Application of phase correction to improve the interpretation of crude oil spectra obtained using 7 T Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Cho, Yunju; Qi, Yulin; O'Connor, Peter B; Barrow, Mark P; Kim, Sunghwan

2014-01-01

In this study, a phase-correction technique was applied to the study of crude oil spectra obtained using a 7 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). 7 T FT-ICR MS had not been widely used for oil analysis due to the lower resolving power compared with high field FT-ICR MS. For low field instruments, usage of data that has not been phase-corrected results in an inability to resolve critical mass splits of C3 and SH4 (3.4 mDa), and (13)C and CH (4.5 mDa). This results in incorrect assignments of molecular formulae, and discontinuous double bond equivalents (DBE) and carbon number distributions of S1, S2, and hydrocarbon classes are obtained. Application of phase correction to the same data, however, improves the reliability of assignments and produces continuous DBE and carbon number distributions. Therefore, this study clearly demonstrates that phase correction improves data analysis and the reliability of assignments of molecular formulae in crude oil anlayses.

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

PubMed

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

2005-06-01

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

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

NASA Astrophysics Data System (ADS)

McKenna, Amy

2013-03-01

The depletion of terrestrial global oil reserves has shifted oil exploration into offshore and ultra-deep water (> 5000 ft) oil reserves to meet global energy demands. Deep water reservoirs are currently in production in many parts of the world, including the Gulf of Mexico, but production is complicated by the water depth and thick salt caps that challenge reservoir characterization / production. The explosion aboard the Deepwater Horizon in April 2010 resulted in an estimated total release of ~5 million barrels (BP claims that they collected ~1M barrels, for a net release of 4 M) of light, sweet crude oil into the Gulf of Mexico and shifted attention toward the environmental risks associated with offshore oil production. The growing emphasis on deep water and ultra-deep water oil production poses a significant environmental threat, and increased regulations require that oil companies minimize environmental impact to prevent oil spills, and mitigate environmental damage when spills occur. Every oil spill is unique. The molecular transformations that occur to petroleum after contact with seawater depend on the physical and chemical properties of the spilled oil, environmental conditions, and deposition environment. Molecular-level knowledge of the composition, distribution, and total mass of released hydrocarbons is essential to disentangle photo- and bio-degradation, source identification, and long-term environmental impact of hydrocarbons released into the environment. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is unsurpassed in its ability to characterize complex mixtures at the level of elemental composition assignment. Only FT-ICR mass spectrometry can routinely achieve the required minimum resolving power necessary to elucidate molecular-level characterization of crude oil. Conversely, the spectral complexity of petroleum facilitates identification of systematic errors in the accumulation, transfer, excitation, and detection events in the FT-ICR experiment. For example, the high density of peaks at each nominal mass unit provides unprecedented insight into how excitation conditions affect ion motion during detection. Aggregated oil (i.e., tar balls, tar mats) that reached the surface exhibits a more than two-fold increase in the total number of detected species, with an increased number of oxygenated species. Principal component analysis (PCA) applied to two possible source oils (contained within the same ship) and weathered samples provide the first application of FT-ICR MS for source identification. Molecular formulae from parent and weathered oil indicate that the lightest petroleum fractions (saturated hydrocarbons) are the most readily oxidized components, and can serve as a template to determine chemical transformations that occur throughout the water column. The ability to differentiate and catalogue compositional changes that occur to oil after its release into the environment relies heavily on gains achieved in nearly all steps in the FT-ICR mass spectral experiment required to accommodate larger ion populations inherent to heavily weathered crude oil. Here, we present the requirement for FT-ICR MS for comprehensive oil spill characterization, and highlight advances made to FT-ICR MS experimental conditions developed from petroleum characterization. Work supported by DMR-06-54118, NSF CHE-10-49753 (RAPID), BP/The Gulf of Mexico Research Initiative, and the State of Florida

Analysis of Monoclonal Antibodies in Human Serum as a Model for Clinical Monoclonal Gammopathy by Use of 21 Tesla FT-ICR Top-Down and Middle-Down MS/MS

NASA Astrophysics Data System (ADS)

He, Lidong; Anderson, Lissa C.; Barnidge, David R.; Murray, David L.; Hendrickson, Christopher L.; Marshall, Alan G.

2017-05-01

With the rapid growth of therapeutic monoclonal antibodies (mAbs), stringent quality control is needed to ensure clinical safety and efficacy. Monoclonal antibody primary sequence and post-translational modifications (PTM) are conventionally analyzed with labor-intensive, bottom-up tandem mass spectrometry (MS/MS), which is limited by incomplete peptide sequence coverage and introduction of artifacts during the lengthy analysis procedure. Here, we describe top-down and middle-down approaches with the advantages of fast sample preparation with minimal artifacts, ultrahigh mass accuracy, and extensive residue cleavages by use of 21 tesla FT-ICR MS/MS. The ultrahigh mass accuracy yields an RMS error of 0.2-0.4 ppm for antibody light chain, heavy chain, heavy chain Fc/2, and Fd subunits. The corresponding sequence coverages are 81%, 38%, 72%, and 65% with MS/MS RMS error 4 ppm. Extension to a monoclonal antibody in human serum as a monoclonal gammopathy model yielded 53% sequence coverage from two nano-LC MS/MS runs. A blind analysis of five therapeutic monoclonal antibodies at clinically relevant concentrations in human serum resulted in correct identification of all five antibodies. Nano-LC 21 T FT-ICR MS/MS provides nonpareil mass resolution, mass accuracy, and sequence coverage for mAbs, and sets a benchmark for MS/MS analysis of multiple mAbs in serum. This is the first time that extensive cleavages for both variable and constant regions have been achieved for mAbs in a human serum background.

Vacuum compatible sample positioning device for matrix assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry imaging

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

Aizikov, Konstantin; Lin, Tzu-Yung; Department of Electrical and Computer Engineering, Boston University, Boston, Massachusetts 02215

The high mass accuracy and resolving power of Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS) make them ideal mass detectors for mass spectrometry imaging (MSI), promising to provide unmatched molecular resolution capabilities. The intrinsic low tolerance of FT-ICR MS to RF interference, however, along with typically vertical positioning of the sample, and MSI acquisition speed requirements present numerous engineering challenges in creating robotics capable of achieving the spatial resolution to match. This work discusses a two-dimensional positioning stage designed to address these issues. The stage is capable of operating in {approx}1 x 10{sup -8} mbar vacuum. The rangemore » of motion is set to 100 mm x 100 mm to accommodate large samples, while the positioning accuracy is demonstrated to be less than 0.4 micron in both directions under vertical load over the entire range. This device was integrated into three different matrix assisted laser desorption/ionization (MALDI) FT-ICR instruments and showed no detectable RF noise. The ''oversampling'' MALDI-MSI experiments, under which the sample is completely ablated at each position, followed by the target movement of the distance smaller than the laser beam, conducted on the custom-built 7T FT-ICR MS demonstrate the stability and positional accuracy of the stage robotics which delivers high spatial resolution mass spectral images at a fraction of the laser spot diameter.« less

Probing the Mechanisms of an Air Amplifier using a LTQ-FT-ICR-MS and Fluorescence Spectroscopy

PubMed Central

Dixon, R. Brent; Muddiman, David C.; Hawkridge, Adam M.; Fedorov, A. G.

2008-01-01

We report the first quantitative assessment of electrosprayed droplet/ion focusing enabled by the use of a voltage-assisted air amplifier between an electrospray ionization emitter and a hybrid linear ion trap Fourier transform ion cyclotron resonance mass spectrometer (ESI-LTQ-FT-ICR-MS). A solution of fluorescent dye was electrosprayed with a stainless steel mesh screen placed in front of the MS inlet capillary acting as a gas-permeable imaging plate for fluorescence spectroscopy. Without use of the air amplifier no detectable FT-ICR signal was observed, as well as no detectable fluorescence on the screen upon imaging using a fluorescence scanner. When the air amplifier was turned ON while electrospraying the fluorescent dye, FT-ICR mass spectra with high signal to noise ratio were obtained with an average ion injection time of 21 milliseconds for an AGC target value of 5 × 105. Imaging of the screen using a fluorescence scanner produced a distinct spot of cross-sectional area ~33.5 mm2 in front of the MS inlet capillary. These experimental results provide direct evidence of aerodynamic focusing of electrosprayed droplets/ions enabled by an air amplifier, resulting in improved electrospray droplet/ion capture efficiency and reduced ion injection time. A second set of experiments was carried out to explore whether the air amplifier assists in desolvation. By electrospraying a mix of quaternary amines, ratios of increasingly hydrophobic molecules were obtained. Observation of the solvophobic effect associated with electrospray ionization resulted in a higher abundance of the hydrophobic molecule. This bias was eliminated when the air amplifier was turned ON and a response indicative of the respective component concentrations of the molecules in the bulk solution was observed. PMID:17855111

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Top-down mass spectrometry imaging of intact proteins by laser ablation ESI FT-ICR MS.

PubMed

Kiss, András; Smith, Donald F; Reschke, Brent R; Powell, Matthew J; Heeren, Ron M A

2014-05-01

Laser ablation ESI (LAESI) is a recent development in MS imaging. It has been shown that lipids and small metabolites can be imaged in various samples such as plant material, tissue sections or bacterial colonies without any sample pretreatment. Further, LAESI has been shown to produce multiply charged protein ions from liquids or solid surfaces. This presents a means to address one of the biggest challenges in MS imaging; the identification of proteins directly from biological tissue surfaces. Such identification is hindered by the lack of multiply charged proteins in common MALDI ion sources and the difficulty of performing tandem MS on such large, singly charged ions. We present here top-down identification of intact proteins from tissue with a LAESI ion source combined with a hybrid ion-trap FT-ICR mass spectrometer. The performance of the system was first tested with a standard protein with electron capture dissociation and infrared multiphoton dissociation fragmentation to prove the viability of LAESI FT-ICR for top-down proteomics. Finally, the imaging of a tissue section was performed, where a number of intact proteins were measured and the hemoglobin α chain was identified directly from tissue using CID and infrared multiphoton dissociation fragmentation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metabolite profiling and fingerprinting of Suillus species (Basidiomycetes) by electrospray mass spectrometry.

PubMed

Heinke, Ramona; Schöne, Pia; Arnold, Norbert; Wessjohann, Ludger; Schmidt, Jürgen; Schmidt, Jürgen

2014-01-01

The genus Suillus is known for the occurrence of a series of prenylated phenols and boviquinones. The extracts of four different Suillus species [S. bovinus, S. granulatus, S. tridentinus and S.variegatus) were investigated by using rapid ultra-performance Liquid chromatography/electrospray ionization mass spectrometry (UPLC/ESI-MS) and direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). While direct infusion ESI-FT-ICR mass spectra give a fast overview concerning the elemental compositions of the compounds and, therefore, hints to the main metabolites, UPLC/ESI-tandem mass spectrometry is shown to be a useful tool for their identification. A principal component analysis (PCA) and hierarchical cluster analysis (HCA) based on the UPLC/ESI-MS clearly showed that the metabolite profiles can be used not only for the identification and classification of such fungi but also as a sophisticated and powerful tool for the chemotaxonomy of fungi. Furthermore, a clear discrimination of various types of biological samples (fruiting bodies versus mycelial cultures) is also possible. The orthogonal partial least squares (OPLS) two-class models of both UPLC/ESI-MS and ESI-FT-ICR-MS possess a clear differentiation of two compared Suillus species representing the between class variation and the within class variation. Based on generated S-plots and Loading plots, statistically significant metabolites could be identified as potential biomarker for one species.

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

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

Sudasinghe, Nilusha; Cort, John R.; Hallen, Richard

2014-12-01

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

Evaluating Changes in the Molecular Composition and Optical Properties of Pacific Ocean Dissolved Organic Matter (DOM) caused by Borodeuteride Reduction

NASA Astrophysics Data System (ADS)

Bianca, M.; Blough, N. V.; Del Vecchio, R.; Cartisano, C. M.; Schmitt-Kopplin, P.; Gonsior, M.

2016-02-01

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) is a powerful tool to obtain detailed molecular information for complex DOM and was combined in this study with optical measurements to determine the molecular fingerprint of Pacific Ocean DOM before and after borodeuteride reduction. Selective chemical reductions, using sodium borodeuteride, has been previously demonstrated to produce unique mass markers of ketone and aldehyde-containing species in ultrahigh resolution mass spectrometry. These functional groups have also been proposed to be responsible for chromophoric dissolved organic matter (CDOM) long wavelength optical properties through charge transfer interactions and their chemical reduction has shown to irreversibly alter the CDOM optical properties. ESI-FT-ICR MS coupled with borodeuteride reduction was thus applied to reference material, Suwannee River Fulvic Acid (SRFA), and CDOM extracts collected from Station ALOHA, in the North Pacific Ocean during December 2014. Results showed distinct differences between samples collected at different depths, indicating that the combination of FT-ICR-MS with borodeuteride reduction is a useful analytical tool to further understand marine DOM molecular composition. When this method is combined with optical measurements, specific insights into the CDOM composition can also be obtained.

Tracking changes in the optical properties and molecular composition of dissolved organic matter during drinking water production.

PubMed

Lavonen, E E; Kothawala, D N; Tranvik, L J; Gonsior, M; Schmitt-Kopplin, P; Köhler, S J

2015-11-15

Absorbance, 3D fluorescence and ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were used to explain patterns in the removal of chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) at the molecular level during drinking water production at four large drinking water treatment plants in Sweden. When dissolved organic carbon (DOC) removal was low, shifts in the dissolved organic matter (DOM) composition could not be detected with commonly used DOC-normalized parameters (e.g. specific UV254 absorbance - SUVA), but was clearly observed by using differential absorbance and fluorescence or ESI-FT-ICR-MS. In addition, we took a novel approach by identifying how optical parameters were correlated to the elemental composition of DOM by using rank correlation to connect optical properties to chemical formulas assigned to mass peaks from FT-ICR-MS analyses. Coagulation treatment selectively removed FDOM at longer emission wavelengths (450-600 nm), which significantly correlated with chemical formulas containing oxidized carbon (average carbon oxidation state ≥ 0), low hydrogen to carbon ratios (H/C: average ± SD = 0.83 ± 0.13), and abundant oxygen-containing functional groups (O/C = 0.62 ± 0.10). Slow sand filtration was less efficient in removing DOM, yet selectively targeted FDOM at shorter emission wavelengths (between 300 and 450 nm), which commonly represents algal rather than terrestrial sources. This shorter wavelength FDOM correlated with chemical formulas containing reduced carbon (average carbon oxidation state ≤ 0), with relatively few carbon-carbon double bonds (H/C = 1.32 ± 0.16) and less oxygen per carbon (O/C = 0.43 ± 0.10) than those removed during coagulation. By coupling optical approaches with FT-ICR-MS to characterize DOM, we were for the first time able to confirm the molecular composition of absorbing and fluorescing DOM selectively targeted during drinking water treatment. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS.

PubMed

Benigni, Paolo; Marin, Rebecca; Sandoval, Kathia; Gardinali, Piero; Fernandez-Lima, Francisco

2017-03-03

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry-Fourier transform-ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

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

Smith, Donald F.; Schulz, Carl; Konijnenburg, Marco

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

Structural characterization of arginine-vasopressin and lysine-vasopressin by Fourier- transform ion cyclotron resonance mass spectrometry and infrared multiphoton dissociation.

PubMed

Bianco, Giuliana; Battista, Fabio; Buchicchio, Alessandro; Amarena, Concetta G; Schmitt-Kopplin, Philippe; Guerrieri, Antonio

2015-01-01

Arginine-vasopressin (AVP) and lysine-vasopressin (LVP) were analyzed by reversed-phase liquid chromatography/mass spectrometry (LC-MS) using Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) electrospray ionization (ESI) in the positive ion mode. LVP and AVP exhibited the protonated adduct [M+H](+) as the predominant ion at m/z 1056.43965 and at m/z 1084.44561, respectively. Infrared multiphoton dissociation (IRMPD), using a CO(2) laser source at a wavelength of 10.6 μm, was applied to protonated vasopressin molecules. The IRMPD mass spectra presented abundant mass fragments essential for a complete structural information. Several fragment ions, shared between two target molecules, are discussed in detail. Some previously unpublished fragments were identified unambiguously utilizing the high resolution and accurate mass information provided by the FT-ICR mass spectrometer. The opening of the disulfide loop and the cleavage of the peptide bonds within the ring were observed even under low-energy fragmentation conditions. Coupling the high-performance FT-ICR mass spectrometer with IRMPD as a contemporary fragmentation technique proved to be very promising for the structural characterization of vasopressin.

Molecular characterization and comparison of shale oils generated by different pyrolysis methods

USGS Publications Warehouse

Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

2012-01-01

Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

Evidence for electron-based ion generation in radio-frequency ionization.

PubMed

Olaitan, Abayomi D; Zekavat, Behrooz; Solouki, Touradj

2016-01-01

Radio-frequency ionization (RFI) is a novel ionization method coupled to mass spectrometry (MS) for analysis of semi-volatile and volatile organic compounds (VOCs). Despite the demonstrated capabilities of RFI MS for VOC analysis in both positive- and negative-ion modes, mechanism of RFI is not completely understood. Improved understanding of the ion generation process in RFI should expand its utility in MS. Here, we studied the possibility of electron emission in RFI using both direct charged particle current measurements and indirect electron detection in a 9.4-T Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. We show that RF-generated electrons can be trapped in the ICR cell and, subsequently, reacted with neutral hexafluorobenzene (C6 F6 ) molecules to generate C6 F6 (●-) . Intensity of observed C6 F6 (●-) species correlated with the number of trapped electrons and decreased as a function of electron quenching period. We also measured the electron attachment rate constant of hexafluorobenzene using a post-RF electron trapping experiment. Measured electron attachment rate constant of hexafluorobenzene (1.19 (±0.53) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) for post-RF FT-ICR MS agreed with the previously reported value (1.60 (±0.30) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) from low-pressure ICR MS measurements. Experimental results from direct and indirect electron measurements suggest that RFI process involves RF-generated electrons under ultrahigh vacuum conditions. Copyright © 2015 John Wiley & Sons, Ltd.

Usage of FT-ICR-MS Metabolomics for Characterizing the Chemical Signatures of Barrel-Aged Whisky

PubMed Central

Roullier-Gall, Chloé; Signoret, Julie; Hemmler, Daniel; Witting, Michael A.; Kanawati, Basem; Schäfer, Bernhard; Gougeon, Régis D.; Schmitt-Kopplin, Philippe

2018-01-01

Whisky can be described as a complex matrix integrating the chemical history from the fermented cereals, the wooden barrels, the specific distillery processes, aging, and environmental factors. In this study, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS), we analyzed 150 whisky samples from 49 different distilleries, 7 countries, and ranging from 1 day new make spirit to 43 years of maturation with different types of barrel. Chemometrics revealed the unexpected impact of the wood history on the distillate's composition during barrel aging, regardless of the whisky origin. Flavonols, oligolignols, and fatty acids are examples of important chemical signatures for Bourbon casks, whereas a high number of polyphenol glycosides, including for instance quercetin-glucuronide or myricetin-glucoside as potential candidates, and carbohydrates would discriminate Sherry casks. However, the comparison of barrel aged rums and whiskies revealed specific signatures, highlighting the importance of the initial composition of the distillate and the distillery processes. PMID:29520358

Usage of FT-ICR-MS Metabolomics for characterizing the chemical signatures of barrel-aged whisky

NASA Astrophysics Data System (ADS)

Roullier-Gall, Chloé; Signoret, Julie; Hemmler, Daniel; Witting, Michael A.; Kanawati, Basem; Schäfer, Bernhard; Gougeon, Régis D.; Schmitt-Kopplin, Philippe

2018-02-01

Whisky can be described as a complex matrix integrating the chemical history from the fermented cereals, the wooden barrels, the specific distillery processes, ageing and environmental factors. In this study, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS), we analysed 150 whisky samples from 49 different distilleries, 7 countries, and ranging from 1 day new make spirit to 43 years of maturation with different types of barrel. Chemometrics revealed the unexpected impact of the wood history on the distillatés composition during barrel ageing, regardless of the whisky origin. Flavonols, oligolignols and fatty acids are examples of important chemical signatures for Bourbon casks, whereas a high number of polyphenol glycosides, including for instance quercetin-glucuronide or myricetin-glucoside as potential candidates, and carbohydrates would discriminate Sherry casks. However, the comparison of barrel aged rums and whiskies revealed specific signatures, highlighting the importance of the initial composition of the distillate and the distillery processes.

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

Glycoproteomics of cerebrospinal fluid in neurodegenerative disease

NASA Astrophysics Data System (ADS)

Sihlbom, Carina; Davidsson, Pia; Emmett, Mark R.; Marshall, Alan G.; Nilsson, Carol L.

2004-05-01

Cerebrospinal fluid (CSF) from individual patients with Alzheimer's disease (AD) was separated by narrow range two-dimensional (2D) gel electrophoresis and analyzed by electrospray FT-ICR MS in this glycoproteomic study. Because several altered proteins in the comparison between AD patients and healthy controls individuals are isoforms of glycoproteins, it is important to determine if the modifying glycans are also altered. FT-ICR MS and fragmentation of glycopeptides with infrared multiphoton dissociation (IRMPD) offers abundant fragment ions through breakage at the glycosidic linkages with excellent mass accuracy, which facilitates the structural determination of the site-specific N-linked glycosylation. We present results from a structural comparison of proteins from three AD patients and three control individuals of different glycosylated isomers of [alpha]-1-antitrypsin, [beta]-trace and apolipoprotein J.

Application of Printed Circuit Board Technology to FT-ICR MS Analyzer Cell Construction and Prototyping

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

Leach, Franklin E.; Norheim, Randolph V.; Anderson, Gordon A.

Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS) remains themass spectrometry platform that provides the highest levels of performance for mass accuracy and resolving power, there is room for improvement in analyzer cell design as the ideal quadrupolar trapping potential has yet to be generated for a broadband MS experiment. To this end, analyzer cell designs have improved since the field’s inception, yet few research groups participate in this area because of the high cost of instrumentation efforts. As a step towards reducing this barrier to participation and allowing for more designs to be physically tested, we introduce amore » method of FT-ICR analyzer cell prototyping utilizing printed circuit boards at modest vacuum conditions. This method allows for inexpensive devices to be readily fabricated and tested over short intervals and should open the field to laboratories lacking or unable to access high performance machine shop facilities because of the required financial investment.« less

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer.

PubMed

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D; Wolff, Jeremy J; Somogyi, Árpád; Pedder, Randall E; Quintyn, Royston S; Morrison, Lindsay J; Easterling, Michael L; Paša-Tolić, Ljiljana; Wysocki, Vicki H

2017-01-03

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.

Chemical profile of pineapple cv. Vitória in different maturation stages using electrospray ionization mass spectrometry.

PubMed

Ogawa, Elizângela M; Costa, Helber B; Ventura, José A; Caetano, Luiz Cs; Pinto, Fernanda E; Oliveira, Bruno G; Barroso, Maria Eduarda S; Scherer, Rodrigo; Endringer, Denise C; Romão, Wanderson

2018-02-01

Pineapple is the fruit of Ananas comosus var. comosus plant, being cultivated in tropical areas and has high energy content and nutritional value. Herein, 30 samples of pineapple cv. Vitória were analyzed as a function of the maturation stage (0-5) and their physico-chemical parameters monitored. In addition, negative-ion mode electrospray ionization mass spectrometry [ESI(-)FT-ICR MS] was used to identify and semi-quantify primary and secondary metabolites present in the crude and phenolic extracts of pineapple, respectively. Physico-chemical tests show an increase in the total soluble solids (TSS) values and in the TSS/total titratable acidity ratio as a function of the maturity stage, where a maximum value was observed in stage 3 (¾ of the fruit is yellow, which corresponds to the color of the fruit peel). ESI(-)FT-ICR MS analysis for crude extracts showed the presence mainly of sugars as primary metabolites present in deprotonated molecule form ([M - H] - and [2 M - H] - ions) whereas, for phenolic fractions, 11 compounds were detected, being the most abundant in the third stage of maturation. This behavior was confirmed by quantitative analysis of total polyphenols. ESI-FT-ICR MS was efficient in identifying primary (carbohydrates and organic acids) and secondary metabolites (13 phenolic compounds) presents in the crude and phenolic extract of the samples, respectively. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Application of mass spectrometry in the characterization of chemicals in coal-derived liquids.

PubMed

Liu, Fang-Jing; Fan, Maohong; Wei, Xian-Yong; Zong, Zhi-Min

2017-07-01

Coal-derived liquids (CDLs) are primarily generated from pyrolysis, carbonization, gasification, direct liquefaction, low-temperature extraction, thermal dissolution, and mild oxidation. CDLs are important feedstocks for producing value-added chemicals and clean liquid fuels as well as high performance carbon materials. Accordingly, the compositional characterization of chemicals in CDLs at the molecular level with advanced analytical techniques is significant for the efficient utilization of CDLs. Although reviews on advancements have been rarely reported, great progress has been achieved in this area by using gas chromatography/mass spectrometry (GC/MS), two-dimensional GC-time of flight mass spectrometry (GC × GC-TOFMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This review focuses on characterizing hydrocarbon, oxygen-containing, nitrogen-containing, sulfur-containing, and halogen-containing chemicals in various CDLs with these three mass spectrometry techniques. Small molecular (< 500 u), volatile and semi-volatile, and less polar chemicals in CDLs have been identified with GC/MS and GC × GC-TOFMS. By equipped with two-dimensional GC, GC × GC-TOFMS can achieve a clearly chromatographic separation of complex chemicals in CDLs without prior fractionation, and thus can overcome the disadvantages of co-elution and serious peak overlap in GC/MS analysis, providing much more compositional information. With ultrahigh resolving power and mass accuracy, FT-ICR MS reveals a huge number of compositionally distinct compounds assigned to various chemical classes in CDLs. It shows excellent performance in resolving and characterizing higher-molecular, less volatile, and polar chemicals that cannot be detected by GC/MS and GC × GC-TOFMS. The application of GC × GC-TOFMS and FT-ICR MS to chemical characterization of CDLs is not as prevalent as that of petroleum and largely remains to be developed in many respects. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:543-579, 2017. © 2016 Wiley Periodicals, Inc.

Characterization of unknown brominated disinfection byproducts during chlorination using ultrahigh resolution mass spectrometry.

PubMed

Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Zheng, Hongdie; Yang, Min

2014-03-18

Brominated disinfection byproducts (Br-DBPs), formed from the reaction of disinfectant(s) with natural organic matter in the presence of bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. To date, only a few Br-DBPs in drinking water have been identified, while a significant portion of Br-DBPs in drinking water is still unknown. In this study, negative ion electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown Br-DBPs in artificial drinking water. In total, 441 formulas for one-bromine-containing products and 37 formulas for two-bromine-containing products, most of which had not been previously reported, were detected in the chlorinated sample. Most Br-DBPs have corresponding chlorine-containing analogues with identical CHO composition. In addition, on-resonance collision-induced dissociation (CID) of single ultrahigh resolved bromine containing mass peaks was performed in the ICR cell to isolate single bromine-containing components in a very complex natural organic matter spectrum and provide structure information. Relatively abundant neutral loss of CO2 was observed in MS-MS spectra, indicating that the unknown Br-DBPs are rich in carboxyl groups. The results demonstrate that the ESI FT-ICR MS method could provide valuable molecular composition and structure information on unknown Br-DBPs.

Fractionation and characterization of dissolved organic matter (DOM) in refinery wastewater by revised phase retention and ion-exchange adsorption solid phase extraction followed by ESI FT-ICR MS.

PubMed

Fang, Zhi; He, Chen; Li, Yongyong; Chung, Keng H; Xu, Chunming; Shi, Quan

2017-01-01

Although the progress of high resolution mass spectrometry in the past decade has enabled the molecular characterization of dissolved organic matter (DOM) in water as a whole, fractionation of DOM is necessary for a comprehensive characterization due to its super-complex nature. Here we proposed a method for the fractionation of DOM in a wastewater based on solubility and acidic-basic properties. Solid phase extraction (SPE) cartridges with reversed phase retention and ion-exchange adsorption capacities, namely MAX and MCX, were used in succession to fractionate a petroleum refinery wastewater into four fractions: hydrophobic acid (HOA), hydrophobic neutral (HON), hydrophobic base (HOB), and hydrophilic substance (HIS) fractions. According to the total organic carbon (TOC) analysis, 72.6% (in term of TOC) of DOM was extracted in hydrophobic fractions, in which HON was the most abundant. Hydrophobic extracts were characterized by negative and positive ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), respectively. Compounds with multiple oxygen atoms were predominant in the HOA, which were responded strongly in the negative ESI MS. Nitrogen containing compounds were the major detected species by positive ion ESI in all hydrophobic fractions. The molecular composition of the DOM were discussed based on the FT-ICR MS results. The fractionation provided salt free samples which enables the direct analysis of the fractions by ESI and a deep insight into the molecular composition of DOM in the wastewater. The method is potential for routine evaluation of DOM in industry wastewaters, as well as environmental water samples. Copyright © 2016. Published by Elsevier B.V.

A regional study of the seasonal variation in the molecular composition of rainwater

NASA Astrophysics Data System (ADS)

Cottrell, Barbara A.; Gonsior, Michael; Isabelle, Lorne M.; Luo, W.; Perraud, Véronique; McIntire, Theresa M.; Pankow, James F.; Schmitt-Kopplin, Philippe; Cooper, William J.; Simpson, André J.

2013-10-01

Rainwater is not only a critical source of drinking and agricultural water but it plays a key role in the fate and transport of contaminants through their removal by wet deposition. Rainwater is a complex mixture of organic compounds yet despite its importance its spatial and temporal variability are not well understood and less than 50% of the organic matter has been characterized. In-depth analytical approaches were used in this study to characterize the seasonal variation in rainwater composition. Rainwater samples were collected over a one-year period in Scarborough, Ontario, Canada. The seasonal variation of atmospheric organic carbon (AOC) in rainwater was analyzed by excitation-emission matrix spectroscopy (EEMs), 1D and 2D NMR with compound identification by spectral database matching, GC-MS, FT-ICR-MS, and GC × GC-TOFMS. This combination of techniques provided four complementary datasets, with less than 10% overlap, of anthropogenic and biogenic AOC. NMR with database matching identified over 100 compounds, primarily carboxylic acids, carbohydrates, and nitrogen-containing compounds. GC × GC-TOFMS analysis identified 344 compounds in two rain events with 33% of the compounds common to both events. FT-ICR-MS generated a seasonally dependent profile of 1226-1575 molecular ions of CHO, CHOS, and CHON elemental composition. FT-ICR-MS and GC × GC-TOFMS datasets were compared using van Krevelen diagrams (H/C vs. O/C), the H/C ratio vs. mass/charge (m/z), and the carbon oxidation state/carbon number matrix. Fluorescence patterns were correlated with NMR results resulting in the identification one seasonally-dependent component of chromophoric dissolved organic matter (CDOM). This study demonstrated the importance of using of an integrated analytical approach to monitor the compositional variation of AOC.

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

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

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. Here in this study, an SID device was designed and successfully installed in amore » hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. Lastly, SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

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

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on non-covalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybridmore » FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 kDa to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

DOE PAGES

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.; ...

2016-12-02

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. Here in this study, an SID device was designed and successfully installed in amore » hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. Lastly, SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Molecular-Scale Characterization of Natural Organic Matter From A Uranium Contaminated Aquifer and its Utilization by Native Microbial Communities

NASA Astrophysics Data System (ADS)

Mouser, P. J.; Wilkins, M. J.; Williams, K. H.; Smith, D. F.; Paša-Tolić, L.

2011-12-01

The availability and form of natural organic matter (NOM) strongly influences rates of microbial metabolism and associated redox processes in subsurface environments. This is an important consideration in metal-contaminated aquifers, such as the DOE's Rifle Integrated Field Research Challenge (IFRC) site, where naturally occurring suboxic conditions in groundwater may play an important function in controlling uranium mobility, and therefore the long-term stewardship of the site. Currently, the biophysiochemical processes surrounding the nature of the aquifer and its role in controlling the fate and transport of uranium are poorly understood. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with electrospray ionization (ESI), we characterized dissolved organic matter (DOM) chemistry for three surface and groundwater sources at Rifle and assessed microbial utilization in batch incubation experiments. FT-ICR-MS uniquely offers ultrahigh mass measurement accuracy and resolving power for polar organics, in addition to enabling elemental composition assignments of these compounds. Samples were collected from the Colorado River, a shallow groundwater aquifer adjacent to the river, and a spring/seep discharge point upgradient from the aquifer. DOM was concentrated and purified from each source and analyzed using FT-ICR-MS with ESI. We identified between 6,000 and 7,000 formulae at each location, with the river sample having the smallest and the spring sample having the largest number of identified peaks. The groundwater and spring samples contained DOM with a large percentage of formulae containing nitrogen and sulfur species, while the river sample was dominated by carbon, hydrogen, and oxygen species. Less than 38% of the formulae were shared between any two samples, indicating a significant level of uniqueness across the samples. Unsaturated hydrocarbons, cellulose, and lipids were rapidly utilized by indigenous bacteria during a 24-day incubation period, and presumably transformed to more recalcitrant lignins and protein-type molecules. These findings indicate that FT-ICR-MS with ESI is an effective method for characterizing molecular-scale differences in DOM from complex environments. We also provide preliminary evidence that certain DOM fractions are more efficiently utilized by indigenous microbial communities and likely play an important role in controlling reducing conditions in heterogeneous subsurface environments.

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

PubMed

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

2016-09-01

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

Fourier transform (FT)-artifacts and power-function resolution filter in Fourier transform mass spectrometry.

PubMed

Kanawati, Basem; Bader, Theresa M; Wanczek, Karl-Peter; Li, Yan; Schmitt-Kopplin, Philippe

2017-10-15

Peak picking algorithms in mass spectrometry face the challenge of picking the correct signals from a mass spectrum. In some cases signal wiggles (side lobes) are also chosen in the produced mass list as if they were real signals. Constraints which are defined in such algorithms do not always guarantee wiggle-free accurate mass list generation out of raw mass spectra. This problem intensifies with acquisitions, which are accompanied by longer transients. Thus, the problem represents a contemporary issue, which propagates with modern high-memory digitizers and exists in both MS and MS/MS spectra. A solariX FTMS mass spectrometer with an Infinity ICR cell (Bruker Daltonics, Bremen, Germany) coupled to a 12 Tesla magnet (Magnex, UK) was used for the experimental study. Time-domain transients of several different data point lengths 512k, 1M, 2M, 4M, 8M were obtained and were Fourier-transformed to obtain frequency spectra which show the effect of the transient truncation on sinc wiggle developments in FT-ICR-MS. MATLAB simulations were also performed to investigate the origin of the Fourier transform (FT)-artifacts. A new filter has been developed to identify and remove FT-artifacts (sinc side lobes) from both frequency and mass spectra. The newly developed filter is based on distinguishing between the FWHM of the correct frequency/mass signals and the FWHM of their corresponding wiggles. The filter draws a reliable confidence limit of resolution range, within which a correct frequency/mass signal is identified. The filter is applicable over a wide mass range of metabolic interest (100-1200 amu). The origin of FT-artifacts due to time-domain transient truncations was thoroughly investigated both experimentally and by simulations in this study. A new solution for this problem with automatic recognition and elimination of these FT-artifacts (side lobes/wiggles) is provided, which is independent of any intensity thresholds, magnetic field strengths and time-domain transient lengths. Copyright © 2017 John Wiley & Sons, Ltd.

Relationships Between Dissolved Organic Matter Composition and Photochemistry in Lakes of Diverse Trophic Status.

PubMed

Maizel, Andrew C; Li, Jing; Remucal, Christina K

2017-09-05

The North Temperate Lakes Long-Term Ecological Research site includes seven lakes in northern Wisconsin that vary in hydrology, trophic status, and landscape position. We examine the molecular composition of dissolved organic matter (DOM) within these lakes using Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) and quantify DOM photochemical activity using probe compounds. Correlations between the relative intensity of individual molecular formulas and reactive species production demonstrate the influence of DOM composition on photochemistry. For example, highly aromatic, tannin-like formulas correlate positively with triplet formation rates, but negatively with triplet quantum yields, as waters enriched in highly aromatic formulas exhibit much higher rates of light absorption, but only slightly higher rates of triplet production. While commonly utilized optical properties also correlate with DOM composition, the ability of FT-ICR MS to characterize DOM subpopulations provides unique insight into the mechanisms through which DOM source and environmental processing determine composition and photochemical activity.

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

PubMed

Darebna, Petra; Novak, Petr; Kucera, Radek; Topolcan, Ondrej; Sanda, Miloslav; Goldman, Radoslav; Pompach, Petr

2017-02-05

Alternations in the glycosylation of proteins have been described in connection with several cancers, including hepatocellular carcinoma (HCC) and colorectal cancer. Analytical tools, which use combination of liquid chromatography and mass spectrometry, allow precise and sensitive description of these changes. In this study, we use MRM and FT-ICR operating in full-MS scan, to determine ratios of intensities of specific glycopeptides in HCC, colorectal cancer, and liver metastasis of colorectal cancer. Haptoglobin, hemopexin and complement factor H were detected after albumin depletion and the N-linked glycopeptides with fucosylated glycans were compared with their non-fucosylated forms. In addition, sialylated forms of an O-linked glycopeptide of hemopexin were quantified in the same samples. We observe significant increase in fucosylation of all three proteins and increase in bi-sialylated O-glycopeptide of hemopexin in HCC of hepatitis C viral (HCV) etiology by both LC-MS methods. The results of the MRM and full-MS scan FT-ICR analyses provide comparable quantitative readouts in spite of chromatographic, mass spectrometric and data analysis differences. Our results suggest that both workflows allow adequate relative quantification of glycopeptides and suggest that HCC of HCV etiology differs in glycosylation from colorectal cancer and liver metastasis of colorectal cancer. The article compares N- and O-glycosylation of several serum proteins in different diseases by a fast and easy sample preparation procedure in combination with high resolution Fourier transform ion cyclotron resonance mass spectrometry. The results show successful glycopeptides relative quantification in a complex peptide mixture by the high resolution instrument and the detection of glycan differences between the different types of cancer diseases. The presented method is comparable to conventional targeted MRM approach but allows additional curation of the data. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

Darebna, Petra; Novak, Petr; Kucera, Radek; Topolcan, Ondrej; Sanda, Miloslav; Goldman, Radoslav; Pompach, Petr

2018-01-01

Alternations in the glycosylation of proteins have been described in connection with several cancers, including hepatocellular carcinoma (HCC) and colorectal cancer. Analytical tools, which use combination of liquid chromatography and mass spectrometry, allow precise and sensitive description of these changes. In this study, we use MRM and FT-ICR operating in full-MS scan, to determine ratios of intensities of specific glycopeptides in HCC, colorectal cancer, and liver metastasis of colorectal cancer. Haptoglobin, hemopexin and complement factor H were detected after albumin depletion and the N-linked glycopeptides with fucosylated glycans were compared with their non-fucosylated forms. In addition, sialylated forms of an O-linked glycopeptide of hemopexin were quantified in the same samples. We observe significant increase in fucosylation of all three proteins and increase in bisialylated O-glycopeptide of hemopexin in HCC of hepatitis C viral (HCV) etiology by both LC-MS methods. The results of the MRM and full-MS scan FT-ICR analyses provide comparable quantitative readouts in spite of chromatographic, mass spectrometric and data analysis differences. Our results suggest that both workflows allow adequate relative quantification of glycopeptides and suggest that HCC of HCV etiology differs in glycosylation from colorectal cancer and liver metastasis of colorectal cancer. Significance The article compares N- and O-glycosylation of several serum proteins in different diseases by a fast and easy sample preparation procedure in combination with high resolution Fourier transform ion cyclotron resonance mass spectrometry. The results show successful glycopeptides relative quantification in a complex peptide mixture by the high resolution instrument and the detection of glycan differences between the different types of cancer diseases. The presented method is comparable to conventional targeted MRM approach but allows additional curation of the data. PMID:27646713

Biomarkers to Assess Possible Biological Effects on Reproductive Potential, Immune Function, and Energetic Fitness of Bottlenose Dolphins Exposed to Sounds Consistent with Naval Sonars

DTIC Science & Technology

2013-09-30

ion modes. The resulting chromatograms were then processed using XCMS (alignment and peak picking ). The data were processed with in-house...UHPLC liquid chromatography Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry ( MS ). A standard method was developed for rapid analysis...extraction protocols and then implemented LC- MS / MS analyses on our Thermo Fisher Scientific TSQ Vantage triple quadrupole mass spectrometer. This

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry at the Cyclotron Frequency.

PubMed

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

2017-04-01

The phenomenon of ion cyclotron resonance allows for determining mass-to-charge ratio, m/z, of an ensemble of ions by means of measurements of their cyclotron frequency, ω c . In Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the ω c quantity is usually unavailable for direct measurements: the resonant state is located close to the reduced cyclotron frequency (ω + ), whereas the ω c and the corresponding m/z values may be calculated via theoretical derivation from an experimental estimate of the ω + quantity. Here, we describe an experimental observation of a new resonant state, which is located close to the ω c frequency and is established because of azimuthally-dependent trapping electric fields of the recently developed ICR cells with narrow aperture detection electrodes. We show that in mass spectra, peaks close to ω + frequencies can be reduced to negligible levels relative to peaks close to ω c frequencies. Due to reduced errors with which the ω c quantity is obtained, the new resonance provides a means of cyclotron frequency measurements with precision greater than that achieved when ω + frequency peaks are employed. The described phenomenon may be considered for a development into an FT-ICR MS technology with increased mass accuracy for applications in basic research, life, and environmental sciences. Graphical Abstract ᅟ.

Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides.

PubMed

Lv, Jitao; Zhang, Shuzhen; Wang, Songshan; Luo, Lei; Cao, Dong; Christie, Peter

2016-03-01

Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

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

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

Anderton, Christopher R.; Chu, Rosalie K.; Tolic, Nikola

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

Molecular Signature of Organic Carbon Along a Salinity Gradient in Suwannee River Plume

NASA Astrophysics Data System (ADS)

Liu, Y.; Bianchi, T. S.; Ward, N. D.; Arellano, A. R.; Paša-Tolić, L.; Tolic, N.; Kuo, L. J.

2016-12-01

Humic and fulvic acid isolates from Suwannee River dissolved organic matter (DOM) have served as reference standards for the International Humic Substances Society (IHSS) for many decades. The large database on Suwannee DOM provides an excellent framework to further expand the application of Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) in characterizing the chemical composition of aquatic DOM. In this study, we examined the DOM signature of the lower Suwannee River and plume region at 5 stations along a salinity gradient (0 to 28) using FT-ICR-MS. The chemical characteristics of DOM show distinct differences across this steep salinity gradient. In general, samples collected from the coastal station have lower carbon number and are less aromatic. Molecular level analysis reveals that the magnitude weighted proportion of lipids increased as salinity increased. Interestingly, a similar trend was observed for lignin-like compounds. Target quantification of lignin-phenols showed that while the concentrations of these compounds were lower at the coastal station, the DOC-normalized concentrations were not significantly different between the river and coastal stations. In addition to traditional DOM moieties, we identified for the first time, halogenated organic compounds (HOC). We observed more chlorinated compounds in DOM and increased Cl/C as salinity increased. A relatively high proportion of halogenated lipids (compared to non-halogenated) were observed in the total pool of HOC across all stations. Although not significant in relative proportion, halogenated lignin-like compounds were the most abundant HOC moieties in our samples. CO2 concentrations decreased and became more 13C-enriched along the salinity gradient, ranging from 3,990 ppm (13CO2 = -17.3‰) at salinity 0 to 520 ppm (13CO2 = -7.5‰) at salinity 28, indicating high levels of DOM degradation in the river and a shift to primary production in the marine receiving waters, which is consistent with trends of lipid and lignin-like compounds observed with FT-ICR-MS.

In-depth molecular characterization and biodegradability of water-extractable organic nitrogen in Erhai Lake sediment.

PubMed

Zhang, Li; Wang, Shengrui; Yang, Jiachun; Xu, Kechen

2018-05-08

Dissolved organic nitrogen (DON) constitutes a significant fraction of the total dissolved nitrogen content of most aquatic systems and is thus a major nitrogen source for bacteria and phytoplankton. The present work applied Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to a compound-level analysis of the depth-dependent molecular composition of water-extractable organic nitrogen (WEON) in lake sediment. The study focused on Erhai Lake, China. It was found that a large portion (from 16.33 ± 7.87 to 39.54 ± 5.77%) of the WEON in the lake sediment was reactive under cultivation by algal or bacteria. The WEON in the mid-region of Erhai sediment particularly exhibited a lower bioavailability, having been less affected by the basin environment. The FT-ICR MS results revealed the presence of thousands of compounds in the Erhai Lake sediment samples collected at different depths, with the N-containing compounds accounting for 28.3-34.4% of all the compounds. The WEON molecular weight was also observed to increase with increasing sediment depth. A van Krevelen diagram showed that the lignin-type components were dominant (~ 56.2%) in the sediment WEON, contributing to its stabilization and reducing the risk of sediment nutrient release. The FT-ICR MS results further revealed 204 overlapping formulas of WEON for each core sediment sample, attributable to the presence of refractory components. It was observed that 78.4% of the formulas were within the lignin-like region, suggesting unique allochthonous DON sources. The aliphatic component proportion of all the unique formulas was also found to increase with increasing sediment depth. This indicates that, with the development and evolution of the Erhai Basin, the more labile WEON components were transformed into more stable lignin-like substrates, with a positive effect on the Lake Erhai ecosystem. Graphical abstract ᅟ.

Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry as a Platform for Characterizing Multimeric Membrane Protein Complexes

NASA Astrophysics Data System (ADS)

Lippens, Jennifer L.; Nshanian, Michael; Spahr, Chris; Egea, Pascal F.; Loo, Joseph A.; Campuzano, Iain D. G.

2018-01-01

Membrane protein characterization is consistently hampered by challenges with expression, purification, and solubilization. Among several biophysical techniques employed for their characterization, native-mass spectrometry (MS) has emerged as a powerful tool for the analysis of membrane proteins and complexes. Here, two MS platforms, the FT-ICR and Q-ToF, have been explored to analyze the homotetrameric water channel protein, AquaporinZ (AqpZ), under non-denaturing conditions. This 97 kDa membrane protein complex can be readily liberated from the octylglucoside (OG) detergent micelle under a range of instrument conditions on both MS platforms. Increasing the applied collision energy of the FT-ICR collision cell yielded varying degrees of tetramer (97 kDa) liberation from the OG micelles, as well as dissociation into the trimeric (72 kDa) and monomeric (24 kDa) substituents. Tandem-MS on the Q-ToF yielded higher intensity tetramer signal and, depending on the m/z region selected, the observed monomer signal varied in intensity. Precursor ion selection of an m/z range above the expected protein signal distribution, followed by mild collisional activation, is able to efficiently liberate AqpZ with a high S/N ratio. The tetrameric charge state distribution obtained on both instruments demonstrated superpositioning of multiple proteoforms due to varying degrees of N-terminal formylation. [Figure not available: see fulltext.

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

Treesearch

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

2014-01-01

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

Extracting biomolecule collision cross sections from the high-resolution FT-ICR mass spectral linewidths.

PubMed

Jiang, Ting; Chen, Yu; Mao, Lu; Marshall, Alan G; Xu, Wei

2016-01-14

It is known that the ion collision cross section (CCS) may be calculated from the linewidth of a Fourier transform ion cyclotron resonance (FT-ICR) mass spectral peak at elevated pressure (e.g., ∼10(-6) Torr). However, the high mass resolution of FT-ICR is sacrificed in those experiments due to high buffer gas pressure. In this study, we describe a linewidth correction method to eliminate the windowing-induced peak broadening effect. Together with the energetic ion-neutral collision model previously developed by our group, this method enables the extraction of CCSs of biomolecules from high-resolution FT-ICR mass spectral linewidths, obtained at a typical operating buffer gas pressure of modern FT-ICR instruments (∼10(-10) Torr). CCS values of peptides including MRFA, angiotensin I, and bradykinin measured by the proposed method agree well with ion mobility measurements, and the unfolding of protein ions (ubiquitin) at higher charge states is also observed.

Vacuum Ultraviolet Photodissociation and Fourier Transform–Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry: Revisited

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

Shaw, Jared B.; Robinson, Errol W.; Pasa-Tolic, Ljiljana

2016-02-16

We revisited the implementation of UVPD within the ICR cell of a FT-ICR mass spectrometer. UVPD performance characteristics were examined in the context of recent developments in the understanding of UVPD and in-cell tandem mass spectrometry. Efficient UVPD and photo-ECD of a model peptide and small protein within the ICR cell of a FT-ICR mass spectrometer are accomplished through appropriate modulation of laser pulse timing relative to ion magnetron motion and the potential applied to an ion optical element that photons impinge on. It is shown that UVPD yields efficient and extensive fragmentation resulting in excellent sequence coverage for modelmore » peptide and protein cations.« less

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.

Fast Profiling of Natural Pigments in Different Spirulina (Arthrospira platensis) Dietary Supplements by DI-FT-ICR and Evaluation of their Antioxidant Potential by Pre-Column DPPH-UHPLC Assay.

PubMed

Sommella, Eduardo; Conte, Giulio Maria; Salviati, Emanuela; Pepe, Giacomo; Bertamino, Alessia; Ostacolo, Carmine; Sansone, Francesca; Prete, Francesco Del; Aquino, Rita Patrizia; Campiglia, Pietro

2018-05-11

Arthrospira platensis , better known as Spirulina, is one of the most important microalgae species. This cyanobacterium possesses a rich metabolite pattern, including high amounts of natural pigments. In this study, we applied a combined strategy based on Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Ultra High-Performance Liquid Chromatography (UHPLC) for the qualitative/quantitative characterization of Spirulina pigments in three different commercial dietary supplements. FT-ICR was employed to elucidate the qualitative profile of Spirulina pigments, in both direct infusion mode (DIMS) and coupled to UHPLC. DIMS showed to be a very fast (4 min) and accurate (mass accuracy ≤ 0.01 ppm) tool. 51 pigments were tentatively identified. The profile revealed different classes, such as carotenes, xanthophylls and chlorophylls. Moreover, the antioxidant evaluation of the major compounds was assessed by pre-column reaction with the DPPH radical followed by fast UHPLC-PDA separation, highlighting the contribution of single analytes to the antioxidant potential of the entire pigment fraction. β-carotene, diadinoxanthin and diatoxanthin showed the highest scavenging activity. The method took 40 min per sample, comprising reaction. This strategy could represent a valid tool for the fast and comprehensive characterization of Spirulina pigments in dietary supplements, as well as in other microalgae-based products.

Vacuum Ultraviolet Photodissociation and Fourier Transform-Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry: Revisited.

PubMed

Shaw, Jared B; Robinson, Errol W; Paša-Tolić, Ljiljana

2016-03-15

We revisited the implementation of 193 nm ultraviolet photodissociation (UVPD) within the ion cyclotron resonance (ICR) cell of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. UVPD performance characteristics were examined in the context of recent developments in the understanding of UVPD and in-cell tandem mass spectrometry. Efficient UVPD and photo-ECD of a model peptide and proteins within the ICR cell of a FT-ICR mass spectrometer are accomplished through appropriate modulation of laser pulse timing, relative to ion magnetron motion and the potential applied to an ion optical element upon which photons impinge. It is shown that UVPD yields efficient and extensive fragmentation, resulting in excellent sequence coverage for model peptide and protein cations.

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

Hill, N.C.; Limbach, P.A.; Shomo, R.E. II

The coupling of an autoneutralizing SF{sup {minus}}{sub 6} fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis (e.g., production of abundant pseudomolecular (M+H){sup +} ions) of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with {ital tetra}-butylammonium bromide and a Tylenol{sup ( )} sample.more » The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon{sup ( )}. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.« less

Fast neutral beam ion source coupled to a Fourier transform ion cyclotron resonance mass spectrometer

NASA Astrophysics Data System (ADS)

Hill, Nicholas C.; Limbach, Patrick A.; Shomo, Ronald E., II; Marshall, Alan G.; Appelhans, Anthony D.; Delmore, James E.

1991-11-01

The coupling of an autoneutralizing SF-6 fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis [e.g., production of abundant pseudomolecular (M+H)+ ions] of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with tetra-butylammonium bromide and a Tylenol■ sample. The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon■. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.

IR, FT-ICR-MS studies on (1'S, 6'S)-1-cyclopropyl-7-(2,8-diazabicyclo[4.3.0] non-8-yl)-6-fluoro-8-methoxy-4-oxo-1,4-dihydroquinoline-3-carboxylic acid hydrochloride salt.

PubMed

Lin, Zhiwei

2014-01-01

The infrared spectra of (1'S, 6'S)-1-cyclopropyl-7-(2,8-diazabicyclo[4.3.0] non-8-yl)-6-fluoro-8-methoxy-4-oxo-1,4-dihydroquinoline-3-carboxylic acid hydrochloride salt (CLF-HCl) were studied and compared with free base. Their fragmentation pathways were investigated using tandem mass spectrometric (MS/MS) techniques on Fourier-transform ion cyclotron resonance spectrum, and many characteristic fragment ions were found. Copyright © 2013 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Characterization of non-polar aromatic hydrocarbons in crude oil using atmospheric pressure laser ionization and Fourier transform ion cyclotron resonance mass spectrometry (APLI FT-ICR MS).

PubMed

Schrader, Wolfgang; Panda, Saroj K; Brockmann, Klaus J; Benter, Thorsten

2008-07-01

We report on the successful application of the recently introduced atmospheric pressure laser ionization (APLI) method as a novel tool for the analysis of crude oil and its components. Using Fourier transform ion cyclotron resonance mass spectrometry, unambiguous determination of key compounds in this complex matrix with unprecedented sensitivity is presented.

Molecular characterization of lake sediment WEON by Fourier transform ion cyclotron resonance mass spectrometry and its environmental implications.

PubMed

Zhang, Li; Wang, Shengrui; Xu, Yisheng; Shi, Quan; Zhao, Haichao; Jiang, Bin; Yang, Jiachun

2016-12-01

The compositional properties of water-extractable organic nitrogen (WEON) affect its behavior in lake ecosystems. This work is the first comprehensive study using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the characterization of the molecular composition of WEON in lake sediment. In sediments of Erhai Lake in China, this study found complex WEON species, with N-containing compounds in the northern, central, and southern regions contributing 34.47%, 42.44%, and 40.6%, respectively, of total compounds. Additionally, a van Krevelen diagram revealed that lignin components were dominant in sediment WEON structures (68% of the total), suggesting terrestrial sources. Furthermore, this study applied ESI-FT-ICR-MS to the examination of the environmental processes of lake sediment WEON on a molecular level. The results indicated that sediment depth impacted WEON composition and geochemical processes. Compared with other ecosystems, the double bond equivalent (DBE) value was apparently lower in Erhai sediment, indicating the presence of relatively fewer and smaller aromatic compounds. In addition, the presence of a large number of N-containing species and abundant oxidized nitrogen functional compounds that were likely to biodegrade may have further increased the potential releasing risk of WEON from Erhai sediment under certain environmental conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradability and Molecular Composition of Dissolved Organic Nitrogen in Urban Stormwater Runoff and Outflow Water from a Stormwater Retention Pond.

PubMed

Lusk, Mary G; Toor, Gurpal S

2016-04-05

Dissolved organic nitrogen (DON) can be a significant part of the reactive N in aquatic ecosystems and can accelerate eutrophication and harmful algal blooms. A bioassay method was coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to determine the biodegradability and molecular composition of DON in the urban stormwater runoff and outflow water from an urban stormwater retention pond. The biodegradability of DON increased from 10% in the stormwater runoff to 40% in the pond outflow water and DON was less aromatic and had lower overall molecular weight in the pond outflow water than in the stormwater runoff. More than 1227 N-bearing organic formulas were identified with FT-ICR-MS in the stormwater runoff and pond outflow water, which were only 13% different in runoff and outflow water. These molecular formulas represented a wide range of biomolecules such as lipids, proteins, amino sugars, lignins, and tannins in DON from runoff and pond outflow water. This work implies that the urban infrastructure (i.e., stormwater retention ponds) has the potential to influence biogeochemical processes in downstream water bodies because retention ponds are often a junction between the natural and the built environment.

Molecular evidence of heavy-oil weathering following the M/V Cosco Busan spill: insights from Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Lemkau, Karin L; McKenna, Amy M; Podgorski, David C; Rodgers, Ryan P; Reddy, Christopher M

2014-04-01

Recent studies have highlighted a critical need to investigate oil weathering beyond the analytical window afforded by conventional gas chromatography (GC). In particular, techniques capable of detecting polar and higher molecular weight (HMW; > 400 Da) components abundant in crude and heavy fuel oils (HFOs) as well as transformation products. Here, we used atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI FT-ICR MS) to identify molecular transformations in oil-residue samples from the 2007 M/V Cosco Busan HFO spill (San Francisco, CA). Over 617 days, the abundance and diversity of oxygen-containing compounds increased relative to the parent HFO, likely from bio- and photodegradation. HMW, highly aromatic, alkylated compounds decreased in relative abundance concurrent with increased relative abundance of less alkylated stable aromatic structures. Combining these results with GC-based data yielded a more comprehensive understanding of oil spill weathering. For example, dealkylation trends and the overall loss of HMW species observed by FT-ICR MS has not previously been documented and is counterintuitive given losses of lower molecular weight species observed by GC. These results suggest a region of relative stability at the interface of these techniques, which provides new indicators for studying long-term weathering and identifying sources.

Chemical Composition and Potential Environmental Impacts of Water-Soluble Polar Crude Oil Components Inferred from ESI FT-ICR MS

PubMed Central

Liu, Yina; Kujawinski, Elizabeth B.

2015-01-01

Polar petroleum components enter marine environments through oil spills and natural seepages each year. Lately, they are receiving increased attention due to their potential toxicity to marine organisms and persistence in the environment. We conducted a laboratory experiment and employed state-of-the-art Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the polar petroleum components within two operationally-defined seawater fractions: the water-soluble fraction (WSF), which includes only water-soluble molecules, and the water-accommodated fraction (WAF), which includes WSF and microscopic oil droplets. Our results show that compounds with higher heteroatom (N, S, O) to carbon ratios (NSO:C) than the parent oil were selectively partitioned into seawater in both fractions, reflecting the influence of polarity on aqueous solubility. WAF and WSF were compositionally distinct, with unique distributions of compounds across a range of hydrophobicity. These compositional differences will likely result in disparate impacts on environmental health and organismal toxicity, and thus highlight the need to distinguish between these often-interchangeable terminologies in toxicology studies. We use an empirical model to estimate hydrophobicity character for individual molecules within these complex mixtures and provide an estimate of the potential environmental impacts of different crude oil components. PMID:26327219

Continuous summer export of nitrogen-rich organic matter from the Greenland Ice Sheet inferred by ultrahigh resolution mass spectrometry.

PubMed

Lawson, Emily C; Bhatia, Maya P; Wadham, Jemma L; Kujawinski, Elizabeth B

2014-12-16

Runoff from glaciers and ice sheets has been acknowledged as a potential source of bioavailable dissolved organic matter (DOM) to downstream ecosystems. This source may become increasingly significant as glacial melt rates increase in response to future climate change. Recent work has identified significant concentrations of bioavailable carbon and iron in Greenland Ice Sheet (GrIS) runoff. The flux characteristics and export of N-rich DOM are poorly understood. Here, we employed electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to determine the elemental compositions of DOM molecules in supraglacial water and subglacial runoff from a large GrIS outlet glacier. We provide the first detailed temporal analysis of the molecular composition of DOM exported over a full melt season. We find that DOM pools in supraglacial and subglacial runoff are compositionally diverse and that N-rich material is continuously exported throughout the melt season, as the snowline retreats further inland. Identification of protein-like compounds and a high proportion of N-rich DOM, accounting for 27-41% of the DOM molecules identified by ESI FT-ICR MS, may suggest a microbial provenance and high bioavailability of glacially exported DOM to downstream microbial communities.

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

PubMed

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

2018-03-01

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H] - . Nevertheless, NH 3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous C x H y O z bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. Graphical Abstract ᅟ.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Collision cross section measurements for biomolecules within a high-resolution FT-ICR cell: theory.

PubMed

Guo, Dan; Xin, Yi; Li, Dayu; Xu, Wei

2015-04-14

In this study, an energetic hard-sphere ion-neutral collision model was proposed to bridge-link ion collision cross section (CCS) with the image current collected from a high-resolution Fourier transform ion cyclotron resonance (FT-ICR) cell. By investigating the nonlinear effects induced by high-order electric fields and image charge forces, the energetic hard-sphere collision model was validated through experiments. Suitable application regions for the energetic hard-sphere collision model, as well as for the conventional Langevin and hard-sphere collision models, were also discussed. The energetic hard-sphere collision model was applied in the extraction of ion CCSs from high-resolution FT-ICR mass spectra. Discussions in the present study also apply to FT-Orbitraps and FT-quadrupole ion traps.

Relationships between Molecular Composition and Optical Properties of Dissolved Organic Matter

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

FT-ICR mass spectrometric and density functional theory studies of sulfate prenucleation clusters

NASA Astrophysics Data System (ADS)

Lemke, K. H.

2012-12-01

Recent mass spectrometric1 and relaxation spectroscopic studies2 of metal sulfate salts have demonstrated that aqueous clusters play an important role in sulfate prenucleation processes. While such studies provide evidence that that ion clusters are nucleation relevant species, ultra-high resolution mass spectrumetry, in particular, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) can provide additional valuable information about the molecular composition and stability of individual ion clusters. Prompted by the above studies, our group has begun a systematic survey of metal sulfate clusters using FT-ICR mass spectrometry. Here, I report stoichiometries, structures and thermodynamic properties of calcium sulfate ion clusters, both "dry" and microsolvated, using electrospray ionization FT-ICR mass spectrometry in combination with semi-empirical methods and M062X/aug-cc-PVXZ level density functional theory calculations. In electrosprayed dilute aqueous solutions of CaSO4 (1-20mM), droplet desolvation results in the formation of stable doubly-charged clusters of [Ca(CaSO4)m(H2O)n]+2 (m≤10 & n≤9) as well as larger quadruply-charged ion clusters [Ca2(CaSO4)m(H2O)n]+4 with m≤23 and n≤10, demonstrating considerable sulfate nucleation potential in undersaturated electrolyte solutions. An attempt was also made to assess the extent of ion cluster aggregation in solution prior to electrospray ionization by measuring ion mass spectra at different solution concentrations. In brief, an increase in calcium sulfate concentration from 1-10mM results in a continuous increase in polynuclear ion cluster species, while smaller clusters, for instance, Ca[CaSO4]+2 and corresponding hydrated forms, become increasingly less abundant. Building on semi-empirical methods, M062X calculations have been applied to predict calcium sulfate cluster geometries, both "dry" and microsolvated, as well as the size-dependent evolution of clustering and hydration energies. 1Schoeder et al. (2011) J.Am.Chem.Soc., 133, 2444; 2Chen et al. (2005) J.Sol.Chem., 34, 1045;

Determination of heavy polycyclic aromatic hydrocarbons by non-aqueous reversed phase liquid chromatography: Application and limitation in refining streams.

PubMed

Panda, Saroj K; Muller, Hendrik; Al-Qunaysi, Thunayyan A; Koseoglu, Omer R

2018-01-19

The heavy polycyclic aromatic hydrocarbons (HPAHs) cause detrimental effects to hydrocracker operations by deactivating the catalysts and depositing in the downstream of the reactor/ exchangers. Therefore, it is essential to continuously monitor the accumulation of HPAHs in a hydrocracker unit. To accurately measure the concentration of HPAHs, the development of a fast and reliable analytical method is inevitable. In this work, an analytical method based on non-aqueous reversed phase chromatography in combination with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was developed. As a first step, five different types of stationary phases were evaluated for the separation of HPAHs in non-aqueous mode and the best suited phase was further used for the fractionation of HPAHs in a fractionator bottom sample obtained from a refinery hydrocracker unit. The eight major fractions or peaks obtained from the separation were further characterized by UV spectroscopy and FT-ICR MS and the compounds in the fractions were tentatively confirmed as benzoperylene, coronene, methylcoronene, naphthenocoronene, benzocoronene, dibenzoperylene, naphthocoronene and ovalene. The developed liquid chromatography method can be easily adapted in a refinery laboratory for the quantitation of HPAHs in hydrocracking products. The method was further tested to check the interference of sulfur aromatics and/or large alkylated aromatic hydrocarbons on the determination of HPAHs in hydrocracking products. Copyright © 2017 Elsevier B.V. All rights reserved.

Visualizing DOM super-spectrum covariance in vanKrevelen space

NASA Astrophysics Data System (ADS)

Fatland, D. R.; Kalawe, J.; Stubbins, A.; Spencer, R. G.; Sleighter, R. L.; Abdulla, H. A.; Dittmar, T.

2011-12-01

We investigate the fate of terrigenous organic matter, DOM exported to the coastal marine environ. Many methods (fluor., FT-ICR-MS, NMR, 13C, lignin, etc) help characterize this DOM. We define a 'super spectrum' as amalgamation of analyses to a data stack and we search for physically significant patterns therein beginning with covariance across 31 samples from six circum-Arctic rivers: The Ob, Kolyma, Mackenzie, Yukon, Lena, and Yenisey sampled five times throughout the year. A vanKrevelen diagram is convenient to view distributions of molecules provided by Fourier Transform Ion Cyclotron Resonance Mass Spectometry (FT-ICR-MS). We augment this distribution space in the vertical dimension, for example to show peak height, molecular mass, principle component weighting or covariance. We use Worldwide Telescope, a virtual globe with strong data support from Microsoft Research to explore covariance results along 3+ dimensions (adding brightness, color and a parameter slide). The results show interesting covariance e.g. between molecules and PARAFAC peaks, a step towards fluorophore and cohort identification in the terrigenous DOM spectrum. Given the geoscience explosion in data volume and data complexity we feel these results should survive beyond the end point of a journal article. We are building a cloud-based Library on the Microsoft Azure platform to support this and subsequent analyses to enable data and methods to carry over and benefit other research groups and objectives.

The Exometabolome of Two Model Strains of the Roseobacter Group: A Marketplace of Microbial Metabolites

PubMed Central

Wienhausen, Gerrit; Noriega-Ortega, Beatriz E.; Niggemann, Jutta; Dittmar, Thorsten; Simon, Meinhard

2017-01-01

Recent studies applying Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) showed that the exometabolome of marine bacteria is composed of a surprisingly high molecular diversity. To shed more light on how this diversity is generated we examined the exometabolome of two model strains of the Roseobacter group, Phaeobacter inhibens and Dinoroseobacter shibae, grown on glutamate, glucose, acetate or succinate by FT-ICR-MS. We detected 2,767 and 3,354 molecular formulas in the exometabolome of each strain and 67 and 84 matched genome-predicted metabolites of P. inhibens and D. shibae, respectively. The annotated compounds include late precursors of biosynthetic pathways of vitamins B1, B2, B5, B6, B7, B12, amino acids, quorum sensing-related compounds, indole acetic acid and methyl-(indole-3-yl) acetic acid. Several formulas were also found in phytoplankton blooms. To shed more light on the effects of some of the precursors we supplemented two B1 prototrophic diatoms with the detected precursor of vitamin B1 HET (4-methyl-5-(β-hydroxyethyl)thiazole) and HMP (4-amino-5-hydroxymethyl-2-methylpyrimidine) and found that their growth was stimulated. Our findings indicate that both strains and other bacteria excreting a similar wealth of metabolites may function as important helpers to auxotrophic and prototrophic marine microbes by supplying growth factors and biosynthetic precursors. PMID:29075248

Structural measurements and cell line studies of the copper-PEG-Rifampicin complex against Mycobacterium tuberculosis.

PubMed

Manning, Thomas; Mikula, Rachel; Wylie, Greg; Phillips, Dennis; Jarvis, Jackie; Zhang, Fengli

2015-02-01

The bacterium responsible for tuberculosis is increasing its resistance to antibiotics resulting in new multidrug-resistant Mycobacterium tuberculosis (MDR-TB) and extensively drug-resistant tuberculosis (XDR-TB). In this study, several analytical techniques including NMR, FT-ICR, MALDI-MS, LC-MS and UV/Vis are used to study the copper-Rifampicin-Polyethylene glycol (PEG-3350) complex. The copper (II) cation is a carrier for the antibiotic Rifampicin as well as nutrients for the bacterium. The NIH-NIAID cell line containing several Tb strains (including antibiotic resistant strains) is tested against seven copper-PEG-RIF complex variations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rapid Analysis of Microalgal Triacylglycerols with Direct-Infusion Mass Spectrometry

DOE PAGES

Christensen, Earl; Sudasinghe, Nilusha; Dandamudi, Kodanda Phani Raj; ...

2015-09-01

Cultivation of microalgae has the potential to provide lipid-derived feedstocks for conversion to liquid transportation fuels. Lipid extracts from microalgae are significantly more complex than those of traditional seed oils, and their composition changes significantly throughout the microalgal growth period. With three acyl side chains per molecule, triglycerides (TAGs) are an important fuel precursor, and the distribution of acyl chain composition for TAGs has a significant impact on fuel properties and processing. Therefore, determination of the distribution of microalgal TAG production is needed to assess the value of algal extracts designed for fuel production and to optimize strain, cultivation, andmore » harvesting practices. Methods utilized for TAG speciation commonly involve complicated and time-consuming chromatographic techniques. Here we present a method for TAG speciation and quantification based on direct-infusion mass spectrometry, which provides rapid characterization of TAG profiles without chromatographic separation. Specifically, we utilize Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to provide a reference library of TAGs for the microalgae Nannochloropsis sp. that provides the basis for high-throughput TAG quantitation by time-of-flight mass spectrometry (TOF MS). In conclusion, we demonstrate the application of this novel approach for lipid characterization with respect to TAG compound distribution, which informs both immediate and future strain and process optimization strategies.« less

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

Christensen, Earl; Sudasinghe, Nilusha; Dandamudi, Kodanda Phani Raj

Cultivation of microalgae has the potential to provide lipid-derived feedstocks for conversion to liquid transportation fuels. Lipid extracts from microalgae are significantly more complex than those of traditional seed oils, and their composition changes significantly throughout the microalgal growth period. With three acyl side chains per molecule, triglycerides (TAGs) are an important fuel precursor, and the distribution of acyl chain composition for TAGs has a significant impact on fuel properties and processing. Therefore, determination of the distribution of microalgal TAG production is needed to assess the value of algal extracts designed for fuel production and to optimize strain, cultivation, andmore » harvesting practices. Methods utilized for TAG speciation commonly involve complicated and time-consuming chromatographic techniques. Here we present a method for TAG speciation and quantification based on direct-infusion mass spectrometry, which provides rapid characterization of TAG profiles without chromatographic separation. Specifically, we utilize Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to provide a reference library of TAGs for the microalgae Nannochloropsis sp. that provides the basis for high-throughput TAG quantitation by time-of-flight mass spectrometry (TOF MS). In conclusion, we demonstrate the application of this novel approach for lipid characterization with respect to TAG compound distribution, which informs both immediate and future strain and process optimization strategies.« less

Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry

PubMed Central

Prokai, Laszlo; Stevens, Stanley M.

2016-01-01

Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae. PMID:26784186

Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry.

PubMed

Prokai, Laszlo; Stevens, Stanley M

2016-01-16

Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae.

Fourier transform ion cyclotron resonance mass resolution and dynamic range limits calculated by computer modeling of ion cloud motion.

PubMed

Vladimirov, Gleb; Hendrickson, Christopher L; Blakney, Greg T; Marshall, Alan G; Heeren, Ron M A; Nikolaev, Eugene N

2012-02-01

Particle-in-Cell (PIC) ion trajectory calculations provide the most realistic simulation of Fourier transform ion cyclotron resonance (FT-ICR) experiments by efficient and accurate calculation of the forces acting on each ion in an ensemble (cloud), including Coulomb interactions (space charge), the electric field of the ICR trap electrodes, image charges on the trap electrodes, the magnetic field, and collisions with neutral gas molecules. It has been shown recently that ion cloud collective behavior is required to generate an FT-ICR signal and that two main phenomena influence mass resolution and dynamic range. The first is formation of an ellipsoidal ion cloud (termed "condensation") at a critical ion number (density), which facilitates signal generation in an FT-ICR cell of arbitrary geometry because the condensed cloud behaves as a quasi-ion. The second phenomenon is peak coalescence. Ion resonances that are closely spaced in m/z coalesce into one resonance if the ion number (density) exceeds a threshold that depends on magnetic field strength, ion cyclotron radius, ion masses and mass difference, and ion initial spatial distribution. These two phenomena decrease dynamic range by rapid cloud dephasing at small ion density and by cloud coalescence at high ion density. Here, we use PIC simulations to quantitate the dependence of coalescence on each critical parameter. Transitions between independent and coalesced motion were observed in a series of the experiments that systematically varied ion number, magnetic field strength, ion radius, ion m/z, ion m/z difference, and ion initial spatial distribution (the present simulations begin from elliptically-shaped ion clouds with constant ion density distribution). Our simulations show that mass resolution is constant at a given magnetic field strength with increasing ion number until a critical value (N) is reached. N dependence on magnetic field strength, cyclotron radius, ion mass, and difference between ion masses was determined for two ion ensembles of different m/z, equal abundance, and equal cyclotron radius. We find that N and dynamic range depend quadratically on magnetic field strength in the range 1-21 Tesla. Dependences on cyclotron radius and Δm/z are linear. N depends on m/z as (m/z)(-2). Empirical expressions for mass resolution as a function of each of the experimental parameters are presented. Here, we provide the first exposition of the origin and extent of trade-off between FT-ICR MS dynamic range and mass resolution (defined not as line width, but as the separation between the most closely resolved masses). © American Society for Mass Spectrometry, 2011

Direct and non-destructive proof of authenticity for the 2nd generation of Brazilian real banknotes via easy ambient sonic spray ionization mass spectrometry.

PubMed

Schmidt, Eduardo Morgado; Franco, Marcos Fernando; Regino, Karen Gomes; Lehmann, Eraldo Luiz; Arruda, Marco Aurélio Zezzi; de Carvalho Rocha, Werickson Fortunato; Borges, Rodrigo; de Souza, Wanderley; Eberlin, Marcos Nogueira; Correa, Deleon Nascimento

2014-12-01

Using a desorption/ionization technique, easy ambient sonic-spray ionization coupled to mass spectrometry (EASI-MS), documents related to the 2nd generation of Brazilian Real currency (R$) were screened in the positive ion mode for authenticity based on chemical profiles obtained directly from the banknote surface. Characteristic profiles were observed for authentic, seized suspect counterfeit and counterfeited homemade banknotes from inkjet and laserjet printers. The chemicals in the authentic banknotes' surface were detected via a few minor sets of ions, namely from the plasticizers bis(2-ethylhexyl)phthalate (DEHP) and dibutyl phthalate (DBP), most likely related to the official offset printing process, and other common quaternary ammonium cations, presenting a similar chemical profile to 1st-generation R$. The seized suspect counterfeit banknotes, however, displayed abundant diagnostic ions in the m/z 400-800 range due to the presence of oligomers. High-accuracy FT-ICR MS analysis enabled molecular formula assignment for each ion. The ions were separated by 44 m/z, which enabled their characterization as Surfynol® 4XX (S4XX, XX=40, 65, and 85), wherein increasing XX values indicate increasing amounts of ethoxylation on a backbone of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfynol® 104). Sodiated triethylene glycol monobutyl ether (TBG) of m/z 229 (C10H22O4Na) was also identified in the seized counterfeit banknotes via EASI(+) FT-ICR MS. Surfynol® and TBG are constituents of inks used for inkjet printing. Copyright © 2014. Published by Elsevier Ireland Ltd.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins.

PubMed

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-03-24

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks ("seeds") for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn's largest moon, Titan.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins

PubMed Central

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-01-01

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks (“seeds”) for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn’s largest moon, Titan. PMID:27023520

Latitude and pH driven trends in the molecular composition of DOM across a north south transect along the Yenisei River

NASA Astrophysics Data System (ADS)

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2013-12-01

We used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) to identify the molecular composition of dissolved organic matter (DOM) collected from different ecosystems along a transect crossing Siberia’s northern and middle Taiga. This information is urgently needed to help elucidate global carbon cycling and export through Russian rivers. In total, we analyzed DOM samples from eleven Yenisei tributaries and seven bogs. Freeze-dried and re-dissolved DOM was desalted via solid phase extraction (SPE) and eluted in methanol for ESI-FT-ICR-MS measurements. We recorded 15209 different masses and identified 7382 molecular formulae in the mass range between m/z = 150 and 800. We utilized the relative FT-ICR-MS signal intensities of 3384 molecular formulae above a conservatively set limit of detection and summarized the molecular characteristics for each measurement using ten magnitude-weighted parameters ((O/C)w, (H/C)w, (N/C)w, (DBE)w, (DBE/C)w, (DBE/O)w, (DBE-O)w, (C#)w, (MW)w and (AI)w) for redundancy analysis. Consequently, we revealed that the molecular composition of DOM depends mainly on pH and geographical latitude. After applying variation partitioning to the peak data, we isolated molecular formulae that were strongly positive or negatively correlated with latitude and pH. We used the chemical information from 13 parameters (C#, H#, N#, O#, O/C, H/C, DBE, DBE/C, DBE/O, AI, N/C, DBE-O and MW) to characterize the extracted molecular formulae. Using latitude along the gradient representing climatic variation, we found a higher abundance of smaller molecules, nitrogen-containing compounds and unsaturated Cdbnd C functionalities at higher latitudes. As possible reasons for the different molecular characteristics occurring along this gradient, we suggested that the decomposition was temperature dependent resulting to a higher abundance of non-degraded lignin-derived phenolic substances. We demonstrated that bog samples, which were differentiated from river samples by their lower pH values, distinguish themselves by their higher unsaturation and molecular size. These molecular characteristics might suggest less phenol oxidase degradation occurs alongside a higher abundance of phenolic substances in bogs due to low pH and anoxic conditions. We concluded that heating at the higher latitudes will increase decomposition and feedback on the nitrogen cycle due to the increased mineralization of organic nitrogen compounds, although the peat system will be less affected due to pH inhibition.

Application of Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) in Petroleomics: Analysis of Condensed Aromatics Standards, Crude Oil, and Paraffinic Fraction.

PubMed

Tose, Lilian V; Murgu, Michael; Vaz, Boniek G; Romão, Wanderson

2017-11-01

Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °C min -1 , and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250-1300 and 200-1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000 Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M] +• , and protonated cations, [M + H] + , with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1 ppm) would be assigned. Graphical Abstract ᅟ.

Application of Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) in Petroleomics: Analysis of Condensed Aromatics Standards, Crude Oil, and Paraffinic Fraction

NASA Astrophysics Data System (ADS)

Tose, Lilian V.; Murgu, Michael; Vaz, Boniek G.; Romão, Wanderson

2017-08-01

Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °C min-1, and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250-1300 and 200-1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000 Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M]+•, and protonated cations, [M + H]+, with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1 ppm) would be assigned. [Figure not available: see fulltext.

Sunlight creates oxygenated species in water-soluble fractions of Deepwater Horizon oil.

PubMed

Ray, Phoebe Z; Chen, Huan; Podgorski, David C; McKenna, Amy M; Tarr, Matthew A

2014-09-15

In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid-liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O5), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O2). Higher-order oxygen classes (O5-O9) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N1) concurrent with an increased abundance of N1Ox classes after irradiation. The predominance of higher-order oxygen classes indicates that multiple photochemical pathways exist that result in oxidation of petroleum compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

Application of Tandem Two-Dimensional Mass Spectrometry for Top-Down Deep Sequencing of Calmodulin

NASA Astrophysics Data System (ADS)

Floris, Federico; Chiron, Lionel; Lynch, Alice M.; Barrow, Mark P.; Delsuc, Marc-André; O'Connor, Peter B.

2018-06-01

Two-dimensional mass spectrometry (2DMS) involves simultaneous acquisition of the fragmentation patterns of all the analytes in a mixture by correlating their precursor and fragment ions by modulating precursor ions systematically through a fragmentation zone. Tandem two-dimensional mass spectrometry (MS/2DMS) unites the ultra-high accuracy of Fourier transform ion cyclotron resonance (FT-ICR) MS/MS and the simultaneous data-independent fragmentation of 2DMS to achieve extensive inter-residue fragmentation of entire proteins. 2DMS was recently developed for top-down proteomics (TDP), and applied to the analysis of calmodulin (CaM), reporting a cleavage coverage of about 23% using infrared multiphoton dissociation (IRMPD) as fragmentation technique. The goal of this work is to expand the utility of top-down protein analysis using MS/2DMS in order to extend the cleavage coverage in top-down proteomics further into the interior regions of the protein. In this case, using MS/2DMS, the cleavage coverage of CaM increased from 23% to 42%.

Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry.

PubMed

Tao, Yeqing; Fang, Pengfei; Kim, Sunghoon; Guo, Min; Young, Nicolas L; Marshall, Alan G

2017-01-01

Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18) is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA), a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX) for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

Label-Free Relative Quantitation of Isobaric and Isomeric Human Histone H2A and H2B Variants by Fourier Transform Ion Cyclotron Resonance Top-Down MS/MS.

PubMed

Dang, Xibei; Singh, Amar; Spetman, Brian D; Nolan, Krystal D; Isaacs, Jennifer S; Dennis, Jonathan H; Dalton, Stephen; Marshall, Alan G; Young, Nicolas L

2016-09-02

Histone variants are known to play a central role in genome regulation and maintenance. However, many variants are inaccessible by antibody-based methods or bottom-up tandem mass spectrometry due to their highly similar sequences. For many, the only tractable approach is with intact protein top-down tandem mass spectrometry. Here, ultra-high-resolution FT-ICR MS and MS/MS yield quantitative relative abundances of all detected HeLa H2A and H2B isobaric and isomeric variants with a label-free approach. We extend the analysis to identify and relatively quantitate 16 proteoforms from 12 sequence variants of histone H2A and 10 proteoforms of histone H2B from three other cell lines: human embryonic stem cells (WA09), U937, and a prostate cancer cell line LaZ. The top-down MS/MS approach provides a path forward for more extensive elucidation of the biological role of many previously unstudied histone variants and post-translational modifications.

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

PubMed

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

2017-05-01

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

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

PubMed

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

2015-04-01

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

Molecular biogeochemical provinces in the Atlantic Surface Ocean

NASA Astrophysics Data System (ADS)

Koch, B. P.; Flerus, R.; Schmitt-Kopplin, P.; Lechtenfeld, O. J.; Bracher, A.; Cooper, W.; Frka, S.; Gašparović, B.; Gonsior, M.; Hertkorn, N.; Jaffe, R.; Jenkins, A.; Kuss, J.; Lara, R. J.; Lucio, M.; McCallister, S. L.; Neogi, S. B.; Pohl, C.; Roettgers, R.; Rohardt, G.; Schmitt, B. B.; Stuart, A.; Theis, A.; Ying, W.; Witt, M.; Xie, Z.; Yamashita, Y.; Zhang, L.; Zhu, Z. Y.; Kattner, G.

2010-12-01

One of the most important aspects to understand marine organic carbon fluxes is to resolve the molecular mechanisms which convert fresh, labile biomolecules into semi-labile and refractory dissolved and particulate organic compounds in the ocean. In this interdisciplinary project, which was performed on a cruise with RV Polarstern, we carried out a detailed molecular characterisation of dissolved organic matter (DOM) on a North-South transect in the Atlantic surface ocean in order to relate the data to different biological, climatic, oceanographic, and meteorological regimes as well as to terrestrial input from riverine and atmospheric sources. Our goal was to achieve a high resolution data set for the biogeochemical characterisation of the sources and reactivity of DOM. We applied ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS), nutrient, trace element, amino acid, and lipid analyses and other biogeochemical measurements for 220 samples from the upper water column (0-200m) and eight deep profiles. Various spectroscopic techniques were applied continuously in a constant sample water flow supplied by a fish system and the moon pool. Radiocarbon dating enabled assessing DOC residence time. Bacterial abundance and production provided a metabolic context for the DOM characterization work and pCO2 concentrations. Combining molecular organic techniques and inductively coupled plasma mass spectrometry (ICP-MS) established an important link between organic and inorganic biogeochemical studies. Multivariate statistics, primarily based on FT-ICR-MS data for 220 samples, allowed identifying geographical clusters which matched ecological provinces proposed previously by Longhurst (2007). Our study demonstrated that marine DOM carries molecular information reflecting the “history” of ocean water masses. This information can be used to define molecular biogeochemical provinces and to improve our understanding of element fluxes in the ocean. Future “organic geotraces” studies should focus on extracting and establishing new organic proxies which are suitable to characterize and, in particular, quantify organic matter sources and transformation processes in the ocean. Longhurst AR (2007) Ecological geography of the sea. Academic Press, San Diego, 542 pp.

Depth-dependent variations of sedimentary dissolved organic matter composition in a eutrophic lake: Implications for lake restoration.

PubMed

Xu, Huacheng; Guo, Laodong; Jiang, Helong

2016-02-01

Dissolved organic matter (DOM) plays a significant role in regulating nutrients and carbon cycling and the reactivity of trace metals and other contaminants in the environment. However, the environmental/ecological role of sedimentary DOM is highly dependent on organic composition. In this study, fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis, two dimensional correlation spectroscopy (2D-COS), and ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) were applied to investigate the depth-dependent variations of sediment-leached DOM components in a eutrophic lake. Results of EEM-PARAFAC and 2D-COS showed that fluorescent humic-like component was preferentially degraded microbially over fulvic-like component at greater sediment depths, and the relative abundance of non-fluorescent components decreased with increasing depth, leaving the removal rate of carbohydrates > lignins. The predominant sedimentary DOM components derived from FT-ICR-MS were lipids (>50%), followed by lignins (∼15%) and proteins (∼15%). The relative abundance of carbohydrates, lignins, and condensed aromatics decreased significantly at greater depths, whereas that of lipids increased in general with depth. There existed a significant negative correlation between the short-range ordered (SRO) minerals and the total dissolved organic carbon concentration or the relative contents of lignins and condensed aromatics (p < 0.05), suggesting that SRO mineral sorption plays a significant role in controlling the composition heterogeneity and releasing of DOM in lake sediments. Higher metal binding potential observed for DOM at deeper sediment depth (e.g., 25-30 cm) supported the ecological safety of sediment dredging technique from the viewpoint of heavy metal de-toxicity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chemical Composition of Microbe-Derived Dissolved Organic Matter in Cryoconite in Tibetan Plateau Glaciers: Insights from Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Analysis.

PubMed

Feng, Lin; Xu, Jianzhong; Kang, Shichang; Li, Xiaofei; Li, Yang; Jiang, Bin; Shi, Quan

2016-12-20

Cryoconite in mountain glaciers plays important roles in glacial ablation and biogeochemical cycles. In this study, the composition and sources of dissolved organic matter (DOM) in cryoconite from the ablation regions of two Tibetan Plateau glaciers were determined using electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence spectrometry. A marked absorbance between 300 and 350 nm in the DOM absorption spectra was observed which was consistent with microbe-derived mycosporine-like amino acids. Fluorescence excitation-emission matrices showed that DOM had intense signals at protein-like substance peaks and weak signals at humic-like substance peaks. The high-resolution mass spectra of FT-ICR-MS showed cryoconite DOM from both glaciers contained diverse lignins, lipids, proteins, and unsaturated hydrocarbons. The lipids and proteins were consistent with material from microbial sources, and the lignins and unsaturated hydrocarbons were probably from vascular plant material supplied in atmospheric aerosols and debris from around the glaciers. Almost one-third of the identified DOM molecules had low C/N ratios (≤20), indicating their high bioavailability. Using a conservative cryoconite distribution on Chinese mountain glacier surfaces (6%) and an average debris mass per square meter of cryoconite (292 ± 196 g m -2 ), we found that the amount of DOC produced in cryoconite on Chinese glaciers as much as 0.23 ± 0.1 Gg per cryoconite formation process. This dissolved organic carbon may absorb solar radiation, accelerate glacial melting, and be an important source of bioavailable DOM to proglacial and downstream aquatic ecosystems.

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

PubMed

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

2012-10-15

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

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.

The Molecular Composition of Dissolved Organic Matter in Forest Soils as a Function of pH and Temperature

PubMed Central

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2015-01-01

We examined the molecular composition of forest soil water during three different seasons at three different sites, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). We examined oxic soils and tested the hypothesis that pH and season correlate with the molecular composition of dissolved organic matter (DOM). We used molecular formulae and their relative intensity from ESI-FT-ICR-MS for statistical analysis. Applying unconstrained and constrained ordination methods, we observed that pH, dissolved organic carbon (DOC) concentration and season were the main factors correlating with DOM molecular composition. This result is consistent with a previous study where pH was a main driver of the molecular differences between DOM from oxic rivers and anoxic bog systems in the Yenisei River catchment. At a higher pH, the molecular formulae had a lower degree of unsaturation and oxygenation, lower molecular size and a higher abundance of nitrogen-containing compounds. These characteristics suggest a higher abundance of tannin connected to lower pH that possibly inhibited biological decomposition. Higher biological activity at a higher pH might also be related to the higher abundance of nitrogen-containing compounds. Comparing the seasons, we observed a decrease in unsaturation, molecular diversity and the number of nitrogen-containing compounds in the course of the year from March to November. Temperature possibly inhibited biological degradation during winter, which could cause the accumulation of a more diverse compound spectrum until the temperature increased again. Our findings suggest that the molecular composition of DOM in soil pore waters is dynamic and a function of ecosystem activity, pH and temperature. PMID:25793306

Surface-induced dissociation: a unique tool for studying energetics and kinetics of the gas-phase fragmentation of large ions

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

Laskin, Julia

2015-01-01

Surface-induced dissociation (SID) is valuable tool for investigating activation and dissociation of large ions in tandem mass spectrometry. This account summarizes key findings from studies of the energetics and mechanisms of complex ion dissociation, in which SID experiments were combined with Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data. These studies used time- and collision-energy-resolved SID experiments and SID combined with resonant ejection of selected fragment ions on a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Fast ion activation by collision with a surface combined with the long and variable timescale of a FT-ICR MS is perfectlymore » suited for studying the energetics and dynamics of complex ion dissociation in the gas phase. Modeling of time- and collision-energy-resolved SID enables accurate determination of energy and entropy effects in the dissociation process. It has been demonstrated that entropy effects play an important role in determining the dissociation rates of both covalent and non-covalent bonds in large gaseous ions. SID studies have provided important insights on the competition between charge-directed and charge-remote fragmentation in even-electron peptide ions and the role of charge and radical site on the energetics of the dissociation of odd-electron peptide ions. Furthermore, this work examined factors that affect the strength of non-covalent binding, as well as the competition between covalent and non-covalent bond cleavages and between proton and electron transfer in model systems. Finally, SID studies have been used to understand the factors affecting nucleation and growth of clusters in solution and the gas phase.« less

Molecular fractionation of dissolved organic matter with metal salts.

PubMed

Riedel, Thomas; Biester, Harald; Dittmar, Thorsten

2012-04-17

Coagulation of dissolved organic matter (DOM) by hydrolyzing metals is an important environmental process with particular relevance, e.g., for the cycling of organic matter in metal-rich aquatic systems or the flocculation of organic matter in wastewater treatment plants. Often, a nonremovable fraction of DOM remains in solution even at low DOM/metal ratios. Because coagulation by metals results from interactions with functional groups, we hypothesize that noncoagulating fractions have a distinct molecular composition. To test the hypothesis, we analyzed peat-derived dissolved organic matter remaining in solution after mixing with salts of Ca, Al, and Fe using 15 T Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Addition of metals resulted in a net removal of DOM. Also a reduction of molecular diversity was observed, as the number of peaks from the ESI-FT-ICR-MS spectra decreased. At DOM/metal ratios of ∼9 Ca did not show any preference for distinct molecular fractions, while Fe and Al removed preferentially the most oxidized compounds (O/C ratio >0.4) of the peat leachate. Lowering DOM/metal ratios to ∼1 resulted in further removal of less oxidized as well as more aromatic compounds ("black carbon"). Molecular composition in the residual solution after coagulation was more saturated, less polar, and less oxidized compared to the original peat leachate and exhibited a surprising similarity with DOM of marine origin. By identifying more than 9200 molecular formulas we can show that structural properties (saturation and aromaticity) and oxygen content of individual DOM molecules play an important role in coagulation with metals. We conclude that polyvalent cations not only alter the net mobility but also the very molecular composition of DOM in aquatic environments.

Further insight into the roles of the chemical composition of dissolved organic matter (DOM) on ultrafiltration membranes as revealed by multiple advanced DOM characterization tools.

PubMed

Ly, Quang Viet; Hur, Jin

2018-06-01

This study assessed the relative contributions of different constitutes in dissolved organic matter (DOM) with two different sources (i.e., urban river and effluent) to membrane fouling on three types of ultrafiltration (UF) membranes via excitation emission matrix - parallel factor analysis (EEM-PARAFAC), size exclusion chromatography (SEC), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Two polyethersulfone membranes with different pore sizes and one regenerated cellulose membrane were used as representative hydrophobic (HPO) and hydrophilic (HPI) UF membranes, respectively. Although size exclusion effect was found to be the most prevailing rejection mechanism, the behaviors of individual fluorescent components (one tryptophan-like, one microbial-humic-like, and terrestrial humic-like) and different size fractions upon the UF filtration revealed that chemical interactions (e.g., hydrophobic interactions and hydrogen bonding) between DOM and membrane might play important roles in UF membrane fouling, especially for small sized DOM molecules. Based on the molecular level composition determined by FT-ICR-MS, the CHOS formula group showed a greater removal tendency toward the HPO membrane, while the CHONS group was prone to be removed by the HPI membrane. The changes in the overall molecular composition of DOM upon UF filtration were highly dependent on the sources of DOM. The molecules of more acidic nature tended to remain in the permeate of effluent DOM, while the river DOM was shifted into more nitrogen-enriched composition after filtration. Regardless of the DOM sources, the HPO membrane with a smaller pore size led to the most pronounced changes in the molecular composition of DOM. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

Jarvis, Jacqueline M.; Billing, Justin M.; Corilo, Yuri E.

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

From Supercomputer Modeling to Highest Mass Resolution in FT-ICR.

PubMed

N Nikolaev, Evgene; N Vladimirov, Gleb; Jertz, Roland; Baykut, Gökhan

2013-01-01

Understanding of behavior of ion ensembles inside FT-ICR cell based on the computer simulation of ion motion gives rise to the new ideas of cell designs. The recently introduced novel FT-ICR cell based on a Penning ion trap with specially shaped excitation and detection electrodes prevents distortion of ion cyclotron motion phases (normally caused by non-ideal electric trapping fields) by averaging the trapping DC electric field during the ion motion in the ICR cell. Detection times of 5 min resulting in resolving power close to 40,000,000 have been reached for reserpine at m/z 609 at a magnetic field of only 7 Tesla. Fine structures of resolved 13Cn isotopic cluster groups could be measured for molecular masses up to 5.7 kDa (insulin) with resolving power of 4,000,000 at 7 Tesla. Based on resolved fine structure patterns atomic compositions can be directly determined using a new developed algorithm for fine structure processing. Mass spectra of proteins and multimers of proteins reaching masses up to 186 kDa (enolase tetramer) could be measured with isotopic resolution. For instance, at 7 Tesla resolving power of 800,000 was achieved for enolase dimer (96 kDa) and 500,000 for molecular masses above 100 kDa. Experimental data indicate that there is practically no limit for the resolving power of this ICR cell except by collisional damping in the ultrahigh vacuum chamber.

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

NASA Astrophysics Data System (ADS)

Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

2008-09-01

Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50 500 Da in the rainwater. Three main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, and S- and nitrogen containing CHONS compounds. Organic acids commonly identified in precipitation were detected, as well as linear alkylbenzene sulfonates, which are persistent pollutants commonly measured in river water, seawater, and sediments, but to our knowledge, not previously documented in atmospheric samples. Within the three main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitroxy-organosulfates were identified. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

A novel microreactor approach for analysis of ketones and aldehydes in breath.

PubMed

Fu, Xiao-An; Li, Mingxiao; Biswas, Souvik; Nantz, Michael H; Higashi, Richard M

2011-11-21

We report a fabricated microreactor with thousands of micropillars in channels. Each micropillar surface is chemically functionalized to selectively preconcentrate gaseous ketones and aldehydes of exhaled breath and to enhance ultra-trace, rapid analysis by direct-infusion Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry (MS). The micropillar reactive coating contains the quaternary ammonium aminooxy salt 2-(aminooxy)ethyl-N,N,N-trimethylammonium iodide (ATM) for capturing trace carbonyl VOCs by means of an oximation reaction. We demonstrate the utility of this approach for detection of C(1) to C(12) aldehydes and ketones in exhaled breath, but the approach is applicable to any gaseous sample.

Spectral Accuracy and Sulfur Counting Capabilities of the LTQ-FT-ICR and the LTQ-Orbitrap XL for Small Molecule Analysis

NASA Astrophysics Data System (ADS)

Blake, Samantha L.; Walker, S. Hunter; Muddiman, David C.; Hinks, David; Beck, Keith R.

2011-12-01

Color Index Disperse Yellow 42 (DY42), a high-volume disperse dye for polyester, was used to compare the capabilities of the LTQ-Orbitrap XL and the LTQ-FT-ICR with respect to mass measurement accuracy (MMA), spectral accuracy, and sulfur counting. The results of this research will be used in the construction of a dye database for forensic purposes; the additional spectral information will increase the confidence in the identification of unknown dyes found in fibers at crime scenes. Initial LTQ-Orbitrap XL data showed MMAs greater than 3 ppm and poor spectral accuracy. Modification of several Orbitrap installation parameters (e.g., deflector voltage) resulted in a significant improvement of the data. The LTQ-FT-ICR and LTQ-Orbitrap XL (after installation parameters were modified) exhibited MMA ≤ 3 ppm, good spectral accuracy (χ2 values for the isotopic distribution ≤ 2), and were correctly able to ascertain the number of sulfur atoms in the compound at all resolving powers investigated for AGC targets of 5.00 × 105 and 1.00 × 106.

Properties of bio-oil generated by a pyrolysis of forest cedar residuals with the movable Auger-type reactor

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

Nishimura, Shun; Ebitani, Kohki, E-mail: ebitani@jaist.ac.jp; Miyazato, Akio

Our research project has developed the new movable reactor for bio-oil production in 2013 on the basis of Auger-type system. This package would be a great impact due to the concept of local production for local consumption in the hilly and mountainous area in not only Japan but also in the world. Herein, we would like to report the properties of the bio-oil generated by the developing Auger-type movable reactor. The synthesized bio-oil possessed C: 46.2 wt%, H: 6.5 wt%, N: wt%, S: <0.1 wt%, O: 46.8 wt% and H{sub 2}O: 18.4 wt%, and served a good calorific value ofmore » 18.1 MJ/kg. The spectroscopic and mass analyses such as FT-IR, GC-MS, {sup 13}C-NMR and FT-ICR MS supported that the bio-oil was composed by the fine mixtures of methoxy phenols and variety of alcohol or carboxylic acid functional groups. Thus, it is suggested that the bio-oil generated by the new movable Auger-type reactor has a significant potential as well as the existing bio-oil reported previously.« less

Polymer architectures via mass spectrometry and hyphenated techniques: A review.

PubMed

Crotty, Sarah; Gerişlioğlu, Selim; Endres, Kevin J; Wesdemiotis, Chrys; Schubert, Ulrich S

2016-08-17

This review covers the application of mass spectrometry (MS) and its hyphenated techniques to synthetic polymers of varying architectural complexities. The synthetic polymers are discussed as according to their architectural complexity from linear homopolymers and copolymers to stars, dendrimers, cyclic copolymers and other polymers. MS and tandem MS (MS/MS) has been extensively used for the analysis of synthetic polymers. However, the increase in structural or architectural complexity can result in analytical challenges that MS or MS/MS cannot overcome alone. Hyphenation to MS with different chromatographic techniques (2D × LC, SEC, HPLC etc.), utilization of other ionization methods (APCI, DESI etc.) and various mass analyzers (FT-ICR, quadrupole, time-of-flight, ion trap etc.) are applied to overcome these challenges and achieve more detailed structural characterizations of complex polymeric systems. In addition, computational methods (software: MassChrom2D, COCONUT, 2D maps etc.) have also reached polymer science to facilitate and accelerate data interpretation. Developments in technology and the comprehension of different polymer classes with diverse architectures have significantly improved, which allow for smart polymer designs to be examined and advanced. We present specific examples covering diverse analytical aspects as well as forthcoming prospects in polymer science. Copyright © 2016 Elsevier B.V. All rights reserved.

Towards unsupervised polyaromatic hydrocarbons structural assignment from SA-TIMS-FTMS data.

PubMed

Benigni, Paolo; Marin, Rebecca; Fernandez-Lima, Francisco

2015-10-01

With the advent of high resolution ion mobility analyzers and their coupling to ultrahigh resolution mass spectrometers, there is a need to further develop a theoretical workflow capable of correlating experimental accurate mass and mobility measurements with tridimensional candidate structures. In the present work, a general workflow is described for unsupervised tridimensional structural assignment based on accurate mass measurements, mobility measurements, in silico 2D-3D structure generation, and theoretical mobility calculations. In particular, the potential of this workflow will be shown for the analysis of polyaromatic hydrocarbons from Coal Tar SRM 1597a using selected accumulation - trapped ion mobility spectrometry (SA-TIMS) coupled to Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). The proposed workflow can be adapted to different IMS scenarios, can utilize different collisional cross-section calculators and has the potential to include MS n and IMS n measurements for faster and more accurate tridimensional structural assignment.

Effect of the Basic Residue on the Energetics, Dynamics and Mechanisms of Gas- Phase Fragmentation of Protonated Peptides

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

Laskin, Julia; Yang, Zhibo; Song, Tao

2010-11-17

The effect of the basic residue on the energetics, dynamics and mechanisms of backbone fragmentation of protonated peptides was investigated. Time- and collision energy-resolved surface-induced dissociation (SID) of singly protonated peptides with the N-terminal arginine residue and their analogs, in which arginine is replaced with less basic lysine and histidine residues was examined using in a specially configured Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). SID experiments demonstrated very different kinetics of formation of several primary product ions of peptides with and without arginine residue. The energetics and dynamics of these pathways were determined from the RRKM modelingmore » of the experimental data. Comparison between the kinetics and energetics of fragmentation of arginine-containing peptides and the corresponding methyl ester derivatives provides important information on the effect of dissociation pathways involving salt bridge (SB) intermediates on the observed fragmentation behavior. It is found that because pathways involving SB intermediates are characterized by low threshold energies, they efficiently compete with classical oxazolone pathways of arginine-containing peptides on a long timescale of the FT-ICR instrument. In contrast, fragmentation of histidine- and lysine-containing peptides is largely determined by classical oxazolone pathways. Because SB pathways are characterized by negative activation entropies, fragmentation of arginine-containing peptides is kinetically hindered and observed at higher collision energies as compared to their lysine- and histidine-containing analogs.« less

A novel mice model of metabolic syndrome: the high-fat-high-fructose diet-fed ICR mice.

PubMed

Zhuhua, Zhang; Zhiquan, Wang; Zhen, Yang; Yixin, Niu; Weiwei, Zhang; Xiaoyong, Li; Yueming, Liu; Hongmei, Zhang; Li, Qin; Qing, Su

2015-01-01

Currently, the metabolic syndrome (MS) is occurring at growing rates worldwide, raising extensive concerns on the mechanisms and therapeutic interventions for this disorder. Herein, we described a novel method of establishing MS model in rodents. Male Institute of Cancer Research (ICR) mice were fed with high-fat-high-fructose (HFHF) diet or normal chow (NC) respectively for 12 weeks. Metabolic phenotypes were assessed by glucose tolerance test, insulin tolerance test and hyperinsulinemic-euglycemic clamp. Blood pressure was measured by a tail-cuff system. At the end of the experiment, mice were sacrificed, and blood and tissues were harvested for subsequent analysis. Serum insulin levels were measured by ELISA, and lipid profiles were determined biochemically. The HFHF diet-fed ICR mice exhibited obvious characteristics of the components of MS, including obvious obesity, severe insulin resistance, hyperinsulinemia, dislipidemia, significant hypertension and hyperuricemia. Our data suggest that HFHF diet-fed ICR mice may be a robust and efficient animal model that could well mimic the basic pathogenesis of human MS.

Application of Tandem Two-Dimensional Mass Spectrometry for Top-Down Deep Sequencing of Calmodulin.

PubMed

Floris, Federico; Chiron, Lionel; Lynch, Alice M; Barrow, Mark P; Delsuc, Marc-André; O'Connor, Peter B

2018-06-04

Two-dimensional mass spectrometry (2DMS) involves simultaneous acquisition of the fragmentation patterns of all the analytes in a mixture by correlating their precursor and fragment ions by modulating precursor ions systematically through a fragmentation zone. Tandem two-dimensional mass spectrometry (MS/2DMS) unites the ultra-high accuracy of Fourier transform ion cyclotron resonance (FT-ICR) MS/MS and the simultaneous data-independent fragmentation of 2DMS to achieve extensive inter-residue fragmentation of entire proteins. 2DMS was recently developed for top-down proteomics (TDP), and applied to the analysis of calmodulin (CaM), reporting a cleavage coverage of about ~23% using infrared multiphoton dissociation (IRMPD) as fragmentation technique. The goal of this work is to expand the utility of top-down protein analysis using MS/2DMS in order to extend the cleavage coverage in top-down proteomics further into the interior regions of the protein. In this case, using MS/2DMS, the cleavage coverage of CaM increased from ~23% to ~42%. Graphical Abstract Two-dimensional mass spectrometry, when applied to primary fragment ions from the source, allows deep-sequencing of the protein calmodulin.

Linear excitation and detection in Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Grosshans, Peter B.; Chen, Ruidan; Limbach, Patrick A.; Marshall, Alan G.

1994-11-01

We present the first Fourier transform ion cyclotron resonance (FT-ICR) ion trap designed to produce both a linear spatial variation of the excitation electric potential field and a linear response of the detection circuit to the motion of the confined ions. With this trap, the magnitude of the detected signal at a given ion cyclotron frequency varies linearly with both the number of ions of given mass-to-charge ratio and also with the magnitude-mode excitation signal at the ion cyclotron orbital frequency; the proportionality constant is mass independent. Interestingly, this linearization may be achieved with any ion trap geometry. The excitation/detection design consists of an array of capacitively coupled electrodes which provide a voltage-divider network that produces a nearly spatially homogeneous excitation electric field throughout the linearized trap; resistive coupling to the electrodes isolates the a.c. excitation (or detection) circuit from the d.c. (trapping) potential. The design is based on analytical expressions for the potential associated with each electrode, from which we are able to compute the deviation from linearity for a trap with a finite number of elements. Based on direct experimental comparisons to an unmodified cubic trap, the linearized trap demonstrates the following performance advantages at the cost of some additional mechanical complexity: (a) signal response linearly proportional to excitation electric field amplitude; (b) vastly reduced axial excitation/ejection for significantly improved ion relative abundance accuracy; (c) elimination of harmonics and sidebands of the fundamental frequencies of ion motion. As a result, FT-ICR mass spectra are now more reproducible. Moreover, the linearized trap should facilitate the characterization of other fundamental aspects of ion behavior in an ICR ion trap, e.g. effects of space charge, non-quadrupolar electrostatic trapping field, etc. Furthermore, this novel design should improve significantly the precision of ion relative abundance and mass accuracy measurements, while removing spectral artifacts of the detection process. We discuss future modifications that linearize the spatial variation of the electrostatic trapping electric field as well, thereby completing the linearization of the entire FT-ICR mass spectrometric techniques. Suggested FT-ICR mass spectrometric applications for the linearized trap are discussed.

Deamidation and transamidation of substance P by tissue transglutaminase revealed by electron-capture dissociation fourier transform mass spectrometry.

PubMed

Fornelli, Luca; Schmid, Adrien W; Grasso, Luigino; Vogel, Horst; Tsybin, Yury O

2011-01-10

Tissue transglutaminase (tTGase) catalyzes both deamidation and transamidation of peptides and proteins by using a peptidyl glutamine as primary substrate. A precise consensus sequence for the enzyme is unknown and the ratio between deamidated and transamidated (or cross-linked) reaction products is highly substrate-dependent. Due to its overlapping body distribution with tTGase and ease of manipulation with tandem mass spectrometry, we used the neuropeptide substance P as a model to investigate the associated enzymatic kinetics and reaction products. Online liquid-chromatography Fourier-transform ion-cyclotron-resonance mass spectrometry (FT-ICR MS) combined with electron-capture dissociation (ECD) was employed to study the tTGase-induced modifications of substance P. A particular strength of ECD for peptide-enzyme reaction product monitoring is its ability to distinguish isomeric amino acids, for example, Glu and iso-Glu, by signature product ions. Our studies show that the primary reaction observed is deamidation, with the two consecutive glutamine residues converted sequentially into glutamate: first Gln(5) , and subsequently Gln(6) . We then applied ECD FT-ICR MS to identify the transamidation site on an enzymatically cross-linked peptide, which turned out to correspond to Gln(5) . Three populations of substance-P dimers were detected that differed by the number of deamidated Gln residues. The higher reactivity of Gln(5) over Gln(6) was further confirmed by cross-linking SP with monodansylcadaverine (MDC). Overall, our approach described herein is of a general importance for mapping both enzymatically induced post-translational protein modifications and cross-linking. Finally, in vitro Ca-signaling assays revealed that the main tTGase reaction product, the singly deamidated SP (RPKPEQFFGLM-NH(2) ), has increased agonist potency towards its natural receptor, thus confirming the biologically relevant role of deamidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uncoupling of Bacterial and Terrigenous Dissolved Organic Matter Dynamics in Decomposition Experiments

PubMed Central

Herlemann, Daniel P. R.; Manecki, Marcus; Meeske, Christian; Pollehne, Falk; Labrenz, Matthias; Schulz-Bull, Detlef; Dittmar, Thorsten; Jürgens, Klaus

2014-01-01

The biodegradability of terrigenous dissolved organic matter (tDOM) exported to the sea has a major impact on the global carbon cycle, but our understanding of tDOM bioavailability is fragmentary. In this study, the effects of preparative tDOM isolation on microbial decomposition were investigated in incubation experiments consisting of mesocosms containing mesohaline water from the Baltic Sea. Dissolved organic carbon (DOC) consumption, molecular DOM composition, bacterial activities, and shifts in bacterial community structure were compared between mesocosms supplemented with riverine tDOM, either as filtered, particle-free river water or as a concentrate obtained by lyophilization/tangential ultrafiltration, and those containing only Baltic Sea water or river water. As shown using ultra-high-resolution mass spectrometry (15 Tesla Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) covering approximately 4600 different DOM compounds, the three DOM preparation protocols resulted in distinct patterns of molecular DOM composition. However, despite DOC losses of 4–16% and considerable bacterial production, there was no significant change in DOM composition during the 28-day experiment. Moreover, tDOM addition affected neither DOC degradation nor bacterial dynamics significantly, regardless of the tDOM preparation. This result suggested that the introduced tDOM was largely not bioavailable, at least on the temporal scale of our experiment, and that the observed bacterial activity and DOC decomposition mainly reflected the degradation of unknown, labile, colloidal and low-molecular weight DOM, both of which escape the analytical window of FT-ICR-MS. In contrast to the different tDOM preparations, the initial bacterial inoculum and batch culture conditions determined bacterial community succession and superseded the effects of tDOM addition. The uncoupling of tDOM and bacterial dynamics suggests that mesohaline bacterial communities cannot efficiently utilize tDOM and that in subarctic estuaries other factors are responsible for the removal of imported tDOM. PMID:24718626

Is the molecular diversity of marine dissolved organic matter already imprinted in the exometabolome of single strains?

NASA Astrophysics Data System (ADS)

Noriega-Ortega, B. E.; Wienhausen, G.; Dittmar, T.; Simon, M.; Niggemann, J.

2016-02-01

Dissolved organic matter (DOM) in the ocean, the marine geometabolome, is an extremely complex mixture composed of a wide variety of compounds. The molecular chemodiversity affects the function and turnover rate of DOM in the ocean. We hypothesize that the active microbial community essentially contributes to the complexity of the DOM pool through uptake and excretion of compounds. We tested this hypothesis in culture experiments with fully-sequenced strains of the Roseobacter clade. Bacteria of the Roseobacter clade are among the most abundant microbial players in the ocean. We studied the exometabolome of two representatives of the Roseobacter clade, Phaeobacter inhibens DSM 17395 and Dinoroseobacter shibae. The organisms were grown separately in cultures on defined single model substrates (acetate, succinate, glutamate, glucose). We used a non-targeted analytical approach via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the exometabolome at the molecular level, complemented by compound-specific analyses of free and combined amino acids and carbohydrates. The exometabolome composition varied between the tested strains, which released a different suite of compounds depending on the growth phase as well as on growth conditions (substrate). Both organisms exhibited a core exometabolome with compounds released when growing on either substrate and at all growth phases, and a variable exometabolome specific for different substrates and growth phases. However, only a small fraction of the exometabolites detected by FT-ICR-MS could be directly linked to the genome or transcriptome. We interpret these findings as evidence for the excretion of molecularly highly-diverse metabolic waste, whose composition is dependent on the metabolic state and genetic repertoire of the organisms. The molecular diversity of compounds excreted by a single strain is extraordinary and is likely the reason for the molecular diversity of natural DOM in the ocean.

Isolated cognitive relapses in multiple sclerosis.

PubMed

Pardini, Matteo; Uccelli, Antonio; Grafman, Jordan; Yaldizli, Özgür; Mancardi, Gianluigi; Roccatagliata, Luca

2014-09-01

While cognition can be affected during sensorimotor multiple sclerosis (MS) relapses, the relevance of isolated cognitive relapses (ICRs ie, those occurring in absence of new sensorimotor symptoms) remain poorly characterised. Here, we decided to explore the relationship between ICR, subjective evaluation of cognitive performance and long-term cognitive decline in a group of subjects with relapsing-remitting MS. We analysed the cognitive performance of 99 clinically stable relapsing-remitting MS for whom data from four consequent clinical and cognitive evaluations were available, that is, a baseline evaluation (t₀), followed in the subsequent 6 months by a second evaluation performed not later than 2 weeks after a routine brain scan positive for at least one area of gadolinium enhancement (t₁) and two gadolinium enhancement-negative follow-up evaluations after 6 months (t₂) and 1 year (t₃) from t₁. Based on published literature, we defined as a meaningful change in cognition a transient reduction of Symbol Digit Modalities Test score of at least four points at t₁ compared with t₀ and t₂. ICRs were found in 17 patients and were not associated with subjective cognitive deficits or depression. Subjects who presented with an ICR at t₁ presented with a significantly reduced cognitive performance at the follow-up evaluations compared with patients without ICR. We showed that ICRs were not associated with changes in mood, fatigue levels or cognitive performance self-evaluations. Our study introduces an operational definition of ICRs and suggests to their role as a factor for cognitive decline in MS. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry.

PubMed

Remucal, Christina K; Cory, Rose M; Sander, Michael; McNeill, Kristopher

2012-09-04

Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses <600 Da in a complex mixture, such as SRFA. The most intense masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.

A novel mice model of metabolic syndrome: the high-fat-high-fructose diet-fed ICR mice

PubMed Central

Zhuhua, Zhang; Zhiquan, Wang; Zhen, Yang; Yixin, Niu; Weiwei, Zhang; Xiaoyong, Li; Yueming, Liu; Hongmei, Zhang; Li, Qin; Qing, Su

2015-01-01

Currently, the metabolic syndrome (MS) is occurring at growing rates worldwide, raising extensive concerns on the mechanisms and therapeutic interventions for this disorder. Herein, we described a novel method of establishing MS model in rodents. Male Institute of Cancer Research (ICR) mice were fed with high-fat-high-fructose (HFHF) diet or normal chow (NC) respectively for 12 weeks. Metabolic phenotypes were assessed by glucose tolerance test, insulin tolerance test and hyperinsulinemic-euglycemic clamp. Blood pressure was measured by a tail-cuff system. At the end of the experiment, mice were sacrificed, and blood and tissues were harvested for subsequent analysis. Serum insulin levels were measured by ELISA, and lipid profiles were determined biochemically. The HFHF diet-fed ICR mice exhibited obvious characteristics of the components of MS, including obvious obesity, severe insulin resistance, hyperinsulinemia, dislipidemia, significant hypertension and hyperuricemia. Our data suggest that HFHF diet-fed ICR mice may be a robust and efficient animal model that could well mimic the basic pathogenesis of human MS. PMID:26134356

Intact and Top-Down Characterization of Biomolecules and Direct Analysis Using Infrared Matrix-Assisted Laser Desorption Electrospray Ionization Coupled to FT-ICR Mass Spectrometry

PubMed Central

Sampson, Jason S.; Murray, Kermit K.; Muddiman, David C.

2013-01-01

We report the implementation of an infrared laser onto our previously reported matrix-assisted laser desorption electrospray ionization (MALDESI) source with ESI post-ionization yielding multiply charged peptides and proteins. Infrared (IR)-MALDESI is demonstrated for atmospheric pressure desorption and ionization of biological molecules ranging in molecular weight from 1.2 to 17 kDa. High resolving power, high mass accuracy single-acquisition Fourier transform ion cyclotron resonance (FT-ICR) mass spectra were generated from liquid-and solid-state peptide and protein samples by desorption with an infrared laser (2.94 µm) followed by ESI post-ionization. Intact and top-down analysis of equine myoglobin (17 kDa) desorbed from the solid state with ESI post-ionization demonstrates the sequencing capabilities using IR-MALDESI coupled to FT-ICR mass spectrometry. Carbohydrates and lipids were detected through direct analysis of milk and egg yolk using both UV- and IR-MALDESI with minimal sample preparation. Three of the four classes of biological macromolecules (proteins, carbohydrates, and lipids) have been ionized and detected using MALDESI with minimal sample preparation. Sequencing of O-linked glycans, cleaved from mucin using reductive β-elimination chemistry, is also demonstrated. PMID:19185512

Evaluation of arterial stiffness by finger-toe pulse wave velocity: optimization of signal processing and clinical validation.

PubMed

Obeid, Hasan; Khettab, Hakim; Marais, Louise; Hallab, Magid; Laurent, Stéphane; Boutouyrie, Pierre

2017-08-01

Carotid-femoral pulse wave velocity (PWV) (cf-PWV) is the gold standard for measuring aortic stiffness. Finger-toe PWV (ft-PWV) is a simpler noninvasive method for measuring arterial stiffness. Although the validity of the method has been previously assessed, its accuracy can be improved. ft-PWV is determined on the basis of a patented height chart for the distance and the pulse transit time (PTT) between the finger and the toe pulpar arteries signals (ft-PTT). The objective of the first study, performed in 66 patients, was to compare different algorithms (intersecting tangents, maximum of the second derivative, 10% threshold and cross-correlation) for determining the foot of the arterial pulse wave, thus the ft-PTT. The objective of the second study, performed in 101 patients, was to investigate different signal processing chains to improve the concordance of ft-PWV with the gold-standard cf-PWV. Finger-toe PWV (ft-PWV) was calculated using the four algorithms. The best correlations relating ft-PWV and cf-PWV, and relating ft-PTT and carotid-femoral PTT were obtained with the maximum of the second derivative algorithm [PWV: r = 0.56, P < 0.0001, root mean square error (RMSE) = 0.9 m/s; PTT: r = 0.61, P < 0.001, RMSE = 12 ms]. The three other algorithms showed lower correlations. The correlation between ft-PTT and carotid-femoral PTT further improved (r = 0.81, P < 0.0001, RMSE = 5.4 ms) when the maximum of the second derivative algorithm was combined with an optimized signal processing chain. Selecting the maximum of the second derivative algorithm for detecting the foot of the pressure waveform, and combining it with an optimized signal processing chain, improved the accuracy of ft-PWV measurement in the current population sample. Thus, it makes ft-PWV very promising for the simple noninvasive determination of aortic stiffness in clinical practice.

Identification of water-soluble polar organics in air and vehicular emitted particulate matter using ultrahigh resolution mass spectrometry and Capillary electrophoresis - mass spectrometry.

NASA Astrophysics Data System (ADS)

Schmitt-Kopplin, P.; Yassine, M.; Gebefugi, I.; Hertkorn, N.; Dabek-Zlotorzynska, E.

2009-04-01

The effects of aerosols on human health, atmospheric chemistry, and climate are among the central topics in current environmental health research. Detailed and accurate measurements of the chemical composition of air particulate matter (PM) represent a challenging analytical task. Minute sample amounts are usually composed of several main constituents and hundreds of minor and trace constituents. Moreover, the composition of individual particles can be fairly uniform or very different (internally or externally mixed aerosols), depending on their origin and atmospheric aging processes (coagulation, condensation / evaporation, chemical reaction). The aim of the presentation was the characterization of the organic matter (OM) fraction of environmental aerosols which is not accessible by GC-methods, either because of their high molecular weight, their polarity or due to thermal instability. We also describe the main chemical characteristics of complexe oligomeric organic fraction extracted from different aerosols collected in urban and rural area in Germany and Canada. Mass spectrometry (MS) became an essential tool used by many prominent leaders of the biological research community and the importance of MS to the future of biological research is now clearly evident as in the fields of Proteomics and Metabolomics. Especially Fourier Transform Ion Cyclotron Mass Spectrometry (ICR-FT/MS) is an ultrahigh resolution MS that allows new approach in the analysis of complex mixtures. The mass resolution (< 200 ppb) allowed assigning the elemental composition (C, H, O, N, S…) to each of the obtained mass peaks and thus already a description of the mixture in terms of molecular composition. This possibility is used by the authors together with a high resolution separation method of charged compounds: capillary electrophoresis. A CE-ESI-MS method using an ammonium acetate based background electrolyte (pH 4.7) was developed for the determination of isomeric benzoic acids in atmospheric aerosols and vehicular emission. UltraTrol LN was employed as the pre-coated polymer to suppress the EOF (0.3 ×10-9 m2V-1s-1) and achieve a baseline separation of studied acids. Good repeatability for migration time (RSD <1%, N=10) was obtained without coating regeneration. The high pre-coating stability allowed coupling of CE to MS without ion suppression in MS. In scanning mode and using field-amplified sample injection with electrokinetic injection (-5 kV for 60 s), LODs (S/N =3) ranged from 2.5 to 6 µg/L for standard target analytes prepared in deionized water. In the presence of 100 mg/L of sulphate (added to simulate a sample matrix), LODs ranged from 8 to 90 µg/L. Several aromatic acids were identified in atmospheric and diesel-engine emitted particular matter. In off-line combination with the electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS), this method provided accurate molecular mass determination of unknowns containing various functionalised carboxylic and sulfonic acids, and allowed their formula to be proposed.

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

PubMed

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

2012-09-05

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

Chemical profile of mango (Mangifera indica L.) using electrospray ionisation mass spectrometry (ESI-MS).

PubMed

Oliveira, Bruno G; Costa, Helber B; Ventura, José A; Kondratyuk, Tamara P; Barroso, Maria E S; Correia, Radigya M; Pimentel, Elisângela F; Pinto, Fernanda E; Endringer, Denise C; Romão, Wanderson

2016-08-01

Mangifera indica L., mango fruit, is consumed as a dietary supplement with purported health benefits; it is widely used in the food industry. Herein, the chemical profile of the Ubá mango at four distinct maturation stages was evaluated during the process of growth and maturity using negative-ion mode electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI(-)FT-ICR MS) and physicochemical characterisation analysis (total titratable acidity (TA), total soluble solids (TSS), TSS/TA ratio, and total polyphenolic content). Primary (organic acids and sugars) and secondary metabolites (polyphenolic compounds) were mostly identified in the third maturation stage, thus indicating the best stage for harvesting and consuming the fruit. In addition, the potential cancer chemoprevention of the secondary metabolites (phenolic extracts obtained from mango samples) was evaluated using the induction of quinone reductase activity, concluding that fruit polyphenols have the potential for cancer chemoprevention. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-field FT-ICR-MS and aromaticity equivalent approach for structural identification of water soluble organic compounds (WSOC)

NASA Astrophysics Data System (ADS)

Harir, Mourad; Yassine, Mahmoud M.; Dabek-Zlotorzynska, Ewa; Hertkorn, Norbert; Schmitt-Kopplin, Philippe

2015-04-01

Organic aerosol (OA) makes up a large and often dominant fraction, (20 to 90%) of the submicron atmospheric particulate mass, and its effects are becoming increasingly important in determining climatic and health effects of atmospheric aerosols. Despite the abundance of OA, our understanding of the sources, formation processes and atmospheric properties of OA is limited. Atmospheric OA has both primary (directly emitted) and secondary (formed in the atmosphere from precursor gases) sources, which can be natural (e.g. vegetation) and/or anthropogenic (e.g. fossil-based vehicle exhaust or biomass burning). A significant fraction of OA contains as much as 20-70% of water soluble organic compounds (WSOC). The WSOC fraction is a very complex mixture of low volatility, polyfunctional aliphatic and aromatic compounds containing carboxyl, alcohol, carbonyl, sulfo, nitro, and other functionalities. This high degree of chemical complexity of atmospheric organics has inspired a number of sophisticated approaches that are capable of identifying and detecting a variety of different analytes in OA. Accordingly, one of the most challenging areas of atmospheric particulate matter (PM) analysis is to comprehend the molecular complexity of the OA, especially WSOC fraction, a significant component of atmospheric fine PM (PM2.5). The sources of WSOC are not well understood, especially the relative contributions of primary vs. secondary organic aerosol. Therefore, the molecular characterization of WSOC is important because it allows gaining insight into aerosol sources and underlying mechanisms of secondary organic aerosols (SOA) formation and transformation. In this abstract, molecular characterization of WSOC was achieved using high-field mass spectrometry FT-ICR-MS and aromaticity equivalent approach. Aromaticity equivalent (Xc), defined recently as a new parameter calculated from the assigned molecular formulas (complementary to the aromaticity index [1]), is introduced to improve identification and characterization of aromatic and condensed aromatic compounds in WSOC [2]. We proposed threshold values of Xc≥ 2.5000 and Xc≥ 2.7143 as ambiguous minimum criteria for the presence of aromatic structure and condensed aromatic compounds, respectively. The advantage of employing this parameter is that Xc would have a constant value for each proposed core structure regardless the degree of alkylation, and thus visual representation and structural interpretations of the spectra become advantageous for characterizing and comparing complex samples. Diesel particulate matter (DPM) and two atmospheric aerosols collected in the industrial area affected by biomass burning events were used to study the applicability of the proposed criteria for the improved identification of aromatic and condensed aromatic structures in complex mixtures in the FT-ICR mass spectra. References [1] Koch.BP, Dittmar.T. From mass to structure: an aromaticity index for high-resolution mass data of natural organic matter. Rapid Commun. Mass Spectrom. 2006, 20, 926-932 [2] Yassine.MM, Harir.M, Dabek-Zlotorzynska.E, Schmitt-Kopplin.Ph. Structural characterization of organic aerosol using Fourier transform ion cyclotron resonance mass spectrometry: Aromaticity equivalent approach. Rapid Commun. Mass Spectrom. 2014. 28. 2445-2454

Advanced characterisation of organic matter in oil sands and tailings sands used for land reclamation by Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS)

NASA Astrophysics Data System (ADS)

Noah, M.; Vieth-Hillebrand, A.; Wilkes, H.

2012-04-01

The Athabasca region of northern Alberta, Canada, is home to deposits of oil sands containing vast amounts (~ 173 billion barrels) of heavily biodegraded petroleum. Oil sands are recovered by surface mining or by in situ steam injection. The extraction of bitumen from oil sands by caustic hot water processing results in large volumes of fluid tailings, which are stored in on-site settling basins. There the tailings undergo a compaction and dewatering process, producing a slowly densifying suspension. The released water is recycled for extraction. The fine tailings will be reclaimed as either dry or wet landscapes. [1] To produce 1 barrel of crude oil, 2 tons of oil sand and 2 - 3 tons of water (including recycled water) are required. [2] Open pit mining and the extraction of the bitumen from the oil sands create large and intense disturbances of different landscapes. The area currently disturbed by mining operations covers about 530 km2 and the area of tailing ponds surpasses 130 km2. An issue of increasing importance is the land remediation and reclamation of oil sand areas in Canada and the reconstruction of these disturbed landscapes back to working ecosystems similar to those existing prior to mining operations. An important issue in this context is the identification of oil sand-derived organic compounds in the tailings, their environmental behaviour and the resulting chances and limitations with respect to land reclamation. Furthermore the biodegradation processes that occur in the tailings and that could lead to a decrease in hazardous organic compounds are important challenges, which need to be investigated. This presentation will give a detailed overview of our compositional and quantitative characterisation of the organic matter in oil sand, unprocessed and processed mature fine tailings samples as well as in tailings sands used as part of land reclamation. The analytical characterisation is based on the extraction of the soluble organic matter, its subsequent separation into asphaltenes, aliphatic hydrocarbons, aromatic hydrocarbons, neutral nitrogen, sulphur, oxygen (NSO) compounds and carboxylic acids. The asphaltene fractions are analysed using pyrolysis-GC, all other fractions are analysed by GC-MS. Additionally Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) is used to study the chemical composition of the samples on the molecular level using different ionisation methods.

Pyrrole Oligoglycosides from the Starfish Acanthaster planci Suppress Lipopolysaccharide-Induced Nitric Oxide Production in RAW264.7 Macrophages.

PubMed

Vien, Le Thi; Hanh, Tran Thi Hong; Huong, Phan Thi Thanh; Dang, Nguyen Hai; Thanh, Nguyen Van; Lyakhova, Ekaterina; Cuong, Nguyen Xuan; Nam, Nguyen Hoai; Kiem, Phan Van; Kicha, Alla; Minh, Chau Van

2016-11-01

Two new pyrrole oligoglycosides, plancipyrrosides A and B (1 and 2), were isolated from methanol extract of the Vietnamese starfish Acanthaster planci using various chromatographic procedures. Their structures were elucidated by spectroscopic methods including one and two dimensional (1D- and 2D)-NMR and Fourier transform ion cyclotron resonance (FT-ICR)-MS. The finding of 1 and 2 represents the third case of pyrrole oligoglycosides obtaining reported to date. Moreover, plancipyrroside B (2) exhibits a potent inhibitory effect on lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 cells with IC 50 of 5.94±0.34 µM, whereas plancipyrroside A (1) shows this inhibitory activity with IC 50 of 16.61±1.85 µM.

Analysis of archaeological triacylglycerols by high resolution nanoESI, FT-ICR MS and IRMPD MS/MS: Application to 5th century BC-4th century AD oil lamps from Olbia (Ukraine)

NASA Astrophysics Data System (ADS)

Garnier, Nicolas; Rolando, Christian; Høtje, Jakob Munk; Tokarski, Caroline

2009-07-01

This work presents the precise identification of triacylglycerols (TAGs) extracted from archaeological samples using a methodology based on nanoelectrospray and Fourier transform mass spectrometry. The archaeological TAG identification needs adapted sample preparation protocols to trace samples in advanced degradation state. More precisely, the proposed preparation procedure includes extraction of the lipid components from finely grinded ceramic using dichloromethane/methanol mixture with additional ultrasonication treatment, and TAG purification by solid phase extraction on a diol cartridge. Focusing on the analytical approach, the implementation of "in-house" species-dependent TAG database was investigated using MS and InfraRed Multiphoton Dissociation (IRMPD) MS/MS spectra; several vegetal oils, dairy products and animal fats were studied. The high mass accuracy of the Fourier transform analyzer ([Delta]m below 2.5 ppm) provides easier data interpretation, and allows distinction between products of different origins. In details, the IRMPD spectra of the lithiated TAGs reveal fragmentation reactions including loss of free neutral fatty acid and loss of fatty acid as [alpha],[beta]-unsaturated moieties. Based on the developed preparation procedure and on the constituted database, TAG extracts from 5th century BC to 4th century AD Olbia lamps were analyzed. The structural information obtained succeeds in identifying that bovine/ovine fats were used as fuel used in these archaeological Olbia lamps.

Nucleic Acid analysis by fourier transform ion cyclotron resonance mass spectrometry at the beginning of the twenty-first century.

PubMed

Frahm, J L; Muddiman, D C

2005-01-01

Mass spectrometers measure an intrinsic property (i.e., mass) of a molecule, which makes it an ideal platform for nucleic acid analysis. Importantly, the unparalleled capabilities of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry further extend its usefulness for nucleic acid analysis. The beginning of the twenty-first century has been marked with notable advances in the field of FT-ICR mass spectrometry analysis of nucleic acids. Some of these accomplishments include fundamental studies of nucleic acid properties, improvements in sample clean up and preparation, better methods to obtain higher mass measurement accuracy, analysis of noncovalent complexes, tandem mass spectrometry, and characterization of peptide nucleic acids. This diverse range of studies will be presented herein.

Rhamnolipids Produced by Indigenous Acinetobacter junii from Petroleum Reservoir and its Potential in Enhanced Oil Recovery

PubMed Central

Dong, Hao; Xia, Wenjie; Dong, Honghong; She, Yuehui; Zhu, Panfeng; Liang, Kang; Zhang, Zhongzhi; Liang, Chuanfu; Song, Zhaozheng; Sun, Shanshan; Zhang, Guangqing

2016-01-01

Biosurfactant producers are crucial for incremental oil production in microbial enhanced oil recovery (MEOR) processes. The isolation of biosurfactant-producing bacteria from oil reservoirs is important because they are considered suitable for the extreme conditions of the reservoir. In this work, a novel biosurfactant-producing strain Acinetobacter junii BD was isolated from a reservoir to reduce surface tension and emulsify crude oil. The biosurfactants produced by the strain were purified and then identified via electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). The biosurfactants generated by the strain were concluded to be rhamnolipids, the dominant rhamnolipids were C26H48O9, C28H52O9, and C32H58O13. The optimal carbon source and nitrogen source for biomass and biosurfactant production were NaNO3 and soybean oil. The results showed that the content of acid components increased with the progress of crude oil biodegradation. A glass micromodel test demonstrated that the strain significantly increased oil recovery through interfacial tension reduction, wettability alteration and the mobility of microorganisms. In summary, the findings of this study indicate that the newly developed BD strain and its metabolites have great potential in MEOR. PMID:27872613

Rhamnolipids Produced by Indigenous Acinetobacter junii from Petroleum Reservoir and its Potential in Enhanced Oil Recovery.

PubMed

Dong, Hao; Xia, Wenjie; Dong, Honghong; She, Yuehui; Zhu, Panfeng; Liang, Kang; Zhang, Zhongzhi; Liang, Chuanfu; Song, Zhaozheng; Sun, Shanshan; Zhang, Guangqing

2016-01-01

Biosurfactant producers are crucial for incremental oil production in microbial enhanced oil recovery (MEOR) processes. The isolation of biosurfactant-producing bacteria from oil reservoirs is important because they are considered suitable for the extreme conditions of the reservoir. In this work, a novel biosurfactant-producing strain Acinetobacter junii BD was isolated from a reservoir to reduce surface tension and emulsify crude oil. The biosurfactants produced by the strain were purified and then identified via electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). The biosurfactants generated by the strain were concluded to be rhamnolipids, the dominant rhamnolipids were C 26 H 48 O 9 , C 28 H 52 O 9 , and C 32 H 58 O 13 . The optimal carbon source and nitrogen source for biomass and biosurfactant production were NaNO 3 and soybean oil. The results showed that the content of acid components increased with the progress of crude oil biodegradation. A glass micromodel test demonstrated that the strain significantly increased oil recovery through interfacial tension reduction, wettability alteration and the mobility of microorganisms. In summary, the findings of this study indicate that the newly developed BD strain and its metabolites have great potential in MEOR.

Influences of Temperature and Metal on Subcritical Hydrothermal Liquefaction of Hyperaccumulator: Implications for the Recycling of Hazardous Hyperaccumulators.

PubMed

Qian, Feng; Zhu, Xiangdong; Liu, Yuchen; Shi, Quan; Wu, Longhua; Zhang, Shicheng; Chen, Jianmin; Ren, Zhiyong Jason

2018-02-20

Waste Sedum plumbizincicola, a zinc (Zn) hyperaccumulator during phytoremediation, was recycled via a subcritical hydrothermal liquefaction (HTL) reaction into multiple streams of products, including hydrochar, bio-oil, and carboxylic acids. Results show approximately 90% of Zn was released from the S. plumbizincicola biomass during HTL at an optimized temperature of 220 °C, and the release risk was mitigated via HTL reaction for hydrochar production. The low-Zn hydrochar (∼200 mg/kg compared to original plant of 1558 mg/kg) was further upgraded into porous carbon (PC) with high porosity (930 m 2 /g) and excellent capability of carbon dioxide (CO 2 ) capture (3 mmol/g). The porosity, micropore structure, and graphitization degree of PCs were manipulated by the thermal recalcitrance of hydrochar. More importantly, results showed that the released Zn 2+ could effectively promote the production of acetic acid via the oxidation of furfural (FF) and 5-(hydroxymethyl)-furfural (HMF). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with negative electrospray ionization analysis confirmed the deoxygenation and depolymerization reactions and the production of long chain fatty acids during HTL reaction of S. plumbizincicola. This work provides a new path for the recycling of waste hyperaccumulator biomass into value-added products.

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

PubMed

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

2012-04-17

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

A database application for pre-processing, storage and comparison of mass spectra derived from patients and controls

PubMed Central

Titulaer, Mark K; Siccama, Ivar; Dekker, Lennard J; van Rijswijk, Angelique LCT; Heeren, Ron MA; Sillevis Smitt, Peter A; Luider, Theo M

2006-01-01

Background Statistical comparison of peptide profiles in biomarker discovery requires fast, user-friendly software for high throughput data analysis. Important features are flexibility in changing input variables and statistical analysis of peptides that are differentially expressed between patient and control groups. In addition, integration the mass spectrometry data with the results of other experiments, such as microarray analysis, and information from other databases requires a central storage of the profile matrix, where protein id's can be added to peptide masses of interest. Results A new database application is presented, to detect and identify significantly differentially expressed peptides in peptide profiles obtained from body fluids of patient and control groups. The presented modular software is capable of central storage of mass spectra and results in fast analysis. The software architecture consists of 4 pillars, 1) a Graphical User Interface written in Java, 2) a MySQL database, which contains all metadata, such as experiment numbers and sample codes, 3) a FTP (File Transport Protocol) server to store all raw mass spectrometry files and processed data, and 4) the software package R, which is used for modular statistical calculations, such as the Wilcoxon-Mann-Whitney rank sum test. Statistic analysis by the Wilcoxon-Mann-Whitney test in R demonstrates that peptide-profiles of two patient groups 1) breast cancer patients with leptomeningeal metastases and 2) prostate cancer patients in end stage disease can be distinguished from those of control groups. Conclusion The database application is capable to distinguish patient Matrix Assisted Laser Desorption Ionization (MALDI-TOF) peptide profiles from control groups using large size datasets. The modular architecture of the application makes it possible to adapt the application to handle also large sized data from MS/MS- and Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry experiments. It is expected that the higher resolution and mass accuracy of the FT-ICR mass spectrometry prevents the clustering of peaks of different peptides and allows the identification of differentially expressed proteins from the peptide profiles. PMID:16953879

A database application for pre-processing, storage and comparison of mass spectra derived from patients and controls.

PubMed

Titulaer, Mark K; Siccama, Ivar; Dekker, Lennard J; van Rijswijk, Angelique L C T; Heeren, Ron M A; Sillevis Smitt, Peter A; Luider, Theo M

2006-09-05

Statistical comparison of peptide profiles in biomarker discovery requires fast, user-friendly software for high throughput data analysis. Important features are flexibility in changing input variables and statistical analysis of peptides that are differentially expressed between patient and control groups. In addition, integration the mass spectrometry data with the results of other experiments, such as microarray analysis, and information from other databases requires a central storage of the profile matrix, where protein id's can be added to peptide masses of interest. A new database application is presented, to detect and identify significantly differentially expressed peptides in peptide profiles obtained from body fluids of patient and control groups. The presented modular software is capable of central storage of mass spectra and results in fast analysis. The software architecture consists of 4 pillars, 1) a Graphical User Interface written in Java, 2) a MySQL database, which contains all metadata, such as experiment numbers and sample codes, 3) a FTP (File Transport Protocol) server to store all raw mass spectrometry files and processed data, and 4) the software package R, which is used for modular statistical calculations, such as the Wilcoxon-Mann-Whitney rank sum test. Statistic analysis by the Wilcoxon-Mann-Whitney test in R demonstrates that peptide-profiles of two patient groups 1) breast cancer patients with leptomeningeal metastases and 2) prostate cancer patients in end stage disease can be distinguished from those of control groups. The database application is capable to distinguish patient Matrix Assisted Laser Desorption Ionization (MALDI-TOF) peptide profiles from control groups using large size datasets. The modular architecture of the application makes it possible to adapt the application to handle also large sized data from MS/MS- and Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry experiments. It is expected that the higher resolution and mass accuracy of the FT-ICR mass spectrometry prevents the clustering of peaks of different peptides and allows the identification of differentially expressed proteins from the peptide profiles.

Environmental drivers of dissolved organic matter molecular composition in the Delaware Estuary

NASA Astrophysics Data System (ADS)

Osterholz, Helena; Kirchman, David L.; Niggemann, Jutta; Dittmar, Thorsten

2016-11-01

Estuaries as connectors of freshwater and marine aquatic systems are hotspots of biogeochemical element cycling. In one of the best studied temperate estuaries, the Delaware Estuary (USA), we investigated the variability of dissolved organic matter (DOM) over five sampling cruises along the salinity gradient in August and November of 3 consecutive years. Dissolved organic carbon (DOC) concentrations were more variable in the upper reaches of the estuary (245±49 µmol L-1) than at the mouth of the estuary (129±14 µmol L-1). Bulk DOC decreased conservatively along the transect in November but was non-conservative with increased DOC concentrations mid-estuary in August. Detailed analysis of the solid-phase extractable DOM pool via ultrahigh resolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) revealed compositional differences at the molecular level that were not reflected in changes in concentration. Besides the mixing of terrestrial and marine endmember signatures, river discharge levels and biological activity were found to impact DOM molecular composition. DOM composition changed less between August and November than along the salinity gradient. Relative contributions of presumed photolabile DOM compounds did not reveal non-conservative behavior indicative of photochemical processing; suggesting that on the timescales of estuarine mixing photochemical removal of molecules plays a minor role in the turbid Delaware Bay. Overall, a large portion of molecular formulae overlapped between sampling campaigns and persisted during estuarine passage. Extending the analysis to the structural level via the fragmentation of molecular masses in the FT-ICR-MS cell, we found that the relative abundance of isomers along the salinity gradient did not change, indicating a high structural similarity of aquatic DOM independent of the origin. These results point towards a recalcitrant character of the DOM supplied by the Delaware River. We demonstrate that in addition to bulk DOC quantification, detailed information on molecular composition is essential for constraining sources of DOM and to identify the processes that impact estuarine DOM, thereby controlling amount and composition of DOM eventually discharged to the ocean through estuaries.

Export of Dissolved Organic Carbon following Prescribed Fire on Forested Watersheds: Implications for Watershed Management for Drinking Water Supply

NASA Astrophysics Data System (ADS)

Zhang, W.; Olivares, C. I.; Uzun, H.; Erdem, C. U.; Trettin, C.; Liu, Y.; Robinson, E. R.; Karanfil, T.; Chow, A. T.

2016-12-01

Detrital material in forest watersheds is the major terrestrial source of dissolved organic matter (DOM) and disinfection byproduct (DBP) precursors in surface source waters, but it is also the fuel for forest fires. Prescribed fire, as a fuel reduction technique is intended to reduce the amount of forest detritus, and therefore the risk of wildfire. Accordingly, periodic prescribed fire can reduce the accumulation of detritus on forest floor and the amount of DOM export after forest treatments. To evaluate the effects of prescribed fire on water quality, we conducted a controlled study on a paired first-order watershed system that includes a 160 ha treatment watershed (WS77) and 200 ha control watershed (WS80) on the Santee Experimental Forest, near Charleston South Carolina. WS77 has been used for prescribed fire research since the 1960's, the current experimental burn occurred on April, 2016. WS80 has not been managed or burned for at least 55 years. Gauging stations were equipped with in-situ TOC sensors and flow-proportional water samplers for monitoring temporal trends on water quality. Water samples taken from the first runoff event from both watersheds including rising limb, peak discharge, and falling limb were used for detailed chemical characterizations including DOC and nutrient concentrations, coagulation efficiency, and DBP formation such as trihalomethanes (THMs) and halocacetic acids (HAAs) from chlorination as well as N-nitrosodimethylamine (NDMA) from chlorination, and chemical formula assignment on DOM using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) before and after chlorination and chloramination. Preliminary FT-ICR-MS data shows that DOM chemical compositions are different between raw samples collected from WS77 and WS80. Chlorination resulted in a shift toward lower molecular mass compared to the raw materials. While chloramination did not cause a drastic mass shift, such a treatment also produced DOM moieties that are significantly different from the raw material. Based on our understanding, this watershed-scale study is the first field-scale study to evaluate the effects of prescribed fire on treatability of drinking water supplies.

A new perspective on the apparent solubility of dissolved black carbon

NASA Astrophysics Data System (ADS)

Wagner, Sasha; Ding, Yan; Jaffé, Rudolf

2017-09-01

Black carbon (BC), pyrogenic organic matter generated from the incomplete combustion of biomass, is ubiquitous in the environment. The molecular structures which comprise the BC pool of compounds are defined by their condensed aromatic core structures polysubstituted with O-containing functionalities (e.g., carboxyl groups). Despite the apparent hydrophobicity of BC molecules, a considerable portion of BC is translocated from terrestrial to aquatic systems in the form of dissolved BC (DBC). However, the specific biogeochemical mechanisms which control the transfer of BC from the land to the water remain elusive. In the current study, the apparent solubility of DBC was inferred from octanol-water partition coefficients (Kow) modeled for proposed DBC structures with varying degrees of polycondensation and polar functionality. Modeled Kow values indicated that DBC molecules with small aromatic ring systems and high degrees of hydrophilic functionality may be truly solubilized in the aqueous phase. However, large and highly condensed DBC structures yielded high Kow values, which suggested that a considerable portion of the DBC pool which has been quantified in aquatic environments is not truly dissolved. We hypothesized that other DOM components may act as mediators in the solubilization of condensed aromatic molecules and serve to increase the solubility of DBC via hydrophobic, intermolecular associations. This hypothesis was tested through controlled leaching experiments to determine whether the mobilization of DBC from particulate soils and chars became enhanced in the presence of DOM. However, we observed that characteristics inherent to each sample type had a greater influence than added DOM on the apparent solubility of DBC. In addition, the direct comparison of molecular marker (benzenepolycarboxylic acids) and ultrahigh resolution mass spectral data (FT-ICR/MS) on leachates obtained from the same set of soils and char did not show a clear overlap in DBC quantification or characterization between the two analytical methods. Correlations between FT-ICR/MS results and BPCA were not significant possibly due to differences in the methodological windows and/or small sample size. Our results were unable to provide evidence in support of proposed hydrophobic interactions between DOM and DBC, suggesting that other physical/chemical mechanisms play important roles in the dissolution of BC.

Understanding DOC Mobilization Dynamics Through High Frequency Measurements in a Headwater Catchment

NASA Astrophysics Data System (ADS)

Werner, B.; Musolff, A.; Lechtenfeld, O.; de Rooij, G. H.; Fleckenstein, J. H.

2017-12-01

Increasing dissolved organic carbon (DOC) exports from headwater catchments impact the quality of downstream waters and pose challenges to water supply. The importance of riparian zones for DOC export from catchments in humid, temperate climates has generally been acknowledged, but the hydrological controls and biogeochemical factors that govern mobilization of DOC from riparian zones remain elusive. By analyzing high-frequency time series of UV-VIS based water quality we therefore aim at a better understanding on temporal dynamics of DOC mobilization and exports. In a first step a one year high frequency (15 minutes) data set from a headwater catchment in the Harz Mountains (Germany) was systematically analyzed for event-based patterns in DOC concentrations. Here, a simplistic linear model was generated to explain DOC concentration level and variability in the stream. Furthermore, spectral (e.g. slopes and SUVA254) and molecular (FT-ICR-MS) characterization of DOC was used to fingerprint in-stream DOC during events. Continuous DOC concentrations were best predicted (R², NSE = 0.53) by instantaneous discharge (Q) and antecede wetness conditions of the last 30 days (AWC30 = Precip.30/PET30) as well as mean air temperature (Tmean30) and mean discharge (Qmean30) of the preceding 30 days. Analyses of 36 events revealed seasonal trends for the slope, intercept and R² of linear log(DOC)-log(Q) regressions that can be best explained by the mean air temperature of the preceding 15 days. Continuously available optical DOC quality parameters SUVA254 and spectral slope (275 nm - 295 nm) systematically changed with shifts in discharge and in DOC concentration. This is underlined by selected FT-ICR-MS measurements indicating higher DOC aromaticity and oxygen content at high flow conditions. The change of DOC quality parameters during events indicate a shift in the activated source zones: DOC with a different quality was mobilized during high flow conditions when higher groundwater levels connected formerly disconnected DOC source zones to the stream. We conclude that the high concentration variability of DOC can be explained by a few controlling variables only. These variables can be linked to event-based DOC source activation and more seasonal controls of DOC production.

Characterization of organic matter in cloud waters sampled at the puy de Dôme mountain using FT-ICR-MS

NASA Astrophysics Data System (ADS)

Bianco, A.; Chaumerliac, N.; Vaitilingom, M.; Deguillaume, L.; Bridoux, M. C.

2017-12-01

The chemical composition of organic matter in cloud water is highly complex. The organic species result from their dissolution from the gas phase or from the soluble fraction of the particle phase. They are also produced by aqueous phase reactivity. Several low molecular weight organic species have been quantified such as aldehydes and carboxylic acids. Recently, amino acids were also detected in cloud water and their presence is related to the presence of microorganisms. Compounds presenting similarities with high molecular weight organic substances or HULIS found in aerosols were also observed in clouds. Overall, these studies mainly focused on individual compounds or functional groups rather than the complex mixture at the molecular level. This study presents a non-targeted approach to characterize the organic matter in clouds. Samples were collected at the puy de Dôme Mountain (France). Two cloud water samples (June & July 2016) were analyzed using high resolution mass spectrometry (ESI-FT-ICR-MS 9.4T). A reversed solid phase extraction (SPE) procedure was performed to concentrate dissolved organic matter components. Composer (v.1.5.3) software was used to filter the mass spectral data, recalibrate externally the dataset and calculate all possible formulas for detected anions. The first cloud sample (June) resulted from air mass coming from the North (North Sea) while the second one (July) resulted from air mass coming from the West (Atlantic Ocean). Thus, both cloud events derived from marine air masses but were characterized by different hydrogen peroxide concentration and dissolved organic carbon content and were sampled at different periods during the day. Elemental compositions of 6487 and 3284 unique molecular species were identified in each sample. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS & CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 800 Da were detected. The main class is CHNO (53% for both samples) while sulfur-containing compounds represent for the two samples respectively 21 & 14% of the total assigned molecular formulas. CHO compounds molecular formulas are respectively 25 & 32%. Among the two samples, only 2490 molecular formulas were found common to the two samples.

A Robust Two-Dimensional Separation for Top-Down Tandem Mass Spectrometry of the Low-Mass Proteome

PubMed Central

Lee, Ji Eun; Kellie, John F.; Tran, John C.; Tipton, Jeremiah D.; Catherman, Adam D.; Thomas, Haylee M.; Ahlf, Dorothy R.; Durbin, Kenneth R.; Vellaichamy, Adaikkalam; Ntai, Ioanna; Marshall, Alan G.; Kelleher, Neil L.

2010-01-01

For fractionation of intact proteins by molecular weight (MW), a sharply improved two-dimensional (2D) separation is presented to drive reproducible and robust fractionation before top-down mass spectrometry of complex mixtures. The “GELFrEE” (i.e., gel-eluted liquid fraction entrapment electrophoresis) approach is implemented by use of Tris-glycine and Tris-tricine gel systems applied to human cytosolic and nuclear extracts from HeLa S3 cells, to achieve a MW-based fractionation of proteins from 5 to >100 kDa in 1 h. For top-down tandem mass spectroscopy (MS/MS) of the low-mass proteome (5–25 kDa), between 5 and 8 gel-elution (GE) fractions are sampled by nanocapillary-LC-MS/MS with 12 or 14.5 tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers. Single injections give about 40 detectable proteins, about half of which yield automated ProSight identifications. Reproducibility metrics of the system are presented, along with comparative analysis of protein targets in mitotic versus asynchronous cells. We forward this basic 2D approach to facilitate wider implementation of top-down mass spectrometry and a variety of other protein separation and/or characterization approaches. PMID:19747844

Halogenated Organic Compounds Identified in Hydraulic Fracturing Wastewaters Using Ultrahigh Resolution Mass Spectrometry.

PubMed

Luek, Jenna L; Schmitt-Kopplin, Philippe; Mouser, Paula J; Petty, William Tyler; Richardson, Susan D; Gonsior, Michael

2017-05-16

Large volumes of water return to the surface following hydraulic fracturing of deep shale formations to retrieve oil and natural gas. Current understanding of the specific organic constituents in these hydraulic fracturing wastewaters is limited to hydrocarbons and a fraction of known chemical additives. In this study, we analyzed hydraulic fracturing wastewater samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) as a nontargeted technique to assign unambiguous molecular formulas to singly charged molecular ions. Halogenated molecular formulas were identified and confirmed using isotopic simulation and MS-MS fragmentation spectra. The abundance of halogenated organic compounds in flowback fluids rather than older wastewaters suggested that the observed molecular ions might have been related to hydraulic fracturing additives and related subsurface reactions, such as through the reaction of shale-extracted chloride, bromide, and iodide with strong oxidant additives (e.g., hypochlorite, persulfate, hydrogen peroxide) and subsequently with diverse dissolved organic matter. Some molecular ions matched the exact masses of known disinfection byproducts including diiodoacetic acid, dibromobenzoic acid, and diiodobenzoic acid. The identified halogenated organic compounds, particularly iodinated organic molecules, are absent from inland natural systems and these compounds could therefore play an important role as environmental tracers.

Mass spectrometric and theoretical investigation of sulfate clusters in nanoscale water droplets

NASA Astrophysics Data System (ADS)

Lemke, K.

2017-12-01

The solvation of sulfate clusters of varying size and charge in water clusters and in nanoscale water droplets has been studied using electrospray ionization (ESI) FT-MS and density functional theory (DFT) molecular simulations. ESI mass spectra of solvated [Mg(MgSO4)m]2+(H2O)n with m≤10 and up to 15 water molecules have been recorded, and ion cluster experiments have been undertaken using a custom-modified FT-ICR mass spectrometer with the ability of IRMPD for ion dissociation. We present equilibrium geometries and energies for [Mg(MgSO4)m]2+(H2O)n, water-free and solvated with up to 100 water molecules, using swarm-based optimizers and DFT level calculations. Dominant cluster species identified following ESI of dilute (1-5 mM) MgSO4 solutions include hexa- and octa-nuclear magnesium sulfate ions, water-free and with a full first shell of water molecules. The largest clusters identified are magnesium sulfate decamers, i.e. [Mg(MgSO4)10]2+(H2O)n, with n≤15. As a very first step towards understanding the distribution and intensity of ESI ion mass spectra, we have identified the global minima of [Mg(MgSO4)m]2+(H2O)n with m≤10 and n≤100, and located likely global minima of magnesium sulfate clusters in the gas phase and in nano-scale water droplets. We will present a summary of the structural and energetic trends of solvated magnesium sulfate clusters, with a particular focus on structural transitions induced by cluster growth and solvation, the occurrence of "magic" number cluster species, their energetic properties and their potential role as atmospheric aqueous species.

Metabolic Fingerprint of PS3-Induced Resistance of Grapevine Leaves against Plasmopara viticola Revealed Differences in Elicitor-Triggered Defenses

PubMed Central

Adrian, Marielle; Lucio, Marianna; Roullier-Gall, Chloé; Héloir, Marie-Claire; Trouvelot, Sophie; Daire, Xavier; Kanawati, Basem; Lemaître-Guillier, Christelle; Poinssot, Benoît; Gougeon, Régis; Schmitt-Kopplin, Philippe

2017-01-01

Induction of plant resistance against pathogens by defense elicitors constitutes an attractive strategy to reduce the use of fungicides in crop protection. However, all elicitors do not systematically confer protection against pathogens. Elicitor-induced resistance (IR) thus merits to be further characterized in order to understand what makes an elicitor efficient. In this study, the oligosaccharidic defense elicitors H13 and PS3, respectively, ineffective and effective to trigger resistance of grapevine leaves against downy mildew, were used to compare their effect on the global leaf metabolism. Ultra high resolution mass spectrometry (FT-ICR-MS) analysis allowed us to obtain and compare the specific metabolic fingerprint induced by each elicitor and to characterize the associated metabolic pathways. Moreover, erythritol phosphate was identified as a putative marker of elicitor-IR. PMID:28261225

Top-Down Analysis of Highly Post-Translationally Modified Peptides by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Guerrero, Andres; Lerno, Larry; Barile, Daniela; Lebrilla, Carlito B.

2015-03-01

Bovine κ-caseinoglycomacropeptide (GMP) is a highly modified peptide from κ-casein produced during the cheese making process. The chemical nature of GMP makes analysis by traditional proteomic approaches difficult, as the peptide bears a strong net negative charge and a variety of post-translational modifications. In this work, we describe the use of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) for the top-down analysis of GMP. The method allows the simultaneous detection of different GMP forms that result from the combination of amino acid genetic variations and post-translational modifications, specifically phosphorylation and O-glycosylation. The different GMP forms were identified by high resolution mass spectrometry in both negative and positive mode and confirmation was achieved by tandem MS. The results showed the predominance of two genetic variants of GMP that occur as either mono- or bi-phosphorylated species. Additionally, these four forms can be modified with up to two O-glycans generally sialylated. The results demonstrate the presence of glycosylated, bi-phosphorylated forms of GMP never described before.

Inorganics in Organics: Tracking down the Intrinsic Equilibriums between Organic Molecules and Trace Elements in Oceanic Waters

NASA Astrophysics Data System (ADS)

Lechtenfeld, O. J.; Koch, B. P.; Kattner, G.

2010-12-01

Recent developments in analytical instrumentation enable to describe biogeochemical processes in oceanic waters on a molecular level. This is the prerequisite to integrate biological and geochemical parameters and to develop chemical cycles on a global perspective. The state-of-the-art Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) applications for dissolved organic matter (DOM) focus mainly on carbon, hydrogen, oxygen and nitrogen isotopes. Implementation of sulfur and especially phosphorus in the molecular formula assignment has been questionable because of ambiguous calculated elemental formulas. On the other hand, many compounds bearing these elements are well known to occur in the dissolved state as part of the permanent recycling processes (e.g. phospholipids, phosphonates) but analytics of dissolved organic phosphorus (DOP) and sulfur (DOS) are often hampered by the large inorganic P and S pools. Even less is known about complexation characteristics of the DOM moieties. Although electrochemical methods provide some information about trace metal speciation, the high amount of organic molecules and its insufficient description as chemical functional classes prevent the assignment of trace metals to ligand classes. Nevertheless, it is undoubtful that a varying but extensive amount of transition metals is bond in form of organic complexes. Hyphenation of reversed phase high performance liquid chromatography (RP-HPLC) with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) is a valuable tool to study these metal-organic interactions in a qualitative and quantitative approach. We established a desolvation method that allows direct transfer of high organic solvent loads into the plasma. Thus, in combination with internal standardization and external calibration, the investigation of a broad polarity scale was possible. This approach overcomes previous restrictions to non-organic solvent separation techniques like size exclusion chromatography (SEC). We used solid phase extracted DOM (SPE-DOM) from Atlantic and Southern Ocean water samples to show that organic sulfur and phosphorus species can be separated via RP-HPLC and that the partitioning can be correlated to trace metal binding capabilities in the different fractions. A molecular level investigation of these fractions via FT-ICR-MS revealed further details of the complexation features and connects the polarity-based separation on a C18 column to O/C and H/C elemental ratios. With our study, we showed that biologically relevant transition metals (e.g. Fe, Ni, Cu) and uranium are intrinsic constituents of the DOM fractions. Moreover, a comparison between samples from different ecological provinces and diagenetic conditions was performed to highlight the benefits of this approach for future marine biogeochemical research.

Metabolomics reveals metabolic biomarkers of Crohn's disease

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

Jansson, J.K.; Willing, B.; Lucio, M.

The causes and etiology of Crohn's disease (CD) are currently unknown although both host genetics and environmental factors play a role. Here we used non-targeted metabolic profiling to determine the contribution of metabolites produced by the gut microbiota towards disease status of the host. Ion Cyclotron Resonance Fourier Transform Mass Spectrometry (ICR-FT/MS) was used to discern the masses of thousands of metabolites in fecal samples collected from 17 identical twin pairs, including healthy individuals and those with CD. Pathways with differentiating metabolites included those involved in the metabolism and or synthesis of amino acids, fatty acids, bile acids and arachidonicmore » acid. Several metabolites were positively or negatively correlated to the disease phenotype and to specific microbes previously characterized in the same samples. Our data reveal novel differentiating metabolites for CD that may provide diagnostic biomarkers and/or monitoring tools as well as insight into potential targets for disease therapy and prevention.« less

Ultra-high performance supercritical fluid chromatography hyphenated to atmospheric pressure chemical ionization high resolution mass spectrometry for the characterization of fast pyrolysis bio-oils.

PubMed

Crepier, Julien; Le Masle, Agnès; Charon, Nadège; Albrieux, Florian; Duchene, Pascal; Heinisch, Sabine

2018-06-01

Extensive characterization of complex mixtures requires the combination of powerful analytical techniques. A Supercritical Fluid Chromatography (SFC) method was previously developed, for the specific case of fast pyrolysis bio oils, as an alternative to gas chromatography (GC and GC × GC) or liquid chromatography (LC and LC × LC), both separation methods being generally used prior to mass spectrometry (MS) for the characterization of such complex matrices. In this study we investigated the potential of SFC hyphenated to high resolution mass spectrometry (SFC-HRMS) for this characterization using Negative ion Atmospheric Pressure Chemical ionization ((-)APCI) for the ionization source. The interface between SFC and (-)APCI/HRMS was optimized from a mix of model compounds with the objective of maximizing the signal to noise ratio. The main studied parameters included both make-up flow-rate and make-up composition. A methodology for the treatment of APCI/HRMS data is proposed. This latter allowed for the identification of molecular formulae. Both SFC-APCI/HRMS method and data processing method were applied to a mixture of 36 model compounds, first analyzed alone and then spiked in a bio-oil. In both cases, 19 compounds could be detected. Among them 9 could be detected in a fast pyrolysis bio-oil by targeted analysis. The whole procedure was applied to the characterization of a bio-oil using helpful representations such as mass-plots, van Krevelen diagrams and heteroatom class distributions. Finally the results were compared with those obtained with a Fourier Transform ion-cyclotron resonance mass spectrometer (FT-ICR/MS). Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of the low molecular weight fraction of serum by LC-dual ESI-FT-ICR mass spectrometry: precision of retention time, mass, and ion abundance.

PubMed

Johnson, Kenneth L; Mason, Christopher J; Muddiman, David C; Eckel, Jeanette E

2004-09-01

This study quantifies the experimental uncertainty for LC retention time, mass measurement precision, and ion abundance obtained from replicate nLC-dual ESI-FT-ICR analyses of the low molecular weight fraction of serum. We used ultrafiltration to enrich the < 10-kDa fraction of components from the high-abundance proteins in a pooled serum sample derived from ovarian cancer patients. The THRASH algorithm for isotope cluster detection was applied to five replicate nLC-dual ESI-FT-ICR chromatograms. A simple two-level grouping algorithm was applied to the more than 7000 isotope clusters found in each replicate and identified 497 molecular species that appeared in at least four of the replicates. In addition, a representative set of 231 isotope clusters, corresponding to 188 unique molecular species, were manually interpreted to verify the automated algorithm and to set its tolerances. For nLC retention time reproducibility, 95% of the 497 species had a 95% confidence interval of the mean of +/- 0.9 min or less without the use of chromatographic alignment procedures. Furthermore, 95% of the 497 species had a mass measurement precision of < or = 3.2 and < or = 6.3 ppm for internally and externally calibrated spectra, respectively. Moreover, 95% of replicate ion abundance measurements, covering an ion abundance range of approximately 3 orders of magnitude, had a coefficient of variation of less than 62% without using any normalization functions. The variability of ion abundance was independent of LC retention time, mass, and ion abundance quartile. These measures of analytical reproducibility establish a statistical rationale for differentiating healthy and disease patient populations for the elucidation of biomarkers in the low molecular fraction of serum. Copyright 2004 American Chemical Society

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

PubMed

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

2018-01-01

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

A low noise single-transistor transimpedance preamplifier for Fourier-transform mass spectrometry using a T feedback network

PubMed Central

Lin, Tzu-Yung; Green, Roger J.; O’Connor, Peter B.

2012-01-01

A novel single-transistor transimpedance preamplifier has been introduced for improving performance in Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry. A low noise junction field-effect transistor (JFET), BF862, is used as the main amplification stage of this trans-impedance preamplifier, and a T-shaped feedback network is introduced as both the feedback and the gate biasing solutions. The T feedback network has been studied using an operational amplifier (Op Amp), AD8099. Such a feedback system allows ∼100-fold less feedback resistance at a given transimpedance, hence preserving bandwidth, which is beneficial to applications demanding high gain. The single-transistor preamplifier yields a tested transimpedance of ∼104 Ω (80 dBΩ) in the frequency range between 1 kHz and 1 MHz (mass-to-charge ratio, m/z, of around 180-180k for a 12-T FT-ICR system), with a low power consumption of ∼6 mW, which implies that this preamplifier is well suited to a 12-T FT-ICR mass spectrometer. In trading noise performance for higher trans-impedance, an alternative preamplifier design, an AD8099 preamplifier with the T feedback network, has also been studied with a capability of ∼106 Ω (120 dBΩ) transimpedance in the same frequency range. The resistive components in the T feedback network reported here can be replaced by complex impedances, which allows adaptation of this feedback system to other frequency, transimpedance, and noise characteristics for applications not only in other mass spectrometers, such as Orbitrap, time-of-flight (TOF), and ion trap systems, but also in other charge/current detecting systems such as spectroscopy systems, microscopy systems, optical communication systems, or charge-coupled devices (CCDs). PMID:23020394

A low noise single-transistor transimpedance preamplifier for Fourier-transform mass spectrometry using a T feedback network.

PubMed

Lin, Tzu-Yung; Green, Roger J; O'Connor, Peter B

2012-09-01

A novel single-transistor transimpedance preamplifier has been introduced for improving performance in Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry. A low noise junction field-effect transistor (JFET), BF862, is used as the main amplification stage of this trans-impedance preamplifier, and a T-shaped feedback network is introduced as both the feedback and the gate biasing solutions. The T feedback network has been studied using an operational amplifier (Op Amp), AD8099. Such a feedback system allows ~100-fold less feedback resistance at a given transimpedance, hence preserving bandwidth, which is beneficial to applications demanding high gain. The single-transistor preamplifier yields a tested transimpedance of ~10(4) Ω (80 dBΩ) in the frequency range between 1 kHz and 1 MHz (mass-to-charge ratio, m/z, of around 180-180k for a 12-T FT-ICR system), with a low power consumption of ~6 mW, which implies that this preamplifier is well suited to a 12-T FT-ICR mass spectrometer. In trading noise performance for higher trans-impedance, an alternative preamplifier design, an AD8099 preamplifier with the T feedback network, has also been studied with a capability of ~10(6) Ω (120 dBΩ) transimpedance in the same frequency range. The resistive components in the T feedback network reported here can be replaced by complex impedances, which allows adaptation of this feedback system to other frequency, transimpedance, and noise characteristics for applications not only in other mass spectrometers, such as Orbitrap, time-of-flight (TOF), and ion trap systems, but also in other charge/current detecting systems such as spectroscopy systems, microscopy systems, optical communication systems, or charge-coupled devices (CCDs).

Extending the analytical window for water-soluble organic matter in sediments by aqueous Soxhlet extraction

NASA Astrophysics Data System (ADS)

Schmidt, Frauke; Koch, Boris P.; Witt, Matthias; Hinrichs, Kai-Uwe

2014-09-01

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 μm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Investigation of Cu-, Zn- and Fe-containing human brain proteins using isotopic-enriched tracers by LA-ICP-MS and MALDI-FT-ICR-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Becker, J. Sabine

2005-04-01

Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.

Comprehensive Characterization of Swine Cardiac Troponin T Proteoforms by Top-Down Mass Spectrometry

NASA Astrophysics Data System (ADS)

Lin, Ziqing; Guo, Fang; Gregorich, Zachery R.; Sun, Ruixiang; Zhang, Han; Hu, Yang; Shanmuganayagam, Dhanansayan; Ge, Ying

2018-04-01

Cardiac troponin T (cTnT) regulates the Ca2+-mediated interaction between myosin thick filaments and actin thin filaments during cardiac contraction and relaxation. cTnT is released into the blood following injury, and increased serum levels of the protein are used clinically as a biomarker for myocardial infarction. Moreover, mutations in cTnT are causative in a number of familial cardiomyopathies. With the increasing use of large animal (swine) model to recapitulate human diseases, it is essential to characterize species-dependent protein sequence variants, alternative RNA splicing, and post-translational modifications (PTMs), but challenges remain due to the incomplete database and lack of validation of the predicted splicing isoforms. Herein, we integrated top-down mass spectrometry (MS) with online liquid chromatography (LC) and immunoaffinity purification to comprehensively characterize miniature swine cTnT proteoforms, including those arising from alternative RNA splicing and PTMs. A total of seven alternative splicing isoforms of cTnT were identified by LC/MS from swine left ventricular tissue, with each isoform containing un-phosphorylated and mono-phosphorylated proteoforms. The phosphorylation site was localized to Ser1 for the mono-phosphorylated proteoforms of cTnT1, 3, 4, and 6 by online MS/MS combining collisionally activated dissociation (CAD) and electron transfer dissociation (ETD). Offline MS/MS on Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer with CAD and electron capture dissociation (ECD) was then utilized to achieve deep sequencing of mono-phosphorylated cTnT1 (35.2 kDa) with a high sequence coverage of 87%. Taken together, this study demonstrated the unique advantage of top-down MS in the comprehensive characterization of protein alternative splicing isoforms together with PTMs. [Figure not available: see fulltext.

Oligomers Formed Through In-cloud Metylglyoxal Reactions: Chemical Composition, Properties, and Mechanisms Investigated by Ultra-high Resolution FT-ICR Mass Spectrometry

EPA Science Inventory

Secondary organic aerosol (SOA) is a substantial component of total atmospheric organic particulate matter, but little is known about the composition of SOA formed through cloud processing. We conducted aqueous phase photooxidation experiments of methylglyoxal and hydroxyl radica...

Functional Groups and Structural Insights of Water-Soluble Organic Carbon using Ultrahigh Resolution FT-ICR Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Mazzoleni, L. R.; Habib, D.; Zhao, Y.; Dalbec, M.; Samburova, V.; Hallar, G.; Zielinska, B.; Lowenthal, D.

2013-12-01

Water-soluble organic carbon (WSOC) is a complex mixture of thousands of organic compounds which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of WSOC is needed to evaluate the effect of aerosol composition upon aerosol physical properties. Products of gas phase, aqueous phase and particle phase reactions contribute to pre-existing aerosol organic mass or nucleate new aerosol particles. Thus, ambient aerosols carry a complex array of WSOC components with variable chemical signatures depending upon its origin and aerosol life-cycle processes. In this work, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize aerosol WSOC collected during the summer of 2010 at the Storm Peak Laboratory (3210 m a.s.l.) near Steamboat Springs, CO. Approximately 4000 molecular formulas were assigned in the mass range of m/z 100-800 after negative-ion electrospray ionization. The observed trends indicate significant non-oxidative accretion reaction pathways for the formation of high molecular weight WSOC components closely associated with terpene ozonolysis secondary organic aerosol (SOA). The aerosol WSOC was further characterized using ultrahigh resolution tandem MS analysis with infrared multiphoton dissociation to determine the functional groups and structural properties of 1700 WSOC species up to m/z 600. Due to the complex nature of the WSOC, multiple precursor ions were simultaneously fragmented. The exact mass measurements of the precursor and product ions facilitated molecular formula assignments and matching of neutral losses. The most important neutral losses are CO2, H2O, CH3OH, HNO3, CH3NO3, SO3 and SO4. The presence and frequency of these losses indicate the type of functional groups contained in the precursor structures. Consistent with the acidic nature of WSOC compounds, the most frequently observed losses were CO2 (~65%), H2O (~60%) and CH3OH (~40%). Several of the studied precursors had two or more losses associated with them and combinations of neutral losses such as, H4O2, CH2O3, C2H4O3 and C2O4. These neutral losses clearly indicate a multifunctional nature of the studied aerosol WSOC. Analysis of the fragment ions which were not associated with typical neutral losses indicates an overall aliphatic SOA-like structure with regular differences of 14 Da and 18 Da between low molecular weight fragment ions. Many of the fragment ions were observed in 85% or more of the MS2 spectra. The patterns observed in the low molecular weight fragment ions were very consistent over all of the mass spectra providing evidence for the significance of the non-oxidative accretion formation pathways.

Parallel Spectral Acquisition with an Ion Cyclotron Resonance Cell Array.

PubMed

Park, Sung-Gun; Anderson, Gordon A; Navare, Arti T; Bruce, James E

2016-01-19

Mass measurement accuracy is a critical analytical figure-of-merit in most areas of mass spectrometry application. However, the time required for acquisition of high-resolution, high mass accuracy data limits many applications and is an aspect under continual pressure for development. Current efforts target implementation of higher electrostatic and magnetic fields because ion oscillatory frequencies increase linearly with field strength. As such, the time required for spectral acquisition of a given resolving power and mass accuracy decreases linearly with increasing fields. Mass spectrometer developments to include multiple high-resolution detectors that can be operated in parallel could further decrease the acquisition time by a factor of n, the number of detectors. Efforts described here resulted in development of an instrument with a set of Fourier transform ion cyclotron resonance (ICR) cells as detectors that constitute the first MS array capable of parallel high-resolution spectral acquisition. ICR cell array systems consisting of three or five cells were constructed with printed circuit boards and installed within a single superconducting magnet and vacuum system. Independent ion populations were injected and trapped within each cell in the array. Upon filling the array, all ions in all cells were simultaneously excited and ICR signals from each cell were independently amplified and recorded in parallel. Presented here are the initial results of successful parallel spectral acquisition, parallel mass spectrometry (MS) and MS/MS measurements, and parallel high-resolution acquisition with the MS array system.

Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.

2012-04-01

Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein-protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent.

Development of a three component complex to increase isoniazid efficacy against isoniazid resistant and nonresistant Mycobacterium tuberculosis.

PubMed

Manning, Thomas; Plummer, Sydney; Baker, Tess; Wylie, Greg; Clingenpeel, Amy C; Phillips, Dennis

2015-10-15

The bacterium responsible for causing tuberculosis has evolved resistance to antibiotics used to treat the disease, resulting in new multidrug resistant Mycobacterium tuberculosis (MDR-TB) and extensively drug resistant M. tuberculosis (XDR-TB) strains. Analytical techniques (1)H and (13)C Nuclear Magnetic Resonance (NMR), Fourier Transform-Ion Cyclotron Resonance with Electrospray Ionization (FT-ICR/ESI), and Matrix Assisted Laser Desorption Ionization-Mass Spectrometry (MALDI-TOF-MS) were used to study different aspects of the Cu(II)-polyethylene glycol (PEG-3350)-sucrose-isoniazid and Cu(II)-polyethylene glycol (PEG3350)-glucose-isoniazid complexes. The Cu(II) cation, sucrose or glucose, and the aggregate formed by PEG primarily serve as a composite drug delivery agent for the frontline antibiotic, however the improvement in MIC values produced with the CU-PEG-SUC-INH complex suggest an additional effect. Several Cu-PEG-SUC-INH complex variations were tested against INH resistant and nonresistant strains of M. tuberculosis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Liquid chromatography-mass spectrometry in metabolomics research: mass analyzers in ultra high pressure liquid chromatography coupling.

PubMed

Forcisi, Sara; Moritz, Franco; Kanawati, Basem; Tziotis, Dimitrios; Lehmann, Rainer; Schmitt-Kopplin, Philippe

2013-05-31

The present review gives an introduction into the concept of metabolomics and provides an overview of the analytical tools applied in non-targeted metabolomics with a focus on liquid chromatography (LC). LC is a powerful analytical tool in the study of complex sample matrices. A further development and configuration employing Ultra-High Pressure Liquid Chromatography (UHPLC) is optimized to provide the largest known liquid chromatographic resolution and peak capacity. Reasonably UHPLC plays an important role in separation and consequent metabolite identification of complex molecular mixtures such as bio-fluids. The most sensitive detectors for these purposes are mass spectrometers. Almost any mass analyzer can be optimized to identify and quantify small pre-defined sets of targets; however, the number of analytes in metabolomics is far greater. Optimized protocols for quantification of large sets of targets may be rendered inapplicable. Results on small target set analyses on different sample matrices are easily comparable with each other. In non-targeted metabolomics there is almost no analytical method which is applicable to all different matrices due to limitations pertaining to mass analyzers and chromatographic tools. The specifications of the most important interfaces and mass analyzers are discussed. We additionally provide an exemplary application in order to demonstrate the level of complexity which remains intractable up to date. The potential of coupling a high field Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (ICR-FT/MS), the mass analyzer with the largest known mass resolving power, to UHPLC is given with an example of one human pre-treated plasma sample. This experimental example illustrates one way of overcoming the necessity of faster scanning rates in the coupling with UHPLC. The experiment enabled the extraction of thousands of features (analytical signals). A small subset of this compositional space could be mapped into a mass difference network whose topology shows specificity toward putative metabolite classes and retention time. Copyright © 2013 Elsevier B.V. All rights reserved.

Optimization of a two stage light gas gun. M.S. Thesis

NASA Technical Reports Server (NTRS)

Rynearson, R. J.; Rand, J. L.

1972-01-01

Performance characteristics of the Texas A&M University light gas gun are presented along with a review of basic gun theory and popular prediction methods. A computer routine based on the simple isentropic compression method is discussed. Results from over 60 test shots are given which demonstrate an increase in gun muzzle velocity from 9.100 ft/sec. to 19,000 ft/sec. The data gathered indicated the Texas A&M light gas gun more closely resembles an isentropic compression gun rather than a shock compression gun.

Dissolved organic carbon (DOC) in soil extracts investigated by FT-ICR-MS

NASA Astrophysics Data System (ADS)

Hofmann, D.; Steffen, D.; Jablonowski, N. D.; Burauel, P.

2012-04-01

Soil drying and rewetting usually increases the release of xenobiotics like pesticides present in agricultural soils. Besides the effect on the release of two aged 14C-labeled pesticide residues we focus on the characterisation of simultaneously remobilized dissolved organic carbon (DOC) to gain new insights into structure and stability aspects of soil organic carbon fractions. The test soil (gleyic cambisol; Corg 1.2%, pH 7.2) was obtained from the upper soil layer of two individual outdoor lysimeter studies containing either environmentally long-term aged 14C residues of the herbicide ethidimuron (0-10 cm depth; time of aging: 9 years) or methabenzthiazuron (0-30 cm depth; time of aging: 17 years). Soil samples (10 g dry soil equivalents) were (A=dry/wet) previously dried (45°C) or (B=wet/wet) directly mixed with pure water (1+2, w:w), shaken (150 rpm, 1 h), and centrifuged (2000 g). This extraction procedure was repeated several individual times, for both setups. The first three individual extractions, respectively were used for further investigations. Salt was removed from samples prior analysis because of a possible quench effect in the electrospray (ESI) source by solid phase extraction (SPE) with Chromabond C18 Hydra-cartridges (Macherey-Nagel) and methanol as backextraction solvent. The so preconcentrated and desalted samples were introduced by flow injection analysis (FIA) in a fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS), equipped with an ESI source and a 7 T supra-conducting magnet (LTQ-FT Ultra, ThermoFisher Scientific). This technique is the key technique for complex natural systems attributed by their outstanding mass resolution (used 400.000 at m/z 400 Da) and mass accuracy (≤ 1ppm) by simultaneously providing molecular level details of thousands of compounds and was successful applied for the investigations of natural organic matter (NOM) different sources like marine and surface water, soil, sediment, bog and crude oil. The characteristics of measured DOM mass spectra were demonstrated. Furthermore, an algorithm to compute all chemically relevant C,H,O-, C,H,(O,S),N- as well as C,H,(O),S molecular compositions, designed and exercised by ourself using Scilab routines, was used for entire structure elucidation. Various methods for data evaluation of such an amount of peaks are applied to describe the characteristics of DOC. The van Krevelen diagram is widely used to classify the DOC compounds regarding polarity and aromaticity, whereas the Kendrick diagram allow to identify ions with elemental formulas that differ only in CH2, and molecular formulas with similar Kendrick Mass Defect (KMD) can be sorted by nominal mass series. Both kind of diagrams were developed and results are discussed together with the findings of ETD, MBT, and metabolites after soil drying and rewetting. Overall, the results suggest that intermittent soil drying and rewetting alters the disaggregation of soil aggregates, resulting in a release of entrapped organic carbon as well as pesticide molecules.

A pilot study: subclinical hypothyroidism and free thyroid hormone measurement by immunoassay and mass spectrometry.

PubMed

Gounden, Verena; Jonklaas, Jacqueline; Soldin, Steven J

2014-03-20

The diagnosis of subclinical hypothyroidism is defined as the presence of an elevated thyroid stimulating hormone (TSH) with a normal free thyroxine (FT4) level. The commonly used direct analogue immunoassays for the measurement of FT4 have been shown to have poor performance at the upper and lower limits of the FT4 reference interval. The purpose of this pilot study was to investigate the percentage of individuals classified as having subclinical hypothyroidism with a standard immunoassay, that actually have low free thyroid hormone levels by mass spectrometry measurements. Outpatient samples with elevated TSH values and normal FT4 concentrations as per standard immunoassay methods were collected. FT4 and free triiodothyronine (FT3) analyses were performed on these samples using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Sixty five percent (n=26) of patients (n=40) had (LC-MS/MS) FT4 or FT3 or both FT4 and FT3 values below mass spectrometry reference limits. Our findings indicate that the direct analogue immunoassay method for FT4 measurement results in a significant proportion of patients being misclassified as having subclinical hypothyroidism. Published by Elsevier B.V.

Screening of synthetic PDE-5 inhibitors and their analogues as adulterants: analytical techniques and challenges.

PubMed

Patel, Dhavalkumar Narendrabhai; Li, Lin; Kee, Chee-Leong; Ge, Xiaowei; Low, Min-Yong; Koh, Hwee-Ling

2014-01-01

The popularity of phosphodiesterase type 5 (PDE-5) enzyme inhibitors for the treatment of erectile dysfunction has led to the increase in prevalence of illicit sexual performance enhancement products. PDE-5 inhibitors, namely sildenafil, tadalafil and vardenafil, and their unapproved designer analogues are being increasingly used as adulterants in the herbal products and health supplements marketed for sexual performance enhancement. To date, more than 50 unapproved analogues of prescription PDE-5 inhibitors were found as adulterants in the literature. To avoid detection of such adulteration by standard screening protocols, the perpetrators of such illegal products are investing time and resources to synthesize exotic analogues and devise novel means for adulteration. A comprehensive review of conventional and advance analytical techniques to detect and characterize the adulterants is presented. The rapid identification and structural elucidation of unknown analogues as adulterants is greatly enhanced by the wide myriad of analytical techniques employed, including high performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), liquid chromatography mass-spectrometry (LC-MS), nuclear magnetic resonance (NMR) spectroscopy, vibrational spectroscopy, liquid chromatography-Fourier transform ion cyclotron resonance-mass spectrometry (LC-FT-ICR-MS), liquid chromatograph-hybrid triple quadrupole linear ion trap mass spectrometer with information dependent acquisition, ultra high performance liquid chromatography-time of flight-mass spectrometry (UHPLC-TOF-MS), ion mobility spectroscopy (IMS) and immunoassay methods. The many challenges in detecting and characterizing such adulterants, and the need for concerted effort to curb adulteration in order to safe guard public safety and interest are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Extending the Dynamic Range of the Ion Trap by Differential Mobility Filtration

PubMed Central

Hall, Adam B.; Coy, Stephen L.; Kafle, Amol; Glick, James; Nazarov, Erkinjon

2013-01-01

A miniature, planar, differential ion mobility spectrometer (DMS) was interfaced to an LCQ classic ion trap to conduct selective ion filtration prior to mass analysis in order to extend the dynamic range of the trap. Space charge effects are known to limit the functional ion storage capacity of ion trap mass analyzers and this, in turn, can affect the quality of the mass spectral data generated. This problem is further exacerbated in the analysis of mixtures where the indiscriminate introduction of matrix ions results in premature trap saturation with non-targeted species, thereby reducing the number of parent ions that may be used to conduct MS/MS experiments for quantitation or other diagnostic studies. We show that conducting differential mobility-based separations prior to mass analysis allows the isolation of targeted analytes from electrosprayed mixtures preventing the indiscriminate introduction of matrix ions and premature trap saturation with analytically unrelated species. Coupling these two analytical techniques is shown to enhance the detection of a targeted drug metabolite from a biological matrix. In its capacity as a selective ion filter, the DMS can improve the analytical performance of analyzers such as quadrupole (3-D or linear) and ion cyclotron resonance (FT-ICR) ion traps that depend on ion accumulation. PMID:23797861

Changes in Brain Metallome/Metabolome Pattern due to a Single i.v. Injection of Manganese in Rats

PubMed Central

Neth, Katharina; Lucio, Marianna; Walker, Alesia; Zorn, Julia; Schmitt-Kopplin, Philippe; Michalke, Bernhard

2015-01-01

Exposure to high concentrations of Manganese (Mn) is known to potentially induce an accumulation in the brain, leading to a Parkinson related disease, called manganism. Versatile mechanisms of Mn-induced brain injury are discussed, with inactivation of mitochondrial defense against oxidative stress being a major one. So far, studies indicate that the main Mn-species entering the brain are low molecular mass (LMM) compounds such as Mn-citrate. Applying a single low dose MnCl2 injection in rats, we observed alterations in Mn-species pattern within the brain by analysis of aqueous brain extracts by size-exclusion chromatography—inductively coupled plasma mass spectrometry (SEC-ICP-MS). Additionally, electrospray ionization—ion cyclotron resonance-Fourier transform-mass spectrometry (ESI-ICR/FT-MS) measurement of methanolic brain extracts revealed a comprehensive analysis of changes in brain metabolisms after the single MnCl2 injection. Major alterations were observed for amino acid, fatty acid, glutathione, glucose and purine/pyrimidine metabolism. The power of this metabolomic approach is the broad and detailed overview of affected brain metabolisms. We also correlated results from the metallomic investigations (Mn concentrations and Mn-species in brain) with the findings from metabolomics. This strategy might help to unravel the role of different Mn-species during Mn-induced alterations in brain metabolism. PMID:26383269

Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar+ + CH3 and O2+ + CH3 (Postprint)

DTIC Science & Technology

2015-01-13

Gross group using a Chen nozzle coupled to a Fourier transform ion cyclotron reso- nance (FT-ICR) mass spectrometer for reactions of the benzyl radical...reactions: A Fourier transform ion cyclotron resonance study of allyl radical reacting with aromatic radical cations. Int. J. Mass Spectrom. 2009, 287, 8

Pediatric Reference Intervals for Free Thyroxine and Free Triiodothyronine

PubMed Central

Jang, Megan; Guo, Tiedong; Soldin, Steven J.

2009-01-01

Background The clinical value of free thyroxine (FT4) and free triiodothyronine (FT3) analysis depends on the reference intervals with which they are compared. We determined age- and sex-specific reference intervals for neonates, infants, and children 0–18 years of age for FT4 and FT3 using tandem mass spectrometry. Methods Reference intervals were calculated for serum FT4 (n = 1426) and FT3 (n = 1107) obtained from healthy children between January 1, 2008, and June 30, 2008, from Children's National Medical Center and Georgetown University Medical Center Bioanalytical Core Laboratory, Washington, DC. Serum samples were analyzed using isotope dilution liquid chromatography tandem mass spectrometry (LC/MS/MS) with deuterium-labeled internal standards. Results FT4 reference intervals were very similar for males and females of all ages and ranged between 1.3 and 2.4 ng/dL for children 1 to 18 years old. FT4 reference intervals for 1- to 12-month-old infants were 1.3–2.8 ng/dL. These 2.5 to 97.5 percentile intervals were much tighter than reference intervals obtained using immunoassay platforms 0.48–2.78 ng/dL for males and 0.85–2.09 ng/dL for females. Similarly, FT3 intervals were consistent and similar for males and females and for all ages, ranging between 1.5 pg/mL and approximately 6.0 pg/mL for children 1 month of age to 18 years old. Conclusions This is the first study to provide pediatric reference intervals of FT4 and FT3 for children from birth to 18 years of age using LC/MS/MS. Analysis using LC/MS/MS provides more specific quantification of thyroid hormones. A comparison of the ultrafiltration tandem mass spectrometric method with equilibrium dialysis showed very good correlation. PMID:19583487

Neural correlates of "Theory of Mind" in very preterm born children.

PubMed

Mossad, Sarah I; Smith, Mary Lou; Pang, Elizabeth W; Taylor, Margot J

2017-11-01

Very preterm (VPT) birth (<32 weeks' gestational age) has been implicated in social-cognitive deficits including Theory of Mind (ToM); the ability to attribute mental states to others and understand that those beliefs can differ from one's own or reality. The neural bases for ToM deficits in VPT born children have not been examined. We used magnetoencephalography (MEG) for its excellent spatial and temporal resolution to determine the neural underpinnings of ToM in 24 VPT and 24 full-term born (FT) children (7-13 years). VPT children performed more poorly on neuropsychological measures of ToM but not inhibition. In the MEG task, both FT children and VPT children recruited regions involved in false belief processing such as the rIFG (VPT: 275-350 ms, FT: 250-375 ms) and left inferior temporal gyrus (VPT: 375-450 ms, FT: 325-375 ms) and right fusiform gyrus (VPT: 150-200 ms, FT: 175-250 ms). The rIPL (included in the temporal-parietal junction) was recruited in FT children (475-575 ms) and the lTPJ in VPT children (500-575 ms). However, activations in all regions were reduced in the VPT compared to the FT group. We suggest that with increasing social-cognitive demands such as varying the type of scenarios in the standardized measure of ToM, reduced activations in the rIFG and TPJ in the VPT group may reflect the decreased performance. With access to both spatial and temporal information, we discuss the role of domain general and specific regions of the ToM network in both groups. Hum Brain Mapp 38:5577-5589, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Metabolic profile of esculin in rats by ultra high performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Wang, Yinan; Zhao, Min; Ou, Yingfu; Zeng, Bowen; Lou, Xinyu; Wang, Miao; Zhao, Chunjie

2016-05-01

Esculin, a coumarin derivative found in Fraxinus rhynchophylla, has been reported to possess multiple biological activities. This present study is designed to investigate the metabolic profile of esculin in vivo based on ultra high performance liquid chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry (UHPLC-FT-ICR-MS) for the first time. After oral administration of esculin (100 mg/kg) for rats, plasma, urine, feces and bile samples were collected to screen metabolites. As a result, a total of 19 metabolites (10 phase I metabolites and 9 phase II metabolites) were found and identified. Results showed that metabolic pathways of esculin included hydrolysis, dehydrogenation, hydroxylation, methylation, dehydrogenation, glucuronidation, sulfation, and glycine conjugation. It was also found that after oral administration of esculin, the esculin could be metabolized to esculetin in vivo via deglycosylation, and esculetin was found in all biological samples. This study also laid solid basis for in-depth development of esculin and provided important information for clarifying the biotransformation process of esculin in vivo. Copyright © 2016 Elsevier B.V. All rights reserved.

Metabolic profile of salidroside in rats using high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Han, Fei; Li, Yan-ting; Mao, Xin-juan; Zhang, Xiao-shu; Guan, Jiao; Song, Ai-hua; Yin, Ran

2016-03-01

A high-performance liquid chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry (HPLC-FT-ICR MS) method was developed to study the in vivo metabolism of salidroside for the first time. Plasma, urine, bile, and feces samples were collected from male rats after a single intragastric gavage of salidroside at a dose of 50 mg/kg. Besides the parent drug, a total of seven metabolites (three phase I and four phase II metabolites) were detected and tentatively identified by comparing their mass spectrometry profiles with those of salidroside. Results indicated that metabolic pathways of salidroside in male rats included hydroxylation, dehydrogenation, glucuronidation, and sulfate conjugation. Among them, glucuronidation and sulfate conjugation were the major metabolic reactions. And most important, the detection of the sulfation metabolite of p-tyrosol provides a clue for whether the deglycosylation of salidroside occurs in vivo after intragastric gavage. In summary, results obtained in this study may contribute to the better understanding of the safety and mechanism of action of salidroside.

Formularity: Software for Automated Formula Assignment of Natural and Other Organic Matter from Ultrahigh-Resolution Mass Spectra.

PubMed

Tolić, Nikola; Liu, Yina; Liyu, Andrey; Shen, Yufeng; Tfaily, Malak M; Kujawinski, Elizabeth B; Longnecker, Krista; Kuo, Li-Jung; Robinson, Errol W; Paša-Tolić, Ljiljana; Hess, Nancy J

2017-12-05

Ultrahigh resolution mass spectrometry, such as Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), can resolve thousands of molecular ions in complex organic matrices. A Compound Identification Algorithm (CIA) was previously developed for automated elemental formula assignment for natural organic matter (NOM). In this work, we describe software Formularity with a user-friendly interface for CIA function and newly developed search function Isotopic Pattern Algorithm (IPA). While CIA assigns elemental formulas for compounds containing C, H, O, N, S, and P, IPA is capable of assigning formulas for compounds containing other elements. We used halogenated organic compounds (HOC), a chemical class that is ubiquitous in nature as well as anthropogenic systems, as an example to demonstrate the capability of Formularity with IPA. A HOC standard mix was used to evaluate the identification confidence of IPA. Tap water and HOC spike in Suwannee River NOM were used to assess HOC identification in complex environmental samples. Strategies for reconciliation of CIA and IPA assignments were discussed. Software and sample databases with documentation are freely available.

Molecular-level dynamics of refractory dissolved organic matter

NASA Astrophysics Data System (ADS)

Niggemann, J.; Gerdts, G.; Dittmar, T.

2012-04-01

Refractory dissolved organic matter (DOM) accounts for most of the global oceanic organic carbon inventory. Processes leading to its formation and factors determining its stability are still largely unknown. We hypothesize that refractory DOM carries a universal molecular signature. Characterizing spatial and temporal variability in this universal signature is a key to understanding dynamics of refractory DOM. We present results from a long-term study of the DOM geo-metabolome in the open North Sea. Geo-metabolomics considers the entity of DOM as a population of compounds, each characterized by a specific function and reactivity in the cycling of energy and elements. Ten-thousands of molecular formulae were identified in DOM by ultrahigh resolution mass spectrometry analysis (FT-ICR-MS, Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry). The DOM pool in the North Sea was influenced by a complex interplay of processes that produced, transformed and degraded dissolved molecules. We identified a stable fraction in North Sea DOM with a molecular composition similar to deep ocean DOM. Molecular-level changes in this stable fraction provide novel information on dynamics and interactions of refractory DOM.

Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

PubMed

González-Navarrete, Patricio; Schlangen, Maria; Wu, Xiao-Nan; Schwarz, Helmut

2016-02-24

The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions.

PubMed

Li, Jilai; Zhou, Shaodong; Schlangen, Maria; Weiske, Thomas; Schwarz, Helmut

2016-10-10

The reactivity of the cationic gold carbide [AuC] + (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC] + has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Comparison of Different Heterotrophic Bacteria on the Decomposition of DOC molecule

NASA Astrophysics Data System (ADS)

Xie, R.; Zheng, Q.; Jiao, N.

2016-02-01

Marine dissolved organic carbon (DOC) pool is one of the largest reservoirs of organic carbon on Earth. Heterotrophic bacteria are the primary biotic force regulating the fate of marine DOC. Comparison of genomic data, microbes belonging to different clades have diverse DOC molecule utilization genes. That's give us a hint that different microbial groups may have their own pattern to decompose DOC, biosynthesize diverse DOC molecule and contribute to the in situ DOC reservoirs in the ocean. The interaction between marine microbes and DOC molecule is hotspots in current research. We will choose some important microbial groups (e.g., Roseobacter, Altermonas, Halomonas, SAR11 and CFB) to identify their contribution to environmental DOC pool and their specific recalcitrant DOC component using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Combined with the composition of hydrolases, lyases and ligases in their genomes, we try to establish a linkage between the specific DOC composition and microbial genetic information. Future more the environmental metagenomic data would help us understand the relationship between the endemic DOC composition and microbial communities in the environment.

Proteomic Analysis of Human Tendon and Ligament: Solubilization and Analysis of Insoluble Extracellular Matrix in Connective Tissues.

PubMed

Sato, Nori; Taniguchi, Takako; Goda, Yuichiro; Kosaka, Hirofumi; Higashino, Kosaku; Sakai, Toshinori; Katoh, Shinsuke; Yasui, Natsuo; Sairyo, Koichi; Taniguchi, Hisaaki

2016-12-02

Connective tissues such as tendon, ligament and cartilage are mostly composed of extracellular matrix (ECM). These tissues are insoluble, mainly due to the highly cross-linked ECM proteins such as collagens. Difficulties obtaining suitable samples for mass spectrometric analysis render the application of modern proteomic technologies difficult. Complete solubilization of them would not only elucidate protein composition of normal tissues but also reveal pathophysiology of pathological tissues. Here we report complete solubilization of human Achilles tendon and yellow ligament, which is achieved by chemical digestion combined with successive protease treatment including elastase. The digestion mixture was subjected to liquid chromatography-mass spectrometry. The low specificity of elastase was overcome by accurate mass analysis achieved using FT-ICR-MS. In addition to the detailed proteome of both tissues, we also quantitatively determine the major protein composition of samples, by measuring peak area of some characteristic peptides detected in tissue samples and in purified proteins. As a result, differences between human Achilles tendon and yellow ligament were elucidated at molecular level.

Oligomers, organosulfates, and nitroxy organosulfates identified in rainwater

NASA Astrophysics Data System (ADS)

Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

2008-12-01

Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50 percent of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We document the presence of 552 unique compounds in the rainwater over a mass range of 50-500 Da, in four compound classes (i.e., CHO, CHOS, CHON, and CHONS). The presence of oligomers, organosulfates, nitroxy organosulfates, organic acids, and linear alkylbenzene sulfonates is reported. Some compounds detected have distinct primary sources; however, the composition of the bulk of this material suggests it is formed in the atmosphere and composed of known contributors to secondary organic aerosol. For example, eight oligomer series known to form through aqueous photooxidation of methylglyoxal and organosulfate compounds known to form from 4 precursors in smog chamber experiments were identified in the rainwater samples. The oligomers, organosulfates, and nitroxy organosulfates detected in the rainwater could all contribute to the HULIS fraction of atmospheric organic matter.

Identification of cell wall proteins in the flax (Linum usitatissimum) stem.

PubMed

Day, Arnaud; Fénart, Stéphane; Neutelings, Godfrey; Hawkins, Simon; Rolando, Christian; Tokarski, Caroline

2013-03-01

Sequential salt (CaCl2 , LiCl) extractions were used to obtain fractions enriched in cell wall proteins (CWPs) from the stem of 60-day-old flax (Linum usitatissimum) plants. High-resolution FT-ICR MS analysis and the use of recently published genomic data allowed the identification of 11 912 peptides corresponding to a total of 1418 different proteins. Subcellular localization using TargetP, Predotar, and WoLF PSORT led to the identification of 152 putative flax CWPs that were classified into nine different functional classes previously established for Arabidopsis thaliana. Examination of different functional classes revealed the presence of a number of proteins known to be involved in, or potentially involved in cell-wall metabolism in plants. The flax stem cell wall proteome was also compared with transcriptomic data previously obtained on comparable samples. This study represents a major contribution to the identification of CWPs in flax and will lead to a better understanding of cell wall biology in this species. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Systematic Study on the Generation of Multimetallic Lanthanide Fullerene ions by Laser Ablation Mass Spectrometry.

PubMed

Wang, Yiyun; Ma, LiFu; Mu, Lei; Ren, Juan; Kong, Xianglei

2018-06-01

Laser ablation masss spectromety has been previously proved to be a powerful tool for studying endohedro metallofullerene (EMF) ions. Our previous study showed the possiblity of forming multi-metallofullerene ions containg more than six metal atoms for La, Y and Lu. Thus, it is important to conduct a systematic study on the generation of multi-metallofullerenes and their distribuitons for all lanthanide elements. Experiments were performed on a 7.0 T Fourier transform ion cyclotron resonance (FT ICR) mass spectrometer. Laser ablation mass spectra were obtained by laser irradiation on mixtures of graphene and MCl 3 on a stainless steel plate, applying a 355 nm Nd: YAG laser with a typical energy of 2.5 mJ/pulse. Reaction test experiments were performed by introducing O 2 into the FT ICR cell with a pulse valve. Multi-metallofullerene ions Ce2-4C2m+, Pr2-4C2m+, Gd2-4C2m+, Nd3C2m+, Dy2-3C2m+, Tb2-7C2m+, Ho2-6C2m+ were observed in the mass spectra. For metal Sm and Eu, no multi-metallofullerene ion was observed. No reaction with O 2 was observed in the reaction experiments, verifying that these species had endohedral structures. For the observed series of multi-metallofullerene ions, tri-metallofullerene ions dominated their mass spectra. The results were further compared with previously generated EMF ions for La, Er, Tm, Yb and Lu. Endohedral lanthanide metallofullerene ions were generated by laser ablation of graphene and the corresponding metal salts MCl 3 (M = Ce, Pr, Nd, Gd, Tb, Dy and Ho) and studied with a FT ICR mass spectrometer. Typically, multi-metallofullerene ions of TbnC2m+2≤n≤780≤2m≤176, Ho6C2m+2≤n≤674≤2m≤162 were observed. The results show that the formation of multi-EMF ions containing lanthanides that have +3 and +4 oxidation states is easier than those containing +2 oxidation states in the process of laser ablation. This article is protected by copyright. All rights reserved.

Electrospray ionization of uranyl-citrate complexes

NASA Astrophysics Data System (ADS)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures and charge state distributions.

Conductive carbon tape used for support and mounting of both whole animal and fragile heat-treated tissue sections for MALDI MS imaging and quantitation.

PubMed

Goodwin, Richard J A; Nilsson, Anna; Borg, Daniel; Langridge-Smith, Pat R R; Harrison, David J; Mackay, C Logan; Iverson, Suzanne L; Andrén, Per E

2012-08-30

Analysis of whole animal tissue sections by MALDI MS imaging (MSI) requires effective sample collection and transfer methods to allow the highest quality of in situ analysis of small or hard to dissect tissues. We report on the use of double-sided adhesive conductive carbon tape during whole adult rat tissue sectioning of carboxymethyl cellulose (CMC) embedded animals, with samples mounted onto large format conductive glass and conductive plastic MALDI targets, enabling MSI analysis to be performed on both TOF and FT-ICR MALDI mass spectrometers. We show that mounting does not unduly affect small molecule MSI detection by analyzing tiotropium abundance and distribution in rat lung tissues, with direct on-tissue quantitation achieved. Significantly, we use the adhesive tape to provide support to embedded delicate heat-stabilized tissues, enabling sectioning and mounting to be performed that maintained tissue integrity on samples that had previously been impossible to adequately prepare section for MSI analysis. The mapping of larger peptidomic molecules was not hindered by tape mounting samples and we demonstrate this by mapping the distribution of PEP-19 in both native and heat-stabilized rat brains. Furthermore, we show that without heat stabilization PEP-19 degradation fragments can detected and identified directly by MALDI MSI analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Association reactions at low pressure. 5: The CH3(+)/HCN system. A final word?

NASA Technical Reports Server (NTRS)

Anicich, Vincent G.; Sen, Atish D.; Huntress, Wesley, Jr.; McEwan, Murray J.

1995-01-01

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a re-examination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism, does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion. Previous studies either 'lost' this product in the extremely large protonated HCN signal that is always present when HCN is used, or discounted it for various reasons. We have been able to show by ion cyclotron resonance (ICR) techniques (both FT-ICR and tandem ICR-dempster-ICR) that the radiative association product does react with the HCN to form the protonated HCN ion.

Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole

NASA Astrophysics Data System (ADS)

Saglam, S.; Disli, A.; Erdogdu, Y.; Marchewka, M. K.; Kanagathara, N.; Bay, B.; Güllüoğlu, M. T.

2015-01-01

In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, 1H NMR, 13C-APT and LC-MS spectroscopy techniques. The FT-IR, 1H NMR and 13C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G** basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities.

Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole.

PubMed

Saglam, S; Disli, A; Erdogdu, Y; Marchewka, M K; Kanagathara, N; Bay, B; Güllüoğlu, M T

2015-01-25

In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, (1)H NMR, (13)C-APT and LC-MS spectroscopy techniques. The FT-IR, (1)H NMR and (13)C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G(**), cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G(**) basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of magnetic field inhomogeneity on ion cyclotron motion coherence at high magnetic field.

PubMed

Vladimirov, Gleb; Kostyukevich, Yury; Hendrickson, Christopher L; Blakney, Greg T; Nikolaev, Eugene

2015-01-01

A three-dimensional code based on the particle-in-cell algorithm modified to account for the inhomogeneity of the magnetic field was applied to determine the effect of Z(1), Z(2), Z(3), Z(4), X, Y, ZX, ZY, XZ(2) YZ(2), XY and X(2)-Y(2) components of an orthogonal magnetic field expansion on ion motion during detection in an FT-ICR cell. Simulations were performed for magnetic field strengths of 4.7, 7, 14.5 and 21 Tesla, including experimentally determined magnetic field spatial distributions for existing 4.7 T and 14.5 T magnets. The effect of magnetic field inhomogeneity on ion cloud stabilization ("ion condensation") at high numbers of ions was investigated by direct simulations of individual ion trajectories. Z(1), Z(2), Z(3) and Z(4) components have the largest effect (especially Z(1)) on ion cloud stability. Higher magnetic field strength and lower m/z demand higher relative magnetic field homogeneity to maintain cloud coherence for a fixed time period. The dependence of mass resolving power upper limit on Z(1) inhomogeneity is evaluated for different magnetic fields and m/z. The results serve to set the homogeneity requirements for various orthogonal magnetic field components (shims) for future FT-ICR magnet design.

Experimental Investigations of the Internal Energy of Molecules Evaporated via Laser-induced Acoustic Desorption into a Fourier-transform Ion Cyclotron Resonance Mass Spectrometer (LIAD/FT-ICR)

PubMed Central

Shea, Ryan C.; Petzold, Christopher J.; Liu, Ji-ang; Kenttämaa, Hilkka I.

2008-01-01

The internal energy of neutral gas-phase organic and biomolecules, evaporated by means of laser-induced acoustic desorption (LIAD) into a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR), was investigated through several experimental approaches. The desorbed molecules were demonstrated not to undergo degradation during the desorption process by collecting LIAD-evaporated molecules and subjecting them to analysis by electrospray ionization/quadrupole ion trap mass spectrometry. Previously established gas-phase basicity (GB) values were remeasured for LIAD-evaporated organic molecules and biomolecules with the use of the bracketing method. No endothermic reactions were observed. The remeasured basicity values are in close agreement with the values reported in the literature. The amount of internal energy deposited during LIAD is concluded to be less than a few kcal/mol. Chemical ionization with a series of proton transfer reagents was employed to obtain a breakdown curve for a protonated dipeptide, val-pro, evaporated by LIAD. Comparison of this breakdown curve with a previously published analogous curve obtained by using substrate-assisted laser desorption (SALD) to evaporate the peptide suggests that the molecules evaporated via LIAD have less internal energy than those evaporated via SALD. PMID:17263513

Appendices for Fort George G. Meade Active Sanitary Landfill and Clean Fill Dump Remedial Investigation Report

DTIC Science & Technology

1992-12-01

l 1 . . )-4 La 4 U 0v a .,4- ai m == = z cC " C1L U ,-4 w =& n4) .cUU >4 C 0 La 0 3 2L -- adV) u -14 0 ( 0 01 rZ N00. w-4 cz Cs0. Z -14 .CL C L" M a...8217 - ’ - ’ -- ’ - ’ - ’ - ’ La I• i I 40 a SPT 1 18 19 9 41 134-41-69 0 X - CH MOTTLED LIGHT GREY(N7) MOD. REDDISI BROd(ICR4/6), i rCRY, CLAY, HARD HI A. a a a a a a a 45...ffmJ 3’ TO MRFACE(3’ SSDIVEN SPL.IT SON AT COMPLETON FT.S-RES SHELBY TUBE AFTER HRS. FT.OSTa PISTON S * 24 HRS. FT. DE--DI5NM CORE BARLSAPE 5PT

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

NASA Astrophysics Data System (ADS)

Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

2016-11-01

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Forensic Drug Identification, Confirmation, and Quantification Using Fully Integrated Gas Chromatography with Fourier Transform Infrared and Mass Spectrometric Detection (GC-FT-IR-MS).

PubMed

Lanzarotta, Adam; Lorenz, Lisa; Voelker, Sarah; Falconer, Travis M; Batson, JaCinta S

2018-05-01

This manuscript is a continuation of a recent study that described the use of fully integrated gas chromatography with direct deposition Fourier transform infrared detection and mass spectrometric detection (GC-FT-IR-MS) to identify and confirm the presence of sibutramine and AB-FUBINACA. The purpose of the current study was to employ the GC-FT-IR portion of the same instrument to quantify these compounds, thereby demonstrating the ability to identify, confirm, and quantify drug substances using a single GC-FT-IR-MS unit. The performance of the instrument was evaluated by comparing quantitative analytical figures of merit to those measured using an established, widely employed method for quantifying drug substances, high performance liquid chromatography with ultraviolet detection (HPLC-UV). The results demonstrated that GC-FT-IR was outperformed by HPLC-UV with regard to sensitivity, precision, and linear dynamic range (LDR). However, sibutramine and AB-FUBINACA concentrations measured using GC-FT-IR were not significantly different at the 95% confidence interval compared to those measured using HPLC-UV, which demonstrates promise for using GC-FT-IR as a semi-quantitative tool at the very least. The most significant advantage of GC-FT-IR compared to HPLC-UV is selectivity; a higher level of confidence regarding the identity of the analyte being quantified is achieved using GC-FT-IR. Additional advantages of using a single GC-FT-IR-MS instrument for identification, confirmation, and quantification are efficiency, increased sample throughput, decreased consumption of laboratory resources (solvents, chemicals, consumables, etc.), and thus cost.

Prolactin levels during short- and long-term cross-sex hormone treatment: an observational study in transgender persons.

PubMed

Nota, N M; Dekker, M J H J; Klaver, M; Wiepjes, C M; van Trotsenburg, M A; Heijboer, A C; den Heijer, M

2017-08-01

The cause of prolactin alterations in transgender persons is often assigned to oestrogens, but the precise cause and time course during different phases of cross-sex hormone treatment (CHT) remain unclear. In this study, we prospectively examined prolactin levels in 55 female-to-males (FtMs) and 61 male-to-females (MtFs) during the first year of CHT. Because long-term prolactin data were not available in this population, we studied these levels in a retrospective population of 25 FtMs and 38 MtFs who underwent gonadectomy. FtMs were treated with testosterone and MtFs with estradiol, with or without the anti-androgen cyproterone acetate (CPA) (after gonadectomy CPA is cessated). During the first year of CHT, prolactin decreased with 25% (95CI: -33%, -12%) in FtMs and increased with 193% (95CI: 156%, 219%) in MtFs. Eighteen MtFs developed hyperprolactinemia (≥0.6 IU L -1 ). In the retrospective population, post-gonadectomy levels in FtMs were lower than baseline levels (-39%; 95CI: -51%, -20%) while in MtFs post-gonadectomy levels and baseline levels were comparable (-6%; 95CI: -24%, 15%). No hyperprolactinemia was found after gonadectomy. In conclusion, in FtMs, prolactin decreased consistently during CHT and in MtFs, prolactin increased during pre-surgical CHT but normalised after gonadectomy. It is likely that CPA induces increasing prolactin levels in MtFs. © 2016 Blackwell Verlag GmbH.

Characterization of Linum usitatissimum L. oil obtained from different extraction technique and in vitro antioxidant potential of supercritical fluid extract

PubMed Central

Chauhan, Rishika; Chester, Karishma; Khan, Yasmeen; Tamboli, Ennus Tajuddin; Ahmad, Sayeed

2015-01-01

Aim: Present investigation was aimed to characterize the fixed oil of Linum usitatissimum L. using five different extraction methods: Supercritical fluid extraction (SFE), ultrasound-assistance, soxhlet extraction, solvent extraction, and three phase partitioning method. Materials and Methods: The SFE conditions (temperature, pressure, and volume of CO2) were optimized prior for better yield. The extracted oils were analyzed and compared for their physiochemical parameters, high performance thin layer chromatography (HPTLC), gas chromatography-mass spectrometry (GC-MS), and Fourier-transformed infrared spectroscopy (FT-IR) fingerprinting. Antioxidant activity was also determined using 1,1-diphenyl-2-picrylhydrazyl and superoxide scavenging method. Result: The main fatty acids were α-linolenic acid, linoleic acid, palmitic acid, and stearic acid as obtained by GC-MS. HPTLC analysis revealed the presence of similar major components in chromatograms. Similarly, the pattern of peaks, as obtained in FT-IR and GC-MS spectra of same oils by different extraction methods, were superimposable. Conclusion: Analysis reported that the fixed oil of L. usitatissimum L. is a good source of n-3 fatty acid with the significant antioxidant activity of oil obtained from SFE extraction method. PMID:26681884

[Correlation of serum sex hormone levels with metabolic syndrome in elderly men].

PubMed

Xiao, H Y; Lu, Y H; Gong, Y P; Cheng, X L; Tian, H; Li, C L

2016-03-08

To investigate the relationship between sex hormones and metabolic syndrome (MS), as well as its components in elderly men. 1 505 elderly men (≥60 years old, mean age 75.4±9.7 years old) who participated in a routine health screening examination in PLA general hospital from May to June in 2012 were enrolled in this cross-sectional study. Serum lipids, glucose and sex hormones were measured along with body height, weight and blood pressure. Free testosterone (FT) and bioavailable testosterone (BT) were calculated. The correlation of serum sex hormones with the presence of MS and its components were analyzed. The prevalence of MS was 21.7% (326/1 505) in this study. Elderly men with MS had lower levels of sex hormone-binding globulin (SHBG), total testosterone (TT), FT and BT than those without MS. The levels of SHBG, TT, FT and BT were significantly lower in the overweight/obesity group, hyperglycemia group and dyslipidemia group than those in the respective control groups (P<0.05). Logistic regression analysis showed that the SHBG level was an independent risk factor for MS in elderly men(OR=0.977, 95%CI: 0.964-0.989, P<0.001), while the levels of TT, FT and BT were not associated with MS. The prevalence of MS gradually increased with decreasing of SHBG values (P<0.001). When comparing subjects in the lowest and highest quartile of SHBG, the former group demonstrated a 2.13-fold increase in the odds ratio for MS after adjusting for age, smoking, drinking and other sex hormone indices. In elderly men, lower SHBG level, not TT, FT or BT may be an independent predictor for the prevalence of MS, in which the mechanism requires further studies.

Sociodemographic and clinical features of gender identity disorder: an Italian multicentric evaluation.

PubMed

Fisher, Alessandra D; Bandini, Elisa; Casale, Helen; Ferruccio, Naika; Meriggiola, Maria C; Gualerzi, Anna; Manieri, Chiara; Jannini, Emmanuele; Mannucci, Edoardo; Monami, Matteo; Stomaci, Niceta; Delle Rose, Augusto; Susini, Tommaso; Ricca, Valdo; Maggi, Mario

2013-02-01

Male to female (MtFs) and female to male (FtMs) subjects with gender identity disorder (GID) seem to differ with regard to some sociodemographic and clinical features. Currently, no descriptive studies focusing on MtFs and FtMs attending an Italian clinic are available. To describe the sociodemographic characteristics of a GID population seeking assistance for gender transition and to assess possible differences in those features between MtFs and FtMs. A consecutive series of 198 patients was evaluated for gender dysphoria from July 2008 to May 2011 in four dedicated centers. A total of 140 subjects (mean age 32.6 ± 9.0 years old) meeting the criteria for GID, with their informed consent and without genital reassignment surgery having already been performed, were considered (92 MtFs and 48 FtMs). Diagnosis was based on formal psychiatric classification criteria. Medical history and sociodemographic characteristics were investigated. Subjects were asked to complete the Body Uneasiness Test (a self-rating scale exploring different areas of body-related psychopathology), Symptom Checklist-90 Revised (a self-rating scale to measure psychological state), and the Bem Sex Role Inventory (a self-rating scale to evaluate gender role). The presence of psychiatric comorbidities was evaluated using the Structured Clinical Interviews for Diagnostic and Statistical Manual of Mental Disorders, 4th Edition, Text Revision (DSM-IV-TR) (SCID I and SCID II). Several significant differences were found between MtFs and FtMs regarding lifestyle and sociodemographic factors and in psychometric test scores. No differences were found in terms of psychiatric comorbidity. This is the first large study reporting the sociodemographic characteristics of a GID sample referring to Italian clinics, and it provides different profiles for MtFs and FtMs. In particular, FtMs display significantly better social functioning. © 2012 International Society for Sexual Medicine.

[Preparation of scopolamine hydrobromide nanoparticles-in-microsphere system].

PubMed

Lü, Wei-ling; Hu, Jin-hong; Zhu, Quan-gang; Li, Feng-qian

2010-07-01

This study is to prepare scopolamine hydrobromide nanoparticles-in-microsphere system (SH-NiMS) and evaluate its drug release characteristics in vitro. SH nanoparticles were prepared by ionic crosslinking method with tripolyphosphate (TPP) as crosslinker and chitosan as carrier. Orthogonal design was used to optimize the formulation of SH nanoparticles, which took the property of encapsulation efficiency and drug loading as evaluation parameters. With HPMC as carrier, adjusted the parameters of spray drying technique and sprayed the SH nanoparticles in microspheres encaposulated by HPMC was formed and which is called nanoparticles-in-microsphere system (NiMS). SH-NiMS appearances were observed by SEM, structure was obsearved by FT-IR and the release characteristics in vitro were evaluated. The optimized formulation of SH nanoparticles was TPP/CS 1:3 (w/w), HPMC 0.3%, SH 0.2%. The solution peristaltic speed of the spray drying technique was adjusted to 15%, and the temperature of inlet was 110 degrees C. The encapsulation product yeild, drug loading and particle sizes of SH-NiMS were 94.2%, 20.4%, and 1256.5 nm, respectively. The appearances and the structure of SH-NiMS were good. The preparation method of SH-NiMS is stable and reliable to use, which provide a new way to develop new dosage form.

Solar photolysis versus TiO2-mediated solar photocatalysis: a kinetic study of the degradation of naproxen and diclofenac in various water matrices.

PubMed

Kanakaraju, Devagi; Motti, Cherie A; Glass, Beverley D; Oelgemöller, Michael

2016-09-01

Given that drugs and their degradation products are likely to occur as concoctions in wastewater, the degradation of a mixture of two nonsteroidal anti-inflammatory drugs (NSAIDs), diclofenac (DCF) and naproxen (NPX), was investigated by solar photolysis and titanium dioxide (TiO2)-mediated solar photocatalysis using an immersion-well photoreactor. An equimolar ratio (1:1) of both NSAIDs in distilled water, drinking water, and river water was subjected to solar degradation. Solar photolysis of the DCF and NPX mixture was competitive particularly in drinking water and river water, as both drugs have the ability to undergo photolysis. However, the addition of TiO2 in the mixture significantly enhanced the degradation rate of both APIs compared to solar photolysis alone. Mineralization, as measured by chemical oxygen demand (COD), was incomplete under all conditions investigated. TiO2-mediated solar photocatalytic degradation of DCF and NPX mixtures produced 15 identifiable degradants corresponding to degradation of the individual NSAIDs, while two degradation products with much higher molecular weight than the parent NSAIDs were identified by liquid chromatography mass spectrometry (LC-MS) and Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS). This study showed that the solar light intensity and the water matrix appear to be the main factors influencing the overall performance of the solar photolysis and TiO2-mediated solar photocatalysis for degradation of DCF and NPX mixtures.

Molecular Characterization of Thiols in Fossil Fuels by Michael Addition Reaction Derivatization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wang, Meng; Zhao, Suoqi; Liu, Xuxia; Shi, Quan

2016-10-04

Thiols widely occur in sediments and fossil fuels. However, the molecular composition of these compounds is unclear due to the lack of appropriate analytical methods. In this work, a characterization method for thiols in fossil fuels was developed on the basis of Michael addition reaction derivatization followed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Model thiol compound studies showed that thiols were selectively reacted with phenylvinylsulfone and transformed to sulfones with greater than 98% conversions. This method was applied to a coker naphtha, light and heavy gas oils, and crude oils from various geological sources. The results showed that long alkyl chain thiols are readily present in petroleum, which have up to 30 carbon atoms. Large DBE dispersity of thiols indicates that naphthenic and aromatic thiols are also present in the petroleum. This method is capable of detecting thiol compounds in the part per million range by weight. This method allows characterization of thiols in a complex hydrocarbon matrix, which is complementary to the comprehensive analysis of sulfur compounds in fossil fuels.

Composition of dissolved organic matter in groundwater

NASA Astrophysics Data System (ADS)

Longnecker, Krista; Kujawinski, Elizabeth B.

2011-05-01

Groundwater constitutes a globally important source of freshwater for drinking water and other agricultural and industrial purposes, and is a prominent source of freshwater flowing into the coastal ocean. Therefore, understanding the chemical components of groundwater is relevant to both coastal and inland communities. We used electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to examine dissolved organic compounds in groundwater prior to and after passage through a sediment-filled column containing microorganisms. The data revealed that an unexpectedly high proportion of organic compounds contained nitrogen and sulfur, possibly due to transport of surface waters from septic systems and rain events. We matched 292 chemical features, based on measured mass:charge ( m/z) values, to compounds stored in the Kyoto Encyclopedia of Genes and Genomes (KEGG). A subset of these compounds (88) had only one structural isomer in KEGG, thus supporting tentative identification. Most identified elemental formulas were linked with metabolic pathways that produce polyketides or with secondary metabolites produced by plants. The presence of polyketides in groundwater is notable because of their anti-bacterial and anti-cancer properties. However, their relative abundance must be quantified with appropriate analyses to assess any implications for public health.

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water.

PubMed

Wang, Xin; Wang, Juan; Li, Kuixiao; Zhang, Haifeng; Yang, Min

2018-01-01

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter (EfOM) in the treated effluents of municipal wastewater treatment plants (WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of EfOM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation-sedimentation-ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) method and compared to that of natural organic matter (NOM) in the local source water from a reservoir. It was found that the molecular composition of EfOM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in EfOM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted. Copyright © 2017. Published by Elsevier B.V.

Wine microbiology is driven by vineyard and winery anthropogenic factors.

PubMed

Grangeteau, Cédric; Roullier-Gall, Chloé; Rousseaux, Sandrine; Gougeon, Régis D; Schmitt-Kopplin, Philippe; Alexandre, Hervé; Guilloux-Benatier, Michèle

2017-03-01

The effects of different anthropic activities (vineyard: phytosanitary protection; winery: pressing and sulfiting) on the fungal populations of grape berries were studied. The global diversity of fungal populations (moulds and yeasts) was performed by pyrosequencing. The anthropic activities studied modified fungal diversity. Thus, a decrease in biodiversity was measured for three successive vintages for the grapes of the plot cultivated with Organic protection compared to plots treated with Conventional and Ecophyto protections. The fungal populations were then considerably modified by the pressing-clarification step. The addition of sulfur dioxide also modified population dynamics and favoured the domination of the species Saccharomyces cerevisiae during fermentation. The non-targeted chemical analysis of musts and wines by FT-ICR-MS showed that the wines could be discriminated at the end of alcoholic fermentation as a function of adding SO 2 or not, but also and above all as a function of phytosanitary protection, regardless of whether these fermentations took place in the presence of SO 2 or not. Thus, the existence of signatures in wines of chemical diversity and microbiology linked to vineyard protection has been highlighted. © 2016 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Formularity: Software for Automated Formula Assignment of Natural and Other Organic Matter from Ultrahigh-Resolution Mass Spectra

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

Tolić, Nikola; Liu, Yina; Liyu, Andrey

Ultrahigh-resolution mass spectrometry, such as Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS), can resolve thousands of molecular ions in complex organic matrices. A Compound Identification Algorithm (CIA) was previously developed for automated elemental formula assignment for natural organic matter (NOM). In this work we describe a user friendly interface for CIA, titled Formularity, which includes an additional functionality to perform search of formulas based on an Isotopic Pattern Algorithm (IPA). While CIA assigns elemental formulas for compounds containing C, H, O, N, S, and P, IPA is capable of assigning formulas for compounds containing other elements. We used halogenatedmore » organic compounds (HOC), a chemical class that is ubiquitous in nature as well as anthropogenic systems, as an example to demonstrate the capability of Formularity with IPA. A HOC standard mix was used to evaluate the identification confidence of IPA. The HOC spike in NOM and tap water were used to assess HOC identification in natural and anthropogenic matrices. Strategies for reconciliation of CIA and IPA assignments are discussed. Software and sample databases with documentation are freely available from the PNNL OMICS software repository https://omics.pnl.gov/software/formularity.« less

New Approach for Studying Slow Fragmentation Kinetics in FT-ICR: Surface-Induced Dissociation Combined with Resonant Ejection

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

Laskin, Julia; Futrell, Jean H.

2015-02-01

We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5 ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95 eV. The kinetics of peptidemore » fragmentation are probed by varying the delay time between resonant ejection and fragment ion detection at a constant total reaction time. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.« less

New analytical technique for establishing the quality of Soil Organic Matter affected by a wildfire. A first approach using Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Jiménez-Morillo, Nicasio T.; González-Pérez, José A.; Waggoner, Derek C.; Almendros, Gonzalo; González-Vila, Francisco J.; Hatcher, Patrick G.

2016-04-01

Introduction: Fire is one of the most important modulator factors of the environment and the forest. It is able to induce chemical and biological shifts and these, in turn, can alter the physical properties of soil. Generally, fire affects the most reactive fraction, soil organic matter (SOM) (González-Pérez et al., 2004) resulting in changes to several soil properties and functions. To study changes in SOM following a wildfire, researchers can count on several traditional as well as new analytical techniques. One of the most recently employed techniques is Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). This new powerful ultra-high resolution mass spectral technique, together with graphic interpretation tools such as van Krevelen diagrams (Kim et al, 2003), may be used to shed light on alterations caused by the burning of SOM. The objective of this research is to study fire impacts on SOM, using a sandy soil collected under a Cork oak (Quercus suber) in Doñana National Park, Southwest Spain. that was affected by a wildfire in August 2012. Methods: The impact of fire on SOM was studied in various different sieve fractions (coarse, 1-2 mm, and fine, <0.05 mm) collected in a burned area and an adjacent unburned control site with the same physiographic conditions. Alkaline extracts of SOM from each soil sample were examined using a Bruker Daltonics 12 Tesla Apex Qe FT-ICR-MS equipped with an Apollo II ESI ion source (operating in negative ion mode). The ESI voltages were optimized for each sample, and all spectra were internally calibrated following the procedure of (Sleighter and Hatcher, 2007), after which, peaks were assigned unique molecular formulas using a MatLab script written in house by Dr. Wassim Obeid of Old Dominion University. Results: The van Krevelen diagrams together with the relative intensity of each chemical compound, both obtained by FT-ICR-MS, allowed us to assess SOM quality for each sample and size fractions. The chemical compounds were grouped into the 7 main families; condensed aromatic compounds, unspecific aromatics, tannins, lignin, lipids, protein and carbohydrate derived. The unburnt SOM in the coarse fraction was mainly composed of compounds with a high intensity in the tannin-like, lignin-like and carbohydrate-like regions of the van Krevelen diagram, whereas the SOM in the fine fraction showed a high intensity in the lipid-like and protein-like regions. These results suggest that the SOM in the coarse fraction was less altered than that of the fine fraction; the latter believed to be subjected to higher microbial activity. We suggest that the observed changes occurs via a methylation process, producing a SOM that is highly humified (Jiménez-Morillo et al., 2014). The SOM in the coarse fraction affected by fire, showed a high relative intensity of chemical compounds in the carbohydrate-like and lignin-like regions, indicating the input of fresh organic matter. The presence of molecular formulas which plot in the aromatic and condensed aromatics regions also indicates that this fraction may have contributions from a second, more recalcitrant, organic carbon pool. The appearance of aromatic and condensed aromatic compounds could suggest that, in this fraction the fire induced condensation processes. In the burnt fine fraction, two different SOM sources of alteration could be identified; i) from microbial origin with high relative intensity of lipid-like and protein-like compounds and ii) fire origin with large amounts of condensed aromatic compounds and a high contribution from the carbohydrate-like compounds region. We suggest that these results indicate both, condensation processes yielding black carbon like materials and additions from the coarse fraction during fire mediated distillation process. Acknowledgements: This study is part of the results of the GEOFIRE Project (CGL2012-38655-C04-01) funded by the Spanish Ministry for Economy and Competitiveness. N.T Jiménez-Morillo is funded by a FPI research grant and EEBB 2015 research grant (BES-2013-062573 and EEBB-I-15-09334 respectively). In addition, we thank the large number of individuals in the Hatcher research group who contributed indirectly to the work presented here. References: González-Pérez JA, González-Vila FJ, Almendros G, Knicker H. 2004. The effect of fire on soil organic matter - a review. Environment International 30, 855-870. DOI:10.1016/j.envint.2004.02.003. Jiménez-Morillo NT, González-Pérez JA, Jordán A, Zavala LM, de la Rosa JM, Jiménez-González MA, González-Vila FJ. 2014. Organic matter fractions controlling soil water repellency in sandy soils from the Doñana National Park (Southwestern Spain). Land Degradation & Development. DOI: 10.1002/ldr.2314. Kim S, Kramer RW, and Hatcher PG. 2003. An informative graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter - the van Krevelen diagram. Analytical Chemistry, 75: 5336-5344. DOI: 10.1021/ac034415p Sleighter RL, Hatcher PG. 2007. The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter. Journal of Mass Spectrometry. 2007; 42: 559-574. DOI: 10.1002/jms.1221

Simultaneous determination of some artificial sweeteners in ternary formulations by FT-IR and EI-MS

NASA Astrophysics Data System (ADS)

Tosa, Nicoleta; Moldovan, Zaharie; Bratu, Ioan

2012-02-01

Artificial sweeteners are widely used in food, beverage and pharmaceutical industries all over the world. In this study some non-nutritive sweeteners such as aspartame, acesulfame-K, sodium cyclamate and sodium saccharin were simultaneously determined in ternary mixtures using FT-IR and EI-MS measurements. FT-IR method is based on direct measurements of the peak height values and area centered on 1736 cm-1, 836 cm-1, 2854 cm-1 and 1050 cm-1 for aspartame, acesulfame-K, sodium cyclamate and sodium saccharin, respectively. Mass spectrometry determinations show the characteristic peaks at m/z 91 and 262 for aspartame,m/z 43 and 163 acesulfame-K,m/z 83 and 97 for sodium cyclamate andm/z 104 and 183 for sodium saccharin. The results obtained by EI-MS in different formulations are in agreement with the FT-IR ones and provide also essential data concerning the purity grade of the components. It is concluded that FT-IR and EI-MS procedures developed in this work represent a fast, sensitive and low cost alternative in the quality control of such sweeteners in different ternary formulations.

Bone protein “extractomics”: comparing the efficiency of bone protein extractions of Gallus gallus in tandem mass spectrometry, with an eye towards paleoproteomics

PubMed Central

DeHart, Caroline J.; Schweitzer, Mary H.; Thomas, Paul M.; Kelleher, Neil L.

2016-01-01

Proteomic studies of bone require specialized extraction protocols to demineralize and solubilize proteins from within the bone matrix. Although various protocols exist for bone protein recovery, little is known about how discrete steps in each protocol affect the subset of the bone proteome recovered by mass spectrometry (MS) analyses. Characterizing these different “extractomes” will provide critical data for development of novel and more efficient protein extraction methodologies for fossils. Here, we analyze 22 unique sub-extractions of chicken bone and directly compare individual extraction components for their total protein yield and diversity and coverage of bone proteins identified by MS. We extracted proteins using different combinations and ratios of demineralizing reagents, protein-solubilizing reagents, and post-extraction buffer removal methods, then evaluated tryptic digests from 20 µg aliquots of each fraction by tandem MS/MS on a 12T FT-ICR mass spectrometer. We compared total numbers of peptide spectral matches, peptides, and proteins identified from each fraction, the redundancy of protein identifications between discrete steps of extraction methods, and the sequence coverage obtained for select, abundant proteins. Although both alpha chains of collagen I (the most abundant protein in bone) were found in all fractions, other collagenous and non-collagenous proteins (e.g., apolipoprotein, osteonectin, hemoglobin) were differentially identified. We found that when a standardized amount of extracted proteins was analyzed, extraction steps that yielded the most protein (by weight) from bone were often not the ones that produced the greatest diversity of bone proteins, or the highest degree of protein coverage. Generally, the highest degrees of diversity and coverage were obtained from demineralization fractions, and the proteins found in the subsequent solubilization fractions were highly redundant with those in the previous fraction. Based on these data, we identify future directions and parameters to consider (e.g., proteins targeted, amount of sample required) when applying discrete parts of these protocols to fossils. PMID:27812413

Atmo-metabolomics: a new measurement approach for investigating aerosol composition and ecosystem functioning.

NASA Astrophysics Data System (ADS)

Rivas-Ubach, A.; Liu, Y.; Sardans, J.; Tfaily, M. M.; Kim, Y. M.; Bourrianne, E.; Paša-Tolić, L.; Penuelas, J.; Guenther, A. B.

2016-12-01

Aerosols play crucial roles in the processes controlling the composition of the atmosphere and the functioning of ecosystems. Gaining a deeper understanding of the chemical composition of aerosols is one of the major challenges for atmospheric and climate scientists and is beginning to be recognized as important for ecological research. Better comprehension of aerosol chemistry can potentially provide valuable information on atmospheric processes such as oxidation of organics and the production of cloud condensation nuclei as well as provide an approximation of the general status of an ecosystem through the measurement of certain stress biomarkers. In this study, we describe an efficient aerosol sampling method, the metabolite extraction and the analytical procedures for the chemical characterization of aerosols, namely, the atmo-metabolome. We used mass spectrometry (MS) coupled to liquid chromatography (LC-MS), gas chromatography (GC-MS) and Fourier transform ion cyclotron resonance (FT-ICR-MS) to characterize the atmo-metabolome of two marked seasons; spring and summer. Our sampling and extraction methods demonstrated to be suitable for aerosol chemical characterization with any of the analytical platforms used in this study. The atmo-metabolome between spring and summer showed overall statistically differences. We identified several metabolites that can be attributed to pollen and other plant-related aerosols. Spring aerosols exhibit higher concentrations of metabolites linked to higher plant activity while summer samples had higher concentrations of metabolites that may reflect certain oxidative stresses in primary producers. Moreover, the elemental composition of aerosols showed clear different between seasons. Summer aerosols were generally higher in molecular weight and with higher O/C ratios, indicating higher oxidation levels and condensation of compounds relative to spring. Our method represents an advanced approach for characterizing the composition of aerosols that will benefit scientists attempting to understand complex atmospheric processes and the ecosystem status across a whole ecoregion.

Mass Spectral Investigation of Laboratory Made Tholins and Their Reaction Products: Implications to Tholin Surface Chemistry on Titan

NASA Astrophysics Data System (ADS)

Somogyi, Arpad; Smith, M. A.

2006-09-01

The success of the Huygens mission does not overshadow the importance of laboratory simulations of gas-phase and surface reactions that might occur in Titan's atmosphere and surface, respectively. We present here our latest results on chemical reactions (hydrolysis, peroxidation and hydrogenation) of laboratory made tholins obtained by FT-ICR mass spectrometry. The laboratory synthesis of tholins has been described in our earlier papers [1,2]. Overall, we conclude that our laboratory tholins are reactive materials that undergo fast hydrolysis, oxidation and reduction. Thus, if the tholin on Titan's surface resemble our laboratory made tholins, it can be considered as a potential starting material for several synthetic processes that can provide organic compounds of pre-biotic interest. Hydrolysis reactions occur with rate constants of 2-10 hour-1 at room temperature. Formal water addition to several species of CxHyNz has been observed by detecting the formation of CxHy+2NzO species. MS/MS fragmentation of the oxygen containing ions leads to the loss of water, ammonia, HCN, acetonitrile, etc. This suggests that tholin hydrolysis may occur in temporary melted ponds of water/ammonia ice on Titan. Peroxidation, which can be considered as a very harsh oxidation, leads to mono-, and multiple oxygenated compounds within a few minutes. The MS/MS fragmentation of these compounds suggests the presence of organic amides and, presumably, amino acid like compounds. Hydrogenation leads to compounds in which the originally present carbon-carbon or carbon-nitrogen double and triple bonds are saturated. H/D exchange experiments show different kinetics depending on the degree of unsaturation/saturation and the number of N atoms. [1] Sarker, N.; Somogyi, A.; Lunine, J. I.; Smith, M. A. Astrobiology, 2003, 3, 719-726. [2] Somogyi, A.; Oh, C-H.; Lunine, J. I.; Smith, M. A. J. Am. Soc. Mass Spectrom. 2005, 16, 850-859.

77 FR 17081 - Information Collection Requests to Office of Management and Budget

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-23

... Information Collection Requests (ICRs) to the Office of Management and Budget (OMB), Office of Information and.... FOR FURTHER INFORMATION CONTACT: Contact Ms. Kenlinishia Tyler, Office of Information Management... DEPARTMENT OF HOMELAND SECURITY Coast Guard [USCG-2012-0082] Information Collection Requests to...

76 FR 57749 - Information Collection Request to Office of Management and Budget

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-16

... Information Collection Requests (ICRs) to the Office of Management and Budget (OMB), Office of Information and.... FOR FURTHER INFORMATION CONTACT: Ms. Kenlinishia Tyler, Office of Information Management, telephone... reception facility standards. Advance notice information from vessels ensures effective management of...

Improving Large-Scale Testing Capability by Modifying the 40- by 80-ft Wind Tunnel

NASA Technical Reports Server (NTRS)

Mort, Kenneth W.; Soderman, Paul T.; Eckert, William T.

1979-01-01

Interagency studies conducted during the last several years have indicated the need to Improve full-scale testing capabilities. The studies showed that the most effective trade between test capability and facility cost was provided by re-powering the existing Ames Research Center 40- by 80-ft Wind Tunnel to Increase the maximum speed from about 100 m/s (200 knots) lo about 150 m/s (300 knots) and by adding a new 24- by 37-m (80- by 120-ft) test section powered for about a 50-m/s (100-knot) maximum speed. This paper reviews the design of the facility, a few or its capabilities, and some of its unique features.

Prospective In Vivo Comparison of Damaged and Healthy-Appearing Articular Cartilage Specimens in Patients With Femoroacetabular Impingement: Comparison of T2 Mapping, Histologic Endpoints, and Arthroscopic Grading.

PubMed

Ho, Charles P; Surowiec, Rachel K; Frisbie, David D; Ferro, Fernando P; Wilson, Katharine J; Saroki, Adriana J; Fitzcharles, Eric K; Dornan, Grant J; Philippon, Marc J

2016-08-01

To describe T2 mapping values in arthroscopically determined International Cartilage Repair Society (ICRS) grades in damaged and healthy-appearing articular cartilage waste specimens from arthroscopic femoroacetabular impingement (FAI) treatment. Furthermore, we sought to compare ICRS grades of the specimens with biochemical, immunohistochemistry and histologic endpoints and assess correlations with T2 mapping. Twenty-four patients were prospectively enrolled, consecutively, between December 2011 and August 2012. Patients were included if they were aged 18 years or older and met criteria that followed the clinical indications for arthroscopy to treat FAI. Patients with prior hip trauma including fracture or dislocation or who have undergone prior hip surgery were excluded. All patients received a preoperative sagittal T2 mapping scan of the hip joint. Cartilage was graded intraoperatively using the ICRS grading system, and graded specimens were collected as cartilage waste for histologic, biochemical, and immunohistochemistry analysis. Forty-four cartilage specimens (22 healthy-appearing, 22 damaged) were analyzed. Median T2 values were significantly higher among damaged specimens (55.7 ± 14.9 ms) than healthy-appearing specimens (49.3 ± 12.3 ms; P = .043), which was most exaggerated among mild (grade 1 or 2) defects where the damaged specimens (58.1 ± 16.4 ms) were significantly higher than their paired healthy-appearing specimens (48.7 ± 15.4 ms; P = .026). Severely damaged specimens (grade 3 or 4) had significantly lower cumulative H&E than their paired healthy-appearing counterparts (P = .02) but was not statistically significant among damaged specimens with mild (grade 1 or 2) defects (P = .198). Among healthy-appearing specimens, median T2 and the percentage of collagen fibers oriented parallel were significantly correlated (rho = 0.425, P = .048). This study outlines the potential for T2 mapping to identify early cartilage degeneration in patients undergoing arthroscopy to treat FAI. Findings in ICRS grade 1 and 2 degeneration corresponded to an increase in T2 values. Further biochemical evaluation revealed a significant difference between healthy-appearing cartilage and late degeneration in cumulative H&E as well as significantly lower percentage of collagen fibers oriented parallel and a higher percentage of collagen fibers oriented randomly when considering all grades of cartilage damage. Level II, prospective comparative study. Copyright © 2016 Arthroscopy Association of North America. Published by Elsevier Inc. All rights reserved.

Vibrational analysis, NBO analysis, NMR, UV-VIS, hyperpolarizability analysis of Trimethadione by density functional theory

NASA Astrophysics Data System (ADS)

Vijayachamundeeswari, S. P.; Yagna Narayana, B.; Jone Pradeepa, S.; Sundaraganesan, N.

2015-11-01

Trimethadione (TMD) is an anticonvulsant drug widely used against absences seizures. We have characterised the TMD by various spectra including UV-VIS, IR, Raman, GC-MS and NMR. In this work, we made use of Density Functional Theory (DFT) B3LYP method with 6-31G (d, p) basis set, to calculate the molecular structure of TMD, and predicted its infrared, Raman and ultraviolet spectra for the first time. FT-IR and FT-Raman spectra were recorded in the region 4000-400 cm-1 and 3500-50 cm-1, respectively. The vibrational frequencies were calculated and scaled values were compared with the experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes. The optimized geometry parameters were calculated. NMR chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. The predicted first hyperpolarizibility also shows that the molecule might have convincingly good nonlinear optical (NLO) activities. The calculated HOMO-LUMO energy gap discloses that charge transfer occurs within the molecule.

Analysis of Silicones Released from Household Items and Baby Articles by Direct Analysis in Real Time-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Gross, Jürgen H.

2015-03-01

Direct analysis in real time-mass spectrometry (DART-MS) enables screening of articles of daily use made of polydimethylsiloxanes (PDMS), commonly known as silicone rubber, to assess their tendency to release low molecular weight silicone oligomers. DART-MS analyses were performed on a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Flexible silicone baking molds, a watch band, and a dough scraper, as baby articles different brands of pacifiers, nipples, and a teething ring have been examined. While somewhat arbitrarily chosen, the set can be regarded as representative of household items, baby articles, and other objects made of silicone rubber. For comparison, two brands of silicone septa and as blanks a glass slide and a latex pacifier were included. Differences between the objects were mainly observed in terms of molecular weight distribution and occasional release of other compounds in addition to PDMS. Other than that, all objects made of silicone rubber released significant amounts of PDMS during DART analysis. To provide a coarse quantification, a calibration based on silicone oil was established, which delivered PDMS losses from 20 μg to >100 μg during the 16-s period per measurement. Also, the extraction of baking molds in rapeseed oil demonstrated a PDMS release at the level of 1 μg mg-1. These findings indicate a potential health hazard from frequent or long-term use of such items. This work does not intend to blame certain brands of such articles. Nonetheless, a higher level of awareness of this source of daily silicone intake is suggested.

Analysis of silicones released from household items and baby articles by direct analysis in real time-mass spectrometry.

PubMed

Gross, Jürgen H

2015-03-01

Direct analysis in real time-mass spectrometry (DART-MS) enables screening of articles of daily use made of polydimethylsiloxanes (PDMS), commonly known as silicone rubber, to assess their tendency to release low molecular weight silicone oligomers. DART-MS analyses were performed on a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Flexible silicone baking molds, a watch band, and a dough scraper, as baby articles different brands of pacifiers, nipples, and a teething ring have been examined. While somewhat arbitrarily chosen, the set can be regarded as representative of household items, baby articles, and other objects made of silicone rubber. For comparison, two brands of silicone septa and as blanks a glass slide and a latex pacifier were included. Differences between the objects were mainly observed in terms of molecular weight distribution and occasional release of other compounds in addition to PDMS. Other than that, all objects made of silicone rubber released significant amounts of PDMS during DART analysis. To provide a coarse quantification, a calibration based on silicone oil was established, which delivered PDMS losses from 20 μg to >100 μg during the 16-s period per measurement. Also, the extraction of baking molds in rapeseed oil demonstrated a PDMS release at the level of 1 μg mg(-1). These findings indicate a potential health hazard from frequent or long-term use of such items. This work does not intend to blame certain brands of such articles. Nonetheless, a higher level of awareness of this source of daily silicone intake is suggested.

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IR-MALDESI MASS SPECTROMETRY IMAGING OF BIOLOGICAL TISSUE SECTIONS USING ICE AS A MATRIX

PubMed Central

Robichaud, Guillaume; Barry, Jeremy A.; Muddiman, David C.

2014-01-01

Infrared Matrix-Assisted Laser Desorption Electrospray Ionization (IR-MALDESI) Mass Spectrometry imaging of biological tissue sections using a layer of deposited ice as an energy absorbing matrix was investigated. Dynamics of plume ablation were first explored using a nanosecond exposure shadowgraphy system designed to simultaneously collect pictures of the plume with a camera and collect the FT-ICR mass spectrum corresponding to that same ablation event. Ablation of fresh tissue analyzed with and without using ice as a matrix were both compared using this technique. Effect of spot-to-spot distance, number of laser shots per pixel and tissue condition (matrix) on ion abundance was also investigated for 50 µm thick tissue sections. Finally, the statistical method called design of experiments was used to compare source parameters and determine the optimal conditions for IR-MALDESI of tissue sections using deposited ice as a matrix. With a better understanding of the fundamentals of ablation dynamics and a systematic approach to explore the experimental space, it was possible to improve ion abundance by nearly one order of magnitude. PMID:24385399

The (CA)n polymorphism of ERβ gene is associated with FtM transsexualism.

PubMed

Fernández, Rosa; Esteva, Isabel; Gómez-Gil, Esther; Rumbo, Teresa; Almaraz, Mari Cruz; Roda, Ester; Haro-Mora, Juan-Jesús; Guillamón, Antonio; Pásaro, Eduardo

2014-03-01

Transsexualism is a gender identity disorder with a multifactorial etiology. Neurodevelopmental processes and genetic factors seem to be implicated. The aim of this study was to investigate the possible influence of the sex hormone-related genes ERβ (estrogen receptor β), AR (androgen receptor), and CYP19A1 (aromatase) in the etiology of female-to-male (FtM) transsexualism. In 273 FtMs and 371 control females, we carried out a molecular analysis of three variable regions: the CA repeats in intron 5 of ERβ; the CAG repeats in exon 1 of AR, and the TTTA repeats in intron 4 of CYP19A1. We investigated the possible influence of genotype on transsexualism by performing a molecular analysis of the variable regions of genes ERβ, AR, and CYP19A1 in 644 individuals (FtMs and control females). FtMs differed significantly from control group with respect to the median repeat length polymorphism ERβ (P = 0.002) but not with respect to the length of the other two studied polymorphisms. The repeat numbers in ERβ were significantly higher in FtMs than in control group, and the likelihood of developing transsexualism was higher (odds ratio: 2.001 [1.15-3.46]) in the subjects with the genotype homozygous for long alleles. There is an association between the ERβ gene and FtM transsexualism. Our data support the finding that ERβ function is directly proportional to the size of the analyzed polymorphism, so a greater number of repeats implies greater transcription activation, possibly by increasing the function of the complex hormone ERβ receptor and thereby encouraging less feminization or a defeminization of the female brain and behavior. © 2013 International Society for Sexual Medicine.

Optimal percutaneous coronary intervention in patients with ST-elevation myocardial infarction and multivessel disease: An updated, large-scale systematic review and meta-analysis.

PubMed

Nguyen, An Vu; Thanh, Le Van; Kamel, Mohamed Gomaa; Abdelrahman, Sara Attia Mahmoud; El-Mekawy, Mohamed; Mokhtar, Mohamed Ashraf; Ali, Aya Ashraf; Hoang, Nam Nguyen Nho; Vuong, Nguyen Lam; Abd-Elhay, Fatma Abd-Elshahed; Omer, Omer Abdelbagi; Mohamed, Ahmed Abdou; Hirayama, Kenji; Huy, Nguyen Tien

2017-10-01

Our study aimed to compare three different percutaneous coronary intervention (PCI) approaches: culprit-only (COR) and complete (CR) revascularization - categorizing into immediate (ICR) or staged (SCR). We searched 13 databases for randomized controlled trials. Articles were included if they compared at least two strategies. To have more studies in each analysis, an adjusted analysis was performed using person-years to incorporate follow-up durations and obtain pooled rate ratios (RR), with their corresponding 95% confidence interval. Thirteen trials were included with a population of 2830 patients. COR significantly increased major adverse cardiac event (MACE) (adjusted RR 1.67, 95% CI: 1.27-2.19) and repeat revascularization (2.12, 1.67-2.69), which was driven by repeat PCI, without any difference in all-cause mortality and myocardial infarction (MI) compared to CR. When categorizing CR into SCR and ICR, the trend repeated with COR increased MACE (1.99, 1.53-2.6 for ICR), cardiovascular mortality (2.06, 1.07-3.96 for ICR), MI for ICR (1.72, 1.04-2.86), repeat revascularization and repeat PCI for both ICR and SCR. Non-cardiovascular mortality, stroke, nephropathy, re-hospitalization, stent thrombosis and bleeding were similar among all approaches. In MVD-STEMI patients, CR is better than COR in terms of MACE, cardiovascular mortality, repeat revascularization with no difference in safety outcomes. There was a trend towards to a reduction of cardiovascular mortality and MI in ICR compared to SCR when each matched with COR; even though there is no statistically significant difference between ICR and SCR when compared together. Copyright © 2017 Elsevier B.V. All rights reserved.

D-isoascorbyl palmitate: lipase-catalyzed synthesis, structural characterization and process optimization using response surface methodology.

PubMed

Sun, Wen-Jing; Zhao, Hong-Xia; Cui, Feng-Jie; Li, Yun-Hong; Yu, Si-Lian; Zhou, Qiang; Qian, Jing-Ya; Dong, Ying

2013-07-08

Isoascorbic acid is a stereoisomer of L-ascorbic acid, and widely used as a food antioxidant. However, its highly hydrophilic behavior prevents its application in cosmetics or fats and oils-based foods. To overcome this problem, D-isoascorbyl palmitate was synthesized in the present study for improving the isoascorbic acid's oil solubility with an immobilized lipase in organic media. The structural information of synthesized product was clarified using LC-ESI-MS, FT-IR, 1H and 13C NMR analysis, and process parameters for high yield of D-isoascorbyl palmitate were optimized by using One-factor-at-a-time experiments and response surface methodology (RSM). The synthesized product had the purity of 95% and its structural characteristics were confirmed as isoascorbyl palmitate by LC-ESI-MS, FT-IR, 1H, and 13C NMR analysis. Results from "one-factor-at-a-time" experiments indicated that the enzyme load, reaction temperature and D-isoascorbic-to-palmitic acid molar ratio had a significant effect on the D-isoascorbyl palmitate conversion rate. 95.32% of conversion rate was obtained by using response surface methodology (RSM) under the the optimized condition: enzyme load of 20% (w/w), reaction temperature of 53°C and D- isoascorbic-to-palmitic acid molar ratio of 1:4 when the reaction parameters were set as: acetone 20 mL, 40 g/L of molecular sieves content, 200 rpm speed for 24-h reaction time. The findings of this study can become a reference for developing industrial processes for the preparation of isoascorbic acid ester, which might be used in food additives, cosmetic formulations and for the synthesis of other isoascorbic acid derivatives.

D-isoascorbyl palmitate: lipase-catalyzed synthesis, structural characterization and process optimization using response surface methodology

PubMed Central

2013-01-01

Background Isoascorbic acid is a stereoisomer of L-ascorbic acid, and widely used as a food antioxidant. However, its highly hydrophilic behavior prevents its application in cosmetics or fats and oils-based foods. To overcome this problem, D-isoascorbyl palmitate was synthesized in the present study for improving the isoascorbic acid’s oil solubility with an immobilized lipase in organic media. The structural information of synthesized product was clarified using LC-ESI-MS, FT-IR, 1H and 13C NMR analysis, and process parameters for high yield of D-isoascorbyl palmitate were optimized by using One–factor-at-a-time experiments and response surface methodology (RSM). Results The synthesized product had the purity of 95% and its structural characteristics were confirmed as isoascorbyl palmitate by LC-ESI-MS, FT-IR, 1H, and 13C NMR analysis. Results from “one–factor-at-a-time” experiments indicated that the enzyme load, reaction temperature and D-isoascorbic-to-palmitic acid molar ratio had a significant effect on the D-isoascorbyl palmitate conversion rate. 95.32% of conversion rate was obtained by using response surface methodology (RSM) under the the optimized condition: enzyme load of 20% (w/w), reaction temperature of 53°C and D- isoascorbic-to-palmitic acid molar ratio of 1:4 when the reaction parameters were set as: acetone 20 mL, 40 g/L of molecular sieves content, 200 rpm speed for 24-h reaction time. Conclusion The findings of this study can become a reference for developing industrial processes for the preparation of isoascorbic acid ester, which might be used in food additives, cosmetic formulations and for the synthesis of other isoascorbic acid derivatives. PMID:23835418

Noninvasive detection of lung cancer using exhaled breath

PubMed Central

Fu, Xiao-An; Li, Mingxiao; Knipp, Ralph J; Nantz, Michael H; Bousamra, Michael

2014-01-01

Early detection of lung cancer is a key factor for increasing the survival rates of lung cancer patients. The analysis of exhaled breath is promising as a noninvasive diagnostic tool for diagnosis of lung cancer. We demonstrate the quantitative analysis of carbonyl volatile organic compounds (VOCs) and identification of lung cancer VOC markers in exhaled breath using unique silicon microreactor technology. The microreactor consists of thousands of micropillars coated with an ammonium aminooxy salt for capture of carbonyl VOCs in exhaled breath by means of oximation reactions. Captured aminooxy-VOC adducts are analyzed by nanoelectrospray Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry (MS). The concentrations of 2-butanone, 2-hydroxyacetaldehyde, 3-hydroxy-2-butanone, and 4-hydroxyhexenal (4-HHE) in the exhaled breath of lung cancer patients (n = 97) were significantly higher than in the exhaled breath of healthy smoker and nonsmoker controls (n = 88) and patients with benign pulmonary nodules (n = 32). The concentration of 2-butanone in exhaled breath of patients (n = 51) with stages II though IV non–small cell lung cancer (NSCLC) was significantly higher than in exhaled breath of patients with stage I (n = 34). The carbonyl VOC profile in exhaled breath determined using this new silicon microreactor technology provides for the noninvasive detection of lung cancer. PMID:24402867

Bioactive Potential of Marine Macroalgae from the Central Red Sea (Saudi Arabia) Assessed by High-Throughput Imaging-Based Phenotypic Profiling

PubMed Central

Kremb, Stephan; Müller, Constanze; Schmitt-Kopplin, Philippe; Voolstra, Christian R.

2017-01-01

Marine algae represent an important source of novel natural products. While their bioactive potential has been studied to some extent, limited information is available on marine algae from the Red Sea. This study aimed at the broad discovery of new bioactivities from a collection of twelve macroalgal species from the Central Red Sea. We used imaging-based High-Content Screening (HCS) with a diverse spectrum of cellular markers for detailed cytological profiling of fractionated algal extracts. The cytological profiles for 3 out of 60 algal fractions clustered closely to reference inhibitors and showed strong inhibitory activities on the HIV-1 reverse transcriptase in a single-enzyme biochemical assay, validating the suggested biological target. Subsequent chemical profiling of the active fractions of two brown algal species by ultra-high resolution mass spectrometry (FT-ICR-MS) revealed possible candidate molecules. A database query of these molecules led us to groups of compounds with structural similarities, which are suggested to be responsible for the observed activity. Our work demonstrates the versatility and power of cytological profiling for the bioprospecting of unknown biological resources and highlights Red Sea algae as a source of bioactives that may serve as a starting point for further studies. PMID:28335513

Molecular Characterization of Organosulfur Compounds in Biodiesel and Diesel Fuel Secondary Organic Aerosol

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

Blair, Sandra L.; MacMillan, Amanda C.; Drozd, Greg T.

Secondary organic aerosol (SOA), formed in a process of photooxidization of diesel fuel, biodiesel fuel, and 20% biodiesel fuel/80% diesel fuel mixture, are prepared under high-NOx conditions in the presence and absence of sulfur dioxide (SO2), ammonia (NH3), and relative humidity (RH). The composition of condensed-phase organic compounds in SOA is measured using several analytical techniques including aerosol mass spectrometry (AMS), high-resolution nanospray desorption electrospray ionization mass spectrometry (nano-DESI/HRMS), and ultra high resolution and mass accuracy 21T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). Results demonstrate that sulfuric acid and condensed organosulfur species formed in photooxidation experimentsmore » with SO2 are present in the SOA particles. Fewer organosulfur species are formed in the high humidity experiments, performed at RH 90%, in comparison with experiments done under dry conditions. There is a strong overlap of organosulfur species observed in this study with previous field and chamber studies of SOA. Many mass spectrometry peaks of organosulfates (R–OS(O)2OH) in field studies previously designated as biogenic or of unknown origin might have originated from anthropogenic sources, such as photooxidation of hydrocarbons present in diesel and biodiesel fuel.« less

Variations of DOM quality in inflows of a drinking water reservoir: linking of van Krevelen diagrams with EEMF spectra by rank correlation.

PubMed

Herzsprung, Peter; von Tümpling, Wolf; Hertkorn, Norbert; Harir, Mourad; Büttner, Olaf; Bravidor, Jenny; Friese, Kurt; Schmitt-Kopplin, Philippe

2012-05-15

Elevated concentrations of dissolved organic matter (DOM) such as humic substances in raw water pose significant challenges during the processing of the commercial drinking water supplies. This is a relevant issue in Saxony, Central East Germany, and many other regions worldwide, where drinking water is produced from raw waters with noticeable presence of chromophoric DOM (CDOM), which is assumed to originate from forested watersheds in spring regions of the catchment area. For improved comprehension of DOM molecular composition, the seasonal and spatial variations of humic-like fluorescence and elemental formulas in the catchment area of the Muldenberg reservoir were recorded by excitation emission matrix fluorescence (EEMF) and ultrahigh-resolution mass spectrometry (FT-ICR-MS). The Spearman rank correlation was applied to link the EEMF intensities with exact molecular formulas and their corresponding relative mass peak abundances. Thereby, humic-like fluorescence could be allocated to the pool of oxygen-rich and relatively unsaturated components with stoichiometries similar to those of tannic acids, which are suspected to have a comparatively high disinfection byproduct formation potential associated with the chlorination of raw water. Analogous relationships were established for UV absorption at 254 nm (UV(254)) and dissolved organic carbon (DOC) and compared to the EEMF correlation.

Geochemistry of Dissolved Organic Matter in a Spatially Highly Resolved Groundwater Petroleum Hydrocarbon Plume Cross-Section.

PubMed

Dvorski, Sabine E-M; Gonsior, Michael; Hertkorn, Norbert; Uhl, Jenny; Müller, Hubert; Griebler, Christian; Schmitt-Kopplin, Philippe

2016-06-07

At numerous groundwater sites worldwide, natural dissolved organic matter (DOM) is quantitatively complemented with petroleum hydrocarbons. To date, research has been focused almost exclusively on the contaminants, but detailed insights of the interaction of contaminant biodegradation, dominant redox processes, and interactions with natural DOM are missing. This study linked on-site high resolution spatial sampling of groundwater with high resolution molecular characterization of DOM and its relation to groundwater geochemistry across a petroleum hydrocarbon plume cross-section. Electrospray- and atmospheric pressure photoionization (ESI, APPI) ultrahigh resolution mass spectrometry (FT-ICR-MS) revealed a strong interaction between DOM and reactive sulfur species linked to microbial sulfate reduction, i.e., the key redox process involved in contaminant biodegradation. Excitation emission matrix (EEM) fluorescence spectroscopy in combination with Parallel Factor Analysis (PARAFAC) modeling attributed DOM samples to specific contamination traits. Nuclear magnetic resonance (NMR) spectroscopy evaluated the aromatic compounds and their degradation products in samples influenced by the petroleum contamination and its biodegradation. Our orthogonal high resolution analytical approach enabled a comprehensive molecular level understanding of the DOM with respect to in situ petroleum hydrocarbon biodegradation and microbial sulfate reduction. The role of natural DOM as potential cosubstrate and detoxification reactant may improve future bioremediation strategies.

First Signal on the Cryogenic Fourier-Transform Ion Cyclotron Resonance Mass Spectrometer

PubMed Central

Lin, Cheng; Mathur, Raman; Aizikov, Kostantin; O'Connor, Peter B.

2009-01-01

The construction and achievement of the first signal on a cryogenic Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR-MS) are reported here, demonstrating proof-of-concept of this new instrument design. Building the FTICR cell into the cold bore of a superconducting magnet provided advantages over conventional warm bore design. At 4.2 K, the vacuum system cryopumps itself, thus removing the requirement for a large bore to achieve the desired pumping speed for maintaining base pressure. Furthermore, because the bore diameter has been reduced, the amount of magnet wire needed to achieve high field and homogeneity was also reduced, greatly decreasing the cost/Tesla of the magnet. The current instrument implements an actively shielded 14-Tesla magnet of vertical design with an external matrix assisted laser desorption/ionization (MALDI) source. The first signal was obtained by detecting the laser desorbed/ionized (LDI) C60+• ions, with the magnet at 7 Tesla, unshimmed, and the preamplifier mounted outside of the vacuum chamber at room temperature. A subsequent experiment done with the magnet at 14 Tesla and properly shimmed produced a C60 spectrum showing ∼350,000 resolving power at m/z ∼720. Increased magnetic field strength improves many FTMS performance parameters simultaneously, particularly mass resolving power and accuracy. PMID:17931882

Effect-directed analysis: Current status and future challenges

NASA Astrophysics Data System (ADS)

Hong, Seongjin; Giesy, John P.; Lee, Jung-Suk; Lee, Jong-Hyeon; Khim, Jong Seong

2016-09-01

Effect-directed analysis (EDA) has become useful for identification of toxicant(s) that occur in mixtures in the environment, especially those that are causative agents of specific adverse effects. Here, we summarize and review EDA methodology including preparation of samples, biological analyses, fractionations, and instrumental analyses, highlighting key scientific advancements. A total of 63 documents since 1999 (Scopus search) including 46 research articles, 13 review papers, and 4 project descriptions, have been collected and reviewed in this study. At the early stage (1999-2010), most studies that applied EDA focused on organic extracts of freshwater and coastal contaminated sediments and wastewater. Toxic effects were often measured using cell-based bioassays ( in vitro) and the causative chemicals were identified by use of low resolution gas chromatography with mass selective detector (GCMSD). More recently (2010-present), EDA has been extended to various matrices such as biota, soil, crude oil, and suspended solids and techniques have been improved to include determination of bioavailability in vivo. In particular, methods for non-target screenings of organic chemicals in environmental samples using cutting-edge instrumentation such as time of flight-mass spectrometry (ToF-MS), Fourier transform-ion cyclotron resonance (FT-ICR), and Orbitrap mass spectrometer have been developed. This overview provides descriptions of recent improvements of EDA and suggests future research directions based on current understandings and limitations.

Bioactive Potential of Marine Macroalgae from the Central Red Sea (Saudi Arabia) Assessed by High-Throughput Imaging-Based Phenotypic Profiling.

PubMed

Kremb, Stephan; Müller, Constanze; Schmitt-Kopplin, Philippe; Voolstra, Christian R

2017-03-20

Marine algae represent an important source of novel natural products. While their bioactive potential has been studied to some extent, limited information is available on marine algae from the Red Sea. This study aimed at the broad discovery of new bioactivities from a collection of twelve macroalgal species from the Central Red Sea. We used imaging-based High-Content Screening (HCS) with a diverse spectrum of cellular markers for detailed cytological profiling of fractionated algal extracts. The cytological profiles for 3 out of 60 algal fractions clustered closely to reference inhibitors and showed strong inhibitory activities on the HIV-1 reverse transcriptase in a single-enzyme biochemical assay, validating the suggested biological target. Subsequent chemical profiling of the active fractions of two brown algal species by ultra-high resolution mass spectrometry (FT-ICR-MS) revealed possible candidate molecules. A database query of these molecules led us to groups of compounds with structural similarities, which are suggested to be responsible for the observed activity. Our work demonstrates the versatility and power of cytological profiling for the bioprospecting of unknown biological resources and highlights Red Sea algae as a source of bioactives that may serve as a starting point for further studies.

Biodiesel production from municipal secondary sludge.

PubMed

Kumar, Manish; Ghosh, Pooja; Khosla, Khushboo; Thakur, Indu Shekhar

2016-09-01

In the present study, feasibility of biodiesel production from freeze dried sewage sludge was studied and its yield was enhanced by optimization of the in situ transesterification conditions (temperature, catalyst and concentration of sludge solids). Optimized conditions (45°C, 5% catalyst and 0.16g/mL sludge solids) resulted in a 20.76±0.04% biodiesel yield. The purity of biodiesel was ascertained by GC-MS, FT-IR and NMR ((1)H and (13)C) spectroscopy. The biodiesel profile obtained revealed the predominance of methyl esters of fatty acids such as oleic, palmitic, myristic, stearic, lauric, palmitoleic and linoleic acids indicating potential use of sludge as a biodiesel feedstock. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biomarkers to Assess Possible Biological Effects on Reproductive Potential, Immune Function, and Energetic Fitness of Bottlenose Dolphins Exposed to Sounds Consistent with Naval Sonars

DTIC Science & Technology

2011-09-30

creatinine, calcium, ALK.phos, AST(SGOT), ALT(SGPT), total bilirubin, total protein and albumin); iron, LDH; phosphate; and uric acid . For liver function...assays AST, ALT, total bilirubin, and uric acid are most relevant, whereas for kidney function, BUN and creatinine are of particular interest. For...formic acid (for analysis in the positive ion mode) and in methanol:water 4:1 with 10 mM ammonium acetate (for the negative ion mode). FT-ICR mass

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

75 FR 21603 - Information Collection; Submission for OMB Review, Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-26

... information collection request (ICR), entitled the Pilot for Volunteer Management ROI Measurement System, to... in this Federal Register: (1) By fax to: (202) 395-6974, Attention: Ms. Sharon Mar, OMB Desk Officer... approval of a pilot version of a tool designed to measure the return on investment for recruiting and...

A Review of the Status of Brain Structure Research in Transsexualism.

PubMed

Guillamon, Antonio; Junque, Carme; Gómez-Gil, Esther

2016-10-01

The present review focuses on the brain structure of male-to-female (MtF) and female-to-male (FtM) homosexual transsexuals before and after cross-sex hormone treatment as shown by in vivo neuroimaging techniques. Cortical thickness and diffusion tensor imaging studies suggest that the brain of MtFs presents complex mixtures of masculine, feminine, and demasculinized regions, while FtMs show feminine, masculine, and defeminized regions. Consequently, the specific brain phenotypes proposed for MtFs and FtMs differ from those of both heterosexual males and females. These phenotypes have theoretical implications for brain intersexuality, asymmetry, and body perception in transsexuals as well as for Blanchard's hypothesis on sexual orientation in homosexual MtFs. Falling within the aegis of the neurohormonal theory of sex differences, we hypothesize that cortical differences between homosexual MtFs and FtMs and male and female controls are due to differently timed cortical thinning in different regions for each group. Cross-sex hormone studies have reported marked effects of the treatment on MtF and FtM brains. Their results are used to discuss the early postmortem histological studies of the MtF brain.

Reading the molecular signature of ecosystems in dissolved organic matter

NASA Astrophysics Data System (ADS)

Simon, Carsten; Roth, Vanessa-Nina; Dittmar, Thorsten; Gleixner, Gerd

2017-04-01

To make forecasts about the behavior, origin and fate of dissolved organic matter (DOM) in the environment, we need further insights into the molecular composition of this complex mixture. The development of soft ionization procedures and mass spectrometers capable of ultrahigh resolution (Fourier-Transform Mass Spectrometry, FTMS) have opened important new horizons in this regard. However, the application of such systems is restricted due to high purchase and maintenance costs. The introduction of the improved version of the Orbitrap FTMS analyzer ("Elite") in 2011 could open new perspectives for the molecular-level investigation of DOM, as it combines high performance with lower overall costs. We compared the Orbitrap with an established FT-ICR-MS (ion cyclotron resonance, 15 Tesla) to assess the potential of this analyzer on a broad set of 17 terrestrial and aquatic DOM samples prepared by solid phase extraction (SPE-DOM, Dittmar et al. 2008). The dataset included groundwater, soil water from different depths and vegetation covers (forests, grassland), as well as bog, river, lake and marine waters. We here show that the Orbitrap analyzer is able to detect hard-to-resolve nitrogen and sulfur containing compounds (triplet signal [CHO]N2O2, [CHO]C5, [CHO]C2H4S) up to a mass-to-charge ratio of 430 and well retrieves the intensity information of the FT-ICR-MS. Both points have been recently reported as major obstacles in the detailed molecular-level analyses of DOM by Orbitrap systems (Hawkes et al. 2016). In our data, slight deviations in intensity representation were only found in samples characterized by stronger aromaticity, and especially in the lower mass range (below m/z 250). A subset of > 6000 formulae detected in both sets was used to further characterize the sample set on a molecular level. The derived ecological information, as assessed by ordination and post-ordination gradient fitting, was highly consistent among both datasets. A dominating first coordinate (65% of variation) described a gradient of saturation/ aromaticity, going along with contribution changes of the respective molecular groups. This gradient was also linked to allover spectrum intensity. The second coordinate represented a gradient in contribution of heteroatoms and allover number of formulae per sample. Interestingly, the third coordinate separated the relatively strongly reworked groundwater and marine DOM samples based on intensity-weighted average mass and number of C and O atoms per sample. About 150 formulae were only detected in one or two samples of the set, and could possibly contain further ecosystem-specific information. Ongoing research using mass spectrometric fragmentation analysis aims to identify these and previously reported (Roth et al. 2014) ecosystem-specific molecules. References Dittmar, T., Koch, B., Hertkorn, N. & G. Kattner (2008). Limnol. Oceanogr.: Methods 6, 230-235. Roth, V.-N., Dittmar, T., Gaupp, R. & G. Gleixner (2014). Vadose Zone J. 13. doi:10.2136/vzj2013.09.0162 Hawkes, J. A., Dittmar, T., Patriarca, C., Tranvik, L. and J. Bergquist (2016). Anal. Chem., 88 (15), pp 7698-7704.

Generation of chemical movies: FT-IR spectroscopic imaging of segmented flows.

PubMed

Chan, K L Andrew; Niu, X; deMello, A J; Kazarian, S G

2011-05-01

We have previously demonstrated that FT-IR spectroscopic imaging can be used as a powerful, label-free detection method for studying laminar flows. However, to date, the speed of image acquisition has been too slow for the efficient detection of moving droplets within segmented flow systems. In this paper, we demonstrate the extraction of fast FT-IR images with acquisition times of 50 ms. This approach allows efficient interrogation of segmented flow systems where aqueous droplets move at a speed of 2.5 mm/s. Consecutive FT-IR images separated by 120 ms intervals allow the generation of chemical movies at eight frames per second. The technique has been applied to the study of microfluidic systems containing moving droplets of water in oil and droplets of protein solution in oil. The presented work demonstrates the feasibility of the use of FT-IR imaging to study dynamic systems with subsecond temporal resolution.

Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Lim, H. J.; Park, J. H.; Babar, Z.

2015-12-01

Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (<5% RH) of room temperature (~25oC) in ~8 m3 KNU smog chamber. SOA was collected on Teflon-coated glass fiber filter, which was extracted using acetonitrile and analyzed by ultrahigh resolution 15T FT-ICR MS. UHR MS data were interpreted in various ways including molecular formula, Kendrick diagram, van Krevelen diagram, and double bond equivalent values. Substantially large fractions of them are nitrogen containing species. Thousands of individual species of SOA were identified. For SOA in the absence of NOx. intensity normalized mean O/C, H/C, N/C, OM/OC ratios were 0.43, 1.52, 0.02, and 1.68, respectively. For SOA in the presence of NOx, those ratios were 0.52, 0.95, 0.08, and 1.48, respectively. 4 different oligomer formation mechanisms (addition, H abstraction, hydrolysis and de-hydrolysis reaction) were examined on the basis of SOA compositions. Detailed discussion will be presented on the molecular structure and building block of oligomers in SOA as well as the evolution of individual elemental composition by multi-generation reactions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-01350000).

Distinct signatures of host–microbial meta-metabolome and gut microbiome in two C57BL/6 strains under high-fat diet

PubMed Central

Walker, Alesia; Pfitzner, Barbara; Neschen, Susanne; Kahle, Melanie; Harir, Mourad; Lucio, Marianna; Moritz, Franco; Tziotis, Dimitrios; Witting, Michael; Rothballer, Michael; Engel, Marion; Schmid, Michael; Endesfelder, David; Klingenspor, Martin; Rattei, Thomas; Castell, Wolfgang zu; de Angelis, Martin Hrabé; Hartmann, Anton; Schmitt-Kopplin, Philippe

2014-01-01

A combinatory approach using metabolomics and gut microbiome analysis techniques was performed to unravel the nature and specificity of metabolic profiles related to gut ecology in obesity. This study focused on gut and liver metabolomics of two different mouse strains, the C57BL/6J (C57J) and the C57BL/6N (C57N) fed with high-fat diet (HFD) for 3 weeks, causing diet-induced obesity in C57N, but not in C57J mice. Furthermore, a 16S-ribosomal RNA comparative sequence analysis using 454 pyrosequencing detected significant differences between the microbiome of the two strains on phylum level for Firmicutes, Deferribacteres and Proteobacteria that propose an essential role of the microbiome in obesity susceptibility. Gut microbial and liver metabolomics were followed by a combinatory approach using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and ultra performance liquid chromatography time of tlight MS/MS with subsequent multivariate statistical analysis, revealing distinctive host and microbial metabolome patterns between the C57J and the C57N strain. Many taurine-conjugated bile acids (TBAs) were significantly elevated in the cecum and decreased in liver samples from the C57J phenotype likely displaying different energy utilization behavior by the bacterial community and the host. Furthermore, several metabolite groups could specifically be associated with the C57N phenotype involving fatty acids, eicosanoids and urobilinoids. The mass differences based metabolite network approach enabled to extend the range of known metabolites to important bile acids (BAs) and novel taurine conjugates specific for both strains. In summary, our study showed clear alterations of the metabolome in the gastrointestinal tract and liver within a HFD-induced obesity mouse model in relation to the host–microbial nutritional adaptation. PMID:24906017

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

PubMed

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

2016-07-01

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

Effects of cross-sex hormone treatment on cortical thickness in transsexual individuals.

PubMed

Zubiaurre-Elorza, Leire; Junque, Carme; Gómez-Gil, Esther; Guillamon, Antonio

2014-05-01

Untreated transsexuals have a brain cortical phenotype. Cross-sex hormone treatments are used to masculinize or feminize the bodies of female-to-male (FtMs) or male-to-female (MtFs) transsexuals, respectively. A longitudinal design was conducted to investigate the effects of treatments on brain cortical thickness (CTh) of FtMs and MtFs. This study investigated 15 female-to-male (FtMs) and 14 male-to-female (MtFs) transsexuals prior and during at least six months of cross-sex hormone therapy treatment. Brain MRI imaging was performed in a 3-Tesla TIM-TRIO Siemens scanner. T1-weighted images were analyzed with FreeSurfer software to obtain CTh as well as subcortical volumetric values. Changes in brain CTh thickness and volumetry associated to changes in hormonal levels due to cross-sex hormone therapy. After testosterone treatment, FtMs showed increases of CTh bilaterally in the postcentral gyrus and unilaterally in the inferior parietal, lingual, pericalcarine, and supramarginal areas of the left hemisphere and the rostral middle frontal and the cuneus region of the right hemisphere. There was a significant positive correlation between the serum testosterone and free testosterone index changes and CTh changes in parieto-temporo-occipital regions. In contrast, MtFs, after estrogens and antiandrogens treatment, showed a general decrease in CTh and subcortical volumetric measures and an increase in the volume of the ventricles. Testosterone therapy increases CTh in FtMs. Thickening in cortical regions is associated to changes in testosterone levels. Estrogens and antiandrogens therapy in MtFs is associated to a decrease in the CTh that consequently induces an enlargement of the ventricular system. © 2014 International Society for Sexual Medicine.

Experimental and theoretical studies on the structure and spectroscopic properties of (E)-1-(2-aminophenyl)-3-(pyridine-4-yl) prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Cruz Ortiz, Andrés Felipe; Sánchez López, Alberto; García Ríos, Alejandro; Cuenú Cabezas, Fernando; Rozo Correa, Ciro Eduardo

2015-10-01

(E)-1-(2-aminophenyl)-3-(pyridine-4-yl)prop-2-en-1-one (or simply 2-aminochalcone) was synthetized and characterized by elemental analysis, FT-IR, NMR, MS and XRD. Molecular geometry optimization, vibrational harmonic frequencies, 1H and 13C NMR chemical shifts were calculated by ab initio (HF and MP2) and density functional theory (DFT) methods, with B3LYP and B3PW91 functionals, using GAUSSIAN 09 program package without any constraint on the geometry. With VEDA software vibrational frequencies were assigned in terms of the potential energy distribution. A detailed interpretation of the FT-IR, NMR and XRD, experimental and calculated, is reported. The HOMO and LUMO energy gap that reflects the chemical activity of the molecule were also studied by DFT and above basis set. All theoretical results correspond to a great extent to experimental ones.

Intact Protein Analysis at 21 Tesla and X-Ray Crystallography Define Structural Differences in Single Amino Acid Variants of Human Mitochondrial Branched-Chain Amino Acid Aminotransferase 2 (BCAT2)

NASA Astrophysics Data System (ADS)

Anderson, Lissa C.; Håkansson, Maria; Walse, Björn; Nilsson, Carol L.

2017-09-01

Structural technologies are an essential component in the design of precision therapeutics. Precision medicine entails the development of therapeutics directed toward a designated target protein, with the goal to deliver the right drug to the right patient at the right time. In the field of oncology, protein structural variants are often associated with oncogenic potential. In a previous proteogenomic screen of patient-derived glioblastoma (GBM) tumor materials, we identified a sequence variant of human mitochondrial branched-chain amino acid aminotransferase 2 as a putative factor of resistance of GBM to standard-of-care-treatments. The enzyme generates glutamate, which is neurotoxic. To elucidate structural coordinates that may confer altered substrate binding or activity of the variant BCAT2 T186R, a 45 kDa protein, we applied combined ETD and CID top-down mass spectrometry in a LC-FT-ICR MS at 21 T, and X-Ray crystallography in the study of both the variant and non-variant intact proteins. The combined ETD/CID fragmentation pattern allowed for not only extensive sequence coverage but also confident localization of the amino acid variant to its position in the sequence. The crystallographic experiments confirmed the hypothesis generated by in silico structural homology modeling, that the Lys59 side-chain of BCAT2 may repulse the Arg186 in the variant protein (PDB code: 5MPR), leading to destabilization of the protein dimer and altered enzyme kinetics. Taken together, the MS and novel 3D structural data give us reason to further pursue BCAT2 T186R as a precision drug target in GBM. [Figure not available: see fulltext.

Honeybee Venom Proteome Profile of Queens and Winter Bees as Determined by a Mass Spectrometric Approach

PubMed Central

Danneels, Ellen L.; Van Vaerenbergh, Matthias; Debyser, Griet; Devreese, Bart; de Graaf, Dirk C.

2015-01-01

Venoms of invertebrates contain an enormous diversity of proteins, peptides, and other classes of substances. Insect venoms are characterized by a large interspecific variation resulting in extended lists of venom compounds. The venom composition of several hymenopterans also shows different intraspecific variation. For instance, venom from different honeybee castes, more specifically queens and workers, shows quantitative and qualitative variation, while the environment, like seasonal changes, also proves to be an important factor. The present study aimed at an in-depth analysis of the intraspecific variation in the honeybee venom proteome. In summer workers, the recent list of venom proteins resulted from merging combinatorial peptide ligand library sample pretreatment and targeted tandem mass spectrometry realized with a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS/MS). Now, the same technique was used to determine the venom proteome of queens and winter bees, enabling us to compare it with that of summer bees. In total, 34 putative venom toxins were found, of which two were never described in honeybee venoms before. Venom from winter workers did not contain toxins that were not present in queens or summer workers, while winter worker venom lacked the allergen Api m 12, also known as vitellogenin. Venom from queen bees, on the other hand, was lacking six of the 34 venom toxins compared to worker bees, while it contained two new venom toxins, in particularly serine proteinase stubble and antithrombin-III. Although people are hardly stung by honeybees during winter or by queen bees, these newly identified toxins should be taken into account in the characterization of a putative allergic response against Apis mellifera stings. PMID:26529016

Sulfinylated Azadecalins act as functional mimics of a pollen germination stimulant in Arabidopsis pistils

PubMed Central

Qin, Yuan; Wysocki, Ronald J; Somogyi, Arpad; Feinstein, Yelena; Franco, Jessica Y; Tsukamoto, Tatsuya; Dunatunga, Damayanthi; Levy, Clara; Smith, Steven; Simpson, Robert; Gang, David; Johnson, Mark A; Palanivelu, Ravishankar

2011-01-01

SUMMARY Polarized cell elongation is triggered by small molecule cues during development of diverse organisms. During plant reproduction, pollen interactions with the stigma result in the polar outgrowth of a pollen tube, which delivers sperm cells to the female gametophyte to effect double fertilization. In many plants, pistils stimulate pollen germination. However, in Arabidopsis, the effect of pistils on pollen germination and the pistil factors that stimulate pollen germination remain poorly characterized. Here, we demonstrate that stigma, style, and ovules in Arabidopsis pistils stimulate pollen germination. We isolated an Arabidopsis pistil extract fraction that stimulates Arabidopsis pollen germination, and employed ultrahigh resolution ESI FT-ICR and MS/MS techniques to accurately determine the mass (202.126 daltons) of a compound that is specifically present in this pistil extract fraction. Using the molecular formula (C10H19NOS) and tandem mass spectral fragmentation patterns of the m/z (mass to charge ratio) 202.126 ion, we postulated chemical structures, devised protocols, synthesized N-Methanesulfinyl 1- and 2-azadecalins that are close structural mimics of the m/z 202.126 ion, and showed that they are sufficient to stimulate Arabidopsis pollen germination in vitro (30 µM stimulated ~50% germination) and elicit accession-specific response. Although N-Methanesulfinyl 2-azadecalin stimulated pollen germination in three species of Lineage I of Brassicaceae, it did not induce a germination response in Sisymbrium irio (Lineage II of Brassicaceae) and tobacco, indicating that activity of the compound is not random. Our results show that Arabidopsis pistils promote germination by producing azadecalin-like molecules to ensure rapid fertilization by the appropriate pollen. PMID:21801250

Gender and Age Impacts on the Association Between Thyroid Function and Metabolic Syndrome in Chinese

PubMed Central

Meng, Zhaowei; Liu, Ming; Zhang, Qing; Liu, Li; Song, Kun; Tan, Jian; Jia, Qiang; Zhang, Guizhi; Wang, Renfei; He, Yajing; Ren, Xiaojun; Zhu, Mei; He, Qing; Wang, Shen; Li, Xue; Hu, Tianpeng; Liu, Na; Upadhyaya, Arun; Zhou, Pingping; Zhang, Jianping

2015-01-01

Abstract The relationship between thyroid dysfunction and metabolic syndrome (MS) is complex. We aimed to explore the impact of gender and age on their association in a large Chinese cohort. This cross-sectional study enrolled 13,855 participants (8532 male, 5323 female), who self-reported as healthy without any known previous diseases. Clinical data including anthropometric measurements, thyroid function, and serum metabolic parameters were collected. The associations between thyroid function and MS of both genders were analyzed separately after dividing thyroid-stimulating hormone (TSH), free triiodothyronine (FT3), and age into subgroups. MS risks were calculated by binary logistic regression models. Young males had significantly higher MS prevalence than females, yet after menopause, females had higher prevalence than males. Females had higher incidence of thyroid dysfunction than males. By using TSH quartiles as the categorical variables and the lowest quartile as reference, significantly increased MS risk was demonstrated in quartile 4 for males, yet quartiles 3 and 4 for females. By using FT3 quartiles as the categorical variables, significantly increased MS risk was demonstrated in quartile 2 to 4 for females only. By using age subgroups as the categorical variables, significantly increased MS risk was shown in both genders, with females (4.408–58.455) higher than males (2.588–4.943). Gender and age had substantial influence on thyroid function and MS. Females with high TSH and high FT3 had higher MS risks than males. Aging was a risk for MS, especially for females. Urgent need is necessary to initiate interventional programs. PMID:26683929

Kinetics and evolved gas analysis for pyrolysis of food processing wastes using TGA/MS/FT-IR.

PubMed

Özsin, Gamzenur; Pütün, Ayşe Eren

2017-06-01

The objective of this study was to identify the pyrolysis of different bio-waste produced by food processing industry in a comprehensible manner. For this purpose, pyrolysis behaviors of chestnut shells (CNS), cherry stones (CS) and grape seeds (GS) were investigated by thermogravimetric analysis (TGA) combined with a Fourier-transform infrared (FT-IR) spectrometer and a mass spectrometer (MS). In order to make available theoretical groundwork for biomass pyrolysis, activation energies were calculated with the help of four different model-free kinetic methods. The results are attributed to the complex reaction schemes which imply parallel, competitive and complex reactions during pyrolysis. During pyrolysis, the evolution of volatiles was also characterized by FT-IR and MS. The main evolved gases were determined as H 2 O, CO 2 and hydrocarbons such as CH 4 and temperature dependent profiles of the species were obtained. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon dioxide sequestration by chemolithotrophic oleaginous bacteria for production and optimization of polyhydroxyalkanoate.

PubMed

Kumar, Manish; Gupta, Asmita; Thakur, Indu Shekhar

2016-08-01

The present work involved screening of a previously reported carbon concentrating oleaginous bacterial strain Serratia sp. ISTD04 for production of PHA and optimization of process parameters for enhanced PHA and biomass generation. The selected bacterial strain was screened for PHA production based on Nile red staining followed by visualization under fluorescence microscope. Spectrofluorometric measurement of Nile red fluorescence of the bacterial culture was also done. Confirmatory analysis of PHA accumulation by GC-MS revealed the presence of 3-hydroxyvalerate. Detection of characteristic peaks in the FT-IR spectrum further confirmed the production of PHA by the bacterium. Response Surface Methodology was used for optimization of pH and carbon sources' concentrations for higher PHA production. There was almost a 2 fold increase in the production of PHA following optimization as compared to un-optimized condition. The study thus establishes the production of PHA by Serratia sp. ISTD04. Copyright © 2016 Elsevier Ltd. All rights reserved.

Androgen Concentrations in Umbilical Cord Blood and Their Association with Maternal, Fetal and Obstetric Factors

PubMed Central

Keelan, Jeffrey A.; Mattes, Eugen; Tan, HaiWei; Dinan, Andrew; Newnham, John P.; Whitehouse, Andrew J. O.; Jacoby, Peter; Hickey, Martha

2012-01-01

The aim of this study was to measure umbilical blood androgen concentrations in a birth cohort using a highly specific liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay and assesses the effects of sex, labor, and gestational age on fetal androgen levels at birth. We performed a prospective cohort study of androgen concentrations in mixed arterial and venous umbilical cord serum from 803 unselected singleton pregnancies from a general obstetric population in Western Australia. Total testosterone (TT), Δ4-androstenedione, and dehydroepiandrosterone were extracted from archived cord serum samples and measured using LC-MS/MS. SHBG was measured by ELISA; free testosterone (FT) and bioavailable testosterone (BioT) values were also calculated. Median values for all three androgens were generally lower than previously published values. Levels of TT, FT, BioT, and SHBG were significantly higher in male verses female neonates (P<0.0001), while dehydroepiandrosterone levels were higher in females (P<0.0001). Labor was associated with a significant (∼15–26%) decrease in median cord blood TT and FT levels (both sexes combined), but a modest (∼16–31%) increase in SHBG, Δ4-androstenedione, and dehydroepiandrosterone concentrations. TT and FT were significantly negatively correlated with gestational age at delivery, while SHBG, Δ4-androstenedione, and dehydroepiandrosterone were positively correlated. Antenatal glucocorticoid administration also had a significant effect in the multiple regression models. This is the first study to report umbilical cord androgen levels in a large unselected population of neonates using LC-MS/MS. Our findings suggest that previous studies have over-estimated cord androgen levels, and that fetal, maternal, and obstetric factors influence cord androgen levels differentially. Caution should be exercised when interpreting previously-published data that have not taken all of these factors into account. PMID:22916165

An LC-IMS-MS Platform Providing Increased Dynamic Range for High-Throughput Proteomic Studies

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

Baker, Erin Shammel; Livesay, Eric A.; Orton, Daniel J.

2010-02-05

A high-throughput approach and platform using 15 minute reversed-phase capillary liquid chromatography (RPLC) separations in conjunction with ion mobility spectrometry-mass spectrometry (IMS-MS) measurements was evaluated for the rapid analysis of complex proteomics samples. To test the separation quality of the short LC gradient, a sample was prepared by spiking twenty reference peptides at varying concentrations from 1 ng/mL to 10 µg/mL into a tryptic digest of mouse blood plasma and analyzed with both a LC-Linear Ion Trap Fourier Transform (FT) MS and LC-IMS-TOF MS. The LC-FT MS detected thirteen out of the twenty spiked peptides that had concentrations ≥100 ng/mL.more » In contrast, the drift time selected mass spectra from the LC-IMS-TOF MS analyses yielded identifications for nineteen of the twenty peptides with all spiking level present. The greater dynamic range of the LC-IMS-TOF MS system could be attributed to two factors. First, the LC-IMS-TOF MS system enabled drift time separation of the low concentration spiked peptides from the high concentration mouse peptide matrix components, reducing signal interference and background, and allowing species to be resolved that would otherwise be obscured by other components. Second, the automatic gain control (AGC) in the linear ion trap of the hybrid FT MS instrument limits the number of ions that are accumulated to reduce space charge effects, but in turn limits the achievable dynamic range compared to the TOF detector.« less

78 FR 19728 - Information Collection Request Sent to the Office of Management and Budget (OMB) for Approval...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-02

..., MS 2042-PDM, 4401 North Fairfax Drive, Arlington, VA 22203 (mail), or hope[email protected] (email... request additional information about this ICR, contact Hope Grey at hope[email protected] (email) or 703- 358... organization, and spiritual life of Alaska Native cultures. The large majority of these villages are in remote...

Analysis and optimization of process parameters for production of polyhydroxyalkanoates along with wastewater treatment by Serratia sp. ISTVKR1.

PubMed

Gupta, Asmita; Kumar, Madan; Thakur, Indu Shekhar

2017-10-01

A previously reported biodegrading bacterial strain Serratia sp. ISTVKR1 was studied for polyhydroxyalkanoate (PHA) production along with wastewater contaminant removal. Nile red fluorescence, GC-MS, FT-IR, NMR and TEM confirmed the accumulation of homopolymer poly-3-hydroxyvalerate (PHV) within the bacterial cells. Analysis of culture after 72h of bacterial treatment showed maximum COD removal (8.4-fold), non-detection of organic contaminants such as 1H-Cyclopropa [a] naphthalene (R.T.=10.12) using GC-MS and increased proportion of elements like Cr, Mn, Fe, Ni, Cu, Cd and Pb in the bacterial cell pellets by SEM-EDX analysis. Optimization of process parameters for enhanced PHA production along with wastewater treatment done using Response Surface Methodology (RSM) showed 5% and 0.74% increase in the PHA production (0.3368±0.13gL -1 ) and % COD reduction (88.93±2.41) of wastewater, respectively. The study, thus established the production of PHA along with wastewater contaminant removal by Serratia sp. ISTVKR1. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical cross-linking of the urease complex from Helicobacter pylori and analysis by Fourier transform ion cyclotron resonance mass spectrometry and molecular modeling

NASA Astrophysics Data System (ADS)

Carlsohn, Elisabet; Ångström, Jonas; Emmett, Mark R.; Marshall, Alan G.; Nilsson, Carol L.

2004-05-01

Chemical cross-linking of proteins is a well-established method for structural mapping of small protein complexes. When combined with mass spectrometry, cross-linking can reveal protein topology and identify contact sites between the peptide surfaces. When applied to surface-exposed proteins from pathogenic organisms, the method can reveal structural details that are useful in vaccine design. In order to investigate the possibilities of applying cross-linking on larger protein complexes, we selected the urease enzyme from Helicobacter pylori as a model. This membrane-associated protein complex consists of two subunits: [alpha] (26.5 kDa) and [beta] (61.7 kDa). Three ([alpha][beta]) heterodimers form a trimeric ([alpha][beta])3 assembly which further associates into a unique dodecameric 1.1 MDa complex composed of four ([alpha][beta])3 units. Cross-linked peptides from trypsin-digested urease complex were analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and molecular modeling. Two potential cross-linked peptides (present in the cross-linked sample but undetectable in [alpha], [beta], and native complex) were assigned. Molecular modeling of urease [alpha][beta] complex and trimeric urease units ([alpha][beta])3 revealed a linkage site between the [alpha]-subunit and the [beta]-subunit, and an internal cross-linkage in the [beta]-subunit.

Effects of dissolved organic matter (DOM) sources and nature of solid extraction sorbent on recoverable DOM composition: Implication into potential lability of different compound groups.

PubMed

Chen, Meilian; Kim, Sunghwan; Park, Jae-Eun; Kim, Hyun Sik; Hur, Jin

2016-07-01

Noting the source-dependent properties of dissolved organic matter (DOM), this study explored the recoverable compounds by solid phase extraction (SPE) of two common sorbents (C18 and PPL) eluted with methanol solvent for contrasting DOM sources via fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Fresh algae and leaf litter extracts DOM, one riverine DOM, and one upstream lacustrine DOM were selected for the comparison. C18 sorbent was generally found to extract more diverse molecular formula, relatively higher molecular weight, and more heteroatomic DOM compounds within the studied mass range than PPL sorbent except for the leaf litter extract. Even with the same sorbent, the main molecular features of the two end member DOM were distributed on different sides of the axes of a multivariate ordination, indicating the source-dependent characteristics of the recoverable compounds by the sorbents. In addition, further examination of the molecular formula uniquely present in the two end members and the upstream lake DOM suggested that proteinaceous, tannin-like, and heteroatomic DOM constituents might be potential compound groups which are labile and easily degraded during their mobilization into downstream watershed. This study provides new insights into the sorbent selectivity of DOM from diverse sources and potential lability of various compound groups.

Identification of water-soluble heavy crude oil organic-acids, bases, and neutrals by electrospray ionization and field desorption ionization fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Stanford, Lateefah A; Kim, Sunghwan; Klein, Geoffrey C; Smith, Donald F; Rodgers, Ryan P; Marshall, Alan G

2007-04-15

We identify water-soluble (23 degrees C) crude oil NSO nonvolatile acidic, basic, and neutral crude oil hydrocarbons by negative-ion ESI and continuous flow FD FT-ICR MS at an average mass resolving power, m/deltam50% = 550,000. Of the 7000+ singly charged acidic species identified in South American crude oil, surprisingly, many are water-soluble, and much more so in pure water than in seawater. The truncated m/z distributions for water-soluble components exhibit preferential molecular weight, size, and heteroatom class influences on hydrocarbon solubility. Acidic water-soluble heteroatomic classes detected at >1% relative abundance include O, O2, O3, O4, OS, O2S, O3S, O4S, NO2, NO3, and NO4. Parent oil class abundance does not directly relate to abundance in the water-soluble fraction. Acidic oxygen-containing classes are most prevalent in the water-solubles, whereas acidic nitrogen-containing species are least soluble. In contrast to acidic nitrogen-containing heteroatomic classes, basic nitrogen classes are water-soluble. Water-soluble heteroatomic basic classes detected at >1% relative abundance include N, NO, NO2, NS, NS2, NOS, NO2S, N2, N2O, N2O2, OS, O2S, and O2S2.

Crustacean hyperglycemic and vitellogenesis-inhibiting hormones in the lobster Homarus gammarus.

PubMed

Ollivaux, Céline; Vinh, Joëlle; Soyez, Daniel; Toullec, Jean-Yves

2006-05-01

Crustacean hyperglycemic hormone (CHH) and vitellogenesis-inhibiting hormone (VIH), produced by the X organ-sinus gland neurosecretory complex, belong to a peptide group referred to as the CHH family, which is widely distributed in arthropods. In this study, genetic variants and post-translationally modified isoforms of CHH and VIH were characterized in the European lobster Homarus gammarus. With the use of RP-HPLC and ELISA with specific antibodies that discriminate between stereoisomers of CHH and VIH, two groups of CHH-immunoreactive peaks were characterized from HPLC fractions of sinus gland extract (CHH A and CHH B); each group contained two variants (CHH and D-Phe3CHH). In the same way, two VIH-immunoreactive peaks (VIH and D-Trp4VIH) were demonstrated in HPLC fractions from sinus gland extract. The masses of these different neuropeptides were determined by FT-ICR MS: CHH A and CHH B spectra exhibited monoisotopic ions at 8557.05 Da and 8527.04 Da, respectively, and both VIH isomers displayed an m/z value of 9129.19 Da. Two full-length cDNAs encoding preprohomones of CHH A and CHH B and only one cDNA for VIH precursor were cloned and sequenced from X organ RNA. Comparison of CHH sequences between European lobster and other Astacoidea suggests that the most hydrophobic form appeared first during crustacean evolution.

Energetics and Dynamics of Dissociation of Deprotonated Peptides: Fragmentation of Angiotensin Analogs

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

Laskin, Julia; Yang, Zhibo

2011-12-01

We present a first study of the energetics and dynamics of dissociation of deprotonated peptides using time- and collision-energy resolved surface-induced dissociation (SID) experiments. SID of four model peptides: RVYIHPF, HVYIHPF, DRVYIHPF, and DHVYIHPF was studied using a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for studying ion-surface collisions. Energy and entropy effects for the overall decomposition of the precursor ion were deduced by modeling the time- and collision energy-resolved survival curves using an RRKM based approach developed in our laboratory. The results were compared to the energetics and dynamics of dissociation of the correspondingmore » protonated species. We demonstrate that acidic peptides are less stable in the negative mode because of the low threshold associated with the kinetically hindered loss of H2O from [M-H]- ions. Comparison between the two basic peptides indicates that the lower stability of the [M-H]- ion of RVYIHPF as compared to HVYIHPF towards fragmentation is attributed to the differences in fragmentation mechanisms. Specifically, threshold energy associated with losses of NH3 and NHCNH from RVYIHPF is lower than the barrier for backbone fragmentation that dominates gas-phase decomposition of HVYIHPF. The results provide a first quantitative comparison between the energetics and dynamics of dissociation of [M+H]+ and [M-H]- ions of acidic and basic peptides.« less

Recovery of polyhydroxyalkanoates from municipal secondary wastewater sludge.

PubMed

Kumar, Manish; Ghosh, Pooja; Khosla, Khushboo; Thakur, Indu Shekhar

2018-05-01

In the current study, the feasibility of utilizing municipal secondary wastewater sludge for Polyhydroxyalkanoate (PHA) extraction was improved by optimization of various parameters (temperature, duration and concentration of sludge solids). Optimized process parameters resulted in PHA recovery of 0.605 g, significantly higher than un-optimized conditions. The characterization of PHA was carried out by GC-MS, FT-IR and NMR ( 1 H and 13 C) spectroscopy. The PHA profile was found to be dominated by mcl PHA (58%) along with other diverse PHA. The results of the present study show rich diversity of PHA extracted from a raw material which is readily available at minimal cost. In conclusion, exploring the potential of wastes for production of bioplastics not only reduces the cost of bioplastic production, but also provides a sustainable means for waste management. Copyright © 2018 Elsevier Ltd. All rights reserved.

[Sociodemographic and Clinical Characteristics of Transsexual Individuals who Applied to a Psychiatry Clinic for Sex Reassignment Surgery].

PubMed

Turan, Şenol; Aksoy Poyraz, Cana; İnce, Ezgi; Sakallı Kani, Ayşe; Emül, Hacı Murat; Duran, Alaattin

2015-01-01

The aim of the study was to investigate sociodemographic and clinical characteristics of people with gender dysphoria and differences of sociodemographic and clinical characteristics between female-to-male (FtM) and male-to-female (MtF) transsexual individuals. This study examined retrospectively sociodemographic and clinical characteristics of 139 cases with the diagnosis of gender dysphoria who were willing to undergo sex reassignment surgery and were referred to the Cerrahpaşa Medical Faculty between 2007-2013. Among 139 patients with gender dysphoria 102 were MtF (73,4%), and 37 patients were FtM (26,6%). In MtFs, rates of working in jobs which do not require high education level, unemployment, being a sex worker (p < 0,001), drug use (p = 0,017), and not having the health insurance (p < 0,001) were found to be significantly higher than FtMs. Rates of receiving psychotherapy for gender dysphoria (p = 0,001) and starting hormone therapy under the supervision of a doctor (p < 0,001) were significantly higher in FtMs, however higher rates of taking hormone therapy (p < 0,001) and undergoing surgery for sex reassignment (p < 0,001) were observed in the MtFs. There are significant differences both in sociodemographic characteristics and clinical characteristics between MtFs and FtMs. However further studies would be needed to identify underlying causes.

Structural, physicochemical characterization, theoretical studies of carboxamides and their Cu(II), Zn(II) complexes having antibacterial activities against E. coli

NASA Astrophysics Data System (ADS)

Aktan, Ebru; Gündüzalp, Ayla Balaban; Özmen, Ümmühan Özdemir

2017-01-01

The carboxamides; N,N‧-bis(thiophene-2-carboxamido)-1,3-diaminopropanol (L1) and N,N‧-bis(furan-2-carboxamido)-1,3-diaminopropanol (L2) were synthesized and characterized using 1H NMR, 13C NMR, LC-MS and FT-IR spectrum. The molecular geometries of these molecules were optimized by DFT/B3LYP method with 6-311G(d,p) basis set in Gaussian 09 software. The geometrical parameters, frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP) mapped surfaces were calculated by the same basis set. Dinuclear Cu(II) and Zn(II) complexes having general formula as [MLCl]2Cl2.nH2O (in which M = Cu(II),Zn(II); n = 0,2) were also synthesized and characterized using LC-MS and FT-IR spectrum, thermogravimetric analysis (TGA/DTA curves), magnetic moments and molar conductivities. Coordination was found to be through carbonyl oxygen and two chlorine atoms as bridging in distorted tetrahedral geometry. The optimized structures, geometrical parameters, frontier molecular orbitals (FMOs) and dipole moments of metal complexes were also obtained by DFT/B3LYP method with LanL2DZ basis set. Antibacterial activities of the compounds were screened against E. coli using microdilution method (MIC's in μg/mL). The activity results show that the corresponding compounds exhibit good to moderate antibacterial effects when compared with sulfamethoxazole and sulfisoxazole antibiotics as positive controls. Also, metal complexes have remarkable increase in their activities than parent ligands against E. coli which is mostly effected by [Cu(L2)Cl]2Cl2 complex as potential antibacterial agent.

Characterization and differentiation of high energy cyclic organic peroxides by GC/FT-IR, GC-MS, FT-IR, and Raman microscopy

NASA Astrophysics Data System (ADS)

Pena, Alvaro J.; Pacheco-Londono, Leonardo; Figueroa, Javier; Rivera-Montalvo, Luis A.; Roman-Velazquez, Felix R.; Hernandez-Rivera, Samuel P.

2005-05-01

The characterization of Tetracetone Tetraperoxide (TRATRP), Triacetone Triperoxide (TATP), Diacetone Diperoxide (DADP), Tricyclohexylidene Triperoxide and Dibenzo Diperoxide using GC-MS, GC-FTIR, FTIR, FT-NMR and Raman Spectroscopy is reported. These compounds were synthesized, purified and characterized in the laboratory in order to develop methodologies for their trace detection. During this study, TATP has been synthesized by different methods obtaining high purity and good yields, even using common household products. DADP synthetic routes reported in the literature were verified. The methods described, including those that produce mixtures with TATP and other peroxides forms were also tested. This study will also focused in the preparation of other cyclic peroxides, including Hexamethelene Triperoxide Diamine (HMTD) and different forms of cyclic peroxides from ketones. This issue of thermodynamic versus kinetic control of secondary products of all syntheses and the effect of temperature in the distribution sub products of the syntheses was also addressed. A vibrational differentiation study of was carried out. Differences were found computationally in the υ(O-O), υ(C-O), δ(CH3-C) and δ(C-O) for Raman and IR bands and retention time and fragment patron for GC-MS and GC-FT-IR.

APETx4, a Novel Sea Anemone Toxin and a Modulator of the Cancer-Relevant Potassium Channel KV10.1.

PubMed

Moreels, Lien; Peigneur, Steve; Galan, Diogo T; De Pauw, Edwin; Béress, Lászlo; Waelkens, Etienne; Pardo, Luis A; Quinton, Loïc; Tytgat, Jan

2017-09-13

The human ether-à-go-go channel (hEag1 or K V 10.1) is a cancer-relevant voltage-gated potassium channel that is overexpressed in a majority of human tumors. Peptides that are able to selectively inhibit this channel can be lead compounds in the search for new anticancer drugs. Here, we report the activity-guided purification and electrophysiological characterization of a novel K V 10.1 inhibitor from the sea anemone Anthopleura elegantissima . Purified sea anemone fractions were screened for inhibitory activity on K V 10.1 by measuring whole-cell currents as expressed in Xenopus laevis oocytes using the two-microelectrode voltage clamp technique. Fractions that showed activity on Kv10.1 were further purified by RP-HPLC. The amino acid sequence of the peptide was determined by a combination of MALDI- LIFT-TOF/TOF MS/MS and CID-ESI-FT-ICR MS/MS and showed a high similarity with APETx1 and APETx3 and was therefore named APETx4. Subsequently, the peptide was electrophysiologically characterized on K V 10.1. The selectivity of the toxin was investigated on an array of voltage-gated ion channels, including the cardiac human ether-à-go-go-related gene potassium channel (hERG or Kv11.1). The toxin inhibits K V 10.1 with an IC 50 value of 1.1 μM. In the presence of a similar toxin concentration, a shift of the activation curve towards more positive potentials was observed. Similar to the effect of the gating modifier toxin APETx1 on hERG, the inhibition of Kv10.1 by the isolated toxin is reduced at more positive voltages and the peptide seems to keep the channel in a closed state. Although the peptide also induces inhibitory effects on other K V and Na V channels, it exhibits no significant effect on hERG. Moreover, APETx4 induces a concentration-dependent cytotoxic and proapoptotic effect in various cancerous and noncancerous cell lines. This newly identified K V 10.1 inhibitor can be used as a tool to further characterize the oncogenic channel K V 10.1 or as a scaffold for the design and synthesis of more potent and safer anticancer drugs.

Quantum-chemical, NMR, FT IR, and ESI MS studies of complexes of colchicine with Zn(II).

PubMed

Jankowski, Wojciech; Kurek, Joanna; Barczyński, Piotr; Hoffmann, Marcin

2017-04-01

Colchicine is a tropolone alkaloid from Colchicinum autumnale. It shows antifibrotic, antimitotic, and anti-inflammatory activities, and is used to treat gout and Mediterranean fever. In this work, complexes of colchicine with zinc(II) nitrate were synthesized and investigated using DFT, 1 H and 13 C NMR, FT IR, and ESI MS. The counterpoise-corrected and uncorrected interaction energies of these complexes were calculated. We also calculated their 1 H, 13 C NMR, and IR spectra and compared them with the corresponding experimentally obtained data. According to the ESI MS mass spectra, colchicine forms stable complexes with zinc(II) nitrate that have various stoichiometries: 2:1, 1:1:1, and 2:1:1 with respect to colchichine, Zn(II), and nitrate ion. All of the complexes were investigated using the quantum theory of atoms in molecules (QTAIM). The calculated and the measured spectra showed differences before and after the complexation process. Calculated electron densities and bond critical points indicated the presence of bonds between the ligands and the central cation in the investigated complexes that satisfied the quantum theory of atoms in molecules. Graphical Abstract DFT, NMR, FT IR, ESI MS, QTAIM and puckering studies of complexes of colchicine with Zn(II).

Evaluation of Fungal Deterioration in Liquidambar orientalis Mill. heartwood by FT-IR and light microscopy.

Treesearch

Nural Yilgor; Dilek Dogu; Roderquita Moore; Evren Terzi; S. Nami Kartal

2013-01-01

The chemical and morphological changes in heartwood specimens of Liquidambar orientalis Mill. caused by the white-rot fungus Trametes versicolor and the brown-rot fungi Tyromyces palustris and Gloeophyllum trabeum were studied by wet chemistry, FT-IR, GC-MS analyses, and photo-...

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

PubMed

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

2017-05-29

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

Dissolved organic nitrogen in urban streams: Biodegradability and molecular composition studies.

PubMed

Lusk, Mary G; Toor, Gurpal S

2016-06-01

A portion of the dissolved organic nitrogen (DON) is biodegradable in water bodies, yet our knowledge of the molecular composition and controls on biological reactivity of DON is limited. Our objective was to investigate the biodegradability and molecular composition of DON in streams that drain a gradient of 19-83% urban land use. Weekly sampling over 21 weeks suggested no significant relationship between urban land use and DON concentration. We then selected two streams that drain 28% and 83% urban land use to determine the biodegradability and molecular composition of the DON by coupling 5-day bioassay experiments with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Both urban streams contained a wide range of N-bearing biomolecular formulas and had >80% DON in lignin-like compounds, with only 5-7% labile DON. The labile DON consisted mostly of lipid-and protein-like structures with high H/C and low O/C values. Comparison of reactive formulas and formed counterparts during the bioassay experiments indicated a shift toward more oxygenated and less saturated N-bearing DON formulas due to the microbial degradation. Although there was a little net removal (5-7%) of organic-bound N over the 5-day bioassay, there was some change to the carbon skeleton of DON compounds. These results suggest that DON in urban streams contains a complex mixture of compounds such as lipids, proteins, and lignins of variable chemical structures and biodegradability. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Ephemeral Signature of Permafrost Carbon in an Arctic Fluvial Network

NASA Astrophysics Data System (ADS)

Spencer, R. G.; Drake, T.; Guillemette, F.; Chanton, J.; Podgorski, D. C.; Zimov, N.

2016-12-01

Arctic fluvial networks process, outgas, and transport significant quantities of terrestrial organic carbon (OC). The contribution from permafrost thaw, however, remains uncertain. A primary obstacle to quantifying the contribution of permafrost OC is its high biodegradability, since it is lost to microbial respiration soon after thaw. In this study, we investigate the by-product of respiration (dissolved inorganic carbon; DIC) at maximum late-summer thaw in sites spanning the fluvial network in order to assess whether the microbial consumption of permafrost imparts a persisting aged (14C-depleted) signature on the DIC pool. Using keeling-curve incubations, we show that water column bacteria respire different sources of dissolved OC (DOC) downstream. Evidence of permafrost respiration (production of aged DIC) was only present in permafrost-influenced sites. In the non-permafrost sites, ambient DIC was modern, which does not preclude respiration of permafrost OC upstream since depleted 14C in DIC can be easily overwhelmed by modern (14C-enriched) DIC. DOC compositional analysis via FT-ICR-MS showed that aliphatic and nitrogen containing compounds were associated with the production of aged DIC, which provides insight as to why permafrost OC is likely rapidly respired upon thaw. Overall, the results from this study demonstrate the complications of using 14C-DIC as a geochemical tracer for permafrost. We highlight the need for novel and unique conservative geochemical tracers to quantify the release and fate of permafrost OC in fluvial systems.

Post-translational modifications of linker histone H1 variants in mammals

NASA Astrophysics Data System (ADS)

Starkova, T. Yu; Polyanichko, A. M.; Artamonova, T. O.; Khodorkovskii, M. A.; Kostyleva, E. I.; Chikhirzhina, E. V.; Tomilin, A. N.

2017-02-01

The covalent modifications of the linker histone H1 and the core histones are thought to play an important role in the control of chromatin functioning. Histone H1 variants from K562 cell line (hH1), mouse (mH1) and calf (cH1) thymi were studied by matrix-activated laser desorption/ionization fourier transform ion cyclotron resonance mass-spectroscopy (MALDI-FT-ICR-MS). The proteomics analysis revealed novel post-translational modifications of the histone H1, such as meK34-mH1.4, meK35-cH1.1, meK35-mH1.1, meK75-hH1.2, meK75-hH1.3, acK26-hH1.4, acK26-hH1.3 and acK17-hH1.1. The comparison of the hH1, mH1 and cH1 proteins has demonstrated that the types and positions of the post-translational modifications of the globular domains of the H1.2-H1.4 variants are very conservative. However, the post-translational modifications of the N- and C-terminal tails of H1.2, H1.3 and H1.4 are different. The differences of post-translational modifications in the N- and C-terminal tails of H1.2, H1.3 and H1.4 likely lead to the differences in DNA-H1 and H1-protein interactions.

Optimization of technological procedure for amygdalin isolation from plum seeds (Pruni domesticae semen)

PubMed Central

Savic, Ivan M.; Nikolic, Vesna D.; Savic-Gajic, Ivana M.; Nikolic, Ljubisa B.; Ibric, Svetlana R.; Gajic, Dragoljub G.

2015-01-01

The process of amygdalin extraction from plum seeds was optimized using central composite design (CCD) and multilayer perceptron (MLP). The effect of time, ethanol concentration, solid-to-liquid ratio, and temperature on the amygdalin content in the extracts was estimated using both mathematical models. The MLP 4-3-1 with exponential function in hidden layer and linear function in output layer was used for describing the extraction process. MLP model was more superior compared with CCD model due to better prediction ability. According to MLP model, the suggested optimal conditions are: time of 120 min, 100% (v/v) ethanol, solid-to liquid ratio of 1:25 (m/v) and temperature of 34.4°C. The predicted value of amygdalin content in the dried extract (25.42 g per 100 g) at these conditions was experimentally confirmed (25.30 g per 100 g of dried extract). Amygdalin (>90%) was isolated from the complex extraction mixture and structurally characterized by FT-IR, UV, and MS methods. PMID:25972881

User’s Manual for the Generalized Computer Program System Open-Channel Flow and Sedimentation TABS-2. Main Text and Appendices A through O.

DTIC Science & Technology

1985-08-01

American Society of Civil Engineers,, No. HYIL. Ariathurai, R. 1974 (Aug). A Finite Element Model for Sediment Transport in Estuaries, Ph. D. Thesis ...11 aml ms po GR PH C 1.2 ś, I i 2 "’-..04/85 a I -- . a.., 4 4 - 4 I --.. - £ . ,. 04/85 4 444 4 9*4*4449 444 A4 A44 4 4 4 4 4 4 * 4 44 4 4 4 p 4...VEL MAGNITUDE (HOURS) CFT /SEC) (FT/SEC) (F/SEC) (FT) (FT) STATUS (FiSEC) (FT/SEC) (FT/SEC) .00 -. 115 -. 043 -. 123 5.501 100.507 MET -. 112 -. 069

15. OLD ROAD BRIDGE MISSISSIPPI, MONROE CO., ABERDEEN (EAST ABERDEEN) ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

15. OLD ROAD BRIDGE MISSISSIPPI, MONROE CO., ABERDEEN (EAST ABERDEEN) One mile E of Aberdeen, 1000 ft. N of (1978) U.S. 45 bridge. Oblique view of bridge, in early 1900s. Credit: Evans Memorial Library, Aberdeen, MS. No date. Sarcone Photography, Columbus, Ms. Sep 1978. - Bridges of the Upper Tombigbee River Valley, Columbus, Lowndes County, MS

Metabolic Features of Protochlamydia amoebophila Elementary Bodies – A Link between Activity and Infectivity in Chlamydiae

PubMed Central

Watzka, Margarete; Wultsch, Anna; Tziotis, Dimitrios; Montanaro, Jacqueline; Richter, Andreas; Schmitt-Kopplin, Philippe; Horn, Matthias

2013-01-01

The Chlamydiae are a highly successful group of obligate intracellular bacteria, whose members are remarkably diverse, ranging from major pathogens of humans and animals to symbionts of ubiquitous protozoa. While their infective developmental stage, the elementary body (EB), has long been accepted to be completely metabolically inert, it has recently been shown to sustain some activities, including uptake of amino acids and protein biosynthesis. In the current study, we performed an in-depth characterization of the metabolic capabilities of EBs of the amoeba symbiont Protochlamydia amoebophila. A combined metabolomics approach, including fluorescence microscopy-based assays, isotope-ratio mass spectrometry (IRMS), ion cyclotron resonance Fourier transform mass spectrometry (ICR/FT-MS), and ultra-performance liquid chromatography mass spectrometry (UPLC-MS) was conducted, with a particular focus on the central carbon metabolism. In addition, the effect of nutrient deprivation on chlamydial infectivity was analyzed. Our investigations revealed that host-free P. amoebophila EBs maintain respiratory activity and metabolize D-glucose, including substrate uptake as well as host-free synthesis of labeled metabolites and release of labeled CO2 from 13C-labeled D-glucose. The pentose phosphate pathway was identified as major route of D-glucose catabolism and host-independent activity of the tricarboxylic acid (TCA) cycle was observed. Our data strongly suggest anabolic reactions in P. amoebophila EBs and demonstrate that under the applied conditions D-glucose availability is essential to sustain metabolic activity. Replacement of this substrate by L-glucose, a non-metabolizable sugar, led to a rapid decline in the number of infectious particles. Likewise, infectivity of Chlamydia trachomatis, a major human pathogen, also declined more rapidly in the absence of nutrients. Collectively, these findings demonstrate that D-glucose is utilized by P. amoebophila EBs and provide evidence that metabolic activity in the extracellular stage of chlamydiae is of major biological relevance as it is a critical factor affecting maintenance of infectivity. PMID:23950718

Aquatic plant-derived changes in oil sands naphthenic acid signatures determined by low-, high- and ultrahigh-resolution mass spectrometry.

PubMed

Headley, John V; Peru, Kerry M; Armstrong, Sarah A; Han, Xiumei; Martin, Jonathan W; Mapolelo, Mmilili M; Smith, Donald F; Rogers, Ryan P; Marshall, Alan G

2009-02-01

Mass spectrometry is a common tool for studying the fate of complex organic compound mixtures in oil sands processed water (OSPW), but a comparison of low-, high- ( approximately 10 000), and ultrahigh-resolution ( approximately 400 000) instrumentation for this purpose has not previously been made. High-resolution quadrupole time-of-flight mass spectrometry (QTOF MS) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), with negative-ion electrospray ionization, provided evidence for the selective dissipation of components in OSPW. Dissipation of oil sands naphthenic acids (NAs with general formula C(n)H(2n+z)O(2) where n is the number of carbon atoms, and Z is zero or a negative even number describing the number of rings) was masked (by components such as fatty acids, O(3), O(5), O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) species) at low resolution (1000) when using a triple quadrupole mass spectrometer. Changes observed in the relative composition of components in OSPW appear to be due primarily to the presence of plants, specifically cattails (Typha latifolia) and their associated microorganisms. The observed dissipation included a range of heteratomic species containing O(2), O(3), O(4), and O(5), present in Athabasca oil sands acid extracts. For the heteratomic O(2) species, namely naphthenic acids, an interesting structural relationship suggests that low and high carbon number NAs are dissipated by the plants preferentially, with a minimum around C(14)/C(15). Other heteratomic species containing O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) appear to be relatively recalcitrant to the cattails and were not dissipated to the same extent in planted systems. Copyright 2009 John Wiley & Sons, Ltd.

Metabolic study of paeoniflorin and total paeony glucosides from Paeoniae Radix Rubra in rats by high-performance liquid chromatography coupled with sequential mass spectrometry.

PubMed

Zhu, Lijun; Sun, Shanshan; Hu, Yanxi; Liu, Yufeng

2018-04-01

A clear understanding of the metabolism of Traditional Chinese Medicines is extremely important in their rational clinical application and effective material foundation research. A novel and reliable strategy was performed to find more metabolites of paeoniflorin, determine the metabolites of total paeony glucosides (TPG) by means of determining those metabolites of paeoniflorin, and compare the metabolism differences between paeoniflorin and TPG by intragastric administration. This strategy was characterized as follows. Firstly, the rats were divided into two groups (the paeoniflorin group and the TPG group) to find differences in metabolism mechanisms between paeoniflorin and TPG. Secondly, UPLC-FT-ICR MS and UPLC-Q-TOF MS 2 were applied to obtain accurate molecular weight and structural information, respectively. Thirdly, the metabolites were tentatively identified by a combination of data-processing methods including mass defect screening, characteristic neutral loss screening and product ion screening. Finally, a comparative study was employed in the metabolism of paeoniflorin and TPG. Based on the strategy, 18 metabolites of paeoniflorin (including four new compounds) and 11 metabolites of TPG (including two new compounds) were identified. In all of the identified metabolites of paeoniflorin, two metabolites in rat plasma, four metabolites in rat urine and six metabolites in rat feces were found for the first time after paeoniflorin administration. The results indicate that hydrolyzation of the ester bond and glucosidic band and conjugation with glucuronide were the major metabolic pathways of paeoniflorin. The metabolites of paeoniflorin and TPG in rat plasma, urine and feces have been detected for the first time after intragastric administration. The results may contribute to a better understanding of the metabolism mechanism and provide a scientific rationale for researching the material basis of paeoniflorin and TPG in vivo. Copyright © 2017 John Wiley & Sons, Ltd.

Crash Test of an MD-500 Helicopter with a Deployable Energy Absorber Concept

NASA Technical Reports Server (NTRS)

Littell, Justin D.; Jackson, Karen E.; Kellas, Sotiris

2010-01-01

On December 2, 2009, a full scale crash test was successfully conducted of a MD-500 helicopter at the NASA Langley Research Center Landing and Impact Research Facility . The purpose of this test was to evaluate a novel composite honeycomb deployable energy absorbing (DEA) concept for attenuation of structural and crew loads during helicopter crashes under realistic crash conditions. The DEA concept is an alternative to external airbags, and absorbs impact energy through crushing. In the test, the helicopter impacted the concrete surface with 11.83 m/s (38.8 ft/s) horizontal, 7.80 m/s (25.6 ft/s) vertical and 0.15 m/s (0.5 ft/s) lateral velocities; corresponding to a resultant velocity of 14.2 m/s (46.5 ft/s). The airframe and skid gear were instrumented with accelerometers and strain gages to determine structural integrity and load attenuation, while the skin of the airframe was covered with targets for use by photogrammetry to record gross vehicle motion before, during, and after the impact. Along with the collection of airframe data, one Hybrid III 50th percentile anthropomorphic test device (ATD), two Hybrid II 50th percentile ATDs and a specialized human surrogate torso model (HSTM) occupant were seated in the airframe and instrumented for the collection of occupant loads. Resultant occupant data showed that by using the DEA, the loads on the Hybrid II and Hybrid III ATDs were in the Low Risk regime for the injury criteria, while structural data showed the airframe retained its structural integrity post crash. Preliminary results show that the DEA is a viable concept for the attenuation of impact loads.

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

PubMed

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

2006-02-01

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

Molecular structure, spectral studies, NBO, HOMO-LUMO profile, MEP and Mulliken analysis of 3β,6β-dichloro-5α-hydroxy-5α-cholestane

NASA Astrophysics Data System (ADS)

Alam, Mahboob; Park, Soonheum

2018-05-01

The synthesis of 3β,6β-dichloro-5α-hydroxy-5α-cholestane (in general, steroidal chlorohydrin or steroidal halohydrin) and theoretical study of the structure are reported in this paper. The individuality of chlorohydrin was confirmed by FT-IR, NMR, MS, CHN microanalysis and X-ray crystallography. DFT calculations on the titled molecule have been performed. The molecular structure and spectra explained by Gaussian hybrid computational analysis theory (B3LYP) are found to be in correlation with the experimental data obtained from the various spectrophotometric techniques. The theoretical geometry optimization data were compared with the X-ray data. The vibrational bands appearing in the FT-IR are assigned with accuracy using harmonic frequencies along with intensities and animated modes. Molecular properties like NBO, HOMO-LUMO analysis, chemical reactivity descriptors, MEP mapping and dipole moment have been dealt at same level of theory. The calculated electronic spectrum of chlorohydrin is interpreted on the basis of TD-DFT calculations.

Serial Escape System For Aircraft Crews

NASA Technical Reports Server (NTRS)

Wood, Kenneth E.

1990-01-01

Emergency escape system for aircraft and aerospace vehicles ejects up to seven crewmembers, one by one, within 120 s. Intended for emergencies in which disabled craft still in stable flight at no more than 220 kn (113 m/s) equivalent airspeed and sinking no faster than 110 ft/s (33.5 m/s) at altitudes up to 50,000 ft (15.2 km). Ejection rockets load themselves from magazine after each crewmember ejected. Jumpmaster queues other crewmembers and helps them position themselves on egress ramp. Rockets pull crewmembers clear of aircraft structure. Provides orderly, controlled exit and avoids ditching at sea or landing in rough terrain.

Optimization of Adenovirus 40 and 41 Recovery from Tap Water

EPA Science Inventory

Currently, the U.S. Environmental Protection Agency’s Information Collection Rule (ICR) for the primary concentration of viruses from drinking and surface waters uses the 1MDS filter; however, a more cost effective option, the NanoCeram® filter, has been shown to recover comparab...

Evaluation of Reflexive Valve Logic for a Shipboard Firemain

DTIC Science & Technology

2000-01-12

firemain valves can be used to measure flow rate [2-5]. In addition, several device-level communication technologies such as Lon Works, Modbus, Profibus ...19,20]: Continuity dp ,d(pV)_0 dt 8K (1) Where p = fluid density, lbm/ft3 (kg/m3) t = time, s V = fluid velocity, ft/s (m/s) x = location

Body Satisfaction and Physical Appearance in Gender Dysphoria.

PubMed

van de Grift, Tim C; Cohen-Kettenis, Peggy T; Steensma, Thomas D; De Cuypere, Griet; Richter-Appelt, Hertha; Haraldsen, Ira R H; Dikmans, Rieky E G; Cerwenka, Susanne C; Kreukels, Baudewijntje P C

2016-04-01

Gender dysphoria (GD) is often accompanied by dissatisfaction with physical appearance and body image problems. The aim of this study was to compare body satisfaction with perceived appearance by others in various GD subgroups. Data collection was part of the European Network for the Investigation of Gender Incongruence. Between 2007 and 2012, 660 adults who fulfilled the criteria of the DSM-IV gender identity disorder diagnosis (1.31:1 male-to-female [MtF]:female-to-male [FtM] ratio) were included into the study. Data were collected before the start of clinical gender-confirming interventions. Sexual orientation was measured via a semi-structured interview whereas onset age was based on clinician report. Body satisfaction was assessed using the Body Image Scale. Congruence of appearance with the experienced gender was measured by means of a clinician rating. Overall, FtMs had a more positive body image than MtFs. Besides genital dissatisfaction, problem areas for MtFs included posture, face, and hair, whereas FtMs were mainly dissatisfied with hip and chest regions. Clinicians evaluated the physical appearance to be more congruent with the experienced gender in FtMs than in MtFs. Within the MtF group, those with early onset GD and an androphilic sexual orientation had appearances more in line with their gender identity. In conclusion, body image problems in GD go beyond sex characteristics only. An incongruent physical appearance may result in more difficult psychological adaptation and in more exposure to discrimination and stigmatization.

Improved ion optics for introduction of ions into a 9.4-T Fourier transform ion cyclotron resonance mass spectrometer

DOE PAGES

Chen, Yu; Leach, Franklin E.; Kaiser, Nathan K.; ...

2015-01-19

Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides unparalleled mass accuracy and resolving power.[1],[2] With electrospray ionization (ESI), ions are typically transferred into the mass spectrometer through a skimmer, which serves as a conductance-limiting orifice. However, the skimmer allows only a small fraction of incoming ions to enter the mass spectrometer. An ion funnel, originally developed by Smith and coworkers at Pacific Northwest National Laboratory (PNNL)[3-5] provides much more efficient ion focusing and transfer. The large entrance aperture of the ion funnel allows almost all ions emanating from a heated capillary to be efficiently captured and transferred, resulting inmore » nearly lossless transmission.« less

The Methane to Carbon Dioxide Ratio Produced during Peatland Decomposition and a Simple Approach for Distinguishing This Ratio

NASA Astrophysics Data System (ADS)

Chanton, J.; Hodgkins, S. B.; Cooper, W. T.; Glaser, P. H.; Corbett, J. E.; Crill, P. M.; Saleska, S. R.; Rich, V. I.; Holmes, B.; Hines, M. E.; Tfaily, M.; Kostka, J. E.

2014-12-01

Peatland organic matter is cellulose-like with an oxidation state of approximately zero. When this material decomposes by fermentation, stoichiometry dictates that CH4 and CO2 should be produced in a ratio approaching one. While this is generally the case in temperate zones, this production ratio is often departed from in boreal peatlands, where the ratio of belowground CH4/CO2 production varies between 0.1 and 1, indicating CO2 production by a mechanism in addition to fermentation. The in situ CO2/CH4 production ratio may be ascertained by analysis of the 13C isotopic composition of these products, because CO2 production unaccompanied by methane production produces CO2 with an isotopic composition similar to the parent organic matter while methanogenesis produces 13C depleted methane and 13C enriched CO2. The 13C enrichment in the subsurface CO2 pool is directly related to the amount of if formed from methane production and the isotopic composition of the methane itself. Excess CO2 production is associated with more acidic conditions, Sphagnum vegetation, high and low latitudes, methane production dominated by hydrogenotrophic methane production, 13C depleted methane, and generally, more nutrient depleted conditions. Three theories have been offered to explain these observations— 1) inhibition of acetate utilization, acetate build-up and diffusion to the surface and eventual aerobic oxidation, 2) the use of humic acids as electron acceptors, and the 3) utilization of organic oxygen to produce CO2. In support of #3, we find that 13C-NMR, Fourier transform infrared (FT IR) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) clearly show the evolution of polysaccharides and cellulose towards more decomposed humified alkyl compounds stripped of organic oxygen utilized to form CO2. Such decomposition results in more negative carbon oxidation states varying from -1 to -2. Coincident with this reduction in oxidation state, is the greater production of methane. Changing climatic conditions may alter the balance of the factors which affect the CO2/CH4 ratio by changing the water balance of the peatland, nutrient status, or temperature.

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Chicken, beams, and Campylobacter: rapid differentiation of foodborne bacteria via vibrational spectroscopy and MALDI-mass spectrometry.

PubMed

Muhamadali, Howbeer; Weaver, Danielle; Subaihi, Abdu; AlMasoud, Najla; Trivedi, Drupad K; Ellis, David I; Linton, Dennis; Goodacre, Royston

2016-01-07

Campylobacter species are one of the main causes of food poisoning worldwide. Despite the availability of established culturing and molecular techniques, due to the fastidious nature of these microorganisms, simultaneous detection and species differentiation still remains challenging. This study focused on the differentiation of eleven Campylobacter strains from six species, using Fourier transform infrared (FT-IR) and Raman spectroscopies, together with matrix-assisted laser desorption ionisation-time of flight-mass spectrometry (MALDI-TOF-MS), as physicochemical approaches for generating biochemical fingerprints. Cluster analysis of data from each of the three analytical approaches provided clear differentiation of each Campylobacter species, which was generally in agreement with a phylogenetic tree based on 16S rRNA gene sequences. Notably, although C. fetus subspecies fetus and venerealis are phylogenetically very closely related, using FT-IR and MALDI-TOF-MS data these subspecies were readily differentiated based on differences in the lipid (2920 and 2851 cm(-1)) and fingerprint regions (1500-500 cm(-1)) of the FT-IR spectra, and the 500-2000 m/z region of the MALDI-TOF-MS data. A finding that was further investigated with targeted lipidomics using liquid chromatography-mass spectrometry (LC-MS). Our results demonstrate that such metabolomics approaches combined with molecular biology techniques may provide critical information and knowledge related to the risk factors, virulence, and understanding of the distribution and transmission routes associated with different strains of foodborne Campylobacter spp.

Microbial and long-range terrestrial contributions of organic matter to Antarctica

NASA Astrophysics Data System (ADS)

Antony, R.; Grannas, A. M.; Priest, A. S.; Sleighter, R. L.; Meloth, T.; Hatcher, P.

2012-12-01

Composition and cycling of dissolved organic matter in glacial systems is important because of its great significance to global carbon dynamics, snow photochemistry, and air-snow exchange processes. But, due to the trace nature of specific organic components in Polar ice sheets, detecting and studying these species in molecular level detail has been an analytical challenge. Electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) enabled the elucidation of molecular level details of natural organic matter in snow samples collected along a coast to inland transect from the Princesses Elizabeth Land, East Antarctica. Thousands of distinct molecular species comprising of different compound classes were identified providing clues to the nature and sources of organic carbon in Antarctic snow. The major biochemical classes of compounds detected were lignins, tannins, carbohydrates, proteins, amino sugars, lipids, unsaturated hydrocarbons and condensed aromatics. Specifically, lignin molecules comprising up to 50% and compounds derived from algal and microbial biomass comprising up to 45% of the total assigned formulas dominated the organic carbon pool. The identification of a variety of lignin compounds demonstrates substantial input of vascular plant-derived materials to the identified molecular species, presumably from long range atmospheric transport and deposition. The detection of proteins, lipids and amino sugars suggests that a large proportion of the identified supraglacial organic matter likely originates from in situ microbial activity. This corroborates well with the presence of significant numbers of bacteria, picoplankton and microalgae in these samples. These results suggest that organic matter in the supraglacial environments have both a microbial and terrestrial provenance.

Intrinsic Controls of Groundwater-Surface Water Dissolved Organic Carbon Quality and Quantity on Hyporheic Carbon Oxidation.

NASA Astrophysics Data System (ADS)

Garayburu-Caruso, V. A.; Stegen, J.; Graham, E.

2017-12-01

Inputs of dissolved organic carbon (DOC) and nutrients from groundwater (GW) and surface water (SW) to the hyporheic zone strongly influence biogeochemical processes. Despite increased research efforts, we still lack a mechanistic understanding of the conditions driving elevated hyporheic metabolism. This work explores hyporheic carbon oxidation from a thermodynamic perspective by evaluating changes in metabolic rates within hyporheic zone sediments in response to changes on DOC concentration and thermodynamic profiles that are characteristic of GW and SW sources. We hypothesize that GW DOC is protected from microbial oxidation due to low concentration and that SW DOC is protected due low thermodynamic favorability. Further, we propose that GW-SW mixing can simultaneously overcome both limitations and stimulate carbon oxidation. Hyporheic sediments from the Hanford site in Richland, WA were exposed to ambient, 2-,5- and 10-fold concentrations of natural DOC from SW and GW sources, separately, and incubated at in-situ temperature. The two DOC sources supply contrasting thermodynamic profiles, with GW providing lower concentration but more thermodynamically favorable DOC and SW higher concentration, more recalcitrant DOC. Across DOC treatments we characterized time series of oxygen concentration, DOC concentration, and pH as well as endpoint measurements of DOC thermodynamics using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our results suggest that hyporheic metabolism of distinct carbon pools (GW or SW) can be limited by concentration or thermodynamic favorability. Our work provides an experimental approach to contribute to mechanistic understanding of freshwater carbon oxidation, and a process-based foundation for the development of watershed-scale hydrobiogeochemical models.

Microbial Communities and Organic Matter Composition in Surface and Subsurface Sediments of the Helgoland Mud Area, North Sea

PubMed Central

Oni, Oluwatobi E.; Schmidt, Frauke; Miyatake, Tetsuro; Kasten, Sabine; Witt, Matthias; Hinrichs, Kai-Uwe; Friedrich, Michael W.

2015-01-01

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30–530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments. PMID:26635758

Evidence for abiotic sulfurization of marine dissolved organic matter in sulfidic environments

NASA Astrophysics Data System (ADS)

Pohlabeln, A. M.; Niggemann, J.; Dittmar, T.

2016-02-01

Sedimentary organic matter abiotically sulfurizes in sulfidic marine environments. Here we hypothesize that sulfurization also affects dissolved organic matter (DOM), and that sulfidic marine environments are sources of dissolved organic sulfur (DOS) to the ocean. To test these hypotheses we studied solid-phase extractable (SPE) DOS in the Black Sea at various water column depths (oxic and anoxic) and in sediment porewaters from the German Wadden Sea. The concentration and molecular composition of SPE-DOS from these sites and from the oxic water columns of the North Sea (Germany) and of the North Pacific were compared. In support of our hypotheses, SPE-DOS concentrations were elevated in sulfidic waters compared to oxic waters. For a detailed molecular characterization of SPE-DOS, selective wet-chemical alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). These experiments included harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation to test for thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides. Additionally, collision-induced fragmentation experiments were applied to test for sulfonic acids. The tests revealed that the sulfonic acid group was the main structural feature in SPE-DOS, independent of the environmental conditions of the sampling site. Only in Wadden Sea anoxic porewater also non-aromatic thioethers were found which are presumably not stable in oxic waters. The findings from our field studies were confirmed in laboratory experiments, where we abiotically sulfurized marine and algal-derived DOM under conditions similar to that in anoxic marine sediments.

Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

NASA Astrophysics Data System (ADS)

Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

2012-12-01

Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

Autonomous Control Modes and Optimized Path Guidance for Shipboard Landing in High Sea States

DTIC Science & Technology

2015-11-16

a degraded visual environment, workload during the landing task begins to approach the limits of a human pilot’s capability. It is a similarly...Figure 2. Approach Trajectory ±4 ft landing error ±8 ft landing error ±12 ft landing error Flight Path -3000...heave and yaw axes. Figure 5. Open loop system generation ±4 ft landing error ±8 ft landing error ±12 ft landing error -10 -8 -6 -4 -2 0 2 4

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Quantitative determination and evaluation of Paris polyphylla var. yunnanensis with different harvesting times using UPLC-UV-MS and FT-IR spectroscopy in combination with partial least squares discriminant analysis.

PubMed

Yang, Yuan-Gui; Zhang, Ji; Zhao, Yan-Li; Zhang, Jin-Yu; Wang, Yuan-Zhong

2017-07-01

A rapid method was developed and validated by ultra-performance liquid chromatography-triple quadrupole mass spectroscopy with ultraviolet detection (UPLC-UV-MS) for simultaneous determination of paris saponin I, paris saponin II, paris saponin VI and paris saponin VII. Partial least squares discriminant analysis (PLS-DA) based on UPLC and Fourier transform infrared (FT-IR) spectroscopy was employed to evaluate Paris polyphylla var. yunnanensis (PPY) at different harvesting times. Quantitative determination implied that the various contents of bioactive compounds with different harvesting times may lead to different pharmacological effects; the average content of total saponins for PPY harvested at 8 years was higher than that from other samples. The PLS-DA of FT-IR spectra had a better performance than that of UPLC for discrimination of PPY from different harvesting times. Copyright © 2016 John Wiley & Sons, Ltd.

Analysis of yellow "fat" deposits on Inuit boots.

PubMed

Edwards, Howell G M; Stern, Ben; Burgio, Lucia; Kite, Marion

2009-08-01

Irregular residues of a yellow deposit that was assumed to be seal fat used for waterproofing were observed in the creases of the outer surface of a pair of Inuit boots from Arctic Canada. A sample of this deposit detached from one of these areas on these boots was examined initially by FT-Raman microscopy, from which interesting and rather surprising results demanded further analysis using FT-IR and GC-MS. The non-destructive Raman spectroscopic analysis yielded spectra which indicated the presence of a tree resin from the Pinaceae sp. The Raman spectra were also characteristic of a well-preserved keratotic protein and indicative of adherent skin. Subsequent FT-IR spectroscopic analysis supported the attribution of a Pinaceae resin to the yellow deposit. GC-MS analysis of the same deposits identified the presence of pimaric, sandaracopimaric, dehydroabietic and abietic acids, all indicative of an aged Pinaceae resin. These results confirmed that the Inuit people had access to tree resins which they probably used as a waterproofing agent.

Spectrum of metabolic dysfunction in relationship with hyperandrogenemia in obese adolescent girls with polycystic ovary syndrome.

PubMed

Alemzadeh, Ramin; Kichler, Jessica; Calhoun, Mariaelena

2010-06-01

Polycystic ovary syndrome (PCOS) in adult women is associated with increased risk of metabolic syndrome (MS) and atherosclerosis. We evaluated the spectrum of metabolic dysfunction in relationship with hyperandrogenemia (HA) in adolescent girls with PCOS. Ovulatory function, acne, hirsutism (HS), body mass index (BMI), body composition, fasting lipids, glucose, insulin, free testosterone (FT), high-sensitivity C-reactive protein (hs-CRP), and HbA1c were evaluated in 103 girls. The homeostatic assessment model equations (HOMA-IR and HOMA-%B) were used for determination of insulin resistance and beta-cell function respectively. The oligo-ovulation (Oligo)+HA+HS (n=44), Oligo+HA (n=28), and Oligo+HS (n=31) phenotypes had similar BMI. However, hyperandrogenemic phenotypes had higher prevalence of acanthosis nigricans (AN) and acne (P<0.01) and higher insulin, HOMA-IR, HOMA-%B, HbA1c, and hs-CRP levels than Oligo+HS group (P<0.01). Serum FT was correlated with HOMA-IR (r=0.38, P<0.01), HOMA-%B (r=0.49, P<0.01), hs-CRP (r=0.42, P<0.01), AN (r=0.39, P<0.01), and HbA1c (r=0.27, P<0.01). Furthermore, 34% of girls met diagnostic criteria for MS displaying higher BMI, FT, HOMA-%B, HOMA-IR, hs-CRP, and HbA1c than subjects without MS (P<0.01). Using combined HOMA-IR>or=4.0 and hs-CRP>3.0 cut-off values, 71.4% of MS versus 23.5% non-MS group were considered at risk of diabetes and atherosclerosis (P<0.0001). Hyperandrogenemic PCOS phenotypes have greatest degree of insulin resistance and inflammation. The use of insulin resistance and inflammatory markers may help identify adolescent girls with PCOS at risk of cardiometabolic syndrome.

A new algorithm using cross-assignment for label-free quantitation with LC-LTQ-FT MS.

PubMed

Andreev, Victor P; Li, Lingyun; Cao, Lei; Gu, Ye; Rejtar, Tomas; Wu, Shiaw-Lin; Karger, Barry L

2007-06-01

A new algorithm is described for label-free quantitation of relative protein abundances across multiple complex proteomic samples. Q-MEND is based on the denoising and peak picking algorithm, MEND, previously developed in our laboratory. Q-MEND takes advantage of the high resolution and mass accuracy of the hybrid LTQ-FT MS mass spectrometer (or other high-resolution mass spectrometers, such as a Q-TOF MS). The strategy, termed "cross-assignment", is introduced to increase substantially the number of quantitated proteins. In this approach, all MS/MS identifications for the set of analyzed samples are combined into a master ID list, and then each LC-MS run is searched for the features that can be assigned to a specific identification from that master list. The reliability of quantitation is enhanced by quantitating separately all peptide charge states, along with a scoring procedure to filter out less reliable peptide abundance measurements. The effectiveness of Q-MEND is illustrated in the relative quantitative analysis of Escherichia coli samples spiked with known amounts of non-E. coli protein digests. A mean quantitation accuracy of 7% and mean precision of 15% is demonstrated. Q-MEND can perform relative quantitation of a set of LC-MS data sets without manual intervention and can generate files compatible with the Guidelines for Proteomic Data Publication.

Measuring fecal testosterone in females and fecal estrogens in males: comparison of RIA and LC/MS/MS methods for wild baboons (Papio cynocephalus)

PubMed Central

Gesquiere, Laurence R.; Ziegler, Toni E.; Chen, Patricia A.; Epstein, Katherine A.; Alberts, Susan C.; Altmann, Jeanne

2014-01-01

The development of non-invasive methods, particularly fecal determination, has made possible the assessment of hormone concentrations in wild animal populations. However, measuring fecal metabolites needs careful validation for each species and for each sex. We investigated whether radioimmunoassays (RIAs) previously used to measure fecal testosterone (fT) in male baboons and fecal estrogens (fE) in female baboons were well suited to measure these hormones in the opposite sex. We compared fE and fT concentrations determined by RIA to those measured by liquid chromatography combined with triple quadropole mass spectrometry (LC/MS/MS), a highly specific method. Additionally, we conducted a biological validation to assure that the measurements of fecal concentrations reflected physiological levels of the hormone of interest. Several tests produced expected results that led us to conclude that our RIAs can reliably measure fT and fE in both sexes, and that within-sex comparisons of these measures are valid: (i) fTRIA were significantly correlated to fTLC/MS/MS for both sexes; (ii) fTRIA were higher in adult than in immature males; (iii) fTRIA were higher in pregnant than non-pregnant females; (iv) fERIA were correlated with 17β-estradiol (fE2) and with estrone (fE1) determined by LC/MS/MS in pregnant females; (v) fERIA were significantly correlated with fE2 in non-pregnant females and nearly significantly correlated in males; (vi) fERIA were higher in adult males than in immature males. fERIA were higher in females than in males, as predicted, but unexpectedly, fTRIA were higher in females than in males, suggesting a difference in steroid metabolism in the two sexes; consequently, we conclude that while within-sex comparisons are valid, fTRIA should not be used for intersexual comparisons. Our results should open the field to important additional studies, as to date the roles of testosterone in females and estrogens in males have been little investigated. PMID:24798581

Combining TXRF, FT-IR and GC-MS information for identification of inorganic and organic components in black pigments of rock art from Alero Hornillos 2 (Jujuy, Argentina).

PubMed

Vázquez, Cristina; Maier, Marta S; Parera, Sara D; Yacobaccio, Hugo; Solá, Patricia

2008-06-01

Archaeological samples are complex in composition since they generally comprise a mixture of materials submitted to deterioration factors largely dependent on the environmental conditions. Therefore, the integration of analytical tools such as TXRF, FT-IR and GC-MS can maximize the amount of information provided by the sample. Recently, two black rock art samples of camelid figures at Alero Hornillos 2, an archaeological site located near the town of Susques (Jujuy Province, Argentina), were investigated. TXRF, selected for inorganic information, showed the presence of manganese and iron among other elements, consistent with an iron and manganese oxide as the black pigment. Aiming at the detection of any residual organic compounds, the samples were extracted with a chloroform-methanol mixture and the extracts were analyzed by FT-IR, showing the presence of bands attributable to lipids. Analysis by GC-MS of the carboxylic acid methyl esters prepared from the sample extracts, indicated that the main organic constituents were saturated (C(16:0) and C(18:0)) fatty acids in relative abundance characteristic of degraded animal fat. The presence of minor C(15:0) and C(17:0) fatty acids and branched-chain iso-C(16:0) pointed to a ruminant animal source.

Multiple Nucleosome Positioning Sites Regulate the CTCF-Mediated Insulator Function of the H19 Imprinting Control Region†

PubMed Central

Kanduri, Meena; Kanduri, Chandrasekhar; Mariano, Piero; Vostrov, Alexander A.; Quitschke, Wolfgang; Lobanenkov, Victor; Ohlsson, Rolf

2002-01-01

The 5′ region of the H19 gene harbors a methylation-sensitive chromatin insulator within an imprinting control region (ICR). Insertional mutagenesis in combination with episomal assays identified nucleosome positioning sequences (NPSs) that set the stage for the remarkably precise distribution of the four target sites for the chromatin insulator protein CTCF to nucleosome linker sequences in the H19 ICR. Changing positions of the NPSs resulted in loss of both CTCF target site occupancy and insulator function, suggesting that the NPSs optimize the fidelity of the insulator function. We propose that the NPSs ensure the fidelity of the repressed status of the maternal Igf2 allele during development by constitutively maintaining availability of the CTCF target sites. PMID:11971967

Sex differences in verbal fluency during adolescence: a functional magnetic resonance imaging study in gender dysphoric and control boys and girls.

PubMed

Soleman, Remi S; Schagen, Sebastian E E; Veltman, Dick J; Kreukels, Baudewijntje P C; Cohen-Kettenis, Peggy T; Lambalk, Cornelis B; Wouters, Femke; Delemarre-van de Waal, Henriette A

2013-08-01

In the literature, verbal fluency (VF) is generally described as a female-favoring task. Although it is conceivable that this sex difference only evolves during adolescence or adulthood under influence of sex steroids, this has never been investigated in young adolescents. First, to assess sex differences in VF performance and regional brain activation in adolescents. Second, to determine if untreated transsexual adolescents differ from their sex of birth with regard to VF performance and regional brain activation. Twenty-five boys, 26 girls, 8 Male-to-Female transsexual adolescents (MtFs), and 14 Female-to-Male transsexual adolescents (FtMs) were tested in a cross-sectional study, while performing a phonetic and semantic VF task within an MRI scanner. Functional MRI response during VF task. Boys and girls produced similar amounts of words, but the group MtFs produced significantly more words in the phonetic condition compared to control boys, girls, and FtMs. During the semantic condition, no differences were found. With regard to brain activity, control boys showed more activation in the right Rolandic operculum, a small area adjacent to Broca's area, compared to girls. No significant differences in brain activity were found comparing transsexual adolescents, although sub-threshold activation was found in the right Rolandic operculum indicating a trendwise increase in activation from control girls to FtMs to MtFs to control boys. The better performance of MtFs is consistent with our expectation that MtFs perform better on female-favoring tasks. Moreover, they produced more words than girls and FtMs. Even though a trendwise linear increase in brain activity between the four groups only approached significance, it may indicate differences in individuals with gender identity disorder compared to their birth sex. Although our findings should thus be interpreted with caution, they suggest a biological basis for both transgender groups performing in-between the two sexes. © 2013 International Society for Sexual Medicine.

Understanding ligand effects in gold clusters using mass spectrometry

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

Johnson, Grant E.; Laskin, Julia

This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because “each-atom-counts” toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation ofmore » numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted that may be compared with the results of high-level theoretical calculations. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom-built instrument combined with in situ time of flight secondary ion mass spectrometry (TOF-SIMS). Jointly, this multipronged experimental approach allows characterization of the full spectrum of relevant phenomena including cluster synthesis, ligand exchange, thermochemistry, surface immobilization, and reactivity. The fundamental insights obtained from this work will facilitate the directed synthesis of gold clusters with predetermined size and properties for specific applications.« less

The source and distribution of thermogenic dissolved organic matter in the ocean

NASA Astrophysics Data System (ADS)

Dittmar, T.; Suryaputra, I. G. N. A.; Paeng, J.

2009-04-01

Thermogenic organic matter (ThOM) is abundant in the environment. ThOM is produced at elevated temperature and pressure in deep sediments and earth's crust, and it is also a residue of fossil fuel and biomass burning ("black carbon"). Because of its refractory character, it accumulates in soils and sediments and, therefore, may sequester carbon from active cycles. It was hypothesized that a significant component of marine dissolved organic matter (DOM) might be thermogenic. Here we present a detailed data set on the distribution of thermogenic DOM in major water masses of the deep and surface ocean. In addition, several potential sources of thermogenic DOM to the ocean were investigated: active seeps of brine fluids in the deep Gulf of Mexico, rivers, estuaries and submarine groundwaters. Studies on deep-sea hydrothermal vents and aerosol deposition are ongoing. All DOM samples were isolated from seawater via solid phase extraction (SPE-DOM). ThOM was quantified in the extracts as benzene-polycarboxylic acids (BPCAs) after nitric acid oxidation via high-performance liquid chromatography and diode array detection (HPLC-DAD). BPCAs are produced exclusively from fused ring systems and are therefore unambiguous molecular tracers for ThOM. In addition to BPCA determination, the molecular composition and structure of ThOM was characterized in detail via ultrahigh resolution mass spectrometry (FT-ICR-MS). All marine and river DOM samples yielded significant amounts of BPCAs. The cold seep system in the deep Gulf of Mexico, but also black water rivers (like the Suwannee River) were particularly rich in ThOM. Up to 10% of total dissolved organic carbon was thermogenic in both systems. The most abundant BPCA was benzene-pentacarboxylic acid (B5CA). The molecular composition of BPCAs and the FT-ICR-MS data indicate a relatively small number (5-8) of fused aromatic rings per molecule. Overall, the molecular BPCA patterns were very similar independent of the source of ThOM. Petroleum-derived ThOM in the deep Gulf of Mexico had very similar structures than fused ring systems in asphaltenes, but also ThOM in the rivers and groundwaters was similar. First data on aerosols, on the other had, show a clear difference between particulate and dissolved samples. ThOM from aerosols and most soils was characterized by an abundance of benzene-hexacarboxylic acid (B6CA), different from thermogenic DOM. Dissolution processes may cause partial breakdown of larger fused ring systems and thus cause similar structural units in all DOM samples. In the deep ocean, the distribution of thermogenic DOM was relatively homogeneous throughout the water column. The concentration of carbon that resides in thermogenic polycyclic aromatic hydrocarbon varied between 610 and 800 nM (1.5-2% of total dissolved organic carbon). The total amount of thermogenic DOM in the deep ocean is approx. one Peta mole carbon globally. The relatively homogenous distribution of thermogenic DOM in the abyssal ocean indicates that thermogenic DOM behaves virtually inert in the abyssal environment. One of the most striking features is that the oldest water masses, which are not enriched in industrial products (such as the Freon CFC-12) showed highest concentrations of thermogenic DOM. The younger water masses such as Antarctic bottom and intermediate waters are not particularly enriched in thermogenic DOM. This distribution suggests a preindustrial origin of ThOM in the deep ocean. Rivers and deep-sea seep systems were both identified as potential sources of ThOM to the deep ocean. Radiocarbon dating on BPCAs will provide further evidence for the origin of BC in the deep ocean.

Pigment from Streptomyces bellus MSA1 isolated from marine sediments

NASA Astrophysics Data System (ADS)

Srinivasan, M.; Merlyn Keziah, S.; Hemalatha, M.; Subathra Devi, C.

2017-11-01

The existing study is purposeful on the intracellular pigment extraction from actinomycetes isolated from Kovalam Beach regions of Chennai, Tamil Nadu, India. Only one actinobacterial isolate showed pigmented growth out of total 4 isolates. Ethyl acetate as the solvent was used in cell disruption technique for the extraction of intracellular pigments. UV-Visible spectrophotometry, FT-IR spectroscopy, HPLC and GC-MS were used for the partial characterization of the pigment. The extracted pigment was applied for the preparation of lip balm and assessing its textile dyeing property. In addition, the extracted pigment was analysed for antioxidant, antibacterial activity, MTT assay and haemolytic activity. On optimization, dextrose and maltose were the best carbon sources. The finest nitrogen sources were found to be casein and peptone. The optimum temperature range was 35°C -40°C and optimal pH was found to be between 6.0 and 8.0. The obtained results showed potent antioxidant activity and found to be non-toxic to human erythrocytes.

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Expert System for Test Program Set Fault Candidate Selection

DTIC Science & Technology

1989-09-01

Mark Herbst Mr. Paul Janusz Mr. Wayne Lee Ms. Patricia Lyon Ms. Sharyn McDowell Mr. Richard Payne Ms. Elizabeth Parliman Mr. Albert Stanbury Ms. Allison...SMCAR-ESP-L AMSMC-QA(R) AMSMC-QAK-B(R), R. Fer Rock Island, IL 61299-6000 28 Commander U.S. Army Materiel Command ATTN: AMCQA-E, Mr. Chris Neubert AMCPD...ATTN: AMSEL-PA-MT-S, Mr. Paul Kogut Mr. Andy Mills AMSEL-PA AMSEL-PA-DL AMSEL-RD-SE-CRM-CM AMSEL-RD-SE-AST Ft. Monmouth, NJ 07703-5023 35 Director U.S

Annual tendency of research papers used ICR mice as experimental animals in biomedical research fields.

PubMed

Kim, Ji Eun; Nam, Jung Hoon; Cho, Joon Young; Kim, Kil Soo; Hwang, Dae Youn

2017-06-01

Institute of Cancer Research (ICR) mice have been widely used in various research fields including toxicology, oncology, pharmacology, and pharmaceutical product safety testing for decades. However, annual tendency of research papers involving ICR mice in various biomedical fields has not been previously analyzed. In this study, we examined the numbers of papers that used ICR mice as experimental animals in the social science, natural science, engineering, medicine-pharmacy, marine agriculture-fishery, and art-kinesiology fields by analyzing big data. Numbers of ICR mouse-used papers gradually increased from 1961 to 2014, but small decreases were observed in 2015 and 2016. The largest number of ICR-used papers were published in the medicine-pharmacy field, followed by natural science and art-kinesiology fields. There were no ICR mouse-used papers in other fields. Furthermore, ICR mice have been widely employed in cell biology studies within the natural science field as well as in biochemistry and pathology in the medicine-pharmacy field. Few ICR mouse-used papers were published in exercise biochemistry and exercise nutrition in the art-kinesiology field. Regardless in most fields, the total numbers of published papers involving ICR mice were higher in 2014 than in other years, although the numbers in some fields including dentistry, veterinary science, and dermatology were high in 2016. Taken together, the present study shows that various ICR stocks, including Korl:ICR mice, are widely employed as experimental animals in various biomedical research fields.

Annual tendency of research papers used ICR mice as experimental animals in biomedical research fields

PubMed Central

Kim, Ji Eun; Nam, Jung Hoon; Cho, Joon Young; Kim, Kil Soo

2017-01-01

Institute of Cancer Research (ICR) mice have been widely used in various research fields including toxicology, oncology, pharmacology, and pharmaceutical product safety testing for decades. However, annual tendency of research papers involving ICR mice in various biomedical fields has not been previously analyzed. In this study, we examined the numbers of papers that used ICR mice as experimental animals in the social science, natural science, engineering, medicine-pharmacy, marine agriculture-fishery, and art-kinesiology fields by analyzing big data. Numbers of ICR mouse-used papers gradually increased from 1961 to 2014, but small decreases were observed in 2015 and 2016. The largest number of ICR-used papers were published in the medicine-pharmacy field, followed by natural science and art-kinesiology fields. There were no ICR mouse-used papers in other fields. Furthermore, ICR mice have been widely employed in cell biology studies within the natural science field as well as in biochemistry and pathology in the medicine-pharmacy field. Few ICR mouse-used papers were published in exercise biochemistry and exercise nutrition in the art-kinesiology field. Regardless in most fields, the total numbers of published papers involving ICR mice were higher in 2014 than in other years, although the numbers in some fields including dentistry, veterinary science, and dermatology were high in 2016. Taken together, the present study shows that various ICR stocks, including Korl:ICR mice, are widely employed as experimental animals in various biomedical research fields. PMID:28747984

Fourier transform power spectrum is a potential measure of tissue alignment in standard MRI: A multiple sclerosis study.

PubMed

Sharma, Shrushrita; Zhang, Yunyan

2017-01-01

Loss of tissue coherency in brain white matter is found in many neurological diseases such as multiple sclerosis (MS). While several approaches have been proposed to evaluate white matter coherency including fractional anisotropy and fiber tracking in diffusion-weighted imaging, few are available for standard magnetic resonance imaging (MRI). Here we present an image post-processing method for this purpose based on Fourier transform (FT) power spectrum. T2-weighted images were collected from 19 patients (10 relapsing-remitting and 9 secondary progressive MS) and 19 age- and gender-matched controls. Image processing steps included: computation, normalization, and thresholding of FT power spectrum; determination of tissue alignment profile and dominant alignment direction; and calculation of alignment complexity using a new measure named angular entropy. To test the validity of this method, we used a highly organized brain white matter structure, corpus callosum. Six regions of interest were examined from the left, central and right aspects of both genu and splenium. We found that the dominant orientation of each ROI derived from our method was significantly correlated with the predicted directions based on anatomy. There was greater angular entropy in patients than controls, and a trend to be greater in secondary progressive MS patients. These findings suggest that it is possible to detect tissue alignment and anisotropy using traditional MRI, which are routinely acquired in clinical practice. Analysis of FT power spectrum may become a new approach for advancing the evaluation and management of patients with MS and similar disorders. Further confirmation is warranted.

Fourier Transform Infrared (FT-IR) and Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) Imaging of Cerebral Ischemia: Combined Analysis of Rat Brain Thin Cuts Toward Improved Tissue Classification.

PubMed

Balbekova, Anna; Lohninger, Hans; van Tilborg, Geralda A F; Dijkhuizen, Rick M; Bonta, Maximilian; Limbeck, Andreas; Lendl, Bernhard; Al-Saad, Khalid A; Ali, Mohamed; Celikic, Minja; Ofner, Johannes

2018-02-01

Microspectroscopic techniques are widely used to complement histological studies. Due to recent developments in the field of chemical imaging, combined chemical analysis has become attractive. This technique facilitates a deepened analysis compared to single techniques or side-by-side analysis. In this study, rat brains harvested one week after induction of photothrombotic stroke were investigated. Adjacent thin cuts from rats' brains were imaged using Fourier transform infrared (FT-IR) microspectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The LA-ICP-MS data were normalized using an internal standard (a thin gold layer). The acquired hyperspectral data cubes were fused and subjected to multivariate analysis. Brain regions affected by stroke as well as unaffected gray and white matter were identified and classified using a model based on either partial least squares discriminant analysis (PLS-DA) or random decision forest (RDF) algorithms. The RDF algorithm demonstrated the best results for classification. Improved classification was observed in the case of fused data in comparison to individual data sets (either FT-IR or LA-ICP-MS). Variable importance analysis demonstrated that both molecular and elemental content contribute to the improved RDF classification. Univariate spectral analysis identified biochemical properties of the assigned tissue types. Classification of multisensor hyperspectral data sets using an RDF algorithm allows access to a novel and in-depth understanding of biochemical processes and solid chemical allocation of different brain regions.

Differential Induction of Immunogenic Cell Death and Interferon Expression in Cancer Cells by Structured ssRNAs.

PubMed

Lee, Jaewoo; Lee, Youngju; Xu, Li; White, Rebekah; Sullenger, Bruce A

2017-06-07

Activation of the RNA-sensing pattern recognition receptor (PRR) in cancer cells leads to cell death and cytokine expression. This cancer cell death releases tumor antigens and damage-associated molecular patterns (DAMPs) that induce anti-tumor immunity. However, these cytokines and DAMPs also cause adverse inflammatory and thrombotic complications that can limit the overall therapeutic benefits of PRR-targeting anti-cancer therapies. To overcome this problem, we generated and evaluated two novel and distinct ssRNA molecules (immunogenic cell-killing RNA [ICR]2 and ICR4). ICR2 and ICR4 differentially stimulated cell death and PRR signaling pathways and induced different patterns of cytokine expression in cancer and innate immune cells. Interestingly, DAMPs released from ICR2- and ICR4-treated cancer cells had distinct patterns of stimulation of innate immune receptors and coagulation. Finally, ICR2 and ICR4 inhibited in vivo tumor growth as effectively as poly(I:C). ICR2 and ICR4 are potential therapeutic agents that differentially induce cell death, immune stimulation, and coagulation when introduced into tumors. Copyright © 2017 The American Society of Gene and Cell Therapy. Published by Elsevier Inc. All rights reserved.

Improving CID, HCD, and ETD FT MS/MS degradome-peptidome identifications using high accuracy mass information

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

Shen, Yufeng; Tolic, Nikola; Purvine, Samuel O.

2011-11-07

The peptidome (i.e. processed and degraded forms of proteins) of e.g. blood can potentially provide insights into disease processes, as well as a source of candidate biomarkers that are unobtainable using conventional bottom-up proteomics approaches. MS dissociation methods, including CID, HCD, and ETD, can each contribute distinct identifications using conventional peptide identification methods (Shen et al. J. Proteome Res. 2011), but such samples still pose significant analysis and informatics challenges. In this work, we explored a simple approach for better utilization of high accuracy fragment ion mass measurements provided e.g. by FT MS/MS and demonstrate significant improvements relative to conventionalmore » descriptive and probabilistic scores methods. For example, at the same FDR level we identified 20-40% more peptides than SEQUEST and Mascot scoring methods using high accuracy fragment ion information (e.g., <10 mass errors) from CID, HCD, and ETD spectra. Species identified covered >90% of all those identified from SEQUEST, Mascot, and MS-GF scoring methods. Additionally, we found that the merging the different fragment spectra provided >60% more species using the UStags method than achieved previously, and enabled >1000 peptidome components to be identified from a single human blood plasma sample with a 0.6% peptide-level FDR, and providing an improved basis for investigation of potentially disease-related peptidome components.« less

The parental non-equivalence of imprinting control regions during mammalian development and evolution.

PubMed

Schulz, Reiner; Proudhon, Charlotte; Bestor, Timothy H; Woodfine, Kathryn; Lin, Chyuan-Sheng; Lin, Shau-Ping; Prissette, Marine; Oakey, Rebecca J; Bourc'his, Déborah

2010-11-18

In mammals, imprinted gene expression results from the sex-specific methylation of imprinted control regions (ICRs) in the parental germlines. Imprinting is linked to therian reproduction, that is, the placenta and imprinting emerged at roughly the same time and potentially co-evolved. We assessed the transcriptome-wide and ontology effect of maternally versus paternally methylated ICRs at the developmental stage of setting of the chorioallantoic placenta in the mouse (8.5dpc), using two models of imprinting deficiency including completely imprint-free embryos. Paternal and maternal imprints have a similar quantitative impact on the embryonic transcriptome. However, transcriptional effects of maternal ICRs are qualitatively focused on the fetal-maternal interface, while paternal ICRs weakly affect non-convergent biological processes, with little consequence for viability at 8.5dpc. Moreover, genes regulated by maternal ICRs indirectly influence genes regulated by paternal ICRs, while the reverse is not observed. The functional dominance of maternal imprints over early embryonic development is potentially linked to selection pressures favoring methylation-dependent control of maternal over paternal ICRs. We previously hypothesized that the different methylation histories of ICRs in the maternal versus the paternal germlines may have put paternal ICRs under higher mutational pressure to lose CpGs by deamination. Using comparative genomics of 17 extant mammalian species, we show here that, while ICRs in general have been constrained to maintain more CpGs than non-imprinted sequences, the rate of CpG loss at paternal ICRs has indeed been higher than at maternal ICRs during evolution. In fact, maternal ICRs, which have the characteristics of CpG-rich promoters, have gained CpGs compared to non-imprinted CpG-rich promoters. Thus, the numerical and, during early embryonic development, functional dominance of maternal ICRs can be explained as the consequence of two orthogonal evolutionary forces: pressure to tightly regulate genes affecting the fetal-maternal interface and pressure to avoid the mutagenic environment of the paternal germline.

The Parental Non-Equivalence of Imprinting Control Regions during Mammalian Development and Evolution

PubMed Central

Bestor, Timothy H.; Woodfine, Kathryn; Lin, Chyuan-Sheng; Lin, Shau-Ping; Prissette, Marine; Oakey, Rebecca J.; Bourc'his, Déborah

2010-01-01

In mammals, imprinted gene expression results from the sex-specific methylation of imprinted control regions (ICRs) in the parental germlines. Imprinting is linked to therian reproduction, that is, the placenta and imprinting emerged at roughly the same time and potentially co-evolved. We assessed the transcriptome-wide and ontology effect of maternally versus paternally methylated ICRs at the developmental stage of setting of the chorioallantoic placenta in the mouse (8.5dpc), using two models of imprinting deficiency including completely imprint-free embryos. Paternal and maternal imprints have a similar quantitative impact on the embryonic transcriptome. However, transcriptional effects of maternal ICRs are qualitatively focused on the fetal-maternal interface, while paternal ICRs weakly affect non-convergent biological processes, with little consequence for viability at 8.5dpc. Moreover, genes regulated by maternal ICRs indirectly influence genes regulated by paternal ICRs, while the reverse is not observed. The functional dominance of maternal imprints over early embryonic development is potentially linked to selection pressures favoring methylation-dependent control of maternal over paternal ICRs. We previously hypothesized that the different methylation histories of ICRs in the maternal versus the paternal germlines may have put paternal ICRs under higher mutational pressure to lose CpGs by deamination. Using comparative genomics of 17 extant mammalian species, we show here that, while ICRs in general have been constrained to maintain more CpGs than non-imprinted sequences, the rate of CpG loss at paternal ICRs has indeed been higher than at maternal ICRs during evolution. In fact, maternal ICRs, which have the characteristics of CpG-rich promoters, have gained CpGs compared to non-imprinted CpG-rich promoters. Thus, the numerical and, during early embryonic development, functional dominance of maternal ICRs can be explained as the consequence of two orthogonal evolutionary forces: pressure to tightly regulate genes affecting the fetal-maternal interface and pressure to avoid the mutagenic environment of the paternal germline. PMID:21124941

Utilizing mass spectrometry imaging to map the thyroid hormones triiodothyronine and thyroxine in Xenopus tropicalis tadpoles.

PubMed

Goto-Inoue, Naoko; Sato, Tomohiko; Morisasa, Mizuki; Kashiwagi, Akihiko; Kashiwagi, Keiko; Sugiura, Yuki; Sugiyama, Eiji; Suematsu, Makoto; Mori, Tsukasa

2018-02-01

Thyroid hormones are not only responsible for thermogenesis and energy metabolism in animals, but also have an important role in cell differentiation and development. Amphibian metamorphosis provides an excellent model for studying the remodeling of the body. This metamorphic organ remodeling is induced by thyroid hormones, and a larval body is thus converted into an adult one. The matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry (MS) imaging technology is expected to be a suitable tool for investigating small bioreactive molecules. The present study describes the distribution of the thyroid hormones, i.e., triiodothyronine (T3) and thyroxine (T4) and their inactive form reverse T3 (rT3) in Xenopus tropicalis tadpoles using two different types of imaging techniques, MS/MS and Fourier transform (FT)-MS imaging. As a result of MS/MS imaging, we demonstrated that T3 was mainly distributed in the gills. T4 was faintly localized in the eyes, inner gills, and intestine during metamorphosis. The intensity of T3 in the gills and the intensity of T4 in the body fluids were increased during metamorphosis. Moreover, the localization of the inactive form rT3 was demonstrated to be separate from T3, namely in the intestine and muscles. In addition, FT-MS imaging could utilize simultaneous imaging including thyroid hormone. This is the first report to demonstrate the molecular distribution of thyroid hormones themselves and to discriminate T3, T4, and rT3 in animal tissues.

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Top-down approach for the direct characterization of low molecular weight heparins using LC-FT-MS.

PubMed

Li, Lingyun; Zhang, Fuming; Zaia, Joseph; Linhardt, Robert J

2012-10-16

Low molecular heparins (LMWHs) are structurally complex, heterogeneous, polydisperse, and highly negatively charged mixtures of polysaccharides. The direct characterization of LMWH is a major challenge for currently available analytical technologies. Electrospray ionization (ESI) liquid chromatography-mass spectrometry (LC-MS) is a powerful tool for the characterization complex biological samples in the fields of proteomics, metabolomics, and glycomics. LC-MS has been applied to the analysis of heparin oligosaccharides, separated by size exclusion, reversed phase ion-pairing chromatography, and chip-based amide hydrophilic interaction chromatography (HILIC). However, there have been limited applications of ESI-LC-MS for the direct characterization of intact LMWHs (top-down analysis) due to their structural complexity, low ionization efficiency, and sulfate loss. Here we present a simple and reliable HILIC-Fourier transform (FT)-ESI-MS platform to characterize and compare two currently marketed LMWH products using the top-down approach requiring no special sample preparation steps. This HILIC system relies on cross-linked diol rather than amide chemistry, affording highly resolved chromatographic separations using a relatively high percentage of acetonitrile in the mobile phase, resulting in stable and high efficiency ionization. Bioinformatics software (GlycReSoft 1.0) was used to automatically assign structures within 5-ppm mass accuracy.

Charge Retention by Organometallic Dications on Self-Assembled Monolayer Surfaces

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

Laskin, Julia; Wang, Peng

2014-05-15

Charge retention by mass-selected ruthenium trisbipyridine dications, or Ru(bpy)32+, soft-landed onto self-assembled monolayer (SAM) surfaces of 1H, 1H, 2H, 2H-perfluorodecane-1-thiol (FSAM), 11-mercaptoundecanoic acid (COOH-SAM), and 11-amino-1-undecanethiol (HSAM) on gold was examined using in situ time-resolved secondary ion mass spectrometry in a Fourier transform ion cyclotron resonance apparatus (FT-ICR SIMS). FT-ICR SIMS analysis was performed during ion soft-landing and for 8–15 hours after the ion beam was switched off. Our results demonstrate efficient retention of the doubly charged precursor ion on the FSAM and COOH-SAM surfaces manifested by the abundant Ru(bpy)32+ ions in the SIMS spectra. In contrast, only the singlymore » charged Ru(bpy)3+ and Ru(bpy)2+ ions were observed on HSAM, indicating rapid loss of at least one charge by the deposited dications. The signal of Ru(bpy)32+ on COOH-SAM remained almost constant for more than 8 hours after the end of ion soft-landing, while a relatively fast decay followed by a plateau region was observed on the FSAM surface. However, we found that SIMS analysis of Ru(bpy)32+ ions soft-landed onto FSAM is complicated by facile ion-molecule reactivity occurring either on the surface or in the SIMS plume, making it difficult to accurately measure the charge reduction kinetics. Efficient retention of the doubly charged Ru(bpy)32+ ions on COOH-SAM is remarkably different from facile neutralization of protonated peptides deposited onto this surface reported in previous studies. Our results indicate different mechanisms of charge reduction of protonated molecules and permanent ions, such as Ru(bpy)32+, on SAM surfaces. Thus, we propose that proton loss is the major charge reduction channel for the protonated species, while electron transfer through the insulating SAM is responsible for the charge loss by permanent ions. Fundamental understanding of charge reduction phenomena is essential for controlled preparation of catalytically active substrates using ion soft-landing.« less

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Landing Characteristics of the Apollo Spacecraft with Deployed Heat Shield Impact Attenuation Systems

NASA Technical Reports Server (NTRS)

Stubbs, Sandy M.

1965-01-01

An experimental investigation was made to determine the landing characteristics of a 1/4-scale dynamic model of the Apollo spacecraft command module using two different active (heat shield deployed prior to landing) landing systems for impact attenuation. One landing system (configuration 1) consisted of six hydraulic struts and eight crushable honeycomb struts. The other landing system (configuration 2), consisted of four hydraulic struts and six strain straps. Tests made on water and the hard clay-gravel composite landing surfaces simulated parachute letdown (vertical) velocities of 23 ft/sec (7.0 m/s) (full scale). Landings made on the sand landing surface simulated vertical velocities of 30 ft/sec (9.1 m/s). Horizontal velocities of from 0 to 50 ft/sec (15 m/s) were simulated. Landing attitudes ranged from -30'degrees to 20 degrees, and the roll attitudes were O degrees, 90 degrees, and 180 degrees. For configuration 1, maximum normal accelerations at the vehicle center of gravity for landings on water, sand, and the hard clay-gravel composite surface were 9g, 20g, and 18g, respectively. The maximum normal center-of-gravity acceleration for configuration 2 which was landed only on the hard clay-gravel landing surface was approximately 19g. Accelerations for configuration 2 were generally equal to or lower than accelerations for configuration 1 and normal.

Maternal Urinary Triclosan Concentration in Relation to Maternal and Neonatal Thyroid Hormone Levels: A Prospective Study.

PubMed

Wang, Xu; Ouyang, Fengxiu; Feng, Liping; Wang, Xia; Liu, Zhiwei; Zhang, Jun

2017-06-27

Triclosan (TCS) is a synthetic antibacterial chemical widely used in personal care products. TCS exposure has been associated with decreased thyroid hormone levels in animals, but human studies are scarce and controversial. We evaluated the association between maternal TCS exposure and thyroid hormone levels of mothers and newborns. TCS was measured by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in urine samples collected during gestational weeks 38.8±1.1 from 398 pregnant women in a prospective birth cohort enrolled in 2012-2013 in Shanghai, China. Maternal serum levels of free thyroxine (FT 4 ), thyroid-stimulating hormone (TSH), and thyroid peroxidase antibody (TPOAb) were obtained from medical records. Cord blood levels of free triiodothyronine (FT 3 ), FT 4 , TSH, and TPOAb were measured. Multiple linear and logistic regression models were used to examine the relationship between maternal urinary TCS and thyroid hormone levels. TCS was detectable (≥0.1 ng/mL) in 98.24% of maternal urine samples with tertile of urinary TCS levels: low (>0.1-2.75 μg/g.Cr), medium (2.75–9.78 μg/g.Cr), and high (9.78–427.38 μg/g.Cr). With adjustment for potential confounders, cord blood log(FT 3 )pmol/L concentration was 0.11 lower in newborns of mothers with medium and high urinary TCS levels compared with those with low levels. At third trimester, the high TCS concentration was associated with 0.03 [95% confidence interval (CI) −0.08, −0.02] lower maternal serum log(FT 4 )pmol/L, whereas the medium TCS concentration was associated with 0.15 (95% CI: −0.28, −0.03) lower serum log(TSH)mIU/L with adjustment for covariates. Our results suggest significant inverse associations between maternal urinary TCS and cord blood FT 3 as well as maternal blood FT 4 concentrations at third trimester. https://doi.org/10.1289/EHP500.

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2010-08-12

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2012-04-24

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Ranging/tracking system for proximity operations

NASA Technical Reports Server (NTRS)

Nilsen, P.; Udalov, S.

1982-01-01

The hardware development and testing phase of a hand held radar for the ranging and tracking for Shuttle proximity operations are considered. The radar is to measure range to a 3 sigma accuracy of 1 m (3.28 ft) to a maximum range of 1850 m (6000 ft) and velocity to a 3 sigma accuracy of 0.03 m/s (0.1 ft/s). Size and weight are similar to hand held radars, frequently seen in use by motorcycle police officers. Meeting these goals for a target in free space was very difficult to obtain in the testing program; however, at a range of approximately 700 m, the 3 sigma range error was found to be 0.96 m. It is felt that much of this error is due to clutter in the test environment. As an example of the velocity accuracy, at a range of 450 m, a 3 sigma velocity error of 0.02 m/s was measured. The principles of the radar and recommended changes to its design are given. Analyses performed in support of the design process, the actual circuit diagrams, and the software listing are included.

TH-CD-202-12: Online Inter-Beam Replanning Based On Real-Time Dose Reconstruction

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

Kamerling, CP; Fast, MF; Ziegenhein, P

Purpose: This work provides a proof-of-concept study for online replanning during treatment delivery for step-and-shoot prostate SBRT, based on real-time dose reconstruction. Online replanning is expected to improve the trade-off between target coverage and organ-at-risk dose in the presence of intra-fractional motion. Methods: We have implemented an online replanning workflow on top of our previously reported real-time dose reconstruction software which connects to an Elekta research linac. The treatment planning system DynaPlan was extended to (1) re-optimize and sequence treatment plans (in clockwise beam order) before each beam, based on actual delivered dose, in a timeframe limited by the gantrymore » rotation between subsequent beams, and (2) send the respective segments to the delivery control software DynaTrack which starts/continues treatment immediately.To investigate the impact of a reduced safety margin, we have created and delivered (on a linac emulator) a conventional CTV+5/3mm (I) and a reduced CTV+1mm margin (II) treatment plan for a prostate patient. We have assessed CTV coverage with and without inter-beam replanning, all exposed to a gradual target shift of 0–5mm in posterior and inferior direction from start until the end of delivery. Results: For the reconstructed conventional plan (I), D98 for CTV was 100% of D98 of the planned dose. For the reconstructed margin-reduced plan (II), D98 for CTV was 95% of the planned D98 without replanning, but could be recovered to 99% by replanning for each beam. Plan (II) with replanning resulted in a decrease for bladder V90% by 88% and an increase to rectum V90% by 9% compared to the conventional plan (I). Dose calculation/accumulation was performed in <15ms per MLC aperture, replanning in <15s per beam. Conclusion: We have shown that online inter-beam replanning is technically feasible and potentially allows for a margin reduction. Future investigation considering motion-robust replanning optimization parameters is in progress. We acknowledge support of the MLC research from Elekta AB. This work is supported by Cancer Research UK under Programme C33589/A19908. Research at ICR is also supported by Cancer Research UK under Programme C33589/A19727 and NHS funding to the NIHR Biomedical Research Centre at RMH and ICR.« less

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2010-12-10

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Development of helicopter engine seals

NASA Technical Reports Server (NTRS)

Lynwander, P.

1973-01-01

An experimental evaluation of main shaft seals for helicopter gas turbine engines was conducted with shaft speeds to 213 m/s(700 ft/sec), air pressures to 148 N/sq cm (215 psia), and air temperatures to 645 K (675 F). Gas leakage test results indicate that conventional seals will not be satisfactory for high-pressure sealing because of excessive leakage. The self-acting face seal, however, had significantly lower leakage and operated with insignificant wear during a 150-hour endurance test at sliding speeds to 145 m/s (475 ft/sec), air pressures to 124 N/sq cm (180 psia), and air temperatures to 408 K (275 F). Wear measurements indicate that noncontact operation was achieved at shaft speeds of 43,000 rpm. Evaluation of the self-acting circumferential seal was inconclusive because of seal dimensional variations.

Dietary fat and gut microbiota interactions determine diet-induced obesity in mice.

PubMed

Kübeck, Raphaela; Bonet-Ripoll, Catalina; Hoffmann, Christina; Walker, Alesia; Müller, Veronika Maria; Schüppel, Valentina Luise; Lagkouvardos, Ilias; Scholz, Birgit; Engel, Karl-Heinz; Daniel, Hannelore; Schmitt-Kopplin, Philippe; Haller, Dirk; Clavel, Thomas; Klingenspor, Martin

2016-12-01

Gut microbiota may promote positive energy balance; however, germfree mice can be either resistant or susceptible to diet-induced obesity (DIO) depending on the type of dietary intervention. We here sought to identify the dietary constituents that determine the susceptibility to body fat accretion in germfree (GF) mice. GF and specific pathogen free (SPF) male C57BL/6N mice were fed high-fat diets either based on lard or palm oil for 4 wks. Mice were metabolically characterized at the end of the feeding trial. FT-ICR-MS and UPLC-TOF-MS were used for cecal as well as hepatic metabolite profiling and cecal bile acids quantification, respectively. Hepatic gene expression was examined by qRT-PCR and cecal gut microbiota of SPF mice was analyzed by high-throughput 16S rRNA gene sequencing. GF mice, but not SPF mice, were completely DIO resistant when fed a cholesterol-rich lard-based high-fat diet, whereas on a cholesterol-free palm oil-based high-fat diet, DIO was independent of gut microbiota. In GF lard-fed mice, DIO resistance was conveyed by increased energy expenditure, preferential carbohydrate oxidation, and increased fecal fat and energy excretion. Cecal metabolite profiling revealed a shift in bile acid and steroid metabolites in these lean mice, with a significant rise in 17β-estradiol, which is known to stimulate energy expenditure and interfere with bile acid metabolism. Decreased cecal bile acid levels were associated with decreased hepatic expression of genes involved in bile acid synthesis. These metabolic adaptations were largely attenuated in GF mice fed the palm-oil based high-fat diet. We propose that an interaction of gut microbiota and cholesterol metabolism is essential for fat accretion in normal SPF mice fed cholesterol-rich lard as the main dietary fat source. This is supported by a positive correlation between bile acid levels and specific bacteria of the order Clostridiales (phylum Firmicutes ) as a characteristic feature of normal SPF mice fed lard. In conclusion, our study identified dietary cholesterol as a candidate ingredient affecting the crosstalk between gut microbiota and host metabolism.

Final Report: Process Models of the Equilibrium Size & State of Organic/Inorganic Aerosols for the Development of Large Scale Atmospheric Models & the Analysis of Field Data

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

Wexler, Anthony Stein; Clegg, Simon Leslie

2013-10-26

Our work addressed the following elements of the Call for Proposals: (i) “to improve the theoretical representation of aerosol processes studied in ASP laboratory or field studies”, (ii) “to enhance the incorporation of aerosol process information into modules suitable for large-scale or global atmospheric models”, and (iii) “provide systematic experimental validation of process model predictions ... using data from targeted laboratory and field experiments”. Achievements to the end of 2012 are described in four previous reports, and include: new models of densities and surface tensions of pure (single solute) and mixed aqueous solutions of typical aerosol composition under all atmosphericmore » conditions (0 to 100% RH and T > 150 K); inclusion of these models into the widely used Extended Aerosol Inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php); the addition of vapor pressure calculators for organic compounds to the E-AIM website; the ability of include user-defined organic compounds and/or lumped surrogates in gas/aerosol partitioning calculations; the development of new equations to represent the properties of soluble aerosols over the entire concentration range (using methods based upon adsorption isotherms, and derived using statistical mechanics), including systems at close to zero RH. These results are described in publications 1-6 at the end of this report, and on the “News” page of the E-AIM website (http://www.aim.env.uea.ac.uk/aim/info/news.html). During 2012 and 2013 we have collaborated in a combined observation and lab-based study of the water uptake of the organic component of atmospheric aerosols (PI Gannet Hallar, of the Desert Research Institute). The aerosol samples were analyzed using several complementary techniques (GC/MS, FT-ICR MS, and ion chromatography) to produce a very complete organic “speciation” including both polar and non-polar compounds. Hygroscopic growth factors of the samples were measured, and we have just completed comparisons of the data with our process model predictions based upon the inorganic and organic composition of the samples.« less

Non-riverine pathways of terrigenous carbon to the ocean

NASA Astrophysics Data System (ADS)

Dittmar, T.

2007-12-01

The extent and nature of non-riverine fluxes of carbon from land to ocean are poorly understood. Tidal pumping from highly productive coastal environments, atmospheric deposition and submarine groundwater discharge can be significant transport mechanisms for carbon to the ocean. Evidence is mounting that tidally-induced porewater fluxes ("outwelling") of dissolved organic matter (DOM) from mangroves and salt marshes alone may be similar in magnitude as the global riverine flux of DOM. Tidal pumping of dissolved inorganic carbon (DIC) might exceed organic carbon fluxes by far, but the existing knowledge on DIC outwelling is too scarce for a first global estimate. Results from two case studies on the biogeochemistry of DOM outwelling are presented, from the mangroves in Northern Brazil and the salt marshes in the Northern Gulf of Mexico. Ongoing research in the Northern Gulf of Mexico indicates that outwelling and groundwater inputs probably exceed riverine DOM fluxes in this region. Similar observations were made in Northern Brazil. There, the fate of mangrove-derived DOM could be traced from its source in the mangrove sediments to the outer North Brazil shelf by using a combination of isotopic and molecular approaches. Reversed-phase liquid chromatography / mass spectrometry (LC/MS) provided a multifaceted array of information that mirrors the molecular complexity of DOM. Statistical analyses on these data revealed significant differences between mangrove and open-ocean DOM which successively disappeared by irradiating the samples with natural sunlight. Nuclear magnetic resonance analyses yielded concurrent results. Ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) is the only technique capable of resolving and identifying individual elemental compositions in these complex mixtures. We applied this technique for characterizing mangrove-derived DOM and to assess the molecular changes that occur in the initial stages of outwelling. The different approaches concordantly show the presence of photodegraded mangrove DOM on the North Brazil shelf. During transport offshore, sunlight efficiently destroyed aromatic molecules, removing about one third of mangrove-derived DOM. The remainder was refractory and may thus be distributed over the oceans.

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2010-07-27

... Quality Standard Implementation Rule (Renewal), EPA ICR No. 2236.03, OMB Control No. 2060-0594 AGENCY...: EPA ICR No. 2236.03, OMB Control No. 2060-0594. ICR status: This ICR is scheduled to expire on July 31...

Complex tissue-specific epigenotypes in Russell-Silver Syndrome associated with 11p15 ICR1 hypomethylation.

PubMed

Azzi, Salah; Blaise, Annick; Steunou, Virginie; Harbison, Madeleine D; Salem, Jennifer; Brioude, Frédéric; Rossignol, Sylvie; Habib, Walid Abi; Thibaud, Nathalie; Neves, Cristina Das; Jule, Marilyne Le; Brachet, Cécile; Heinrichs, Claudine; Bouc, Yves Le; Netchine, Irène

2014-10-01

Russell-Silver Syndrome (RSS) is a prenatal and postnatal growth retardation syndrome caused mainly by 11p15 ICR1 hypomethylation. Clinical presentation is heterogeneous in RSS patients with 11p15 ICR1 hypomethylation. We previously identified a subset of RSS patients with 11p15 ICR1 and multilocus hypomethylation. Here, we examine the relationships between IGF2 expression, 11p15 ICR1 methylation, and multilocus imprinting defects in various cell types from 39 RSS patients with 11p15 ICR1 hypomethylation in leukocyte DNA. 11p15 ICR1 hypomethylation was more pronounced in leukocytes than in buccal mucosa cells. Skin fibroblast IGF2 expression was correlated with the degree of ICR1 hypomethylation. Different tissue-specific multilocus methylation defects coexisted in 38% of cases, with some loci hypomethylated and others hypermethylated within the same cell type in some cases. Our new results suggest that tissue-specific epigenotypes may lead to clinical heterogeneity in RSS. © 2014 WILEY PERIODICALS, INC.

Trimester-Specific Changes in Maternal Thyroid Hormone, Thyrotropin, and Thyroglobulin Concentrations During Gestation: Trends and Associations Across Trimesters in Iodine Sufficiency

PubMed Central

Soldin, O.P.; Tractenberg, R.E.; Hollowell, J.G.; Jonklaas, J.; Janicic, N.; Soldin, S.J.

2013-01-01

Objectives To describe the interrelationships of thyroid functions based on trimester-specific concentrations in healthy, iodine-sufficient pregnant women across trimesters, and postpartum. Methods Circulating total 3,5,3′-triidothyronine (T3) and thyroxine (T4) concentrations were determined simultaneously using liquid chromatography tandem mass-spectrometry (LC/MS/MS). Free thyroxine (FT4), thyroid-stimulating hormone (TSH), and thyroglobulin (Tg) were measured using immunoassay techniques. Linear mixed effects models and correlations were calculated to determine trends and associations, respectively, in concentrations. Results and conclusions Trimester-specific T3, FT4, TSH, and Tg concentrations were significantly different between the first and third trimesters (all p < 0.05); second and third trimester values were not significantly different for FT4, TSH, and Tg (all p > 0.25) although T3 was significantly higher in the third, relative to the second trimester. T4 was not significantly different at any trimester (all p > 0.80). With two exceptions, analyte concentrations tended not to be correlated at each trimester and at 1-year postpartum. One exception was that T3 and T4 tended to be associated (all p < 0.05) at all time points except the third trimester (ρ = 0.239, p > 0.05). T4 and FT4 concentrations tended to correlate positively during pregnancy (ρ 0.361–0.382, all p < 0.05) but not postpartum (ρ = 0.179, p > 0.05). Trends suggest that trimester-specific measurements of T3, FT4, Tg, and possibly TSH are warranted. PMID:15650363

A serum glycomics approach to breast cancer biomarkers.

PubMed

Kirmiz, Crystal; Li, Bensheng; An, Hyun Joo; Clowers, Brian H; Chew, Helen K; Lam, Kit S; Ferrige, Anthony; Alecio, Robert; Borowsky, Alexander D; Sulaimon, Shola; Lebrilla, Carlito B; Miyamoto, Suzanne

2007-01-01

Because the glycosylation of proteins is known to change in tumor cells during the development of breast cancer, a glycomics approach is used here to find relevant biomarkers of breast cancer. These glycosylation changes are known to correlate with increasing tumor burden and poor prognosis. Current antibody-based immunochemical tests for cancer biomarkers of ovarian (CA125), breast (CA27.29 or CA15-3), pancreatic, gastric, colonic, and carcinoma (CA19-9) target highly glycosylated mucin proteins. However, these tests lack the specificity and sensitivity for use in early detection. This glycomics approach to find glycan biomarkers of breast cancer involves chemically cleaving oligosaccharides (glycans) from glycosylated proteins that are shed or secreted by breast cancer tumor cell lines. The resulting free glycan species are analyzed by MALDI-FT-ICR MS. Further structural analysis of the glycans can be performed in FTMS through the use of tandem mass spectrometry with infrared multiphoton dissociation. Glycan profiles were generated for each cell line and compared. These methods were then used to analyze sera obtained from a mouse model of breast cancer and a small number of serum samples obtained from human patients diagnosed with breast cancer or patients with no known history of breast cancer. In addition to the glycosylation changes detected in mice as mouse mammary tumors developed, glycosylation profiles were found to be sufficiently different to distinguish patients with cancer from those without. Although the small number of patient samples analyzed so far is inadequate to make any legitimate claims at this time, these promising but very preliminary results suggest that glycan profiles may contain distinct glycan biomarkers that may correspond to glycan "signatures of cancer."

Physical and chemical evolution of dissolved organic matter across the ablation season on a glacier in the central Tibet Plateau

NASA Astrophysics Data System (ADS)

Feng, L.; An, Y.; Xu, J.; Kang, S.; Xiaofei, L.

2017-12-01

The physical evolution (metamorphism) of snow is known to affect the chemical composition of dissolved organic matter (DOM) within it. Here we present a comprehensive study on the Dongkemadi glacier in the central Tibetan Plateau by collecting surface snow/ice samples from May to October 2015. The samples were grouped into four categories based on their physical descriptions, representing the different stages of the snowmelt (i.e., fresh snow, fine firn, coarse firn, and glacier ice). The concentrations of dissolved organic carbon (DOC) decreased from fresh snow (26.8 μmol L-1) to fine firn (15.0 μmol L-1) and enriched from fine firn to coarse firn (26.1 μmol L-1) and glacier ice (34.4 μmol L-1). This reflected the dynamic variation of DOC during the snowmelt. Excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) identified three protein-like components (C1, C2 and C4) and one microbial humic-like component (C3), which indicated a significant microbially derived DOM in the surface snow/ice. Molecular level composition of DOM identified by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) also shown newly produced molecular during the snowmelt. These results suggest that the snowmelt could not only induce a loss of DOM but also intensified the in situ microbial activities that enriched and modified it. These findings are important in understanding the evolution of the physical and chemical characteristics of the DOM during the ablation season and shed some light on the nature of the biogeochemical cycles in cryospheric regions.

Molecular Hysteresis of Dissolved Organic Matter in the Connecticut River Watershed

NASA Astrophysics Data System (ADS)

Wagner, S.; Hoyle, J. B.; Matt, S.; Raymond, P. A.; Saiers, J. E.; Dittmar, T.; Stubbins, A.

2017-12-01

Rainfall-runoff processes have emerged as key controllers of the quantity and quality of terrestrial dissolved organic matter (DOM) exported from the landscape to inland waters. Hydrological events result in increased river discharge and a concomitant release of large amounts of DOM into fluvial networks. This study is part of a Macrosystems project which aims to test the Pulse-Shunt Concept: where rivers are converted from active to passive pipes during high discharge events ("pulse"), transporting labile, terrestrial DOM downstream ("shunt"), and relocating biogeochemical hotspots for DOM from the upper to the lower reaches of the watershed. The primary objective of our study was to track hysteretic changes in riverine DOM molecular composition over the course of a storm event. Samples were collected from nested watersheds in the Passumpsic River catchment, a tributary of the Connecticut River (USA). High resolution monitoring (via in-situ sondes) and high frequency collection of discreet samples (for FT-ICR/MS and other analyses) was necessary to capture short-term, hydrologically-driven variations in DOM concentration and composition. At the onset of the discharge event, we observed a unique DOM signature, enriched in aliphatic, and potentially biolabile, DOM. During peak discharge, and along the falling limb of the hydrograph, an aromatic, terrestrial-type DOM signature was more prevalent. These initial findings support the pulse-shunt hypothesis, providing evidence for the release of labile forms of DOM into rivers during the onset of a storm event, which apparently persists across low-to-high stream orders. Insights into the molecular hysteresis of fluvial DOM spotlights the impact of watershed hydrology on biogeochemical cycling in river networks.

Coupling Deep Transcriptome Analysis with Untargeted Metabolic Profiling in Ophiorrhiza pumila to Further the Understanding of the Biosynthesis of the Anti-Cancer Alkaloid Camptothecin and Anthraquinones

PubMed Central

Yamazaki, Mami; Mochida, Keiichi; Asano, Takashi; Nakabayashi, Ryo; Chiba, Motoaki; Udomson, Nirin; Yamazaki, Yasuyo; Goodenowe, Dayan B.; Sankawa, Ushio; Yoshida, Takuhiro; Toyoda, Atsushi; Totoki, Yasushi; Sakaki, Yoshiyuki; Góngora-Castillo, Elsa; Buell, C. Robin; Sakurai, Tetsuya; Saito, Kazuki

2013-01-01

The Rubiaceae species, Ophiorrhiza pumila, accumulates camptothecin, an anti-cancer alkaloid with a potent DNA topoisomerase I inhibitory activity, as well as anthraquinones that are derived from the combination of the isochorismate and hemiterpenoid pathways. The biosynthesis of these secondary products is active in O. pumila hairy roots yet very low in cell suspension culture. Deep transcriptome analysis was conducted in O. pumila hairy roots and cell suspension cultures using the Illumina platform, yielding a total of 2 Gb of sequence for each sample. We generated a hybrid transcriptome assembly of O. pumila using the Illumina-derived short read sequences and conventional Sanger-derived expressed sequence tag clones derived from a full-length cDNA library constructed using RNA from hairy roots. Among 35,608 non-redundant unigenes, 3,649 were preferentially expressed in hairy roots compared with cell suspension culture. Candidate genes involved in the biosynthetic pathway for the monoterpenoid indole alkaloid camptothecin were identified; specifically, genes involved in post-strictosamide biosynthetic events and genes involved in the biosynthesis of anthraquinones and chlorogenic acid. Untargeted metabolomic analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) indicated that most of the proposed intermediates in the camptothecin biosynthetic pathway accumulated in hairy roots in a preferential manner compared with cell suspension culture. In addition, a number of anthraquinones and chlorogenic acid preferentially accumulated in hairy roots compared with cell suspension culture. These results suggest that deep transcriptome and metabolome data sets can facilitate the identification of genes and intermediates involved in the biosynthesis of secondary products including camptothecin in O. pumila. PMID:23503598

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

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

Zhou, Mowei; Yan, Jing; Romano, Christine A.

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase Mnx from Bacillus sp. PL-12 has been successfully overexpressed in active form, unexpectedly, as a protein complex with a molecular weight of 211 kDa with no homology to known proteins in the database. We have recently used surface induced dissociation (SID) and ion mobility – mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data frommore » the native mass spectrometry experiment led to a plausible model of this unknown multicopper oxidase which has been difficult to study by conventional structural biology methods. However, because each subunit of Mnx binds copper ions as cofactor at varying ratios, there were remaining ambiguities in assigning some of the observed peaks to metal-binding species because of the sample heterogeneity and limited mass resolution. In this study, we performed SID in a modified Fourier transform – ion cyclotron resonance (FT-ICR) mass spectrometer for obtaining the ultimate resolution on the released subcomplexes of Mnx. The high mass accuracy and resolution unveiled unexpected artificial modifications in the protein that have been previously thought to be iron bound species based on lower resolution data. Additionally, most released subcomplexes were isotopically resolved for defining metal binding stoichiometry at each structural level. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes.« less

Photochemical Degradation of Petroleum-Derived Water-Soluble Organics into the Background Dissolved Organic Carbon Pool

NASA Astrophysics Data System (ADS)

Podgorski, D. C.; Ray, P. Z.; Roland, N. V.; Corilo, Y. E.; Tarr, M. A.; Guillemette, F.; Spencer, R. G.

2016-02-01

Water-soluble organic (WSO) photoproducts produced from Macondo crude oil (MC252) and a heavy fuel oil (HFO), a surrogate for that which was spilled into the San Francisco Bay by the M/V Cosco Busan, were isolated and irradiated with simulated sunlight to examine the photochemical fate of the products in aquatic ecosystems. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals marked transformations in the elemental composition of WSOs at specific irradiation periods across a time series that correspond with shifts in bulk properties determined with optical measurements. Blue shifts in EEMs spectra correlate with an increase in formulas classified as unsaturated, high oxygen while the polyphenols and unsaturated, low oxygen compounds decrease. The characteristic A and C humic- and fulvic-like FDOM signatures begin to appear in the EEM spectra of WSOs that were irradiated for as little as 8 to 12 hours, the equivalent of 2 to 3 days of natural sunlight. The presence of the A and C signatures correlate to elemental compositions that exhibit a further decrease in the unsaturated, low oxygen and subsequent increase of unsaturated, high oxygen and highly oxygenated aliphatic compounds. Furthermore, van Krevelen plots reveal a shift toward the compositional space associated with carboxyl-rich aromatic moieties (CRAM) as a function of irradiation period and the appearance of the humic- and fulvic-like FDOM signatures in the EEM spectra. Although the photodegraded WSO products show similarities in FDOM and elemental composition to representative natural dissolved organic matter from their respective pools, persistent petroleum signatures that are not photoactive are still detected. Future studies are required to examine the bioavailability of these photodegraded WSO products to determine if they degrade or persist in the environment.

Chemodiversity of dissolved organic matter in the Amazon Basin

NASA Astrophysics Data System (ADS)

Gonsior, Michael; Valle, Juliana; Schmitt-Kopplin, Philippe; Hertkorn, Norbert; Bastviken, David; Luek, Jenna; Harir, Mourad; Bastos, Wanderley; Enrich-Prast, Alex

2016-07-01

Regions in the Amazon Basin have been associated with specific biogeochemical processes, but a detailed chemical classification of the abundant and ubiquitous dissolved organic matter (DOM), beyond specific indicator compounds and bulk measurements, has not yet been established. We sampled water from different locations in the Negro, Madeira/Jamari and Tapajós River areas to characterize the molecular DOM composition and distribution. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC) revealed a large proportion of ubiquitous DOM but also unique area-specific molecular signatures. Unique to the DOM of the Rio Negro area was the large abundance of high molecular weight, diverse hydrogen-deficient and highly oxidized molecular ions deviating from known lignin or tannin compositions, indicating substantial oxidative processing of these ultimately plant-derived polyphenols indicative of these black waters. In contrast, unique signatures in the Madeira/Jamari area were defined by presumably labile sulfur- and nitrogen-containing molecules in this white water river system. Waters from the Tapajós main stem did not show any substantial unique molecular signatures relative to those present in the Rio Madeira and Rio Negro, which implied a lower organic molecular complexity in this clear water tributary, even after mixing with the main stem of the Amazon River. Beside ubiquitous DOM at average H / C and O / C elemental ratios, a distinct and significant unique DOM pool prevailed in the black, white and clear water areas that were also highly correlated with EEM-PARAFAC components and define the frameworks for primary production and other aspects of aquatic life.

Source to sink characterization of dissolved organic matter in a tropical karst system

NASA Astrophysics Data System (ADS)

Lechleitner, Franziska; Lang, Susan Q.; McIntyre, Cameron; Baldini, James U. L.; Dittmar, Thorsten; Eglinton, Timothy I.

2016-04-01

Karst systems are widespread surface features present on all continents. They are characterized by complex hydrology with a multitude of possible flow regimes, from diffuse seepage through the host rock to fracture flow in larger conduits. As stalagmite proxy records are important indicators of past terrestrial climate conditions, detailed understanding of the biogeochemistry of cave systems and their relationships to the overlying karst network is crucial. Microbial communities that drive the carbon cycle in caves are nourished by dissolved organic matter (DOM) carried with water into the cave system. Water samples from the Yok Balum cave in Belize were collected for DOM analysis, including soil waters, drip waters and pool waters from inside the cave. Additionally, DOM extracts from a stalagmite from the same cave were analysed to examine DOM signatures and test their applicability for reconstruction of environmental conditions. Ultrahigh-resolution mass spectrometry (via the ESI-FT-ICR-MS technique) yielded detailed molecular fingerprints on DOM from these samples. Several thousand molecular formulae of DOM compounds were identified. In addition, radiocarbon analyses were performed on the DOM samples to gain information on karst turnover times. A principal component analysis of the molecular data revealed a clear gradient between soil waters and cave waters, as soil waters were enriched in highly unsaturated oxygen-rich compounds (typical for vascular plants), which were much less abundant in drip waters. Conversely, peptides, which can originate from bacterial processes, were present only in the drip waters. Our data clearly show connectivity between the cave and overlaying soils, and reworking of DOM by the cave bacterial community. Furthermore, we found molecular evidence for the selective removal of vascular plant-derived DOM in the caves, possibly due to abiotic interactions with minerals.

Global latitudinal trends in peat recalcitrance quantified with calibrated FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Hodgkins, S. B.; Richardson, C. J.; Dommain, R.; Wang, H.; Glaser, P. H.; Verbeke, B. A.; Rogers, K.; Winkler, B. R.; Missilmani, M.; Flanagan, N. E.; Ho, M.; Hoyt, A.; Harvey, C. F.; Cobb, A.; Rich, V. I.; Vining, S. R.; Hough, M.; Saleska, S. R.; Podgorski, D. C.; Tfaily, M. M.; Wilson, R.; Holmes, B.; de La Cruz, F.; Toufaily, J.; Hamdan, R.; Cooper, W. T.; Chanton, J.

2017-12-01

Peatlands are a major global carbon reservoir (528-600 Pg). Most peat is found at high latitudes, where organic matter decomposition is slowed by cold temperatures and water-saturated conditions. Nonetheless, a significant portion of global peatland carbon (10-30%) is in tropical peatlands. The factors that allow peat accumulation in warm climates remain uncertain, raising the question of whether these factors may preserve peat in boreal regions as they warm. In this study, we examined peat and plant chemistry across a latitudinal transect from the Arctic to the tropics. Carbohydrate and aromatic contents were estimated based on a newly-developed analysis method for Fourier transform infrared (FTIR) spectra. In this method, peaks are baseline-corrected and normalized to the integrated spectral area using an automated R script, then calibrated to known concentrations using standards. This technique showed trends that were in agreement with those seen with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and 13C-NMR spectroscopy. Along the latitudinal transect, we found that near-surface (sub)tropical peat has lower carbohydrate and greater aromatic content than near-surface high-latitude peat, leading to recalcitrance that allows (sub)tropical peat to persist despite warm temperatures. The chemistry of (sub)tropical peat reflects a combination of recalcitrant plant inputs, and more extensive humification driven by higher temperatures. Because we observed similar declines in carbohydrate content with depth in high-latitude peat deposits, our data explain recent field-scale deep peat warming experiments in which catotelm (deeper) peat remained stable in the face of temperature increases up to 9 °C. We suggest that high-latitude deep peat reservoirs may be stabilized in the face of climate change by their ultimately lower carbohydrate and higher aromatic composition, similar to tropical peats.

Effects of NOx on the molecular composition of secondary organic aerosol formed by the ozonolysis and photooxidation of α-pinene

NASA Astrophysics Data System (ADS)

Park, Jun-Hyun; Babar, Zaeem Bin; Baek, Sun Jong; Kim, Hyun Sik; Lim, Ho-Jin

2017-10-01

The molecular composition of secondary organic aerosol (SOA), obtained from the ozonolysis and photooxidation of α-pinene, was investigated using ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) in negative ion mode electrospray ionization (ESI). SOA formation was performed in an indoor smog chamber. The molecular formulae of individual species were identified on the basis of the measured ionic mass using guidelines, such as number of atoms, elemental ratios, and the nitrogen rule. In each of the SOAs obtained, 815-3501 monomeric and oligomeric (mainly dimeric) species were identified below m/z 800. From ozonolysis, mainly 95% of the typical oxygenated species (CHO) were detected, whereas from photooxidation under high NOx conditions, 32% of nitrogen-containing species (CHON) were detected. Several common intense species (e.g., C9H14O6, C10H14O6, C10H16O5, C17H26O7, C19H28O9, C10H15NO8, and C10H15NO9) could be listed as candidate tracers for the conventional tracers for α-pinene SOA. The increased percentage of CHON as a primary effect of NOx on the SOA composition evidently affected other physicochemical parameters, such as elemental ratios (i.e., O/C, H/C, and N/C), the double-bond equivalent (DBE), the carbon oxidation state (OSC), and the organic-mass-to-carbon ratio (OM/OC). The O/C and OM/OC for CHON were greater than those observed for CHO, indicating that nitrogen preferentially exists in the oxidized form (e.g., -ONO2). The complexity of oligomerization was observed in DBE and OM/OC according to the number of carbon atoms.

Hydrolysis of Laboratory Made Tholins in Aqueous Solutions: Implications for Prebiotic Chemistry on Titan

NASA Astrophysics Data System (ADS)

Neish, Catherine; Somogyi, Á.; Lunine, J.; Smith, M.

2008-09-01

Laboratory experiments that simulate the reactions occurring in Titan's thick nitrogen-methane atmosphere produce complex organic precipitates known as tholins. Tholins have the general formula CxHyNz, and are spectrally similar to Titan's haze. When placed in liquid water, specific water soluble compounds in the tholins have been shown to produce oxygenated organic species with activation energies in the range of 60 ± 10 kJ mol-1 and half-lives between 0.3 and 17 days at 273 K (Neish et al. 2008). Oxygen incorporation into such materials - a necessary step towards the formation of biological molecules - is therefore fast compared to the freezing of impact melts and cryolavas on Titan. The rates quoted above are for reactions occurring in pure liquid water. The composition of impact melts and lavas on Titan are not likely to be pure water, but rather contain a few percent ammonia. Tobie et al. (2005) predict that Titan has a subsurface water layer with an ammonia concentration of 14 wt. % in the present era. The presence of ammonia would likely change the reaction rates and yields of the hydrolysis reactions of tholins. We have therefore extended our work to include the measurement of tholin hydrolysis rate coefficients in ammonia-water solutions. In this work, tholins were synthesized from a 0.98 N2/0.02 CH4 atmosphere in a high voltage AC flow discharge reactor, and dissolved in a 13 wt. % ammonia-water solution. Rates were determined by monitoring intensity changes of select species over time using high resolution FT-ICR MS. Comparisons between rates of similar species observed at different pH will be presented. This work was supported by the NASA Exobiology Program. C. Neish was supported by an NSERC Postgraduate Scholarship.

Sources, compositions, and optical properties of humic-like substances in Beijing during the 2014 APEC summit: Results from dual carbon isotope and Fourier-transform ion cyclotron resonance mass spectrometry analyses.

PubMed

Mo, Yangzhi; Li, Jun; Jiang, Bin; Su, Tao; Geng, Xiaofei; Liu, Junwen; Jiang, Haoyu; Shen, Chengde; Ding, Ping; Zhong, Guangcai; Cheng, Zhineng; Liao, Yuhong; Tian, Chongguo; Chen, Yingjun; Zhang, Gan

2018-08-01

Humic-like substances (HULIS) are a class of high molecular weight, light-absorbing compounds that are highly related to brown carbon (BrC). In this study, the sources and compositions of HULIS isolated from fine particles collected in Beijing, China during the 2014 Asia-Pacific Economic Cooperation (APEC) summit were characterized based on carbon isotope ( 13 C and 14 C) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses, respectively. HULIS were the main light-absorbing components of water-soluble organic carbon (WSOC), accounting for 80.2 ± 6.1% of the WSOC absorption capacity at 365 nm. The carbon isotope data showed that HULIS had a lower non-fossil contribution (53 ± 4%) and were less enriched with 13 C (-24.2 ± 0.6‰) relative to non-HULIS (62 ± 8% and -20.8 ± 0.3‰, respectively). The higher relative intensity fraction of sulfur-containing compounds in HULIS before and after APEC was attributed to higher sulfur dioxide levels emitted from fossil fuel combustion, whereas the higher fraction of nitrogen-containing compounds during APEC may have been due to the relatively greater contribution of non-fossil compounds or the influence of nitrate radical chemistry. The results of investigating the relationships among the sources, elemental compositions, and optical properties of HULIS demonstrated that the light absorption of HULIS appeared to increase with increasing unsaturation degree, but decrease with increasing oxidation level. The unsaturation of HULIS was affected by both sources and aging level. Copyright © 2018 Elsevier Ltd. All rights reserved.

Molecular alteration of marine dissolved organic matter under experimental hydrothermal conditions

NASA Astrophysics Data System (ADS)

Hawkes, Jeffrey A.; Hansen, Christian T.; Goldhammer, Tobias; Bach, Wolfgang; Dittmar, Thorsten

2016-02-01

Marine dissolved organic matter (DOM) is a large (660 Pg) pool of reduced carbon that is subject to thermal alteration in hydrothermal systems and sedimentary basins. In natural high-temperature hydrothermal systems, DOM is almost completely removed, but the mechanism and temperature dependence of this removal have not been studied to date. We investigated molecular-level changes to DOM that was solid-phase extracted (SPE-DOM) from the deep ocean of the North Pacific Ocean. This complex molecular mixture was experimentally exposed to temperatures between 100 and 380 °C over the course of two weeks in artificial seawater, and was then characterised on a molecular level via ultrahigh-resolution Fourier-transform ion cyclotron mass spectrometry (FT-ICR-MS). Almost 93% of SPE-DOM was removed by the treatment at 380 °C, and this removal was accompanied by a consistent pattern of SPE-DOM alteration across the temperatures studied. Higher molecular weight and more oxygen rich compounds were preferentially removed, suggesting that decarboxylation and dehydration of carboxylic acid and alcohol groups are the most rapid degradation mechanisms. Nitrogen containing compounds followed the same overall trends as those containing just C, H and O up to 300 °C. Above this temperature, the most highly altered samples contained very little of the original character of marine DOM, instead being mainly composed of very low intensity N- and S- containing molecules with a high H/C ratio (>1.5). Our results suggest that abiotic hydrothermal alteration of SPE-DOM may already occur at temperatures above 68 °C. Our experiments were conducted without a sedimentary or mineral phase, and demonstrate that profound molecular alteration and almost complete removal of marine SPE-DOM requires nothing more than heating in a seawater matrix.

Hydrothermal Liquefaction Biocrude Compositions Compared to Petroleum Crude and Shale Oil

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

Jarvis, Jacqueline M.; Billing, Justin M.; Hallen, Richard T.

We provide a direct and detailed comparison of the chemical composition of petroleum crude oil (from the Gulf of Mexico), shale oil, and three biocrudes (i.e., clean pine, microalgae Chlorella sp., and sewage sludge feedstocks) generated by hydrothermal liquefaction (HTL). Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that HTL biocrudes are compositionally more similar to shale oil than petroleum crude oil and that only a few heteroatom classes (e.g., N1, N2, N1O1, and O1) are common to organic sediment- and biomass-derived oils. All HTL biocrudes contain a diverse range of oxygen-containing compounds when compared tomore » either petroleum crude or shale oil. Overall, petroleum crude and shale oil are compositionally dissimilar to HTL oils, and >85% of the elemental compositions identified within the positive-ion electrospray (ESI) mass spectra of the HTL biocrudes were not present in either the petroleum crude or shale oil (>43% for negative-ion ESI). Direct comparison of the heteroatom classes that are common to both organic sedimentand biomass-derived oils shows that HTL biocrudes generally contain species with both smaller core structures and a lower degree of alkylation relative to either the petroleum crude or the shale oil. Three-dimensional plots of carbon number versus molecular double bond equivalents (with observed abundance as the third dimension) for abundant molecular classes reveal the specific relationship of the composition of HTL biocrudes to petroleum and shale oils to inform the possible incorporation of these oils into refinery operations as a partial amendment to conventional petroleum feeds.« less

Dissolved organic matter in sea spray: a transfer study from marine surface water to aerosols

NASA Astrophysics Data System (ADS)

Schmitt-Kopplin, P.; Liger-Belair, G.; Koch, B. P.; Flerus, R.; Kattner, G.; Harir, M.; Kanawati, B.; Lucio, M.; Tziotis, D.; Hertkorn, N.; Gebefügi, I.

2012-04-01

Atmospheric aerosols impose direct and indirect effects on the climate system, for example, by absorption of radiation in relation to cloud droplets size, on chemical and organic composition and cloud dynamics. The first step in the formation of Organic primary aerosols, i.e. the transfer of dissolved organic matter from the marine surface into the atmosphere, was studied. We present a molecular level description of this phenomenon using the high resolution analytical tools of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR). Our experiments confirm the chemoselective transfer of natural organic molecules, especially of aliphatic compounds from the surface water into the atmosphere via bubble bursting processes. Transfer from marine surface water to the atmosphere involves a chemical gradient governed by the physicochemical properties of the involved molecules when comparing elemental compositions and differentiating CHO, CHNO, CHOS and CHNOS bearing compounds. Typical chemical fingerprints of compounds enriched in the aerosol phase were CHO and CHOS molecular series, smaller molecules of higher aliphaticity and lower oxygen content, and typical surfactants. A non-targeted metabolomics analysis demonstrated that many of these molecules corresponded to homologous series of oxo-, hydroxy-, methoxy-, branched fatty acids and mono-, di- and tricarboxylic acids as well as monoterpenes and sugars. These surface active biomolecules were preferentially transferred from surface water into the atmosphere via bubble bursting processes to form a significant fraction of primary organic aerosols. This way of sea spray production leaves a selective biological signature of the surface water in the corresponding aerosol that may be transported into higher altitudes up to the lower atmosphere, thus contributing to the formation of secondary organic aerosol on a global scale or transported laterally with possible deposition in the context of global biogeocycling.

Applications of Fourier Transform Ion Cyclotron Resonance (FT-ICR) and Orbitrap Based High Resolution Mass Spectrometry in Metabolomics and Lipidomics.

PubMed

Ghaste, Manoj; Mistrik, Robert; Shulaev, Vladimir

2016-05-25

Metabolomics, along with other "omics" approaches, is rapidly becoming one of the major approaches aimed at understanding the organization and dynamics of metabolic networks. Mass spectrometry is often a technique of choice for metabolomics studies due to its high sensitivity, reproducibility and wide dynamic range. High resolution mass spectrometry (HRMS) is a widely practiced technique in analytical and bioanalytical sciences. It offers exceptionally high resolution and the highest degree of structural confirmation. Many metabolomics studies have been conducted using HRMS over the past decade. In this review, we will explore the latest developments in Fourier transform mass spectrometry (FTMS) and Orbitrap based metabolomics technology, its advantages and drawbacks for using in metabolomics and lipidomics studies, and development of novel approaches for processing HRMS data.

Applications of Fourier Transform Ion Cyclotron Resonance (FT-ICR) and Orbitrap Based High Resolution Mass Spectrometry in Metabolomics and Lipidomics

PubMed Central

Ghaste, Manoj; Mistrik, Robert; Shulaev, Vladimir

2016-01-01

Metabolomics, along with other “omics” approaches, is rapidly becoming one of the major approaches aimed at understanding the organization and dynamics of metabolic networks. Mass spectrometry is often a technique of choice for metabolomics studies due to its high sensitivity, reproducibility and wide dynamic range. High resolution mass spectrometry (HRMS) is a widely practiced technique in analytical and bioanalytical sciences. It offers exceptionally high resolution and the highest degree of structural confirmation. Many metabolomics studies have been conducted using HRMS over the past decade. In this review, we will explore the latest developments in Fourier transform mass spectrometry (FTMS) and Orbitrap based metabolomics technology, its advantages and drawbacks for using in metabolomics and lipidomics studies, and development of novel approaches for processing HRMS data. PMID:27231903

Generation and characterization of a distonic biradical anion formed from an enediynone prodrug in the gas phase.

PubMed

Yang, Linan; Bekele, Tefsit; Lipton, Mark A; Kenttämaa, Hilkka I

2013-04-01

A negatively charged biradical intermediate was successfully generated in the gas phase via cyclization of the deprotonated bicyclo[8.3.0]trideca-12-ene-2,7-diyn-1-one precursor. The inherent negative charge of this biradical allows its characterization via collision-activated dissociation and reactions with a variety of neutral substrates in an FT-ICR mass spectrometer. Although the biradical is unreactive toward reagents that usually react rapidly with positively charged biradicals, such as dimethyl disulfide, it reacts with the halogen-containing substrates carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane via bromine or chlorine atom abstraction, which supports its biradical structure. The results presented in this study indicate that cyclizations commonly used in solution to form biradical intermediates from enediyne compounds may also occur in the gas phase.

Generation and Characterization of a Distonic Biradical Anion Formed from an Enediynone Prodrug in the Gas Phase

PubMed Central

Yang, Linan; Bekele, Tefsit; Lipton, Mark A.

2013-01-01

A negatively charged biradical intermediate was successfully generated in the gas phase via cyclization of the deprotonated bicyclo[8.3.0]trideca-12-ene-2,7-diyn-1-one precursor. The inherent negative charge of this biradical allows its characterization via collision-activated dissociation and reactions with a variety of neutral substrates in an FT-ICR mass spectrometer. Although the biradical is unreactive toward reagents that usually react rapidly with positively charged biradicals, such as dimethyl disulfide, it reacts with the halogen-containing substrates carbon tetrachloride, carbon tetrabromide and bromotrichloromethane via bromine or chlorine atom abstraction, which supports its biradical structure. The results presented in this study indicate that cyclizations commonly used in solution to form biradical intermediates from enediyne compounds may also occur in the gas phase. PMID:23512422

Probing peptide fragment ion structures by combining sustained off-resonance collision-induced dissociation and gas-phase H/D exchange (SORI-HDX) in Fourier transform ion-cyclotron resonance (FT-ICR) instruments.

PubMed

Somogyi, Arpád

2008-12-01

The usefulness of gas-phase H/D exchange is demonstrated to probe heterogeneous fragment and parent ion populations. Singly and multiply protonated peptides/proteins were fragmented by using sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The fragments and the surviving precursor ions then all undergo H/D exchange in the gas-phase with either D(2)O or CD(3)OD under the same experimental conditions. Usually, 10 to 60 s of reaction time is adequate to monitor characteristic differences in the H/D exchange kinetic rates. These differences are then correlated to isomeric ion structures. The SORI-HDX method can be used to rapidly test fragment ion structures and provides useful insights into peptide fragmentation mechanisms.

Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

2017-09-01

The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

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Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-29

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Integrated Aero-Servo-Thermo-Propulso-Elasticity (ASTPE) for Hypersonic Scramjet Vehicle Design/Analysis

DTIC Science & Technology

2009-12-04

heat flux q, see Figure 4.6 - Optimized Weights Winitia, = 0.777 Ibm /ft 2, Wfma! = 0.543 Ibm /ft 2 Shown in Table 4.1 are the optimization results...vehicle: no (0), yes (1), or optimize (2) ideriv - Calculate derivatives: no (0), yes (1) itps - If itps is 1, then prepare for tps and smb. ideriv and... itps cannot be 1 at one time ifeedback - If 1, then gets weight and Cg information from SMB and TPSOPT (1) = height set (1), matrix (2) OUTPUT FILE

Is continuous infusion of imipenem always the best choice?

PubMed

Suchánková, Hana; Lipš, Michal; Urbánek, Karel; Neely, Michael N; Strojil, Jan

2017-03-01

Monte Carlo simulations allow prediction and comparison of concentration-time profiles arising from different dosing regimens in a defined population, provided a population pharmacokinetic model has been established. The aims of this study were to evaluate the population pharmacokinetics of imipenem in critically ill patients with hospital-acquired pneumonia (HAP) and to assess the probability of target attainment (PTA) and cumulative fraction of response (CFR) using EUCAST data. A two-compartment model based on a data set of 19 subjects was employed. Various dosage regimens at 0.5-h and 3-h infusion rates and as continuous infusion were evaluated against the pharmacodynamic targets of 20%fT >MIC , 40%fT >MIC and 100%fT >MIC . For the target of 40%fT >MIC , all 0.5-h infusion regimens achieved optimal exposures (CFR ≥ 90%) against Escherichia coli and Staphylococcus aureus, with nearly optimal exposure against Klebsiella pneumoniae (CFR ≥ 89.4%). The 3-h infusions and continuous infusion exceeded 97% CFR against all pathogens with the exception of Pseudomonas aeruginosa and Acinetobacter spp., where the maximum CFRs were 85.5% and 88.4%, respectively. For the 100%fT >MIC target, only continuous infusion was associated with nearly optimal exposures. Higher PTAs for the targets of 40%fT >MIC and 100%fT >MIC were achieved with 3-h infusions and continuous infusion in comparison with 0.5-h infusions; however, continuous infusion carries a risk of not reaching the MIC of less susceptible pathogens in a higher proportion of patients. In critically ill patients with HAP with risk factors for Gram-negative non-fermenting bacteria, maximum doses administered as extended infusions may be necessary. Copyright © 2017 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

Convection from Hemispherical and Conical Model Ice Roughness Elements in Stagnation Region Flows

NASA Technical Reports Server (NTRS)

Hughes, Michael T.; Shannon, Timothy A.; McClain, Stephen T.; Vargas, Mario; Broeren, Andy

2016-01-01

To improve ice accretion prediction codes, more data regarding ice roughness and its effects on convective heat transfer are required. The Vertical Icing Studies Tunnel (VIST) at NASA Glenn Research was used to model realistic ice roughness in the stagnation region of a NACA 0012 airfoil. In the VIST, a test plate representing the leading 2% chord of the airfoil was subjected to flows of 7.62 m/s (25 ft/s), 12.19 m/s (40 ft/s), and 16.76 m/s (55 ft/s). The test plate was fitted with multiple surfaces or sets of roughness panels, each with a different representation of ice roughness. The sets of roughness panels were constructed using two element distribution patterns that were created based on a laser scan of an iced airfoil acquired in the Icing Research Tunnel at NASA Glenn. For both roughness patterns, surfaces were constructed using plastic hemispherical elements, plastic conical elements, and aluminum conical elements. Infrared surface thermometry data from tests run in the VIST were used to calculate area averaged heat transfer coefficient values. The values from the roughness surfaces were compared to the smooth control surface, showing convective enhancement as high as 400% in some cases. The data gathered during this study will ultimately be used to improve the physical modeling in LEWICE or other ice accretion codes and produce predictions of in-flight ice accretion on aircraft surfaces with greater confidence.

The Dornier Wind Tunnel

NASA Technical Reports Server (NTRS)

Schlichting, H

1938-01-01

After completion of the required calibrations, the Dornier open-throat tunnel is now in operation. With an elliptic test section of 3 by 4 m (9.84 by 3.12 ft.), its length is 7 m (22.97 ft.), its maximum horsepower 800, and its maximum air speed 60 m/s (134.2 mph). As to local uniformity of velocity, static pressure as well as jet direction, and turbulence factor, this tunnel is on par with those of the good German and foreign research labs.

Development of Bottom Oil Recovery Systems. Revised

DTIC Science & Technology

2014-02-01

designed a recovery system based on dredging technology. It could handle harsh wind /wave conditions but has significant logistical requirements, due...Knots m/s Meter(s) per second M/T Motor tanker M/V Motor vessel m Meter or meters m2 Square meters m3 Cubic meters MBTA Migratory Bird ...usable for some bottom types. Wind 30 kts (45-kt gusts) Wave 0-2m (0-5ft) Current 0-2 kts Lightning ɝmiles Minimum depth of about 9m (30 ft

Conformational analysis, X-ray crystallographic, FT-IR, FT-Raman, DFT, MEP and molecular docking studies on 1-(1-(3-methoxyphenyl) ethylidene) thiosemicarbazide

NASA Astrophysics Data System (ADS)

Saravanan, R. R.; Seshadri, S.; Gunasekaran, S.; Mendoza-Meroño, R.; Garcia-Granda, S.

2015-03-01

Conformational analysis, X-ray crystallographic, FT-IR, FT-Raman, DFT, MEP and molecular docking studies on 1-(1-(3-methoxyphenyl) ethylidene) thiosemicarbazide (MPET) are investigated. From conformational analysis the examination of the positions of a molecule taken and the energy changes is observed. The docking studies of the ligand MPET with target protein showed that this is a good molecule which docks well with target related to HMG-CoA. Hence MPET can be considered for developing into a potent anti-cholesterol drug. MEP assists in optimization of electrostatic interactions between the protein and the ligand. The MEP surface displays the molecular shape, size and electrostatic potential values. The optimized geometry of the compound was calculated from the DFT-B3LYP gradient calculations employing 6-31G (d, p) basis set and calculated vibrational frequencies are evaluated via comparison with experimental values.

Psychometric properties of the Italian version of the Cognitive Reserve Scale (I-CRS).

PubMed

Altieri, Manuela; Siciliano, Mattia; Pappacena, Simona; Roldán-Tapia, María Dolores; Trojano, Luigi; Santangelo, Gabriella

2018-05-04

The original definition of cognitive reserve (CR) refers to the individual differences in cognitive performance after a brain damage or pathology. Several proxies were proposed to evaluate CR (education, occupational attainment, premorbid IQ, leisure activities). Recently, some scales were developed to measure CR taking into account several cognitively stimulating activities. The aim of this study is to adapt the Cognitive Reserve Scale (I-CRS) for the Italian population and to explore its psychometric properties. I-CRS was administered to 547 healthy participants, ranging from 18 to 89 years old, along with neuropsychological and behavioral scales to evaluate cognitive functioning, depressive symptoms, and apathy. Cronbach's α, corrected item-total correlations, and the inter-item correlation matrix were calculated to evaluate the psychometric properties of the scale. Linear regression analysis was performed to build a correction grid of the I-CRS according to demographic variables. Correlational analyses were performed to explore the relationships between I-CRS and neuropsychological and behavioral scales. We found that age, sex, and education influenced the I-CRS score. Young adults and adults obtained higher I-CRS scores than elderly adults; women and participants with high educational attainment scored higher on I-CRS than men and participants with low education. I-CRS score correlated poorly with cognitive and depression scale scores, but moderately with apathy scale scores. I-CRS showed good psychometric properties and seemed to be a useful tool to assess CR in every adult life stage. Moreover, our findings suggest that apathy rather than depressive symptoms may interfere with the building of CR across the lifespan.

FT-NIR: A Tool for Process Monitoring and More.

PubMed

Martoccia, Domenico; Lutz, Holger; Cohen, Yvan; Jerphagnon, Thomas; Jenelten, Urban

2018-03-30

With ever-increasing pressure to optimize product quality, to reduce cost and to safely increase production output from existing assets, all combined with regular changes in terms of feedstock and operational targets, process monitoring with traditional instruments reaches its limits. One promising answer to these challenges is in-line, real time process analysis with spectroscopic instruments, and above all Fourier-Transform Near Infrared spectroscopy (FT-NIR). Its potential to afford decreased batch cycle times, higher yields, reduced rework and minimized batch variance is presented and application examples in the field of fine chemicals are given. We demonstrate that FT-NIR can be an efficient tool for improved process monitoring and optimization, effective process design and advanced process control.

75 FR 52734 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Cooling...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-27

... Facilities (Renewal), EPA ICR No. 2060.04, OMB Control No. 2040-0257 AGENCY: Environmental Protection Agency...: Cooling Water Intake Structure Phase II Existing Facilities (Renewal). ICR Numbers: EPA ICR No. 2060.04... (EPA ICR No. 2060.03) covers the last 2 years of the permit approval period (i.e., years 4 and 5 after...

Ionic current rectification in organic solutions with quartz nanopipettes.

PubMed

Yin, Xiaohong; Zhang, Shudong; Dong, Yitong; Liu, Shujuan; Gu, Jing; Chen, Ye; Zhang, Xin; Zhang, Xianhao; Shao, Yuanhua

2015-09-01

The study of behaviors of ionic current rectification (ICR) in organic solutions with quartz nanopipettes is reported. ICR can be observed even in organic solutions using quartz pipettes with diameters varied from several to dozens of nanometers, and the direction of ICR is quite different from the ICR observed in aqueous phase. The influences of pore size, electrolyte concentration, and surface charge on the ICR have been investigated carefully. Water in organic solutions affects the direction and extent of ICR significantly. Mechanisms about the formation of an electrical double layer (EDL) on silica in organic solutions with different amount of water have been proposed. An improved method, which can be employed to detect trace water in organic solutions, has been implemented based on Au ultramicroelectrodes with cathodic differential pulse stripping voltammetry.

Reactivity improvement of cellulolytic enzyme lignin via mild hydrothermal modification.

PubMed

Ma, Zhuoming; Tang, Jiafa; Li, Shujun; Suo, Enxiang

2017-12-01

Isolated by the cellulolytic enzyme lignin (CEL) process, water-alcohol (1:1, v/v) was introduced as co-solvent in the process of the hydrothermal treatment. The modification parameters such as reaction temperature and time, solid-to-liquid ratio, and catalysts (NaOH and NaOAlO 2 ) have been investigated in terms of the specific lignin properties, such as the phenolic hydroxyl content (OH phen ), DPPH free radical scavenging rate, and formaldehyde value. The CELs were also characterized by GPC, FT-IR and 1 H NMR spectroscopy, and Py-GC/MS. The key data are under optimal lignin modification conditions (solid-to-liquid ratio of 1:10 (w/v) and a temperature of 250°C for 60min) are: OH phen content: 2.50mmol/g; half maximal inhibitory concentration (IC 50 ) towards DPPH free radicals: 88.2mg/L; formaldehyde value: 446.9g/kg). Both base catalysts decrease the residue rate, but phenol reactivities of the products were also detracted. Py-GC/MS results revealed that modified lignin had a higher phenolic composition than the CEL did, especially the modified lignin without catalyst (ML), which represented 74.51% phenolic content. Copyright © 2017. Published by Elsevier Inc.

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Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-02

... 264, Subpart CC and 40 CFR Part 265). ICR Numbers: EPA ICR Number 1593.08, OMB Control Number 2060... ICR Number 1593.08, OMB Control Number 2060-0318; expiration date October 31, 2010. (6) NESHAP for..., subpart CC and 40 CFR part 265), Docket ID Number: EPA-HQ-OECA-2010-0370, EPA ICR Number 1593.08, OMB...

Motion Path of the Instant Center of Rotation in the Cervical Spine During In Vivo Dynamic Flexion-Extension: Implications for Artificial Disc Design and Evaluation of Motion Quality Following Arthrodesis

PubMed Central

Anderst, William; Baillargeon, Emma; Donaldson, William; Lee, Joon; Kang, James

2013-01-01

Study Design Case-control. Objective To characterize the motion path of the instant center of rotation (ICR) at each cervical motion segment from C2 to C7 during dynamic flexion-extension in asymptomatic subjects. To compare asymptomatic and single-level arthrodesis patient ICR paths. Summary of Background Data The ICR has been proposed as an alternative to range of motion (ROM) for evaluating the quality of spine movement and for identifying abnormal midrange kinematics. The motion path of the ICR during dynamic motion has not been reported. Methods 20 asymptomatic controls, 12 C5/C6 and 5 C6/C7 arthrodesis patients performed full ROM flexion-extension while biplane radiographs were collected at 30 Hz. A previously validated tracking process determined three-dimensional vertebral position with sub-millimeter accuracy. The finite helical axis method was used to calculate the ICR between adjacent vertebrae. A linear mixed-model analysis identified differences in the ICR path among motion segments and between controls and arthrodesis patients. Results From C2/C3 to C6/C7, the mean ICR location moved superior for each successive motion segment (p < .001). The AP change in ICR location per degree of flexion-extension decreased from the C2/C3 motion segment to the C6/C7 motion segment (p < .001). Asymptomatic subject variability (95% CI) in the ICR location averaged ±1.2 mm in the SI direction and ±1.9 mm in the AP direction over all motion segments and flexion-extension angles. Asymptomatic and arthrodesis groups were not significantly different in terms of average ICR position (all p ≥ .091) or in terms of the change in ICR location per degree of flexion-extension (all p ≥ .249). Conclusions To replicate asymptomatic in vivo cervical motion, disc replacements should account for level-specific differences in the location and motion path of ICR. Single-level anterior arthrodesis does not appear to affect cervical motion quality during flexion-extension. PMID:23429677

DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

NASA Astrophysics Data System (ADS)

Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

2018-05-01

The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

Structural Characterization of Core Region in Erwinia amylovora Lipopolysaccharide.

PubMed

Casillo, Angela; Ziaco, Marcello; Lindner, Buko; Merino, Susana; Mendoza-Barberá, Elena; Tomás, Juan M; Corsaro, Maria Michela

2017-03-04

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

Quantitative OCT-based longitudinal evaluation of intracorneal ring segment implantation in keratoconus.

PubMed

Pérez-Merino, Pablo; Ortiz, Sergio; Alejandre, Nicolas; Jiménez-Alfaro, Ignacio; Marcos, Susana

2013-09-09

To characterize the geometrical properties of keratoconic corneas upon intracorneal ring segments (ICRS) implantation, using custom-developed optical coherence tomography (OCT). Ten keratoconic corneas were measured pre- and post-ICRS surgery (7, 30, and 90 days). Corneal topographic and pachymetric maps were obtained from three-dimensional (3D) images acquired with OCT, provided with custom algorithms for image analysis, distortion correction, and quantification. The 3D positioning of the ICRS was also estimated longitudinally, relative to the pupil center and iris plane. Preoperatively, the average corneal radii of curvature were 7.02 ± 0.54 mm (anterior) and 5.40 ± 0.77 mm (posterior), and the minimum corneal thickness was 384 ± 60 μm. At 90 days, the average corneal radii of curvature were 7.26 ± 0.53 mm (anterior) and 5.44 ± 0.71 mm (posterior), and the minimum corneal thickness was 396 ± 46 μm. ICRS implantation produced a significant decrease of corneal power (by 1.71 ± 1.83 diopters [D] at 90 days). Corneal irregularities (defined by high order Zernike terms of the corneal elevation maps) and the corneal thickness distribution decreased in some patients and increased in others. The 3D ICRS depth matched the planned ICRS depth well (within 23.93 ± 23.49 μm). On average, ICRS showed an overall tilt of -6.8 ± 2.6° (temporal) and -2.1 ± 0.8° (superior) at 7 days. Spectral OCT (sOCT) provided with distortion correction and analysis tools, is an excellent instrument for evaluating the changes produced by ICRS in keratoconic corneas, and for analyzing the 3D ICRS position during the follow up. ICRS produced flattening on the anterior corneal surface, although the benefit for corneal surface regularization varied across patients.

Quantitative DNA methylation analysis improves epigenotype-phenotype correlations in Beckwith-Wiedemann syndrome

PubMed Central

Calvello, Mariarosaria; Tabano, Silvia; Colapietro, Patrizia; Maitz, Silvia; Pansa, Alessandra; Augello, Claudia; Lalatta, Faustina; Gentilin, Barbara; Spreafico, Filippo; Calzari, Luciano; Perotti, Daniela; Larizza, Lidia; Russo, Silvia; Selicorni, Angelo; Sirchia, Silvia M; Miozzo, Monica

2013-01-01

Beckwith-Wiedemann syndrome (BWS) is a rare disorder characterized by overgrowth and predisposition to embryonal tumors. BWS is caused by various epigenetic and/or genetic alterations that dysregulate the imprinted genes on chromosome region 11p15.5. Molecular analysis is required to reinforce the clinical diagnosis of BWS and to identify BWS patients with cancer susceptibility. This is particularly crucial prenatally because most signs of BWS cannot be recognized in utero. We established a reliable molecular assay by pyrosequencing to quantitatively evaluate the methylation profiles of ICR1 and ICR2. We explored epigenotype-phenotype correlations in 19 patients that fulfilled the clinical diagnostic criteria for BWS, 22 patients with suspected BWS, and three fetuses with omphalocele. Abnormal methylation was observed in one prenatal case and 19 postnatal cases, including seven suspected BWS. Seven cases showed ICR1 hypermethylation, five cases showed ICR2 hypomethylation, and eight cases showed abnormal methylation of ICR1 and ICR2 indicating paternal uniparental disomy (UPD). More cases of ICR1 alterations and UPD were found than expected. This is likely due to the sensitivity of this approach, which can detect slight deviations in methylation from normal levels. There was a significant correlation (p < 0.001) between the percentage of ICR1 methylation and BWS features: severe hypermethylation (range: 75–86%) was associated with macroglossia, macrosomia, and visceromegaly, whereas mild hypermethylation (range: 55–59%) was associated with umbilical hernia and diastasis recti. Evaluation of ICR1 and ICR2 methylation by pyrosequencing in BWS can improve epigenotype-phenotype correlations, detection of methylation alterations in suspected cases, and identification of UPD. PMID:23917791

Invasive cervical resorption following orthodontic treatment: Two cases involving the same patient.

PubMed

Yoshpe, Margarita; Kaufman, Arieh; Lin, Shaul; Gabay, Eran; Einy, Shmuel

2016-01-01

Invasive cervical resorption (ICR), a destructive form of external root resorption, is characterized by invasion of the fibrovascular tissue. This phenomenon is very rare and appears in 0.02% of the general population where the leading factors are orthodontics in addition to trauma, restorations, and bleaching. Heavy orthodontic force may increase the incidence to 1%. One of the main concerns regarding ICR is that it is often misdiagnosed with conventional diagnostic tools. In recent decades, a cone beam computed tomography (CBCT) imaging technique has become more common and can lead to a more accurate diagnosis and treatment plan. This case report describes a possible association between orthodontic treatment and ICR of a 14-year-old male, 18 months post orthodontic treatment. ICR in the mandibular right canine was diagnosed and verified by CBCT, and underwent combined endodontic-periodontal treatment. However, after orthodontic forced eruption was performed on this tooth to improve the bone defect, ICR was diagnosed on the mandibular right second premolar. The possible association between orthodontic treatment and ICR is discussed, as ICR was noted following orthodontic treatment on both occasions. This case report stresses the importance of ICR early detection by close attention to periodic radiographic checkups during orthodontic treatment. The use of modern diagnostic tools is highly recommended in suspicious cases. A case is described in which the patient underwent two types of orthodontic treatment in the mandible at different time periods and developed ICR in two different teeth.

Quantum mechanical, spectroscopic study (FT-IR and FT - Raman), NBO analysis, HOMO-LUMO, first order hyperpolarizability and docking studies of a non-steroidal anti-inflammatory compound

NASA Astrophysics Data System (ADS)

Sakthivel, S.; Alagesan, T.; Muthu, S.; Abraham, Christina Susan; Geetha, E.

2018-03-01

Experimental and theoretical studies on the optimized geometrical structure, electronic and vibrational characteristics of (+)-(S)-2-(6-methoxynaphthalen-2-yl) propanoic acid are presented employing B3LYP/6-311++G (d,p) basis set. Simulated FT-IR and FT-Raman spectra were in concurrence with the observed spectra attained in a spectral range of FT-IR (4000 - 400 cm-1) and FT-Raman (4000 - 100 cm-1). Quantum chemical calculations and the comprehensive vibrational assignments of wavenumbers of the optimized geometry using Potential Energy Distribution (PED) were calculated with scaled quantum mechanics. The infrared intensities and Raman intensities of (+)-(S)-2-(6-methoxynaphthalen-2-yl) propanoic acid were reported. Frontier molecular orbital analysis and reactivity parameters were calculated. Molecular Electrostatic Potential (MEP), Natural Bond Orbital (NBO) analysis, Non Linear Optical (NLO) behavior and thermodynamic properties were studied. In addition, the Mulliken charge distribution and Fukui function were analyzed. Molecular docking was used to dock in the title molecule into the active site of the protein 5L9B which belongs to the class of proteins exhibiting the property as a HIF1A (Hypoxia-inducible factor 1-alpha) expression inhibitor and the minimum binding energy was detected to be -6.2 kcal/mol.

Spectroscopic (FT-IR, FT-Raman, NMR and UV-Visible) and quantum chemical studies of molecular geometry, Frontier molecular orbital, NLO, NBO and thermodynamic properties of salicylic acid.

PubMed

Suresh, S; Gunasekaran, S; Srinivasan, S

2014-11-11

The solid phase FT-IR and FT-Raman spectra of 2-hydroxybenzoic acid (salicylic acid) have been recorded in the region 4000-400 and 4000-100 cm(-1) respectively. The optimized molecular geometry and fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method and a comparative study between Hartree Fork (HF) method at 6-311++G(d,p) level basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimentally obtained FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated potential energy distribution (PED). The time dependent DFT method is employed to predict its absorption energy and oscillator strength. The linear polarizability (α) and the first order hyper polarizability (β) values of the investigated molecule have been computed. The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) are also performed. Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Published by Elsevier B.V.

STS-37 MS Jerome Apt during water egress exercise in JSC's WETF Bldg 29

NASA Technical Reports Server (NTRS)

1990-01-01

STS-37 Mission Specialist (MS) Jerome Apt, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above pool via a parachute harness during water egress exercises in JSC's Weightless Environment Training Facility (WETF) Bldg 29. Apt simulates emergency egress from a Space Shuttle. The WETF's 25-ft pool served as a simulated ocean into which a parachute landing might be made.

STS-39 MS Hieb prepares for emergency egress exercises in JSC's WETF Bldg 29

NASA Technical Reports Server (NTRS)

1990-01-01

STS-39 Mission Specialist (MS) Richard J. Hieb, wearing launch and entry suit (LES), parachute pack, and communications carrier assembly (CCA), listens to instructions prior to emergency egress bailout exercises in JSC's Weightless Environment Training Facility (WETF) Bldg 29. The WETF's 25 ft deep pool will simulate the ocean. Crewmembers will practice procedures necessary in the event of an emergency onboard the Space Shuttle requiring a water landing.

STS-37 MS Linda M. Godwin during water egress exercise in JSC's WETF Bldg 29

NASA Technical Reports Server (NTRS)

1990-01-01

STS-37 Mission Specialist (MS) Linda M. Godwin, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above pool via a parachute harness during water egress exercises in JSC's Weightless Environment Training Facility (WETF) Bldg 29. Godwin simulates emergency egress from a Space Shuttle. The WETF's 25-ft pool served as a simulated ocean into which a parachute landing might be made.

Distinct human α(1,3)-fucosyltransferases drive Lewis-X/sialyl Lewis-X assembly in human cells.

PubMed

Mondal, Nandini; Dykstra, Brad; Lee, Jungmin; Ashline, David J; Reinhold, Vernon N; Rossi, Derrick J; Sackstein, Robert

2018-05-11

In humans, six α(1,3)-fucosyltransferases (α(1,3)-FTs: FT3/FT4/FT5/FT6/FT7/FT9) reportedly fucosylate terminal lactosaminyl glycans yielding Lewis-X (Le X ; CD15) and/or sialyl Lewis-X (sLe X ; CD15s), structures that play key functions in cell migration, development, and immunity. Prior studies analyzing α(1,3)-FT specificities utilized either purified and/or recombinant enzymes to modify synthetic substrates under nonphysiological reaction conditions or molecular biology approaches wherein α(1,3)-FTs were expressed in mammalian cell lines, notably excluding investigations using primary human cells. Accordingly, although significant insights into α(1,3)-FT catalytic properties have been obtained, uncertainty persists regarding their human Le X /sLe X biosynthetic range across various glycoconjugates. Here, we undertook a comprehensive evaluation of the lactosaminyl product specificities of intracellularly expressed α(1,3)-FTs using a clinically relevant primary human cell type, mesenchymal stem cells. Cells were transfected with modified mRNA encoding each human α(1,3)-FT, and the resultant α(1,3)-fucosylated lactosaminyl glycoconjugates were analyzed using a combination of flow cytometry and MS. The data show that biosynthesis of sLe X is driven by FTs-3, -5, -6, and -7, with FT6 and FT7 having highest potency. FT4 and FT9 dominantly biosynthesize Le X , and, among all FTs, FT6 holds a unique capacity in creating sLe X and Le X determinants across protein and lipid glycoconjugates. Surprisingly, FT4 does not generate sLe X on glycolipids, and neither FT4, FT6, nor FT9 synthesizes the internally fucosylated sialyllactosamine VIM-2 (CD65s). These results unveil the relevant human lactosaminyl glycans created by human α(1,3)-FTs, providing novel insights on how these isoenzymes stereoselectively shape biosynthesis of vital glycoconjugates, thereby biochemically programming human cell migration and tuning human immunologic and developmental processes. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Definitive screening design enables optimization of LC-ESI-MS/MS parameters in proteomics.

PubMed

Aburaya, Shunsuke; Aoki, Wataru; Minakuchi, Hiroyoshi; Ueda, Mitsuyoshi

2017-12-01

In proteomics, more than 100,000 peptides are generated from the digestion of human cell lysates. Proteome samples have a broad dynamic range in protein abundance; therefore, it is critical to optimize various parameters of LC-ESI-MS/MS to comprehensively identify these peptides. However, there are many parameters for LC-ESI-MS/MS analysis. In this study, we applied definitive screening design to simultaneously optimize 14 parameters in the operation of monolithic capillary LC-ESI-MS/MS to increase the number of identified proteins and/or the average peak area of MS1. The simultaneous optimization enabled the determination of two-factor interactions between LC and MS. Finally, we found two parameter sets of monolithic capillary LC-ESI-MS/MS that increased the number of identified proteins by 8.1% or the average peak area of MS1 by 67%. The definitive screening design would be highly useful for high-throughput analysis of the best parameter set in LC-ESI-MS/MS systems.

75 FR 43970 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-27

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2013-01-02

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Subsurface Conditions at Site 16 Lone Star Army Ammunition Plant, Texas

DTIC Science & Technology

1989-04-01

fully acceptable or appropriate. . . 35 . The intercepts of three st-faces with borings were analyzed to establish any inclinatio- fot comparison to...conspicuously steeper slope. 38. In descending southeastward, the ground water loses more than 13 ft of head in a horizontal distance of only about 35 ft...Extractables CLSS13*6- Vol. organic 24 CLSS13*5-N Metals 6.3 90 26 35 -7 CLSS 13*5-S Sulf ides CLSS13*5-MS Extractables CLSS13*5- Vol. organic 25 CLSS13*4-N

Fleet Mix Planning in the U.S. Coast Guard: Issues and Challenges for DSS

DTIC Science & Technology

1991-10-28

Dean of Research REPORT DOCUMENTATION PAGE Wo,,Odo,,od Pui reprtig bLden fr * a co&3n o .r~in, i estimated to aeae 1 h=r per response REWki ft bus...or any 8er a . cmde d ft on ot fflornm idud gaiggms~c redcxng tuis burden. Io Wast wgon Head*ms Serviow ,e c. D fornirtomahon O m and Report...AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING/MONITORING AGENCY REPORT NUMBER Naval Postgraduate School Monterey, Ca 93943 N/ A 1 1. SUPPLEMENTARY NOTES

Optimization of antioxidant and antiglycated activities of polysaccharides from Arthrocnemum indicum leaves.

PubMed

Mzoughi, Zeineb; Chaouch, Mohamed Aymen; Hammi, Khaoula Mkadmini; Hafsa, Jawhar; Le Cerf, Didier; Ksouri, Riadh; Majdoub, Hatem

2018-07-01

Central composite design was performed to optimize uronic acid rate, esterification degree, total antioxidant ability and antiglycation capacity of carbohydrates from Arthrocnemum indicum leaves. Three independent variables were opted: extraction temperature, time and ratio (solvent/material). The optimal settings were: extraction temperature of 80°C, time of 288min and (solvent/solid) ratio of 40mL/g. Under these settings, uronic acid rate and esterification degree were 49.29%, 30.24%, respectively, whereas total antioxidant activity and antiglycation capacity was 35.81mg ascorbic acid equivalents/g matter and 69.81%, respectively. Colorimetric assays showed that total sugar and uronic acid contents for polysaccharide were 71.78% and 49.24%, respectively. Furthermore, Preliminary structure study was performed via various methods including FT-IR, NMR and UV-vis analysis. SEC analyzes revealed that polysaccharide had an average molecular weight of 2179kDa. Moreover, GC-MS analyzes showed that extracted polysaccharide was a pectic polysaccharide which formed of arabinose, mannose, galactose, rhamnose, glucose and xylose in the molar percentage of 66.68%, 3.93%, 12.71%, 6.31%, 6.08% and 4.29%, respectively. This results revealed that extracted polysaccharide can be employed as source of natural antioxidants and as possible antiglycated agents. Copyright © 2018 Elsevier B.V. All rights reserved.

Gas-phase cationic benzoylation of ambient aromatic substrates studied with the decay technique

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

Occhiucci, G.; Cacace, F.; Speranza, M.

1986-03-05

The gas-phase benzoylation of typical ambient aromatic substrates PhY (Y = OH, OMe, and NH/sub 2/) has been investigated by a combination of the decay technique and of FT ICR mass spectrometry. Labeled phenylium ions, C/sub 6/X/sub 5//sup +/ (X = H and T), from the decay of multiply tritiated benzene, C/sub 6/X/sub 6/, have been allowed to react with excess CO-containing traces of PhY (Y = OH, OMe, and NH/sub 2/), in the pressure range from 90 to 650 torr. Radio GLC and HPLC of the tritiated products demonstrate two competitive reaction channels, i.e., phenylation and benzoylation of themore » aromatic substrates. The results indicate a sharp kinetic bias of the gaseous phenylium ions for the aromatic substrates, measured by an apparent k/sub CO//k/sub PhY/ ratio of 0.12 (Y = OH), 0.13 (Y = OMe), and 0.04 (Y = NH/sub 2/) in the systems at nearly atmospheric pressure. Gas-phase benzoylation displays a high intramolecular selectivity, occurring exclusively at the n-type center of PhOH and PhNH/sub 2/. In the case of PhOMe, appreciable ring benzoylation is observed, characterized by a remarkably high (up to 30:1) bias for the para position. The mechanistic features of the gas-phase benzoylation and phenylation processes, deduced from the decay and the ICR experiments, are discussed and compared with those of related aromatic acylation and alkylation reactions occurring in the dilute gas state. 30 references, 2 tables.« less

Synthesis, structural characterization and theoretical studies of a new Schiff base 4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl) imino)methyl)phenol

NASA Astrophysics Data System (ADS)

Cuenú, Fernando; Londoño-Salazar, Jennifer; Torres, John Eduard; Abonia, Rodrigo; D'Vries, Richard F.

2018-01-01

4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl)imino)methyl)phenol (4-OHFPz) was synthesized and characterized by FT-IR, MS, NMR, and single-crystal X-ray diffraction. Optimization of molecular geometry, vibrational frequencies, and chemical shifts were calculated by using the methods of density functional theory (DFT) with B3LYP and B3PW91 as functionals and Hartree-Fock with 6-311G++(d,p) as basis set using the GAUSSIAN 09 program package. With the VEDA 4 software, the vibrational frequencies were assigned in terms of the potential energy distribution (PED). The equilibrium geometries calculated by all methods were compared with X-ray diffraction results, indicating that the theoretical results matches well with the experimental ones. The data obtained from the vibrational analysis and the calculated NMR are consistent with the experimental spectra.

V/STOL model fan stage rig design report

NASA Technical Reports Server (NTRS)

Cheatham, J. G.; Creason, T. L.

1983-01-01

A model single-stage fan with variable inlet guide vanes (VIGV) was designed to demonstrate efficient point operation while providing flow and pressure ratio modulation capability required for a V/STOL propulsion system. The fan stage incorporates a split-flap VIGV with an independently actuated ID flap to permit independent modulation of fan and core engine airstreams, a flow splitter integrally designed into the blade and vanes to completely segregate fan and core airstreams in order to maximize core stream supercharging for V/STOL operation, and an EGV with a variable leading edge fan flap for rig performance optimization. The stage was designed for a maximum flow size of 37.4 kg/s (82.3 lb/s) for compatibility with LeRC test facility requirements. Design values at maximum flow for blade tip velocity and stage pressure ratio are 472 m/s (1550 ft/s) and 1.68, respectively.

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Design Sensitivity for a Subsonic Aircraft Predicted by Neural Network and Regression Models

NASA Technical Reports Server (NTRS)

Hopkins, Dale A.; Patnaik, Surya N.

2005-01-01

A preliminary methodology was obtained for the design optimization of a subsonic aircraft by coupling NASA Langley Research Center s Flight Optimization System (FLOPS) with NASA Glenn Research Center s design optimization testbed (COMETBOARDS with regression and neural network analysis approximators). The aircraft modeled can carry 200 passengers at a cruise speed of Mach 0.85 over a range of 2500 n mi and can operate on standard 6000-ft takeoff and landing runways. The design simulation was extended to evaluate the optimal airframe and engine parameters for the subsonic aircraft to operate on nonstandard runways. Regression and neural network approximators were used to examine aircraft operation on runways ranging in length from 4500 to 7500 ft.

Validation of ATR FT-IR to identify polymers of plastic marine debris, including those ingested by marine organisms.

PubMed

Jung, Melissa R; Horgen, F David; Orski, Sara V; Rodriguez C, Viviana; Beers, Kathryn L; Balazs, George H; Jones, T Todd; Work, Thierry M; Brignac, Kayla C; Royer, Sarah-Jeanne; Hyrenbach, K David; Jensen, Brenda A; Lynch, Jennifer M

2018-02-01

Polymer identification of plastic marine debris can help identify its sources, degradation, and fate. We optimized and validated a fast, simple, and accessible technique, attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR), to identify polymers contained in plastic ingested by sea turtles. Spectra of consumer good items with known resin identification codes #1-6 and several #7 plastics were compared to standard and raw manufactured polymers. High temperature size exclusion chromatography measurements confirmed ATR FT-IR could differentiate these polymers. High-density (HDPE) and low-density polyethylene (LDPE) discrimination is challenging but a clear step-by-step guide is provided that identified 78% of ingested PE samples. The optimal cleaning methods consisted of wiping ingested pieces with water or cutting. Of 828 ingested plastics pieces from 50 Pacific sea turtles, 96% were identified by ATR FT-IR as HDPE, LDPE, unknown PE, polypropylene (PP), PE and PP mixtures, polystyrene, polyvinyl chloride, and nylon. Published by Elsevier Ltd.

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Microbiology neutralization of zearalenone using Lactococcus lactis and Bifidobacterium sp.

PubMed

Król, A; Pomastowski, P; Rafińska, K; Railean-Plugaru, V; Walczak, J; Buszewski, B

2018-01-01

The aim of the study was to neutralize zearalenone by lactic acid bacteria (LAB) such as Lactococcus lactis and Bifidobacterium sp. and investigate the mechanism of zearalenone (ZEA) binding. Neutralization of ZEA by LAB was confirmed by identification of binding kinetics and spectroscopic studies such as Fourier transform infrared spectroscopy (FT-IR) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The obtained results showed that the kinetic process of zearalenone binding to L. lactis is not homogeneous but is expressed with an initial rapid stage with about 90% of ZEA biosorption and with a much slower second step. In case of Bifidobacterium sp., the neutralization process is homogeneous; the main stage can be described with about 88% of ZEA biosorption. MALDI-TOF-MS measurements and FTIR analysis confirmed the uptake of zearalenone molecules by bacterial species. Moreover, the assessment of dead and live lactic acid bacteria cells after zearalenone treatment was performed using fluorescence microscopy. Graphical abstract Microbiology neutralization of zearalenone using Lactococcus lactis and Bifidobacterium sp. was confirmed by identification of binding kinetics and spectroscopic studies such as FT-IR spectroscopy and MALDI-TOF-MS spectrometry. The mechanism of ZEA binding was also investigated.

Invasive cervical resorption and the oro-facial cleft patient: a review and case series.

PubMed

O'Mahony, A; McNamara, C; Ireland, A; Sandy, J; Puryer, J

2017-05-12

Introduction Invasive cervical resorption (ICR) has an unknown aetiology, yet it exhibits very aggressive behaviour compared with typical external root resorption, posing a high risk of tooth loss.Aim To investigate the number of patients at the Dublin Cleft Prosthodontic Department with an oro-facial cleft who experienced ICR and to identify any possible aetiological factors.Materials and method A retrospective investigation of all oro-facial cleft patients treated at the Dublin Cleft Prosthodontic Department, St James's Hospital, Dublin. All patients' clinical and radiological records were reviewed. Patients where tooth loss became inevitable due to Class 4 ICR were analysed.Results From 588 oro-facial cleft patients, 14 (2.38%) patients with ICR were identified. Of these eight (57%) were female and six (43%) were male. Mean age at diagnosis was 28 years (range = 16-49 years). Cleft type: six (42.1%) unilateral cleft lip and palate, eight (57.9%) bilateral cleft lip and palate. Seventeen ICR affected teeth in total, with eleven (65%) maxillary central incisors, two (12%) maxillary lateral incisors, four (23%) maxillary canines, and one (7%) central, lateral and canine affected. Some, (N = 10, 71.4%) presented with ICR resulting in immediate tooth loss. Other patients (N = 4, 28.6%) developed ICR during or following prosthodontic treatment at the Cleft Centre. Tooth loss for this cohort, though not immediate, was inevitable. All had undergone fixed orthodontic appliance treatment and twelve had received dento-alveolar bone grafts. A number (N = 7, 50%) had undergone osteotomy, two (14%) had received night guard vital dental whitening and one had a history of trauma.Conclusions ICR, given its aggressive nature and ill-understood aetiology, poses significant treatment challenges. The most severe form of ICR (Class 4) leads inevitably to tooth loss. The slow-moderate progression of ICR may explain the late presentation found in this study, reinforcing the importance of long-term follow-up of this special dental care group.

STS-52 MS Jemison, in LES/LEH, during JSC WETF bailout exercise

NASA Technical Reports Server (NTRS)

1992-01-01

STS-52 Columbia, Orbiter Vehicle (OV) 102, Mission Specialist (MS) Tamara E. Jernigan, wearing launch and entry suit (LES) and launch and entry helmet (LEH), listens to a briefing about water landings during an emergency egress (bailout) training exercise in JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool. Jernigan waits her turn to be dropped into the WETF's 25-ft deep pool which will simulate the ocean during of her water landing.

STS-37 Mission Specialist (MS) Godwin floating in life raft in JSC WETF pool

NASA Technical Reports Server (NTRS)

1990-01-01

STS-37 Mission Specialist (MS) Linda M. Godwin, wearing launch and entry suit (LES) and launch and entry helmet (LEH), floats in a one-person life raft during a training session in JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool. She was simulating steps involved in emergency egress from a Space Shuttle. The WETF's 25-ft deep pool served as a simulated ocean into which a parachute landing might be made.

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Examinations of the matrix isolation fourier transform infrared spectra of organic compounds: Part XII

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

Coleman, W. M., III; Gordon, B. M.; Lawrence, B. M.

1989-02-01

Matrix isolation Fourier transform infrared spectra (MI/FT-IR), massspectra (MS), carbon-13 Nuclear Magnetic Resonance (/sup 13/C-NMR) spectra,condensed-phase infrared spectra, and vapor-phase infrared (IR)spectra are presented for a series of terpene compounds. Subtle differencesin positional and configurational isomers commonly found withterpenes could be easily detected by the MI/FT-IR spectra. The resultsare comparable in some aspects to those obtainable from /sup 13/C-NMR andthin-film IR; however, most importantly, they are acquired at the lownanogram level for MI/FT-IR, as compared to the milligram level forthe other techniques. These results represent an advance in the technologyavailable for the analysis of complex mixtures such as essential oilscontainingmore » terpene-like molecules.« less

Isopropanolic black cohosh extract and recurrence-free survival after breast cancer.

PubMed

Henneicke-von Zepelin, H H; Meden, H; Kostev, K; Schröder-Bernhardi, D; Stammwitz, U; Becher, H

2007-03-01

To investigate the influence of an isopropanolic Cimicifuga racemosa extract (iCR) on recurrence-free survival after breast cancer, including estrogen-dependent tumors. This pharmacoepidemiologic observational retrospective cohort study examined breast cancer patients treated at general, gynecological and internal facilities linked to a medical database in Germany. The main endpoint was disease-free survival following a diagnosis of breast cancer. The impact of treatment with iCR following diagnosis was analyzed by Cox-proportional hazards models, controlling for age and other confounders. Of 18,861 patients, a total of 1,102 had received an iCR therapy. The mean overall observation time was 3.6 years. Results showed that iCR was not associated with an increase in the risk of recurrence but associated with prolonged disease-free survival. After 2 years following initial diagnosis, 14% of the control group had developed a recurrence, while the iCR group reached this proportion after 6.5 years. The primary Cox regression model controlling for age, tamoxifen use and other confounders demonstrated a protractive effect of iCR on the rate of recurrence (hazard ratio 0.83, 95% confidence interval 0.69 0.99). This effect remained consistent throughout all variations of the statistical model, including subgroup analyses. TNM status was unknown but did not bias the iCR treatment decision as investigated separately. Hence, it was assumed to be equally distributed between treatment groups. Correlation analyses showed good internal and external validity of the database. An increase in the risk of breast cancer recurrence for women having had iCR treatment, compared to women not treated with iCR is unlikely.

Defining ICR-Mo, an intrinsic colistin resistance determinant from Moraxella osloensis.

PubMed

Wei, Wenhui; Srinivas, Swaminath; Lin, Jingxia; Tang, Zichen; Wang, Shihua; Ullah, Saif; Kota, Vishnu Goutham; Feng, Youjun

2018-05-14

Polymyxin is the last line of defense against severe infections caused by carbapenem-resistant gram-negative pathogens. The emergence of transferable MCR-1/2 polymyxin resistance greatly challenges the renewed interest in colistin (polymyxin E) for clinical treatments. Recent studies have suggested that Moraxella species are a putative reservoir for MCR-1/2 genetic determinants. Here, we report the functional definition of ICR-Mo from M. osloensis, a chromosomally encoded determinant of colistin resistance, in close relation to current MCR-1/2 family. ICR-Mo transmembrane protein was prepared and purified to homogeneity. Taken along with an in vitro enzymatic detection, MALDI-TOF mass spectrometry of bacterial lipid A pools determined that the ICR-Mo enzyme might exploit a possible "ping-pong" mechanism to accept the phosphoethanolamine (PEA) moiety from its donor phosphatidylethanolamine (PE) and then transfer it to the 1(or 4')-phosphate position of lipid A via an ICR-Mo-bound PEA adduct. Structural decoration of LPS-lipid A by ICR-Mo renders the recipient strain of E. coli resistant to polymyxin. Domain swapping assays indicate that the two domains of ICR-Mo cannot be functionally-exchanged with its counterparts in MCR-1/2 and EptA, validating its phylogenetic position in a distinct set of MCR-like genes. Structure-guided functional mapping of ICR-Mo reveals a PE lipid substrate recognizing cavity having a role in enzymatic catalysis and the resultant conference of antibiotic resistance. Expression of icr-Mo in E. coli significantly prevents the formation of reactive oxygen species (ROS) induced by colistin. Taken together, our results define a member of a group of intrinsic colistin resistance genes phylogenetically close to the MCR-1/2 family, highlighting the evolution of transferable colistin resistance.

Idiopathic condylar resorption: The current understanding in diagnosis and treatment

PubMed Central

Young, Andrew

2017-01-01

Idiopathic condylar resorption (ICR) is a condition with no known cause, which manifests as progressive malocclusion, esthetic changes, and often pain. Cone-beam computed tomography and magnetic resonance imaging are the most valuable imaging methods for diagnosis and tracking, compared to the less complete and more distorted images provided by panoramic radiographs, and the higher radiation of 99mtechnetium-methylene diphosphonate. ICR has findings that overlap with osteoarthritis, inflammatory arthritis, physiologic resorption/remodeling, congenital disorders affecting the mandible, requiring thorough image analysis, physical examination, and history-taking. Correct diagnosis and determination of whether the ICR is active or inactive are essential when orthodontic or prosthodontic treatment is anticipated as active ICR can undo those treatments. Several treatments for ICR have been reported with the goals of either halting the progression of ICR or correcting the deformities that it caused. These treatments have varying degrees of success and adverse effects, but the rarity of the condition prevents any evidence-based recommendations. PMID:28584413

The characterization of natural gemstones using non-invasive FT-IR spectroscopy: New data on tourmalines.

PubMed

Mercurio, Mariano; Rossi, Manuela; Izzo, Francesco; Cappelletti, Piergiulio; Germinario, Chiara; Grifa, Celestino; Petrelli, Maurizio; Vergara, Alessandro; Langella, Alessio

2018-02-01

Fourteen samples of tourmaline from the Real Museo Mineralogico of Federico II University (Naples) have been characterized through multi-methodological investigations (EMPA-WDS, SEM-EDS, LA-ICP-MS, and FT-IR spectroscopy). The samples show different size, morphology and color, and are often associated with other minerals. Data on major and minor elements allowed to identify and classify tourmalines as follows: elbaites, tsilaisite, schorl, dravites, uvites and rossmanite. Non-invasive, non-destructive FT-IR and in-situ analyses were carried out on the same samples to validate this chemically-based identification and classification. The results of this research show that a complete characterization of this mineral species, usually time-consuming and expensive, can be successfully achieved through non-destructive FT-IR technique, thus representing a reliable tool for a fast classification extremely useful to plan further analytical strategies, as well as to support gemological appraisals. Copyright © 2017 Elsevier B.V. All rights reserved.

Performance and noise of a low pressure ratio variable pitch fan designed for general aviation applications. [Langley 30 x 60 Tunnel

NASA Technical Reports Server (NTRS)

Metzger, F. B.; Menthe, R. W.; Mccolgan, C. J.

1980-01-01

A limited study has been conducted to establish the performance and noise characteristics of a low design tip speed (168 m/s, 550 ft/sec) low pressure ratio (1.04) variable pitch fan which was tested in the Langley 30 X 60 tunnel. This fan was designed for minimum noise when installed in the tail mount location of a twin engine aircraft which normally has both nose and tail mounted propulsors. Measurements showed the fan noise to be very close to predictions made during the design of the fan and extremely low in level (65 dBA at 1000 ft) with no acoustic treatment. This is about 8 dB lower than the unshrouded 2 blade propeller normally used in this installation. On the basis of tests conducted during this program, it appears that this level could be further reduced by 2 dBA if optimized acoustic treatments were installed in the fan duct. Even the best of the shrouded propellers tested previously were 7 dB higher in level than the Q-Fan without acoustic treatment. It was found that the cruise performance of this fan was within 5% of the predicted efficiency of 72%. Evaluation of the performance data indicated that disturbances in the inflow to the fan were the probable cause of the reduced performance.

77 FR 37899 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

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2012-06-25

... Large Household and Commercial Appliances (Renewal) AGENCY: Environmental Protection Agency (EPA... Commercial Appliances (Renewal). ICR Numbers: EPA ICR Number 1954.05, OMB Control Number 2060-0457. ICR... household and commercial appliances facilities. Estimated Number of Respondents: 102. Frequency of Response...

ENVIRONMENTAL ANALYSIS BY AB INITIO QUANTUM MECHANICAL COMPUTATION AND GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED SPECTROMETRY.

EPA Science Inventory

Computational chemistry, in conjunction with gas chromatography/mass spectrometry/Fourier transform infrared spectrometry (GC/MS/FT-IR), was used to tentatively identify seven tetrachlorobutadiene (TCBD) isomers detected in an environmental sample. Computation of the TCBD infrare...

In-flight cabin smoke control.

PubMed

Eklund, T I

1996-12-31

Fatal accidents originating from in-flight cabin fires comprise only about 1% of all fatal accidents in the civil jet transport fleet. Nevertheless, the impossibility of escape during flight accentuates the hazards resulting from low visibility and toxic gases. Control of combustion products in an aircraft cabin is affected by several characteristics that make the aircraft cabin environment unique. The aircraft fuselage is pressurized in flight and has an air distribution system which provides ventilation jets from the ceiling level air inlets running along the cabin length. A fixed quantity of ventilation air is metered into the cabin and air discharge is handled primarily by pressure controlling outflow valves in the rear lower part of the fuselage. Earlier airplane flight tests on cabin smoke control used generators producing minimally buoyant smoke products that moved with and served as a telltales for overall cabin ventilation flows. Analytical studies were done with localized smoke production to predict the percent of cabin length that would remain smoke-free during continuous generation. Development of a buoyant smoke generator allowed simulation of a fire plume with controllable simulated temperature and heat release rates. Tests on a Boeing 757, modified to allow smoke venting out through the top of the cabin, showed that the buoyant smoke front moved at 0.46m/s (1.5ft/sec) with and 0.27m/sec (0.9ft/sec) against, the axial ventilation airflow. Flight tests in a modified Boeing 727 showed that a ceiling level counterflow of about 0.55m/sec (1.8ft/sec) was required to arrest the forward movement of buoyant smoke. A design goal of 0.61m/s (2ft/sec) axial cabin flow would require a flow rate of 99m3/min (3500ft3/min) in a furnished Boeing 757. The current maximum fresh air cabin ventilation flow is 78m3/min (2756 ft3/min). Experimental results indicate that buoyancy effects cause smoke movement behaviour that is not predicted by traditional design analyses and flight test methodologies. Augmenting available ventilation for smoke control remains a design and safety challenge.

SIMPATIQCO: a server-based software suite which facilitates monitoring the time course of LC-MS performance metrics on Orbitrap instruments.

PubMed

Pichler, Peter; Mazanek, Michael; Dusberger, Frederico; Weilnböck, Lisa; Huber, Christian G; Stingl, Christoph; Luider, Theo M; Straube, Werner L; Köcher, Thomas; Mechtler, Karl

2012-11-02

While the performance of liquid chromatography (LC) and mass spectrometry (MS) instrumentation continues to increase, applications such as analyses of complete or near-complete proteomes and quantitative studies require constant and optimal system performance. For this reason, research laboratories and core facilities alike are recommended to implement quality control (QC) measures as part of their routine workflows. Many laboratories perform sporadic quality control checks. However, successive and systematic longitudinal monitoring of system performance would be facilitated by dedicated automatic or semiautomatic software solutions that aid an effortless analysis and display of QC metrics over time. We present the software package SIMPATIQCO (SIMPle AuTomatIc Quality COntrol) designed for evaluation of data from LTQ Orbitrap, Q-Exactive, LTQ FT, and LTQ instruments. A centralized SIMPATIQCO server can process QC data from multiple instruments. The software calculates QC metrics supervising every step of data acquisition from LC and electrospray to MS. For each QC metric the software learns the range indicating adequate system performance from the uploaded data using robust statistics. Results are stored in a database and can be displayed in a comfortable manner from any computer in the laboratory via a web browser. QC data can be monitored for individual LC runs as well as plotted over time. SIMPATIQCO thus assists the longitudinal monitoring of important QC metrics such as peptide elution times, peak widths, intensities, total ion current (TIC) as well as sensitivity, and overall LC-MS system performance; in this way the software also helps identify potential problems. The SIMPATIQCO software package is available free of charge.

SIMPATIQCO: A Server-Based Software Suite Which Facilitates Monitoring the Time Course of LC–MS Performance Metrics on Orbitrap Instruments

PubMed Central

2012-01-01

While the performance of liquid chromatography (LC) and mass spectrometry (MS) instrumentation continues to increase, applications such as analyses of complete or near-complete proteomes and quantitative studies require constant and optimal system performance. For this reason, research laboratories and core facilities alike are recommended to implement quality control (QC) measures as part of their routine workflows. Many laboratories perform sporadic quality control checks. However, successive and systematic longitudinal monitoring of system performance would be facilitated by dedicated automatic or semiautomatic software solutions that aid an effortless analysis and display of QC metrics over time. We present the software package SIMPATIQCO (SIMPle AuTomatIc Quality COntrol) designed for evaluation of data from LTQ Orbitrap, Q-Exactive, LTQ FT, and LTQ instruments. A centralized SIMPATIQCO server can process QC data from multiple instruments. The software calculates QC metrics supervising every step of data acquisition from LC and electrospray to MS. For each QC metric the software learns the range indicating adequate system performance from the uploaded data using robust statistics. Results are stored in a database and can be displayed in a comfortable manner from any computer in the laboratory via a web browser. QC data can be monitored for individual LC runs as well as plotted over time. SIMPATIQCO thus assists the longitudinal monitoring of important QC metrics such as peptide elution times, peak widths, intensities, total ion current (TIC) as well as sensitivity, and overall LC–MS system performance; in this way the software also helps identify potential problems. The SIMPATIQCO software package is available free of charge. PMID:23088386

Medical Modeling of Particle Size Effects for CB Inhalation Hazards

DTIC Science & Technology

2015-09-01

0:: 0 D.. w 0:: ... J <C 0 -z J : 0 w ~ Defense Threat Reduction Agency 8725 John J . Kingman Road, MS-6201 Fort Belvoir, VA 22060...DTRIAC/ J9STT, 8725 JOHN J . KINGMAN ROAD, MS-6201, FT BELVOIR, VA 22060-6201, IF YOUR ADDRESS IS INCORRECT, IF YOU WISH THAT IT BE DELETED FROM...Millage, Gene E. McClellan, Bahman Asgharian, Joshua J . Bergman, Darren R. Oldson, and Sharon A. Watson Applied Research Associates, Inc. Health

Annual Report to Congress, Fiscal Year 1997. A Report by the Scientific Advisory Board of the Strategic Environmental Research and Development Program.

DTIC Science & Technology

1998-03-01

Environmental Research June 18, 1998 Ms. Joyce Chiras Defense Technical Information Center DTIC/OCA Suite 0944 8725 John J. Kingman Road Ft. Belvoir, VA 22060...6218 Re: Strategic Environmental Research and Development Program (SERDP) Annual Reports to Congress - FY 1997 Dear Ms. Chiras : Enclosed are copies of...Achievement in Water Science and Technology, National Water Research Institute, 1996; The Gordon Maskew Fair Award, American Academy of Environmental

STS-32 MS Dunbar wearing LES prepares for WETF water egress training

NASA Technical Reports Server (NTRS)

1989-01-01

STS-32 Mission Specialist (MS) Bonnie J. Dunbar, wearing a launch and entry suit (LES), orange parachute harness and life vest, is briefed on emergency egress procedures in JSC's Weightless Environment Training Facility (WETF) Bldg 29. During the exercises the crew practiced the procedures to follow in the event of an emergency aboard the Space Shuttle and familiarized themselves with post-Challenger pole system of emergency egress. The crewmembers will simulate parachuting into water by using the WETF's nearby 25 ft deep pool.

STS-45 MS Foale dons EMU with technicians' help in JSC's WETF Bldg 29

NASA Technical Reports Server (NTRS)

1991-01-01

STS-45 Atlantis, Orbiter Vehicle (OV) 104, Mission Specialist (MS) C. Michael Foale stands on a platform as technicians help him don his extravehicular mobility unit (EMU). The technicians are preparing to connect the EMU upper and lower torsos at the waist ring. When fully suited, Foale will be lowered into a nearby 25 ft deep pool for an underwater simulation of contingency extravehicular activity (EVA) procedures. The pool is located in JSC's Weightless Environment Training Facility (WETF) Bldg 29.

STS-37 Mission Specialist (MS) Jerome Apt floats in raft in JSC's WETF pool

NASA Technical Reports Server (NTRS)

1990-01-01

STS-37 Mission Specialist (MS) Jerome Apt, wearing launch and entry suit (LES) and launch and entry helmet (LEH), propels his one-person life raft by splashing water during emergency egress exercise in JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool. Apt, floating in the life raft, was simulating the steps involved in emergency egress from a Space Shuttle. The WETF's 25-ft pool served as a simulated ocean into which a parachute landing might be made.

Convective Enhancement of Icing Roughness Elements in Stagnation Region Flows

NASA Technical Reports Server (NTRS)

Hughes, Michael T.; McClain, Stephen T.; Vargas, Mario; Broeren, Andy

2015-01-01

To improve existing ice accretion simulation codes, more data regarding ice roughness and its effects on convective heat transfer are required. To build on existing research on this topic, this study used the Vertical Icing Studies Tunnel (VIST) at NASA Glenn Research to model realistic ice roughness in the stagnation region of a NACA 0012 airfoil. Using the VIST, a test plate representing the leading 2% chord of the airfoil was subjected to flows of 7.62 m/s (25 ft/s), 12.19 m/s (40 ft/s), and 16.76 m/s (55 ft/s). The test plate was fitted with 3 surfaces, each with a different representation of ice roughness: 1) a control surface with no ice roughness, 2) a surface with ice roughness with element height scaled by 10x and streamwise rough zone width from the stagnation point scaled by 10x, and 3) a surface with ice roughness with element height scaled by 10x and streamwise rough zone width from the stagnation point scaled by 25x. Temperature data from the tests were recorded using an infrared camera and thermocouples imbedded in the test plate. From the temperature data, a convective heat transfer coefficient map was created for each case. Additional testing was also performed to validate the VIST's flow quality. These tests included five-hole probe and hot-wire probe velocity traces to provide flow visualization and to study boundary layer formation on the various test surfaces. The knowledge gained during the experiments will help improve ice accretion codes by providing heat transfer coefficient validation data and by providing flow visualization data helping understand current and future experiments performed in the VIST.

Sex steroids, insulin sensitivity and sympathetic nerve activity in relation to affective symptoms in women with polycystic ovary syndrome.

PubMed

Jedel, Elizabeth; Gustafson, Deborah; Waern, Margda; Sverrisdottir, Yrsa Bergmann; Landén, Mikael; Janson, Per Olof; Labrie, Fernand; Ohlsson, Claes; Stener-Victorin, Elisabet

2011-11-01

Affective symptoms are poorly understood in polycystic ovary syndrome (PCOS). Clinical signs of hyperandrogenism and high serum androgens are key features in PCOS, and women with PCOS are more likely to be overweight or obese, as well as insulin resistant. Further, PCOS is associated with high sympathetic nerve activity. To elucidate if self-reported hirsutism, body mass index (BMI) and waistline, circulating sex steroids, sex hormone-binding globulin (SHBG), insulin sensitivity and sympathetic nerve activity are associated with depression and anxiety-related symptoms in women with PCOS. Seventy-two women with PCOS, aged 21-37 years, were recruited from the community. Hirsutism was self-reported using the Ferriman-Gallway score. Serum estrogens, sex steroid precursors, androgens and glucuronidated androgen metabolites were analyzed by gas and liquid chromatography/mass spectroscopy (GC-MS/LC-MS/MS) and SHBG by chemiluminiscent microparticle immunoassay (CMIA). Insulin sensitivity was measured with euglycemic hyperinsulinemic clamp. Sympathetic nerve activity was measured with microneurography. Symptoms of depression and anxiety were self-reported using the Montgomery Åsberg Depression Rating Scale (MADRS-S) and the Brief Scale for Anxiety (BSA-S). Circulating concentrations of testosterone (T) (P=0.026), free T (FT) (P=0.025), and androstane-3α 17β-diol-3glucuronide (3G) (P=0.029) were lower in women with depression symptoms of potential clinical relevance (MADR-S≥11). The odds of having a MADRS-S score ≥11 were higher with lower FT and 3G. No associations with BSA-S were noted. Lower circulating FT and 3G were associated with worse self-reported depression symptoms. The relationship between mental health, sex steroids and corresponding metabolites in PCOS requires further investigation. Copyright © 2011 Elsevier Ltd. All rights reserved.

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... . FOR FURTHER INFORMATION CONTACT: Rachel Lentz, Office of Brownfields and Land Revitalization, (5105T.... Title: Brownfields Program--Accomplishment Reporting (Renewal). ICR numbers: EPA ICR No. 2104.04, OMB... and Brownfields Revitalization Act (Pub. L. 107-118) (``the Brownfields Amendments'') was signed into...

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2011-02-09

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Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Witt, Matthias; Fuchser, Jens; Koch, Boris P

2009-04-01

The complex natural organic matter standard Suwannee river fulvic acid (SRFA) was analyzed by negative ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS) using on-resonance collision induced dissociation (CID) of single ultrahigh resolved mass peaks in the ICR cell. Molecular formula assignment of precursor masses resulted in exactly one molecular formula for each of the peaks. Analyses of the corresponding fragment spectra and comparison to different standard substances revealed specific neutral losses and fragmentation patterns which result in structures consisting of a high degree of carboxyl- and fewer hydroxyl groups. The comparison of fragmented mass peaks within different pseudohomologous series (CH(2)-series, and CH(4) vs O exchange) suggested structurally based differences between these series. CID FTICR MS allowed isolating single mass peaks in a very complex natural organic matter spectrum. Subsequently, fragmentation gave structural insights into this material. Our results suggest that the structural diversity in complex humic substances is not as high as expected.

Exhaustive methylation analysis revealed uneven profiles of methylation at IGF2/ICR1/H19 11p15 loci in Russell Silver syndrome.

PubMed

Azzi, Salah; Steunou, Virginie; Tost, Jörg; Rossignol, Sylvie; Thibaud, Nathalie; Das Neves, Cristina; Le Jule, Marilyne; Habib, Walid Abi; Blaise, Annick; Koudou, Yves; Busato, Florence; Le Bouc, Yves; Netchine, Irène

2015-01-01

The structural organisation of the human IGF2/ICR1/H19 11p15 domain is very complex, and the mechanisms underlying its regulation are poorly understood. The Imprinted Center Region 1 (ICR1) contains seven binding sites for the zinc-finger protein CTCF (CBS: CTCF Binding Sites); three additional differentially methylated regions (DMR) are located at the H19 promoter (H19DMR) and two in the IGF2 gene (DMR0 and DMR2), respectively. Loss of imprinting at the IGF2/ICR1/H19 domain results in two growth disorders with opposite phenotypes: Beckwith-Wiedemann syndrome and Russell Silver syndrome (RSS). Despite the IGF2/ICR1/H19 locus being widely studied, the extent of hypomethylation across the domain remains not yet addressed in patients with RSS. We assessed a detailed investigation of the methylation status of the 11p15 ICR1 CBS1-7, IGF2DMR0 and H19DMR (H19 promoter) in a population of controls (n=50) and RSS carrying (n=104) or not (n=65) carrying a hypomethylation at the 11p15 ICR1 region. The methylation indexes (MI) were balanced at all regions in the control population and patients with RSS without any as yet identified molecular anomaly. Interestingly, patients with RSS with ICR1 hypomethylation showed uneven profiles of methylation among the CBSs and DMRs. Furthermore, normal MIs at CBS1 and CBS7 were identified in 9% of patients. The hypomethylation does not spread equally throughout the IGF2/ICR1/H19 locus, and some loci could have normal MI, which may lead to underdiagnosis of patients with RSS with ICR1 hypomethylation. The uneven pattern of methylation suggests that some CBSs may play different roles in the tridimensional chromosomal looping regulation of this locus. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

78 FR 24392 - Proposed Collection; Comment Request

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2013-04-25

... Information Center (DTIC), Marketing and Registration Division, 8725 John J. Kingman Road, Suite 0944, ATTN: Ms. Angela Davis, Ft. Belvoir, VA 22060- 6218, or call the DTIC Marketing and Registration Division at (703) 767-8207. Title; Associated Form; and OMB Number: Customer Satisfaction Surveys--Generic...

An efficient and environment-friendly method of removing graphene oxide in wastewater and its degradation mechanisms.

PubMed

Zhang, Chao-Zhi; Li, Ting; Yuan, Yang; Xu, Jianqiang

2016-06-01

Graphene and graphene oxide (GO) have already existed in air, water and soil due to their popular application in functional materials. However, degradation of graphene and GO in wastewater has not been reported. Degradation of GO plays a key role in the elimination of graphene and GO in wastewater due to graphene being easily oxidized to GO. In this paper, GO was completely degraded to give CO2 by Photo-Fenton. The degradation intermediates were determined by UV-vis absorption spectra, elemental analysis (EA), fourier transform infrared (FT-IR) and liquid chromatography-mass spectrometry (LC-MS). Experimental results showed that graphene oxide was completely degraded to give CO2 after 28 days. Based on UV, FT-IR, LC-MS spectra and EA data of these degradation intermediates, the degradation mechanisms of GO were supposed. This paper suggests an efficient and environment-friendly method to degrade GO and graphene. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-precision half-life determination for the superallowed β+ emitter Ga62

NASA Astrophysics Data System (ADS)

Grinyer, G. F.; Finlay, P.; Svensson, C. E.; Ball, G. C.; Leslie, J. R.; Austin, R. A. E.; Bandyopadhyay, D.; Chaffey, A.; Chakrawarthy, R. S.; Garrett, P. E.; Hackman, G.; Hyland, B.; Kanungo, R.; Leach, K. G.; Mattoon, C. M.; Morton, A. C.; Pearson, C. J.; Phillips, A. A.; Ressler, J. J.; Sarazin, F.; Savajols, H.; Schumaker, M. A.; Wong, J.

2008-01-01

The half-life of the superallowed β+ emitter Ga62 has been measured at TRIUMF's Isotope Separator and Accelerator facility using a fast-tape-transport system and 4π continuous-flow gas proportional counter to detect the positrons from the decay of Ga62 to the daughter Zn62. The result, T1/2=116.100±0.025 ms, represents the most precise measurement to date (0.022%) for any superallowed β-decay half-life. When combined with six previous measurements of the Ga62 half-life, a new world average of T1/2=116.121±0.021 ms is obtained. This new half-life measurement results in a 20% improvement in the precision of the Ga62 superallowed ft value while reducing its mean by 0.9σ to ft=3074.3(12) s. The impact of this half-life measurement on precision tests of the CVC hypothesis and isospin symmetry breaking corrections for A⩾62 superallowed decays is discussed.

Review: LC coupled to low- and high-resolution mass spectrometry for new psychoactive substance screening in biological matrices - Where do we stand today?

PubMed

Meyer, Markus R; Maurer, Hans H

2016-07-13

The field of new psychoactive substances (NPS) is highly dynamic and the situation changes from year to year. Therefore, the current review provides a timely update about the latest developments to help analysts keep the pace with NPS distribution. It covers PubMed-listed studies published between January 2014 and January 2016 dealing with the application of liquid chromatography (LC) coupled low- and high-resolution mass spectrometry (MS) for broad screenings for NPS in clinical (CT) and forensic (FT) toxicology. Latest developments and applications are highlighted and selected papers critically discussed. Comprehensive tables summarizing all discussed articles complete the overview. Finally, an outlook on the future of LC coupled MS in CT and FT is provided and readers will learn why low-resolution mass spectrometry might remain the standard for the next couple of years at least for easy-to-use quantitative screening procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

Self-acting seals for helicopter engines

NASA Technical Reports Server (NTRS)

Lynwander, P.

1975-01-01

An experimental evaluation was conducted with NASA-designed self-acting face and circumferential seals for use in the main shaft positions of advanced gas turbine engines. The seals featured Rayleigh step pads (self-acting geometry) for lift augmentation. The tested seals incorporated design improvements over previous self-acting configurations. Self-acting face seals were tested to speeds of 214 m/s (700 ft/sec, 63700 rpm), air pressures of 216.8 N/sq cm abs (314.7 psia), and air temperatures of 688K (778 F). Self-acting circumferential seals were tested to speeds of 183 m/s (600 ft/sec, 47700 rpm), air pressures of 61.8 N/sq cm abs (89.7 psia), and air temperatures of 711 K (820 F). Self-acting face-seals are capable of operating at conditions exceeding conventional seal capability. The limit on speed capability was found to be the flatness of the seal-seat. The self-acting circumferential seal design tested requires further development for use in advanced engines.

Determination of fenitrothion in water using a voltammetric sensor based on a polymer-modified glassy carbon electrode.

PubMed

Amare, Meareg; Abicho, Samuel; Admassie, Shimelis

2014-01-01

A glassy carbon electrode (GCE) modified with poly(4-amino-3-hydroxynaphthalene sulfonic acid) (poly-AHNSA) was used for the selective and sensitive determination of fenitrothion (FT) organophosphorus pesticide in water. The electrochemical behavior of FT at the bare GCE and the poly-AHNSA/GCE were compared using cyclic voltammetry. Enhanced peak current response and shift to a lower potential at the polymer-modified electrode indicated the electrocatalytic activity of the polymer film towards FT. Under optimized solution and method parameters, the adsorptive stripping square wave voltammetric reductive peak current of FT was linear to FT concentration in the range of 0.001 to 6.6 x 10(-6) M, and the LOD obtained (3delta/m) was 7.95 x 10(-10) M. Recoveries in the range 96-98% of spiked FT in tap water and reproducible results with RSD of 2.6% (n = 5) were obtained, indicating the potential applicability of the method for the determination of trace levels of FT in environmental samples.

Effects of simulated artificial gravity on human performance

NASA Technical Reports Server (NTRS)

Green, J. A.; Peacock, J. L.

1972-01-01

The ability of test subjects to perform operational type tasks was evaluated at rotational rates to 6 rpm and radii to 78 ft (24 m). The tasks included fine motor activity, mental operations, postural equilibrium, cargo handling, radial and tangential locomotion. Performance data indicate that 6 rpm presents a physiological limit at radii to 75 ft (23 m). Radial locomotion was not found to produce excessive adverse stimuli, and tangential locomotion was readily accomplished at walking rates of 2 of 4.8 ft/s (.6 to 1.4 m/s). The absence of vision dramatically reduced an individual's postural equilibrium during rotation. The use of selected anti-motion pharmaceuticals had, generally, a positive effect upon psychomotor performance at 6 rpm, but did not prove to be a panacea for the adverse effects of rotation at this rate.

Petroleum Refinery Information Collection Request (ICR) Emissions Test Report for BP-Husky Refining LLC

EPA Pesticide Factsheets

On March 31, 2011, U.S. EPA sent a Section 114 letter to the BP-Husky Refining Company in Oregon, Ohio stating that the facility was subject to the ICR and that certain information would need to be submitted by the facility to satisfy U.S. EPA’s ICR.

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Hermes CX-7: Air transport system design simulation

NASA Technical Reports Server (NTRS)

Amer, Brian; Barter, John; Colucci, Jay; Foley, Caryn; Kockler, James; Rapp, David; Zeiger, Matthew

1992-01-01

The Hermes CX-7 has been designed to service the overnight parcel package delivery needs of the cities of Aeroworld as determined in the G-Dome Enterprises market survey. The design optimization centers on the prime goal of servicing the needs of these cities as efficiently and profitably as possible. The greatest factors which affect the design of an aircraft for the mission outlined in the Request for Proposal are cost, construction feasibility and effectiveness of the design. Other influencing factors are given by the constraints of the market, including a maximum takeoff and landing distance of 60 feet, storage capability in a container of size 5 ft. x 3 ft. x 2 ft., cargo packages of 2 inch and 4 inch cubes, and ability to turn with a radius no larger than 60 feet. Safety considerations such as flying at or below Mach one (30 ft/s) and controllability and maintainability of the aircraft must also be designed into the aircraft. Another influential factor is the efficiency of the aircraft which involves optimizations and tradeoffs of such factors as weight, lifting surface sizing, structural redundancy, and material costs.