-S at One-millimeter (ASAGAO): X-Ray AGN Properties of Millimeter-selected Galaxies

NASA Astrophysics Data System (ADS)

Ueda, Y.; Hatsukade, B.; Kohno, K.; Yamaguchi, Y.; Tamura, Y.; Umehata, H.; Akiyama, M.; Ao, Y.; Aretxaga, I.; Caputi, K.; Dunlop, J. S.; Espada, D.; Fujimoto, S.; Hayatsu, N. H.; Imanishi, M.; Inoue, A. K.; Ivison, R. J.; Kodama, T.; Lee, M. M.; Matsuoka, K.; Miyaji, T.; Morokuma-Matsui, K.; Nagao, T.; Nakanishi, K.; Nyland, K.; Ohta, K.; Ouchi, M.; Rujopakarn, W.; Saito, T.; Tadaki, K.; Tanaka, I.; Taniguchi, Y.; Wang, T.; Wang, W.-H.; Yoshimura, Y.; Yun, M. S.

2018-01-01

We investigate the X-ray active galactic nucleus (AGN) properties of millimeter galaxies in the Great Observatories Origins Deep Survey South (GOODS-S) field detected with the Atacama Large Millimeter/submillimeter Array (ALMA), by utilizing the Chandra 7-Ms data, the deepest X-ray survey to date. Our millimeter galaxy sample comes from the ASAGAO survey covering 26 arcmin2 (12 sources at a 1.2 mm flux-density limit of ≈ 0.6 mJy), supplemented by the deeper but narrower 1.3 mm survey of a part of the ASAGAO field by Dunlop et al. Ofthe 25 total millimeter galaxies, 14 have Chandra counterparts. The observed AGN fractions at z=1.5{--}3 are found to be {90}-19+8% and {57}-25+23% for the ultra-luminous and luminous infrared galaxies with log {L}{IR}/{L}ȯ = 12–12.8 and log {L}{IR}/{L}ȯ = 11.5–12, respectively. The majority (∼2/3) of the ALMA and/or Herschel detected X-ray AGNs at z = 1.5‑3 appear to be star-formation-dominant populations, having {L}{{X}}/ {L}{IR} ratios smaller than the “simultaneous evolution” value expected from the local black-hole-mass-to-stellar-mass ({M}{BH}–M *) relation. On the basis of the {L}{{X}} and stellar mass relation, we infer that a large fraction of star-forming galaxies at z=1.5{--}3 have black hole masses that are smaller than those expected from the local {M}{BH}–M * relation. This contrasts previous reports on luminous AGNs at the same redshifts detected in wider and shallower surveys, which are subject to selection biases against lower luminosity AGNs. Our results are consistent with an evolutionary scenario in which star formation occurs first, and an AGN-dominant phase follows later, in objects that finally evolve into galaxies with classical bulges.

INFRARED LUMINOSITIES AND DUST PROPERTIES OF z approx 2 DUST-OBSCURED GALAXIES

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

Bussmann, R. S.; Dey, Arjun; Jannuzi, B. T.

We present SHARC-II 350 mum imaging of twelve 24 mum bright (F{sub 24m}u{sub m} > 0.8 mJy) Dust-Obscured Galaxies (DOGs) and Combined Array for Research in Millimeter-wave Astronomy (CARMA) 1 mm imaging of a subset of two DOGs. These objects are selected from the Booetes field of the NOAO Deep Wide-Field Survey. Detections of four DOGs at 350 mum imply infrared (IR) luminosities which are consistent to within a factor of 2 of expectations based on a warm-dust spectral energy distribution (SED) scaled to the observed 24 mum flux density. The 350 mum upper limits for the 8 non-detected DOGsmore » are consistent with both Mrk 231 and M82 (warm-dust SEDs), but exclude cold dust (Arp 220) SEDs. The two DOGs targeted at 1 mm were not detected in our CARMA observations, placing strong constraints on the dust temperature: T{sub dust} > 35-60 K. Assuming these dust properties apply to the entire sample, we find dust masses of approx3 x 10{sup 8} M{sub sun}. In comparison to other dusty z approx 2 galaxy populations such as submillimeter galaxies (SMGs) and other Spitzer-selected high-redshift sources, this sample of DOGs has higher IR luminosities (2 x 10{sup 13} L{sub sun} versus 6 x 10{sup 12} L{sub sun} for the other galaxy populations) that are driven by warmer dust temperatures (>35-60 K versus approx30 K) and lower inferred dust masses (3 x 10{sup 8} M{sub sun} versus 3 x 10{sup 9} M{sub sun}). Wide-field Herschel and Submillimeter Common-User Bolometer Array-2 surveys should be able to detect hundreds of these power-law-dominated DOGs. We use the existing Hubble Space Telescope and Spitzer/InfraRed Array Camera data to estimate stellar masses of these sources and find that the stellar to gas mass ratio may be higher in our 24 mum bright sample of DOGs than in SMGs and other Spitzer-selected sources. Although much larger sample sizes are needed to provide a definitive conclusion, the data are consistent with an evolutionary trend in which the formation of massive galaxies at z approx 2 involves a submillimeter bright, cold-dust, and star-formation-dominated phase followed by a 24 mum bright, warm-dust and AGN-dominated phase.« less

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

Gundlach-Graham, Alexander W.; Dennis, Elise; Ray, Steven J.

Here we describe the first combination of a Distance-of-Flight Mass Spectrometry (DOFMS) instrument and an inductively coupled plasma (ICP) ion source. DOFMS is a velocity-based MS technique in which ions of a range of mass-to-charge (m/z) values are detected simultaneously along the length of a spatially selective detector. As a relative of time-of-flight (TOF) MS, DOFMS leverages benefits fromboth TOFMS and spatially dispersive MS. The simultaneous detection of groups of m/z values improves dynamic range by spreading ion signal across many detector elements and reduces correlated noise by signal ratioing. To ascertain the performance characteristics of the ICP-DOFMS instrument, wemore » have employed a microchannel-plate/phosphor detection assembly with a scientific CCD to capture images of the phosphor plate. With this simple (and commercially available) detection scheme, elemental detection limits from 2–30 ng L*1 and a linear dynamic range of 5 orders of magnitude (10–106 ng L1) have been demonstrated. Additionally, a competitive isotope-ratio precision of 0.1% RSD has been achieved with only a 6 s signal integration period. In addition to first figures of merit, this paper outlines technical considerations for the design of the ICP-DOFMS.« less

A rapid high-performance liquid chromatography-tandem mass spectrometry assay for unambiguous detection of different milk species employed in cheese manufacturing.

PubMed

Bernardi, Nadia; Benetti, Giuseppe; Haouet, Naceur M; Sergi, Manuel; Grotta, Lisa; Marchetti, Sonia; Castellani, Federica; Martino, Giuseppe

2015-12-01

The aim of the study was to investigate the possibility to differentiate the 4 most important species in Italian dairy industry (cow, buffalo, sheep, and goat), applying a bottom-up proteomic approach to assess the milk species involved in cheese production. Selective peptides were detected in milk to use as markers in cheese products. Trypsin-digested milk samples of cow, sheep, goat, and buffalo, analyzed by HPLC-tandem mass spectrometry provided species-specific peptides, some of them recognized by Mascot software (Matrix Science Ltd., Boston, MA) as derived from well-known species specific proteins. A multianalyte multiple reaction monitoring method, built with these specific peptides, was successfully applied to cheeses with different composition, showing high specificity in detection of species involved. Neither aging nor production method seemed to affect the response, demonstrating that chosen peptides well act as species markers for dairy products. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Mass Spectrometry Based Ultrasensitive DNA Methylation Profiling Using Target Fragmentation Assay.

PubMed

Lin, Xiang-Cheng; Zhang, Ting; Liu, Lan; Tang, Hao; Yu, Ru-Qin; Jiang, Jian-Hui

2016-01-19

Efficient tools for profiling DNA methylation in specific genes are essential for epigenetics and clinical diagnostics. Current DNA methylation profiling techniques have been limited by inconvenient implementation, requirements of specific reagents, and inferior accuracy in quantifying methylation degree. We develop a novel mass spectrometry method, target fragmentation assay (TFA), which enable to profile methylation in specific sequences. This method combines selective capture of DNA target from restricted cleavage of genomic DNA using magnetic separation with MS detection of the nonenzymatic hydrolysates of target DNA. This method is shown to be highly sensitive with a detection limit as low as 0.056 amol, allowing direct profiling of methylation using genome DNA without preamplification. Moreover, this method offers a unique advantage in accurately determining DNA methylation level. The clinical applicability was demonstrated by DNA methylation analysis using prostate tissue samples, implying the potential of this method as a useful tool for DNA methylation profiling in early detection of related diseases.

Complex organic molecules during low-mass star formation: Pilot survey results

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

Öberg, Karin I.; Graninger, Dawn; Lauck, Trish, E-mail: koberg@cfa.harvard.edu

Complex organic molecules (COMs) are known to be abundant toward some low-mass young stellar objects (YSOs), but how these detections relate to typical COM abundance are not yet understood. We aim to constrain the frequency distribution of COMs during low-mass star formation, beginning with this pilot survey of COM lines toward six embedded YSOs using the IRAM 30 m Telescope. The sample was selected from the Spitzer c2d ice sample and covers a range of ice abundances. We detect multiple COMs, including CH{sub 3}CN, toward two of the YSOs, and tentatively toward a third. Abundances with respect to CH{sub 3}OHmore » vary between 0.7% and 10%. This sample is combined with previous COM observations and upper limits to obtain a frequency distributions of CH{sub 3}CN, HCOOCH{sub 3}, CH{sub 3}OCH{sub 3}, and CH{sub 3}CHO. We find that for all molecules more than 50% of the sample have detections or upper limits of 1%-10% with respect to CH{sub 3}OH. Moderate abundances of COMs thus appear common during the early stages of low-mass star formation. A larger sample is required, however, to quantify the COM distributions, as well as to constrain the origins of observed variations across the sample.« less

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

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

Ovchinnikova, Olga S; Nikiforov, Maxim; Bradshaw, James A

2011-01-01

Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2more » array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.« less

Multispectra CWT-based algorithm (MCWT) in mass spectra for peak extraction.

PubMed

Hsueh, Huey-Miin; Kuo, Hsun-Chih; Tsai, Chen-An

2008-01-01

An important objective in mass spectrometry (MS) is to identify a set of biomarkers that can be used to potentially distinguish patients between distinct treatments (or conditions) from tens or hundreds of spectra. A common two-step approach involving peak extraction and quantification is employed to identify the features of scientific interest. The selected features are then used for further investigation to understand underlying biological mechanism of individual protein or for development of genomic biomarkers to early diagnosis. However, the use of inadequate or ineffective peak detection and peak alignment algorithms in peak extraction step may lead to a high rate of false positives. Also, it is crucial to reduce the false positive rate in detecting biomarkers from ten or hundreds of spectra. Here a new procedure is introduced for feature extraction in mass spectrometry data that extends the continuous wavelet transform-based (CWT-based) algorithm to multiple spectra. The proposed multispectra CWT-based algorithm (MCWT) not only can perform peak detection for multiple spectra but also carry out peak alignment at the same time. The author' MCWT algorithm constructs a reference, which integrates information of multiple raw spectra, for feature extraction. The algorithm is applied to a SELDI-TOF mass spectra data set provided by CAMDA 2006 with known polypeptide m/z positions. This new approach is easy to implement and it outperforms the existing peak extraction method from the Bioconductor PROcess package.

Direct Real-Time Detection of Vapors from Explosive Compounds

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

Ewing, Robert G.; Clowers, Brian H.; Atkinson, David A.

2013-10-03

The real-time detection of vapors from low volatility explosives including PETN, tetryl, RDX and nitroglycerine along with various compositions containing these substances is demonstrated. This was accomplished with an atmospheric flow tube (AFT) using a non-radioactive ionization source and coupled to a mass spectrometer. Direct vapor detection was demonstrated in less than 5 seconds at ambient temperature without sample pre-concentration. The several seconds of residence time of analytes in the AFT provides a significant opportunity for reactant ions to interact with analyte vapors to achieve ionization. This extended reaction time, combined with the selective ionization using the nitrate reactant ionsmore » (NO3- and NO3-•HNO3), enables highly sensitive explosives detection. Observed signals from diluted explosive vapors indicate detection limits below 10 ppqv using selected ion monitoring (SIM) of the explosive-nitrate adduct at m/z 349, 378, 284 and 289 for tetryl, PETN, RDX and NG respectively. Also provided is a demonstration of the vapor detection from 10 different energetic formulations, including double base propellants, plastic explosives and commercial blasting explosives using SIM for the NG, PETN and RDX product ions.« less

Direct real-time detection of vapors from explosive compounds.

PubMed

Ewing, Robert G; Clowers, Brian H; Atkinson, David A

2013-11-19

The real-time detection of vapors from low volatility explosives including PETN, tetryl, RDX, and nitroglycerine along with various compositions containing these substances was demonstrated. This was accomplished with an atmospheric flow tube (AFT) using a nonradioactive ionization source coupled to a mass spectrometer. Direct vapor detection was accomplished in less than 5 s at ambient temperature without sample preconcentration. The several seconds of residence time of analytes in the AFT provided a significant opportunity for reactant ions to interact with analyte vapors to achieve ionization. This extended reaction time, combined with the selective ionization using the nitrate reactant ions (NO3(-) and NO3(-)·HNO3), enabled highly sensitive explosives detection from explosive vapors present in ambient laboratory air. Observed signals from diluted explosive vapors indicated detection limits below 10 ppqv using selected ion monitoring (SIM) of the explosive-nitrate adduct at m/z 349, 378, 284, and 289 for tetryl, PETN, RDX, and NG, respectively. Also provided is a demonstration of the vapor detection from 10 different energetic formulations sampled in ambient laboratory air, including double base propellants, plastic explosives, and commercial blasting explosives using SIM for the NG, PETN, and RDX product ions.

A large sample of shear-selected clusters from the Hyper Suprime-Cam Subaru Strategic Program S16A Wide field mass maps

NASA Astrophysics Data System (ADS)

Miyazaki, Satoshi; Oguri, Masamune; Hamana, Takashi; Shirasaki, Masato; Koike, Michitaro; Komiyama, Yutaka; Umetsu, Keiichi; Utsumi, Yousuke; Okabe, Nobuhiro; More, Surhud; Medezinski, Elinor; Lin, Yen-Ting; Miyatake, Hironao; Murayama, Hitoshi; Ota, Naomi; Mitsuishi, Ikuyuki

2018-01-01

We present the result of searching for clusters of galaxies based on weak gravitational lensing analysis of the ˜160 deg2 area surveyed by Hyper Suprime-Cam (HSC) as a Subaru Strategic Program. HSC is a new prime focus optical imager with a 1.5°-diameter field of view on the 8.2 m Subaru telescope. The superb median seeing on the HSC i-band images of 0.56" allows the reconstruction of high angular resolution mass maps via weak lensing, which is crucial for the weak lensing cluster search. We identify 65 mass map peaks with a signal-to-noise (S/N) ratio larger than 4.7, and carefully examine their properties by cross-matching the clusters with optical and X-ray cluster catalogs. We find that all the 39 peaks with S/N > 5.1 have counterparts in the optical cluster catalogs, and only 2 out of the 65 peaks are probably false positives. The upper limits of X-ray luminosities from the ROSAT All Sky Survey (RASS) imply the existence of an X-ray underluminous cluster population. We show that the X-rays from the shear-selected clusters can be statistically detected by stacking the RASS images. The inferred average X-ray luminosity is about half that of the X-ray-selected clusters of the same mass. The radial profile of the dark matter distribution derived from the stacking analysis is well modeled by the Navarro-Frenk-White profile with a small concentration parameter value of c500 ˜ 2.5, which suggests that the selection bias on the orientation or the internal structure for our shear-selected cluster sample is not strong.

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

Webb, Ian K.; Garimella, Sandilya V. B.; Tolmachev, Aleksey V.

A Structures for Lossless Ion Manipulations (SLIM) module that allows ion mobility separations and the switching of ions between alternative drift paths is described. The SLIM switch component has a “Tee” configuration and allows switching of ions between a linear path and a 90-degree bend. By controlling switching times, ions can be deflected to an alternative channel as a function of their mobilities. In the initial evaluation the switch is used in a static mode and shown compatible with high performance ion mobility separations at 4 torr. In the “dynamic mode” we show that mobility-selected ions can be switched intomore » the alternative channel, and that various ion species can be independently selected based on their mobilities for time-of-flight mass spectrometer (TOF MS) IMS detection and mass analysis. Ultimately, this development also provides the basis for e.g. the selection of specific mobilities for storage and accumulation, and key modules for the assembly of SLIM devices enabling much more complex sequences of ion manipulations.« less

Dark matter interpretations of ATLAS searches for the electroweak production of supersymmetric particles in s = 8 $$ \\sqrt{s}=8 $$ TeV proton-proton collisions

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

Aaboud, M.; Aad, G.; Abbott, B.

2016-09-01

A selection of searches by the ATLAS experiment at the LHC for the electroweak production of SUSY particles are used to study their impact on the constraints on dark matter candidates. The searches use 20 fb-1 of proton-proton collision data at s√=8s=8 TeV. A likelihood-driven scan of a five-dimensional effective model focusing on the gaugino-higgsino and Higgs sector of the phenomenological minimal supersymmetric Standard Model is performed. This scan uses data from direct dark matter detection experiments, the relic dark matter density and precision flavour physics results. Further constraints from the ATLAS Higgs mass measurement and SUSY searches at LEPmore » are also applied. A subset of models selected from this scan are used to assess the impact of the selected ATLAS searches in this five-dimensional parameter space. These ATLAS searches substantially impact those models for which the mass m(χ~01)m(χ~10) of the lightest neutralino is less than 65 GeV, excluding 86% of such models. The searches have limited impact on models with larger m(χ~01)m(χ~10) due to either heavy electroweakinos or compressed mass spectra where the mass splittings between the produced particles and the lightest supersymmetric particle is small.« less

Dark matter interpretations of ATLAS searches for the electroweak production of supersymmetric particles in $$ \\sqrt{s}=8 $$ TeV proton-proton collisions

DOE PAGES

Aaboud, M.; Aad, G.; Abbott, B.; ...

2016-09-30

A selection of searches by the ATLAS experiment at the LHC for the electroweak production of SUSY particles are used to study their impact on the constraints on dark matter candidates. The searches use 20 fb -1 of proton-proton collision data at √s=8 TeV. A likelihood-driven scan of a five-dimensional effective model focusing on the gaugino-higgsino and Higgs sector of the phenomenological minimal supersymmetric Standard Model is performed. This scan uses data from direct dark matter detection experiments, the relic dark matter density and precision flavour physics results. Further constraints from the ATLAS Higgs mass measurement and SUSY searches at LEP are also applied. A subset of models selected from this scan are used to assess the impact of the selected ATLAS searches in this five-dimensional parameter space. These ATLAS searches substantially impact those models for which the mass m(more » $$\\tilde{χ}$$$0\\atop{1}$$) of the lightest neutralino is less than 65 GeV, excluding 86% of such models. The searches have limited impact on models with larger m($$\\tilde{χ}$$$0\\atop{1}$$) due to either heavy electroweakinos or compressed mass spectra where the mass splittings between the produced particles and the lightest supersymmetric particle is small.« less

Age-dependent change in urine proteome of healthy individuals

NASA Astrophysics Data System (ADS)

Dobrokhotov, Igor; Liudmila Pastushkova, MRS.; Larina, Irina; Kononikhin, Alexey

It was analyzed the protein composition of urine samples obtained from twenty Russian cosmonauts and thirty-eight healthy volunteers, that have been selected for the experiments simulating the physiological effects of microgravity. The special sample preparation was performed, followed by liquid chromatography-mass spectrometry. Liquid chromatography-mass spectrometry of the minor proteins was performed on a nano-HPLC Agilent 1100 system (Agilent Technologies Inc., USA) in combination with a LTQ-FT Ultra mass spectrometer (Thermo Electron, Germany). List of masses derived peptides and they fragments have used for search and identification of proteins by database IPI-human (international index of protein) using the program Mascot (MS version 2.0.04 , UK) according to the following criteria: 1 - enzyme-trypsin; 2 - peptide tol. ± 5 ppm; 3 - MS / MS tol. 0.5Da. From list of proteins obtained as a result Mascot-search it was selected only those proteins that were identified based on 2 or more peptides with the rating more than 24. Analysis of the list of proteins was performed using software developed in the laboratory of VA Ivanisenko (ICG SB RAS) Age of healthy individuals was ranged from 18 to 54 years. Depending on the age, the data were divided into three groups: those relating to the group of persons under 25 years (youth and mature age 1), 25-40 years (mature age 2) and 40-54 years (mature age 3) It was detected reliable changes in the number of proteins among groups depending of the age. It was found that the minimum number of different proteins were detected in the urine of the group of young patients (under 25 years old) , and the maximum - was observed in the group of middle-aged persons (25 to 40 years). When the proteins were compared according to their molecular mass it was revealed that in the older group (40-54 years ) there is noticeably smaller percentage of high molecular weight proteins than in groups of young and middle aged persons. Thus, proteomic studies of urine samples can detect reliable age differences between groups of subjects, reflecting both age-specific features of processes of protein reabsorption by the kidneys, and the aging process in general.

Assay Development Process | Office of Cancer Clinical Proteomics Research

Cancer.gov

Typical steps involved in the development of a  mass spectrometry-based targeted assay include: (1) selection of surrogate or signature peptides corresponding to the targeted protein or modification of interest; (2) iterative optimization of instrument and method parameters for optimal detection of the selected peptide; (3) method development for protein extraction from biological matrices such as tissue, whole cell lysates, or blood plasma/serum and proteolytic digestion of proteins (usually with trypsin); (4) evaluation of the assay in the intended biological matrix to determine if e

Novel software for data analysis of Fourier transform ion cyclotron resonance mass spectra applied to natural organic matter.

PubMed

Grinhut, Tzafrir; Lansky, Dedy; Gaspar, Andras; Hertkorn, Norbert; Schmitt-Kopplin, Philippe; Hadar, Yitzhak; Chen, Yona

2010-10-15

Natural organic matter (NOM) occurs as an extremely complex mixture of large, charged molecules that are formed by secondary synthesis reactions. Due to their nature, their full characterization is an important challenge to scientists specializing in NOM as well as analytical chemistry. Ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis enables the identification of thousands of masses in a single measurement. A major challenge in the data analysis process of NOM using the FT-ICR MS technique is the need to sort the entire data set and to present it in an accessible mode. Here we present a simple targeted algorithm called the David Mass Sort (DMS) algorithm which facilitates the detection and counting of consecutive series of masses correlated to any selected mass spacing. This program searches for specific mass differences among all of the masses in a single spectrum against all of the masses in the same spectrum. As a representative case, the current study focuses on the analysis of the well-characterized Suwannee River humic and fulvic acid (SRHA and SRFA, respectively). By applying this algorithm, we were able to find and assess the amount of singly and doubly charged molecules. In addition we present the capabilities of the program to detect any series of consecutive masses correlated to specific mass spacing, e.g. COO, H(2), OCH(2) and O(2). Under several limitations, these mass spacings may be correlated to both chemical and biochemical changes which occur simultaneously during the formation and/or degradation of large mixtures of compounds. Copyright © 2010 John Wiley & Sons, Ltd.

Environmentally selected WIMP dark matter with high-scale supersymmetry breaking

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

Elor, Gilly; Goh, Hock-Seng; Kumar, Piyush

2010-05-01

We explore the possibility that both the weak scale and the thermal relic dark matter abundance are environmentally selected in a multiverse. An underlying supersymmetric theory containing the states of the minimal supersymmetric standard model (MSSM) and singlets, with supersymmetry and R symmetry broken at unified scales, has just two realistic low-energy effective theories. One theory (SM+w-tilde) is the standard model augmented only by the wino, having a mass near 3 TeV, and has a Higgs boson mass in the range of (127-142) GeV. The other theory (SM+h-tilde/s-tilde) has Higgsinos and a singlino added to the standard model. The Higgsmore » boson mass depends on the single new Yukawa coupling of the theory, y, and is near 141 GeV for small y but grows to be as large as 210 GeV as this new coupling approaches strong coupling at high energies. Much of the parameter space of this theory will be probed by direct detection searches for dark matter that push 2 orders of magnitude below the present bounds; furthermore, the dark matter mass and cross section on nucleons are correlated with the Higgs boson mass. The indirect detection signal of monochromatic photons from the Galactic center is computed, and the range of parameters that may be accessible to LHC searches for trilepton events is explored. Taking a broader view, allowing the possibility of R symmetry protection to the TeV scale or axion dark matter, we find four more theories: (SM+axion), two versions of split supersymmetry, and the E-MSSM, where a little supersymmetric hierarchy is predicted. The special Higgs mass value of (141{+-}2) GeV appears in symmetry limits of three of the six theories, (SM+axion), (SM+w-tilde), and (SM+h-tilde/s-tilde), motivating a comparison of other signals of these three theories.« less

The SEEDS High-Contrast Imaging Survey: Exoplanet and Brown Dwarf Survey for Nearby Young Stars Dated with Gyrochronology and Activity Age Indicators

NASA Astrophysics Data System (ADS)

Kuzuhara, Masayuki; Tamura, Motohide; Helminiak, Kris; Mede, Kyle; Brandt, Timothy; Janson, Markus; Kandori, Ryo; Kudo, Tomoyuki; Kusakabe, Nobuhiko; Hashimoto, Jun

2015-12-01

The SEEDS campaign has successfully discovered and characterized exoplanets, brown dwarfs, and circumstellar disks since it began in 2009, via the direct imaging technique. The survey has targeted nearby young stars, as well as stars associated to star-forming regions, the Pleiades open cluster, moving groups, and debris disks. We selected the nearby young stars that have been dated with age indicators based on stellar rotation periods (i.e., gyrochronology) and chromoshperic/coronal activities. Of these, nearly 40 were observed, with ages mainly between 100 and 1000 Myr and distances less than 40 pc. Our observations typically attain the contrast of ~6 x 10-6 at 1'' and better than ~1 x 10-6 beyond 2'', enabling us to detect a planetary-mass companion even around such old stars. Indeed, the SEEDS team reported the discovery that the nearby Sun-like star GJ 504 hosts a Jovian companion GJ 504b, which has a mass of 3-8.5 Jupiter masses that is inferred according to the hot-start cooling models and our estimated system age of 100-510 Myr. The remaining observations out of the selected ~40 stars have resulted in no detection of additional planets or brown dwarf companions. Meanwhile, we have newly imaged a low-mass stellar companion orbiting the G-type star HIP 10321, for which the presence of companion was previously announced via radial velocity technique. The astrometry and radial velocity measurements are simultaneously analyzed to determine the orbit, providing constraints on the dynamical mass of both objects and stellar evolution models. Here we summarize our direct imaging observations for the nearby young stars dated with gyrochrolorogy and activity age indicators. Furthermore, we report the analysis for the HIP 10321 system with the imaged low-mass companion.

Determination of acrylamide levels in selected foods in Brazil.

PubMed

Arisseto, Adriana Pavesi; Toledo, Maria Cecilia; Govaert, Yasmine; Loco, Joris Van; Fraselle, Stéphanie; Weverbergh, Eric; Degroodt, Jean Marie

2007-03-01

Selected carbohydrate-rich foods available on the Brazilian market (111 samples representing 19 product categories) were analysed for acrylamide content using a liquid chromatography-tandem mass spectrometry method. A limit of detection of 10 microg kg(-1), a limit of quantitation of 20 microg kg(-1) and mean recoveries ranging 100 to 115% were obtained during a laboratory validation procedure. The concentration of acrylamide in the samples ranged from <20 to 2528 microg kg(-1), with a considerable variation between individual foodstuffs within the same food product class. The highest levels were found in potato products processed at high temperature and in instant coffee, while the lowest concentrations were detected in cassava- and maize-based products, bread and beer. These results are comparable with those reported in other countries.

Basic design of MRM assays for peptide quantification.

PubMed

James, Andrew; Jorgensen, Claus

2010-01-01

With the recent availability and accessibility of mass spectrometry for basic and clinical research, the requirement for stable, sensitive, and reproducible assays to specifically detect proteins of interest has increased. Multiple reaction monitoring (MRM) or selective reaction monitoring (SRM) is a highly selective, sensitive, and robust assay to monitor the presence and amount of biomolecules. Until recently, MRM was typically used for the detection of drugs and other biomolecules from body fluids. With increased focus on biomarkers and systems biology approaches, researchers in the proteomics field have taken advantage of this approach. In this chapter, we will introduce the reader to the basic principle of designing and optimizing an MRM workflow. We provide examples of MRM workflows for standard proteomic samples and provide suggestions for the reader who is interested in using MRM for quantification.

Analysis and design of a capsule landing system and surface vehicle control system for Mars exploration

NASA Technical Reports Server (NTRS)

Frederick, D. K.; Lashmet, P. K.; Sandor, G. N.; Shen, C. N.; Smith, E. V.; Yerazunis, S. W.

1973-01-01

Problems related to the design and control of a mobile planetary vehicle to implement a systematic plan for the exploration of Mars are reported. Problem areas include: vehicle configuration, control, dynamics, systems and propulsion; systems analysis, terrain modeling and path selection; and chemical analysis of specimens. These tasks are summarized: vehicle model design, mathematical model of vehicle dynamics, experimental vehicle dynamics, obstacle negotiation, electrochemical controls, remote control, collapsibility and deployment, construction of a wheel tester, wheel analysis, payload design, system design optimization, effect of design assumptions, accessory optimal design, on-board computer subsystem, laser range measurement, discrete obstacle detection, obstacle detection systems, terrain modeling, path selection system simulation and evaluation, gas chromatograph/mass spectrometer system concepts, and chromatograph model evaluation and improvement.

A new diketopyrrolopyrrole-based probe for sensitive and selective detection of sulfite in aqueous solution

NASA Astrophysics Data System (ADS)

Yang, Xiaofeng; Cui, Yu; Li, Yexin; Zheng, Luyi; Xie, Lijun; Ning, Rui; Liu, Zheng; Lu, Junling; Zhang, Gege; Liu, Chunxiang; Zhang, Guangyou

2015-02-01

A new probe was synthesized by incorporating an α,β -unsaturated ketone to a diketopyrrolopyrrole fluorophore. The probe had exhibited a selective and sensitive response to the sulfite against other thirteen anions and biothiols (Cys, Hcy and GSH), through the nucleophilic addition of sulfite to the alkene of probe with the detection limit of 0.1 μM in HEPES (10 mM, pH 7.4) THF/H2O (1:1, v/v). Meanwhile, it could be easily observed that the probe for sulfite changed from pink to colorless by the naked eye, and from pink to blue under UV lamp after the sulfite was added for 20 min. The NMR and Mass spectral analysis demonstrated the expected addition of sulfite to the Cdbnd C bonds.

Extractive alkylation of 6-mercaptopurine and determination in plasma by gas chromatography-mass spectrometry.

PubMed

Floberg, S; Hartvig, P; Lindström, B; Lönner-Holm, G; Odlind, B

1981-09-11

An analytical procedure was developed for the determination of 6-mercaptopurine in plasma. Owing to the polar character and low plasma concentration of the compound, extraction and derivatization was carried out directly from the plasma sample by extractive alkylation. Determination was made using gas chromatography-mass spectrometry with multiple-ion detection. Conditions with respect to the rate of formation and the stability of the derivative formed in the extractive alkylation step were evaluated. The selectively of the method to azathioprine and to metabolites was thoroughly investigated. No 6-mercaptopurine was formed from azathioprine added to water or plasma and run through the method. The method enables the detection of 2 ng of 6 mercaptopurine in a 1.0-ml plasma sample. Quantitative determinations were done down to 10 ng/ml 6 mercaptopurine in plasma.

High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

PubMed

Swearingen, Kristian E; Moritz, Robert L

2012-10-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

Application of the Trend Filtering Algorithm for Photometric Time Series Data

NASA Astrophysics Data System (ADS)

Gopalan, Giri; Plavchan, Peter; van Eyken, Julian; Ciardi, David; von Braun, Kaspar; Kane, Stephen R.

2016-08-01

Detecting transient light curves (e.g., transiting planets) requires high-precision data, and thus it is important to effectively filter systematic trends affecting ground-based wide-field surveys. We apply an implementation of the Trend Filtering Algorithm (TFA) to the 2MASS calibration catalog and select Palomar Transient Factory (PTF) photometric time series data. TFA is successful at reducing the overall dispersion of light curves, however, it may over-filter intrinsic variables and increase “instantaneous” dispersion when a template set is not judiciously chosen. In an attempt to rectify these issues we modify the original TFA from the literature by including measurement uncertainties in its computation, including ancillary data correlated with noise, and algorithmically selecting a template set using clustering algorithms as suggested by various authors. This approach may be particularly useful for appropriately accounting for variable photometric precision surveys and/or combined data sets. In summary, our contributions are to provide a MATLAB software implementation of TFA and a number of modifications tested on synthetics and real data, summarize the performance of TFA and various modifications on real ground-based data sets (2MASS and PTF), and assess the efficacy of TFA and modifications using synthetic light curve tests consisting of transiting and sinusoidal variables. While the transiting variables test indicates that these modifications confer no advantage to transit detection, the sinusoidal variables test indicates potential improvements in detection accuracy.

Molecularly imprinted polymers as selective adsorbents for ambient plasma mass spectrometry.

PubMed

Cegłowski, Michał; Smoluch, Marek; Reszke, Edward; Silberring, Jerzy; Schroeder, Grzegorz

2017-05-01

The application of molecularly imprinted polymers (MIPs) as molecular scavengers for ambient plasma ionization mass spectrometry has been reported for the first time. MIPs were synthesized using methacrylic acid as functional monomer; nicotine, propyphenazone, or methylparaben as templates; ethylene glycol dimethacrylate as a cross-linker; and 2,2'-azobisisobutyronitrile as polymerization initiator. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and a quadrupole ion trap mass spectrometer has been used. The heated crucible with programmable temperature allows for desorption of the analytes from MIPs structure which results in their direct introduction into the ion stream. Limits of detection, linearity of the proposed analytical procedure, and selectivities have been determined for three analytes: nicotine, propyphenazone, and methylparaben. The analytes used were chosen from various classes of organic compounds to show the feasibility of the analytical procedure. The limits of detections (LODs) were 10 nM, 10, and 0.5 μM for nicotine, propyphenazone, and methylparaben, respectively. In comparison with the measurements performed for the non-imprinted polymers, the values of LODs were improved for at least one order of magnitude due to preconcentration of the sample and reduction of background noise, contributing to signal suppression. The described procedure has shown linearity in a broad range of concentrations. The overall time of single analysis is short and requires ca. 5 min. The developed technique was applied for the determination of nicotine, propyphenazone, and methylparaben in spiked real-life samples, with recovery of 94.6-98.4%. The proposed method is rapid, sensitive, and accurate which provides a new option for the detection of small organic compounds in various samples. Graphical abstract The experimental setup used for analysis.

THE SPECTRAL EVOLUTION OF THE FIRST GALAXIES. I. JAMES WEBB SPACE TELESCOPE DETECTION LIMITS AND COLOR CRITERIA FOR POPULATION III GALAXIES

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

Zackrisson, Erik; Rydberg, Claes-Erik; Oestlin, Goeran

The James Webb Space Telescope (JWST) is expected to revolutionize our understanding of the high-redshift universe, and may be able to test the prediction that the first, chemically pristine (Population III) stars are formed with very high characteristic masses. Since isolated Population III stars are likely to be beyond the reach of JWST, small Population III galaxies may offer the best prospects of directly probing the properties of metal-free stars. Here, we present Yggdrasil, a new spectral synthesis code geared toward the first galaxies. Using this model, we explore the JWST imaging detection limits for Population III galaxies and investigatemore » to what extent such objects may be identified based on their JWST colors. We predict that JWST should be able to detect Population III galaxies with stellar population masses as low as {approx}10{sup 5} M{sub sun} at z {approx} 10 in ultra deep exposures. Over limited redshift intervals, it may also be possible to use color criteria to select Population III galaxy candidates for follow-up spectroscopy. The colors of young Population III galaxies dominated by direct starlight can be used to probe the stellar initial mass function (IMF), but this requires almost complete leakage of ionizing photons into the intergalactic medium. The colors of objects dominated by nebular emission show no corresponding IMF sensitivity. We also note that a clean selection of Population III galaxies at z {approx} 7-8 can be achieved by adding two JWST/MIRI filters to the JWST/NIRCam filter sets usually discussed in the context of JWST ultra deep fields.« less

Hydrogen sulfide measurement using sulfide dibimane: critical evaluation with electrospray ion trap mass spectrometry

PubMed Central

Shen, Xinggui; Chakraborty, Sourav; Dugas, Tammy R; Kevil, Christopher G

2015-01-01

Accurate measurement of hydrogen sulfide bioavailability remains a technical challenge due to numerous issues involving sample processing, detection methods used, and actual biochemical products measured. Our group and others have reported that reverse phase HPLC detection of sulfide dibimane (SDB) product from the reaction of H2S/HS− with monobromobimane allows for analytical detection of hydrogen sulfide bioavailability in free and other biochemical forms. However, it remains unclear whether possible interfering contaminants may contribute to HPLC SDB peak readings that may result in inaccurate measurements of bioavailable sulfide. In this study, we critically compared hydrogen sulfide dependent SDB detection using reverse phase HPLC (RP-HPLC) versus quantitative SRM electrospray ionization mass spectrometry (ESI/MS) to obtain greater clarity into the validity of the reverse phase HPLC method for analytical measurement of hydrogen sulfide. Using an LCQ-deca ion-trap mass spectrometer, SDB was identified by ESI/MS positive ion mode, and quantified by selected reaction monitoring (SRM) using hydrocortisone as an internal standard. Collision induced dissociation (CID) parameters were optimized at MS2 level for SDB and hydrocortisone. ESI/MS detection of SDB standard was found to be a log order more sensitive than RP-HPLC with a lower limit of 0.25 nM. Direct comparison of tissue and plasma SDB levels using RP-HPLC and ESI/MS methods revealed comparable sulfide levels in plasma, aorta, heart, lung and brain. Together, these data confirm the use of SDB as valid indicator of H2S bioavailability and highlights differences between analytical detection methods. PMID:24932544

An adaptive incremental approach to constructing ensemble classifiers: Application in an information-theoretic computer-aided decision system for detection of masses in mammograms

PubMed Central

Mazurowski, Maciej A.; Zurada, Jacek M.; Tourassi, Georgia D.

2009-01-01

Ensemble classifiers have been shown efficient in multiple applications. In this article, the authors explore the effectiveness of ensemble classifiers in a case-based computer-aided diagnosis system for detection of masses in mammograms. They evaluate two general ways of constructing subclassifiers by resampling of the available development dataset: Random division and random selection. Furthermore, they discuss the problem of selecting the ensemble size and propose two adaptive incremental techniques that automatically select the size for the problem at hand. All the techniques are evaluated with respect to a previously proposed information-theoretic CAD system (IT-CAD). The experimental results show that the examined ensemble techniques provide a statistically significant improvement (AUC=0.905±0.024) in performance as compared to the original IT-CAD system (AUC=0.865±0.029). Some of the techniques allow for a notable reduction in the total number of examples stored in the case base (to 1.3% of the original size), which, in turn, results in lower storage requirements and a shorter response time of the system. Among the methods examined in this article, the two proposed adaptive techniques are by far the most effective for this purpose. Furthermore, the authors provide some discussion and guidance for choosing the ensemble parameters. PMID:19673196

High-Throughput Analysis of Methylmalonic Acid in Serum, Plasma, and Urine by LC-MS/MS. Method for Analyzing Isomers Without Chromatographic Separation.

PubMed

Kushnir, Mark M; Nelson, Gordon J; Frank, Elizabeth L; Rockwood, Alan L

2016-01-01

Measurement of methylmalonic acid (MMA) plays an important role in the diagnosis of vitamin B12 deficiency. Vitamin B12 is an essential cofactor for the enzymatic carbon rearrangement of methylmalonyl-CoA (MMA-CoA) to succinyl-CoA (SA-CoA), and the lack of vitamin B12 leads to elevated concentrations of MMA. Presence of succinic acid (SA) complicates the analysis because mass spectra of MMA and SA are indistinguishable, when analyzed in negative ion mode and the peaks are difficult to resolve chromatographically. We developed a method for the selective analysis of MMA that exploits the significant difference in fragmentation patterns of di-butyl derivatives of the isomers MMA and SA in a tandem mass spectrometer when analyzed in positive ion mode. Tandem mass spectra of di-butyl derivatives of MMA and SA are very distinct; this allows selective analysis of MMA in the presence of SA. The instrumental analysis is performed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in positive ion mode, which is, in combination with selective extraction of acidic compounds, is highly selective for organic acids with multiple carboxyl groups (dicarboxylic, tricarboxylic, etc.). In this method organic acids with a single carboxyl group are virtually undetectable in the mass spectrometer; the only organic acid, other than MMA, that is detected by this method is its isomer, SA. Quantitative measurement of MMA in this method is performed using a deconvolution algorithm, which mathematically resolves the signal corresponding to MMA and does not require chromatographic resolution of the MMA and SA peaks. Because of its high selectivity, the method utilizes isocratic chromatographic separation; reconditioning and re-equilibration of the chromatographic column between injections is unnecessary. The above features of the method allow high-throughput analysis of MMA with analysis cycle time of 1 min.

Small-size mass spectrometer for determining gases and volatile compounds in air during breathing

NASA Astrophysics Data System (ADS)

Kogan, V. T.; Kozlenok, A. V.; Chichagov, Yu. V.; Antonov, A. S.; Lebedev, D. S.; Bogdanov, A. A.; Moroshkin, V. S.; Berezina, A. V.; Viktorova-Leclerc, O. S.; Vlasov, S. A.; Tubol'tsev, Yu. V.

2015-10-01

We describe an automated mass spectrometer for diagnostics of deceases from the composition of exhaled air. It includes a capillary system, which performs a rapid direct feeding of the sample to the instrument without changing substantially its composition and serves for studying the dynamics of variation of the ratio between various components of exhaled air. The membrane system for introducing the sample is intended for determining low concentrations of volatile organic compounds which are biomarkers of pathologies. It is characterized by selective transmittance and ensures the detection limits of target compounds at the parts per million-parts per billion (ppm-ppb) level. A static mass analyzer operating on permanent magnets possesses advantages important for mobile devices as compared to its dynamic analogs: it is more reliable in operation, has a larger dynamic range, and can be used for determining the concentration of components in the mixture one-by-one or simultaneously. The curvilinear output boundary of the magnetic lens of the mass analyzer makes it possible to reduce its weight and size by 2.5 times without deteriorating the mass resolution. We report on the results of testing of the instrument and consider the possibility of its application for early detection of deceases of respiratory and blood circulation system, gastrointestinal tract, and endocrine system.

Liquid chromatography with tandem mass spectrometry for the simultaneous identification and quantification of cardiovascular drugs applied to the detection of substandard and falsified drugs.

PubMed

Bernard, Mélisande; Akrout, Wiem; Van Buu, Christelle Tran; Metz, Carole; Antignac, Marie; Yagoubi, Najet; Do, Bernard

2015-02-01

The counterfeiting of pharmaceuticals has been detected since about 1990 and has alarmingly continued to pick up steam. We have been recently involved in an evaluation program of some of the most commonly prescribed cardiovascular drugs in Africa, for analysing an important number of tablets or capsules obtained from different places in seven African countries. A reversed-phase high-performance liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously control the identity and the quantity of acenocoumarol, amlodipine, atenolol, captopril, furosemide, hydrochlorothiazide and simvastatin in tablets. Their separation was performed on a Kinetex® C(18) (100 mm × 2.1 mm inside diameter, 2.6 μm) column using a gradient elution of 20 mM ammonium formate buffer and acetonitrile (90:10 10:90 v/v) at a flow rate of 0.5 mL/min. The analytes were detected using electrospray ionisation tandem mass spectrometry in both positive and negative modes with multiple reaction monitoring. Tandem mass spectrometry fragmentation patterns of captopril, furosemide and acenocoumarol, up to now not detailed in the literature, were also studied to assist in the selection of the most relevant transitions towards the objectives. The developed method was validated as per International Conference on Harmonisation guidelines with respect to specificity, linearity, trueness, precision, limits of detection and quantification. It has been successfully applied to the control of oral forms of seven cardiovascular drugs collected in African countries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Betaines by Fast Atom Bombardment Mass Spectrometry 1

PubMed Central

Rhodes, David; Rich, Patrick J.; Myers, Ann C.; Reuter, Carol C.; Jamieson, Gene C.

1987-01-01

A rapid, sensitive, and selective method for the determination of betaines is described and discussed. The method entails derivatizing the quaternary ammonium compounds to increase their sensitivity to detection by fast atom bombardment mass spectrometry. Sensitivity of detection increases markedly as the length of the carbon chain of the alcohol used to esterify the betaine carboxylic acid group is increased (C4 > C3 > C2 > C1 > C0). The lower limit of detection of glycine betaine as the n-propyl ester is 0.05 nanomole per microliter of glycerol. Betaine aldehyde can be readily derivatized to the di-n-butyl or di-n-propyl acetal derivatives which exhibit lower limits of detection of about 5 picomoles and 10 picomoles per microliter of glycerol, respectively. Accurate quantification of these compounds is accomplished by the use of deuterium labeled internal standards or quaternary ammonium compound homologs of distinct mass. Methods for the synthesis of these internal standards are reported. Some applications of these methods are illustrated with stable isotope tracer studies on the kinetics of metabolism of choline to betaine aldehyde and glycine betaine in spinach leaf discs, and the identification of several Zea mays genotypes which appear deficient in glycine betaine. Tracer studies with deuterium labeled betaine aldehyde suggest that the deficiency of glycine betaine in one sweet corn hybrid is probably not due to a deficiency in the capacity to oxidize betaine aldehyde. PMID:16665522

Computer-aided Classification of Mammographic Masses Using Visually Sensitive Image Features

PubMed Central

Wang, Yunzhi; Aghaei, Faranak; Zarafshani, Ali; Qiu, Yuchen; Qian, Wei; Zheng, Bin

2017-01-01

Purpose To develop a new computer-aided diagnosis (CAD) scheme that computes visually sensitive image features routinely used by radiologists to develop a machine learning classifier and distinguish between the malignant and benign breast masses detected from digital mammograms. Methods An image dataset including 301 breast masses was retrospectively selected. From each segmented mass region, we computed image features that mimic five categories of visually sensitive features routinely used by radiologists in reading mammograms. We then selected five optimal features in the five feature categories and applied logistic regression models for classification. A new CAD interface was also designed to show lesion segmentation, computed feature values and classification score. Results Areas under ROC curves (AUC) were 0.786±0.026 and 0.758±0.027 when to classify mass regions depicting on two view images, respectively. By fusing classification scores computed from two regions, AUC increased to 0.806±0.025. Conclusion This study demonstrated a new approach to develop CAD scheme based on 5 visually sensitive image features. Combining with a “visual aid” interface, CAD results may be much more easily explainable to the observers and increase their confidence to consider CAD generated classification results than using other conventional CAD approaches, which involve many complicated and visually insensitive texture features. PMID:27911353

Lipidomics by ultrahigh performance liquid chromatography-high resolution mass spectrometry and its application to complex biological samples

PubMed Central

Triebl, Alexander; Trötzmüller, Martin; Hartler, Jürgen; Stojakovic, Tatjana; Köfeler, Harald C

2018-01-01

An improved approach for selective and sensitive identification and quantitation of lipid molecular species using reversed phase chromatography coupled to high resolution mass spectrometry was developed. The method is applicable to a wide variety of biological matrices using a simple liquid-liquid extraction procedure. Together, this approach combines three selectivity criteria: Reversed phase chromatography separates lipids according to their acyl chain length and degree of unsaturation and is capable of resolving positional isomers of lysophospholipids, as well as structural isomers of diacyl phospholipids and glycerolipids. Orbitrap mass spectrometry delivers the elemental composition of both positive and negative ions with high mass accuracy. Finally, automatically generated tandem mass spectra provide structural insight into numerous glycerolipids, phospholipids, and sphingolipids within a single run. Method validation resulted in a linearity range of more than four orders of magnitude, good values for accuracy and precision at biologically relevant concentration levels, and limits of quantitation of a few femtomoles on column. Hundreds of lipid molecular species were detected and quantified in three different biological matrices, which cover well the wide variety and complexity of various model organisms in lipidomic research. Together with a reliable software package, this method is a prime choice for global lipidomic analysis of even the most complex biological samples. PMID:28415015

Lipidomics by ultrahigh performance liquid chromatography-high resolution mass spectrometry and its application to complex biological samples.

PubMed

Triebl, Alexander; Trötzmüller, Martin; Hartler, Jürgen; Stojakovic, Tatjana; Köfeler, Harald C

2017-05-15

An improved approach for selective and sensitive identification and quantitation of lipid molecular species using reversed phase chromatography coupled to high resolution mass spectrometry was developed. The method is applicable to a wide variety of biological matrices using a simple liquid-liquid extraction procedure. Together, this approach combines multiple selectivity criteria: Reversed phase chromatography separates lipids according to their acyl chain length and degree of unsaturation and is capable of resolving positional isomers of lysophospholipids, as well as structural isomers of diacyl phospholipids and glycerolipids. Orbitrap mass spectrometry delivers the elemental composition of both positive and negative ions with high mass accuracy. Finally, automatically generated tandem mass spectra provide structural insight into numerous glycerolipids, phospholipids, and sphingolipids within a single run. Calibration showed linearity ranges of more than four orders of magnitude, good values for accuracy and precision at biologically relevant concentration levels, and limits of quantitation of a few femtomoles on column. Hundreds of lipid molecular species were detected and quantified in three different biological matrices, which cover well the wide variety and complexity of various model organisms in lipidomic research. Together with a software package, this method is a prime choice for global lipidomic analysis of even the most complex biological samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Obscured AGN at z ~ 1 from the zCOSMOS-Bright Survey. I. Selection and optical properties of a [Ne v]-selected sample

NASA Astrophysics Data System (ADS)

Mignoli, M.; Vignali, C.; Gilli, R.; Comastri, A.; Zamorani, G.; Bolzonella, M.; Bongiorno, A.; Lamareille, F.; Nair, P.; Pozzetti, L.; Lilly, S. J.; Carollo, C. M.; Contini, T.; Kneib, J.-P.; Le Fèvre, O.; Mainieri, V.; Renzini, A.; Scodeggio, M.; Bardelli, S.; Caputi, K.; Cucciati, O.; de la Torre, S.; de Ravel, L.; Franzetti, P.; Garilli, B.; Iovino, A.; Kampczyk, P.; Knobel, C.; Kovač, K.; Le Borgne, J.-F.; Le Brun, V.; Maier, C.; Pellò, R.; Peng, Y.; Perez Montero, E.; Presotto, V.; Silverman, J. D.; Tanaka, M.; Tasca, L.; Tresse, L.; Vergani, D.; Zucca, E.; Bordoloi, R.; Cappi, A.; Cimatti, A.; Koekemoer, A. M.; McCracken, H. J.; Moresco, M.; Welikala, N.

2013-08-01

Aims: The application of multi-wavelength selection techniques is essential for obtaining a complete and unbiased census of active galactic nuclei (AGN). We present here a method for selecting z ~ 1 obscured AGN from optical spectroscopic surveys. Methods: A sample of 94 narrow-line AGN with 0.65 < z < 1.20 was selected from the 20k-Bright zCOSMOS galaxy sample by detection of the high-ionization [Ne v] λ3426 line. The presence of this emission line in a galaxy spectrum is indicative of nuclear activity, although the selection is biased toward low absorbing column densities on narrow-line region or galactic scales. A similar sample of unobscured (type 1 AGN) was collected applying the same analysis to zCOSMOS broad-line objects. This paper presents and compares the optical spectral properties of the two AGN samples. Taking advantage of the large amount of data available in the COSMOS field, the properties of the [Ne v]-selected type 2 AGN were investigated, focusing on their host galaxies, X-ray emission, and optical line-flux ratios. Finally, a previously developed diagnostic, based on the X-ray-to-[Ne v] luminosity ratio, was exploited to search for the more heavily obscured AGN. Results: We found that [Ne v]-selected narrow-line AGN have Seyfert 2-like optical spectra, although their emission line ratios are diluted by a star-forming component. The ACS morphologies and stellar component in the optical spectra indicate a preference for our type 2 AGN to be hosted in early-type spirals with stellar masses greater than 109.5 - 10 M⊙, on average higher than those of the galaxy parent sample. The fraction of galaxies hosting [Ne v]-selected obscured AGN increases with the stellar mass, reaching a maximum of about 3% at ≈2 × 1011 M⊙. A comparison with other selection techniques at z ~ 1, namely the line-ratio diagnostics and X-ray detections, shows that the detection of the [Ne v] λ3426 line is an effective method for selecting AGN in the optical band, in particular the most heavily obscured ones, but cannot provide a complete census of type 2 AGN by itself. Finally, the high fraction of [Ne v]-selected type 2 AGN not detected in medium-deep (≈100-200 ks) Chandra observations (67%) is suggestive of the inclusion of Compton-thick (i.e., with NH > 1024 cm-2) sources in our sample. The presence of a population of heavily obscured AGN is corroborated by the X-ray-to-[Ne v] ratio; we estimated, by means of an X-ray stacking technique and simulations, that the Compton-thick fraction in our sample of type 2 AGN is 43 ± 4% (statistical errors only), which agrees well with standard assumptions by XRB synthesis models.

QUANTITATION OF PERCHLORATE ION BY ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS) USING STABLE ASSOCIATION COMPLEXES WITH ORGANIC CATIONS AND BASES TO ENHANCE SELECTIVITY

EPA Science Inventory

Quantitation of trace levels of perchlorate ion in water has become a key issue since this species was discovered in water supplies around the United States. Although ion chromatographic methods presently offer the lowest limit of detection, =40 nm (4ngm1-1), chromatographic ret...

Improved Detection of HER2 by a Quasi-Targeted Proteomics Approach Using Aptamer-Peptide Probe and Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Zhou, Weixian; Xu, Feifei; Li, Danni; Chen, Yun

2018-03-01

Human epidermal growth factor receptor 2 (HER2)-positive breast cancer is a particularly aggressive type of the disease. To date, much evidence has indicated that accurate HER2 status detection is crucial for prognosis and treatment strategy selection. Thus, bioanalytical techniques for early and accurate detection of HER2 have the potential to improve patient care. Currently, the widely used immunohistochemical staining normally has problems with reproducibility and lack of standardization, resulting in poor concordance between laboratories. Aptamers are a good alternative, but the extent of their use in quantitative analysis of HER2 is limited because of the lack of effective detection methods. We developed a quasi-targeted proteomics assay and converted the HER2 signal into the mass response of reporter peptide by a combination of aptamer-peptide probe and LC-MS/MS. The selected aptamer-peptide probe consisted of aptamer HB5 and the substrate peptide GDKAVLGVDPFR that contained the reporter peptide AVLGVDPFR. After characterization of this newly synthesized probe (e.g., conjugation efficiency, stability, binding affinity, specificity, and digestion efficiency), probe binding and trypsin shaving conditions were optimized. The resulting limit of quantification for HER2 was 25 pmol/L. Then, the quasi-targeted proteomics assay was applied to determine the HER2 concentrations in the HER2-positive breast cancer cells BT474 and SK-BR-3, the HER2-negative breast cancer cells MDA-MB-231 and MCF-7, and 36 pairs of human breast primary tumors and adjacent normal tissue samples. The results were highly concordant with those obtained by immunohistochemistry with reflex testing by fluorescent in situ hybridization. Quasi-targeted proteomics can be a quantitative alternative for HER2 detection. © 2017 American Association for Clinical Chemistry.

Preparation of on-plate immobilized metal ion affinity chromatography platform via dopamine chemistry for highly selective isolation of phosphopeptides with matrix assisted laser desorption/ionization mass spectrometry analysis.

PubMed

Shi, Chenyi; Lin, Qinrui; Deng, Chunhui

2015-04-01

In this study, a novel on-plate IMAC technique was developed for highly selective enrichment and isolation of phosphopeptides with high-throughput MALDI-TOF-MS analysis. At first, a MALDI plate was coated with polydopamine (PDA), and then Ti(4+) was immobilized on the PDA-coated plate. The obtained IMAC plate was successfully applied to the highly selective enrichment and isolation of phosphopeptides in protein digests and human serum. Because of no loss of samples, the on-plate IMAC platform exhibits excellent selectivity and sensitivity in the selective enrichment and isolation of phosphopeptides, which provides a potential technique for high selectivity in the detection of low-abundance phosphopeptides in biological samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Trace determination of 13 haloacetamides in drinking water using liquid chromatography triple quadrupole mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Chu, Wenhai; Gao, Naiyun; Yin, Daqiang; Krasner, Stuart W; Templeton, Michael R

2012-04-27

The haloacetamides (HAcAms) are disinfection by-products (DBPs) in drinking water which are currently receiving increased scientific attention due to their elevated toxicity relative to regulated disinfection by-products. A simultaneous determination method of 13 HAcAms, combining solid-phase extraction (SPE) enrichment, liquid chromatographic (LC) separation, and triple quadrupole mass spectrometry (tqMS) detection with atmospheric pressure chemical ionization (APCI) using selective reaction monitoring in positive mode, was developed to measure HAcAms, including chlorinated, brominated, and iodinated analogs. Ammonium chloride and Oasis HLB were selected as the dechlorinating reagent and polymeric SPE sorbent of HAcAm samples. The used tqMS apparatus showed higher sensitivity for the studied HAcAms in the APCI mode than electrospray ionization. 13 HAcAms were separated by LC in 9.0 min, and the detection limits ranged from 7.6 to 19.7 ng/L. The SPE-LC/tqMS method was successfully applied to quantify 13 HAcAms in drinking water samples for the first time, and first indentified tribromoacetamide and chloroiodoacetamide as DBPs in drinking water. Copyright © 2012 Elsevier B.V. All rights reserved.

A simple and selective method for the measurement of azadirachtin and related azadirachtoid levels in fruits and vegetables using liquid chromatography electrospray ionization tandem mass spectrometry.

PubMed

Sarais, Giorgia; Caboni, Pierluigi; Sarritzu, Erika; Russo, Mariateresa; Cabras, Paolo

2008-05-14

Neem-based insecticides containing azadirachtin and related azadirachtoids are widely used in agriculture. Here, we report an analytical method for the rapid and accurate quantification of the insecticide azadirachtin A and B and other azadirachtoids such as salannin, nimbin, and their deacetylated analogues on tomatoes and peaches. Azadirachtoids were extracted from fruits and vegetables with acetonitrile. Using high-performance liquid chromatography/electrospray ionization tandem mass spectrometer, azadirachtoids were selectively detected monitoring the multiple reaction transitions of sodium adduct precursor ions. For azadirachtin A, calibration was linear over a working range of 1-1000 microg/L with r > 0.996. The limit of detection and limit of quantification for azadirachtin A were 0.4 and 0.8 microg/kg, respectively. The presence of interfering compounds in the peach and tomato extracts was evaluated and found to be minimal. Because of the linear behavior, it was concluded that the multiple reaction transitions of sodium adduct ions can be used for analytical purposes, that is, for the identification and quantification of azadirachtin A and B and related azadirachtoids in fruit and vegetable extracts at trace levels.

Liquid Chromatography-Electrospray Ionization Mass Spectrometry Analysis of Limonoids and Flavonoids in Seeds of Grapefruits, Other Citrus Species, and Dietary Supplements.

PubMed

Avula, Bharathi; Sagi, Satyanarayanaraju; Wang, Yan-Hong; Wang, Mei; Gafner, Stefan; Manthey, John A; Khan, Ikhlas A

2016-07-01

A selective UHPLC-DAD-QToF-MS method was developed to screen grapefruit seeds, and the seeds of other Citrus species for limonoid aglycones, acids, glucosides, and flavonoids. These classes of compounds were identified in positive and negative ion modes over a mass-to-charge range from 100-1500. Accurate mass values, elution times, and fragmentation patterns obtained by QToF-mass spectrometry were used to identify or tentatively characterize the compounds detected in the sample of this study. Limonin was the major limonoid in most of the seeds of Citrus species, followed by nomilin. This analytical method was successfully applied for the analysis of commercial extracts and dietary supplements claiming to contain grapefruit seed extract, or extracts made from the seed and other fruit parts such as the peel or pulp. Many commercial products contained large numbers of flavonoids, indicating the use of peel, pulp, or seed coat. This method also permitted detection of synthetic preservatives such as benzethonium chloride, methylparaben, and triclosan in commercial grapefruit seed extract products. Out of the 17 commercial products analyzed, two contained the synthetic antimicrobial agent benzethonium chloride. Georg Thieme Verlag KG Stuttgart · New York.

Simultaneous analysis of strychnine and brucine and their major metabolites by liquid chromatography-electrospray ion trap mass spectrometry.

PubMed

Chen, Xueguo; Lai, Yongquan; Cai, Zongwei

2012-04-01

A liquid chromatography-electrospray ionization-ion trap mass spectrometry (LC-ESI-ITMS) method was developed for the simultaneous analysis of strychnine, brucine and their major metabolites. Strychnine and brucine were individually incubated with rat liver S9 fraction. The incubation samples were pooled together and analyzed with LC-ESI-ITMS in positive ion and full-scan detection mode. The calibration curves of strychnine and brucine in rat liver showed good linearity in ranges of 0.020 to 8.0 µg/mL for strychnine and 0.020 to 8.5 µg/mL for brucine. The limits of detections were both 0.008 µg/mL and the recoveries were 88.3 and 83.2% for strychnine and brucine, respectively. Two metabolites were identified as strychnine N-oxide and brucine N-oxide by comparing the molecular mass, retention time, full-scan mass spectra, tandem MS and MS(3) spectra with those of strychnine and brucine. The developed method provided high sensitivity and selectivity for the determination of poisonous alkaloids and their major metabolites and can be applied in the determination of samples in forensic and clinically toxicological cases.

Detection of bio-signature by microscopy and mass spectrometry

NASA Astrophysics Data System (ADS)

Tulej, M.; Wiesendanger, R.; Neuland, M., B.; Meyer, S.; Wurz, P.; Neubeck, A.; Ivarsson, M.; Riedo, V.; Moreno-Garcia, P.; Riedo, A.; Knopp, G.

2017-09-01

We demonstrate detection of micro-sized fossilized bacteria by means of microscopy and mass spectrometry. The characteristic structures of lifelike forms are visualized with a micrometre spatial resolution and mass spectrometric analyses deliver elemental and isotope composition of host and fossilized materials. Our studies show that high selectivity in isolation of fossilized material from host phase can be achieved while applying a microscope visualization (location), a laser ablation ion source with sufficiently small laser spot size and applying depth profiling method. Our investigations shows that fossilized features can be well isolated from host phase. The mass spectrometric measurements can be conducted with sufficiently high accuracy and precision yielding quantitative elemental and isotope composition of micro-sized objects. The current performance of the instrument allows the measurement of the isotope fractionation in per mill level and yield exclusively definition of the origin of the investigated species by combining optical visualization of investigated samples (morphology and texture), chemical characterization of host and embedded in the host micro-sized structure. Our isotope analyses involved bio-relevant B, C, S, and Ni isotopes which could be measured with sufficiently accuracy to conclude about the nature of the micro-sized objects.

MEASURING THE LUMINOSITY AND VIRIAL BLACK HOLE MASS DEPENDENCE OF QUASAR–GALAXY CLUSTERING AT z ∼ 0.8

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

Krolewski, Alex G.; Eisenstein, Daniel J., E-mail: akrolewski@college.harvard.edu

2015-04-10

We study the dependence of quasar clustering on quasar luminosity and black hole mass by measuring the angular overdensity of photometrically selected galaxies imaged by the Wide-field Infrared Survey Explorer (WISE) about z ∼ 0.8 quasars from SDSS. By measuring the quasar–galaxy cross-correlation function and using photometrically selected galaxies, we achieve a higher density of tracer objects and a more sensitive detection of clustering than measurements of the quasar autocorrelation function. We test models of quasar formation and evolution by measuring the luminosity dependence of clustering amplitude. We find a significant overdensity of WISE galaxies about z ∼ 0.8 quasarsmore » at 0.2–6.4 h{sup −1} Mpc in projected comoving separation. We find no appreciable increase in clustering amplitude with quasar luminosity across a decade in luminosity, and a power-law fit between luminosity and clustering amplitude gives an exponent of −0.01 ± 0.06 (1 σ error). We also fail to find a significant relationship between clustering amplitude and black hole mass, although our dynamic range in true mass is suppressed due to the large uncertainties in virial black hole mass estimates. Our results indicate that a small range in host dark matter halo mass maps to a large range in quasar luminosity.« less

Ground-based detectability of terrestrial and Jovian extrasolar planets: observations of CM Draconis at Lick Observatory.

PubMed

Doyle, L R; Dunham, E T; Deeg, H J; Blue, J E; Jenkins, J M

1996-06-25

The detection of terrestrial-sized extrasolar planets from the ground has been thought to be virtually impossible due to atmospheric scintillation limits. However, we show that this is not the case especially selected (but nevertheless main sequence) stars, namely small eclipsing binaries. For the smallest of these systems, CM Draconis, several months to a few years of photometric observations with 1-m-class telescopes will be sufficient to detect the transits of any short-period planets of sizes > or = 1.5 Earth radii (RE), using cross-correlation analysis with moderately good photometry. Somewhat larger telescopes will be needed to extend this detectability to terrestrial planets in larger eclipsing binary systems. (We arbitrarily define "terrestrial planets" herein as those whose disc areas are closer to that of Earth's than Neptune's i.e., less than about 2.78 RE.) As a "spin-off" of such observations, we will also be able to detect the presence of Jovian-mass planets without transits using the timing of the eclipse minima. Eclipse minima will drift in time as the binary system is offset by a sufficiently massive planet (i.e., one Jupiter mass) about the binary/giant-planet barycenter, causing a periodic variation in the light travel time to the observer. We present here an outline of present observations taking place at the University of California Lick Observatory using the Crossley 0.9-m telescope in collaboration with other observatories (in South Korea, Crete, France, Canary Islands, and New York) to detect or constrain the existence of terrestrial planets around main sequence eclipsing binary star systems, starting with CM Draconis. We demonstrate the applicability of photometric data to the general detection of gas giant planets via eclipse minima timings in many other small-mass eclipsing binary systems as well.

Ground-based detectability of terrestrial and Jovian extrasolar planets: observations of CM Draconis at Lick Observatory

NASA Technical Reports Server (NTRS)

Doyle, L. R.; Dunham, E. T.; Deeg, H. J.; Blue, J. E.; Jenkins, J. M.

1996-01-01

The detection of terrestrial-sized extrasolar planets from the ground has been thought to be virtually impossible due to atmospheric scintillation limits. However, we show that this is not the case especially selected (but nevertheless main sequence) stars, namely small eclipsing binaries. For the smallest of these systems, CM Draconis, several months to a few years of photometric observations with 1-m-class telescopes will be sufficient to detect the transits of any short-period planets of sizes > or = 1.5 Earth radii (RE), using cross-correlation analysis with moderately good photometry. Somewhat larger telescopes will be needed to extend this detectability to terrestrial planets in larger eclipsing binary systems. (We arbitrarily define "terrestrial planets" herein as those whose disc areas are closer to that of Earth's than Neptune's i.e., less than about 2.78 RE.) As a "spin-off" of such observations, we will also be able to detect the presence of Jovian-mass planets without transits using the timing of the eclipse minima. Eclipse minima will drift in time as the binary system is offset by a sufficiently massive planet (i.e., one Jupiter mass) about the binary/giant-planet barycenter, causing a periodic variation in the light travel time to the observer. We present here an outline of present observations taking place at the University of California Lick Observatory using the Crossley 0.9-m telescope in collaboration with other observatories (in South Korea, Crete, France, Canary Islands, and New York) to detect or constrain the existence of terrestrial planets around main sequence eclipsing binary star systems, starting with CM Draconis. We demonstrate the applicability of photometric data to the general detection of gas giant planets via eclipse minima timings in many other small-mass eclipsing binary systems as well.

With the Advent of Tomosynthesis in the Workup of Mammographic Abnormality, is Spot Compression Mammography Now Obsolete? An Initial Clinical Experience.

PubMed

Ni Mhuircheartaigh, Neasa; Coffey, Louise; Fleming, Hannah; O' Doherty, Ann; McNally, Sorcha

2017-09-01

To determine if the routine use of spot compression mammography is now obsolete in the assessment of screen detected masses, asymmetries and architectural distortion since the availability of digital breast tomosynthesis. We introduced breast tomosynthesis in the workup of screen detected abnormalities in our screening center in January 2015. During an initial learning period with tomosynthesis standard spot compression views were also performed. Three consultant breast radiologists retrospectively reviewed all screening mammograms recalled for assessment over the first 6-month period. We assessed retrospectively whether there was any additional diagnostic information obtained from spot compression views not already apparent on tomography. All cases were also reviewed for any additional lesions detected by tomosynthesis, not detected on routine 2-view screening mammography. 548 women screened with standard 2-view digital screening mammography were recalled for assessment in the selected period and a total of 565 lesions were assessed. 341 lesions were assessed by both tomosynthesis and routine spot compression mammography. The spot compression view was considered more helpful than tomosynthesis in only one patient. This was because the breast was inadequately positioned for tomosynthesis and the area in question was not adequately imaged. Apart from this technical error there was no asymmetry, distortion or mass where spot compression provided more diagnostic information than tomosynthesis alone. We detected three additional cancers on tomosynthesis, not detected by routine screening mammography. From our initial experience with tomosynthesis we conclude that spot compression mammography is now obsolete in the assessment of screen detected masses, asymmetries and distortions where tomosynthesis is available. © 2017 Wiley Periodicals, Inc.

Multi-scale textural feature extraction and particle swarm optimization based model selection for false positive reduction in mammography.

PubMed

Zyout, Imad; Czajkowska, Joanna; Grzegorzek, Marcin

2015-12-01

The high number of false positives and the resulting number of avoidable breast biopsies are the major problems faced by current mammography Computer Aided Detection (CAD) systems. False positive reduction is not only a requirement for mass but also for calcification CAD systems which are currently deployed for clinical use. This paper tackles two problems related to reducing the number of false positives in the detection of all lesions and masses, respectively. Firstly, textural patterns of breast tissue have been analyzed using several multi-scale textural descriptors based on wavelet and gray level co-occurrence matrix. The second problem addressed in this paper is the parameter selection and performance optimization. For this, we adopt a model selection procedure based on Particle Swarm Optimization (PSO) for selecting the most discriminative textural features and for strengthening the generalization capacity of the supervised learning stage based on a Support Vector Machine (SVM) classifier. For evaluating the proposed methods, two sets of suspicious mammogram regions have been used. The first one, obtained from Digital Database for Screening Mammography (DDSM), contains 1494 regions (1000 normal and 494 abnormal samples). The second set of suspicious regions was obtained from database of Mammographic Image Analysis Society (mini-MIAS) and contains 315 (207 normal and 108 abnormal) samples. Results from both datasets demonstrate the efficiency of using PSO based model selection for optimizing both classifier hyper-parameters and parameters, respectively. Furthermore, the obtained results indicate the promising performance of the proposed textural features and more specifically, those based on co-occurrence matrix of wavelet image representation technique. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular gas in elliptical galaxies with dust lanes

NASA Technical Reports Server (NTRS)

Wang, Zhong; Kenney, Jeffrey D. P.; Ishizuki, Sumio

1992-01-01

We have searched for CO(1-0) line emission in eight dust lane elliptical and lenticular galaxies using the Nobeyama 45 m telescope. Five of the eight galaxies, including the well-studied elliptical NGC 1052, have CO emission at above the 5-sigma level, with inferred molecular gas masses ranging from 10 exp 8 to a few times 10 exp 9 solar masses. Our selection criterion differs from previous surveys in that it does not depend on the FIR fluxes, and thus is less sensitive to the sizes and distances of the host galaxies or to the degree to which dust is heated. The relatively high detection rate of CO in these ellipticals suggests a close correlation between molecular mass and cold dust. Compared with previously studied samples of FIR selected early-type galaxies, our sample has on average four times more CO emission per unit FIR (40-120 microns) luminosity. If the intrinsic gas-to-dust ratio of these galaxies as similar to that of the Milky Way, then only about 5 percent of the dust mass in dust lane ellipticals radiates substantially at 60 and 100 microns, and the remaining dust must be colder than about 30 K.

Assessment of groundwater, soil-gas, and soil contamination at the Vietnam Armor Training Facility, Fort Gordon, Georgia, 2009-2011

USGS Publications Warehouse

Guimaraes, Wladmir B.; Falls, W. Fred; Caldwell, Andral W.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.

2012-01-01

The U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, Georgia, assessed the groundwater, soil gas, and soil for contaminants at the Vietnam Armor Training Facility (VATF) at Fort Gordon, from October 2009 to September 2011. The assessment included the detection of organic compounds in the groundwater and soil gas, and inorganic compounds in the soil. In addition, organic contaminant assessment included organic compounds classified as explosives and chemical agents in selected areas. The assessment was conducted to provide environmental contamination data to the U.S. Army at Fort Gordon pursuant to requirements of the Resource Conservation and Recovery Act Part B Hazardous Waste Permit process. This report is a revision of "Assessment of soil-gas, surface-water, and soil contamination at the Vietnam Armor Training Facility, Fort Gordon, Georgia, 2009-2010," Open-File Report 2011-1200, and supersedes that report to include results of additional samples collected in July 2011. Four passive samplers were deployed in groundwater wells at the VATF in Fort Gordon. Total petroleum hydrocarbons and benzene and octane were detected above the method detection level at all four wells. The only other volatile organic compounds detected above their method detection level were undecane and pentadecane, which were detected in two of the four wells. Soil-gas samplers were deployed at 72 locations in a grid pattern across the VATF on June 3, 2010, and then later retrieved on June 9, 2010. Total petroleum hydrocarbons were detected in 71 of the 72 samplers (one sampler was destroyed in the field and not analyzed) at levels above the method detection level, and the combined mass of benzene, toluene, ethylbenzene, and total xylene (BTEX) was detected above the detection level in 31 of the 71 samplers that were analyzed. Other volatile organic compounds detected above their respective method detection levels were naphthalene, 2-methyl-naphthalene, tridecane, 1,2,4-trimethylbenzene, and perchloroethylene. After the results of the 71 soil-gas samplers were received, 31 additional passive soil-gas samplers were deployed on July 14, 2011, and retrieved on July 18, 2011. These 31 samplers were deployed on a larger areal scale to better define the extent of the contamination. Total petroleum hydrocarbons were detected above their method detection level at all 31 samplers, whereas BTEX was detected above its method detection level at 17 of the 31 samplers. Other organic compounds detected above their method detection levels were naphthalene, 2-methyl-naphthalene, octane, undecane, tridecane, pentadecane, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, chloroform, and perchloroethylene. Subsequent to the 2010 soil-gas survey, four areas determined to have elevated contaminant mass were selected and sampled for explosives and chemical agents. No detections of explosives or chemical agents above their respective method detection levels were found at any of the sampling locations. The same four locations that were sampled for explosives and chemical agents were selected for the collection of soil samples. A fifth location also was selected on the basis of the elevated contaminant mass of the soil-gas survey. No metals that exceeded the Regional Screening Levels for Industrial Soils, as classified by the U.S. Environmental Protection Agency, were detected at any of the five VATF locations. The soil samples also were compared to values from the ambient, uncontaminated (background) levels for soils in South Carolina, as classified by the South Carolina Department of Health and Environmental Control. Because South Carolina is adjacent to Georgia and the soils in the Coastal Plain are similar, these comparisons are valid. No similar values are available for Georgia to use for comparison purposes. The metals that were detected above the ambient background levels for South Carolina, as classified by the South Carolina Department of Health and Environmental Control, include aluminum, arsenic, barium, beryllium, calcium, chromium, copper, iron, lead, magnesium, manganese, nickel, potassium, sodium, and zinc.

A Wide Area Survey for High-Redshift Massive Galaxies. II. Near-Infrared Spectroscopy of BzK-Selected Massive Star-Forming Galaxies

NASA Astrophysics Data System (ADS)

Onodera, Masato; Arimoto, Nobuo; Daddi, Emanuele; Renzini, Alvio; Kong, Xu; Cimatti, Andrea; Broadhurst, Tom; Alexander, Dave M.

2010-05-01

Results are presented from near-infrared spectroscopic observations of a sample of BzK-selected, massive star-forming galaxies (sBzKs) at 1.5 < z < 2.3 that were obtained with OHS/CISCO at the Subaru telescope and with SINFONI at the Very Large Telescope. Among the 28 sBzKs observed, Hα emission was detected in 14 objects, and for 11 of them the [N II] λ6583 flux was also measured. Multiwavelength photometry was also used to derive stellar masses and extinction parameters, whereas Hα and [N II] emissions have allowed us to estimate star formation rates (SFRs), metallicities, ionization mechanisms, and dynamical masses. In order to enforce agreement between SFRs from Hα with those derived from rest-frame UV and mid-infrared, additional obscuration for the emission lines (that originate in H II regions) was required compared to the extinction derived from the slope of the UV continuum. We have also derived the stellar mass-metallicity relation, as well as the relation between stellar mass and specific SFR (SSFR), and compared them to the results in other studies. At a given stellar mass, the sBzKs appear to have been already enriched to metallicities close to those of local star-forming galaxies of similar mass. The sBzKs presented here tend to have higher metallicities compared to those of UV-selected galaxies, indicating that near-infrared selected galaxies tend to be a chemically more evolved population. The sBzKs show SSFRs that are systematically higher, by up to ~2 orders of magnitude, compared to those of local galaxies of the same mass. The empirical correlations between stellar mass and metallicity, and stellar mass and SSFR are then compared with those of evolutionary population synthesis models constructed either with the simple closed-box assumption, or within an infall scenario. Within the assumptions that are built-in such models, it appears that a short timescale for the star formation (sime100 Myr) and large initial gas mass appear to be required if one wants to reproduce both relations simultaneously. Based on data collected at the Subaru telescope, which is operated by the National Astronomical Observatory of Japan (S04A-081, S05A-098), and on observations collected at the European Southern Observatory, Paranal, Chile (075.A-0439).

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of 86 volatile organic compounds in water by gas chromatography/mass spectrometry, including detections less than reporting limits

USGS Publications Warehouse

Connor, Brooke F.; Rose, Donna L.; Noriega, Mary C.; Murtaugh, Lucinda K.; Abney, Sonja R.

1998-01-01

This report presents precision and accuracy data for volatile organic compounds (VOCs) in the nanogram-per-liter range, including aromatic hydrocarbons, reformulated fuel components, and halogenated hydrocarbons using purge and trap capillary-column gas chromatography/mass spectrometry. One-hundred-four VOCs were initially tested. Of these, 86 are suitable for determination by this method. Selected data are provided for the 18 VOCs that were not included. This method also allows for the reporting of semiquantitative results for tentatively identified VOCs not included in the list of method compounds. Method detection limits, method performance data, preservation study results, and blank results are presented. The authors describe a procedure for reporting low-concentration detections at less than the reporting limit. The nondetection value (NDV) is introduced as a statistically defined reporting limit designed to limit false positives and false negatives to less than 1 percent. Nondetections of method compounds are reported as ?less than NDV.? Positive detections measured at less than NDV are reported as estimated concentrations to alert the data user to decreased confidence in accurate quantitation. Instructions are provided for analysts to report data at less than the reporting limits. This method can support the use of either method reporting limits that censor detections at lower concentrations or the use of NDVs as reporting limits. The data-reporting strategy for providing analytical results at less than the reporting limit is a result of the increased need to identify the presence or absence of environmental contaminants in water samples at increasingly lower concentrations. Long-term method detection limits (LTMDLs) for 86 selected compounds range from 0.013 to 2.452 micrograms per liter (?g/L) and differ from standard method detection limits (MDLs) in that the LTMDLs include the long-term variance of multiple instruments, multiple operators, and multiple calibrations over a longer time. For these reasons, LTMDLs are expected to be slightly higher than standard MDLs. Recoveries for all of the VOCs tested ranged from 36 (tert-butyl formate) to 155 percent (pentachlorobenzene). The majority of the compounds ranged from 85 to 115 percent recovery and had less than 5 percent relative standard deviation for concentrations spiked between 1 to 500 ?g/L in volatile blank-, surface-, and ground-water samples. Recoveries of 60 set spikes at low concentrations ranged from 70 to 114 percent (1,2,3- trimethylbenzene and acetone). Recovery data were collected over 6 months with multiple instruments, operators, and calibrations. In this method, volatile organic compounds are extracted from a water sample by actively purging with helium. The VOCs are collected onto a sorbent trap, thermally desorbed, separated by a Megabore gas chromatographic capillary column, and finally determined by a full-scan quadrupole mass spectrometer. Compound identification is confirmed by the gas chromatographic retention time and by the resultant mass spectrum, typically identified by three unique ions. An unknown compound detected in a sample can be tentatively identified by comparing the unknown mass spectrum to reference spectra in the mass-spectra computer-data system library compiled by the National Institute of Standards and Technology.

Determination of boldenone sulfoconjugate and related steroid sulfates in equine urine by high-performance liquid chromatography/tandem mass spectrometry.

PubMed

Weidolf, L O; Lee, E D; Henion, J D

1988-03-01

Sulfoconjugated anabolic steroids were separated by micro-bore high-performance liquid chromatography. The eluent was introduced into the atmospheric pressure ion source of the triple-quadrupole mass spectrometer via an ion spray liquid chromatograph/mass spectrometer interface operated in the negative ion mode. The limit of detection was 10 pg on-column by selected ion monitoring of the molecular ion and the response increased linearly over a concentration range of 2.4 orders of magnitude. Following work-up by a liquid-solid extraction procedure of equine urine samples, full-scan daughter ion spectra of boldenone sulfate could be obtained up to 17 days after a therapeutic dose of boldenone undecylenate to a horse.

Real-time detection method and system for identifying individual aerosol particles

DOEpatents

Gard, Eric E [San Francisco, CA; Coffee, Keith R [Patterson, CA; Frank, Matthias [Oakland, CA; Tobias, Herbert J [Kensington, CA; Fergenson, David P [Alamo, CA; Madden, Norm [Livermore, CA; Riot, Vincent J [Berkeley, CA; Steele, Paul T [Livermore, CA; Woods, Bruce W [Livermore, CA

2007-08-21

An improved method and system of identifying individual aerosol particles in real time. Sample aerosol particles are collimated, tracked, and screened to determine which ones qualify for mass spectrometric analysis based on predetermined qualification or selection criteria. Screening techniques include one or more of determining particle size, shape, symmetry, and fluorescence. Only qualifying particles passing all screening criteria are subject to desorption/ionization and single particle mass spectrometry to produce corresponding test spectra, which is used to determine the identities of each of the qualifying aerosol particles by comparing the test spectra against predetermined spectra for known particle types. In this manner, activation cycling of a particle ablation laser of a single particle mass spectrometer is reduced.

New method to determine the total carbonyl functional group content in extractable particulate organic matter by tandem mass spectrometry.

PubMed

Dron, J; Zheng, W; Marchand, N; Wortham, H

2008-08-01

A functional group analysis method was developed to determine the quantitative content of carbonyl functional groups in atmospheric particulate organic matter (POM) using constant neutral loss scanning-tandem mass spectrometry (CNLS-MS/MS). The neutral loss method consists in monitoring the loss of a neutral fragment produced by the fragmentation of a precursor ion in a collision cell. The only ions detected are the daughter ions resulting from the loss of the neutral fragment under study. Then, scanning the loss of a neutral fragment characteristic of a functional group enables the selective detection of the compounds bearing the chemical function under study within a complex mixture. The selective detection of carbonyl functional groups was achieved after derivatization with pentafluorophenylhydrazine (PFPH) by monitoring the neutral loss of C(6)F(5)N (181 amu), which was characteristic of a large panel of derivatized carbonyl compounds. The method was tested on 25 reference mixtures of different composition, all containing 24 carbonyl compounds at randomly determined concentrations. The repeatability and calibration tests were satisfying as they resulted in a relative standard deviation below 5% and a linear range between 0.01 and 0.65 mM with a calculated detection limit of 0.0035 mM. Also, the relative deviation induced by changing the composition of the mixture while keeping the total concentration of carbonyl functional groups constant was less than 20%. These reliability experiments demonstrate the high robustness of the developed procedure for accurate carbonyl functional group measurement, which was applied to atmospheric POM samples. Copyright (c) 2008 John Wiley & Sons, Ltd.

Lys48 ubiquitination during the intraerythrocytic cycle of the rodent malaria parasite, Plasmodium chabaudi.

PubMed

González-López, Lorena; Carballar-Lejarazú, Rebeca; Arrevillaga Boni, Gerardo; Cortés-Martínez, Leticia; Cázares-Raga, Febe Elena; Trujillo-Ocampo, Abel; Rodríguez, Mario H; James, Anthony A; Hernández-Hernández, Fidel de la Cruz

2017-01-01

Ubiquitination tags proteins for different functions within the cell. One of the most abundant and studied ubiquitin modification is the Lys48 polyubiquitin chain that modifies proteins for their destruction by proteasome. In Plasmodium is proposed that post-translational regulation is fundamental for parasite development during its complex life-cycle; thus, the objective of this work was to analyze the ubiquitination during Plasmodium chabaudi intraerythrocytic stages. Ubiquitinated proteins were detected during intraerythrocytic stages of Plasmodium chabaudi by immunofluorescent microscopy, bidimensional electrophoresis (2-DE) combined with immunoblotting and mass spectrometry. All the studied stages presented protein ubiquitination and Lys48 polyubiquitination with more abundance during the schizont stage. Three ubiquitinated proteins were identified for rings, five for trophozoites and twenty for schizonts. Only proteins detected with a specific anti- Lys48 polyubiquitin antibody were selected for Mass Spectrometry analysis and two of these identified proteins were selected in order to detect the specific amino acid residues where ubiquitin is placed. Ubiquitinated proteins during the ring and trophozoite stages were related with the invasion process and in schizont proteins were related with nucleic acid metabolism, glycolysis and protein biosynthesis. Most of the ubiquitin detection was during the schizont stage and the Lys48 polyubiquitination during this stage was related to proteins that are expected to be abundant during the trophozoite stage. The evidence that these Lys48 polyubiquitinated proteins are tagged for destruction by the proteasome complex suggests that this type of post-translational modification is important in the regulation of protein abundance during the life-cycle and may also contribute to the parasite cell-cycle progression.

A multi-targeted liquid chromatography-mass spectrometry screening procedure for the detection in human urine of drugs non-prohibited in sport commonly used by the athletes.

PubMed

Mazzarino, Monica; Cesarei, Lorenzo; de la Torre, Xavier; Fiacco, Ilaria; Robach, Paul; Botrè, Francesco

2016-01-05

This work presents an analytical method for the simultaneous analysis in human urine of 38 pharmacologically active compounds (19 benzodiazepine-like substances, 7 selective serotonin reuptake inhibitors, 4 azole antifungal drugs, 5 inhibitors of the phosphodiesterases type 4 and 3 inhibitors of the phosphodiesterase type 5) by liquid-chromatography coupled with tandem mass spectrometry. The above substances classes include both the most common "non banned" drugs used by the athletes (based on the information reported on the "doping control form") and those drugs who are suspected to be performance enhancing and/or act as masking agents in particular conditions. The chromatographic separation was performed by a reverse-phase octadecyl column using as mobile phases acetonitrile and ultra-purified water, both with 0.1% formic acid. The detection was carried out using a triple quadrupole mass spectrometric analyser, positive electro-spray as ionization source and selected reaction monitoring as acquisition mode. Sample pre-treatment consisted in an enzymatic hydrolysis followed by a liquid-liquid extraction in neutral field using tert-butyl methyl-ether. The analytical procedure, once developed, was validated in terms of sensitivity (lower limits of detection in the range of 1-50 ng mL(-1)), specificity (no interferences were detected at the retention time of all the analytes under investigation), recovery (≥60% with a satisfactory repeatability, CV % lower than 10), matrix effect (lower than 30%) and reproducibility of retention times (CV% lower than 0.1) and of relative abundances (CV% lower than 15). The performance and the applicability of the method was evaluated by analyzing real samples containing benzodiazepines (alprazolam, diazepam, zolpidem or zoplicone) or inhibitors of the phosphodiesterases type 5 (sildenafil or vardenafil) and samples obtained incubating two of the phosphodiesterases type 4 studied (cilomilast or roflumilast) with pooled human liver microsomes. All the parent compounds, together with their main phase I metabolites, were clearly detected using the analytical procedures here developed. Copyright © 2015 Elsevier B.V. All rights reserved.

Quantitative analysis of fragrance in selectable one dimensional or two dimensional gas chromatography-mass spectrometry with simultaneous detection of multiple detectors in single injection.

PubMed

Tan, Hui Peng; Wan, Tow Shi; Min, Christina Liew Shu; Osborne, Murray; Ng, Khim Hui

2014-03-14

A selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography-mass spectrometry (GC-MS) system coupled with flame ionization detector (FID) and olfactory detection port (ODP) was employed in this study to analyze perfume oil and fragrance in shower gel. A split/splitless (SSL) injector and a programmable temperature vaporization (PTV) injector are connected via a 2-way splitter of capillary flow technology (CFT) in this selectable (1)D/(2)D GC-MS/FID/ODP system to facilitate liquid sample injections and thermal desorption (TD) for stir bar sorptive extraction (SBSE) technique, respectively. The dual-linked injectors set-up enable the use of two different injector ports (one at a time) in single sequence run without having to relocate the (1)D capillary column from one inlet to another. Target analytes were separated in (1)D GC-MS/FID/ODP and followed by further separation of co-elution mixture from (1)D in (2)D GC-MS/FID/ODP in single injection without any instrumental reconfiguration. A (1)D/(2)D quantitative analysis method was developed and validated for its repeatability - tR; calculated linear retention indices (LRI); response ratio in both MS and FID signal, limit of detection (LOD), limit of quantitation (LOQ), as well as linearity over a concentration range. The method was successfully applied in quantitative analysis of perfume solution at different concentration level (RSD≤0.01%, n=5) and shower gel spiked with perfume at different dosages (RSD≤0.04%, n=5) with good recovery (96-103% for SSL injection; 94-107% for stir bar sorptive extraction-thermal desorption (SBSE-TD). Copyright © 2014 Elsevier B.V. All rights reserved.

Segmentation and detection of breast cancer in mammograms combining wavelet analysis and genetic algorithm.

PubMed

Pereira, Danilo Cesar; Ramos, Rodrigo Pereira; do Nascimento, Marcelo Zanchetta

2014-04-01

In Brazil, the National Cancer Institute (INCA) reports more than 50,000 new cases of the disease, with risk of 51 cases per 100,000 women. Radiographic images obtained from mammography equipments are one of the most frequently used techniques for helping in early diagnosis. Due to factors related to cost and professional experience, in the last two decades computer systems to support detection (Computer-Aided Detection - CADe) and diagnosis (Computer-Aided Diagnosis - CADx) have been developed in order to assist experts in detection of abnormalities in their initial stages. Despite the large number of researches on CADe and CADx systems, there is still a need for improved computerized methods. Nowadays, there is a growing concern with the sensitivity and reliability of abnormalities diagnosis in both views of breast mammographic images, namely cranio-caudal (CC) and medio-lateral oblique (MLO). This paper presents a set of computational tools to aid segmentation and detection of mammograms that contained mass or masses in CC and MLO views. An artifact removal algorithm is first implemented followed by an image denoising and gray-level enhancement method based on wavelet transform and Wiener filter. Finally, a method for detection and segmentation of masses using multiple thresholding, wavelet transform and genetic algorithm is employed in mammograms which were randomly selected from the Digital Database for Screening Mammography (DDSM). The developed computer method was quantitatively evaluated using the area overlap metric (AOM). The mean ± standard deviation value of AOM for the proposed method was 79.2 ± 8%. The experiments demonstrate that the proposed method has a strong potential to be used as the basis for mammogram mass segmentation in CC and MLO views. Another important aspect is that the method overcomes the limitation of analyzing only CC and MLO views. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Simultaneous determination of ethyl carbamate and urea in Korean rice wine by ultra-performance liquid chromatography coupled with mass spectrometric detection.

PubMed

Lee, Gyeong-Hweon; Bang, Dae-Young; Lim, Jung-Hoon; Yoon, Seok-Min; Yea, Myeong-Jai; Chi, Young-Min

2017-10-15

In this study, a rapid method for simultaneous detection of ethyl carbamate (EC) and urea in Korean rice wine was developed. To achieve quantitative analysis of EC and urea, the conditions for Ultra-performance liquid chromatography (UPLC) separation and atmospheric-pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) detection were first optimized. Under the established conditions, the detection limit, relative standard deviation and linear range were 2.83μg/L, 3.75-5.96%, and 0.01-10.0mg/L, respectively, for urea; the corresponding values were 0.17μg/L, 1.06-4.01%, and 1.0-50.0μg/L, respectively, for EC. The correlation between the contents of EC and its precursor urea was determined under specific pH (3.5 and 4.5) and temperature (4, 25, and 50°C) conditions using the developed method. As a result, EC content was increased with greater temperature and lower pH. In Korean rice wine, urea was detected 0.19-1.37mg/L and EC was detected 2.0-7.7μg/L. The method developed in this study, which has the advantages of simplified sample preparation, low detection limits, and good selectivity, was successfully applied for the rapid analysis of EC and urea. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of microcantilever array with ordered nanoporous coatings for selective chemical detection

NASA Astrophysics Data System (ADS)

Lee, J.-H.; Houk, R. T. J.; Robinson, A.; Greathouse, J. A.; Thornberg, S. M.; Allendorf, M. D.; Hesketh, P. J.

2010-04-01

In this paper we demonstrate the potential for novel nanoporous framework materials (NFM) such as metal-organic frameworks (MOFs) to provide selectivity and sensitivity to a broad range of analytes including explosives, nerve agents, and volatile organic compounds (VOCs). NFM are highly ordered, crystalline materials with considerable synthetic flexibility resulting from the presence of both organic and inorganic components within their structure. Detection of chemical weapons of mass destruction (CWMD), explosives, toxic industrial chemicals (TICs), and volatile organic compounds (VOCs) using micro-electro-mechanical-systems (MEMS) devices, such as microcantilevers and surface acoustic wave sensors, requires the use of recognition layers to impart selectivity. Traditional organic polymers are dense, impeding analyte uptake and slowing sensor response. The nanoporosity and ultrahigh surface areas of NFM enhance transport into and out of the NFM layer, improving response times, and their ordered structure enables structural tuning to impart selectivity. Here we describe experiments and modeling aimed at creating NFM layers tailored to the detection of water vapor, explosives, CWMD, and VOCs, and their integration with the surfaces of MEMS devices. Force field models show that a high degree of chemical selectivity is feasible. For example, using a suite of MOFs it should be possible to select for explosives vs. CWMD, VM vs. GA (nerve agents), and anthracene vs. naphthalene (VOCs). We will also demonstrate the integration of various NFM with the surfaces of MEMS devices and describe new synthetic methods developed to improve the quality of VFM coatings. Finally, MOF-coated MEMS devices show how temperature changes can be tuned to improve response times, selectivity, and sensitivity.

Structure-performance relationships of phenyl cinnamic acid derivatives as MALDI-MS matrices for sulfatide detection.

PubMed

Tambe, Suparna; Blott, Henning; Fülöp, Annabelle; Spang, Nils; Flottmann, Dirk; Bräse, Stefan; Hopf, Carsten; Junker, Hans-Dieter

2017-02-01

A key aspect for the further development of matrix-assisted laser desorption ionization (MALDI)-mass spectrometry (MS) is a better understanding of the working principles of MALDI matrices. To address this issue, a chemical compound library of 59 structurally related cinnamic acid derivatives was synthesized. Potential MALDI matrices were evaluated with sulfatides, a class of anionic lipids which are abundant in complex brain lipid mixtures. For each matrix relative mean S/N ratios of sulfatides were determined against 9-aminoacridine as a reference matrix using negative ion mass spectrometry with 355 and 337 nm laser systems. The comparison of matrix features with their corresponding relative mean S/N ratios for sulfatide detection identified correlations between matrix substitution patterns, their chemical functionality, and their MALDI-MS performance. Crystal structures of six selected matrices provided structural insight in hydrogen bond interactions in the solid state. Principal component analysis allowed the additional identification of correlation trends between structural and physical matrix properties like number of exchangeable protons at the head group, MW, logP, UV-Vis, and sulfatide detection sensitivity. Graphical abstract Design, synthesis and mass spectrometric evaluation of MALDI-MS matrix compound libraries allows the identification of matrix structure - MALDI-MS performance relationships using multivariate statistics as a tool.

Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

PubMed Central

Rudd, David; Benkendorff, Kirsten; Voelcker, Nicolas H.

2015-01-01

Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS) methods namely nanostructure-assisted laser desorption ionisation (NALDI) and desorption ionisation on porous silicon (DIOS) surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples. PMID:25786067

MALDI-MS SCREENING FOR PSEUDOURIDINE IN MIXTURES OF SMALL RNAS BY CHEMICAL DERIVATIZATION, RNASE DIGESTION AND SIGNATURE PRODUCTS

PubMed Central

Durairaj, Anita; Limbach, Patrick A.

2010-01-01

We have developed a method to screen for pseudouridines in complex mixtures of small RNAs using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS). First, the unfractionated crude mixture of tRNAs is digested to completion with an endoribonuclease, such as RNase T1, and the digestion products are examined using MALDI-MS. Individual RNAs are identified by their signature digestion products, which arise through the detection of unique mass values after nuclease digestion. Next, the endonuclease digest is derivatized using N-cyclohexyl-N’-(2-morpholinoethyl)-carbodiimide metho-p-toluenesulfonate (CMCT), which selectively modifies all pseudouridine, thiouridine and 2-methylthio-6-isopentenyladenosine nucleosides. MALDI-MS determination of the CMCT-derivatized endonuclease digest reveals the presence of pseudouridine through a 252 Da mass increase over the underivatized digest. Proof-of-concept experiments were conducted using a mixture of Escherichia coli transfer RNAs and endoribonucleases T1 and A. More than 80% of the expected pseudouridines from this mixture were detected using this screening approach, even on a unfractionated sample of tRNAs. This approach should be particularly useful in the identification of putative pseudouridine synthases through detection of their target RNAs and can provide insight into specific small RNAs that may contain pseudouridine. PMID:18973194

Headspace analysis of new psychoactive substances using a Selective Reagent Ionisation-Time of Flight-Mass Spectrometer

PubMed Central

Acton, W. Joe; Lanza, Matteo; Agarwal, Bishu; Jürschik, Simone; Sulzer, Philipp; Breiev, Kostiantyn; Jordan, Alfons; Hartungen, Eugen; Hanel, Gernot; Märk, Lukas; Mayhew, Chris A.; Märk, Tilmann D.

2014-01-01

The rapid expansion in the number and use of new psychoactive substances presents a significant analytical challenge because highly sensitive instrumentation capable of detecting a broad range of chemical compounds in real-time with a low rate of false positives is required. A Selective Reagent Ionisation-Time of Flight-Mass Spectrometry (SRI-ToF-MS) instrument is capable of meeting all of these requirements. With its high mass resolution (up to m/Δm of 8000), the application of variations in reduced electric field strength (E/N) and use of different reagent ions, the ambiguity of a nominal (monoisotopic) m/z is reduced and hence the identification of chemicals in a complex chemical environment with a high level of confidence is enabled. In this study we report the use of a SRI-ToF-MS instrument to investigate the reactions of H3O+, O2+, NO+ and Kr+ with 10 readily available (at the time of purchase) new psychoactive substances, namely 4-fluoroamphetamine, methiopropamine, ethcathinone, 4-methylethcathinone, N-ethylbuphedrone, ethylphenidate, 5-MeO-DALT, dimethocaine, 5-(2-aminopropyl)benzofuran and nitracaine. In particular, the dependence of product ion branching ratios on the reduced electric field strength for all reagent ions was investigated and is reported here. The results reported represent a significant amount of new data which will be of use for the development of drug detection techniques suitable for real world scenarios. PMID:25844048

Extract-filter-shoot liquid chromatography with mass spectrometry for the analysis of vitamin D2 in a powdered supplement capsule and standard reference material 3280.

PubMed

Byrdwell, William Craig

2014-08-01

An "extract-filter-shoot" method for the analysis of vitamin D2, ergocalciferol, in a dry powdered dietary supplement capsule containing rice flour excipient and in a National Institute of Standards and Technology standard reference material 3280 is reported. Quantification of vitamin D2 was done by atmospheric pressure chemical ionization mass spectrometry using selected ion monitoring, two transitions of selected reaction monitoring, and extracted ion chromatograms from full scans. UV detection was used for the quantification of Vitamin D2 in the dry powder capsule, whereas interfering species rendered UV detection unreliable for standard reference material 3280. Average values for standard reference material 3280 ranged from 8.27 ± 0.58 to 8.33 ± 0.57 μg/g using internal standard calibration and response factor approaches, compared to the previous National Institute of Standards and Technology internal value for vitamin D2 of 8.78 ± 0.11 μg/g, and the recently updated reference value of 8.6 ± 2.6 μg/g. The powdered supplement capsule was found to contain 28.19 ± 0.35 to 28.67 ± 0.90 μg/capsule for a capsule labeled to contain 25.00 μg. The triacylglycerol composition of the rice flour excipient in the powdered supplement capsule determined by atmospheric pressure chemical ionization mass spectrometry is also reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography

PubMed Central

Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

2012-01-01

Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemical entities are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its 15N4-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC–NCI-MS using selected-ion monitoring outperformed LC–ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5 h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. PMID:22342210

Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography.

PubMed

Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

2012-04-06

Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemicals are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its (15)N(4)-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC-NCI-MS using selected-ion monitoring outperformed LC-ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. Copyright © 2012 Elsevier B.V. All rights reserved.

Enhanced direct ambient analysis by differential mobility-filtered desorption electrospray ionization-mass spectrometry.

PubMed

Galhena, Asiri S; Harris, Glenn A; Kwasnik, Mark; Fernández, Facundo M

2010-11-15

Desorption electrospray ionization (DESI) is rapidly becoming established as one of the most powerful ionization techniques allowing direct surface analysis by mass spectrometry (MS) in the ambient environment. DESI provides a significant number of unique analytical capabilities for a broad range of applications, both quantitative and qualitative in nature including biological tissue imaging, pharmaceutical quality control, in vivo analysis, proteomics, metabolomics, forensics, and explosives detection. Despite its growing adoption as a powerful high throughput analysis tool, DESI-MS analysis at trace levels often suffers from background chemical interferences generated during the electrospray ionization processes. In order to improve sensitivity and selectivity, a differential mobility (DM) ion separation cell was successfully interfaced to a custom-built DESI ion source. This new hybrid platform can be operated in two modes: the "DM-off" mode for standard DESI analysis and "DM-on mode" where DESI-generated ions are detected after discrimination by the differential mobility cell. The performance of the DESI-DM-MS platform was tested with several samples typically amenable to DESI analysis, including counterfeit pharmaceuticals and binary mixtures of isobaric chemicals of importance in the pharmaceutical and food industries. In the DM-on mode, DESI-MS signal-to-noise ratios were improved by 70-190% when compared to the DM-off mode. Also, the addition of the DM cell enabled selective in-source ion activation of specific DESI-generated precursor ions, providing tandem MS-like spectra in a single stage mass spectrometer.

Selective separation of fluorinated compounds from complex organic mixtures by pyrolysis-comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry.

PubMed

Nakajima, Yoji; Arinami, Yuko; Yamamoto, Kiyoshi

2014-12-29

The usefulness of comprehensive two-dimensional gas chromatography (GC×GC) was demonstrated for the selective separation of fluorinated compounds from organic mixtures, such as kerosene/perfluorokerosene mixtures, pyrolysis products derived from polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture and poly[2-(perfluorohexyl)ethyl acrylate]. Perfluorocarbons were completely separated from hydrocarbons in the two-dimensional chromatogram. Fluorohydrocarbons in the pyrolysis products of polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture were selectively isolated from their hydrocarbon counterparts and regularly arranged according to their chain length and fluorine content in the two-dimensional chromatogram. A reliable structural analysis of the fluorohydrocarbons was achieved by combining effective GC×GC positional information with accurate mass spectral data obtained by high-resolution time-of-flight mass spectrometry (HRTOF-MS). 2-(Perfluorohexyl)ethyl acrylate monomer, dimer, and trimer as well as 2-(perfluorohexyl)ethyl alcohol in poly[2-(perfluorohexyl)ethyl acrylate] pyrolysis products were detected in the bottommost part of the two-dimensional chromatogram with separation from hydrocarbons possessing terminal structure information about the polymer, such as α-methylstyrene. Pyrolysis-GC×GC/HRTOF-MS appeared particularly suitable for the characterization of fluorinated polymer microstructures, such as monomer sequences and terminal groups. Copyright © 2014 Elsevier B.V. All rights reserved.

Gas chromatography/mass spectrometry comprehensive analysis of organophosphorus, brominated flame retardants, by-products and formulation intermediates in water.

PubMed

Cristale, Joyce; Quintana, Jordi; Chaler, Roser; Ventura, Francesc; Lacorte, Silvia

2012-06-08

A multiresidue method based on gas chromatography coupled to quadrupole mass spectrometry was developed to determine organophosphorus flame retardants, polybromodiphenyl ethers (BDEs 28, 47, 99, 100, 153, 154, 183 and 209), new brominated flame retardants, bromophenols, bromoanilines, bromotoluenes and bromoanisoles in water. Two ionization techniques (electron ionization--EI, and electron capture negative ionization--ECNI) and two acquisition modes (selected ion monitoring--SIM, and selected reaction monitoring--SRM) were compared as regards to mass spectral characterization, sensitivity and quantification capabilities. The highest sensitivity, at expenses of identification capacity, was obtained by GC-ECNI-MS/SIM for most of the compounds analyzed, mainly for PBDEs and decabromodiphenyl ethane while GC-EI-MS/MS in SRM was the most selective technique and permitted the identification of target compounds at the pg level, and identification capabilities increased when real samples were analyzed. This method was further used to evaluate the presence and behavior of flame retardants within a drinking water treatment facility. Organophosphorus flame retardants were the only compounds detected in influent waters at levels of 0.32-0.03 μg L⁻¹, and their elimination throughout the different treatment stages was evaluated. Copyright © 2012 Elsevier B.V. All rights reserved.

Full evaporation dynamic headspace in combination with selectable one-dimensional/two-dimensional gas chromatography-mass spectrometry for the determination of suspected fragrance allergens in cosmetic products.

PubMed

Devos, Christophe; Ochiai, Nobuo; Sasamoto, Kikuo; Sandra, Pat; David, Frank

2012-09-14

Suspected fragrance allergens were determined in cosmetic products using a combination of full evaporation-dynamic headspace (FEDHS) with selectable one-dimensional/two-dimensional GC-MS. The full evaporation dynamic headspace approach allows the non-discriminating extraction and injection of both apolar and polar fragrance compounds, without contamination of the analytical system by high molecular weight non-volatile matrix compounds. The method can be applied to all classes of cosmetic samples, including water containing matrices such as shower gels or body creams. In combination with selectable (1)D/(2)D GC-MS, consisting of a dedicated heart-cutting GC-MS configuration using capillary flow technology (CFT) and low thermal mass GC (LTM-GC), a highly flexible and easy-to-use analytical solution is offered. Depending on the complexity of the perfume fraction, analyses can be performed in one-dimensional GC-MS mode or in heart-cutting two-dimensional GC-MS mode, without the need of hardware reconfiguration. The two-dimensional mode with independent temperature control of the first and second dimension column is especially useful to confirm the presence of detected allergen compounds when mass spectral deconvolution is not possible. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of cocaine and metabolites in hair by column-switching LC-MS-MS analysis.

PubMed

Alves, Marcela Nogueira Rabelo; Zanchetti, Gabriele; Piccinotti, Alberto; Tameni, Silvia; De Martinis, Bruno Spinosa; Polettini, Aldo

2013-07-01

A method for rapid, selective, and robust determination of cocaine (CO) and metabolites in 5-mg hair samples was developed and fully validated using a column-switching liquid chromatography-tandem mass spectrometry system (LC-MS-MS). Hair samples were decontaminated, segmented, incubated overnight in diluted HCl, and centrifuged, and the diluted (1:10 with distilled water) extracts were analyzed in positive ionization mode monitoring two reactions per analyte. Quantifier transitions were: m/z 304.2→182.2 for CO, m/z 290.1→168.1 for benzoylecgonine (BE), and m/z 318.2→196.2 for cocaethylene (CE). The lower limit of quantification (LLOQ) was set at 0.05 ng/mg for CO and CE, and 0.012 ng/mg for BE. Imprecision and inaccuracy at LLOQ were lower than 20 % for all analytes. Linearity ranged between 0.05 and 50.0 ng/mg for CO and CE and 0.012 and 12.50 ng/mg for BE. Selectivity, matrix effect, process efficiency, recovery, carryover, cross talk, and autosampler stability were also evaluated during validation. Eighteen real hair samples and five samples from a commercial proficiency testing program were comparatively examined with the proposed multidimensional chromatography coupled with tandem mass spectrometry procedure and our reference gas chromatography coupled to mass spectrometry (GC-MS) method. Compared with our reference GC-MS method, column-switching technique and the high sensitivity of the tandem mass spectrometry detection system allowed to significantly reduce sample amount (×10) with increased sensitivity (×2) and sample throughput (×4), to simplify sample preparation, and to avoid that interfering compounds and ions impaired the ionization and detection of the analytes and deteriorate the performance of the ion source.

Wipe selection for the analysis of surface materials containing chemical warfare agent nitrogen mustard degradation products by ultra-high pressure liquid chromatography-tandem mass spectrometry.

PubMed

Willison, Stuart A

2012-12-28

Degradation products arising from nitrogen mustard chemical warfare agent were deposited on common urban surfaces and determined via surface wiping, wipe extraction, and liquid chromatography–tandem mass spectrometry detection. Wipes investigated included cotton gauze, glass fiber filter, non-woven polyester fiber and filter paper, and surfaces included several porous (vinyl tile, painted drywall, wood) and mostly non-porous (laminate, galvanized steel, glass) surfaces. Wipe extracts were analyzed by ultra-high pressure liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) and compared with high performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) results. An evaluation of both techniques suggests UPLC–MS/MS provides a quick and sensitive analysis of targeted degradation products in addition to being nearly four times faster than a single HPLC run, allowing for greater throughput during a wide-spread release concerning large-scale contamination and subsequent remediation events. Based on the overall performance of all tested wipes, filter paper wipes were selected over other wipes because they did not contain interferences or native species (TEA and DEA) associated with the target analytes, resulting in high percent recoveries and low background levels during sample analysis. Other wipes, including cotton gauze, would require a pre-cleaning step due to the presence of large quantities of native species or interferences of the targeted analytes. Percent recoveries obtained from a laminate surface were 47–99% for all nitrogen mustard degradation products. The resulting detection limits achieved from wipes were 0.2 ng/cm(2) for triethanolamine (TEA), 0.03 ng/cm(2) for N-ethyldiethanolamine (EDEA), 0.1 ng/cm(2) for N-methyldiethanolamine (MDEA), and 0.1 ng/cm(2) for diethanolamine (DEA).

Computational analyses of spectral trees from electrospray multi-stage mass spectrometry to aid metabolite identification.

PubMed

Cao, Mingshu; Fraser, Karl; Rasmussen, Susanne

2013-10-31

Mass spectrometry coupled with chromatography has become the major technical platform in metabolomics. Aided by peak detection algorithms, the detected signals are characterized by mass-over-charge ratio (m/z) and retention time. Chemical identities often remain elusive for the majority of the signals. Multi-stage mass spectrometry based on electrospray ionization (ESI) allows collision-induced dissociation (CID) fragmentation of selected precursor ions. These fragment ions can assist in structural inference for metabolites of low molecular weight. Computational investigations of fragmentation spectra have increasingly received attention in metabolomics and various public databases house such data. We have developed an R package "iontree" that can capture, store and analyze MS2 and MS3 mass spectral data from high throughput metabolomics experiments. The package includes functions for ion tree construction, an algorithm (distMS2) for MS2 spectral comparison, and tools for building platform-independent ion tree (MS2/MS3) libraries. We have demonstrated the utilization of the package for the systematic analysis and annotation of fragmentation spectra collected in various metabolomics platforms, including direct infusion mass spectrometry, and liquid chromatography coupled with either low resolution or high resolution mass spectrometry. Assisted by the developed computational tools, we have demonstrated that spectral trees can provide informative evidence complementary to retention time and accurate mass to aid with annotating unknown peaks. These experimental spectral trees once subjected to a quality control process, can be used for querying public MS2 databases or de novo interpretation. The putatively annotated spectral trees can be readily incorporated into reference libraries for routine identification of metabolites.

Sensitive liquid chromatography-tandem mass spectrometry method for the simultaneous determination of paracetamol and guaifenesin in human plasma.

PubMed

Chen, Xiaoyan; Huang, Jia; Kong, Zhang; Zhong, Dafang

2005-03-25

A rapid and sensitive method for the simultaneous determination of paracetamol and guaifenesin in human plasma was developed and validated, using high-performance liquid chromatographic separation with tandem mass spectrometric detection. After extracted from plasma samples by diethyl ether-dichloromethane (3:2, v/v), the analytes and internal standard osalmide were chromatographed on a C18 column. Detection was performed on a triple quadrupole tandem mass spectrometer by selected reaction monitoring (SRM) mode via atmospheric pressure chemical ionization (APCI). The method was linear in the concentration range of 0.05-20.0 microg/ml for paracetamol and 5.0-2000.0 ng/ml for guaifenesin. The intra- and inter-day precision was within 14% for both paracetamol and guaifenesin. The assay accuracy was within +/-2.4% for the analytes. This is the first assay method described for the simultaneous determination of paracetamol and guaifenesin in plasma using one chromatographic run. The method was successfully employed in a pharmacokinetic study after an oral administration of a multicomponent formulation, containing 650 mg paracetamol, 200 mg guaifenesin, 60 mg pseudoephedrine and 20 mg dextrorphan.

Structural elucidation of new urinary tamoxifen metabolites by liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Lu, Jianghai; He, Chunji; He, Genye; Wang, Xiaobing; Xu, Youxuan; Wu, Yun; Dong, Ying; Ouyang, Gangfeng

2014-07-01

In this study, tamoxifen metabolic profiles were investigated carefully. Tamoxifen was administered to two healthy male volunteers and one female patient suffering from breast cancer. Urinary extracts were analyzed by liquid chromatography quadruple time-of-flight mass spectrometry using full scan and targeted MS/MS techniques with accurate mass measurement. Chromatographic peaks for potential metabolites were selected by using the theoretical [M + H](+) as precursor ion in full-scan experiment and m/z 72, 58 or 44 as characteristic product ions for N,N-dimethyl, N-desmethyl and N,N-didesmethyl metabolites in targeted MS/MS experiment, respectively. Tamoxifen and 37 metabolites were detected in extraction study samples. Chemical structures of seven unreported metabolites were elucidated particularly on the basis of fragmentation patterns observed for these metabolites. Several metabolic pathways containing mono- and di-hydroxylation, methoxylation, N-desmethylation, N,N-didesmethylation, oxidation and combinations were suggested. All the metabolites were detected in the urine samples up to 1 week. Copyright © 2014 John Wiley & Sons, Ltd.

Laser mass spectrometry with circularly polarized light: circular dichroism of cold molecules in a supersonic gas beam.

PubMed

Titze, Katharina; Zollitsch, Tilo; Heiz, Ulrich; Boesl, Ulrich

2014-09-15

An experiment on chiral molecules that combines circular dichroism (CD) spectroscopy, mass-selective detection by laser mass spectrometry (MS), and cooling of molecules by using a supersonic beam is presented. The combination of the former two techniques (CD-laser-MS) is a new method to investigate chiral molecules and is now used by several research groups. Cooling in a supersonic beam supplies a substantial increase in spectroscopic resolution, a feature that has not yet been used in CD spectroscopy. In the experiments reported herein, a large variation in the electronic CD of carbonyl 3-methylcyclopentanone was observed depending on the excited vibrational modes in the n → π* transition. This finding should be of interest for the detection of chiral molecules and for the theoretical understanding of the CD of vibronic bands. It is expected that this effect will show up in other chiral carbonyls because the n → π* transition is typical for the carbonyl group. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new method for differentiating adducts of common drinking water DBPs from higher molecular weight DBPs in electrospray ionization-mass spectrometry analysis.

PubMed

Zhai, Hongyan; Zhang, Xiangru

2009-05-01

With the presence of bromide in source waters, numerous brominated disinfection byproducts (DBPs) are formed during chlorination. Many of them are polar/highly polar DBPs and thus hard to be detected by gas chromatography mass spectrometry. Electrospray ionization triple quadrupole mass spectrometry (ESI-MS/MS) is reported to be an effective method in finding polar brominated DBPs by setting precursor ion scans of m/z 79 and 81. But as a soft ionization technique, ESI could form adducts of common DBPs, which may complicate ESI-MS/MS spectra and hinder the efforts in finding new brominated DBPs. In this paper, a new method was developed for differentiating adducts of common DBPs from higher molecular weight DBPs. This method was based on the ESI-MS/MS precursor ion scans of the fragments that correspond to the molecular ions of common DBPs. Adducts of common DBPs were selectively detected in the ESI-MS/MS spectra of a simulated drinking water sample. Moreover, the structures of several new brominated DBPs in the sample were tentatively proposed.

Determination of cocaine, benzoylecgonine and cocaethylene in human hair by solid-phase microextraction and gas chromatography-mass spectrometry.

PubMed

de Toledo, Fernanda Crossi Pereira; Yonamine, Mauricio; de Moraes Moreau, Regina Lucia; Silva, Ovandir Alves

2003-12-25

The present work describes a highly precise and sensitive method developed to detect cocaine (COC), benzoylecgonine (BE, its main metabolite) and cocaethylene (CE, transesterification product of the coingestion of COC with ethanol) in human head hair samples. The method was based on an alkylchloroformate derivatization of benzoylecgonine and the extraction of the analytes by solid-phase microextraction (SPME). Gas chromatography-mass spectrometry (GC-MS) was used to identify and quantify the analytes in selected ion monitoring mode (SIM). The limits of quantification and detection (LOQ and LOD) were: 0.1 ng/mg for COC and CE, and 0.5 ng/mg for BE. Good inter- and intra-assay precision was observed. The dynamic range of the assay was 0.1-50 ng/mg. The method is not time consuming and was shown to be easy to perform.

Pilot Metabolome-Wide Association Study of Benzo(a)pyrene in Serum from Military Personnel

PubMed Central

Walker, Douglas I.; Pennell, Kurt D.; Uppal, Karan; Xia, Xiaoyan; Hopke, Philip K.; Utell, Mark J.; Phipps, Richard P.; Sime, Patricia J.; Rohrbeck, Patricia; Mallon, COL Timothy M.; Jones, Dean P.

2016-01-01

Objective A pilot study was conducted to test the feasibility of using Department of Defense Serum Repository (DoDSR) samples to study health and exposure-related effects. Methods Thirty unidentified human serum samples were obtained from the DoDSR and analyzed for normal serum metabolites with high-resolution mass spectrometry and serum levels of free benzo(a)pyrene (BaP) by gas chromatography-mass spectrometry. Metabolic associations with BaP were determined using a metabolome wide association study (MWAS) and metabolic pathway enrichment. Results The serum analysis detected normal ranges of glucose, selected amino acids, fatty acids, and creatinine. Free BaP was detected in a broad concentration range. MWAS of BaP showed associations with lipids, fatty acids, and sulfur amino acid metabolic pathways. Conclusion The results show the DoDSR samples are of sufficient quality for chemical profiling of DoD personnel. PMID:27501104

Pilot Metabolome-Wide Association Study of Benzo(a)pyrene in Serum From Military Personnel.

PubMed

Walker, Douglas I; Pennell, Kurt D; Uppal, Karan; Xia, Xiaoyan; Hopke, Philip K; Utell, Mark J; Phipps, Richard P; Sime, Patricia J; Rohrbeck, Patricia; Mallon, Col Timothy M; Jones, Dean P

2016-08-01

A pilot study was conducted to test the feasibility of using Department of Defense Serum Repository (DoDSR) samples to study health and exposure-related effects. Thirty unidentified human serum samples were obtained from the DoDSR and analyzed for normal serum metabolites with high-resolution mass spectrometry and serum levels of free benzo(a)pyrene (BaP) by gas chromatography-mass spectrometry. Metabolic associations with BaP were determined using a metabolome-wide association study (MWAS) and metabolic pathway enrichment. The serum analysis detected normal ranges of glucose, selected amino acids, fatty acids, and creatinine. Free BaP was detected in a broad concentration range. MWAS of BaP showed associations with lipids, fatty acids, and sulfur amino acid metabolic pathways. The results show that the DoDSR samples are of sufficient quality for chemical profiling of DoD personnel.

High Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) for Mass Spectrometry-Based Proteomics

PubMed Central

Swearingen, Kristian E.; Moritz, Robert L.

2013-01-01

SUMMARY High field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, we review recent developments in LC-FAIMS-MS and its application to MS-based proteomics. PMID:23194268

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

Zhang, Xing; Ibrahim, Yehia M.; Chen, Tsung-Chi

We report the first evaluation of a platform coupling a high speed field asymmetric ion mobility spectrometry microchip (µFAIMS) with drift tube ion mobility and mass spectrometry (IMS-MS). The µFAIMS/IMS-MS platform was used to analyze biological samples and simultaneously acquire multidimensional information of detected features from the measured FAIMS compensation fields and IMS drift times, while also obtaining accurate ion masses. These separations thereby increase the overall separation power, resulting increased information content, and provide more complete characterization of more complex samples. The separation conditions were optimized for sensitivity and resolving power by the selection of gas compositions and pressuresmore » in the FAIMS and IMS separation stages. The resulting performance provided three dimensional separations, benefitting both broad complex mixture studies and targeted analyses by e.g. improving isomeric separations and allowing detection of species obscured by “chemical noise” and other interfering peaks.« less

High-performance liquid chromatography/electrospray mass spectrometry for the analysis of modified bases in DNA: 7-(2-hydroxyethyl)guanine, the major ethylene oxide-DNA adduct.

PubMed

Leclercq, L; Laurent, C; De Pauw, E

1997-05-15

A method was developed for the analysis of 7-(2-hydroxyethyl)guanine (7HEG), the major DNA adduct formed after exposure to ethylene oxide (EO). The method is based on DNA neutral thermal hydrolysis, adduct micro-concentration, and final characterization and quantification by HPLC coupled to single-ion monitoring electrospray mass spectrometry (HPLC/SIR-ESMS). The method was found to be selective, sensitive, and easy to handle with no need for enzymatic digestion or previous sample derivatization. Detection limit was found to be close to 1 fmol of adduct injected (10(-10) M), thus allowing the detection of approximately three modified bases on 10(8) intact nucleotides in blood sample analysis. Quantification results are shown for 7HEG after calf thymus DNA and blood exposure to various doses of EO, in both cases obtaining clear dose-response relationships.

Sulfur analysis by inductively coupled plasma-mass spectrometry: A review

NASA Astrophysics Data System (ADS)

Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J. M.; García Alonso, J. I.

2015-06-01

In recent years the number of applications of sulfur (S) analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. In this article we describe in some depth the application of ICP-MS for S analysis with emphasis placed on the sulfur-specific detection by hyphenated techniques such as LC, GC, CE and LA coupled on-line to ICP-MS. The different approaches available for sulfur isotope ratio measurements by ICP-MS are also detailed. Particular attention has been paid to the quantification of peptides/proteins and the analysis of metallopeptides/metalloproteins via sulfur by LC-ICP-MS. Likewise, the speciation analysis of metal-based pharmaceuticals and metallodrugs and non-metal selective detection of pharmaceuticals via S are highlighted. Labeling procedures for metabolic applications are also included. Finally, the measurement of natural variations in S isotope composition with multicollector ICP-MS instruments is also covered in this review.

Analysis and design of a capsule landing system and surface vehicle control system for Mars exporation

NASA Technical Reports Server (NTRS)

Frederick, D. K.; Lashmet, P. K.; Sandor, G. N.; Shen, C. N.; Smith, E. J.; Yerazunis, S. W.

1972-01-01

The problems related to the design and control of a mobile planetary vehicle to implement a systematic plan for the exploration of Mars were investigated. Problem areas receiving attention include: vehicle configuration, control, dynamics, systems and propulsion; systems analysis; navigation, terrain modeling and path selection; and chemical analysis of specimens. The following specific tasks were studied: vehicle model design, mathematical modeling of dynamic vehicle, experimental vehicle dynamics, obstacle negotiation, electromechanical controls, collapsibility and deployment, construction of a wheel tester, wheel analysis, payload design, system design optimization, effect of design assumptions, accessory optimal design, on-board computer subsystem, laser range measurement, discrete obstacle detection, obstacle detection systems, terrain modeling, path selection system simulation and evaluation, gas chromatograph/mass spectrometer system concepts, chromatograph model evaluation and improvement and transport parameter evaluation.

Analysis and design of a capsule landing system and surface vehicle control system for Mars exploration

NASA Technical Reports Server (NTRS)

Frederick, D. K.; Lashmet, P. K.; Sandor, G. N.; Shen, C. N.; Smith, E. J.; Yerazunis, S. W.

1972-01-01

Investigation of problems related to the design and control of a mobile planetary vehicle to implement a systematic plan for the exploration of Mars has been undertaken. Problem areas receiving attention include: vehicle configuration, control, dynamics, systems and propulsion; systems analysis; terrain modeling and path selection; and chemical analysis of specimens. The following specific tasks have been under study: vehicle model design, mathematical modeling of a dynamic vehicle, experimental vehicle dynamics, obstacle negotiation, electromechanical controls, collapsibility and deployment, construction of a wheel tester, wheel analysis, payload design, system design optimization, effect of design assumptions, accessory optimal design, on-board computer sybsystem, laser range measurement, discrete obstacle detection, obstacle detection systems, terrain modeling, path selection system simulation and evaluation, gas chromatograph/mass spectrometer system concepts, chromatograph model evaluation and improvement.

Validated multiclass targeted determination of antibiotics in fish with high performance liquid chromatography-benchtop quadrupole orbitrap hybrid mass spectrometry.

PubMed

Chiesa, Luca; Panseri, Sara; Pasquale, Elisa; Malandra, Renato; Pavlovic, Radmila; Arioli, Francesco

2018-08-30

High performance liquid chromatography, coupled with a benchtop Q-Exactive Orbitrap high-resolution mass spectrometer, was successfully applied for the determination of 24 target antibiotics (selected beta-lactams, tetracyclines, fluoroquinolones, sulfonamids, phenicols, macrolides, cephalosporins, lincosamides, diaminopyrimidine) in fish matrices. The Q-Exactive parameters were carefully studied to accomplish the best compromise between a suitable scan speed and selectivity, considering the restrictions associated with generic sample preparation methodology. Retention time, an exact mass with tolerance of 2 ppm and data-dependent MS 2 spectra were the main identifiers. The method was validated through specificity, linearity, recovery, intra- and inter-day repeatability, decision limit (CCα) and detection capability (CCβ), according to 2002/657/EC. The values of CCα and CCβ ranged from 29.2 to 36.8 and 32.5 to 48.9, respectively, while overall recovery ranged from 91.1 to 105.6%. Fifty fish samples were analysed, showing the sporadic incidence of enrofloxacin, chlortetracycline, oxytetracycline, amoxicillin and trimethoprim, albeit below the maximum residual levels. Copyright © 2018 Elsevier Ltd. All rights reserved.

Imaging charge transfer in a cation-π system: velocity-map imaging of Ag(+)(benzene) photodissociation.

PubMed

Maner, Jonathon A; Mauney, Daniel T; Duncan, Michael A

2015-11-19

Ag(+)(benzene) complexes are generated in the gas phase by laser vaporization and mass selected in a time-of-flight spectrometer. UV laser excitation at either 355 or 266 nm results in dissociative charge transfer (DCT), leading to neutral silver atom and benzene cation products. Kinetic energy release in translationally hot benzene cations is detected using a new instrument designed for photofragment imaging of mass-selected ions. Velocity-map imaging and slice imaging techniques are employed. In addition to the expected translational energy release, DCT of Ag(+)(benzene) produces a distribution of internally hot benzene cations. Compared with experiments at 355 nm, 266 nm excitation produces only slightly higher translational excitation and a much greater fraction of internally hot benzene ions. The maximum kinetic energy release in the photodissociation sets an upper limit on the Ag(+)(benzene) dissociation energy of 32.8 (+1.4/-1.5) kcal/mol.

Status and outlook of CHIP-TRAP: The Central Michigan University high precision Penning trap

NASA Astrophysics Data System (ADS)

Redshaw, M.; Bryce, R. A.; Hawks, P.; Gamage, N. D.; Hunt, C.; Kandegedara, R. M. E. B.; Ratnayake, I. S.; Sharp, L.

2016-06-01

At Central Michigan University we are developing a high-precision Penning trap mass spectrometer (CHIP-TRAP) that will focus on measurements with long-lived radioactive isotopes. CHIP-TRAP will consist of a pair of hyperbolic precision-measurement Penning traps, and a cylindrical capture/filter trap in a 12 T magnetic field. Ions will be produced by external ion sources, including a laser ablation source, and transported to the capture trap at low energies enabling ions of a given m / q ratio to be selected via their time-of-flight. In the capture trap, contaminant ions will be removed with a mass-selective rf dipole excitation and the ion of interest will be transported to the measurement traps. A phase-sensitive image charge detection technique will be used for simultaneous cyclotron frequency measurements on single ions in the two precision traps, resulting in a reduction in statistical uncertainty due to magnetic field fluctuations.

Determination of active components of Ginkgo biloba in human urine by capillary high-performance liquid chromatography/mass spectrometry with on-line column-switching purification.

PubMed

Ding, Shujing; Dudley, Ed; Chen, Lijuan; Plummer, Sue; Tang, Jiandong; Newton, Russell P; Brenton, A Gareth

2006-01-01

Ginkgo biloba is one of the most popular herbal nutritional supplements, with terpene lactones and flavonoids being the two major active components. An on-line purification high-performance liquid chromatography/mass spectrometry (HPLC/MS) method was successfully developed for the quantitative determination of flavonoids and terpene lactones excreted in human urine after ingesting the herbal supplement. Satisfactory separation was obtained using a C18 capillary column made in-house with sample clean-up and pre-concentration achieved using a C18 pre-column with column switching. High selectivity and limits of detection of 1-18 ng/mL were achieved using a selected ion monitoring (SIM) scan in negative ion mode; the on-line solid-phase extraction (SPE) recovery of the active components in Ginkgo biloba determined in this study was greater than 75%. Copyright 2006 John Wiley & Sons, Ltd.

RZ Leonis Minoris bridging between ER Ursae Majoris-type dwarf nova and nova-like system

NASA Astrophysics Data System (ADS)

Kato, Taichi; Ishioka, Ryoko; Isogai, Keisuke; Kimura, Mariko; Imada, Akira; Miller, Ian; Masumoto, Kazunari; Nishino, Hirochika; Kojiguchi, Naoto; Kawabata, Miho; Sakai, Daisuke; Sugiura, Yuki; Furukawa, Hisami; Yamamura, Kenta; Kobayashi, Hiroshi; Matsumoto, Katsura; Wang, Shiang-Yu; Chou, Yi; Ngeow, Chow-Choong; Chen, Wen-Ping; Panwar, Neelam; Lin, Chi-Sheng; Hsiao, Hsiang-Yao; Guo, Jhen-Kuei; Lin, Chien-Cheng; Omarov, Chingis; Kusakin, Anatoly; Krugov, Maxim; Starkey, Donn R.; Pavlenko, Elena P.; Antonyuk, Kirill A.; Sosnjvskij, Aleksei A.; Antonyuk, Oksana I.; Pit, Nikolai V.; Baklanov, Alex V.; Babina, Julia V.; Itoh, Hiroshi; Padovan, Stefano; Akazawa, Hidehiko; Kafka, Stella; de Miguel, Enrique; Pickard, Roger D.; Kiyota, Seiichiro; Shugarov, Sergey Yu.; Chochol, Drahomir; Krushevska, Viktoriia; Sekeráš, Matej; Pikalova, Olga; Sabo, Richard; Dubovsky, Pavol A.; Kudzej, Igor; Ulowetz, Joseph; Dvorak, Shawn; Stone, Geoff; Tordai, Tamás; Dubois, Franky; Logie, Ludwig; Rau, Steve; Vanaverbeke, Siegfried; Vanmunster, Tonny; Oksanen, Arto; Maeda, Yutaka; Kasai, Kiyoshi; Katysheva, Natalia; Morelle, Etienne; Neustroev, Vitaly V.; Sjoberg, George

2016-12-01

We observed RZ LMi, which is renowned for its extremely short (˜19 d) supercycle and is a member of a small, unusual class of cataclysmic variables called ER UMa-type dwarf novae, in 2013 and 2016. In 2016, the supercycles of this object substantially lengthened in comparison to the previous measurements to 35, 32, and 60 d for three consecutive superoutbursts. We consider that the object virtually experienced a transition to the nova-like state (permanent superhumper). This observed behavior reproduced the prediction of the thermal-tidal instability model extremely well. We detected a precursor in the 2016 superoutburst and detected growing (stage A) superhumps with a mean period of 0.0602(1) d in 2016 and in 2013. Combined with the period of superhumps immediately after the superoutburst, the mass ratio is not as small as in WZ Sge-type dwarf novae, having orbital periods similar to RZ LMi. By using least absolute shrinkage and selection operator (Lasso) two-dimensional power spectra, we detected possible negative superhumps with a period of 0.05710(1) d. We estimated an orbital period of 0.05792 d, which suggests a mass ratio of 0.105(5). This relatively large mass ratio is even above that of ordinary SU UMa-type dwarf novae, and it is also possible that the exceptionally high mass-transfer rate in RZ LMi may be a result of a stripped secondary with an evolved core in a system evolving toward an AM CVn-type object.

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

Lieman-Sifry, Jesse; Hughes, A. Meredith; Flaherty, Kevin M.

We present a CO(2-1) and 1240 μ m continuum survey of 23 debris disks with spectral types B9-G1, observed at an angular resolution of 0.″5–1″ with the Atacama Large Millimeter/Submillimeter Array (ALMA). The sample was selected for large infrared excess and age ∼10 Myr, to characterize the prevalence of molecular gas emission in young debris disks. We identify three CO-rich debris disks, plus two additional tentative (3 σ) CO detections. Twenty disks were detected in the continuum at the >3 σ level. For the 12 disks in the sample that are spatially resolved by our observations, we perform an independentmore » analysis of the interferometric continuum visibilities to constrain the basic dust disk geometry, as well as a simultaneous analysis of the visibilities and broadband spectral energy distribution to constrain the characteristic grain size and disk mass. The gas-rich debris disks exhibit preferentially larger outer radii in their dust disks, and a higher prevalence of characteristic grain sizes smaller than the blowout size. The gas-rich disks do not exhibit preferentially larger dust masses, contrary to expectations for a scenario in which a higher cometary destruction rate would be expected to result in a larger mass of both CO and dust. The three debris disks in our sample with strong CO detections are all around A stars: the conditions in disks around intermediate-mass stars appear to be the most conducive to the survival or formation of CO.« less

Overcoming interference with the detection of a stable isotopically labeled microtracer in the evaluation of beclabuvir absolute bioavailability using a concomitant microtracer approach.

PubMed

Jiang, Hao; Titsch, Craig; Zeng, Jianing; Jones, Barry; Joyce, Philip; Gandhi, Yash; Turley, Wesley; Burrell, Richard; Aubry, Anne F; Arnold, Mark E

2017-09-05

The oral absolute bioavailability of beclabuvir in healthy subjects was determined using a microdose (100μg) of the stable isotopically labeled tracer via intravenous (IV) infusion started after oral dosing of beclabuvir (150mg). To simultaneously analyze the concentrations of the IV microtracer ([ 13 C 6 ]beclabuvir) and beclabuvir in plasma samples, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method was initially developed. Surprisingly beclabuvir significantly interfered with the IV microtracer detection when using the selected reaction monitoring (SRM) in the assay. An interfering component from the drug substance was observed using a high resolution mass spectrometer (HRMS). The mass-to-charge (m/z) of the interfering component was -32ppm different from the nominal value for the IV microtracer and thus could not be differentiated in the SRM assay by the unit mass resolution. To overcome this interference, we evaluated two approaches by either monitoring an alternative product ion using the SRM assay or isolating the interfering component using the parallel reaction monitoring (PRM) assay on the HRMS. This case study has demonstrated two practical approaches for overcoming interferences with the detection of stable isotopically labeled IV microtracers in the evaluation of absolute bioavailability, which provides users the flexibility in using either LC-MS/MS or HRMS to mitigate unpredicted interferences in the assay to support microtracer absolute bioavailability studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Hog Charm II tetracycline test screening results compared with a liquid chromatography tandem mass spectrometry 10-μg/kg method.

PubMed

Salter, Robert; Holmes, Steven; Legg, David; Coble, Joel; George, Bruce

2012-02-01

Pork tissue samples that tested positive and negative by the Charm II tetracycline test screening method in the slaughter plant laboratory were tested with the modified AOAC International liquid chromatography tandem mass spectrometry (LC-MS-MS) method 995.09 to determine the predictive value of the screening method at detecting total tetracyclines at 10 μg/kg of tissue, in compliance with Russian import regulations. There were 218 presumptive-positive tetracycline samples of 4,195 randomly tested hogs. Of these screening test positive samples, 83% (182) were positive, >10 μg/kg by LC-MS-MS; 12.8% (28) were false violative, greater than limit of detection (LOD) but <10 μg/kg; and 4.2% (8) were not detected at the LC-MS-MS LOD. The 36 false-violative and not-detected samples represent 1% of the total samples screened. Twenty-seven of 30 randomly selected tetracycline screening negative samples tested below the LC-MS-MS LOD, and 3 samples tested <3 μg/kg chlortetracycline. Results indicate that the Charm II tetracycline test is effective at predicting hogs containing >10 μg/kg total tetracyclines in compliance with Russian import regulations.

Quantitative determination of antidepressants and their select degradates by liquid chromatography/electrospray ionization tandem mass spectrometry in biosolids destined for land application.

PubMed

Niemi, Lydia M; Stencel, Katherine A; Murphy, Madigan J; Schultz, Melissa M

2013-08-06

Antidepressants are one of the most widely dispensed classes of pharmaceuticals in the United States. As wastewater treatment plants are a primary source of pharmaceuticals in the environment, the use of biosolids as fertilizer is a potential route for antidepressants to enter the terrestrial environment. A microsolvent extraction method, utilizing green chemistry, was developed for extraction of the target antidepressants and degradation products from biosolids, or more specifically lagoon biosolids. Liquid chromatography/tandem mass spectrometry was used for quantitative determination of antidepressants in the lagoon biosolid extracts. Recoveries from matrix spiking experiments for the individual antidepressants had an average of 96%. The limits of detection for antidepressant pharmaceuticals and degradates ranged from 0.36 to 8.0 ng/kg wet weight. The method was applied to biosolids destined for land application. A suite of antidepressants was consistently detected in the lagoon biosolid samples, and thus antidepressants are being introduced to terrestrial environments through the land application of these biosolids. Sertraline and norsertraline were the most abundant antidepressant and degradation product detected in the biosolid samples. Detected, individual antidepressant concentrations ranged from 8.5 ng/kg (norfluoxetine) to 420 ng/kg wet weight (norsertraline).

Gaining knowledge from previously unexplained spectra-application of the PTM-Explorer software to detect PTM in HUPO BPP MS/MS data.

PubMed

Chamrad, Daniel C; Körting, Gerhard; Schäfer, Heike; Stephan, Christian; Thiele, Herbert; Apweiler, Rolf; Meyer, Helmut E; Marcus, Katrin; Blüggel, Martin

2006-09-01

A novel software tool named PTM-Explorer has been applied to LC-MS/MS datasets acquired within the Human Proteome Organisation (HUPO) Brain Proteome Project (BPP). PTM-Explorer enables automatic identification of peptide MS/MS spectra that were not explained in typical sequence database searches. The main focus was detection of PTMs, but PTM-Explorer detects also unspecific peptide cleavage, mass measurement errors, experimental modifications, amino acid substitutions, transpeptidation products and unknown mass shifts. To avoid a combinatorial problem the search is restricted to a set of selected protein sequences, which stem from previous protein identifications using a common sequence database search. Prior to application to the HUPO BPP data, PTM-Explorer was evaluated on excellently manually characterized and evaluated LC-MS/MS data sets from Alpha-A-Crystallin gel spots obtained from mouse eye lens. Besides various PTMs including phosphorylation, a wealth of experimental modifications and unspecific cleavage products were successfully detected, completing the primary structure information of the measured proteins. Our results indicate that a large amount of MS/MS spectra that currently remain unidentified in standard database searches contain valuable information that can only be elucidated using suitable software tools.

Lunar Prospector: a Preliminary Surface Remote Sensing Resource Assessment for the Moon

NASA Technical Reports Server (NTRS)

Mardon, A. A.

1992-01-01

The potential existence of lunar volatiles is a scientific discovery that could distinctly change the direction of pathways of inner solar system human expansion. With a dedicated germanium gamma ray spectrometer launched in the early 1990's, surface water concentrations of 0.7 percent could be detected immediately upon full lunar polar orbit operations. The expense of lunar base construction and operation would be dramatically reduced over a scenario with no lunar volatile resources. Global surface mineral distribution could be mapped out and integrated into a GIS database for lunar base site selection. Extensive surface lunar mapping would also result in the utilization of archived Apollo images. A variety of remote sensing systems and their parameters have been proposed for use in the detection of these lunar ice masses. The detection or nondetection of subsurface and surface ice masses in lunar polar crater floors could dramatically direct the development pathways that the human race might follow in its radiation from the Earth to habitable locales in the inner terran solar system. Potential sources of lunar volatiles are described. The use of remote sensing to detect lunar volatiles is addressed.

Paper spray mass spectrometry and PLS-DA improved by variable selection for the forensic discrimination of beers.

PubMed

Pereira, Hebert Vinicius; Amador, Victória Silva; Sena, Marcelo Martins; Augusti, Rodinei; Piccin, Evandro

2016-10-12

Paper spray mass spectrometry (PS-MS) combined with partial least squares discriminant analysis (PLS-DA) was applied for the first time in a forensic context to a fast and effective differentiation of beers. Eight different brands of American standard lager beers produced by four different breweries (141 samples from 55 batches) were studied with the aim at performing a differentiation according to their market prices. The three leader brands in the Brazilian beer market, which have been subject to fraud, were modeled as the higher-price class, while the five brands most used for counterfeiting were modeled as the lower-price class. Parameters affecting the paper spray ionization were examined and optimized. The best MS signal stability and intensity was obtained while using the positive ion mode, with PS(+) mass spectra characterized by intense pairs of signals corresponding to sodium and potassium adducts of malto-oligosaccharides. Discrimination was not apparent neither by using visual inspection nor principal component analysis (PCA). However, supervised classification models provided high rates of sensitivity and specificity. A PLS-DA model using full scan mass spectra were improved by variable selection with ordered predictors selection (OPS), providing 100% of reliability rate and reducing the number of variables from 1701 to 60. This model was interpreted by detecting fifteen variables as the most significant VIP (variable importance in projection) scores, which were therefore considered diagnostic ions for this type of beer counterfeit. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection of seventy-two anabolic and androgenic steroids and/or their esters in horse hair using ultra-high performance liquid chromatography-high resolution mass spectrometry in multiplexed targeted MS2 mode and gas chromatography-tandem mass spectrometry.

PubMed

Choi, Timmy L S; Kwok, Karen Y; Kwok, Wai Him; Tsoi, Yeuki Y K; Wong, Jenny K Y; Wan, Terence S M

2018-06-20

Anabolic and androgenic steroids (AAS) are banned substances in both human and equine sports. They are often administered intramuscularly to horses in esterified forms for the purpose of extending their time of action. The authors' laboratory has previously reported an UHPLC/HRMS method using quadrupole-Orbitrap mass spectrometer in full scan and parallel reaction monitoring (PRM) mode for the detection of 48 AAS and/or their esters in horse hair. However, two injections were required due to the long duty cycle time. In this paper, an UHPLC/HRMS method using multiplexed targeted MS 2 mode was developed and validated to improve the coverage to 65 AAS and/or their esters in a single injection. In addition, a GC/MS/MS method in selected reaction monitoring (SRM) mode was developed to screen for another seven AAS and/or their esters not adequately covered by the UHPLC/HRMS method using the same sample extract after derivatisation with pentafluoropropionic anhydride. The UHPLC/HRMS and GC/MS/MS methods in combination allowed the detection of 72 AAS and/or their esters with estimated limits of detection down to sub to low ppb levels with good interday precision. Method applicability was demonstrated by the detection of boldione and 4-androstenedione in two out-of-competition hair samples and testosterone propionate in a referee hair sample. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical Quartz Crystal Nanobalance (EQCN) Based Biosensor for Sensitive Detection of Antibiotic Residues in Milk.

PubMed

Bhand, Sunil; Mishra, Geetesh K

2017-01-01

An electrochemical quartz crystal nanobalance (EQCN), which provides real-time analysis of dynamic surface events, is a valuable tool for analyzing biomolecular interactions. EQCN biosensors are based on mass-sensitive measurements that can detect small mass changes caused by chemical binding to small piezoelectric crystals. Among the various biosensors, the piezoelectric biosensor is considered one of the most sensitive analytical techniques, capable of detecting antigens at picogram levels. EQCN is an effective monitoring technique for regulation of the antibiotics below the maximum residual limit (MRL). The analysis of antibiotic residues requires high sensitivity, rapidity, reliability and cost effectiveness. For analytical purposes the general approach is to take advantage of the piezoelectric effect by immobilizing a biosensing layer on top of the piezoelectric crystal. The sensing layer usually comprises a biological material such as an antibody, enzymes, or aptamers having high specificity and selectivity for the target molecule to be detected. The biosensing layer is usually functionalized using surface chemistry modifications. When these bio-functionalized quartz crystals are exposed to a particular substance of interest (e.g., a substrate, inhibitor, antigen or protein), binding interaction occurs. This causes a frequency or mass change that can be used to determine the amount of material interacted or bound. EQCN biosensors can easily be automated by using a flow injection analysis (FIA) setup coupled through automated pumps and injection valves. Such FIA-EQCN biosensors have great potential for the detection of different analytes such as antibiotic residues in various matrices such as water, waste water, and milk.

Low-Level Detection of a Bacillus Anthracis Simulant using Love-Wave Biosensors on 36 Degree YX LiTaO3

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

BRANCH,DARREN W.; BROZIK,SUSAN M.

Crucial to low-level detection of biowarfare agents in aqueous environments is the mass sensitivity optimization of Love-wave acoustic sensors. The present work is an experimental study of 36{sup o} YX cut LiTaO{sub 3} based Love-wave devices for detection of pathogenic spores in aqueous conditions. Given that the detection limit (DL) of Love-wave based sensors is a strong function of the overlying waveguide, two waveguide materials have been investigated, which are polyimide and polystyrene. To determine the mass sensitivity of Love-wave sensor, bovine serum albumin (BSA) protein was injected into the Love-wave test cell while recording magnitude and phase shift acrossmore » each sensor. Polyimide had the lowest mass detection limit with an estimated value of 1-2 ng/cm{sup 2}, as compared to polystyrene where DL = 2.0 ng/cm{sup 2}. Suitable chemistries were used to orient antibodies on the Love-wave sensor using adsorbed protein G. The thickness of each biofilm was measured using ellipsometry from which the surface concentrations were calculated. The monoclonal antibody BD8 with a high degree of selectivity for anthrax spores was used to capture the non-pathogenic simulant B. thuringiensis B8 spores. Bacillus Subtilis spores were used as a negative control to determine whether significant non-specific binding would occur. Spore aliquots were prepared using an optical counting method, which permitted removal of background particles for consistent sample preparation. This work demonstrates that Love-wave devices can be used to detect B. anthracis simulant below reported infectious levels.« less

Microcantilever sensor platform for UGV-based detection

NASA Astrophysics Data System (ADS)

Lawrence, Tyson T.; Halleck, A. E.; Schuler, Peter S.; Mahmud, K. K.; Hicks, David R.

2010-04-01

The increased use of Unmanned Ground Vehicles (UGVs) drives the need for new lightweight, low cost sensors. Microelectromechanical System (MEMS) based microcantilever sensors are a promising technology to meet this need, because they can be manufactured at low cost on a mass scale, and are easily integrated into a UGV platform for detection of explosives and other threat agents. While the technology is extremely sensitive, selectivity is a major challenge and the response modes are not well understood. This work summarizes advances in characterizing ultrasensitive microcantilever responses, sampling considerations, and sensor design and cantilever coating methodologies consistent with UGV point detector needs.

Simultaneous analysis of six aldehyde-DNA adducts in salivary DNA of nonsmokers and smokers using stable isotope dilution liquid chromatography electrospray ionization-tandem mass spectrometry.

PubMed

Li, Xiangyu; Liu, Lujuan; Wang, Hongjuan; Chen, Jian; Zhu, Beibei; Chen, Huan; Hou, Hongwei; Hu, Qingyuan

2017-08-15

A stable method, using isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS), to simultaneously determine six aldehyde-DNA adducts was developed and applied to the analysis of human salivary DNA samples. The detection limit of these six DNA adducts was in the range of 0.006-0.014ng/mL and that of the quantification limit was 0.017-0.026ng/mL. The intra-day and inter-day precision of all aldehyde-DNA adducts was <10%. The analysis was completed within 25min. Additionally, a noninvasive technique was used to collect the DNA samples from human saliva. The new method was successfully applied for the analysis of salivary DNA of nonsmokers and smokers. Five aldehyde-DNA adducts were detected in both smoker and nonsmoker salivary DNA, while α-Acr-dG was not detected in all the samples. Among these detected DNA adducts, no significant differences were found between smoker and nonsmoker (p>0.05). This may due to the individual detoxifying differences or environmental and endogenous exposure. Our study provides a rapid and selective method to simultaneously detect six aldehyde-DNA adducts and to assess potential DNA damage induced by aldehydes. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous detection of five different 2-hydroxyethyl-DNA adducts formed by ethylene oxide exposure, using a high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry assay.

PubMed

Tompkins, Elaine M; Jones, Donald J L; Lamb, John H; Marsden, Debbie A; Farmer, Peter B; Brown, Karen

2008-01-01

A method has been developed for the simultaneous detection and quantitation of five different 2-hydroxyethyl-DNA (HE-DNA) adducts that could be formed as a result of exposure to ethylene oxide (EO). In addition to the major N7-HE-guanine (N7-HEG) adducts this assay can also measure the less prevalent but potentially more biologically significant N1-HE-2'-deoxyadenosine (N1-HEdA), O(6)-HE-2'-deoxyguanosine (O(6)-HEdG), N(6)-HE-2'-deoxyadenosine (N(6)-HEdA) and N3-HE-2'-deoxyuridine adducts (N3-HEdU). The method involves the isolation of HE adducts from the unmodified nucleosides by either neutral thermal hydrolysis or enzymatic digestion, followed by high-performance liquid chromatographic (HPLC) purification, before detection and quantification by liquid chromatography tandem mass spectrometry (LC/MS/MS) using selective reaction monitoring (SRM). The limits of detection were in the range 0.5-25 fmol for each individual adduct, making this one of the most sensitive assays available for the detection of N7-HEG. To illustrate the possible applications of the assay, it has been employed in the measurement of endogenous/background and EO-induced HE adducts in a variety of DNA samples.

Impact of compressed breast thickness and dose on lesion detectability in digital mammography: FROC study with simulated lesions in real mammograms

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

Salvagnini, Elena, E-mail: elena.salvagnini@gmail.

Purpose: The aim of this work was twofold: (1) to examine whether, with standard automatic exposure control (AEC) settings that maintain pixel values in the detector constant, lesion detectability in clinical images decreases as a function of breast thickness and (2) to verify whether a new AEC setup can increase lesion detectability at larger breast thicknesses. Methods: Screening patient images, acquired on two identical digital mammography systems, were collected over a period of 2 yr. Mammograms were acquired under standard AEC conditions (part 1) and subsequently with a new AEC setup (part 2), programmed to use the standard AEC settingsmore » for compressed breast thicknesses ≤49 mm, while a relative dose increase was applied above this thickness. The images were divided into four thickness groups: T1 ≤ 29 mm, T2 = 30–49 mm, T3 = 50–69 mm, and T4 ≥ 70 mm, with each thickness group containing 130 randomly selected craniocaudal lesion-free images. Two measures of density were obtained for every image: a BI-RADS score and a map of volumetric breast density created with a software application (VolparaDensity, Matakina, NZ). This information was used to select subsets of four images, containing one image from each thickness group, matched to a (global) BI-RADS score and containing a region with the same (local) VOLPARA volumetric density value. One selected lesion (a microcalcification cluster or a mass) was simulated into each of the four images. This process was repeated so that, for a given thickness group, half the images contained a single lesion and half were lesion-free. The lesion templates created and inserted in groups T3 and T4 for the first part of the study were then inserted into the images of thickness groups T3 and T4 acquired with higher dose settings. Finally, all images were visualized using the ViewDEX software and scored by four radiologists performing a free search study. A statistical jackknife-alternative free-response receiver operating characteristic analysis was applied. Results: For part 1, the alternative free-response receiver operating characteristic curves for the four readers were 0.80, 0.65, 0.55 and 0.56 in going from T1 to T4, indicating a decrease in detectability with increasing breast thickness. P-values and the 95% confidence interval showed no significant difference for the T3-T4 comparison (p = 0.78) while all the other differences were significant (p < 0.05). Separate analysis of microcalcification clusters presented the same results while for mass detection, the only significant difference came when comparing T1 to the other thickness groups. Comparing the scores of part 1 and part 2, results for the T3 group acquired with the new AEC setup and T3 group at standard AEC doses were significantly different (p = 0.0004), indicating improved detection. For this group a subanalysis for microcalcification detection gave the same results while no significant difference was found for mass detection. Conclusions: These data using clinical images confirm results found in simple QA tests for many mammography systems that detectability falls as breast thickness increases. Results obtained with the AEC setup for constant detectability above 49 mm showed an increase in lesion detection with compressed breast thickness, bringing detectability of lesions to the same level.« less

Rapid LC-MS/MS profiling of protein amino acids and metabolically related compounds for large-scale assessment of metabolic phenotypes.

PubMed

Gu, Liping; Jones, A Daniel; Last, Robert L

2012-01-01

Amino acids extracted from a biological matrix can be resolved and measured using a 6-min per sample method through high-performance liquid chromatography with a short C18 column and rapid gradient using the ion-pairing reagent perfluoroheptanoic acid. LC-tandem mass spectrometry with multiple reaction monitoring (MRM) transitions selective for each compound allows simultaneous quantification of the 20 proteinogenic amino acids and 5 metabolically related compounds. Distinct MRM transitions were also established for selective detection of the isomers leucine/isoleucine and threonine/homoserine.

Machine-learning approaches to select Wolf-Rayet candidates

NASA Astrophysics Data System (ADS)

Marston, A. P.; Morello, G.; Morris, P.; van Dyk, S.; Mauerhan, J.

2017-11-01

The WR stellar population can be distinguished, at least partially, from other stellar populations by broad-band IR colour selection. We present the use of a machine learning classifier to quantitatively improve the selection of Galactic Wolf-Rayet (WR) candidates. These methods are used to separate the other stellar populations which have similar IR colours. We show the results of the classifications obtained by using the 2MASS J, H and K photometric bands, and the Spitzer/IRAC bands at 3.6, 4.5, 5.8 and 8.0μm. The k-Nearest Neighbour method has been used to select Galactic WR candidates for observational follow-up. A few candidates have been spectroscopically observed. Preliminary observations suggest that a detection rate of 50% can easily be achieved.

Selective determination of pyridine alkaloids in tobacco by PFTBA ions/analyte molecule reaction ionization ion trap mass spectrometry.

PubMed

Zhang, Jianxun; Ji, Houwei; Sun, Shihao; Mao, Duobin; Liu, Huwei; Guo, Yinlong

2007-10-01

The application of perfluorotributylamine (PFTBA) ions/analyte molecule reaction ionization for the selective determination of tobacco pyridine alkaloids by ion trap mass spectrometry (IT-MS) is reported. The main three PFTBA ions (CF(3)(+), C(3)F(5)(+), and C(5)F(10)N(+)) are generated in the external source and then introduced into ion trap for reaction with analytes. Because the existence of the tertiary nitrogen atom in the pyridine makes it possible for PFTBA ions to react smoothly with pyridine and forms adduct ions, pyridine alkaloids in tobacco were selectively ionized and formed quasi-molecular ion [M + H](+)and adduct ions, including [M + 69](+), [M + 131](+), and [M + 264](+), in IT-MS. These ions had distinct abundances and were regarded as the diagnostic ions of each tobacco pyridine alkaloid for quantitative analysis in selected-ion monitoring mode. Results show that the limit of detection is 0.2 microg/mL, and the relative standard deviations for the seven alkaloids are in the range of 0.71% to 6.8%, and good recovery of 95.6% and 97.2%. The proposed method provides substantially greater selectivity and sensitivity compared with the conventional approach and offers an alternative approach for analysis of tobacco alkaloids.

High Resolution PTR-TOFMS: A New Instrument for Organic Compound Measurements

NASA Astrophysics Data System (ADS)

Hansel, A.; Graus, M.; Mueller, M.; Wisthaler, A.

2007-12-01

Over the last decade proton transfer reaction mass spectrometry (PTR-MS) has become very popular in many scientific fields. PTR-MS allows for the quantitative detection of volatile organic compounds (VOCs) at pptv-level virtually in real time. Monitoring of VOCs with a time resolution of typically a second per compound has, for instance, enabled the tracking of pollution plumes by air-borne measurements, thus revealing the photo- chemical fate of pollutants. It has also been employed in direct eddy covariant flux measurements. This rapidity, however, has been achieved at the cost of the number of compounds to be analyzed and compound selectivity. Conventional PTR-MS can, for example, not distinguish between hydrocarbons and their oxygenated isobaric species, e.g. between naphthalene and octanal or between isoprene and furan. In a mass range up to 200 Dalton, such a task would require a mass resolving power of 5500. The use of a time of flight (TOF) instead of a quadrupole mass analyzer in PTR-MS provides a sufficient high mass resolution to identify the atomic composition of product ions by their exact mass and their characteristic isotope patterns. In addition PTR-TOF-MS can record full mass spectra within a fraction of a second which is a dramatically increase in duty cycle. At the University of Innsbruck a high resolution PTR-TOFMS has recently been developed, coupling a PTR-ion source and a high resolution TOFMS. We achieved a mass resolving power of 6000 (FWHM), and a detection limit of tens to a few hundreds of pptv if integrating mass spectra for one minute. First results and future directions will be discussed in this paper.

The HETDEX pilot survey. V. The physical origin of Lyα emitters probed by near-infrared spectroscopy

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

Song, Mimi; Finkelstein, Steven L.; Gebhardt, Karl

2014-08-10

We present the results from a Very Large Telescope/SINFONI and Keck/NIRSPEC near-infrared spectroscopic survey of 16 Lyα emitters (LAEs) at z = 2.1-2.5 in the COSMOS and GOODS-N fields discovered from the Hobby Eberly Telescope Dark Energy Experiment Pilot Survey. We detect rest-frame optical nebular lines (Hα and/or [O III] λ5007) for 10 of the LAEs and measure physical properties, including the star formation rate (SFR), gas-phase metallicity, gas mass fraction, and Lyα velocity offset. We find that LAEs may lie below the mass-metallicity relation for continuum-selected star-forming galaxies at the same redshift. The LAEs all show velocity shifts ofmore » Lyα relative to the systemic redshift ranging between +85 and +296 km s{sup –1} with a mean of +180 km s{sup –1}. This value is smaller than measured for continuum-selected star-forming galaxies at similar redshifts. The Lyα velocity offsets show a moderate correlation with the measured SFR (2.5σ), but no significant correlations are seen with the SFR surface density, specific SFR, stellar mass, or dynamical mass (≲1.5σ). Exploring the role of dust, kinematics of the interstellar medium (ISM), and geometry on the escape of Lyα photons, we find no signature of selective quenching of resonantly scattered Lyα photons. However, we also find no evidence that a clumpy ISM is enhancing the Lyα equivalent width. Our results suggest that the low metallicity in LAEs may be responsible for yielding an environment with a low neutral hydrogen column density and less dust, easing the escape of Lyα photons over that in continuum-selected star-forming galaxies.« less

An HS-MRM Assay for the Quantification of Host-cell Proteins in Protein Biopharmaceuticals by Liquid Chromatography Ion Mobility QTOF Mass Spectrometry.

PubMed

Doneanu, Catalin; Fang, Jing; Alelyunas, Yun; Yu, Ying Qing; Wrona, Mark; Chen, Weibin

2018-04-17

The analysis of low-level (1-100 ppm) protein impurities (e.g., host-cell proteins (HCPs)) in protein biotherapeutics is a challenging assay requiring high sensitivity and a wide dynamic range. Mass spectrometry-based quantification assays for proteins typically involve protein digestion followed by the selective reaction monitoring/multiple reaction monitoring (SRM/MRM) quantification of peptides using a low-resolution (Rs ~1,000) tandem quadrupole mass spectrometer. One of the limitations of this approach is the interference phenomenon observed when the peptide of interest has the "same" precursor and fragment mass (in terms of m/z values) as other co-eluting peptides present in the sample (within a 1-Da window). To avoid this phenomenon, we propose an alternative mass spectrometric approach, a high selectivity (HS) MRM assay that combines the ion mobility separation of peptide precursors with the high-resolution (Rs ~30,000) MS detection of peptide fragments. We explored the capabilities of this approach to quantify low-abundance peptide standards spiked in a monoclonal antibody (mAb) digest and demonstrated that it has the sensitivity and dynamic range (at least 3 orders of magnitude) typically achieved in HCP analysis. All six peptide standards were detected at concentrations as low as 0.1 nM (1 femtomole loaded on a 2.1-mm ID chromatographic column) in the presence of a high-abundance peptide background (2 µg of a mAb digest loaded on-column). When considering the MW of rabbit phosphorylase (97.2 kDa), from which the spiked peptides were derived, the LOQ of this assay is lower than 50 ppm. Relative standard deviations (RSD) of peak areas (n = 4 replicates) were less than 15% across the entire concentration range investigated (0.1-100 nM or 1-1,000 ppm) in this study.

Discriminating precursors of common fragments for large-scale metabolite profiling by triple quadrupole mass spectrometry.

PubMed

Nikolskiy, Igor; Siuzdak, Gary; Patti, Gary J

2015-06-15

The goal of large-scale metabolite profiling is to compare the relative concentrations of as many metabolites extracted from biological samples as possible. This is typically accomplished by measuring the abundances of thousands of ions with high-resolution and high mass accuracy mass spectrometers. Although the data from these instruments provide a comprehensive fingerprint of each sample, identifying the structures of the thousands of detected ions is still challenging and time intensive. An alternative, less-comprehensive approach is to use triple quadrupole (QqQ) mass spectrometry to analyze predetermined sets of metabolites (typically fewer than several hundred). This is done using authentic standards to develop QqQ experiments that specifically detect only the targeted metabolites, with the advantage that the need for ion identification after profiling is eliminated. Here, we propose a framework to extend the application of QqQ mass spectrometers to large-scale metabolite profiling. We aim to provide a foundation for designing QqQ multiple reaction monitoring (MRM) experiments for each of the 82 696 metabolites in the METLIN metabolite database. First, we identify common fragmentation products from the experimental fragmentation data in METLIN. Then, we model the likelihoods of each precursor structure in METLIN producing each common fragmentation product. With these likelihood estimates, we select ensembles of common fragmentation products that minimize our uncertainty about metabolite identities. We demonstrate encouraging performance and, based on our results, we suggest how our method can be integrated with future work to develop large-scale MRM experiments. Our predictions, Supplementary results, and the code for estimating likelihoods and selecting ensembles of fragmentation reactions are made available on the lab website at http://pattilab.wustl.edu/FragPred. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Weak lensing magnification of SpARCS galaxy clusters

NASA Astrophysics Data System (ADS)

Tudorica, A.; Hildebrandt, H.; Tewes, M.; Hoekstra, H.; Morrison, C. B.; Muzzin, A.; Wilson, G.; Yee, H. K. C.; Lidman, C.; Hicks, A.; Nantais, J.; Erben, T.; van der Burg, R. F. J.; Demarco, R.

2017-12-01

Context. Measuring and calibrating relations between cluster observables is critical for resource-limited studies. The mass-richness relation of clusters offers an observationally inexpensive way of estimating masses. Its calibration is essential for cluster and cosmological studies, especially for high-redshift clusters. Weak gravitational lensing magnification is a promising and complementary method to shear studies, that can be applied at higher redshifts. Aims: We aim to employ the weak lensing magnification method to calibrate the mass-richness relation up to a redshift of 1.4. We used the Spitzer Adaptation of the Red-Sequence Cluster Survey (SpARCS) galaxy cluster candidates (0.2 < z < 1.4) and optical data from the Canada France Hawaii Telescope (CFHT) to test whether magnification can be effectively used to constrain the mass of high-redshift clusters. Methods: Lyman-break galaxies (LBGs) selected using the u-band dropout technique and their colours were used as a background sample of sources. LBG positions were cross-correlated with the centres of the sample of SpARCS clusters to estimate the magnification signal, which was optimally-weighted using an externally-calibrated LBG luminosity function. The signal was measured for cluster sub-samples, binned in both redshift and richness. Results: We measured the cross-correlation between the positions of galaxy cluster candidates and LBGs and detected a weak lensing magnification signal for all bins at a detection significance of 2.6-5.5σ. In particular, the significance of the measurement for clusters with z> 1.0 is 4.1σ; for the entire cluster sample we obtained an average M200 of 1.28 -0.21+0.23 × 1014 M⊙. Conclusions: Our measurements demonstrated the feasibility of using weak lensing magnification as a viable tool for determining the average halo masses for samples of high redshift galaxy clusters. The results also established the success of using galaxy over-densities to select massive clusters at z > 1. Additional studies are necessary for further modelling of the various systematic effects we discussed.

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

Weak-Lensing Mass Calibration of the Atacama Cosmology Telescope Equatorial Sunyaev-Zeldovich Cluster Sample with the Canada-France-Hawaii Telescope Stripe 82 Survey

NASA Technical Reports Server (NTRS)

Battaglia, N.; Leauthaud, A.; Miyatake, H.; Hasseleld, M.; Gralla, M. B.; Allison, R.; Bond, J. R.; Calabrese, E.; Crichton, D.; Devlin, M. J.;

Mass, charge, and energy separation by selective acceleration with a traveling potential hill

NASA Astrophysics Data System (ADS)

Tung, L. Schwager; Barr, W. L.; Lowder, R. S.; Post, R. F.

1996-10-01

A traveling electric potential hill has been used to generate an ion beam with an energy distribution that is mass dependent from a monoenergetic ion beam of mixed masses. This effect can be utilized as a novel method for mass separation applied to identification or enrichment of ions (e.g., of elements, isotopes, or molecules). This theory for mass-selective acceleration is presented here and is shown to be confirmed by experiment and by a time-dependent particle-in-cell computer simulation. Results show that monoenergetic ions with the particular mass of choice are accelerated by controlling the hill potential and the hill velocity. The hill velocity is typically 20%-30% faster than the ions to be accelerated. The ability of the hill to pickup a particular mass uses the fact that small kinetic energy differences in the lab frame appear much larger in the moving hill frame. Ions will gain energy from the approaching hill if their relative energy in the moving hill frame is less than the peak potential of the hill. The final energy of these accelerated ions can be several times the source energy, which facilitates energy filtering for mass purification or identification. If the hill potential is chosen to accelerate multiple masses, the heaviest mass will have the greatest final energy. Hence, choosing the appropriate hill potential and collector retarding voltage will isolate ions with the lightest, heaviest, or intermediate mass. In the experimental device, called a Solitron, purified 20Ne and 22Ne are extracted from a ribbon beam of neon that is originally composed of 20Ne:22Ne in the natural ratio of 91:9. The isotopic content of the processed beam is determined by measuring the energy distribution of the detected current. These results agree with the theory. In addition to mass selectivity, our theory can also be applied to the filtration of an ion beam according to charge state or energy. Because of this variety of properties, the Solitron is envisioned to have broad applications. The primary application is for the enrichment of stable isotopes for medical and industrial tracers. Other applications include mass analysis of unknown gases (atomic and molecular) and metals, extracting single charge states from a multiply charged beam, accelerating the high energy tail in a beam or plasma with a velocity distribution, and beam bunching.

Determination of nandrolone and metabolites in urine samples from sedentary persons and sportsmen.

PubMed

Galán Martín, A M; Mariño, J I; García de Tiedra, M P; Marabé, J J; Caballero Loscos, M J; Mariño, M M

2001-09-25

Metabolites of nandrolone were determined in the urine of several sportsmen, sedentary and post-menopausal women by capillary gas chromatography-mass spectrometry quadrupole (GC-MS) and capillary gas chromatography mass-mass spectrometry ion trap (GC-MS-MS) methods. The method employed was GC-EI-MS with 17alpha-methyltestosterone as internal standard with ethyl ether extraction prior to selected ion monitoring of the bis(trimethylsilyl) ethers at ion masses m/z 405 and 420 for the nandrolone metabolites, and 418 and 403 for nandrolone derivative. Recovery for nandrolone, 19-norandrosterone (19-NA) and 19-noretiocholanolone (19-NE) was 97.20, 94.17 and 95.54%, respectively. Detection limits for nandrolone, 19-NA and 19-NE were 0.03, 0.01 and 0.06 ng/ml. Metabolites of nandrolone (19-NA and 19-NE) were found in 12.5% (n = 40) of sportsmen and 40% (n = 10) of post-menopausal women.

Fingerprinting Breast Cancer vs. Normal Mammary Cells by Mass Spectrometric Analysis of Volatiles

NASA Astrophysics Data System (ADS)

He, Jingjing; Sinues, Pablo Martinez-Lozano; Hollmén, Maija; Li, Xue; Detmar, Michael; Zenobi, Renato

2014-06-01

There is increasing interest in the development of noninvasive diagnostic methods for early cancer detection, to improve the survival rate and quality of life of cancer patients. Identification of volatile metabolic compounds may provide an approach for noninvasive early diagnosis of malignant diseases. Here we analyzed the volatile metabolic signature of human breast cancer cell lines versus normal human mammary cells. Volatile compounds in the headspace of conditioned culture medium were directly fingerprinted by secondary electrospray ionization-mass spectrometry. The mass spectra were subsequently treated statistically to identify discriminating features between normal vs. cancerous cell types. We were able to classify different samples by using feature selection followed by principal component analysis (PCA). Additionally, high-resolution mass spectrometry allowed us to propose their chemical structures for some of the most discriminating molecules. We conclude that cancerous cells can release a characteristic odor whose constituents may be used as disease markers.

Balloon-borne photoionization mass spectrometer for measurement of stratospheric gases

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Maier, E. J. R.

1978-01-01

A balloon-borne photoionization mass spectrometer used to measure stratospheric trace gases is described. Ions are created with photons from high-intensity krypton discharge lamps and a quadrupole mass analyzer is employed for ion identification. Differential pumping is achieved with liquid helium cryopumping. To insure measurement of unperturbed stratospheric air, the entire system is contained in a sealed gondola and the atmospheric sample is taken some distance away during descent. The photoionization technique allows the detection of a low ionization potential constituent, such as nitric oxide, at less than a part in one billion in the presence of the major atmospheric gases and their isotopes. Operation of the mass spectrometer system was demonstrated during a daytime flight from Palestine, Texas on 26 April 1977. The sensitivity achieved and the unique selectivity afforded by this technique offer a capability for trace constituent measurement not possible with the more conventional electron impact ionization approach.

Direct analysis of volatile organic compounds in foods by headspace extraction atmospheric pressure chemical ionisation mass spectrometry.

PubMed

Perez-Hurtado, P; Palmer, E; Owen, T; Aldcroft, C; Allen, M H; Jones, J; Creaser, C S; Lindley, M R; Turner, M A; Reynolds, J C

2017-11-30

The rapid screening of volatile organic compounds (VOCs) by direct analysis has potential applications in the areas of food and flavour science. Currently, the technique of choice for VOC analysis is gas chromatography/mass spectrometry (GC/MS). However, the long chromatographic run times and elaborate sample preparation associated with this technique have led a movement towards direct analysis techniques, such as selected ion flow tube mass spectrometry (SIFT-MS), proton transfer reaction mass spectrometry (PTR-MS) and electronic noses. The work presented here describes the design and construction of a Venturi jet-pump-based modification for a compact mass spectrometer which enables the direct introduction of volatiles for qualitative and quantitative analysis. Volatile organic compounds were extracted from the headspace of heated vials into the atmospheric pressure chemical ionization source of a quadrupole mass spectrometer using a Venturi pump. Samples were analysed directly with no prior sample preparation. Principal component analysis (PCA) was used to differentiate between different classes of samples. The interface is shown to be able to routinely detect problem analytes such as fatty acids and biogenic amines without the requirement of a derivatisation step, and is shown to be able to discriminate between four different varieties of cheese with good intra and inter-day reproducibility using an unsupervised PCA model. Quantitative analysis is demonstrated using indole standards with limits of detection and quantification of 0.395 μg/mL and 1.316 μg/mL, respectively. The described methodology can routinely detect highly reactive analytes such as volatile fatty acids and diamines without the need for a derivatisation step or lengthy chromatographic separations. The capability of the system was demonstrated by discriminating between different varieties of cheese and monitoring the spoilage of meats. © 2017 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

Sixty-Four-Section Cardiac Computed Tomography in Mechanical Prosthetic Heart Valve Dysfunction: Thrombus or Pannus.

PubMed

Gündüz, Sabahattin; Özkan, Mehmet; Kalçik, Macit; Gürsoy, Ozan Mustafa; Astarcioğlu, Mehmet Ali; Karakoyun, Süleyman; Aykan, Ahmet Çağri; Biteker, Murat; Gökdeniz, Tayyar; Kaya, Hasan; Yesin, Mahmut; Duran, Nilüfer Ekşi; Sevinç, Deniz; Güneysu, Tahsin

2015-12-01

Distinguishing pannus and thrombus in patients with prosthetic valve dysfunction is essential for the selection of proper treatment. We have investigated the utility of 64-slice multidetector computed tomography (MDCT) in distinguishing between pannus and thrombus, the latter amenable to thrombolysis. Sixty-two (23 men, mean age 44±14 years) patients with suspected mechanical prosthetic valve dysfunction assessed by transesophageal echocardiography were included in this prospective observational trial. Subsequently, MDCT was performed before any treatment was started. Periprosthetic masses were detected by MDCT in 46 patients, and their attenuation values were measured as Hounsfield Units (HU). Patients underwent thrombolysis unless contraindicated, and those with a contraindication or failed thrombolysis underwent surgery. A mass which was completely lysed or surgically detected as a clot was classified as thrombus, whereas a mass which was surgically detected as tissue overgrowth was classified as pannus. A definitive diagnosis could be achieved in 37 patients with 39 MDCT masses (22 thrombus and 17 pannus). The mean attenuation value of 22 thrombotic masses was significantly lower than that in 17 pannus (87±59 versus 322±122; P<0.001). Area under the receiver operating characteristic curve was 0.96 (95% confidence interval: 0.91-0.99; P<0.001), and a cutoff point of HU≥145 provided high sensitivity (87.5%) and specificity (95.5%) in discriminating pannus from thrombus. Complete lysis was more common for masses with HU<90 compared with those with HU 90 to 145 (100% versus 42.1%; P=0.007). Sixty-four slice MDCT is helpful in identifying masses amenable to thrombolysis in patients with prosthetic valve dysfunction. A high (HU≥145) attenuation suggests pannus overgrowth, whereas a lower value is associated with thrombus formation. A higher attenuation (HU>90) is associated with reduced lysis rates. © 2015 American Heart Association, Inc.

Search for light curve modulations among Kepler candidates. Three very low-mass transiting companions

NASA Astrophysics Data System (ADS)

Lillo-Box, J.; Ribas, A.; Barrado, D.; Merín, B.; Bouy, H.

2016-07-01

Context. Light curve modulations in the sample of Kepler planet candidates allows the disentangling of the nature of the transiting object by photometrically measuring its mass. This is possible by detecting the effects of the gravitational pull of the companion (ellipsoidal modulations) and in some cases, the photometric imprints of the Doppler effect when observing in a broad band (Doppler beaming). Aims: We aim to photometrically unveil the nature of some transiting objects showing clear light curve modulations in the phase-folded Kepler light curve. Methods: We selected a subsample among the large crop of Kepler objects of interest (KOIs) based on their chances to show detectable light curve modulations, I.e., close (a< 12 R⋆) and large (in terms of radius, according to their transit signal) candidates. We modeled their phase-folded light curves with consistent equations for the three effects, namely, reflection, ellipsoidal and beaming (known as REB modulations). Results: We provide detailed general equations for the fit of the REB modulations for the case of eccentric orbits. These equations are accurate to the photometric precisions achievable by current and forthcoming instruments and space missions. By using this mathematical apparatus, we find three close-in very low-mass companions (two of them in the brown dwarf mass domain) orbiting main-sequence stars (KOI-554, KOI-1074, and KOI-3728), and reject the planetary nature of the transiting objects (thus classifying them as false positives). In contrast, the detection of the REB modulations and transit/eclipse signal allows the measurement of their mass and radius that can provide important constraints for modeling their interiors since just a few cases of low-mass eclipsing binaries are known. Additionally, these new systems can help to constrain the similarities in the formation process of the more massive and close-in planets (hot Jupiters), brown dwarfs, and very low-mass companions.

Specific characterization of non-steroidal selective androgen peceptor modulators using supercritical fluid chromatography coupled to ion-mobility mass spectrometry: application to the detection of enobosarm in bovine urine.

PubMed

Beucher, Laure; Dervilly-Pinel, Gaud; Cesbron, Nora; Penot, Mylène; Gicquiau, Audrey; Monteau, Fabrice; Le Bizec, Bruno

2017-02-01

Currently under development for therapeutic purposes in human medicine, non-steroidal selective androgen receptor modulators (non-steroidal SARMs) are also known to impact growth associated pathways. As such, they present a potential for abuse in sports and food-producing animals as interesting alternative anabolic substances. Forbidden since 2008 by the World Anti-Doping Agency (WADA) these compounds are however easily available and could be (mis)used in livestock production as growth promoters. To prevent such practices, dedicated analytical strategies have to be developed for specific and sensitive detection of these compounds in biological matrices. Using an innovative analytical platform constituted of supercritical fluid chromatography coupled to ion mobility-mass spectrometry, the present study enabled efficient separation and identification in urine of 4 of these drugs (andarine, bicalutamide, hydroxyflutamide, and enobosarm) in accordance with European Union criteria (Commission Decision 2002/657/EC). Besides providing information about compounds structure and behaviour in gas phase, such a coupling enabled reaching low limits of detection (LOD < 0.05 ng.mL -1 for andarine and limits of detection < 0.005 ng.mL -1 for the three others) in urine with good repeatability (CV < 21 %). The workflow has been applied to quantitative determination of enobosarm elimination in urine of treated bovine (200 mg, oral). Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine with mass selective detection.

PubMed

Hughes, D L; Ritter, D J; Wilson, R D

2001-11-01

Method development and validation studies have been completed on an assay that will allow the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. The accurate determination of 2,4-D in urine is an important factor in monitoring worker and population exposure. These studies successfully validated a method for the detection of 2,4-D in urine at a limit of quantitation (LOQ) of 5.00 ppb (parts per billion) using gas chromatography with mass selective detection (GC/MSD). The first study involved the determination of 2,4-D in control human urine and urine samples fortified with 2,4-D. Due to chromatographic interference, a second study was conducted using 14C-2,4-D to verify the recoverability of 2,4-D from human urine at low levels using the GC/MSD method. The second study supports the results of the original data. The 2,4-D was extracted from human urine using a procedure involving hydrolysis using potassium hydroxide, followed by a liquid-liquid extraction into methylene chloride. The extracted samples were derivatized with diazomethane. The methylated fraction was analyzed by GC/MSD. Quantitation was made by comparison to methylated reference standards of 2,4-D. Aliquots fortified at 5-, 50-, and 500-ppb levels were analyzed. The overall mean recovery for all fortified samples was 90.3% with a relative standard deviation of 14.31%.

Classification of the medicinal plants of the genus Atractylodes using high-performance liquid chromatography with diode array and tandem mass spectrometry detection combined with multivariate statistical analysis.

PubMed

Cho, Hyun-Deok; Kim, Unyong; Suh, Joon Hyuk; Eom, Han Young; Kim, Junghyun; Lee, Seul Gi; Choi, Yong Seok; Han, Sang Beom

2016-04-01

Analytical methods using high-performance liquid chromatography with diode array and tandem mass spectrometry detection were developed for the discrimination of the rhizomes of four Atractylodes medicinal plants: A. japonica, A. macrocephala, A. chinensis, and A. lancea. A quantitative study was performed, selecting five bioactive components, including atractylenolide I, II, III, eudesma-4(14),7(11)-dien-8-one and atractylodin, on twenty-six Atractylodes samples of various origins. Sample extraction was optimized to sonication with 80% methanol for 40 min at room temperature. High-performance liquid chromatography with diode array detection was established using a C18 column with a water/acetonitrile gradient system at a flow rate of 1.0 mL/min, and the detection wavelength was set at 236 nm. Liquid chromatography with tandem mass spectrometry was applied to certify the reliability of the quantitative results. The developed methods were validated by ensuring specificity, linearity, limit of quantification, accuracy, precision, recovery, robustness, and stability. Results showed that cangzhu contained higher amounts of atractylenolide I and atractylodin than baizhu, and especially atractylodin contents showed the greatest variation between baizhu and cangzhu. Multivariate statistical analysis, such as principal component analysis and hierarchical cluster analysis, were also employed for further classification of the Atractylodes plants. The established method was suitable for quality control of the Atractylodes plants. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous detection of xenon and krypton in equine plasma by gas chromatography-tandem mass spectrometry for doping control.

PubMed

Kwok, Wai Him; Choi, Timmy L S; So, Pui-Kin; Yao, Zhong-Ping; Wan, Terence S M

2017-02-01

Xenon can activate the hypoxia-inducible factors (HIFs). As such, it has been allegedly used in human sports for increasing erythropoiesis. Krypton, another noble gas with reported narcosis effect, can also be expected to be a potential and less expensive erythropoiesis stimulating agent. This has raised concern about the misuse of noble gases as doping agents in equine sports. The aim of the present study is to establish a method for the simultaneous detection of xenon and krypton in equine plasma for the purpose of doping control. Xenon- or krypton-fortified equine plasma samples were prepared according to reported protocols. The target noble gases were simultaneously detected by gas chromatography-triple quadrupole mass spectrometry using headspace injection. Three xenon isotopes at m/z 129, 131, and 132, and four krypton isotopes at m/z 82, 83, 84, and 86 were targeted in selected reaction monitoring mode (with the precursor ions and product ions at identical mass settings), allowing unambiguous identification of the target analytes. Limits of detection for xenon and krypton were about 19 pmol/mL and 98 pmol/mL, respectively. Precision for both analytes was less than 15%. The method has good specificity as background analyte signals were not observed in negative equine plasma samples (n = 73). Loss of analytes under different storage temperatures has also been evaluated. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Relations between stellar mass and electron temperature-based metallicity for star-forming galaxies in a wide mass range

NASA Astrophysics Data System (ADS)

Shi, Wei-Bin; Liang, Yan-Chun; Shao, Xu; Liu, Xiao-Wei; Zhao, Gang; Hammer, Francois; Zhang, Yong; Flores, Hector; Ruan, Gui-Ping; Zhou, Li

2014-07-01

We select 947 star-forming galaxies from SDSS-DR7 with [O III]λ4363 emission lines detected at a signal-to-noise ratio larger than 5σ. Their electron temperatures and direct oxygen abundances are then determined. We compare the results from different methods. t2, the electron temperature in the low ionization region, estimated from t3, that in the high ionization region, is compared using three analysis relations between t2 - t3. These show obvious differences, which result in some different ionic oxygen abundances. The results of t3, t2, O++/H+ and O+/H+ derived by using methods from IRAF and literature are also compared. The ionic abundances O++/H+ are higher than O+/H+ for most cases. The different oxygen abundances derived from Te and the strong-line ratios show a clear discrepancy, which is more obvious following increasing stellar mass and strong-line ratio R23. The sample of galaxies from SDSS with detected [O III]λ4363 have lower metallicites and higher star formation rates, so they may not be typical representatives of the whole population of galaxies. Adopting data objects from Andrews & Martini, Liang et al. and Lee et al. data, we derive new relations of stellar mass and metallicity for star-forming galaxies in a much wider stellar mass range: from 106 Msolar to 1011 Msolar.

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish.

PubMed

Alaee, M; Sergeant, D B; Ikonomou, M G; Luross, J M

2001-09-01

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.

Enzymatic digestion and selective quantification of underivatised delta-9-tetrahydrocannabinol and cocaine in human hair using gas chromatography-mass spectrometry.

PubMed

Breidi, Salah Eddine; Barker, James; Petróczi, Andrea; Naughton, Declan P

2012-01-01

Gas chromatography-mass spectrometric (GC-MS) methods for drug analysis routinely employ derivatising reagents. The aim of this paper was to develop a method for the analysis of two recreational drugs, delta-9-tetrahydrocannabinol (Δ(9)-THC) and cocaine in hair samples using GC-MS, without prior derivatisation, thus allowing the sample to be reanalysed in its original form. An enzymatic digestion technique was also developed. Ten hair samples, that were known positive for either Δ(9)-THC and/or cocaine, were enzymatically digested, extracted, and then analysed by GC-MS. All samples measured contained Δ(9)-THC and one sample contained cocaine. The limits of detection (LOD) and quantification (LOQ) were 0.02 ng/mg and 0.05 ng/mg, respectively, for cocaine and 0.015 ng/mg and 0.02 ng/mg, respectively, for Δ(9)-THC. The wide detection window, ease of direct analysis by GC-MS, lower detection limits of underivatised samples, and the stability of drugs using this technique may offer an improved method of analysis.

Enzymatic Digestion and Selective Quantification of Underivatised Delta-9-Tetrahydrocannabinol and Cocaine in Human Hair Using Gas Chromatography-Mass Spectrometry

PubMed Central

Breidi, Salah Eddine; Barker, James; Petróczi, Andrea; Naughton, Declan P.

2012-01-01

Gas chromatography-mass spectrometric (GC-MS) methods for drug analysis routinely employ derivatising reagents. The aim of this paper was to develop a method for the analysis of two recreational drugs, delta-9-tetrahydrocannabinol (Δ9-THC) and cocaine in hair samples using GC-MS, without prior derivatisation, thus allowing the sample to be reanalysed in its original form. An enzymatic digestion technique was also developed. Ten hair samples, that were known positive for either Δ9-THC and/or cocaine, were enzymatically digested, extracted, and then analysed by GC-MS. All samples measured contained Δ9-THC and one sample contained cocaine. The limits of detection (LOD) and quantification (LOQ) were 0.02 ng/mg and 0.05 ng/mg, respectively, for cocaine and 0.015 ng/mg and 0.02 ng/mg, respectively, for Δ9-THC. The wide detection window, ease of direct analysis by GC-MS, lower detection limits of underivatised samples, and the stability of drugs using this technique may offer an improved method of analysis. PMID:22567573

Simple determination of fluoride in biological samples by headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry.

PubMed

Kwon, Sun-Myung; Shin, Ho-Sang

2015-08-14

A simple and convenient method to detect fluoride in biological samples was developed. This method was based on derivatization with 2-(bromomethyl)naphthalene, headspace solid phase microextraction (HS-SPME) in a vial, and gas chromatography-tandem mass spectrometric detection. The HS-SPME parameters were optimized as follows: selection of CAR/PDMS fiber, 0.5% 2-(bromomethyl)naphthalene, 250 mg/L 15-crown-5-ether as a phase transfer catalyst, extraction and derivatization temperature of 95 °C, heating time of 20 min and pH of 7.0. Under the established conditions, the lowest limits of detection were 9 and 11 μg/L in 1.0 ml of plasma and urine, respectively, and the intra- and inter-day relative standard deviation was less than 7.7% at concentrations of 0.1 and 1.0 mg/L. The calibration curve showed good linearity of plasma and urine with r=0.9990 and r=0.9992, respectively. This method is simple, amenable to automation and environmentally friendly. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of benzothiazole and benzotriazole derivates in tire and clothing textile samples by high performance liquid chromatography-electrospray ionization tandem mass spectrometry.

PubMed

Avagyan, Rozanna; Sadiktsis, Ioannis; Thorsén, Gunnar; Östman, Conny; Westerholm, Roger

2013-09-13

A high performance liquid chromatography-tandem mass spectrometry method utilizing electrospray ionization in positive and negative mode has been developed for the separation and detection of benzothiazole and benzotriazole derivates. Ultra-sonication assisted solvent extraction of these compounds has also been developed and the overall method demonstrated on a selected clothing textile and an automobile tire sample. Matrix effects and extraction recoveries, as well as linearity and limits of detection have been evaluated. The calibration curves spanned over more than two orders of magnitude with coefficients of correlation R(2)>0.99 and the limits of detection and the limits of quantification were in the range 1.7-58pg injected and 18-140pg/g, respectively. The extraction recoveries ranged between 69% and 102% and the matrix effects between 75% and 101%. Benzothiazole and benzotriazole derivates were determined in the textile sample and benzothiazole derivatives determined in the tire sample with good analytical performance. Copyright © 2013 Elsevier B.V. All rights reserved.

Piezoelectric microelectromechanical resonant sensors for chemical and biological detection.

PubMed

Pang, Wei; Zhao, Hongyuan; Kim, Eun Sok; Zhang, Hao; Yu, Hongyu; Hu, Xiaotang

2012-01-07

Piezoelectric microelectromechanical systems (MEMS) resonant sensors, known for their excellent mass resolution, have been studied for many applications, including DNA hybridization, protein-ligand interactions, and immunosensor development. They have also been explored for detecting antigens, organic gas, toxic ions, and explosives. Most piezoelectric MEMS resonant sensors are acoustic sensors (with specific coating layers) that enable selective and label-free detection of biological events in real time. These label-free technologies have recently garnered significant attention for their sensitive and quantitative multi-parameter analysis of biological systems. Since piezoelectric MEMS resonant sensors do more than transform analyte mass or thickness into an electrical signal (e.g., frequency and impedance), special attention must be paid to their potential beyond microweighing, such as measuring elastic and viscous properties, and several types of sensors currently under development operate at different resonant modes (i.e., thickness extensional mode, thickness shear mode, lateral extensional mode, flexural mode, etc.). In this review, we provide an overview of recent developments in micromachined resonant sensors and activities relating to biochemical interfaces for acoustic sensors.

Rapid determination of phenolic compounds and alkaloids of carob flour by improved liquid chromatography tandem mass spectrometry.

PubMed

Ortega, Nàdia; Macià, Alba; Romero, Maria-Paz; Trullols, Esther; Morello, Jose-Ramón; Anglès, Neus; Motilva, Maria-Jose

2009-08-26

An improved chromatographic method was developed using ultra-performance liquid chromatography-tandem mass spectrometry to identify and quantify phenolic compounds and alkaloids, theobromine and caffeine, in carob flour samples. The developed method has been validated in terms of speed, sensitivity, selectivity, peak efficiency, linearity, reproducibility, limits of detection, and limits of quantification. The chromatographic method allows the identification and quantification of 20 phenolic compounds, that is, phenolic acids, flavonoids, and their aglycone and glucoside forms, together with the determination of the alkaloids, caffeine and theobromine, at low concentration levels all in a short analysis time of less than 20 min.

Clinical applications of gas chromatograph/mass spectrometer/computer systems.

PubMed

Horning, M G; Nowlin, J; Butler, C M; Lertratanangkoon, K; Sommer, K; Hill, R M

1975-08-01

Gas chromatograph/mass spectrometer/computer systems can be used to quantify a wide variety of compounds of clinical interest. A quadrupole instrument operated in the chemical ionization (Cl) mode was used in these studies. Because of the sensitivity and specificity of selective ion detection, it is possible to make measurements routinely in the nanogram to picogram range, with 0.1-1.0 ml samples of plasma and 1-5 ml samples or urine. Internal standards, preferably stable-isotope-labeled compounds, were added to the biological samples before isolation was begun. We describe clinical applications of these procedures to problems in toxicology, pharmacokinetics, and perinatal pharmacology.

Black Hole growth and star formation activity in the CDFS

NASA Astrophysics Data System (ADS)

Brusa, Marcella; Fiore, Fabrizio

2010-07-01

We present a study of the properties of obscured Active Galactic Nuclei (AGN) detected in the CDFS 1Ms observation and their host galaxies. We limited the analysis to the MUSIC area, for which deep K-band observations obtained with ISAACatVLT are available, ensuring accurate identifications of the counterparts of the X-ray sources as well as reliable determination of photometric redshifts and galaxy parameters, such as stellar masses and star formation rates. Among other findings, we found that the X-ray selected AGN fraction increases with the stellar mass up to a value of 30% at z>1 and M*>3×1011 M.

Measuring the hydrostatic mass bias in galaxy clusters by combining Sunyaev-Zel'dovich and CMB lensing data

NASA Astrophysics Data System (ADS)

Hurier, G.; Angulo, R. E.

2018-02-01

The cosmological parameters preferred by the cosmic microwave background (CMB) primary anisotropies predict many more galaxy clusters than those that have been detected via the thermal Sunyaev-Zeldovich (tSZ) effect. This discrepancy has attracted considerable attention since it might be evidence of physics beyond the simplest ΛCDM model. However, an accurate and robust calibration of the mass-observable relation for clusters is necessary for the comparison, which has been proven difficult to obtain so far. Here, we present new constraints on the mass-pressure relation by combining tSZ and CMB lensing measurements of optically selected clusters. Consequently, our galaxy cluster sample is independent of the data employed to derive cosmological constrains. We estimate an average hydrostatic mass bias of b = 0.26 ± 0.07, with no significant mass or redshift evolution. This value greatly reduces the discrepancy between the predictions of ΛCDM and the observed abundance of tSZ clusters but agrees with recent estimates from tSZ clustering. On the other hand, our value for b is higher than the predictions from hydrodynamical simulations. This suggests mechanisms that drive large departures from hydrostatic equilibrium and that are not included in the latest simulations, and/or unaccounted systematic errors such as biases in the cluster catalogue that are due to the optical selection.

The Investigation of Chlorates as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Archer, D. P.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P; Stern, J. C.;

1.25-mm observations of luminous infrared galaxies

NASA Technical Reports Server (NTRS)

Carico, David P.; Keene, Jocelyn; Soifer, B. T.; Neugebauer, G.

1992-01-01

Measurements at a wavelength of 1.25 mm have been obtained for 17 IRAS galaxies selected on the basis of high far-infrared luminosity. These measurements are used to estimate the lower and upper limits to the mass of cold dust in infrared galaxies. As a lower limit on dust mass, all of the galaxies can be successfully modeled without invoking any dust colder than the dust responsible for the 60 and 100 micron emission that was detected by IRAS. As an upper limit, it is possible that the dust mass in a number of the galaxies may actually be dominated by cold dust. This large difference between the lower and upper limits is due primarily to uncertainty in the long-wavelength absorption efficiency of the astrophysical dust grains.

Cost-effective binomial sequential sampling of western bean cutworm, Striacosta albicosta (Lepidoptera: Noctuidae), egg masses in corn.

PubMed

Paula-Moraes, S; Burkness, E C; Hunt, T E; Wright, R J; Hein, G L; Hutchison, W D

2011-12-01

Striacosta albicosta (Smith) (Lepidoptera: Noctuidae), is a native pest of dry beans (Phaseolus vulgaris L.) and corn (Zea mays L.). As a result of larval feeding damage on corn ears, S. albicosta has a narrow treatment window; thus, early detection of the pest in the field is essential, and egg mass sampling has become a popular monitoring tool. Three action thresholds for field and sweet corn currently are used by crop consultants, including 4% of plants infested with egg masses on sweet corn in the silking-tasseling stage, 8% of plants infested with egg masses on field corn with approximately 95% tasseled, and 20% of plants infested with egg masses on field corn during mid-milk-stage corn. The current monitoring recommendation is to sample 20 plants at each of five locations per field (100 plants total). In an effort to develop a more cost-effective sampling plan for S. albicosta egg masses, several alternative binomial sampling plans were developed using Wald's sequential probability ratio test, and validated using Resampling for Validation of Sampling Plans (RVSP) software. The benefit-cost ratio also was calculated and used to determine the final selection of sampling plans. Based on final sampling plans selected for each action threshold, the average sample number required to reach a treat or no-treat decision ranged from 38 to 41 plants per field. This represents a significant savings in sampling cost over the current recommendation of 100 plants.