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.

Monitoring the physicochemical degradation of coconut water using ESI-FT-ICR MS.

PubMed

Costa, Helber B; Souza, Lindamara M; Soprani, Letícia C; Oliveira, Bruno G; Ogawa, Elizângela M; Korres, Adriana M N; Ventura, José A; Romão, Wanderson

2015-05-01

Fresh and aged coconut water (CW) samples were introduced directly into the electrospray ionisation (ESI) source, and were combined with the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) technique to characterise in situ chemical compounds produced during natural ageing (from 0 to 15 days) at room temperature (23 °C). The ESI-FT-ICR MS readings were acquired and the data were correlated to conventional methodologies: pH, total titratable acidity (TA), total soluble solids, microbial analyses, and ultraviolet visibility (UV-vis) spectroscopy analysis. In general, the pH and TA values changed after 3 days of storage making the CW unsuitable for consumption. The ESI(-)-FT-ICR data also showed a clear and evident change in the chemical profile of CW after 3 days of ageing in the m/z 150-250 and 350-450 regions. Initially, the relative intensity of the natural markers (the m/z 215 and 377 ions-sugar molecules) decreases as a function of ageing time, with the last marker disappearing after 3 days of ageing. New chemical species were then identified such as: citric (m/z 191), galacturonic (m/z 193), gluconic (m/z 195), and saccharic (m/z 209) acids. ESI(-)-FT-ICR MS is a powerful tool to predict the physicochemical properties of CW, such as the pH and TA, where species such as fructose, glucose, sucrose, and gluconic acid can be used as natural markers to monitor the quality of the fruits. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

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

Characterization of chemical constituents in Rhodiola Crenulate by high-performance liquid chromatography coupled with Fourier-transform ion cyclotron resonance mass spectrometer (HPLC-FT-ICR MS).

PubMed

Han, Fei; Li, Yanting; Mao, Xinjuan; Xu, Rui; Yin, Ran

2016-05-01

In this work, an approach using high-performance liquid chromatography coupled with diode-array detection and Fourier-transform ion cyclotron resonance mass spectrometer (HPLC-FT-ICR MS) for the identification and profiling of chemical constituents in Rhodiola crenulata was developed for the first time. The chromatographic separation was achieved on an Inertsil ODS-3 column (150 mm × 4.6 mm,3 µm) using a gradient elution program, and the detection was performed on a Bruker Solarix 7.0 T mass spectrometer equipped with electrospray ionization source in both positive and negative modes. Under the optimized conditions, a total of 48 chemical compounds, including 26 alcohols and their glycosides, 12 flavonoids and their glycosides, 5 flavanols and gallic acid derivatives, 4 organic acids and 1 cyanogenic glycoside were identified or tentatively characterized. The results indicated that the developed HPLC-FT-ICR MS method with ultra-high sensitivity and resolution is suitable for identifying and characterizing the chemical constituents in R. crenulata. And it provides a helpful chemical basis for further research on R. crenulata. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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

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

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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

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.

Automated metal-free multiple-column nanoLC for improved phosphopeptide analysis sensitivity and throughput

PubMed Central

Zhao, Rui; Ding, Shi-Jian; Shen, Yufeng; Camp, David G.; Livesay, Eric A.; Udseth, Harold; Smith, Richard D.

2009-01-01

We report on the development and characterization of automated metal-free multiple-column nanoLC instrumentation for sensitive and high-throughput analysis of phosphopeptides with mass spectrometry analysis. The system implements a multiple-column capillary LC fluidic design developed for high-throughput analysis of peptides (Anal. Chem. 2001, 73, 3011–3021), incorporating modifications to achieve broad and sensitive analysis of phosphopeptides. The integrated nanoLC columns (50 µm i.d. × 30 cm containing 5 µm C18 particles) and the on-line solid phase extraction columns (150 µm i.d. × 4 cm containing 5 µm C18 particles) were connected to automatic switching valves with non-metal chromatographic accessories, and other modifications to avoid the exposure of the analyte to any metal surfaces during handling, separation, and electrospray ionization. The nanoLC developed provided a separation peak capacity of ∼250 for phosphopeptides (and ∼400 for normal peptides). A detection limit of 0.4 fmol was obtained when a linear ion trap tandem mass spectrometer (Finnegan LTQ) was coupled to a 50-µm i.d. column of the nanoLC. The separation power and sensitivity provided by the nanoLC-LTQ enabled identification of ∼4600 phosphopeptide candidates from ∼60 µg COS-7 cell tryptic digest followed by IMAC enrichment and ∼520 tyrosine phosphopeptides from ∼2 mg of human T cells digests followed by phosphotyrosine peptide immunoprecipitation. PMID:19217835

Absorption Mode FT-ICR Mass Spectrometry Imaging

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

Smith, Donald F.; Kilgour, David P.; Konijnenburg, Marco

2013-12-03

Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields are used to increase mass resolving power. However, a gain in mass resolving power can also be realized by phase correction of the data for absorption mode display. In addition to mass resolving power, absorption mode offers higher mass accuracy and signal-to-noise ratio over the conventional magnitude mode. Here we present the first use of absorption mode formore » Fourier transform ion cyclotron resonance mass spectrometry imaging. The Autophaser algorithm is used to phase correct each spectrum (pixel) in the image and then these parameters are used by the Chameleon work-flow based data processing software to generate absorption mode ?Datacubes? for image and spectral viewing. Absorption mode reveals new mass and spatial features that are not resolved in magnitude mode and results in improved selected ion image contrast.« less

Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Marshall, Alan G.

1998-06-01

As for Fourier transform infrared (FT-IR) interferometry and nuclear magnetic resonance (NMR) spectroscopy, the introduction of pulsed Fourier transform techniques revolutionized ion cyclotron resonance mass spectrometry: increased speed (factor of 10,000), increased sensitivity (factor of 100), increased mass resolution (factor of 10,000-an improvement not shared by the introduction of FT techniques to IR or NMR spectroscopy), increased mass range (factor of 500), and automated operation. FT-ICR mass spectrometry is the most versatile technique for unscrambling and quantifying ion-molecule reaction kinetics and equilibria in the absence of solvent (i.e., the gas phase). In addition, FT-ICR MS has the following analytically important features: speed (~1 second per spectrum); ultrahigh mass resolution and ultrahigh mass accuracy for analysis of mixtures and polymers; attomole sensitivity; MSn with one spectrometer, including two-dimensional FT/FT-ICR/MS; positive and/or negative ions; multiple ion sources (especially MALDI and electrospray); biomolecular molecular weight and sequencing; LC/MS; and single-molecule detection up to 108 Dalton. Here, some basic features and recent developments of FT-ICR mass spectrometry are reviewed, with applications ranging from crude oil to molecular biology.

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

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.

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

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.

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

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

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

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

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.

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

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

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

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.

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.

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).

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

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

Nano-LC FTICR tandem mass spectrometry for top-down proteomics: routine baseline unit mass resolution of whole cell lysate proteins up to 72 kDa.

PubMed

Tipton, Jeremiah D; Tran, John C; Catherman, Adam D; Ahlf, Dorothy R; Durbin, Kenneth R; Lee, Ji Eun; Kellie, John F; Kelleher, Neil L; Hendrickson, Christopher L; Marshall, Alan G

2012-03-06

Current high-throughput top-down proteomic platforms provide routine identification of proteins less than 25 kDa with 4-D separations. This short communication reports the application of technological developments over the past few years that improve protein identification and characterization for masses greater than 25 kDa. Advances in separation science have allowed increased numbers of proteins to be identified, especially by nanoliquid chromatography (nLC) prior to mass spectrometry (MS) analysis. Further, a goal of high-throughput top-down proteomics is to extend the mass range for routine nLC MS analysis up to 80 kDa because gene sequence analysis predicts that ~70% of the human proteome is transcribed to be less than 80 kDa. Normally, large proteins greater than 50 kDa are identified and characterized by top-down proteomics through fraction collection and direct infusion at relatively low throughput. Further, other MS-based techniques provide top-down protein characterization, however at low resolution for intact mass measurement. Here, we present analysis of standard (up to 78 kDa) and whole cell lysate proteins by Fourier transform ion cyclotron resonance mass spectrometry (nLC electrospray ionization (ESI) FTICR MS). The separation platform reduced the complexity of the protein matrix so that, at 14.5 T, proteins from whole cell lysate up to 72 kDa are baseline mass resolved on a nano-LC chromatographic time scale. Further, the results document routine identification of proteins at improved throughput based on accurate mass measurement (less than 10 ppm mass error) of precursor and fragment ions for proteins up to 50 kDa.

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

Application of Fourier-transform ion cyclotron resonance mass spectrometry to metabolic profiling and metabolite identification.

PubMed

Ohta, Daisaku; Kanaya, Shigehiko; Suzuki, Hideyuki

2010-02-01

Metabolomics, as an essential part of genomics studies, intends holistic understanding of metabolic networks through simultaneous analysis of a myriad of both known and unknown metabolites occurring in living organisms. The initial stage of metabolomics was designed for the reproducible analyses of known metabolites based on their comparison to available authentic compounds. Such metabolomics platforms were mostly based on mass spectrometry (MS) technologies enabled by a combination of different ionization methods together with a variety of separation steps including LC, GC, and CE. Among these, Fourier-transform ion cyclotron resonance MS (FT-ICR/MS) is distinguished from other MS technologies by its ultrahigh resolution power in mass to charge ratio (m/z). The potential of FT-ICR/MS as a distinctive metabolomics tool has been demonstrated in nontargeted metabolic profiling and functional characterization of novel genes. Here, we discuss both the advantages and difficulties encountered in the FT-ICR/MS metabolomics studies.

Molecular Characterization of Organosulfates in Urban Aerosols during the Spring Festival by FT-ICR Mass Spectrometry

NASA Astrophysics Data System (ADS)

Xie, Q.; Fu, P.

2017-12-01

Aerosol particles collected at daytime and nighttime in Beijing during the spring festival, including the episodes of various gradient level pollution and short-term pollution raised by fireworks, were analyzed using 15T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). Organosulfates (OSs), tracers for secondary organic aerosol formation, were identified through accurate mass measurements. Both the total number and the arbitrary abundance of OSs were consistent with the total OC concentrations of the aerosol samples. Nitrooxy-organosulfates were more abundant in the nighttime than those in the daytime due to high NOX concentrations at night. Although all subgroups OSs increased with the deterioration of air quality, especially for the relative abundance of aromatic OSs with high double bond equivalents, the percentage contributions of aliphatic OSs with low degree of unsaturation decreased. It was worth to note that aliphatic OSs with a wide range in carbon-chain length of C6-40 were identified in this study. The candidates for their potential precursors were alkanes and fatty acids. Moreover, a large number of aromatic OSs, about two thirds of OSs, were detected. The rapid formation of these compounds in New Year's Eve with plentiful aromatics from firework burning suggests that they may be derived from PAHs. The high carbon and oxygen contents of OSs may indicate the presence of dimmers, even polymers. Our results support the important contribution of anthropogenic precursors to OSs in ambient aerosols on the basis of aromatic and aliphatic OSs, which may have a significant impact on the hygroscopic properties of ambient aerosol particles.

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.

Extension of the analytical window for characterizing aromatic compounds in oils using a comprehensive suite of high-resolution mass spectrometry techniques and double bond equivalence versus carbon number plot

USGS Publications Warehouse

Cho, Yunju; Birdwell, Justin E.; Hur, Manhoi; Lee, Joonhee; Kim, Byungjoo; Kim, Sunghwan

2017-01-01

In this study, comprehensive two-dimensional (2D) gas chromatography–mass spectrometry (GC–MS), atmospheric pressure photoionization (APPI) quadrupole-Orbitrap mass spectrometry (MS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were used to study the aromatic fractions of crude oil and oil shale pyrolysates (shale oils). The collected data were compared and combined in the double bond equivalence (DBE) versus carbon number plot to obtain a more complete understanding of the composition of the oil fractions. The numbers of peaks observed by each technique followed the order 2D GC–MS < Orbitrap MS < FT-ICR MS. The class distributions observed by Orbitrap MS and FT-ICR MS were similar to each other but different from that observed by 2D GC–MS. The DBE and carbon number distributions of the 2D GC–MS and Orbitrap MS data were similar for crude oil aromatics. The FT-ICR MS plots of DBE and carbon number showed an extended range of higher values relative to the other methods. For the aromatic fraction of an oil shale pyrolysate generated by the Fischer assay, only a few nitrogen-containing compounds were observed by 2D GC–MS but a large number of these compounds were detected by Orbitrap MS and FT-ICR MS. This comparison clearly shows that the data obtained from these three techniques can be combined to more completely characterize oil composition. The data obtained by Orbitrap MS and FT-ICR MS agreed well with one another, and the combined DBE versus carbon number plot provided more complete coverage of compounds present in the fractions. In addition, the chemical structure information provided by 2D GC–MS could be matched with the chemical formulas in the DBE versus carbon number plots, providing information not available in ultrahigh-resolution MS results. It was therefore concluded that the combination of 2D GC–MS, Orbitrap MS, and FT-ICR MS in the DBE versus carbon number space facilitates structural assignment of heavy

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.

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

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

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.

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.

Plasma protein absolute quantification by nano-LC Q-TOF UDMSE for clinical biomarker verification

PubMed Central

ILIES, MARIA; IUGA, CRISTINA ADELA; LOGHIN, FELICIA; DHOPLE, VISHNU MUKUND; HAMMER, ELKE

2017-01-01

Background and aims Proteome-based biomarker studies are targeting proteins that could serve as diagnostic, prognosis, and prediction molecules. In the clinical routine, immunoassays are currently used for the absolute quantification of such biomarkers, with the major limitation that only one molecule can be targeted per assay. The aim of our study was to test a mass spectrometry based absolute quantification method for the verification of plasma protein sets which might serve as reliable biomarker panels for the clinical practice. Methods Six EDTA plasma samples were analyzed after tryptic digestion using a high throughput data independent acquisition nano-LC Q-TOF UDMSE proteomics approach. Synthetic Escherichia coli standard peptides were spiked in each sample for the absolute quantification. Data analysis was performed using ProgenesisQI v2.0 software (Waters Corporation). Results Our method ensured absolute quantification of 242 non redundant plasma proteins in a single run analysis. The dynamic range covered was 105. 86% were represented by classical plasma proteins. The overall median coefficient of variation was 0.36, while a set of 63 proteins was found to be highly stable. Absolute protein concentrations strongly correlated with values reviewed in the literature. Conclusions Nano-LC Q-TOF UDMSE proteomic analysis can be used for a simple and rapid determination of absolute amounts of plasma proteins. A large number of plasma proteins could be analyzed, while a wide dynamic range was covered with low coefficient of variation at protein level. The method proved to be a reliable tool for the quantification of protein panel for biomarker verification in the clinical practice. PMID:29151793

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.

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.

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

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

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

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.

Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

USGS Publications Warehouse

Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

2013-01-01

Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols.

PubMed

Zhou, Xibin; Zhang, Yahe; Zhao, Suoqi; Hsu, Chang Samuel; Shi, Quan

2013-12-15

Monohydric alcohols are common in natural products, bio-oils, and medicine. We have found that monohydric alcohols can form O3 (ions containing three oxygen atoms) and O4 adduct ions in negative electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which would significantly affect the composition analysis of alcohols, especially in a complex mixture. It is necessary to study the reaction pathways and the method to eliminate or reduce the 'artifact' adducts. Octadecanol, cholesterol, squalanol and two complex monohydric alcohol mixtures were selected as model compounds. These samples were subjected to negative ion ESI FT-ICR MS analysis. The composition and formation mechanism of adducts were studied by the ultrahigh-resolution accurate mass measurement for elemental composition, along with the MS(2) isolation and collision-induced dissociation (CID) experiments for structural determination. The reaction pathway of O3 adduct formation is the coupling of a monohydric alcohol ion with a CO2 to form a stable O3 ionic species by likely a covalent bond (source of CO2 is not clear). The O4 species are formed by O3 ionic species adducted with an alcohol molecule of the solvent, such as methanol or ethanol, by likely a hydrogen bond. These adduct ions could be eliminated or reduced by increasing collision energy. However, excessive collision energy would fragment monohydric alcohol ions. The formation mechanisms of O3 and O4 adducts from monohydric alcohols in negative ion ESI FT-ICR MS were proposed. The solvent adduction effects can be eliminated or reduced by optimizing the collision energy of CID in FT-ICR MS. Copyright © 2013 John Wiley & Sons, Ltd.

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

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.

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).

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.

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

High-resolution droplet-based fractionation of nano-LC separations onto microarrays for MALDI-MS analysis.

PubMed

Küster, Simon K; Pabst, Martin; Jefimovs, Konstantins; Zenobi, Renato; Dittrich, Petra S

2014-05-20

We present a robust droplet-based device, which enables the fractionation of ultralow flow rate nanoflow liquid chromatography (nano-LC) eluate streams at high frequencies and high peak resolution. This is achieved by directly interfacing the separation column to a micro T-junction, where the eluate stream is compartmentalized into picoliter droplets. This immediate compartmentalization prevents peak dispersion during eluate transport and conserves the chromatographic performance. Subsequently, nanoliter eluate fractions are collected at a rate of one fraction per second on a high-density microarray to retain the separation with high temporal resolution. Chromatographic separations of up to 45 min runtime can thus be archived on a single microarray possessing 2700 sample spots. The performance of this device is demonstrated by fractionating the separation of a tryptic digest of a known protein mixture onto the microarray chip and subsequently analyzing the sample archive using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Resulting peak widths are found to be significantly reduced compared to standard continuous flow spotting technologies as well as in comparison to a conventional nano-LC-electrospray ionization-mass spectrometry interface. Moreover, we demonstrate the advantage of our high-definition nanofractionation device by applying two different MALDI matrices to all collected fractions in an alternating fashion. Since the information that is obtained from a MALDI-MS measurement depends on the choice of MALDI matrix, we can extract complementary information from neighboring spots containing almost identical composition but different matrices.

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.

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.

Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

PubMed Central

Zuber, Jan; Kroll, Marius M.; Rathsack, Philipp; Otto, Matthias

2016-01-01

Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

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.

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.

Calibration of marginal oscillator sensitivity for use in ICR spectrometry

NASA Technical Reports Server (NTRS)

Anicich, V. G.; Huntress, W. T., Jr.

1977-01-01

A constant-reference load is utilized as Q-spoiler in calibrations of relative sensitivity variations of a marginal oscillator with frequency. Frequency-dependent effects troublesome in earlier Q-spoilers are compensated by employing a pure resistive calibration load with compensation for the small distributed capacitance of large resistors. The validity of the approach is demonstrated for a 2:1 mass ratio range, and validity for a mass ratio range greater than 10:1 is claimed. The circuit and technique were developed for use in ion cyclotron resonance (ICR) spectrometric practice.

Orbitrap-MS and FT-ICR-MS of Free and Labile Organic Matter from Carbonaceous Chondrites

NASA Astrophysics Data System (ADS)

Orthous-Daunay, F.-R.; Thissen, R.; Vuitton, V.; Somogyi, A.; Mespoulede, M.; Beck, P.; Bonnet, J.-Y.; Dutuit, O.; Schmitt, B.; Quirico, E.

2011-03-01

We used two types of high-resolution FT-MS to analyze the free and labile organic matter in carbonaceous chondrites of type 1 and 2. The methanol extraction and laser desorption gave access to highly and poorly functionalized molecules respectively.

Sulfites and the wine metabolome.

PubMed

Roullier-Gall, Chloé; Hemmler, Daniel; Gonsior, Michael; Li, Yan; Nikolantonaki, Maria; Aron, Alissa; Coelho, Christian; Gougeon, Régis D; Schmitt-Kopplin, Philippe

2017-12-15

In a context of societal concern about food preservation, the reduction of sulfite input plays a major role in the wine industry. To improve the understanding of the chemistry involved in the SO 2 protection, a series of bottle aged Chardonnay wines made from the same must, but with different concentrations of SO 2 added at pressing were analyzed by ultrahigh resolution mass spectrometry (FT-ICR-MS) and excitation emission matrix fluorescence (EEMF). Metabolic fingerprints from FT-ICR-MS data could discriminate wines according to the added concentration to the must but they also revealed chemistry-related differences according to the type of stopper, providing a wine metabolomics picture of the impact of distinct stopping strategies. Spearman rank correlation was applied to link the statistically modeled EEMF components (parallel factor analysis (PARAFAC)) and the exact mass information from FT-ICR-MS, and thus revealing the extent of sulfur-containing compounds which could show some correlation with fluorescence fingerprints. Copyright © 2017 Elsevier Ltd. All rights reserved.

Recorded ICR Overview Presentations

EPA Pesticide Factsheets

This presentation provides a brief overview of the applicability of the EPA’s Plywood and Composite Wood Products Information Collection Request, or “ICR,” for facilities that produce kiln‐dried lumber.

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

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.

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

Accurate mass measurement: terminology and treatment of data.

PubMed

Brenton, A Gareth; Godfrey, A Ruth

2010-11-01

High-resolution mass spectrometry has become ever more accessible with improvements in instrumentation, such as modern FT-ICR and Orbitrap mass spectrometers. This has resulted in an increase in the number of articles submitted for publication quoting accurate mass data. There is a plethora of terms related to accurate mass analysis that are in current usage, many employed incorrectly or inconsistently. This article is based on a set of notes prepared by the authors for research students and staff in our laboratories as a guide to the correct terminology and basic statistical procedures to apply in relation to mass measurement, particularly for accurate mass measurement. It elaborates on the editorial by Gross in 1994 regarding the use of accurate masses for structure confirmation. We have presented and defined the main terms in use with reference to the International Union of Pure and Applied Chemistry (IUPAC) recommendations for nomenclature and symbolism for mass spectrometry. The correct use of statistics and treatment of data is illustrated as a guide to new and existing mass spectrometry users with a series of examples as well as statistical methods to compare different experimental methods and datasets. Copyright © 2010. Published by Elsevier Inc.

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.

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

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

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.

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.

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

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.

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.

78 FR 33409 - Proposed Information Collection Request; Comment Request; See Item Specific ICR Titles Provided...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-06-04

... Item Specific ICR Titles Provided in the Text AGENCY: Environmental Protection Agency (EPA). ACTION... request (ICR) (See item specific ICR title, EPA ICR Number, and OMB Control Number provided in the text... additional comments to OMB. (1) Docket ID Number: EPA-HQ-OECA-2013-0337; Title: NESHAP for Portland Cement...

78 FR 35023 - Proposed Information Collection Request; Comment Request; See Item Specific ICR Titles Provided...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-06-11

...; See Item Specific ICR Titles Provided in the Text AGENCY: Environmental Protection Agency (EPA... collection request (ICR) (See item specific ICR title, EPA ICR Number, and OMB Control Number provided in the... opportunity to submit additional comments to OMB. (1) Docket ID Number: EPA-HQ-OECA-2013-0303; Title: NSPS for...

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.

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.

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

Complementary online aerosol mass spectrometry and offline FT-IR spectroscopy measurements: Prospects and challenges for the analysis of anthropogenic aerosol particle emissions

NASA Astrophysics Data System (ADS)

Faber, Peter; Drewnick, Frank; Bierl, Reinhard; Borrmann, Stephan

2017-10-01

The aerosol mass spectrometer (AMS) is well established in investigating highly time-resolved dynamics of submicron aerosol chemical composition including organic aerosol (OA). However, interpretation of mass spectra on molecular level is limited due to strong fragmentation of organic substances and potential reactions inside the AMS ion chamber. Results from complementary filter-based FT-IR absorption measurements were used to explain features in high-resolution AMS mass spectra of different types of OA (e.g. cooking OA, cigarette smoking OA, wood burning OA). Using this approach some AMS fragment ions were validated in this study as appropriate and rather specific markers for a certain class of organic compounds for all particle types under investigation. These markers can therefore be used to get deeper insights in the chemical composition of OA based on AMS mass spectra in upcoming studies. However, the specificity of other fragment ions such as C2H4O2+ (m/z 60.02114) remains ambiguous. In such cases, complementary FT-IR measurements allow the interpretation of highly time-resolved AMS mass spectra at the level of molecular functional groups. Furthermore, this study discusses the challenges in reducing inorganic interferences (e.g. from water and ammonium salts) in FT-IR spectra of atmospheric aerosols to decrease spectral uncertainties for better comparisons and, thus, to get more robust results.

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

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.

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.

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

FT3/FT4 ratio predicts non-alcoholic fatty liver disease independent of metabolic parameters in patients with euthyroidism and hypothyroidism

PubMed Central

Gökmen, Fatma Yahyaoğlu; Ahbab, Süleyman; Ataoğlu, Hayriye Esra; Türker, Betül Çavuşoğlu; Çetin, Faik; Türker, Fatih; Mamaç, Rabia Yahyaoğlu; Yenigün, Mustafa

2016-01-01

OBJECTIVE: This study was performed to evaluate the effects of metabolic parameters and thyroid dysfunction on the development of non-alcoholic fatty liver disease (NAFLD). METHODS: The current study evaluated a total of 115 patients, 75 female and 40 male. Physical examination and anthropometric measurements were applied to all participants. Hypothyroidism was considered at a thyroid stimulating hormone level ≥ 4.1 mIU/L. Patients with euthyroidism and patients with hypothyroidism were compared. Abdominal ultrasonography was used to diagnose non-alcoholic fatty liver disease. The participants were further compared with regard to the presence of non-alcoholic fatty liver disease. Logistic regression modeling was performed to identify the relationship between non-alcoholic fatty liver disease and independent variables, such as metabolic parameters and insulin resistance. RESULTS: Non-alcoholic fatty liver disease was identified in 69 patients. The mean waist circumference, body mass index, fasting plasma insulin, HOMA-IR (p<0.001) and FT3/FT4 ratio (p=0.01) values were significantly higher in the patients with NAFLD compared to those without it. Multivariate regression analysis revealed that FT3/FT4 ratio, waist circumference and insulin resistance were independent risk factors for non-alcoholic fatty liver disease. CONCLUSION: Insulin resistance, enlarged waist circumference, elevated body mass index, higher FT3/FT4 ratio and hypertriglyceridemia are independent risk factors for NADLF, whereas hypothyroidism is not directly related to the condition. PMID:27166773

Manipulation of dopamine metabolism contributes to attenuating innate high locomotor activity in ICR mice.

PubMed

Yamaguchi, Takeshi; Nagasawa, Mao; Ikeda, Hiromi; Kodaira, Momoko; Minaminaka, Kimie; Chowdhury, Vishwajit S; Yasuo, Shinobu; Furuse, Mitsuhiro

2017-06-15

Attention-deficit hyperactivity disorder (ADHD) is defined as attention deficiency, restlessness and distraction. The main characteristics of ADHD are hyperactivity, impulsiveness and carelessness. There is a possibility that these abnormal behaviors, in particular hyperactivity, are derived from abnormal dopamine (DA) neurotransmission. To elucidate the mechanism of high locomotor activity, the relationship between innate activity levels and brain monoamines and amino acids was investigated in this study. Differences in locomotor activity between ICR, C57BL/6J and CBA/N mice were determined using the open field test. Among the three strains, ICR mice showed the greatest amount of locomotor activity. The level of striatal and cerebellar DA was lower in ICR mice than in C57BL/6J mice, while the level of L-tyrosine (L-Tyr), a DA precursor, was higher in ICR mice. These results suggest that the metabolic conversion of L-Tyr to DA is lower in ICR mice than it is in C57BL/6J mice. Next, the effects of intraperitoneal injection of (6R)-5, 6, 7, 8-tetrahydro-l-biopterin dihydrochloride (BH 4 ) (a co-enzyme for tyrosine hydroxylase) and L-3,4-dihydroxyphenylalanine (L-DOPA) on DA metabolism and behavior in ICR mice were investigated. The DA level in the brain was increased by BH 4 administration, but the increased DA did not influence behavior. However, L-DOPA administration drastically lowered locomotor activity and increased DA concentration in several parts of the brain. The reduced locomotor activity may have been a consequence of the overproduction of DA. In conclusion, the high level of locomotor activity in ICR mice may be explained by a strain-specific DA metabolism. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

75 FR 7584 - Agency Information Collection Activities; Proposed Collection; Comment Request; EPA-ICR No. 1774...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-22

... Program, OMB Control No. 2060-0350 AGENCY: Environmental Protection Agency (EPA). ACTION: Notice. SUMMARY.... 1774.05, OMB Control No. 2060-0350. ICR status: This ICR is currently scheduled to expire on July 31...

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%.

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.

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

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

77 FR 58127 - Agency Information Collection Activities; Proposed Collection; Comment Request; EPA ICR No. 2104...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-19

... . 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...

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.

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.

Rotation Matrix from the Mean Dynamical Equator and Equinox at J2000.0 to the ICRS

DTIC Science & Technology

2004-01-01

the ICRS is offset from its equinox by ∆o. The angle 0 is the obliquity of the ecliptic on the ICRS, that is the angle between the ICRS equator and... obliquity is caused solely by a change in the position of the pole of the mean ecliptic . Thus, the sole effect of using the rotating definition of the mean...the mean ecliptic as determined by Chapront et al. from LLR observations (23◦26′21.′′41100 ± 0.′′00005). The angle γy is the separation between the

Analysis of human plasma metabolites across different liquid chromatography/mass spectrometry platforms: Cross-platform transferable chemical signatures.

PubMed

Telu, Kelly H; Yan, Xinjian; Wallace, William E; Stein, Stephen E; Simón-Manso, Yamil

2016-03-15

The metabolite profiling of a NIST plasma Standard Reference Material (SRM 1950) on different liquid chromatography/mass spectrometry (LC/MS) platforms showed significant differences. Although these findings suggest caution when interpreting metabolomics results, the degree of overlap of both profiles allowed us to use tandem mass spectral libraries of recurrent spectra to evaluate to what extent these results are transferable across platforms and to develop cross-platform chemical signatures. Non-targeted global metabolite profiles of SRM 1950 were obtained on different LC/MS platforms using reversed-phase chromatography and different chromatographic scales (conventional HPLC, UHPLC and nanoLC). The data processing and the metabolite differential analysis were carried out using publically available (XCMS), proprietary (Mass Profiler Professional) and in-house software (NIST pipeline). Repeatability and intermediate precision showed that the non-targeted SRM 1950 profiling was highly reproducible when working on the same platform (relative standard deviation (RSD) <2%); however, substantial differences were found in the LC/MS patterns originating on different platforms or even using different chromatographic scales (conventional HPLC, UHPLC and nanoLC) on the same platform. A substantial degree of overlap (common molecular features) was also found. A procedure to generate consistent chemical signatures using tandem mass spectral libraries of recurrent spectra is proposed. Different platforms rendered significantly different metabolite profiles, but the results were highly reproducible when working within one platform. Tandem mass spectral libraries of recurrent spectra are proposed to evaluate the degree of transferability of chemical signatures generated on different platforms. Chemical signatures based on our procedure are most likely cross-platform transferable. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

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...

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.

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.

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.

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

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.

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.

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

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

Comparative study of peripheral neuropathy and nerve regeneration in NOD and ICR diabetic mice.

PubMed

Homs, Judit; Ariza, Lorena; Pagès, Gemma; Verdú, Enrique; Casals, Laura; Udina, Esther; Chillón, Miguel; Bosch, Assumpció; Navarro, Xavier

2011-09-01

The non-obese diabetic (NOD) mouse was suggested as an adequate model for diabetic autonomic neuropathy. We evaluated sensory-motor neuropathy and nerve regeneration following sciatic nerve crush in NOD males rendered diabetic by multiple low doses of streptozotocin, in comparison with similarly treated Institute for Cancer Research (ICR) mice, a widely used model for type I diabetes. Neurophysiological values for both strains showed a decline in motor and sensory nerve conduction velocity at 7 and 8 weeks after induction of diabetes in the intact hindlimb. However, amplitudes of compound muscle and sensory action potentials (CMAPs and CNAPs) were significantly reduced in NOD but not in ICR diabetic mice. Morphometrical analysis showed myelinated fiber loss in highly hyperglycemic NOD mice, but no significant changes in fiber size. There was a reduction of intraepidermal nerve fibers, more pronounced in NOD than in ICR diabetic mice. Interestingly, aldose reductase and poly(ADP-ribose) polymerase (PARP) activities were increased already at 1 week of hyperglycemia, persisting until the end of the experiment in both strains. Muscle and nerve reinnervation was delayed in diabetic mice following sciatic nerve crush, being more marked in NOD mice. Thus, diabetes of mid-duration induces more severe peripheral neuropathy and slower nerve regeneration in NOD than in ICR mice. © 2011 Peripheral Nerve Society.

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.

Parts-Per-Billion Mass Measurement Accuracy Achieved through the Combination of Multiple Linear Regression and Automatic Gain Control in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

PubMed Central

Williams, D. Keith; Muddiman, David C.

2008-01-01

Fourier transform ion cyclotron resonance mass spectrometry has the ability to achieve unprecedented mass measurement accuracy (MMA); MMA is one of the most significant attributes of mass spectrometric measurements as it affords extraordinary molecular specificity. However, due to space-charge effects, the achievable MMA significantly depends on the total number of ions trapped in the ICR cell for a particular measurement. Even through the use of automatic gain control (AGC), the total ion population is not constant between spectra. Multiple linear regression calibration in conjunction with AGC is utilized in these experiments to formally account for the differences in total ion population in the ICR cell between the external calibration spectra and experimental spectra. This ability allows for the extension of dynamic range of the instrument while allowing mean MMA values to remain less than 1 ppm. In addition, multiple linear regression calibration is used to account for both differences in total ion population in the ICR cell as well as relative ion abundance of a given species, which also affords mean MMA values at the parts-per-billion level. PMID:17539605

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.

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.

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

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.

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.

Nano-LC/MALDI-MS using a column-integrated spotting probe for analysis of complex biomolecule samples.

PubMed

Hioki, Yusaku; Tanimura, Ritsuko; Iwamoto, Shinichi; Tanaka, Koichi

2014-03-04

Nanoflow liquid chromatography (nano-LC) is an essential technique for highly sensitive analysis of complex biological samples, and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is advantageous for rapid identification of proteins and in-depth analysis of post-translational modifications (PTMs). A combination of nano-LC and MALDI-MS (nano-LC/MALDI-MS) is useful for highly sensitive and detailed analysis in life sciences. However, the existing system does not fully utilize the advantages of each technique, especially in the interface of eluate transfer from nano-LC to a MALDI plate. To effectively combine nano-LC with MALDI-MS, we integrated a nano-LC column and a deposition probe for the first time (column probe) and incorporated it into a nano-LC/MALDI-MS system. Spotting nanoliter eluate droplets directly from the column onto the MALDI plate prevents postcolumn diffusion and preserves the chromatographic resolution. A DHB prespotted plate was prepared to suit the fabricated column probe to concentrate the droplets of nano-LC eluate. The performance of the advanced nano-LC/MALDI-MS system was substantiated by analyzing protein digests. When the system was coupled with multidimensional liquid chromatography (MDLC), trace amounts of glycopeptides that spiked into complex samples were successfully detected. Thus, a nano-LC/MALDI-MS direct-spotting system that eliminates postcolumn diffusion was constructed, and the efficacy of the system was demonstrated through highly sensitive analysis of the protein digests or spiked glycopeptides.

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

Jarvis, Jacqueline M.; Sudasinghe, Nilusha M.; Albrecht, Karl O.

We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The ironporphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICPOES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe=100,728 ppm) and cyanobacteria (Fe=115,450 ppm). Direct infusion FT-ICR MS analysis ofmore » the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron-porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron-porphyrin compounds in the two HTL biocrudes that are structurally similar to metal-porphyrins (e.g. Ni and V) observed in petroleum. No ironporphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron-porphyrin structures in the HTL biocrude are degraded during hydroprocessing. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron-porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.« less

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.

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.

Mercury in US coal: Observations using the COALQUAL and ICR data

USGS Publications Warehouse

Quick, J.C.; Brill, T.C.; Tabet, D.E.

2003-01-01

The COALQUAL data set lists the mercury content of samples collected from the in-ground US coal resource, whereas the ICR data set lists the mercury content of samples collected from coal shipments delivered to US electric utilities. After selection and adjustment of records, the COALQUAL data average 0.17 ??g Hg/g dry coal or 5.8 kg Hg/PJ, whereas the ICR data average 0.10 ??g Hg/g dry coal or 3.5 kg Hg/PJ. Because sample frequency does not correspond to the inground or produced tonnage, these values are not accurate estimates of the mercury content of either in-ground or delivered US coal. Commercial US coal contains less mercury than previously estimated, and its mercury content has declined during the 1990s. Selective mining and more extensive coal washing may accelerate the current trend towards lower mercury content in coal burned at US electric utilities.

[Effects of postnatal lambda-cyhalothrin exposure on synaptic proteins in ICR mouse brain].

PubMed

Bao, Xun-Di; Wang, Qu-Nan; Li, Fang-Fang; Chai, Xiao-Yu; Gao, Ye

2011-04-01

To evaluate the influence on the synaptic protein expression in different brain regions of ICR mice after lambda-cyhalothrin (LCT) exposure during postnatal period. Two male and 4 female healthy ICR mice were put in one cage. It was set as pregnancy if vaginal plug was founded. Offspring were divided into 5 groups randomly, and exposed to LCT (0.01% DMSO solution) at the doses of 0.1, 1.0 and 10.0 mg/kg by intragastric rout every other day from postnatal days (PND) 5 to PND13, control animals were treated with normal saline or DMSO by the same route. The brains were removed from pups on PND 14, the synaptic protein expression levels in cortex, hippocampus and striatum were measured by western blot. GFAP levels of cortex and hippocampus in the LCT exposure group increased with doses, as compared with control group (P < 0.05), while Tuj protein expression did not change significantly in the various brain regions of ICR mice. GAP-43 protein expression levels in the LCT exposed mouse hippocampus and in female ICR mouse cortex increased with doses, as compared with control group (P < 0.05). Presynaptic protein (Synapsin I) expression levels did not change obviously in various brain regions. However, postsynaptic density protein 95 (PSD95) expression levels of the hippocampus and striatum in male offspring of 10.0 mg/kg LCT group, of cortex of female LCT groups, and of female offspring in all exposure groups, of striatum, in 1.0 or 10.0 mg/kg LCT exposure groups significantly decreased (P < 0.05). Early postnatal exposure to LCT affects synaptic protein expression. These effects may ultimately affect the construction of synaptic connections.

Molecular orientation in aligned electrospun polyimide nanofibers by polarized FT-IR spectroscopy.

PubMed

Yang, Haoqi; Jiang, Shaohua; Fang, Hong; Hu, Xiaowu; Duan, Gaigai; Hou, Haoqing

2018-07-05

Quantitative explanation on the improved mechanical properties of aligned electrospun polyimide (PI) nanofibers as the increased imidization temperatures is highly required. In this work, polarized FT-IR spectroscopy is applied to solve this problem. Based on the polarized FT-IR spectroscopy and the molecular model in the fibers, the length of the repeat unit of PI molecule, the angle between the fiber axis and the symmetric stretching direction of carbonyl group on the imide ring, and the angle between the PI molecular axis and fiber axis are all investigated. The Mark-Howink equation is used to calculate the number-average molar mass of PI molecules. The orientation states of PI molecules in the electrospun nanofibers are studied from the number-average molar mass of PI molecules and the average fiber diameter. Quantitative analysis of the orientation factor of PI molecules in the electrospun nanofibers is performed by polarized FT-IR spectroscopy. Copyright © 2018 Elsevier B.V. All rights reserved.

In vivo irritation study of Melastoma malabathricum cream formulation on ICR mice

NASA Astrophysics Data System (ADS)

Yasin, Rabiahtul Adarwiyah Mohd; Jemon, Khairunadwa; Nor, Norefrina Shafinaz Md

2016-11-01

Melastoma malabathricum is a traditional herb that is used to treat wound on skin. It has also been proven to have antiviral activity against Herpes Simplex virus type 1 (HSV-1). In this study, M. malabathricum cream formulation was developed by incorporating M. malabathricum aqueous extract into cream base. The safety and biocompatibility of the formulated cream was investigated by topically applying the cream onto the back of ICR mice skin. Treatment with M. malabathricum was found to accelerate wound contraction with less scar formation. The effect of M. malabathricum has prompted a possibility that M. malabathricum might contribute in enhancing the healing process of cutaneous lesion caused by HSV-1. The formulated cream did not cause any skin irritation or adverse effect to ICR mice when topically applied within seven days of exposure.

Analysis of anthocyanins in commercial fruit juices by using nano-liquid chromatography-electrospray-mass spectrometry and high-performance liquid chromatography with UV-vis detector.

PubMed

Fanali, Chiara; Dugo, Laura; D'Orazio, Giovanni; Lirangi, Melania; Dachà, Marina; Dugo, Paola; Mondello, Luigi

2011-01-01

Nano-LC and conventional HPLC techniques were applied for the analysis of anthocyanins present in commercial fruit juices using a capillary column of 100 μm id and a 2.1 mm id narrow-bore C(18) column. Analytes were detected by UV-Vis at 518 nm and ESI-ion trap MS with HPLC and nano-LC, respectively. Commercial blueberry juice (14 anthocyanins detected) was used to optimize chromatographic separation of analytes and other analysis parameters. Qualitative identification of anthocyanins was performed by comparing the recorded mass spectral data with those of published papers. The use of the same mobile phase composition in both techniques revealed that the miniaturized method exhibited shorter analysis time and higher sensitivity than narrow-bore chromatography. Good intra-day and day-to-day precision of retention time was obtained in both methods with values of RSD less than 3.4 and 0.8% for nano-LC and HPLC, respectively. Quantitative analysis was performed by external standard curve calibration of cyanidin-3-O-glucoside standard. Calibration curves were linear in the concentration ranges studied, 0.1-50 and 6-50 μg/mL for HPLC-UV/Vis and nano-LC-MS, respectively. LOD and LOQ values were good for both methods. In addition to commercial blueberry juice, qualitative and quantitative analysis of other juices (e.g. raspberry, sweet cherry and pomegranate) was performed. The optimized nano-LC-MS method allowed an easy and selective identification and quantification of anthocyanins in commercial fruit juices; it offered good results, shorter analysis time and reduced mobile phase volume with respect to narrow-bore HPLC. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

THE OCCURRENCE OF A NEW GENERATION OF DBPS (BEYOND THE ICR)

EPA Science Inventory

A nationwide survey of 12 full-scale treatment plants for disinfection by-products (DBPs) was initiated in the U.S. in 2000. Approximately 50DBPs that rated a high priority for potential toxicity and were not included in the Information Collection Rule (ICR) are being quantified...

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.

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.

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.

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.

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

75 FR 61481 - Agency Information Collection Activities; Submission of EPA ICR No. 2078.01 to OMB for Review and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-10-05

... identity or contact information unless you provide it in the body of your comment. If you send an e-mail... and other contact information in the body of your comment and with any disk or CD-ROM you submit. If..., OMB Control No. 2060-0528. ICR Status: This ICR is currently scheduled to expire on March 31, 2011. An...

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

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.

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

PubMed Central

Johnson, Grant E.; Gunaratne, K. Don Dasitha; Laskin, Julia

2014-01-01

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces. PMID:24961913

In Situ SIMS and IR Spectroscopy of Well-Defined Surfaces Prepared by Soft Landing of Mass-Selected Ions

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

Johnson, Grant E.; Gunaratne, Kalupathirannehelage Don D.; Laskin, Julia

2014-06-16

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+, onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivitymore » of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.« less

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

76 FR 82322 - Agency Information Collection Activities; Submission for OMB Review; Comment Request; Mass Layoff...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-30

... for OMB Review; Comment Request; Mass Layoff Statistics Program ACTION: Notice. SUMMARY: The... request (ICR) titled, ``Mass Layoff Statistics Program,'' to the Office of Management and Budget (OMB) for... Statistics (BLS). Title of Collection: Mass Layoff Statistics Program. OMB Control Number: 1220-0090...

f(T) gravity and energy distribution in Landau-Lifshitz prescription

NASA Astrophysics Data System (ADS)

Ganiou, M. G.; Houndjo, M. J. S.; Tossa, J.

We investigate in this paper the Landau-Lifshitz energy distribution in the framework of f(T) theory view as a modified version of Teleparallel theory. From some important Teleparallel theory results on the localization of energy, our investigations generalize the Landau-Lifshitz prescription from the computation of the energy-momentum complex to the framework of f(T) gravity as it is done in the modified versions of General Relativity. We compute the energy density in the first step for three plane-symmetric metrics in vacuum. We find for the second metric that the energy density vanishes independently of f(T) models. We find that the Teleparallel Landau-Lifshitz energy-momentum complex formulations for these metrics are different from those obtained in General Relativity for the same metrics. Second, the calculations are performed for the cosmic string spacetime metric. It results that the energy distribution depends on the mass M and the radius r of cosmic string and it is strongly affected by the parameter of the considered quadratic and cubic f(T) models. Our investigation with this metric induces interesting results susceptible to be tested with some astrophysics hypothesis.

Chemical Structural Characteristics of HULIS and Other Fractionated Organic Matter in Urban Aerosols: Results from Mass Spectral and FT-IR Analysis.

PubMed

Chen, Qingcai; Ikemori, Fumikazu; Higo, Hayato; Asakawa, Daichi; Mochida, Michihiro

2016-02-16

The chemical characteristics of complex organic matter in atmospheric aerosols remain poorly understood. Water-insoluble organic matter (WISOM) and water-soluble organic matter (WSOM) in the total suspended particulates collected in the city of Nagoya in summer/early autumn and winter were extracted using multiple solvents. Two fractions of humic-like substances, showing neutral and acidic behavior (HULIS-n and HULIS-a, respectively), and the remaining highly polar part (HP-WSOM) were fractionated from WSOM using solid phase extraction. The chemical structural characteristics and concentrations of the organic matter were investigated using mass spectrometry and Fourier transform infrared (FT-IR) spectroscopy. WISOM and HULIS-n had low O/C ratios (0.1 and 0.4, respectively) and accounted for a large fraction of the organics in aerosols (70%). HULIS-a and HP-WSOM had higher O/C ratios (0.7 and 1.0, respectively), and their concentrations in summer and early autumn were on average ∼2 times higher than those in winter. The mass spectrum and FT-IR analyses suggest the following: (1) WISOM were high-molecular-weight aliphatics (primarily C27-C32) with small proportions of -CH3, -OH, and C═O groups; (2) HULIS-n was abundant in aliphatic structures and hydroxyl groups (primarily C9-C18) and by branched structures; (3) HULIS-a and HP-WSOM contained relatively large amounts of low-molecular-weight carboxylic acids and alcohols (primarily C4-C10); and (4) WISOM and HULIS-n were relatively abundant in amines and organic nitrates.

Separation of ion types in tandem mass spectrometry data interpretation -- a graph-theoretic approach.

PubMed

Yan, Bo; Pan, Chongle; Olman, Victor N; Hettich, Robert L; Xu, Ying

2004-01-01

Mass spectrometry is one of the most popular analytical techniques for identification of individual proteins in a protein mixture, one of the basic problems in proteomics. It identifies a protein through identifying its unique mass spectral pattern. While the problem is theoretically solvable, it remains a challenging problem computationally. One of the key challenges comes from the difficulty in distinguishing the N- and C-terminus ions, mostly b- and y-ions respectively. In this paper, we present a graph algorithm for solving the problem of separating bfrom y-ions in a set of mass spectra. We represent each spectral peak as a node and consider two types of edges: a type-1 edge connects two peaks possibly of the same ion types and a type-2 edge connects two peaks possibly of different ion types, predicted based on local information. The ion-separation problem is then formulated and solved as a graph partition problem, which is to partition the graph into three subgraphs, namely b-, y-ions and others respectively, so to maximize the total weight of type-1 edges while minimizing the total weight of type-2 edges within each subgraph. We have developed a dynamic programming algorithm for rigorously solving this graph partition problem and implemented it as a computer program PRIME. We have tested PRIME on 18 data sets of high accurate FT-ICR tandem mass spectra and found that it achieved ~90% accuracy for separation of b- and y- ions.

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.

Evaluation of Turmeric Powder Adulterated with Metanil Yellow Using FT-Raman and FT-IR Spectroscopy

PubMed Central

Dhakal, Sagar; Chao, Kuanglin; Schmidt, Walter; Qin, Jianwei; Kim, Moon; Chan, Diane

2016-01-01

Turmeric powder (Curcuma longa L.) is valued both for its medicinal properties and for its popular culinary use, such as being a component in curry powder. Due to its high demand in international trade, turmeric powder has been subject to economically driven, hazardous chemical adulteration. This study utilized Fourier Transform-Raman (FT-Raman) and Fourier Transform-Infra Red (FT-IR) spectroscopy as separate but complementary methods for detecting metanil yellow adulteration of turmeric powder. Sample mixtures of turmeric powder and metanil yellow were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1%, and 0.01% (w/w). FT-Raman and FT-IR spectra were acquired for these mixture samples as well as for pure samples of turmeric powder and metanil yellow. Spectral analysis showed that the FT-IR method in this study could detect the metanil yellow at the 5% concentration, while the FT-Raman method appeared to be more sensitive and could detect the metanil yellow at the 1% concentration. Relationships between metanil yellow spectral peak intensities and metanil yellow concentration were established using representative peaks at FT-Raman 1406 cm−1 and FT-IR 1140 cm−1 with correlation coefficients of 0.93 and 0.95, respectively. PMID:28231130

Detection of metanil yellow contamination in turmeric using FT-Raman and FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Dhakal, Sagar; Chao, Kuanglin; Qin, Jianwei; Kim, Moon; Schmidt, Walter; Chan, Dian

2016-05-01

Turmeric is well known for its medicinal value and is often used in Asian cuisine. Economically motivated contamination of turmeric by chemicals such as metanil yellow has been repeatedly reported. Although traditional technologies can detect such contaminants in food, high operational costs and operational complexities have limited their use to the laboratory. This study used Fourier Transform Raman Spectroscopy (FT-Raman) and Fourier Transform - Infrared Spectroscopy (FT-IR) to identify metanil yellow contamination in turmeric powder. Mixtures of metanil yellow in turmeric were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1% and 0.01% (w/w). The FT-Raman and FT-IR spectral signal of pure turmeric powder, pure metanil yellow powder and the 8 sample mixtures were obtained and analyzed independently to identify metanil yellow contamination in turmeric. The results show that FT-Raman spectroscopy and FT-IR spectroscopy can detect metanil yellow mixed with turmeric at concentrations as low as 1% and 5%, respectively, and may be useful for non-destructive detection of adulterated turmeric powder.

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

Molecular cloning and functional analysis of the FLOWERING LOCUS T (FT) homolog GhFT1 from Gossypium hirsutum.

PubMed

Guo, Danli; Li, Chao; Dong, Rui; Li, Xiaobo; Xiao, Xiangwen; Huang, Xianzhong

2015-06-01

FLOWERING LOCUS T (FT) encodes a member of the phosphatidylethanolamine-binding protein (PEBP) family that functions as the mobile floral signal, playing an important role in regulating the floral transition in angiosperms. We isolated an FT-homolog (GhFT1) from Gossypium hirsutum L. cultivar, Xinluzao 33 GhFT1 was predominantly expressed in stamens and sepals, and had a relatively higher expression level during the initiation stage of fiber development. GhFT1 mRNA displayed diurnal oscillations in both long-day and short-day condition, suggesting that the expression of this gene may be under the control of the circadian clock. Subcellular analysis revealed that GhFT1 protein located in the cytoplasm and nucleus. Ectopic expression of GhFT1 in transgenic arabidopsis plants resulted in early flowering compared with wild-type plants. In addition, ectopic expression of GhFT1 in arabidopsis ft-10 mutants partially rescued the extremely late flowering phenotype. Finally, several flowering related genes functioning downstream of AtFT were highly upregulated in the 35S::GhFT1 transgenic arabidopsis plants. In summary, GhFT1 is an FT-homologous gene in cotton that regulates flower transition similar to its orthologs in other plant species and thus it may be a candidate target for promoting early maturation in cotton breeding. © 2014 Institute of Botany, Chinese Academy of Sciences.

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

Toxicological effects of benzo[a]pyrene on DNA methylation of whole genome in ICR mice.

PubMed

Zhao, L; Zhang, S; An, X; Tan, W; Pang, D; Ouyang, H

2015-10-30

It has been well known that alterations in DNA methylation - an important regulator of gene transcription - lead to cancer. Therefore a change in the level of DNA methylation of whole genome has been considered as a biomarker of carcinogenesis. Previously, a large number of experimental results in genetic toxicology have showed that benzo[a]pyrene could cause DNA mutation and fragmentation. However, there was little to no studies on alterations in DNA methylation of genome directly result from exposure to benzo[a]pyrene. In this paper, possible mechanisms of alterations in whole genomic DNA methylation by benzo[a]pyrene were investigated using ICR mice after benzo[a]pyrene exposure. The blood, liver, pancreas, skin, lung and bladder of ICR mice were removed and checked after a fixed time interval (6 hours) of benzo[a]pyrene exposure, and whole genomic DNA methylation level was determined by high performance liquid chromatography (HPLC). The results exhibited tissue specificity, that is, the level of whole genomic DNA methylation decreases significantly in blood and liver, rather than pancreas, lung, skin and bladder of ICR mice. This study investigated the direct relationship between aberrant DNA methylation level and benzo[a]pyrene exposure, which might be helpful to clarify the toxicological mechanism of benzo[a]pyrene in epigenetic perspectives.

Differential effects of MK-801 on cerebrocortical neuronal injury in C57BL/6J, NSA, and ICR mice.

PubMed

Brosnan-Watters, G; Ogimi, T; Ford, D; Tatekawa, L; Gilliam, D; Bilsky, E J; Nash, D

2000-08-01

1. Antagonists of the N-methyl-D-aspartate (NMDA) glutamate (Glu) receptor, including [(+)-5-methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5,10-imine maleate], dizocilpine maleate (MK-801), injure pyramidal neurons in the posterior cingulate/retrosplenial (PC/RS) cortex when administered systemically to adult rats and mice. 2. These results have, to our knowledge, only been reported previously in Harlan Sprague Dawley albino rats and International Cancer Research (ICR) mice, an outbred albino strain. 3. Male Non-Swiss Albino (NSA) mice, an albino outbred strain, and male C57BL/6J (B6) mice, a pigmented inbred strain, were injected systemically with 1 mg/kg of MK-801 in the first experiment. This dose of MK-801 reliably produces cytoplasmic vacuoles in neurons in layers III and IV of the PC/RS cortex in 100% of ICR mice treated 4. There was a significant difference in the number of vacuolated neurons in B6 and NSA mice, as assessed by ANOVA. The NSA were not significantly different than previously examined ICR mice, but the B6 had fewer vacuolated neurons than either of the two outbred strains. 5. In the second experiment, male NSA, ICR, and B6 mice were injected systemically with a high dose, 10 mg/kg, of MK-801. This dose has been demonstrated to result in necrosis in the same population of neurons injured by lower doses of MK-801. 6. An ANOVA indicated that there was a significant difference among the three strains of mice, and a Fisher's protected t revealed that the B6 mice were significantly different from both the NSA and ICR, but that, with our test, those two strains were indistinguishable. 7. Male ICR, NSA, and B6 mice were tested in the holeboard food search task 5 hours after 1 mg/kg of MK-801. There were significant differences between the strains in performance both pre and posttreatment. The effect of the drug was not statistically significant. 8. These results suggest that there may be a genetically mediated difference in the reaction to NMDA

Using ICR and SCID mice as animal models for smallpox to assess antiviral drug efficacy.

PubMed

Titova, Ksenya A; Sergeev, Alexander A; Zamedyanskaya, Alena S; Galahova, Darya O; Kabanov, Alexey S; Morozova, Anastasia A; Bulychev, Leonid E; Sergeev, Artemiy A; Glotova, Tanyana I; Shishkina, Larisa N; Taranov, Oleg S; Omigov, Vladimir V; Zavjalov, Evgenii L; Agafonov, Alexander P; Sergeev, Alexander N

2015-09-01

The possibility of using immunocompetent ICR mice and immunodeficient SCID mice as model animals for smallpox to assess antiviral drug efficacy was investigated. Clinical signs of the disease did not appear following intranasal (i.n.) challenge of mice with strain Ind-3a of variola virus (VARV), even when using the highest possible dose of the virus (5.2 log10 p.f.u.). The 50 % infective doses (ID50) of VARV, estimated by the virus presence or absence in the lungs 3 and 4 days post-infection, were 2.7 ± 0.4 log10 p.f.u. for ICR mice and 3.5 ± 0.7 log10 p.f.u. for SCID mice. After i.n. challenge of ICR and SCID mice with VARV 30 and 50 ID50, respectively, steady reproduction of the virus occurred only in the respiratory tract (lungs and nose). Pathological inflammatory destructive changes were revealed in the respiratory tract and the primary target cells for VARV (macrophages and epithelial cells) in mice, similar to those in humans and cynomolgus macaques. The use of mice to assess antiviral efficacies of NIOCH-14 and ST-246 demonstrated the compliance of results with those described in scientific literature, which opens up the prospect of their use as an animal model for smallpox to develop anti-smallpox drugs intended for humans.

SWiFT Software Quality Assurance Plan.

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

Berg, Jonathan Charles

This document describes the software development practice areas and processes which contribute to the ability of SWiFT software developers to provide quality software. These processes are designed to satisfy the requirements set forth by the Sandia Software Quality Assurance Program (SSQAP). APPROVALS SWiFT Software Quality Assurance Plan (SAND2016-0765) approved by: Department Manager SWiFT Site Lead Dave Minster (6121) Date Jonathan White (6121) Date SWiFT Controls Engineer Jonathan Berg (6121) Date CHANGE HISTORY Issue Date Originator(s) Description A 2016/01/27 Jon Berg (06121) Initial release of the SWiFT Software Quality Assurance Plan

Rapid Screening of Bovine Milk Oligosaccharides in a Whey Permeate Product and Domestic Animal Milks by Accurate Mass Database and Tandem Mass Spectral Library.

PubMed

Lee, Hyeyoung; Cuthbertson, Daniel J; Otter, Don E; Barile, Daniela

2016-08-17

A bovine milk oligosaccharide (BMO) library, prepared from cow colostrum, with 34 structures was generated and used to rapidly screen oligosaccharides in domestic animal milks and a whey permeate powder. The novel library was entered into a custom Personal Compound Database and Library (PCDL) and included accurate mass, retention time, and tandem mass spectra. Oligosaccharides in minute-sized samples were separated using nanoliquid chromatography (nanoLC) coupled to a high resolution and sensitive quadrupole-Time of Flight (Q-ToF) MS system. Using the PCDL, 18 oligosaccharides were found in a BMO-enriched product obtained from whey permeate processing. The usefulness of the analytical system and BMO library was further validated using milks from domestic sheep and buffaloes. Through BMO PCDL searching, 15 and 13 oligosaccharides in the BMO library were assigned in sheep and buffalo milks, respectively, thus demonstrating significant overlap between oligosaccharides in bovine (cow and buffalo) and ovine (sheep) milks. This method was shown to be an efficient, reliable, and rapid tool to identify oligosaccharide structures using automated spectral matching.

Rapid Screening of Bovine Milk Oligosaccharides in a Whey Permeate Product and Domestic Animal Milks by Accurate Mass Database and Tandem Mass Spectral Library

PubMed Central

Lee, Hyeyoung; Cuthbertson, Daniel J.; Otter, Don E.; Barile, Daniela

2018-01-01

A bovine milk oligosaccharide (BMO) library, prepared from cow colostrum, with 34 structures was generated and used to rapidly screen oligosaccharides in domestic animal milks and a whey permeate powder. The novel library was entered into a custom Personal Compound Database and Library (PCDL) and included accurate mass, retention time, and tandem mass spectra. Oligosaccharides in minute-sized samples were separated using nanoliquid chromatography (nanoLC) coupled to a high resolution and sensitive quadrupole-Time of Flight (Q-ToF) MS system. Using the PCDL, 18 oligosaccharides were found in a BMO-enriched product obtained from whey permeate processing. The usefulness of the analytical system and BMO library was further validated using milks from domestic sheep and buffaloes. Through BMO PCDL searching, 15 and 13 oligosaccharides in the BMO library were assigned in sheep and buffalo milks, respectively, thus demonstrating significant overlap between oligosaccharides in bovine (cow and buffalo) and ovine (sheep) milks. This method was shown to be an efficient, reliable, and rapid tool to identify oligosaccharide structures using automated spectral matching. PMID:27428379

FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols

NASA Astrophysics Data System (ADS)

George, Kathryn M.; Ruthenburg, Travis C.; Smith, Jeremy; Yu, Lu; Zhang, Qi; Anastasio, Cort; Dillner, Ann M.

2015-01-01

Recent findings suggest that secondary organic aerosols (SOA) formed from aqueous-phase reactions of some organic species, including phenols, contribute significantly to particulate mass in the atmosphere. In this study, we employ a Fourier transform infrared (FT-IR) spectroscopic technique to identify and quantify the functional group makeup of phenolic SOA. Solutions containing an oxidant (hydroxyl radical or 3,4-dimethoxybenzaldehyde) and either one phenol (phenol, guaiacol, or syringol) or a mixture of phenols mimicking softwood or hardwood emissions were illuminated to make SOA, atomized, and collected on a filter. We produced laboratory standards of relevant organic compounds in order to develop calibrations for four functional groups: carbonyls (Cdbnd O), saturated C-H, unsaturated C-H and O-H. We analyzed the SOA samples with transmission FT-IR to identify and determine the amounts of the four functional groups. The carbonyl functional group accounts for 3-12% of the SOA sample mass in single phenolic SOA samples and 9-14% of the SOA sample mass in mixture samples. No carbonyl functional groups are present in the initial reactants. Varying amounts of each of the other functional groups are observed. Comparing carbonyls measured by FT-IR (which could include aldehydes, ketones, esters, and carboxylic acids) with eight small carboxylic acids measured by ion chromatography indicates that the acids only account for an average of 20% of the total carbonyl reported by FT-IR.

High Resolution MALDI Imaging Mass Spectrometry of Retinal Tissue Lipids

NASA Astrophysics Data System (ADS)

Anderson, David M. G.; Ablonczy, Zsolt; Koutalos, Yiannis; Spraggins, Jeffrey; Crouch, Rosalie K.; Caprioli, Richard M.; Schey, Kevin L.

2014-08-01

Matrix assisted laser desorption ionization imaging mass spectrometry (MALDI IMS) has the ability to provide an enormous amount of information on the abundances and spatial distributions of molecules within biological tissues. The rapid progress in the development of this technology significantly improves our ability to analyze smaller and smaller areas and features within tissues. The mammalian eye has evolved over millions of years to become an essential asset for survival, providing important sensory input of an organism's surroundings. The highly complex sensory retina of the eye is comprised of numerous cell types organized into specific layers with varying dimensions, the thinnest of which is the 10 μm retinal pigment epithelium (RPE). This single cell layer and the photoreceptor layer contain the complex biochemical machinery required to convert photons of light into electrical signals that are transported to the brain by axons of retinal ganglion cells. Diseases of the retina, including age-related macular degeneration (AMD), retinitis pigmentosa, and diabetic retinopathy, occur when the functions of these cells are interrupted by molecular processes that are not fully understood. In this report, we demonstrate the use of high spatial resolution MALDI IMS and FT-ICR tandem mass spectrometry in the Abca4 -/- knockout mouse model of Stargardt disease, a juvenile onset form of macular degeneration. The spatial distributions and identity of lipid and retinoid metabolites are shown to be unique to specific retinal cell layers.

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.

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.

Development of a Fourier-transform ion cyclotron resonance mass spectrometer-ion mobility spectrometer

NASA Astrophysics Data System (ADS)

Bluhm, Brian K.; Gillig, Kent J.; Russell, David H.

2000-11-01

In an effort to incorporate ion-molecule reaction chemistry with ion mobility measurements we designed and constructed a novel instrument that combines a Fourier-transform ion cyclotron resonance (ICR) mass spectrometer with an ion mobility drift cell and a time-of-flight mass spectrometer. Measured mobilities for Ar+ and CO+ in helium are in excellent agreement with accepted literature values demonstrating that there are no adverse effects from the magnetic field on ion mobility measurements. Drift cell pressure, extracted from the measured mobility of Ar+ in helium, indicate that a pressure of ˜0.25 Torr is achieved in the present configuration. There are significant technological challenges associated with combining ICR and ion mobility that occurred during construction of this instrument, such as differential pumping and aperture alignment are presented.

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.

Detection of starch adulteration in onion powder by FT-NIR and FT-IR spectroscopy

USDA-ARS?s Scientific Manuscript database

Adulteration of onion powder with cornstarch was identified by Fourier transform near-infrared (FT-NIR) and Fourier transform infrared (FT-IR) spectroscopy. The reflectance spectra of 180 pure and adulterated samples (1–35 wt% starch) were collected and preprocessed to generate calibration and predi...

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.

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.

Isolation and functional characterization of JcFT, a FLOWERING LOCUS T (FT) homologous gene from the biofuel plant Jatropha curcas.

PubMed

Li, Chaoqiong; Luo, Li; Fu, Qiantang; Niu, Longjian; Xu, Zeng-Fu

2014-05-08

Physic nut (Jatropha curcas L.) is a potential feedstock for biofuel production because Jatropha oil is highly suitable for the production of the biodiesel and bio-jet fuels. However, Jatropha exhibits low seed yield as a result of unreliable and poor flowering. FLOWERING LOCUS T (FT) -like genes are important flowering regulators in higher plants. To date, the flowering genes in Jatropha have not yet been identified or characterized. To better understand the genetic control of flowering in Jatropha, an FT homolog was isolated from Jatropha and designated as JcFT. Sequence analysis and phylogenetic relationship of JcFT revealed a high sequence similarity with the FT genes of Litchi chinensis, Populus nigra and other perennial plants. JcFT was expressed in all tissues of adult plants except young leaves, with the highest expression level in female flowers. Overexpression of JcFT in Arabidopsis and Jatropha using the constitutive promoter cauliflower mosaic virus 35S or the phloem-specific promoter Arabidopsis SUCROSE TRANSPORTER 2 promoter resulted in an extremely early flowering phenotype. Furthermore, several flowering genes downstream of JcFT were up-regulated in the JcFT-overexpression transgenic plant lines. JcFT may encode a florigen that acts as a key regulator in flowering pathway. This study is the first to functionally characterize a flowering gene, namely, JcFT, in the biofuel plant Jatropha.

Isolation and functional characterization of JcFT, a FLOWERING LOCUS T (FT) homologous gene from the biofuel plant Jatropha curcas

PubMed Central

2014-01-01

Background Physic nut (Jatropha curcas L.) is a potential feedstock for biofuel production because Jatropha oil is highly suitable for the production of the biodiesel and bio-jet fuels. However, Jatropha exhibits low seed yield as a result of unreliable and poor flowering. FLOWERING LOCUS T (FT) –like genes are important flowering regulators in higher plants. To date, the flowering genes in Jatropha have not yet been identified or characterized. Results To better understand the genetic control of flowering in Jatropha, an FT homolog was isolated from Jatropha and designated as JcFT. Sequence analysis and phylogenetic relationship of JcFT revealed a high sequence similarity with the FT genes of Litchi chinensis, Populus nigra and other perennial plants. JcFT was expressed in all tissues of adult plants except young leaves, with the highest expression level in female flowers. Overexpression of JcFT in Arabidopsis and Jatropha using the constitutive promoter cauliflower mosaic virus 35S or the phloem-specific promoter Arabidopsis SUCROSE TRANSPORTER 2 promoter resulted in an extremely early flowering phenotype. Furthermore, several flowering genes downstream of JcFT were up-regulated in the JcFT-overexpression transgenic plant lines. Conclusions JcFT may encode a florigen that acts as a key regulator in flowering pathway. This study is the first to functionally characterize a flowering gene, namely, JcFT, in the biofuel plant Jatropha. PMID:24886195

Spontaneous extraskeletal osteosarcoma with various histological growth patterns in the abdominal wall of an ICR mouse

PubMed Central

Ito, Tsuyoshi; Katoh, Yoshitaka; Shimada, Yuko; Ohnuma-Koyama, Aya; Takahashi, Naofumi; Kuwahara, Maki; Harada, Takanori

2015-01-01

Extraskeletal osteosarcoma is extremely rare in mice. This case report demonstrates a spontaneous murine extraskeletal osteosarcoma that exhibited various histological growth patterns in an ICR mouse. At necropsy, the tumor mass was located in the abdominal wall and was 45 × 30 × 25 mm in size. Histopathologically, the tumor showed the following four growth patterns: a solid pattern of polygonal cells embedded in an osteoid eosinophilic matrix with calcification, an irregular sheet pattern of short spindle cells accompanying some eosinophilic multinucleated cells, a fascicular pattern of spindle cells and a cystic pattern lined by short spindle cells. Immunohistochemically, most of the tumor cells were positive for vimentin, proliferating cell nuclear antigen and osterix. The multinucleated cells mentioned above were desmin positive and were regarded as regenerative striated muscles but not tumor cells. Since no clear continuity with normal bone tissues was observed, the tumor was diagnosed as an “extraskeletal osteosarcoma.” PMID:26989300

9-Ft By 7-Ft Supersonic Wind Tunnel Nozzle Improvement Study

NASA Technical Reports Server (NTRS)

Paciano, Eric N.

2014-01-01

Engineers at the Unitary Plan Wind Tunnel at NASA Ames Research Center have recently embarked on a project focused on improving flow quality and tunnel capabilities in the 9-ft by 7-ft supersonic wind tunnel. Collaborating with Jacobs Tech Group, the project has explored potential improvements to the nozzle design using computational fluid dynamics. Preliminary predictions suggest changes to the nozzle design could significantly improve flow quality at the lower operating range (M1.5-1.8), however potential improvements in the upper operating range have yet to be realized.

FT-Raman and FT-IR spectra of some heterobimetallic complexes with phenylcyclopentadienyl ligands

NASA Astrophysics Data System (ADS)

Nie, Chong-Shi; Guo, Jianhua; Qian, Changtao; Tan, Ying

1996-11-01

The FT-Raman and selected IR spectra of 14 heterobimetallic complexes of (CO) 3CrC 6H 5-C 5H 4M(CO) n(NO) mX (M = transition metal, X = other ligands) are reported. FT-Raman exhibits distinct strong characteristic bands of coordinated C 6H 5-C 5H 4 ligand ring deformation near 1540, 1490 and 1280 cm -1 and the coordinated phenyl ring deformation mode near 1000 cm -1, which are negligible in IR spectra. It is also easy to find the M-CO stretching and M-C-O bending as well as phenyl-M stretching bands in the FT-Raman spectra. The v(CO) IR absorptions in THF solution were reasonably assigned according to the local symmetry of the complexes.

Sandia SWiFT Wind Turbine Manual.

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

White, Jonathan; LeBlanc, Bruce Philip; Berg, Jonathan Charles

The Scaled Wind Farm Technology (SWiFT) facility, operated by Sandia National Laboratories for the U.S. Department of Energy's Wind and Water Power Program, is a wind energy research site with multiple wind turbines scaled for the experimental study of wake dynamics, advanced rotor development, turbine control, and advanced sensing for production-scale wind farms. The SWiFT site currently includes three variable-speed, pitch-regulated, three-bladed wind turbines. The six volumes of this manual provide a detailed description of the SWiFT wind turbines, including their operation and user interfaces, electrical and mechanical systems, assembly and commissioning procedures, and safety systems. Further dissemination only asmore » authorized to U.S. Government agencies and their contractors; other requests shall be approved by the originating facility or higher DOE programmatic authority. 111 UNCLASSIFIED UNLIMITED RELEASE Sandia SWiFT Wind Turbine Manual (SAND2016-0746 ) approved by: Department Manager SWiFT Site Lead Dave Minster (6121) Date Jonathan White (6121) Date SWiFT Site Supervisor Dave Mitchell (6121) Date Note: Document revision logs are found after the title page of each volume of this manual. iv« less

FT Duplication Coordinates Reproductive and Vegetative Growth

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

Hsu, Chuan-Yu; Adams, Joshua P.; Kim, Hyejin

2011-01-01

Annual plants grow vegetatively at early developmental stages and then transition to the reproductive stage, followed by senescence in the same year. In contrast, after successive years of vegetative growth at early ages, woody perennial shoot meristems begin repeated transitions between vegetative and reproductive growth at sexual maturity. However, it is unknown how these repeated transitions occur without a developmental conflict between vegetative and reproductive growth. We report that functionally diverged paralogs FLOWERING LOCUS T1 (FT1) and FLOWERING LOCUS T2 (FT2), products of whole-genome duplication and homologs of Arabidopsis thaliana gene FLOWERING LOCUS T (FT), coordinate the repeated cycles ofmore » vegetative and reproductive growth in woody perennial poplar (Populus spp.). Our manipulative physiological and genetic experiments coupled with field studies, expression profiling, and network analysis reveal that reproductive onset is determined by FT1 in response to winter temperatures, whereas vegetative growth and inhibition of bud set are promoted by FT2 in response to warm temperatures and long days in the growing season. The basis for functional differentiation between FT1 and FT2 appears to be expression pattern shifts, changes in proteins, and divergence in gene regulatory networks. Thus, temporal separation of reproductive onset and vegetative growth into different seasons via FT1 and FT2 provides seasonality and demonstrates the evolution of a complex perennial adaptive trait after genome duplication.« less

Spectroscopic (FT-IR, FT-Raman, FT-NMR and UV-Vis) investigation on benzil dioxime using quantum computational methods

NASA Astrophysics Data System (ADS)

Bakkiyaraj, D.; Periandy, S.; Xavier, S.

2016-03-01

The spectral analysis of benzil dioxime is carried out using the FTIR, FT Raman, FT NMR and UV-Vis spectra of the compound with the help of quantum computations by density functional theories. The FT-IR (4000 - 400 cm-1) and FT-Raman (4000-100 cm-1) spectra are recorded in solid phase, the 1H and 13C NMR spectra in DMSO phase and the UV spectrum (200-400 nm) in ethanol phase. The different conformers of the compound and their minimum energies are studied by potential energy surface scan, using semi-empirical method PM6. The computed wavenumbers from different methods are scaled so as to agree with the experimental values and the scaling factors are reported. All the fundamental modes have been assigned based on the potential energy distribution (PED) values and the structure the molecule is analyzed interms of parameters like bond length, bond angle and dihedral angles predicted byB3LYP and CAM-B3LYP methods with cc-pVDZ basis sets. The values of dipole moment (μ), polarizability (α) and hyperpolarizability (β) of the molecule are reported, using which the non -linear optical property of the molecule is discussed. The HOMO-LUMO mappings are reported which reveals the different charge transfer possibilities within the molecule. The isotropic chemical shifts predicted for 1H and 13C atoms using gauge invariant atomic orbital (GIAO) theory show good agreement with experimental shifts and the same is discussed in comparison with atomic charges, predicted by Mullikan and APT charge analysis. NBO analysis is carried out to picture the probable electronic transitions in the molecule.

Establishment and characterization of a new human acinar cell carcinoma cell line, Faraz-ICR, from pancreas.

PubMed

Rezaei, Marzieh; Hosseini, Ahmad; Nikeghbalian, Saman; Ghaderi, Abbas

Basic research in the field of acinar cell carcinoma (ACC) as a rare neoplasm of the pancreas is dependent on the availability of pragmatic model such as new pancreatic cancer cell lines. Thus, establishment and characterization of new pancreatic cancer cell lines from ACC origin are deemed important. Faraz-ICR cell line was derived from a 58-years old woman with pancreatic acinar cell carcinoma by the collagenase digestion protocol. We characterized the cell line by examining its morphology and cytostructural and functional profile. Faraz-ICR has a doubling time of 35 hours and grows in soft agar with a colony-forming efficiency of 25%. The cell had nearly normal pattern of chromosomes in karyotype analysis and Comparative Genomic Hybridization (CGH) array analysis. Evaluation of cells by flowcytometry showed that Faraz-ICR is negative for EpCAM and mesenchymal markers in different passages, and has epithelial nature. Immunofluorescence staining revealed that cells were strongly positive for vimentin, desmin, ezrin, S100, nestin and they were negative for pan-cytokeratins, chromogranin and alpha smooth muscle actin. We were able to establish a new pancreatic carcinoma cell line with partial aspects of Epithelial-mesenchymal transition and aggressiveness. This cell line might be suitable for studying various anticancer drugs and protein profile aiming to see any possible tumor associated marker for ACC. Copyright © 2017 IAP and EPC. Published by Elsevier B.V. All rights reserved.

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.

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.

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

IDENTIFICATION OF BIS(2-CHLOROETHYL) ETHER HYDROLYSIS PRODUCTS BY DIRECT AQUEOUS INJECTION GC/FT-IR

EPA Science Inventory

Gas chromatography coupled to Fourier-transform infrared spectroscopy (GC/FT-IR) is rapidly becoming an accepted analytical technique complementary to GC/mass spectroscopy for identifying organic compounds in mixtures at low to moderate concentrations. irect aqueous injection (DA...

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.

Energy profile, spectroscopic (FT-IR, FT-Raman and FT-NMR) and DFT studies of 4-bromoisophthalic acid

NASA Astrophysics Data System (ADS)

Arjunan, V.; Thirunarayanan, S.; Mohan, S.

2018-04-01

The stable conformer of 4-bromoisophthalic acid (BIPA) has been identified by potential energy profile analysis. All the structural parameters of 4-bromoisophthalic acid are determined by B3LYP method with 6-311++G**, 6-31G** and cc-pVTZ basis sets. The fundamental vibrations are analysed with the use of FT-IR (4000-400 cm-1) and FT-Raman (4000-100 cm-1) spectra. The harmonic vibrational frequencies are theoretically calculated and compared with experimental FTIR and FT-Raman frequencies. The 1H and 13C NMR spectra have been analysed and compared with theoretical 1H and 13C NMR chemical shifts calculated by gauge independent atomic orbital (GIAO) method. The electronic properties, such as HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies are determined by B3LYP/cc-pVTZ method. The electron density distribution and site of chemical reactivity of BIPA molecule have been obtained by mapping electron density isosurface with molecular electrostatic potential (MEP). Stability of the molecules arising from hyperconjugative interactions, charge delocalizations have been analysed by using natural bond orbital (NBO) analysis. The thermodynamic properties and atomic natural charges of the compound are analysed and the reactive sites of the molecule are identified. The global and local reactivity descriptors are evaluated to analyse the chemical reactivity and site selectivity of molecule through Fukui functions.

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

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.

[Effect of selenium on serum TGAb, TMAb, FT3, FT4 and TSH of rats with excessive intake of iodine].

PubMed

Chi, Haiyan; Zhou, Yuping; Li, Li

2012-07-01

To investigate the effect of selenium on the TGAb, TMAb, FT3, FT4 and TSH level of rats with excessive intake of iodine. Wistar rats were divided into three groups by random:normal control, high iodine group and high iodine plus selenium group. Rats in the high iodine plus selenium group were lavaged with sodium selenite for 10 weeks. The levels of serum TGAb, TMAb, FT3, FT4 and TSH were tested at different time of the experiment. There were no significant change on levels of FT3, FT4 and TSH (P > 0.05). The levels of TGAb and TMAb in the high iodine group were increased slowly (P < 0.05), but no significant change was observed in the high iodine plus selenium group. Excessive intake of iodine might induce goiter, and selenium might have antagonistic effect on it.

77 FR 2760 - Proposed Information Collection Request (ICR) for the Mining Voice in the Workplace Survey...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-19

... DEPARTMENT OF LABOR Proposed Information Collection Request (ICR) for the Mining Voice in the...)(A)]. This program helps to ensure that required data can be provided in the desired format...' voice in mining workplaces under the jurisdiction of DOL's Mine Safety and Health Administration (MSHA...

Has your ancient stamp been regummed with synthetic glue? A FT-NIR and FT-Raman study.

PubMed

Simonetti, Remo; Oliveri, Paolo; Henry, Adrien; Duponchel, Ludovic; Lanteri, Silvia

2016-01-01

The potential of FT-NIR and FT-Raman spectroscopies to characterise the gum applied on the backside of ancient stamps was investigated for the first time. This represents a very critical issue for the collectors' market, since gum conditions heavily influence stamp quotations, and fraudulent application of synthetic gum onto damaged stamp backsides to increase their desirability is a well-documented practice. Spectral data were processed by exploratory pattern recognition tools. In particular, application of principal component analysis (PCA) revealed that both of the spectroscopic techniques provide information useful to characterise stamp gum. Examination of PCA loadings and their chemical interpretation confirmed the robustness of the outcomes. Fusion of FT-NIR and FT-Raman spectral data was performed, following both a low-level and a mid-level procedure. The results were critically compared with those obtained separately for the two spectroscopic techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

FT-IR, FT-Raman and UV-visible spectra of potassium 3-furoyltrifluoroborate salt

NASA Astrophysics Data System (ADS)

Iramain, Maximiliano A.; Davies, Lilian; Brandán, Silvia Antonia

2018-04-01

The potassium 3-furoyltrifluoroborate salt has been experimentally characterized by means of FT-IR, FT-Raman and UV-Visible spectroscopies. Here, the predicted FT-IR, FT-Raman and UV-visible spectra by using theoretical B3LYP/6-31G* and 6-311++G** calculations show very good correlations with the corresponding experimental ones. The solvation energies were predicted by using both levels of calculations. The NBO analyses reveal the high stability of the salt by using the B3LYP/6-31G* level of theory while the AIM studies evidence the ionic characteristics of the salt in both media. The strong blue colour observed on the K atom by using the molecular electrostatic potential mapped suggests that this region act as typical electrophilic site. The gap values have revealed that the salt in gas phase is more reactive than in solution, as was reported in the literature while, the F13⋯H6 interaction together with the Ksbnd O bond observed by the studies of their charges could probably modulate the reactivities of this salt in aqueous solution. The force fields were computed with the SQMFF methodology and the Molvib program to perform the complete vibrational analysis. Then, the 39 vibration normal modes classified as 26 A'+ 13 A″ were completely assigned and their force constants are also reported.

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.

5. Aerial view (altitude 5,000 ft.) looking southeast showing Dry ...

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

5. Aerial view (altitude 5,000 ft.) looking southeast showing Dry Dock No. 4. completed (top center). Note major expansion of land mass to south of Dry Dock No. 4 resulting from placement of excavated soils and rock prior to and during construction (8/3/43). Photographer: Mr. Rudnick, PHoM 2/C. - Hunters Point Naval Shipyard, Drydock No. 4, East terminus of Palou Avenue, San Francisco, San Francisco County, CA

Involvement of the BLT2 receptor in the itch-associated scratching induced by 12-(S)-lipoxygenase products in ICR mice

PubMed Central

Kim, H J; Kim, D K; Kim, H; Koh, J Y; Kim, K M; Noh, M S; Lee, S; Kim, S; Park, S H; Kim, J J; Kim, S Y; Lee, C H

2008-01-01

Background and purpose: Recently, we reported that 12(S)-HPETE (12(S)-hydroperoxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid) induces scratching in ICR mice. We hypothesized that 12(S)-HPETE might act as an agonist of the low-affinity leukotriene B4 receptor BLT2. To confirm the involvement of the BLT2 receptor in 12(S)-HPETE-induced scratching, we studied the scratch response using the BLT2 receptor agonists compound A (4′-{[pentanoyl (phenyl) amino]methyl}-1,1′-biphenyl-2-carboxylic acid) and 12(S)-HETE (12(S)-hydroxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid). Experimental approach: A video recording was used to determine whether the BLT2 receptor agonists caused itch-associated scratching in ICR mice. Selective antagonists and several chemicals were used. Key results: Both 12(S)-HETE and compound A dose dependently induced scratching in the ICR mice. The dose–response curve for compound A showed peaks at around 0.005–0.015 nmol per site. Compound A- and 12(S)-HETE-induced scratching was suppressed by capsaicin and naltrexon. We examined the suppressive effects of U75302 (6-[6-(3-hydroxy-1E,5Z-undecadienyl)-2-pyridinyl]-1,5-hexanediol, the BLT1 receptor antagonist) and LY255283 (1-[5-ethyl-2-hydroxy-4-[[6-methyl-6-(1H-tetrazol-5-yl)heptyl]oxy]phenyl]-ethanone, the BLT2 receptor antagonist) on the BLT2 agonist-induced scratching. LY255283 suppressed compound A- and 12(S)-HETE-induced scratching, but U75302 did not. LY255283 required a higher dose to suppress the compound A-induced scratching than it did to suppress the 12(S)-HETE-induced scratching. One of the BLT2 receptor agonists, 12(R)-HETE (12(R)-hydroxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid), also induced scratching in the ICR mice. Conclusions and implications: Our present results corroborate the hypothesis that the BLT2 receptor is involved in 12(S)-lipoxygenase-product-induced scratching in ICR mice. We also confirmed that this animal model could be a valuable means of evaluating the effects of BLT2 receptor

Process Analytical Technology for High Shear Wet Granulation: Wet Mass Consistency Reported by In-Line Drag Flow Force Sensor Is Consistent With Powder Rheology Measured by At-Line FT4 Powder Rheometer.

PubMed

Narang, Ajit S; Sheverev, Valery; Freeman, Tim; Both, Douglas; Stepaniuk, Vadim; Delancy, Michael; Millington-Smith, Doug; Macias, Kevin; Subramanian, Ganeshkumar

2016-01-01

Drag flow force (DFF) sensor that measures the force exerted by wet mass in a granulator on a thin cylindrical probe was shown as a promising process analytical technology for real-time in-line high-resolution monitoring of wet mass consistency during high shear wet granulation. Our previous studies indicated that this process analytical technology tool could be correlated to granulation end point established independently through drug product critical quality attributes. In this study, the measurements of flow force by a DFF sensor, taken during wet granulation of 3 placebo formulations with different binder content, are compared with concurrent at line FT4 Powder Rheometer characterization of wet granules collected at different time points of the processing. The wet mass consistency measured by the DFF sensor correlated well with the granulation's resistance to flow and interparticulate interactions as measured by FT4 Powder Rheometer. This indicated that the force pulse magnitude measured by the DFF sensor was indicative of fundamental material properties (e.g., shear viscosity and granule size/density), as they were changing during the granulation process. These studies indicate that DFF sensor can be a valuable tool for wet granulation formulation and process development and scale up, as well as for routine monitoring and control during manufacturing. Copyright © 2016. Published by Elsevier Inc.

76 FR 27363 - Proposed Information Collection Request (ICR) for the Impact Evaluation of the YouthBuild Program...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-11

... characteristics? What are YouthBuild's impacts on crime and delinquency? What are the program's impacts on social... (ICR) for the Impact Evaluation of the YouthBuild Program; Comment Request AGENCY: Employment and..., collection instruments are clearly understood, and [[Page 27364

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.

Determining Energies and Cross Sections of Individual Ions Using Higher-Order Harmonics in Fourier Transform Charge Detection Mass Spectrometry (FT-CDMS)

NASA Astrophysics Data System (ADS)

Harper, Conner C.; Elliott, Andrew G.; Lin, Haw-Wei; Williams, Evan R.

2018-06-01

A general method for in situ measurements of the energy of individual ions trapped and weighed using charge detection mass spectrometry (CDMS) is described. Highly charged (> 300 e), individual polyethylene glycol (PEG) ions are trapped and oscillate within an electrostatic trap, producing a time domain signal. A segmented Fourier transform (FT) of this signal yields the temporal evolution of the fundamental and harmonic frequencies of ion motion throughout the 500-ms trap time. The ratio of the fundamental frequency and second harmonic (HAR) depends on the ion energy, which is an essential parameter for measuring ion mass in CDMS. This relationship is calibrated using simulated ion signals, and the calibration is compared to the HAR values measured for PEG ion signals where the ion energy was also determined using an independent method that requires that the ions be highly charged (> 300 e). The mean error of 0.6% between the two measurements indicates that the HAR method is an accurate means of ion energy determination that does not depend on ion size or charge. The HAR is determined dynamically over the entire trapping period, making it possible to observe the change in ion energy that takes place as solvent evaporates from the ion and collisions with background gas occur. This method makes it possible to measure mass changes, either from solvent evaporation or from molecular fragmentation (MSn), as well as the cross sections of ions measured using CDMS.

Determining Energies and Cross Sections of Individual Ions Using Higher-Order Harmonics in Fourier Transform Charge Detection Mass Spectrometry (FT-CDMS).

PubMed

Harper, Conner C; Elliott, Andrew G; Lin, Haw-Wei; Williams, Evan R

2018-06-02

A general method for in situ measurements of the energy of individual ions trapped and weighed using charge detection mass spectrometry (CDMS) is described. Highly charged (> 300 e), individual polyethylene glycol (PEG) ions are trapped and oscillate within an electrostatic trap, producing a time domain signal. A segmented Fourier transform (FT) of this signal yields the temporal evolution of the fundamental and harmonic frequencies of ion motion throughout the 500-ms trap time. The ratio of the fundamental frequency and second harmonic (HAR) depends on the ion energy, which is an essential parameter for measuring ion mass in CDMS. This relationship is calibrated using simulated ion signals, and the calibration is compared to the HAR values measured for PEG ion signals where the ion energy was also determined using an independent method that requires that the ions be highly charged (> 300 e). The mean error of 0.6% between the two measurements indicates that the HAR method is an accurate means of ion energy determination that does not depend on ion size or charge. The HAR is determined dynamically over the entire trapping period, making it possible to observe the change in ion energy that takes place as solvent evaporates from the ion and collisions with background gas occur. This method makes it possible to measure mass changes, either from solvent evaporation or from molecular fragmentation (MS n ), as well as the cross sections of ions measured using CDMS. Graphical Abstract.

FT-IR, FT-Raman spectra and DFT calculations of melaminium perchlorate monohydrate.

PubMed

Kanagathara, N; Marchewka, M K; Drozd, M; Renganathan, N G; Gunasekaran, S; Anbalagan, G

2013-08-01

Melaminium perchlorate monohydrate (MPM), an organic material has been synthesized by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MPM crystal belongs to triclinic system with space group P-1. FTIR and FT Raman spectra are recorded at room temperature. Functional group assignment has been made for the melaminium cations and perchlorate anions. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory (DFT) calculations using Firefly (PC GAMESS) version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with experimental values. The assignment of the bands has been made on the basis of the calculated PED. The Mulliken charges, HOMO-LUMO orbital energies are analyzed directly from Firefly program log files and graphically illustrated. HOMO-LUMO energy gap and other related molecular properties are also calculated. The theoretically constructed FT-IR and FT-Raman spectra of MPM coincide with the experimental one. The chemical structure of the compound has been established by (1)H and (13)C NMR spectra. No detectable signal was observed during powder test for second harmonic generation. Copyright © 2013 Elsevier B.V. All rights reserved.

FT-IR, FT-Raman spectra and DFT calculations of melaminium perchlorate monohydrate

NASA Astrophysics Data System (ADS)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

2013-08-01

Melaminium perchlorate monohydrate (MPM), an organic material has been synthesized by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MPM crystal belongs to triclinic system with space group P-1. FTIR and FT Raman spectra are recorded at room temperature. Functional group assignment has been made for the melaminium cations and perchlorate anions. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory (DFT) calculations using Firefly (PC GAMESS) version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with experimental values. The assignment of the bands has been made on the basis of the calculated PED. The Mulliken charges, HOMO-LUMO orbital energies are analyzed directly from Firefly program log files and graphically illustrated. HOMO-LUMO energy gap and other related molecular properties are also calculated. The theoretically constructed FT-IR and FT-Raman spectra of MPM coincide with the experimental one. The chemical structure of the compound has been established by 1H and 13C NMR spectra. No detectable signal was observed during powder test for second harmonic generation.

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.

77 FR 6585 - Proposed Information Collection Request (ICR) for the Impact Evaluation of the YouthBuild Program...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-08

... job characteristics? What are YouthBuild's impacts on crime and delinquency? What are the program's... (ICR) for the Impact Evaluation of the YouthBuild Program; New Collection AGENCY: Employment and... instruments are clearly understood, and the impact of collection requirements on respondents can be properly...

Unlocking Ft: Modeling thermodynamic controls and isotope fractionation factors in nutrient limited environments

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Giannetta, M.; Sanford, R. A.

2017-12-01

In recent years, reactive transport principles have expanded from early applications, largely based in contaminant hydrology, to a wide range of biologically mediated redox environments including marine sedimentary diagenesis, terrestrial metal ore deposits, soils, and critical zone weathering profiles. A common observation across this diversity of systems is that they often function under energetically limited conditions in comparison to those typical of contaminated aquifers subject to engineered remediation techniques. As a result, the kinetic rate expressions traditionally employed within reactive transport frameworks to simulate microbially mediated redox transformations have required modification. This was recognized in a series of seminal papers by Jin and Bethke (2005, 2007) in which the authors expanded upon a Monod rate law to include a thermodynamic potential factor `Ft' which exerts a limitation on the overall rate based on the thermodynamic driving force of the electron transfer reaction. This new rate expression is now commonly implemented within many of the major reactive transport software packages, though appropriate application has yet to be thoroughly demonstrated. Notably, the characteristically large partitioning of stable isotopes during microbially mediated reactions, which is extensively utilized to identify and quantify these redox transformations, has yet to be simulated under conditions in which the Ft term may be expected to exert a significant mass dependent influence. Here, we develop a series of simplified simulations for the microbially mediated reduction of sulfate based on the datasets reported by Jin and Bethke, and apply appropriate mass-bias within the Ft term to consider the extent to which the resulting isotopic fractionation is consistent with that observed in energetically limited systems. We show that the Ft term can exert a significant influence on the observed fractionation factor under common environmental conditions

Nanoscale-alumina induces oxidative stress and accelerates amyloid beta (Aβ) production in ICR female mice

NASA Astrophysics Data System (ADS)

Shah, Shahid Ali; Yoon, Gwang Ho; Ahmad, Ashfaq; Ullah, Faheem; Amin, Faiz Ul; Kim, Myeong Ok

2015-09-01

The adverse effects of nanoscale-alumina (Al2O3-NPs) have been previously demonstrated in both in vitro and in vivo studies, whereas little is known about their mechanism of neurotoxicity. It is the goal of this research to determine the toxic effects of nano-alumina on human neuroblastoma SH-SY5Y and mouse hippocampal HT22 cells in vitro and on ICR female mice in vivo. Nano-alumina displayed toxic effects on SH-SY5Y cell lines in three different concentrations also increased aluminium abundance and induced oxidative stress in HT22 cells. Nano-alumina peripherally administered to ICR female mice for three weeks increased brain aluminium and ROS production, disturbing brain energy homeostasis, and led to the impairment of hippocampus-dependent memory. Most importantly, these nano-particles induced Alzheimer disease (AD) neuropathology by enhancing the amyloidogenic pathway of Amyloid Beta (Aβ) production, aggregation and implied the progression of neurodegeneration in the cortex and hippocampus of these mice. In conclusion, these data demonstrate that nano-alumina is toxic to both cells and female mice and that prolonged exposure may heighten the chances of developing a neurodegenerative disease, such as AD.

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

Phase portraits of general f(T) cosmology

NASA Astrophysics Data System (ADS)

Awad, A.; El Hanafy, W.; Nashed, G. G. L.; Saridakis, Emmanuel N.

2018-02-01

We use dynamical system methods to explore the general behaviour of f(T) cosmology. In contrast to the standard applications of dynamical analysis, we present a way to transform the equations into a one-dimensional autonomous system, taking advantage of the crucial property that the torsion scalar in flat FRW geometry is just a function of the Hubble function, thus the field equations include only up to first derivatives of it, and therefore in a general f(T) cosmological scenario every quantity is expressed only in terms of the Hubble function. The great advantage is that for one-dimensional systems it is easy to construct the phase space portraits, and thus extract information and explore in detail the features and possible behaviours of f(T) cosmology. We utilize the phase space portraits and we show that f(T) cosmology can describe the universe evolution in agreement with observations, namely starting from a Big Bang singularity, evolving into the subsequent thermal history and the matter domination, entering into a late-time accelerated expansion, and resulting to the de Sitter phase in the far future. Nevertheless, f(T) cosmology can present a rich class of more exotic behaviours, such as the cosmological bounce and turnaround, the phantom-divide crossing, the Big Brake and the Big Crunch, and it may exhibit various singularities, including the non-harmful ones of type II and type IV. We study the phase space of three specific viable f(T) models offering a complete picture. Moreover, we present a new model of f(T) gravity that can lead to a universe in agreement with observations, free of perturbative instabilities, and applying the Om(z) diagnostic test we confirm that it is in agreement with the combination of SNIa, BAO and CMB data at 1σ confidence level.

Effect of Mass Flow on Stack Eductor Performance.

DTIC Science & Technology

1984-06-01

absolute viscosity, lbf-sec/ft2 - density, Ibm/ft 3 "function of" ENGLISH LETTER SYMBOLS 2 A - area, in , ft B - atmospheric pressure, in Hg c - sonic... absolute temperature ratio T* - tertiary flow to primary flow absolute temperature t ratio - secondary -o primary mass flow rate ratio W* - tertiary to...secondary to primary absolute Tp temperature ratio TiL tertiary to primary absolute -TE temperature ratio secondary to primary flow density ratio

Organic scintillator detector response simulations with DRiFT

NASA Astrophysics Data System (ADS)

Andrews, M. T.; Bates, C. R.; McKigney, E. A.; Solomon, C. J.; Sood, A.

2016-09-01

This work presents the organic scintillation simulation capabilities of DRiFT, a post-processing Detector Response Function Toolkit for MCNP® output. DRiFT is used to create realistic scintillation detector response functions to incident neutron and gamma mixed-field radiation. As a post-processing tool, DRiFT leverages the extensively validated radiation transport capabilities of MCNP® 6 , which also provides the ability to simulate complex sources and geometries. DRiFT is designed to be flexible, it allows the user to specify scintillator material, PMT type, applied PMT voltage, and quenching data used in simulations. The toolkit's capabilities, which include the generation of pulse shape discrimination plots and full-energy detector spectra, are demonstrated in a comparison of measured and simulated neutron contributions from 252Cf and PuBe, and photon spectra from 22Na and 228Th sources. DRiFT reproduced energy resolution effects observed in EJ-301 measurements through the inclusion of scintillation yield variances, photon transport noise, and PMT photocathode and multiplication noise.

No further gravitational wave modes in F(T) gravity

NASA Astrophysics Data System (ADS)

Bamba, Kazuharu; Capozziello, Salvatore; De Laurentis, Mariafelicia; Nojiri, Shin'ichi; Sáez-Gómez, Diego

2013-11-01

We explore the possibility of further gravitational wave modes in F(T) gravity, where T is the torsion scalar in teleparallelism. It is explicitly demonstrated that gravitational wave modes in F(T) gravity are equivalent to those in General Relativity. This result is achieved by calculating the Minkowskian limit for a class of analytic function of F(T). This consequence is also confirmed by the preservative analysis around the flat background in the weak field limit with the scalar-tensor representation of F(T) gravity.

Characterization of nonpolar lipids and selected steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

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

Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

2011-03-01

Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H2O) upon reaction with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusivelymore » the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.« less

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.

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

Organic Scintillator Detector Response Simulations with DRiFT

DOE PAGES

Andrews, Madison Theresa; Bates, Cameron Russell; Mckigney, Edward Allen; ...

2016-06-11

Here, this work presents the organic scintillation simulation capabilities of DRiFT, a post-processing Detector Response Function Toolkit for MCNPR output. DRiFT is used to create realistic scintillation detector response functions to incident neutron and gamma mixed- field radiation. As a post-processing tool, DRiFT leverages the extensively validated radiation transport capabilities of MCNPR ®6, which also provides the ability to simulate complex sources and geometries. DRiFT is designed to be flexible, it allows the user to specify scintillator material, PMT type, applied PMT voltage, and quenching data used in simulations. The toolkit's capabilities, which include the generation of pulse shape discriminationmore » plots and full-energy detector spectra, are demonstrated in a comparison of measured and simulated neutron contributions from 252Cf and PuBe, and photon spectra from 22Na and 228Th sources. DRiFT reproduced energy resolution effects observed in EJ-301 measurements through the inclusion of scintillation yield variances, photon transport noise, and PMT photocathode and multiplication noise.« 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

Technical Capability Upgrades to the NASA Langley Research Center 8 ft. by 15 ft. Thermal Vacuum Chamber

NASA Technical Reports Server (NTRS)

Thornblom, Mark N.; Beverly, Joshua; O'Connell, Joseph J.; Duncan, Dwight L.

2016-01-01

The 8 ft. by 15 ft. thermal vacuum chamber (TVAC), housed in Building 1250 at the NASA Langley Research Center (LaRC), and managed by the Systems Integration and Test Branch within the Engineering Directorate, has undergone several significant modifications to increase testing capability, safety, and quality of measurements of articles under environmental test. Significant modifications include: a new nitrogen distribution manifold for supplying the shroud and other cold surfaces to liquid nitrogen temperatures; a new power supply and distribution system for accurately controlling a quartz IR lamp suite; a suite of contamination monitoring sensors for outgassing measurements and species identification; a new test article support system; signal and power feed-throughs; elimination of unnecessary penetrations; and a new data acquisition and control commanding system including safety interlocks. This paper will provide a general overview of the LaRC 8 ft. by 15 ft. TVAC chamber, an overview of the new technical capabilities, and will illustrate each upgrade in detail, in terms of mechanical design and predicted performance. Additionally, an overview of the scope of tests currently being performed in the chamber will be documented, and sensor plots from tests will be provided to show chamber temperature and pressure performance with actual flight hardware under test.

Technical Capability Upgrades to the NASA Langley Research Center 6 ft. by 6 ft. Thermal Vacuum Chamber

NASA Technical Reports Server (NTRS)

Thornblom, Mark N.; Beverly, Joshua; O'Connell, Joseph J.; Mau, Johnny C.; Duncan, Dwight L.

2014-01-01

The 6 ft. by 6 ft. thermal vacuum chamber (TVAC), housed in Building 1250 at the NASA Langley Research Center (LaRC), and managed by the Systems Integration and Test Branch within the Engineering Directorate, has undergone several significant modifications to increase testing capability, safety, and quality of measurements of articles under environmental test. Significant modifications include: a new nitrogen thermal conditioning unit for controlling shroud temperatures from -150degC to +150degC; two horizontal auxiliary cold plates for independent temperature control from -150degC to +200degC; a suite of contamination monitoring sensors for outgassing measurements and species identification; signal and power feed-throughs; new pressure gauges; and a new data acquisition and control commanding system including safety interlocks. This presentation will provide a general overview of the LaRC 6 ft. by 6 ft. TVAC chamber, an overview of the new technical capabilities, and illustrate each upgrade in detail, in terms of mechanical design and predicted performance. Additionally, an overview of the scope of tests currently being performed in the chamber will be documented, and sensor plots from tests will be provided to show chamber temperature and pressure performance with actual flight hardware under test.

FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin

NASA Astrophysics Data System (ADS)

Arjunan, V.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

2013-05-01

3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm-1, respectively. 1H and 13C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G**, high level 6-311++G** and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method.

Arabidopsis florigen FT binds to diurnally oscillating phospholipids that accelerate flowering.

PubMed

Nakamura, Yuki; Andrés, Fernando; Kanehara, Kazue; Liu, Yu-chi; Dörmann, Peter; Coupland, George

2014-04-04

Arabidopsis FT protein is a component of florigen, which transmits photoperiodic flowering signals from leaf companion cells to the shoot apex. Here, we show that FT specifically binds phosphatidylcholine (PC) in vitro. A transgenic approach to increase PC levels in vivo in the shoot meristem accelerates flowering whereas reduced PC levels delay flowering, demonstrating that PC levels are correlated with flowering time. The early flowering is related to FT activity, because expression of FT-effector genes is increased in these plants. Simultaneous increase of FT and PC in the shoot apical meristem further stimulates flowering, whereas a loss of FT function leads to an attenuation of the effect of increased PC. Specific molecular species of PC oscillate diurnally, and night-dominant species are not the preferred ligands of FT. Elevating night-dominant species during the day delays flowering. We suggest that FT binds to diurnally changing molecular species of PC to promote flowering.

FT-IR and DFT study of lemon peel

NASA Astrophysics Data System (ADS)

Berezin, K. V.; Likhter, A. M.; Shagautdinova, I. T.; Chernavina, M. L.; Novoselova, A. V.

2017-03-01

Experimental FT-IR spectra of lemon peel are registered in the 650 - 3800 cm-1 range. The influence of peel artificial and natural dehydration on its vibrational spectrum is studied. The colored outer surface of lemon peel is proved not to have a significant impact on FT-IR spectrum. It is determined that only dehydration processes affect the FT-IR vibrational spectrum of the peel when a lemon is stored for 28 days under natural laboratory conditions. Polymer molecule models for dietary fibers, such as cellulose, hemicellulose, pectin, lignin, as well as hesperidin - flavonoid glycoside, and free moisture cluster are developed within the framework of DFT/B3LYP/6-31G(d) theoretical method. By implementing supramolecular approach, modeling of the vibrational FT-IR spectrum of lemon peel is carried out and its detailed theoretical interpretation is presented.

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.

FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin.

PubMed

Arjunan, V; Sakiladevi, S; Marchewka, M K; Mohan, S

2013-05-15

3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. (1)H and (13)C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method. Copyright © 2013 Elsevier B.V. All rights reserved.

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

FT-Raman spectral analysis of human urinary stones.

PubMed

Selvaraju, R; Raja, A; Thiruppathi, G

2012-12-01

FT-Raman spectroscopy is the most useful tool for the purpose of bio-medical diagnostics. In the present study, FT-Raman spectral method is used to investigate the chemical composition of urinary calculi. Urinary calculi multi-components such as calcium oxalate, hydroxyl apatite, struvite and uric acid are studied. FT-Raman spectrum has been recorded in the range of 3500-400 cm(-1). Chemical compounds are identified by Raman spectroscopic technique. The quantitative estimations of calcium oxalate monohydrate (COM) 1463 cm(-1), calcium oxalate dehydrate (COD) 1478 cm(-1), hydroxyl apatite 959 cm(-1), struvite 575 cm(-1), uric acid 1283 cm(-1) and oxammite (ammonium oxalate monohydrate) 2129 cm(-1) are calculated using particular peaks of FT-Raman spectrum. The quantitative estimation of human urinary stones suitable for the single calibration curve was performed. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

A Straightforward and Highly Efficient Precipitation/On-pellet Digestion Procedure Coupled to a Long Gradient Nano-LC Separation and Orbitrap Mass Spectrometry for Label-free Expression Profiling of the Swine Heart Mitochondrial Proteome

PubMed Central

Duan, Xiaotao; Young, Rebecca; Straubinger, Robert M.; Page, Brian J.; Cao, Jin; Wang, Hao; Yu, Haoying; Canty, John M.; Qu, Jun

2009-01-01

For label-free expression profiling of tissue proteomes, efficient protein extraction, thorough and quantitative sample cleanup and digestion procedures, as well as sufficient and reproducible chromatographic separation, are highly desirable but remain challenging. However, optimal methodology has remained elusive, especially for proteomes that are rich in membrane proteins, such as the mitochondria. Here we describe a straightforward and reproducible sample preparation procedure, coupled with a highly selective and sensitive nano-LC/Orbitrap analysis, which enables reliable and comprehensive expression profiling of tissue mitochondria. The mitochondrial proteome of swine heart was selected as a test system. Efficient protein extraction was accomplished using a strong buffer containing both ionic and non-ionic detergents. Overnight precipitation was used for cleanup of the extract, and the sample was subjected to an optimized 2-step, on-pellet digestion approach. In the first step, the protein pellet was dissolved via a 4 h tryptic digestion under vigorous agitation, which nano-LC/LTQ/ETD showed to produce large and incompletely cleaved tryptic peptides. The mixture was then reduced, alkylated, and digested into its full complement of tryptic peptides with additional trypsin. This solvent precipitation/on-pellet digestion procedure achieved significantly higher and more reproducible peptide recovery of the mitochondrial preparation, than observed using a prevalent alternative procedure for label-free expression profiling, SDS-PAGE/in-gel digestion (87% vs. 54%). Furthermore, uneven peptide losses were lower than observed with SDS-PAGE/in-gel digestion. The resulting peptides were sufficiently resolved by a 5 h gradient using a nano-LC configuration that features a low-void-volume, high chromatographic reproducibility, and an LTQ/Orbitrap analyzer for protein identification and quantification. The developed method was employed for label-free comparison of the

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.

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.

DETERMINATION OF OXALATE ION DOPANT LEVEL IN POLYPYRROLE USING FT-IR

PubMed Central

Benally, Kristal J.; GreyEyes, Shawn D.; McKenzie, Jason T.

2014-01-01

A pellet method using standard addition and FT-IR was used to estimate oxalate ion doping levels in electrosynthesized polypyrrole. The method is useful for materials where removal of analyte from an insoluble material is problematic. Here, electrosynthesized oxalate doped polypyrrole is dispersed in potassium bromide. Spikes of sodium oxalate are added and the mixtures pressed into pellets. The oxalate carbonyl absorption peak is then used to quantify the amount of oxalate present in the polypyrrole. The mass fraction of oxalate dopant in polypyrrole was determined to be 0.4 ± 0.1 % and coincides with the original synthesis solution composition. PMID:25598749

Near Zero Energy Housing at Ft. Campbell: Energy Modeling Results

DTIC Science & Technology

2007-05-01

Excellence Baseline Ft. Campbell Single Family Home 2 Story 2,100 ft2 living space 325 ft2 garage 2 x 4 metal frame R-13 batt in wall Asphalt shingle ...Model south facing windows with overhangs to take advantage of solar gain in winter, and shading summer sun Construction cost estimates for

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.

FT overexpression induces precocious flowering and normal reproductive development in Eucalyptus.

PubMed

Klocko, Amy L; Ma, Cathleen; Robertson, Sarah; Esfandiari, Elahe; Nilsson, Ove; Strauss, Steven H

2016-02-01

Eucalyptus trees are among the most important species for industrial forestry worldwide. However, as with most forest trees, flowering does not begin for one to several years after planting which can limit the rate of conventional and molecular breeding. To speed flowering, we transformed a Eucalyptus grandis × urophylla hybrid (SP7) with a variety of constructs that enable overexpression of FLOWERING LOCUS T (FT). We found that FT expression led to very early flowering, with events showing floral buds within 1-5 months of transplanting to the glasshouse. The most rapid flowering was observed when the cauliflower mosaic virus 35S promoter was used to drive the Arabidopsis thaliana FT gene (AtFT). Early flowering was also observed with AtFT overexpression from a 409S ubiquitin promoter and under heat induction conditions with Populus trichocarpa FT1 (PtFT1) under control of a heat-shock promoter. Early flowering trees grew robustly, but exhibited a highly branched phenotype compared to the strong apical dominance of nonflowering transgenic and control trees. AtFT-induced flowers were morphologically normal and produced viable pollen grains and viable self- and cross-pollinated seeds. Many self-seedlings inherited AtFT and flowered early. FT overexpression-induced flowering in Eucalyptus may be a valuable means for accelerating breeding and genetic studies as the transgene can be easily segregated away in progeny, restoring normal growth and form. © 2015 Society for Experimental Biology, Association of Applied Biologists and John Wiley & Sons Ltd.

Adulteration of diesel/biodiesel blends by vegetable oil as determined by Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy.

PubMed

Oliveira, Flavia C C; Brandão, Christian R R; Ramalho, Hugo F; da Costa, Leonardo A F; Suarez, Paulo A Z; Rubim, Joel C

2007-03-28

In this work it has been shown that the routine ASTM methods (ASTM 4052, ASTM D 445, ASTM D 4737, ASTM D 93, and ASTM D 86) recommended by the ANP (the Brazilian National Agency for Petroleum, Natural Gas and Biofuels) to determine the quality of diesel/biodiesel blends are not suitable to prevent the adulteration of B2 or B5 blends with vegetable oils. Considering the previous and actual problems with fuel adulterations in Brazil, we have investigated the application of vibrational spectroscopy (Fourier transform (FT) near infrared spectrometry and FT-Raman) to identify adulterations of B2 and B5 blends with vegetable oils. Partial least square regression (PLS), principal component regression (PCR), and artificial neural network (ANN) calibration models were designed and their relative performances were evaluated by external validation using the F-test. The PCR, PLS, and ANN calibration models based on the Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy were designed using 120 samples. Other 62 samples were used in the validation and external validation, for a total of 182 samples. The results have shown that among the designed calibration models, the ANN/FT-Raman presented the best accuracy (0.028%, w/w) for samples used in the external validation.

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.

Assessment of Non-Traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities

DTIC Science & Technology

2016-03-01

Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities Distribution Statement A. Approved for pubic...cubic meter (m 3 ) cubic foot (ft 3 ) 2.831 685 × 10 –2 cubic meter (m 3 ) Mass /Density pound (lb) 4.535 924 × 10 –1 kilogram (kg) unified...atomic mass unit (amu) 1.660 539 × 10 –27 kilogram (kg) pound- mass per cubic foot (lb ft –3 ) 1.601 846 × 10 1 kilogram per cubic meter (kg m –3

Coupling FT Raman and FT SERS microscopy with TLC plates for in situ identification of chemical compounds

NASA Astrophysics Data System (ADS)

Caudin, J. P.; Beljebbar, A.; Sockalingum, G. D.; Angiboust, J. F.; Manfait, M.

1995-11-01

Direct analysis of sub-femtogram quantities of chemical compounds on thin layer chromatography plates has been made possible by associating Fourier transform Raman microspectroscopy with SERS spectroscopy. The interfacing elements of the FT Raman microscope system are discussed and optimised such that a lateral resolution on the micron scale is achieved in the sample plane. Micro-FT SERS results obtained from a model biological molecule indicate preservation of molecular conformation upon adsorption at the SERS active surface. With NIR radiation it is thus possible to analyse plates with or without fluorescence indicators.

Adaptation of a 15-ft-dia ribbon parachute and a 73-ft cross main recovery parachute for cargo delivery from high altitude

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

Pepper, W.B.; Lucero, H.; Klimas, P.C.

1984-01-01

An existing parachute system has been adapted for delivery of a resupply container at high altitudes from aircraft. The parachute system consists of a 15-ft diameter ribbon parachute reefed for 10 seconds and a 73-ft diameter cross parachute reefed for 10 seconds. A solid state recorder in the 2341 1b drop test vehicle was used to obtain deceleration history with time. Two drop tests using the Navy A7 aircraft were conducted at Stallion Site, White Sands Missile Range, New Mexico. Drop release conditions were 250 KCAS at 20,000 ft above sea level from the first test and 230 KCAS atmore » 22,000 ft msl for the second. A new load transfer bridle was designed and tested to release the first stage parachute and replace a costly mechanical load plate.« less

Microfluidic high performance liquid chromatography-chip hyphenation to inductively coupled plasma-mass spectrometry.

PubMed

Bishop, David P; Blanes, Lucas; Wilson, Alexander B; Wilbanks, Thor; Killeen, Kevin; Grimm, Rudolf; Wenzel, Ross; Major, Derek; Macka, Mirek; Clarke, David; Schmid, Robin; Cole, Nerida; Doble, Philip A

2017-05-12

The Agilent Chip Cube Interface is a microfluidic chip-based technology originally designed for nanospray molecular mass spectrometry in which the sample enrichment, nano-column, tubing, connectors and spray tip were integrated into a single biocompatible chip. Here we describe the hyphenation of the Chip Cube Interface to ICP-MS via modification of the standard HPLC chip design and a new total consumption nebuliser suitable for flow rates as low as 300nLmin -1 . The potential of the instrument to eliminate common nanoLC - ICP-MS shortcomings such as leaks, blockages and band-broadening was demonstrated via analysis of cyanocobalamin in equine plasma. The method was linear over three orders of magnitude with an r 2 of 0.9999, the peak area repeatability was 1.9% (n=7), and the detection limit was 14ngmL -1 . This novel configuration of the Chip Cube Interface coupled to ICP-MS is a suitable platform for the analysis of biomolecules associated with trace metals and speciation applications. Copyright © 2017 Elsevier B.V. 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

Rotating samples in FT-RAMAN spectrometers

NASA Astrophysics Data System (ADS)

De Paepe, A. T. G.; Dyke, J. M.; Hendra, P. J.; Langkilde, F. W.

1997-11-01

It is customary to rotate samples in Raman spectroscopy to avoid absorption or sample heating. In FT-Raman experiments the rotation is always shown (typically 30-60 rpm) because higher speeds are thought to generate noise in the spectra. In this article we show that more rapid rotation is possible. A tablet containing maleic acid and one made up of sub-millimetre silica particles with metoprolol succinate as active ingredient were rotated at different speeds, up to 6760 rpm. The FT-Raman spectra were recorded and studied. We conclude that it is perfectly acceptable to rotate samples up to 1500 rpm.

FT-Raman, FT-IR spectroscopic and DFT studies of hexaphenoxycyclotriphosphazene

NASA Astrophysics Data System (ADS)

Furer, V. L.; Vandyukov, A. E.; Padie, C.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

2016-07-01

The FTIR and FT Raman measurements of zero Gc0‧ -H and first Gc1‧ -H generations of phosphorus dendrimer built from cyclotriphosphazene core with phenoxy and deuterophenoxy terminal groups have been performed. In order to evaluate how much the frequencies, shift when changing the electronics of the system the FTIR and FT Raman spectra of phosphorus‒containing dendron with five terminal oxybenzaldehyde and one ester function Gci‧ have been also studied. Structural optimization and normal mode analysis were obtained for Gc0‧ -H and Gc0‧ -D by the density functional theory (DFT). It is discovered that dendrimer molecule exists in a stable conformation with six phenoxy terminal groups spaced above and below the flat cyclotriphosphazene core. Optimized geometric bond length and angles obtained by DFT show good agreement with a previously-published X-ray study. The phenoxy terminal groups are characterized by the well-defined line at 993 cm-1 in the experimental Raman spectrum of Gc0‧ -H and by line at 960 cm-1 in the Raman spectrum of Gc0‧ -D. Relying on DFT calculations a complete vibrational assignment is proposed for the studied dendrimers. The frequencies and relative intensity of the bands at 1589, 1487 cm-1 in the IR spectra show marked difference in dependence of the substituents on the aromatic ring.

Characterisation of 1,3-diammonium propylselenate monohydrate by XRD, FT-IR, FT-Raman, DSC and DFT studies

NASA Astrophysics Data System (ADS)

Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.; Atalay, Yusuf

2016-03-01

The crystals of 1,3-diammonium propylselenate monohydrate (DAPS) were prepared and characterised X-ray diffraction (XRD), FT-IR, FT-Raman spectroscopy, and DFT/B3LYP methods. It comprises protonated propyl ammonium moieties (diammonium propyl cations), selenate anions and water molecule which are held together by a number of hydrogen bonds and form infinite chains. The XRD data confirm the transfer of two protons from selenic acid to 1,3-diaminopropane molecule. The DAPS complex is stabilised by the presence of O-H···O and N-H···O hydrogen bonds and the electrostatic interactions as well. The N···O and O···O bond distances are 2.82-2.91 and 2.77 Å, respectively. The FT-IR and FT-Raman spectra of 1,3-diammonium propyl selenate monohydrate are recorded and the complete vibrational assignments have been discussed. The geometry is optimised by B3LYP method using 6-311G, 6-311+G and 6-311+G* basis sets and the energy, structural parameters, vibrational frequencies, IR and Raman intensities are determined. Differential scanning colorimetry (DSC) data were also presented to analyse the possibility of the phase transition. Complete natural bonding orbital (NBO) analysis is carried out to analyse the intramolecular electronic interactions and their stabilisation energies. The electrostatic potential of the complex lies in the range +1.902e × 10-2 to -1.902e × 10-2. The limits of total electron density of the complex is +8.43e × 10-2 to -8.43e × 10-2.

Mass measurement errors of Fourier-transform mass spectrometry (FTMS): distribution, recalibration, and application.

PubMed

Zhang, Jiyang; Ma, Jie; Dou, Lei; Wu, Songfeng; Qian, Xiaohong; Xie, Hongwei; Zhu, Yunping; He, Fuchu

2009-02-01

The hybrid linear trap quadrupole Fourier-transform (LTQ-FT) ion cyclotron resonance mass spectrometer, an instrument with high accuracy and resolution, is widely used in the identification and quantification of peptides and proteins. However, time-dependent errors in the system may lead to deterioration of the accuracy of these instruments, negatively influencing the determination of the mass error tolerance (MET) in database searches. Here, a comprehensive discussion of LTQ/FT precursor ion mass error is provided. On the basis of an investigation of the mass error distribution, we propose an improved recalibration formula and introduce a new tool, FTDR (Fourier-transform data recalibration), that employs a graphic user interface (GUI) for automatic calibration. It was found that the calibration could adjust the mass error distribution to more closely approximate a normal distribution and reduce the standard deviation (SD). Consequently, we present a new strategy, LDSF (Large MET database search and small MET filtration), for database search MET specification and validation of database search results. As the name implies, a large-MET database search is conducted and the search results are then filtered using the statistical MET estimated from high-confidence results. By applying this strategy to a standard protein data set and a complex data set, we demonstrate the LDSF can significantly improve the sensitivity of the result validation procedure.

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

Mapping Discrimination Experienced by Indonesian Trans* FtM Persons.

PubMed

Gordon, Danny; Pratama, Mario Prajna

2017-01-01

This work sought to document how Indonesian trans* FtM persons experienced discrimination across the interlinked domains of social networks, religious and educational institutions, employment and the workplace, and health care institutions. Objectives were (1) to map the discrimination experienced by trans* FtM individuals in Indonesia, and (2) to establish the specific priorities of the Indonesian trans* FtM community. In-depth interviews, focus groups, and participant observation was used involving 14 respondents. Findings revealed that respondents experienced othering through rejection, misidentification, harassment, "correction," and bureaucratic discrimination across the five preestablished domains. Health care and a lack of information emerged as areas of particular concern for respondents. This work calls for health care that is sensitive to the needs of trans* FtM people coupled with high-quality information to alleviate the cycles through which discrimination is sustained.

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.

Oil spill source identification by principal component analysis of electrospray ionization Fourier transform ion cyclotron resonance mass spectra.

PubMed

Corilo, Yuri E; Podgorski, David C; McKenna, Amy M; Lemkau, Karin L; Reddy, Christopher M; Marshall, Alan G; Rodgers, Ryan P

2013-10-01

One fundamental challenge with either acute or chronic oil spills is to identify the source, especially in highly polluted areas, near natural oil seeps, when the source contains more than one petroleum product or when extensive weathering has occurred. Here we focus on heavy fuel oil that spilled (~200,000 L) from two suspected fuel tanks that were ruptured on the motor vessel (M/V) Cosco Busan when it struck the San Francisco-Oakland Bay Bridge in November 2007. We highlight the utility of principal component analysis (PCA) of elemental composition data obtained by high resolution FT-ICR mass spectrometry to correctly identify the source of environmental contamination caused by the unintended release of heavy fuel oil (HFO). Using ultrahigh resolution electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry, we uniquely assigned thousands of elemental compositions of heteroatom-containing species in neat samples from both tanks and then applied principal component analysis. The components were based on double bond equivalents for constituents of elemental composition, CcHhN1S1. To determine if the fidelity of our source identification was affected by weathering, field samples were collected at various intervals up to two years after the spill. We are able to identify a suite of polar petroleum markers that are environmentally persistent, enabling us to confidently identify that only one tank was the source of the spilled oil: in fact, a single principal component could account for 98% of the variance. Although identification is unaffected by the presence of higher polarity, petrogenic oxidation (weathering) products, future studies may require removal of such species by anion exchange chromatography prior to mass spectral analysis due to their preferential ionization by ESI.

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

Advances in handheld FT-IR instrumentation

NASA Astrophysics Data System (ADS)

Arnó, Josep; Cardillo, Len; Judge, Kevin; Frayer, Maxim; Frunzi, Michael; Hetherington, Paul; Levy, Dustin; Oberndorfer, Kyle; Perec, Walter; Sauer, Terry; Stein, John; Zuidema, Eric

2012-06-01

FT-IR spectroscopy is the technology of choice to identify solid and liquid phase unknown samples. The challenges of ConOps (Concepts of Operation) in emergency response and military field applications require a significant redesign of the stationary FT-IR bench-top instruments typically used in laboratories. Specifically, field portable units require high levels of resistance against mechanical shock and chemical attack, ease of use in restrictive gear, quick and easy interpretation of results, and reduced size. In the last 20 years, FT-IR instruments have been re-engineered to fit in small suitcases for field portable use and recently further miniaturized for handheld operation. This article introduces the advances resulting from a project designed to overcome the challenges associated with miniaturizing FT-IR instruments. The project team developed a disturbance-corrected permanently aligned cube corner interferometer for improved robustness and optimized opto-mechanical design to maximize optical throughput and signal-to-noise ratios. Thermal management and heat flow were thoroughly modeled and studied to isolate sensitive components from heat sources and provide the widest temperature operation range. Similarly, extensive research on mechanical designs and compensation techniques to protect against shock and vibration will be discussed. A user interface was carefully created for military and emergency response applications to provide actionable information in a visual, intuitive format. Similar to the HazMatID family of products, state-of-the-art algorithms were used to quickly identify the chemical composition of complex samples based on the spectral information. This article includes an overview of the design considerations, tests results, and performance validation of the mechanical ruggedness, spectral, and thermal performance.

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

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.

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...

Extending the ICRF into the Infrared: 2MASS - UCAC Astrometry

NASA Technical Reports Server (NTRS)

Zacharias, Norbert; McCallon, Howard L.; Kopan, Eugene; Cutri, Roc M.

2000-01-01

An external comparison between the infrared 2MASS and the optical UCAC positions was performed, both being on the same system, the ICRS. About 48 million sources in common were identified. Random errors of the 2MASS catalog positions are about 60 to 70 mas per coordinate for the Ks = 4 to 14 range, increasing to about 100 to 150 mas for saturated and very faint stars. Systematic position differences between the 2 catalogs are very small, about 5 to 10 mas as a function of magnitude and color, with somewhat larger errors as a function of right ascension and declination. The extension of the ICRF into the infrared has become a reality.

Effect of microwave treatment on structure of binders based on sodium carboxymethyl starch: FT-IR, FT-Raman and XRD investigations

NASA Astrophysics Data System (ADS)

Kaczmarska, Karolina; Grabowska, Beata; Spychaj, Tadeusz; Zdanowicz, Magdalena; Sitarz, Maciej; Bobrowski, Artur; Cukrowicz, Sylwia

2018-06-01

The paper deals with the influence of the microwave treatment on sodium carboxymethyl starch (CMS-Na) applied as a binder for moulding sands. The Fourier transformation infrared spectrometry (FT-IR), Raman spectroscopy (FT-Raman) and XRD analysis data of native potato starch and three different carboxymethyl starches (CMS-Na) with various degree of substitution (DS) before and after exposition to microwave radiation have been compared. FT-IR studies showed that polar groups present in CMS-Na structure take part in the formation of new hydrogen bonds network after water evaporation. However, these changes depend on DS value of the modified starch. The FT-Raman study confirmed that due to the impact on the samples by microwave, the changes of intensity in the characteristic bands associated with the crystalline regions in the sample were noticed. The X-ray diffraction data for microwave treated CMS-Na samples have been compared with the diffractograms of initial materials and analysis of XRD patterns confirmed that microwave-treated samples exhibit completely amorphous structure. Analysis of structural changes allows to state that the binding of sand grains in moulding sand with CMS-Na polymeric binder consists in the formation of hydrogen bonds networks (physical cross-linking).

Effect of microwave treatment on structure of binders based on sodium carboxymethyl starch: FT-IR, FT-Raman and XRD investigations.

PubMed

Kaczmarska, Karolina; Grabowska, Beata; Spychaj, Tadeusz; Zdanowicz, Magdalena; Sitarz, Maciej; Bobrowski, Artur; Cukrowicz, Sylwia

2018-06-15

The paper deals with the influence of the microwave treatment on sodium carboxymethyl starch (CMS-Na) applied as a binder for moulding sands. The Fourier transformation infrared spectrometry (FT-IR), Raman spectroscopy (FT-Raman) and XRD analysis data of native potato starch and three different carboxymethyl starches (CMS-Na) with various degree of substitution (DS) before and after exposition to microwave radiation have been compared. FT-IR studies showed that polar groups present in CMS-Na structure take part in the formation of new hydrogen bonds network after water evaporation. However, these changes depend on DS value of the modified starch. The FT-Raman study confirmed that due to the impact on the samples by microwave, the changes of intensity in the characteristic bands associated with the crystalline regions in the sample were noticed. The X-ray diffraction data for microwave treated CMS-Na samples have been compared with the diffractograms of initial materials and analysis of XRD patterns confirmed that microwave-treated samples exhibit completely amorphous structure. Analysis of structural changes allows to state that the binding of sand grains in moulding sand with CMS-Na polymeric binder consists in the formation of hydrogen bonds networks (physical cross-linking). Copyright © 2018 Elsevier B.V. All rights reserved.

Functional Characterization of Phalaenopsis aphrodite Flowering Genes PaFT1 and PaFD

PubMed Central

Jang, Seonghoe; Choi, Sang-Chul; Li, Hsing-Yi; An, Gynheung; Schmelzer, Elmon

2015-01-01

We show that the key flowering regulators encoded by Phalaenopsis aphrodite FLOWERING LOCUS T1 (PaFT1) and PaFD share high sequence homologies to these from long-day flowering Arabidopsis and short-day flowering rice. Interestingly, PaFT1 is specifically up-regulated during flowering inductive cooling treatment but is not subjected to control by photoperiod in P. aphrodite. Phloem or shoot apex-specific expression of PaFT1 restores the late flowering of Arabidopsis ft mutants. Moreover, PaFT1 can suppress the delayed flowering caused by SHORT VEGATATIVE PHASE (SVP) overexpression as well as an active FRIGIDA (FRI) allele, indicating the functional conservation of flowering regulatory circuit in different plant species. PaFT1 promoter:GUS in Arabidopsis showed similar staining pattern to that of Arabidopsis FT in the leaves and guard cells but different in the shoot apex. A genomic clone or heat shock-inducible expression of PaFT1 is sufficient to the partial complementation of the ft mutants. Remarkably, ectopic PaFT1 expression also triggers precocious heading in rice. To further demonstrate the functional conservation of the flowering regulators, we show that PaFD, a bZIP transcription factor involved in flowering promotion, interacts with PaFT1, and PaFD partially complemented Arabidopsis fd mutants. Transgenic rice expressing PaFD also flowered early with increased expression of rice homologues of APETALA1 (AP1). Consistently, PaFT1 knock-down Phalaenopsis plants generated by virus-induced gene silencing exhibit delayed spiking. These studies suggest functional conservation of FT and FD genes, which may have evolved and integrated into distinct regulatory circuits in monopodial orchids, Arabidopsis and rice that promote flowering under their own inductive conditions. PMID:26317412

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

FT-Raman Spectroscopy: A Catalyst for the Raman Explosion?

ERIC Educational Resources Information Center

Chase, Bruce

2007-01-01

The limitations of Fourier transform (FT) Raman spectroscopy, which is used to detect and analyze the scattered radiation, are discussed. FT-Raman has served to revitalize a field that was lagging and the presence of Raman instrumentation as a routine analytical tool is established for the foreseeable future.

Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations

NASA Astrophysics Data System (ADS)

Vennila, P.; Govindaraju, M.; Venkatesh, G.; Kamal, C.

2016-05-01

Fourier transform - Infra red (FT-IR) and Fourier transform - Raman (FT-Raman) spectroscopic techniques have been carried out to analyze O-methoxy benzaldehyde (OMB) molecule. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT). The vibrational analysis of stable isomer of OMB has been carried out by FT-IR and FT-Raman in combination with theoretical method simultaneously. The first-order hyperpolarizability and the anisotropy polarizability invariant were computed by DFT method. The atomic charges, hardness, softness, ionization potential, electronegativity, HOMO-LUMO energies, and electrophilicity index have been calculated. The 13C and 1H Nuclear magnetic resonance (NMR) have also been obtained by GIAO method. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Electronic excitation energies, oscillator strength and excited states characteristics were computed by the closed-shell singlet calculation method.

Corticosteroid-induced mandibular growth retardation and palatal malformation in the ICR mouse fetus.

PubMed Central

Silbermann, M; Levitan, S

1979-01-01

Pregnant ICR mice were treated with triamcinolone hexacetonide at various stages of gestation. The mandibular ramus and its condylar cartilage were studied histologically in both viable and non-viable offspring. In addition, measurements were made of the overall height of the posterior vertical dimension of the mandible and of condylar height and width. Significant changes were noted in these parameters. Concomitantly, marked changes were observed in the various zones of the condylar cartilage. A very high incidence of cleft palate was noted in newborn and stillborn mice previously treated with triamcinolone. A possible correlation between mandibular growth retardation and palatal clefting is discussed. Images Fig. 4 Fig. 5 Fig. 9 Fig. 10 Fig. 11 Fig. 12 Fig. 13 Fig. 14 Fig. 15 PMID:489465

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph; Dittmar, Thorsten; Kattner, Gerhard

2005-07-01

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

The spectroscopic properties of anticancer drug Apigenin investigated by using DFT calculations, FT-IR, FT-Raman and NMR analysis

NASA Astrophysics Data System (ADS)

Mariappan, G.; Sundaraganesan, N.; Manoharan, S.

2012-09-01

The FT-Raman and FT-Infrared spectra of solid Apigenin sample were measured in order to elucidate the spectroscopic properties of title molecule in the spectral range of 3500-50 cm-1 and 4000-400 cm-1, respectively. The recorded FT-IR and FT-Raman spectral measurements favor the calculated (by B3LYP/6-31G(d,p) method) structural parameters which are further supported by spectral simulation. Additional support is given by the collected 1H and 13C NMR spectra recorded with the sample dissolved in DMSO. The predicted chemical shifts at the B3LYP/6-31G(d) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). By using TD-DFT method, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and the experimental one is determined. The UV-visible absorption spectra of the compound that dissolved in Ethanol, Methanol and DMSO were recorded in the range of 800-200 nm. The formation of hydrogen bond and the most possible interaction are explained using natural bond orbital (NBO) analysis. In addition, the molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and atomic charges of the title compound were investigated using theoretical calculations. The results are discussed herein and compared with similar molecules whenever appropriate.

Rubus coreanus Miquel ameliorates scopolamine-induced memory impairments in ICR mice.

PubMed

Choi, Mi-Ran; Lee, Min Young; Hong, Ji Eun; Kim, Jeong Eun; Lee, Jae-Yong; Kim, Tae Hwan; Chun, Jang Woo; Shin, Hyun Kyung; Kim, Eun Ji

2014-10-01

The present study investigated the effect of Rubus coreanus Miquel (RCM) on scopolamine-induced memory impairments in ICR mice. Mice were orally administrated RCM for 4 weeks and scopolamine was intraperitoneally injected into mice to induce memory impairment. RCM improved the scopolamine-induced memory impairment in mice. The increase of acetylcholinesterase activity caused by scopolamine was significantly attenuated by RCM treatment. RCM increased the levels of acetylcholine in the brain and serum of mice. The expression of choline acetyltransferase, phospho-cyclic AMP response element-binding protein, and phospho-extracellular signal-regulated kinase was significantly increased within the brain of mice treated with RCM. The brain antioxidant enzyme activity decreased by scopolamine was increased by RCM. These results demonstrate that RCM exerts a memory-enhancing effect via the improvement of cholinergic function and the potentiated antioxidant activity in memory-impaired mice. The results suggest that RCM may be a useful agent for improving memory impairment.

1. Zinc Plant, looking north, down Government Gulch. 610 ft. ...

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

1. Zinc Plant, looking north, down Government Gulch. 610 ft. tall stack replaced original 200 ft. radial brick stack formerly at rear of Cottrell treater. - Sullivan Electrolytic Zinc Plant, Government Gulch, Kellogg, Shoshone County, ID

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.

Nano-liquid chromatography applied to enantiomers separation.

PubMed

Fanali, Salvatore

2017-02-24

This paper presents the state of the art concerning the separation of chiral compounds by means of nano-liquid chromatography (nano-LC). The enantiomers' separation and determination are a subject of fundamental importance in various application fields such as pharmaceutical industry, biomedicine, food, agrochemical etc. Nano-LC is a miniaturized chromatographic technique offering some advantages over conventional ones such as low consumption of mobile phase, sample volume and amount of chiral stationary phase, reduced costs etc. This is reported in the first part of the paper illustrating the features of the nano-LC. In addition, chiral resolution methods are briefly illustrated. Some chiral selectors, used in high-performance liquid chromatography have also been applied in nano-LC including cyclodextrins, glycopeptide antibiotics, modified polysaccharides etc. This is discussed in the second part of the review. Finally some examples of the applications available in literature are reported. Copyright © 2016 Elsevier B.V. All rights reserved.

Testing Viable f(T) Models with Current Observations

NASA Astrophysics Data System (ADS)

Xu, Bing; Yu, Hongwei; Wu, Puxun

2018-03-01

We perform observational tests on the f(T) gravity with the BAO data (including the BOSS DR 12 galaxy sample, the DR12 Lyα-Forests measurement, the new eBOSS DR14 quasar sample, the 6dFGS, and the SDSS), the CMB distance priors from the Planck 2015, the SNIa data from the joint light-curve analysis, the latest H(z) data, and the local value of the Hubble constant. Six different f(T) models are investigated. Furthermore, the ΛCDM is also considered. All models are compared by using the Akaike information criteria (AIC) and the Bayesian information criteria (BIC). Our results show that the ΛCDM remains to be the most favored model by current observations. However, there are also the Hubble constant tension between the Planck measurements and the local Universe observations and the tension between the CMB data and the H(z) data in the ΛCDM. For f(T) models considered in this paper, half, which can reduce to the ΛCDM, have values of {{χ }2}\\min smaller than that of the ΛCDM and can relieve the tensions existing in the ΛCDM. However, they are punished slightly by the BIC due to one extra parameter. Two of six f(T) models, in which the crossing of the phantom divide line can be realized for the equation of state of the effective dark energy and this crossing is shown in this paper to be favored by current observations, are punished by the information criteria. In addition, we find that the logarithmic f(T) model is excluded by cosmological observations.

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.

Fourier Transform Infrared Spectroscopy: Part II. Advantages of FT-IR.

ERIC Educational Resources Information Center

Perkins, W. D.

1987-01-01

This is Part II in a series on Fourier transform infrared spectroscopy (FT-IR). Described are various advantages of FT-IR spectroscopy including energy advantages, wavenumber accuracy, constant resolution, polarization effects, and stepping at grating changes. (RH)

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

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

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

Qualification of heavy water based irradiation device in the JSI TRIGA reactor for irradiations of FT-TIMS samples for nuclear safeguards

NASA Astrophysics Data System (ADS)

Radulović, Vladimir; Kolšek, Aljaž; Fauré, Anne-Laure; Pottin, Anne-Claire; Pointurier, Fabien; Snoj, Luka

2018-03-01

The Fission Track Thermal Ionization Mass Spectrometry (FT-TIMS) method is considered as the reference method for particle analysis in the field of nuclear Safeguards for measurements of isotopic compositions (fissile material enrichment levels) in micrometer-sized uranium particles collected in nuclear facilities. An integral phase in the method is the irradiation of samples in a very well thermalized neutron spectrum. A bilateral collaboration project was carried out between the Jožef Stefan Institute (JSI, Slovenia) and the Commissariat à l'Énergie Atomique et aux Énergies Alternatives (CEA, France) to determine whether the JSI TRIGA reactor could be used for irradiations of samples for the FT-TIMS method. This paper describes Monte Carlo simulations, experimental activation measurements and test irradiations performed in the JSI TRIGA reactor, firstly to determine the feasibility, and secondly to design and qualify a purpose-built heavy water based irradiation device for FT-TIMS samples. The final device design has been shown experimentally to meet all the required performance specifications.

Generalized second law of thermodynamics in f(T) gravity

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

Karami, K.; Abdolmaleki, A., E-mail: KKarami@uok.ac.ir, E-mail: AAbdolmaleki@uok.ac.ir

2012-04-01

We investigate the validity of the generalized second law (GSL) of gravitational thermodynamics in the framework of f(T) modified teleparallel gravity. We consider a spatially flat FRW universe containing only the pressureless matter. The boundary of the universe is assumed to be enclosed by the Hubble horizon. For two viable f(T) models containing f(T) = T+μ{sub 1}((−T)){sup n} and f(T) = T−μ{sub 2}T(1−e{sup βT{sub 0}/T}), we first calculate the effective equation of state and deceleration parameters. Then, (we investigate the null and strong energy conditions and conclude that a sudden future singularity appears in both models. Furthermore, using a cosmographicmore » analysis we check the viability of two models. Finally, we examine the validity of the GSL and find that for both models it) is satisfied from the early times to the present epoch. But in the future, the GSL is violated for the special ranges of the torsion scalar T.« less

Increased left ventricular mass and diastolic dysfunction are associated with endothelial dysfunction in normotensive offspring of subjects with essential hypertension.

PubMed

Zizek, Bogomir; Poredos, Pavel

2007-01-01

We aimed to investigate left ventricular (LV) morphology and function in normotensive offspring of subjects with essential hypertension (familial trait - FT), and to determine the association between LV mass and determinants of LV diastolic function and endothelium-dependent (NO-mediated) dilation of the brachial artery (BA). The study encompassed 76 volunteers of whom 44 were normotonics with FT aged 28-39 (mean 33) years and 32 age-matched controls without FT. LV mass and LV diastolic function was measured using conventional echocardiography and tissue Doppler imaging (TDI). LV diastolic filling properties were assessed and reported as the peak E/A wave ratio, and peak septal annular velocities (E(m) and E(m)/A(m) ratio) on TDI. Using high-resolution ultrasound, BA diameters at rest and during reactive hyperaemia (flow-mediated dilation--FMD) were measured. In subjects with FT, the LV mass index was higher than in controls (92.14+/-24.02 vs 70.08+/-20.58); p<0.001). Offspring of hypertensive families had worse LV diastolic function than control subjects (lower E/A ratio, lower E(m) and E(m)/A(m) ratio; p<0.001). In subjects with FT, FMD was decreased compared with the controls (6.11+/-3.28% vs 10.20+/-2.07%; p<0.001). LV mass index and E(m)/A(m) ratio were associated with FMD (p<0.001). In normotensive individuals with FT, LV morphological and functional changes were found. We demonstrated that an increase in LV mass and alterations in LV diastolic function are related to endothelial dysfunction.

A 928 sq m (10000 sq ft) solar array

NASA Technical Reports Server (NTRS)

Lindberg, D. E.

1972-01-01

As the power requirements for space vehicles increases, the area of solar arrays that convert solar energy to usable electrical power increases. The requirements for a 928 sq m (10,000 sq ft) array, its design, and a full-scale demonstration of one quadrant (232 sq m (2500 sq ft)) deployed in a one-g field are described.

Underivatized oxysterols and nanoLC-ESI-MS: A mismatch.

PubMed

Roberg-Larsen, Hanne; Vesterdal, Caroline; Wilson, Steven Ray; Lundanes, Elsa

2015-07-01

Due to their non-charged character, liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) measurements of oxysterols are often performed after derivatization with e.g. charged Girard reagents. However, derivatization reactions are time-consuming and may require numerous steps to remove excess reagent. In addition, extensive sample handling can be associated with cholesterol autoxidation, resulting in analyte artifacts and hence false positives. Nano scale liquid chromatography in combination with electrospray-mass spectrometry (nanoLC-ESI-MS) is a powerful tool for analyzing limited samples, due to substantially increased sensitivity compared to conventional LC-ESI-MS. The signal enhancement may compensate for the poor ionization of the oxysterols; hence we have explored the possibility to quantify oxysterols without derivatization using nanoLC-ESI-MS. Non-derivatized oxysterols and nanoLC were however not compatible, due to persistent and large carry-over. This was attributed to the extended contribution of surface to volume ratio in such miniaturized systems and interactions with the materials of the nanoLC instrumentation (e.g. adsorption to the fused silica tubing). Two contemporary MS instruments (Q-Exactive™ hybrid quadrupole-Orbitrap and TSQ Quantiva™ triple quadrupole) were used. However, both the MS and MS/MS spectra of non-derivatized oxysterols were ambiguous and/or unrepeatable for both of the instruments employed. Derivatizing oxysterols is more cumbersome, but provides more selective and reliable results, and Girard derivatization+nanoLC-ESI-MS continues to be our recommended choice for measuring oxysterols in very limited samples. These investigations also indicate that extra care should be taken to remove lipids prior to nanoLC of other analytes, as adsorbed oxysterols, etc. can compromise analysis. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of Infection Duration on Habitat Selection and Morphology of Adult Echinostoma caproni (Digenea: Echinostomatidae) in ICR Mice.

PubMed

Platt, Thomas R; Zelmer, Derek A

2016-02-01

The course of infection of Echinostoma caproni was followed in female ICR mice, a permissive laboratory host, from infection to natural termination. Twenty-one mice were infected with 20 metacercariae via oral intubation and housed 3 per cage. Three mice from a randomly selected cage were necropsied at 1 mo intervals. A second group of 15 mice was infected approximately 1 yr later to replace mice negative at necropsy in the first group. Mice in the second group were examined weekly for the presence of eggs in the feces. Mice negative for eggs on consecutive days were killed and necropsied. The location of individual worms and worm clusters were located in 20 segments of the small intestine. Adult worms were killed and fixed in hot formalin, stained, and prepared as whole mounts. Standard measurements were taken using a compound microscope fitted with an ocular micrometer. The infection spontaneously resolved in 10 mice from 7 to 32 wk PI, indicating the host response is highly variable and extending the maximum recorded length of E. caproni infections in ICR mice to 31 wk. A moribund worm was found in the feces of an animal that continued to pass eggs for an additional 2 mo indicating individual variation in worm responses. Worms located preferentially in the ileum (segments 11-13) during the first 3 mo of the infection but shifted to the jejunum (segments 8-9) during weeks 4-6. Morphologically, worms of different ages clustered together in multivariate space, with substantial overlap between the 3- and 4-mo-old infrapopulations and between the 5- and 6-mo-old infrapopulations. Muscular structures increased in size throughout the experiment, while the gonads increased in size for the first 3 mo and then declined during the last 3 mo. The relationship between E. caproni and ICR mice is more nuanced than previously reported. The reduction in gonad size and the shift from the ileum to the jejunum in the last 3 mo likely are related. These changes might be attributable

Applications of liquid-based separation in conjunction with mass spectrometry to the analysis of forensic evidence.

PubMed

Moini, Mehdi

2018-05-01

In the past few years, there has been a significant effort by the forensic science community to develop new scientific techniques for the analysis of forensic evidence. Forensic chemists have been spearheaded to develop information-rich confirmatory technologies and techniques and apply them to a broad array of forensic challenges. The purpose of these confirmatory techniques is to provide alternatives to presumptive techniques that rely on data such as color changes, pattern matching, or retention time alone, which are prone to more false positives. To this end, the application of separation techniques in conjunction with mass spectrometry has played an important role in the analysis of forensic evidence. Moreover, in the past few years the role of liquid separation techniques, such as liquid chromatography and capillary electrophoresis in conjunction with mass spectrometry, has gained significant tractions and have been applied to a wide range of chemicals, from small molecules such as drugs and explosives, to large molecules such as proteins. For example, proteomics and peptidomics have been used for identification of humans, organs, and bodily fluids. A wide range of HPLC techniques including reversed phase, hydrophilic interaction, mixed-mode, supercritical fluid, multidimensional chromatography, and nanoLC, as well as several modes of capillary electrophoresis mass spectrometry, including capillary zone electrophoresis, partial filling, full filling, and micellar electrokenetic chromatography have been applied to the analysis drugs, explosives, and questioned documents. In this article, we review recent (2015-2017) applications of liquid separation in conjunction with mass spectrometry to the analysis of forensic evidence. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Agegraphic Pilgrim Dark Energy in f(T, TG) Gravity

NASA Astrophysics Data System (ADS)

Jawad, Abdul; Debnath, Ujjal

2015-08-01

In this work, we briefly discuss a novel class of modified gravity like f(T, TG) gravity. In this background, we assume the new agegraphic version of pilgrim dark energy and reconstruct f(T, TG) models for two specific values of s. We also discuss the equation of state parameter, squared speed of sound and wDE-w‧DE plane for these reconstructed f(T, TG) models. The equation of state parameter provides phantom-like behavior of the universe. The wDE-w‧DE plane also corresponds to ΛCDM limit, thawing and freezing regions for both models.

Ariel: a UAV designed to fly at 100,000 ft

NASA Astrophysics Data System (ADS)

Papadales, Basil S.; Schoenung, Susan M.

1996-11-01

The Ariel unmanned aerial vehicle (UAV) was designed for NASA Ames Research Center to satisfy emerging civil science needs for subsonic flight at altitudes on the order of 100,000 ft. These include atmospheric monitoring of chemical species and environmental conditions related to global climate change. Ariel may be useful for a variety of civil and military remote sensing applications since, at an altitude of 100,000 ft, the UAV wold fly above all manned aircraft. The Ariel has a gross weight of 6400 lb with a wing span of 105 ft, a little shorter than that of the manned ER-2. Ariel is powered by a new propulsion system called the Bipropellant Expansion Turbine (BET). With a 300 hp BET, Ariel can climb to an altitude of 100,000 ft and loiter at Mach 0.63 for two hours while carrying a 600 lb payload. During this loiter, the UAV travels about 750 nm at 100,000 ft. It is possible to trade payload weight for range or endurance. Further design optimization or use of more advanced technology can result in substantially improved performance. With adequate funding, a proof of concept version of Ariel could be developed for initial flights by the year 2000.

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.

Determination of Structural and Vibrational Properties of 5-QUINOLINECARBOXALDEHYDE Using Experimental Ft-Ir Ft-Raman Techniques and Theoretical HF and DFT Methods

NASA Astrophysics Data System (ADS)

Kumru, Mustafa; Kocademir, Mustafa; Bardakci, Tayyibe

2013-06-01

Quinoline derivatives have been used in several pharmaceuticals. They have vital roles in regulating the functions of DNA and cancerous cells. It's necessary to determine the structures and spectroscopic properties of quinoline derivates. In this study, the FT-IR (including mid and far regions) and FT-Raman spectra of 5-quinolinecarboxaldehyde have been investigated. Hartree-Fock (HF) and density functional B3LYP calculations have also been employed with the 6-311++G(d,p) basis set for investigating the structural and spectroscopic properties of the cis and trans conformers of 5-quinolinecarboxaldehyde. Experimental and theoretical results have been compared and the results are in good agreement with each other. Keywords: 5-quinolinecarboxaldehyde; Vibrational Spectroscopy; FT-IR spectra; FT-Raman spectra; Vibrational Modes; HF; DFT [1] V. Kucuk, A. Altun, M. Kumru, Spectrochim. Acta Part A 85(2012)92-98 [2] M. Kumru, V. Kucuk, T. Bardakci, Spectrochim. Acta Part A 90(2012)28-34 [3] M. Kumru, V. Kucuk, M. Kocademir, Spectrochim. Acta Part A, 96 (2012) 242-251 We thank the Turkish Scientific and Technical Research Council (TUBITAK) for their financial support through National Postdoctoral Research Scholarship Programme and Scientific Research Fund of Fatih University under the project number P50011001 G (1457).

Overexpression of PaFT gene in the wild orchid Phalaenopsis amabilis (L.) Blume

NASA Astrophysics Data System (ADS)

Semiarti, Endang; Mercuriani, Ixora S.; Rizal, Rinaldi; Slamet, Agus; Utami, Bekti S.; Bestari, Ida A.; Aziz-Purwantoro, Moeljopawiro, S.; Jang, Soenghoe; Machida, Y.; Machida, C.

2015-09-01

To shorten vegetative stage and induce transition from vegetative to reproductive stage in orchids, we overexpressed Phalaenopsis amabilis Flowering LocusT (PaFT) gene under the control of Ubiquitin promoter into protocorm of Indonesian Wild Orchid Phalaenopsis amabilis (L.) Blume. The dynamic expression of vegetative gene Phalaenopsis Homeobox1 (POH1) and flowering time gene PaFT has been analyzed. Accumulation of mRNA was detected in shoot and leaves of both transgenic and non transgenic plants by using Reverse transcriptase-PCR (RT-PCR) with specific gene primers for POH1 and PaFT in 24 months old plants. To analyze the POH1 and PaFT genes, three pairs of degenerate primers PaFT degF1R1, F2R2 and F3R3 that amplified 531 bp PaFT cDNA were used. We detected 700 bp PaFTcDNA from leaves and shoots of transgenic plants, but not in NT plants. POH1 mRNA was detected in plants. PaFT protein consists of Phospatidyl Ethanolamine-Binding Protein (PEBP) in interval base 73-483 and CETS family protein at base 7-519, which are important motif for transmembrane protein. We inserted Ubipro::PaFT/pGAS101 into P. amabilis protocorm using Agrobacterium. Analysis of transgenic plants showed that PaFTmRNA was accumulated in leaves of 12 months after sowing, although it is not detected in non transgeic plants. Compare to the wild type (NT plants), ectopic expression of PaFT shows alter phenotype as follows: 31% normal, 19% with short-wavy leaves, 5% form rosette leaves and 45% produced multishoots. Analysis of protein profiles of trasgenic plants showed that a putative PaFT protein (MW 19,7 kDa) was produced in 1eaves and shoots.This means that at 12 months, POH1 gene expression gradually decreased/negatively regulated, the expression of PaFT gene was activated, although there is no flower initiation yet. Some environmental factors might play a role to induce inflorescens. This experiment is in progress.

Analysis of Human Plasma Metabolites across Different Liquid Chromatography - Mass Spectrometry Platforms: Cross-platform Transferable Chemical Signatures

PubMed Central

Telu, Kelly H.; Yan, Xinjian; Wallace, William E.; Stein, Stephen E.; Simón-Manso, Yamil

2016-01-01

RATIONALE The metabolite profiling of a NIST plasma Standard Reference Material (SRM 1950) on different LC-MS platforms showed significant differences. Although these findings suggest caution when interpreting metabolomics results, the degree of overlap of both profiles allowed us to use tandem mass spectral libraries of recurrent spectra to evaluate to what extent these results are transferable across platforms and to develop cross-platform chemical signatures. METHODS Non-targeted global metabolite profiles of SRM 1950 were obtained on different LC-MS platforms using reversed phase chromatography and different chromatographic scales (nano, conventional and UHPLC). The data processing and the metabolite differential analysis were carried out using publically available (XCMS), proprietary (Mass Profiler Professional) and in-house software (NIST pipeline). RESULTS Repeatability and intermediate precision showed that the non-targeted SRM 1950 profiling was highly reproducible when working on the same platform (RSD < 2%); however, substantial differences were found in the LC-MS patterns originating on different platforms or even using different chromatographic scales (conventional HPLC, UHPLC and nanoLC) on the same platform. A substantial degree of overlap (common molecular features) was also found. A procedure to generate consistent chemical signatures using tandem mass spectral libraries of recurrent spectra is proposed. CONLUSIONS Different platforms rendered significantly different metabolite profiles, but the results were highly reproducible when working within one platform. Tandem mass spectral libraries of recurrent spectra are proposed to evaluate the degree of transferability of chemical signatures generated on different platforms. Chemical signatures based on our procedure are most likely cross-platform transferable. PMID:26842580

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.

Completely automated open-path FT-IR spectrometry.

PubMed

Griffiths, Peter R; Shao, Limin; Leytem, April B

2009-01-01

Atmospheric analysis by open-path Fourier-transform infrared (OP/FT-IR) spectrometry has been possible for over two decades but has not been widely used because of the limitations of the software of commercial instruments. In this paper, we describe the current state-of-the-art of the hardware and software that constitutes a contemporary OP/FT-IR spectrometer. We then describe advances that have been made in our laboratory that have enabled many of the limitations of this type of instrument to be overcome. These include not having to acquire a single-beam background spectrum that compensates for absorption features in the spectra of atmospheric water vapor and carbon dioxide. Instead, an easily measured "short path-length" background spectrum is used for calculation of each absorbance spectrum that is measured over a long path-length. To accomplish this goal, the algorithm used to calculate the concentrations of trace atmospheric molecules was changed from classical least-squares regression (CLS) to partial least-squares regression (PLS). For calibration, OP/FT-IR spectra are measured in pristine air over a wide variety of path-lengths, temperatures, and humidities, ratioed against a short-path background, and converted to absorbance; the reference spectrum of each analyte is then multiplied by randomly selected coefficients and added to these background spectra. Automatic baseline correction for small molecules with resolved rotational fine structure, such as ammonia and methane, is effected using wavelet transforms. A novel method of correcting for the effect of the nonlinear response of mercury cadmium telluride detectors is also incorporated. Finally, target factor analysis may be used to detect the onset of a given pollutant when its concentration exceeds a certain threshold. In this way, the concentration of atmospheric species has been obtained from OP/FT-IR spectra measured at intervals of 1 min over a period of many hours with no operator intervention.

[THE USE OF THE MODEL MOUSE ICR--VARIOLA VIRUS FOR EVALUATION OF ANTIVIRAL DRUG EFFICACY].

PubMed

Titova, K A; Sergeev, Al A; Kabanov, A S; Bulychev, L E; Sergeev, Ar A; Galakhova, D O; Shishkina, L N; Zamedyanskaya, A S; Nesterov, A E; Glotov, A G; Taranov, O S; Omigov, V V; Agafonov, A P; Sergeev, A N

2016-01-01

Mice of the ICR outbred population were infected intranasally (i/n) with the variola virus (VARV, strain Ind-3a). Clinical signs of the disease did not appear even at the maximum possible dose of the virus 5.2 lg PFU/head (plaque-forming units per head). In this case, 50% infective dose (ID50) of VARV estimated by the presence or absence of the virus in the lungs three days after infection (p.i.) was equal to 2.7 ± 0.4 lg PFU/head. Taking into account the 10% application of the virus in the lungs during the intranasal infection of the mice, it was adequate to 1.7 lg PFU/lungs. This indicates a high infectivity of the VARV for mice comparable to its infectivity for humans. After the i/n infection of mice with the VARV at a dose 30 ID50/ head the highest concentration of the virus detected in the lungs (4.9 ± 0.0 lg PFU/ml of homogenate) and in nasal cavity tissues (4.8 ± 0.0 lg PFU/ml) were observed. The pathomorphological changes in the respiratory organs of the mice infected with the VARV appeared at 3-5 days p.i., and the VARV reproduction noted in the epithelial cells and macrophages were noticed. When the preparations ST-246 and NIOCH-14 were administered orally at a dose of 60 μg/g of mouse weight up to one day before infection, after 2 hours, 1 and 2 days p.i., the VARV reproduction in the lungs after 3 days p.i. decreased by an order of magnitude. Thus, outbred ICR mice infected with the VARV can be used as a laboratory model of the smallpox when evaluating the therapeutic and prophylactic efficacy of the antismallpox drugs.

Promoting effects of bile acid to intestinal tumorigenesis in gnotobiotic ICR mice.

PubMed

Iwasaki, I; Iwase, H; Yumoto, N; Ide, G

1985-11-01

Gnotobiotes were produced by administrating Lactobacillus plantarum IAM 1041 in ICR strain male germfree mice which were fed by ordinary or high fat diet. Both groups were orally administered 0.3 mg/10 g of body weight (B.W.) of methylazoxymethanol (MAM) acetate. The oral administration of 0.3 mg/10 g/B.W. once a week for 11 consecutive weeks caused a total of 68 adenomatous polyps in the large intestine (an average of 11.4/mouse) of gnotobiotic high fat diet mice and a total of 32 adenomatous polyps (an average of 5.3/mouse) of the ordinary diet mice. There were no malignancies in either of the groups. Bile acids in the feces showed higher values in the high fat diet group than in the ordinary group. Bile acids are a factor which promotes the appearance of intestinal tumors. It was also assumed that the L. plantarum promoted the activation of beta-glucuronidase and alcohol dehydrogenase in the liver and intestine.

FT-IR and FT-Raman characterization of non-cellulosic polysaccharides fractions isolated from plant cell wall.

PubMed

Chylińska, Monika; Szymańska-Chargot, Monika; Zdunek, Artur

2016-12-10

The purpose of this work was to reveal the structural changes of cell wall polysaccharides' fractions during tomato fruit development by analysis of spectral data. Mature green and red ripe tomato fruit were taken into consideration. The FT-IR spectra of water soluble pectin (WSP), imidazole soluble pectin (ISP) and diluted alkali soluble pectin (DASP) contained bands typical for pectins. Whereas for KOH fraction spectra bands typical for hemicelluloses were present. The FT-IR spectra showed the drop down of esterification degree of WSP and ISP polysaccharides during maturation. The changes in polysaccharides structure revealed by spectra were the most visible in the case of pectic polysaccharides. The WSP and DASP fraction pectins molecules length were shortened during tomato maturation and ripening. Whereas the ISP fraction spectra analysis showed that this fraction contained rhamnogalacturonan I, but also for red ripe was rich in pectic galactan comparing with ISP fraction from mature green. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Possibility of Using the ICR Mouse as an Animal Model to Assess Antimonkeypox Drug Efficacy.

PubMed

Sergeev, Al A; Kabanov, A S; Bulychev, L E; Sergeev, Ar A; Pyankov, O V; Bodnev, S A; Galahova, D O; Zamedyanskaya, A S; Titova, K A; Glotov, A G; Taranov, O S; Omigov, V V; Shishkina, L N; Agafonov, A P; Sergeev, A N

2016-10-01

As a result of the conducted experimental studies on intranasal challenge of ICR mice, rabbits and miniature pigs (even in the maximum variant) with the doses of 4.0-5.5 lg PFU of monkeypox virus (MPXV), some clinical signs such as purulent conjunctivitis, blepharitis and ruffled fur were found only in mice. The 50% infective dose (C ID50 ) of MPXV for these animals estimated by the presence of external clinical signs was 4.8 lg PFU, and L ID50 estimated by the virus presence in the lungs of mice 7 days post-infection taking into account its 10% application in the animal respiratory tract was 1.4 lg PFU. When studying the dynamics of MPXV propagation in mice challenged intranasally with 25 L ID50 of MPXV, the maximum pathogen accumulation was revealed in nasal cavity, lungs and brain: 5.7 ± 0.1, 5.5 ± 0.1 and 5.3 ± 0.3 lg PFU/ml, respectively. The pathomorphological examination of these animals revealed the presence and replication of the pathogen in the traditional primary target cells for MPXV (mononuclear phagocyte system cells and respiratory tract epitheliocytes) as well as in some other types of cells (endothelial cells, reticular cells, connective tissue cells). Our use of these animals to assess the antiviral efficacy of some drugs demonstrated the agreement of the results (a significant positive effect of NIOCH-14 and ST-246) with those described in scientific literature, which opens up the prospects of using ICR mice as animal models for monkeypox to develop preventive antismallpox drugs. © 2015 Blackwell Verlag GmbH.

Poplar FT2 Shortens the Juvenile Phase and Promotes Seasonal Flowering[W

PubMed Central

Hsu, Chuan-Yu; Liu, Yunxia; Luthe, Dawn S.; Yuceer, Cetin

2006-01-01

Many woody perennials, such as poplar (Populus deltoides), are not able to form flower buds during the first several years of their life cycle. They must undergo a transition from the juvenile phase to the reproductive phase to be competent to produce flower buds. After this transition, trees begin to form flower buds in the spring of each growing season. The genetic factors that control flower initiation, ending the juvenile phase, are unknown in poplar. The factors that regulate seasonal flower bud formation are also unknown. Here, we report that poplar FLOWERING LOCUS T2 (FT2), a relative of the Arabidopsis thaliana flowering-time gene FT, controls first-time and seasonal flowering in poplar. The FT2 transcript is rare during the juvenile phase of poplar. When juvenile poplar is transformed with FT2 and transcript levels are increased, flowering is induced within 1 year. During the transition between vegetative and reproductive growth in mature trees, FT2 transcripts are abundant during reproductive growth under long days. Subsequently, floral meristems emerge on flanks of the axillary inflorescence shoots. These findings suggest that FT2 is part of the flower initiation pathway in poplar and plays an additional role in regulating seasonal flower initiation that is integrated with the poplar perennial growth habit. PMID:16844908

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.

FT-IR, FT-Raman, UV spectra and DFT calculations on monomeric and dimeric structure of 2-amino-5-bromobenzoic acid.

PubMed

Karabacak, Mehmet; Cinar, Mehmet

2012-02-01

In this work, the molecular conformation, vibrational and electronic transition analysis of 2-amino-5-bromobenzoic acid (2A5BrBA) were presented for the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. FT-IR and FT-Raman spectra were recorded in the regions of 400-4000 cm(-1) and 50-4000 cm(-1), respectively. There are four conformers, C1, C2, C3 and C4 for this molecule. The geometrical parameters, energies and wavenumbers have been obtained for all four conformers. The computational results diagnose the most stable conformer of 2A5BrBA as the C1 form. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Raman activities calculated by DFT method have been converted to the corresponding Raman intensities using Raman scattering theory. The UV spectra of investigated compound were recorded in the region of 200-400 nm for ethanol and water solutions. The electronic properties were evaluated with help of time-dependent DFT (TD-DFT) theoretically and results were compared with experimental observations. The thermodynamic properties of the studied compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures. The observed and the calculated geometric parameters, vibrational wavenumbers and electronic transitions were compared with observed data and found to be in good agreement. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Structural study, NCA, FT-IR, FT-Raman spectral investigations, NBO analysis, thermodynamic functions of N-acetyl-l-phenylalanine.

PubMed

Raja, B; Balachandran, V; Revathi, B

2015-03-05

The FT-IR and FT-Raman spectra of N-acetyl-l-phenylalanine were recorded and analyzed. Natural bond orbital analysis has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. HOMO-LUMO energy gap has been computed with the help of density functional theory. The statistical thermodynamic functions (heat capacity, entropy, vibrational partition function and Gibbs energy) were obtained for the range of temperature 100-1000K. The polarizability, first hyperpolarizability, anisotropy polarizability invariant has been computed using quantum chemical calculations. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the experimental and theoretical spectra values provides important information about the ability of the computational method to describe the vibrational modes. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Solar cycle variation of geosynchronous plasma mass density derived from the frequency of standing Alfvén waves

NASA Astrophysics Data System (ADS)

Takahashi, Kazue; Denton, Richard E.; Singer, Howard J.

2010-07-01

We have studied the solar cycle variation of equatorial plasma mass density ρeq in the plasma trough at geosynchronous altitude. The density was indirectly determined from the frequency, fT3, of the third harmonic of toroidal standing Alfvén waves detected over a 12 year period from 1980 to 1991 with magnetometers on five Geostationary Operational Environmental Satellites (GOES). Realistic models of the ambient magnetic field and field line mass distribution were used in numerically solving the wave equation to relate fT3 to ρeq. Scanning the magnetometer data in a 30 min time window that moved forward in 10 min steps, we obtained 228,382 fT3 samples equivalent to 1586 days of data. The detection rate of fT3 is highest (˜50%) in the prenoon sector, and fT3 and ρeq samples from this sector were used to examine their dependence on F10.7, Kp, and Dst. Overall, F10.7 exhibits the highest correlation with fT3 and ρeq, implying that the solar UV/EUV control of ion production at the ionospheric height is strongly reflected in mass density variations at geosynchronous orbit. Using 27 day medians computed excluding periods of plasmasphere expansion to geosynchronous orbit and geomagnetic storm, we obtained the empirical formula fT3 (mHz) = 38 - 0.097F10.7 and logρeq (amu cm-3) = 0.42 + 0.0039F10.7, where F10.7 is given in the solar flux units 10-22 W · m-2 · Hz-1. This last formula means that with the 27 day F10.7 in the range of 68-255 in the selected solar cycle, the mass density varied by a factor of ˜5 from ˜5 to ˜26 amu cm-3. During extremely quiet times (Kp averaged using a 3 day time scale <1), for which the plasmasphere may extend out to geosynchronous orbit, and during storm periods (Dst < -50 nT), the mass density may be enhanced beyond these values.

Cosmological viability conditions for f(T) dark energy models

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

Setare, M.R.; Mohammadipour, N., E-mail: rezakord@ipm.ir, E-mail: N.Mohammadipour@uok.ac.ir

2012-11-01

Recently f(T) modified teleparallel gravity where T is the torsion scalar has been proposed as the natural gravitational alternative for dark energy. We perform a detailed dynamical analysis of these models and find conditions for the cosmological viability of f(T) dark energy models as geometrical constraints on the derivatives of these models. We show that in the phase space exists two cosmologically viable trajectory which (i) The universe would start from an unstable radiation point, then pass a saddle standard matter point which is followed by accelerated expansion de sitter point. (ii) The universe starts from a saddle radiation epoch,more » then falls onto the stable matter era and the system can not evolve to the dark energy dominated epoch. Finally, for a number of f(T) dark energy models were proposed in the more literature, the viability conditions are investigated.« less

Conducting non-commercial international clinical trials: the ICR-CTSU experience.

PubMed

Fox, Lisa; Toms, Christy; Kernaghan, Sarah; Snowdon, Claire; Bliss, Judith M

2017-09-26

Academic clinical trials play a fundamental role in the development of new treatments, the repurposing of existing treatments and in addressing areas of unmet clinical need. With cancer treatments increasingly targeted at molecular subtypes, and with priority placed on developing new treatments for rare tumour types, the need for international trial participation to access sufficient patient numbers for successful trial conduct is growing. However, lack of harmonisation of international legal, ethical and financial systems can make this challenging and the cost and effort of conducting trials internationally can be considered prohibitive, particularly where the sample size is comparatively small. The Institute of Cancer Research - Clinical Trials and Statistics Unit (ICR-CTSU) is a UK-based academic clinical trials unit that specialises in the design, conduct and analysis of clinical trials of cancer treatments with an expanding portfolio of trials in molecular subtypes of breast and urological cancers and in other rare cancer types. Implementing appropriate mechanisms to enable international participation has therefore been imperative. In this article, we explain how we have approached the challenges involved and describe examples of successful international trial conduct, achieved through robust collaborations with academic and industry partners. Conducting academic trials internationally is challenging but can and should be achieved through appropriate governance mechanisms and strong collaborations.

Mass Spectrometry Based Metabolomics Comparison of Liver Grafts from Donors after Circulatory Death (DCD) and Donors after Brain Death (DBD) Used in Human Orthotopic Liver Transplantation.

PubMed

Hrydziuszko, Olga; Perera, M Thamara P R; Laing, Richard; Kirwan, Jennifer; Silva, Michael A; Richards, Douglas A; Murphy, Nick; Mirza, Darius F; Viant, Mark R

2016-01-01

Use of marginal liver grafts, especially those from donors after circulatory death (DCD), has been considered as a solution to organ shortage. Inferior outcomes have been attributed to donor warm ischaemic damage in these DCD organs. Here we sought to profile the metabolic mechanisms underpinning donor warm ischaemia. Non-targeted Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry metabolomics was applied to biopsies of liver grafts from donors after brain death (DBD; n = 27) and DCD (n = 10), both during static cold storage (T1) as well as post-reperfusion (T2). Furthermore 6 biopsies from DBD donors prior to the organ donation (T0) were also profiled. Considering DBD and DCD together, significant metabolic differences were discovered between T1 and T2 (688 peaks) that were primarily related to amino acid metabolism, meanwhile T0 biopsies grouped together with T2, denoting the distinctively different metabolic activity of the perfused state. Major metabolic differences were discovered between DCD and DBD during cold-phase (T1) primarily related to glucose, tryptophan and kynurenine metabolism, and in the post-reperfusion phase (T2) related to amino acid and glutathione metabolism. We propose tryptophan/kynurenine and S-adenosylmethionine as possible biomarkers for the previously established higher graft failure of DCD livers, and conclude that the associated pathways should be targeted in more exhaustive and quantitative investigations.

Mass Spectrometry Based Metabolomics Comparison of Liver Grafts from Donors after Circulatory Death (DCD) and Donors after Brain Death (DBD) Used in Human Orthotopic Liver Transplantation

PubMed Central

Laing, Richard; Kirwan, Jennifer; Silva, Michael A.; Richards, Douglas A.; Murphy, Nick; Mirza, Darius F.; Viant, Mark R.

2016-01-01

Use of marginal liver grafts, especially those from donors after circulatory death (DCD), has been considered as a solution to organ shortage. Inferior outcomes have been attributed to donor warm ischaemic damage in these DCD organs. Here we sought to profile the metabolic mechanisms underpinning donor warm ischaemia. Non-targeted Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry metabolomics was applied to biopsies of liver grafts from donors after brain death (DBD; n = 27) and DCD (n = 10), both during static cold storage (T1) as well as post-reperfusion (T2). Furthermore 6 biopsies from DBD donors prior to the organ donation (T0) were also profiled. Considering DBD and DCD together, significant metabolic differences were discovered between T1 and T2 (688 peaks) that were primarily related to amino acid metabolism, meanwhile T0 biopsies grouped together with T2, denoting the distinctively different metabolic activity of the perfused state. Major metabolic differences were discovered between DCD and DBD during cold-phase (T1) primarily related to glucose, tryptophan and kynurenine metabolism, and in the post-reperfusion phase (T2) related to amino acid and glutathione metabolism. We propose tryptophan/kynurenine and S-adenosylmethionine as possible biomarkers for the previously established higher graft failure of DCD livers, and conclude that the associated pathways should be targeted in more exhaustive and quantitative investigations. PMID:27835640

Logamediate Inflation in f(T) Teleparallel Gravity

NASA Astrophysics Data System (ADS)

Rezazadeh, Kazem; Abdolmaleki, Asrin; Karami, Kayoomars

2017-02-01

We study logamediate inflation in the context of f(T) teleparallel gravity. f(T)-gravity is a generalization of the teleparallel gravity which is formulated on the Weitzenbock spacetime, characterized by the vanishing curvature tensor (absolute parallelism) and the non-vanishing torsion tensor. We consider an f(T)-gravity model which is sourced by a canonical scalar field. Assuming a power-law f(T) function in the action, we investigate an inflationary universe with a logamediate scale factor. Our results show that, although logamediate inflation is completely ruled out by observational data in the standard inflationary scenario based on Einstein gravity, it can be compatible with the 68% confidence limit joint region of Planck 2015 TT,TE,EE+lowP data in the framework of f(T)-gravity.

Applications of FT-IR spectrophotometry in cancer diagnostics.

PubMed

Bunaciu, Andrei A; Hoang, Vu Dang; Aboul-Enein, Hassan Y

2015-01-01

This review provides a brief background to the application of infrared spectroscopy, including Fourier transform-infrared spectroscopy, in biological fluids. It is not meant to be complete or exhaustive but to provide the reader with sufficient background for selected applications in cancer diagnostics. Fourier transform-infrared spectroscopy (FT-IR) is a fast and nondestructive analytical method. The infrared spectrum of a mixture serves as the basis to quantitate its constituents, and a number of common clinical chemistry tests have proven to be feasible using this approach. This review focuses on biomedical FT-IR applications, published in the period 2009-2013, used for early detection of cancer through qualitative and quantitative analysis.

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.

HvFT1 polymorphism and effect—survey of barley germplasm and expression analysis

PubMed Central

Loscos, Jorge; Igartua, Ernesto; Contreras-Moreira, Bruno; Gracia, M. Pilar; Casas, Ana M.

2014-01-01

Flowering time in plants is a tightly regulated process. In barley (Hordeum vulgare L.), HvFT1, ortholog of FLOWERING LOCUS T, is the main integrator of the photoperiod and vernalization signals leading to the transition from vegetative to reproductive state of the plant. This gene presents sequence polymorphisms affecting flowering time in the first intron and in the promoter. Recently, copy number variation (CNV) has been described for this gene. An allele with more than one copy was linked to higher gene expression, earlier flowering, and an overriding effect of the vernalization mechanism. This study aims at (1) surveying the distribution of HvFT1 polymorphisms across barley germplasm and (2) assessing gene expression and phenotypic effects of HvFT1 alleles. We analyzed HvFT1 CNV in 109 winter, spring, and facultative barley lines. There was more than one copy of the gene (2–5) only in spring or facultative barleys without a functional vernalization VrnH2 allele. CNV was investigated in several regions inside and around HvFT1. Two models of the gene were found: one with the same number of promoters and transcribed regions, and another with one promoter and variable number of transcribed regions. This last model was found in Nordic barleys only. Analysis of HvFT1 expression showed that association between known polymorphisms at the HvFT1 locus and the expression of the gene was highly dependent on the genetic background. Under long day conditions the earliest flowering lines carried a sensitive PpdH1 allele. Among spring cultivars with different number of copies, no clear relation was found between CNV, gene expression and flowering time. This was confirmed in a set of doubled haploid lines of a population segregating for HvFT1 CNV. Earlier flowering in the presence of several copies of HvFT1 was only seen in cultivar Tammi, which carries one promoter, suggesting a relation of gene structure with its regulation. HvCEN also affected to a large extent flowering

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

Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation and NLO, HOMO-LUMO, NBO analysis of organic 2,4,5-trichloroaniline.

PubMed

Govindarajan, M; Karabacak, M; Periandy, S; Tanuja, D

2012-11-01

In this work, the experimental and theoretical study on the molecular structure and vibrational spectra of 2,4,5-trichloroaniline (C(6)H(4)NCl(3), abbreviated as 2,4,5-TClA) were studied. The FT-IR and FT-Raman spectra were recorded. The molecular geometry and vibrational frequencies in the ground state were calculated by using the Hartree-Fock (HF) and density functional theory (DFT) methods (B3LYP) with 6-311++G(d,p) basis set. Comparison of the observed fundamental vibrational frequencies of 2,4,5-TClA with calculated results by HF and DFT indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. Besides, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 2,4,5-TClA molecule may have microscopic nonlinear optical (NLO) behavior with non-zero values. Mulliken atomic charges of 2,4,5-TClA was calculated and compared with aniline and chlorobenzene molecules. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.

Now is the time to demand change to punishing FtP procedures.

PubMed

Mason, Sharon

2016-05-25

Having undergone Nursing and Midwifery Council fitness to practise (FtP) proceedings after raising and escalating concerns, I read with interest your article about nurses facing FtP hearings being 'pushed to breaking point' (analysis, May 11).

Microfluidic chip for peptide analysis with an integrated HPLC column, sample enrichment column, and nanoelectrospray tip.

PubMed

Yin, Hongfeng; Killeen, Kevin; Brennen, Reid; Sobek, Dan; Werlich, Mark; van de Goor, Tom

2005-01-15

Current nano-LC/MS systems require the use of an enrichment column, a separation column, a nanospray tip, and the fittings needed to connect these parts together. In this paper, we present a microfabricated approach to nano-LC, which integrates these components on a single LC chip, eliminating the need for conventional LC connections. The chip was fabricated by laminating polyimide films with laser-ablated channels, ports, and frit structures. The enrichment and separation columns were packed using conventional reversed-phase chromatography particles. A face-seal rotary valve provided a means for switching between sample loading and separation configurations with minimum dead and delay volumes while allowing high-pressure operation. The LC chip and valve assembly were mounted within a custom electrospray source on an ion-trap mass spectrometer. The overall system performance was demonstrated through reversed-phase gradient separations of tryptic protein digests at flow rates between 100 and 400 nL/min. Microfluidic integration of the nano-LC components enabled separations with subfemtomole detection sensitivity, minimal carryover, and robust and stable electrospray throughout the LC solvent gradient.

Beer fermentation: monitoring of process parameters by FT-NIR and multivariate data analysis.

PubMed

Grassi, Silvia; Amigo, José Manuel; Lyndgaard, Christian Bøge; Foschino, Roberto; Casiraghi, Ernestina

2014-07-15

This work investigates the capability of Fourier-Transform near infrared (FT-NIR) spectroscopy to monitor and assess process parameters in beer fermentation at different operative conditions. For this purpose, the fermentation of wort with two different yeast strains and at different temperatures was monitored for nine days by FT-NIR. To correlate the collected spectra with °Brix, pH and biomass, different multivariate data methodologies were applied. Principal component analysis (PCA), partial least squares (PLS) and locally weighted regression (LWR) were used to assess the relationship between FT-NIR spectra and the abovementioned process parameters that define the beer fermentation. The accuracy and robustness of the obtained results clearly show the suitability of FT-NIR spectroscopy, combined with multivariate data analysis, to be used as a quality control tool in the beer fermentation process. FT-NIR spectroscopy, when combined with LWR, demonstrates to be a perfectly suitable quantitative method to be implemented in the production of beer. Copyright © 2014 Elsevier Ltd. All rights reserved.

Structure formation in f(T) gravity and a solution for H0 tension

NASA Astrophysics Data System (ADS)

Nunes, Rafael C.

2018-05-01

We investigate the evolution of scalar perturbations in f(T) teleparallel gravity and its effects on the cosmic microwave background (CMB) anisotropy. The f(T) gravity generalizes the teleparallel gravity which is formulated on the Weitzenböck spacetime, characterized by the vanishing curvature tensor (absolute parallelism) and the non-vanishing torsion tensor. For the first time, we derive the observational constraints on the modified teleparallel gravity using the CMB temperature power spectrum from Planck's estimation, in addition to data from baryonic acoustic oscillations (BAO) and local Hubble constant measurements. We find that a small deviation of the f(T) gravity model from the ΛCDM cosmology is slightly favored. Besides that, the f(T) gravity model does not show tension on the Hubble constant that prevails in the ΛCDM cosmology. It is clear that f(T) gravity is also consistent with the CMB observations, and undoubtedly it can serve as a viable candidate amongst other modified gravity theories.

Application of Fourier transform infrared (FT-IR) spectroscopy in determination of microalgal compositions.

PubMed

Meng, Yingying; Yao, Changhong; Xue, Song; Yang, Haibo

2014-01-01

Fourier transform infrared spectroscopy (FT-IR) was applied in algal strain screening and monitoring cell composition dynamics in a marine microalga Isochrysis zhangjiangensis during algal cultivation. The content of lipid, carbohydrate and protein of samples determined by traditional methods had validated the accuracy of FT-IR method. For algal screening, the band absorption ratios of lipid/amide I and carbo/amide I from FT-IR measurements allowed for the selection of Isochrysis sp. and Tetraselmis subcordiformis as the most potential lipid and carbohydrate producers, respectively. The cell composition dynamics of I. zhangjiangensis measured by FT-IR revealed the diversion of carbon allocation from protein to carbohydrate and neutral lipid when nitrogen-replete cells were subjected to nitrogen limitation. The carbo/amide I band absorption ratio had also been demonstrated to depict physiological status under nutrient stress in T. subcordiformis. FT-IR serves as a tool for the simultaneous measurement of lipid, carbohydrate, and protein content in cell. Copyright © 2013 Elsevier Ltd. All rights reserved.

Advanced sampling techniques for hand-held FT-IR instrumentation

NASA Astrophysics Data System (ADS)

Arnó, Josep; Frunzi, Michael; Weber, Chris; Levy, Dustin

2013-05-01

FT-IR spectroscopy is the technology of choice to identify solid and liquid phase unknown samples. The challenging ConOps in emergency response and military field applications require a significant redesign of the stationary FT-IR bench-top instruments typically used in laboratories. Specifically, field portable units require high levels of resistance against mechanical shock and chemical attack, ease of use in restrictive gear, extreme reliability, quick and easy interpretation of results, and reduced size. In the last 20 years, FT-IR instruments have been re-engineered to fit in small suitcases for field portable use and recently further miniaturized for handheld operation. This article introduces the HazMatID™ Elite, a FT-IR instrument designed to balance the portability advantages of a handheld device with the performance challenges associated with miniaturization. In this paper, special focus will be given to the HazMatID Elite's sampling interfaces optimized to collect and interrogate different types of samples: accumulated material using the on-board ATR press, dispersed powders using the ClearSampler™ tool, and the touch-to-sample sensor for direct liquid sampling. The application of the novel sample swipe accessory (ClearSampler) to collect material from surfaces will be discussed in some detail. The accessory was tested and evaluated for the detection of explosive residues before and after detonation. Experimental results derived from these investigations will be described in an effort to outline the advantages of this technology over existing sampling methods.

FT-IR spectroscopy characterization of schwannoma: a case study

NASA Astrophysics Data System (ADS)

Ferreira, Isabelle; Neto, Lazaro P. M.; das Chagas, Maurilio José; Carvalho, Luís. Felipe C. S.; dos Santos, Laurita; Ribas, Marcelo; Loddi, Vinicius; Martin, Airton A.

2016-03-01

Schwannoma are rare benign neural neoplasia. The clinical diagnosis could be improved if novel optical techniques are performed. Among these techniques, FT-IR is one of the currently techniques which has been applied for samples discrimination using biochemical information with minimum sample preparation. In this work, we report a case of a schwannoma in the cervical region. A histological examination described a benign process. An immunohistochemically examination demonstrated positivity to anti-S100 protein antibody, indicating a diagnosis of schwannoma. The aim of this analysis was to characterize FT-IR spectrum of the neoplastic and normal tissue in the fingerprint (1000-1800 cm-1) and high wavenumber region (2800-3600 cm-1). The IR spectra were collect from tumor tissue and normal nerve samples by a FT-IR spectrophotometer (Spotlight Perkin Elmer 400, USA) with 64 scans, and resolution of 4 cm-1. A total of twenty spectra were recorded (10 from schwannoma and 10 from nerve). Multivariate Analysis was used to classify the data. Through average and standard deviation analysis we observed that the main spectral change occurs at ≍1600 cm-1 (amide I) and ≍1400 cm-1 (amide III) in the fingerprint region, and in CH2/CH3 protein-lipids and OH-water vibrations for the high wavenumber region. In conclusion, FT-IR could be used as a technique for schwannoma analysis helping to establish specific diagnostic.

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.

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

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.

Experimental demonstration of the possible role of Acanthamoeba polyphaga in the infection and disease progression in Buruli Ulcer (BU) using ICR mice

PubMed Central

Azumah, Bright K.; Addo, Phyllis G.; Dodoo, Alfred; Awandare, Gordon; Mosi, Lydia; Boakye, Daniel A.

2017-01-01

The transmission of Buruli ulcer (BU), caused by Mycobacterium ulcerans (MU), remains puzzling although a number of hypothesis including through bites of infected aquatic insects have been proposed. We report the results of experiments using ICR mice that give credence to our hypothesis that Acanthamoeba species may play a role in BU transmission. We cocultured MU N2 and MU 1615 which expresses red fluorescent protein (RFP) and Acanthamoeba polyphaga (AP), and confirmed infected AP by Ziehl-Neelsen (ZN) staining. We tested for viability of MU inside AP and observed strong RFP signals inside both trophozoites and cysts after 3 and 42 days of coculturing respectively. ICR mice were topically treated, either on shaved intact or shaved pinpricked rumps, with one of the following; MU N2 only (2.25 x 106 colony forming units [CFU] / ml), MU N2:AP coculture (2.96 x 104 CFU: 1.6 x 106 cells/ml), AP only (1.6 x 106 cells/ml), PYG medium and sterile distilled water. Both MU N2 only and MU N2:AP elicited reddening on day (D) 31; edema on D 45 and D 44 respectively, and ulcers on D 49 at pinpricked sites only. To ascertain infectivity and pathogenicity of MU N2 only and MU N2:AP, and compare their virulence, the standard mouse footpad inoculation method was used. MU N2:AP elicited reddening in footpads by D 3 compared to D 14 with MU N2 only of the same dose of MU N2 (2.96 x 104 CFU). ZN-stained MU were observed in both thin sectioned and homogenized lesions, and aspirates from infected sites. Viable MU N2 were recovered from cultures of the homogenates and aspirates. This study demonstrates in ICR mice MU transmission via passive infection, and shows that punctures in the skin are prerequisite for infection, and that coculturing of MU with AP enhances pathogenesis. PMID:28329001

Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations.

PubMed

Karthikeyan, N; Prince, J Joseph; Ramalingam, S; Periandy, S

2015-03-15

In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The (13)C and (1)H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

The Histone Acetyltransferase Gcn5 Regulates ncRNA-ICR1 and FLO11 Expression during Pseudohyphal Development in Saccharomyces cerevisiae

PubMed Central

Wang, Long-Chi; Montalvo-Munoz, Fernando; Tsai, Yuan-Chan; Liang, Chung-Yi; Chang, Chun-Chuan; Lo, Wan-Sheng

2015-01-01

Filamentous growth is one of the key features of pathogenic fungi during the early infectious phase. The pseudohyphal development of yeast Saccharomyces cerevisiae shares similar characteristics with hyphae elongation in pathogenic fungi. The expression of FLO11 is essential for adhesive growth and filament formation in yeast and is governed by a multilayered transcriptional network. Here we discovered a role for the histone acetyltransferase general control nonderepressible 5 (Gcn5) in regulating FLO11-mediated pseudohyphal growth. The expression patterns of FLO11 were distinct in haploid and diploid yeast under amino acid starvation induced by 3-amino-1,2,4-triazole (3AT). In diploids, FLO11 expression was substantially induced at a very early stage of pseudohyphal development and decreased quickly, but in haploids, it was gradually induced. Furthermore, the transcription factor Gcn4 was recruited to the Sfl1-Flo8 toggle sites at the FLO11 promoter under 3AT treatment. Moreover, the histone acetylase activity of Gcn5 was required for FLO11 induction. Finally, Gcn5 functioned as a negative regulator of the noncoding RNA ICR1, which is known to suppress FLO11 expression. Gcn5 plays an important role in the regulatory network of FLO11 expression via Gcn4 by downregulating ICR1 expression, which derepresses FLO11 for promoting pseudohyphal development. PMID:25922832

Transcript Profile of Flowering Regulatory Genes in VcFT-Overexpressing Blueberry Plants.

PubMed

Walworth, Aaron E; Chai, Benli; Song, Guo-Qing

2016-01-01

In order to identify genetic components in flowering pathways of highbush blueberry (Vaccinium corymbosum L.), a transcriptome reference composed of 254,396 transcripts and 179,853 gene contigs was developed by assembly of 72.7 million reads using Trinity. Using this transcriptome reference and a query of flowering pathway genes of herbaceous plants, we identified potential flowering pathway genes/transcripts of blueberry. Transcriptome analysis of flowering pathway genes was then conducted on leaf tissue samples of transgenic blueberry cv. Aurora ('VcFT-Aurora'), which overexpresses a blueberry FLOWERING LOCUS T-like gene (VcFT). Sixty-one blueberry transcripts of 40 genes showed high similarities to 33 known flowering-related genes of herbaceous plants, of which 17 down-regulated and 16 up-regulated genes were identified in 'VcFT-Aurora'. All down-regulated genes encoded transcription factors/enzymes upstream in the signaling pathway containing VcFT. A blueberry CONSTANS-LIKE 5-like (VcCOL5) gene was down-regulated and associated with five other differentially expressed (DE) genes in the photoperiod-mediated flowering pathway. Three down-regulated genes, i.e., a MADS-AFFECTING FLOWERING 2-like gene (VcMAF2), a MADS-AFFECTING FLOWERING 5-like gene (VcMAF5), and a VERNALIZATION1-like gene (VcVRN1), may function as integrators in place of FLOWERING LOCUS C (FLC) in the vernalization pathway. Because no CONSTAN1-like or FLOWERING LOCUS C-like genes were found in blueberry, VcCOL5 and VcMAF2/VcMAF5 or VRN1 might be the major integrator(s) in the photoperiod- and vernalization-mediated flowering pathway, respectively. The major down-stream genes of VcFT, i.e., SUPPRESSOR of Overexpression of Constans 1-like (VcSOC1), LEAFY-like (VcLFY), APETALA1-like (VcAP1), CAULIFLOWER 1-like (VcCAL1), and FRUITFULL-like (VcFUL) genes were present and showed high similarity to their orthologues in herbaceous plants. Moreover, overexpression of VcFT promoted expression of all of these

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

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

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.

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

GmFT2a, a soybean homolog of FLOWERING LOCUS T, is involved in flowering transition and maintenance.

PubMed

Sun, Hongbo; Jia, Zhen; Cao, Dong; Jiang, Bingjun; Wu, Cunxiang; Hou, Wensheng; Liu, Yike; Fei, Zhihong; Zhao, Dazhong; Han, Tianfu

2011-01-01

Flowering reversion can be induced in soybean (Glycine max L. Merr.), a typical short-day (SD) dicot, by switching from SD to long-day (LD) photoperiods. This process may involve florigen, putatively encoded by FLOWERING LOCUS T (FT) in Arabidopsis thaliana. However, little is known about the potential function of soybean FT homologs in flowering reversion. A photoperiod-responsive FT homologue GmFT (renamed as GmFT2a hereafter) was cloned from the photoperiod-sensitive cultivar Zigongdongdou. GmFT2a gene expression under different photoperiods was analyzed by real-time quantitative PCR. In situ hybridization showed direct evidence for its expression during flowering-related processes. GmFT2a was shown to promote flowering using transgenic studies in Arabidopsis and soybean. The effects of photoperiod and temperature on GmFT2a expression were also analyzed in two cultivars with different photoperiod-sensitivities. GmFT2a expression is regulated by photoperiod. Analyses of GmFT2a transcripts revealed a strong correlation between GmFT2a expression and flowering maintenance. GmFT2a transcripts were observed continuously within the vascular tissue up to the shoot apex during flowering. By contrast, transcripts decreased to undetectable levels during flowering reversion. In grafting experiments, the early-flowering, photoperiod-insensitive stock Heihe27 promotes the appearance of GmFT2a transcripts in the shoot apex of scion Zigongdongdou under noninductive LD conditions. The photothermal effects of GmFT2a expression diversity in cultivars with different photoperiod-sensitivities and a hypothesis is proposed. GmFT2a expression is associated with flowering induction and maintenance. Therefore, GmFT2a is a potential target gene for soybean breeding, with the aim of increasing geographic adaptation of this crop.

Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

2008-09-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

Acid-base properties, FT-IR, FT-Raman spectroscopy and computational study of 1-(pyrid-4-yl)piperazine.

PubMed

Mary, Y Sheena; Panicker, C Yohannan; Varghese, Hema Tresa; Van Alsenoy, Christian; Procházková, Markéta; Sevčík, Richard; Pazdera, Pavel

2014-01-01

We report the vibrational spectral analysis was carried out using FT-IR and FT-Raman spectroscopy for 1-(pyrid-4-yl)piperazine (PyPi). Single crystals of PyPi suitable for X-ray structural analysis were obtained. The acid-base properties are also reported. PyPi supported on a weak acid cation-exchanger in the single protonated form and this system can be used efficiently as the solid supported analogue of 4-N,N-dimethyl-aminopyridine. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule and with the molecular electrostatic potential map was applied for the reactivity assessment of PyPi molecule toward proton, electrophiles and nucleopholes as well. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated first hyperpolarizability of PyPi is 17.46 times that of urea. Copyright © 2013 Elsevier B.V. All rights reserved.

Spectroscopic characteristic (FT-IR, FT-Raman, UV, 1H and 13C NMR), theoretical calculations and biological activity of alkali metal homovanillates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Kowczyk-Sadowy, M.; Piekut, J.; Regulska, E.; Lewandowski, W.

2016-04-01

The structural and vibrational properties of lithium, sodium, potassium, rubidium and cesium homovanillates were investigated in this paper. Supplementary molecular spectroscopic methods such as: FT-IR, FT-Raman in the solid phase, UV and NMR were applied. The geometrical parameters and energies were obtained from density functional theory (DFT) B3LYP method with 6-311++G** basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned. Geometric and magnetic aromaticity indices, atomic charges, dipole moments, HOMO and LUMO energies were also calculated. The microbial activity of investigated compounds was tested against Bacillus subtilis (BS), Pseudomonas aeruginosa (PA), Escherichia coli (EC), Staphylococcus aureus (SA) and Candida albicans (CA). The relationship between the molecular structure of tested compounds and their antimicrobial activity was studied. The principal component analysis (PCA) was applied in order to attempt to distinguish the biological activities of these compounds according to selected band wavenumbers. Obtained data show that the FT-IR spectra can be a rapid and reliable analytical tool and a good source of information for the quantitative analysis of the relationship between the molecular structure of the compound and its biological activity.

Agrobacterium-mediated transient MaFT expression in mulberry (Morus alba L.) leaves.

PubMed

Wu, Su-Li; Yang, Xiao-Bing; Liu, Li-Qun; Jiang, Tao; Wu, Hai; Su, Chao; Qian, Yong-Hua; Jiao, Feng

2015-01-01

To optimize Agrobacterium-mediated transient transformation assay in mulberry (Morus alba L.), various infiltration methods, Agrobacterium tumefaciens (A. tumefaciens) strains, and bacterial concentrations were tested in mulberry seedlings. Compared with LBA4404, GV3101 harboring pBE2133 plasmids presented stronger GUS signals at 3 days post infiltration using syringe. Recombinant plasmids pBE2133:GFP and pBE2133:GFP:MaFT were successfully constructed. Transient expression of MaFT:GFP protein was found in leaves, petiole (cross section), and shoot apical meristem (SAM) of mulberry according to the GFP signal. Moreover, MaFT:GFP mRNA was also detected in leaves and SAM via RT-PCR and qRT-PCR. An efficient transient transformation system could be achieved in mulberry seedlings by syringe using A. tumefaciens GV3101 at the OD600 of 0.5. The movement of MaFT expression from leaves to SAM might trigger the precocious flowering of mulberry.

Characterization of self assembly layers of octadecanephosphonic acid by polarisation modulation FT-IRRA spectroscopy mapping

NASA Astrophysics Data System (ADS)

Steiner, G.; Sablinskas, V.; Savchuk, O.; Bariseviciute, R.; Jähne, E.; Adler, H. J.; Salzer, R.

2003-12-01

Self assembly layers were studied by a polarization modulation FT-spectroscopy mapping technique. The optical lay out is based on polarization modulation FT infrared reflection absorption spectroscopy (PM-FT-IRRAS). Here we report for the first time on a PM-FT-IRRAS mapping instrument. Octadecanephosphonic acid adsorbed on a patterned aluminum/gold surface was investigated. The nature of chemical bonding at particular surface areas was evaluated by principal component analysis. The most prominent features of the PM-FT-IRRA spectra are the P-O and PO stretching vibrations. It is shown that octadecanephosphonic acid is adsorbed both on Al 2O 3 and on Au. Moreover, PM-FT-IRRAS maps reveal areas of non-equivalent structural features. Lateral dimensions of these areas are in the micrometer range. Such non-equivalencies may control the inhibition potential of SAMs on ignoble metals, hence become crucial to the quality of products as biosensors or microelectronic components.

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.

Molecular structure and vibrational analysis of Trifluoperazine by FT-IR, FT-Raman and UV-Vis spectroscopies combined with DFT calculations.

PubMed

Rajesh, P; Gunasekaran, S; Gnanasambandan, T; Seshadri, S

2015-02-25

The complete vibrational assignment and analysis of the fundamental vibrational modes of Trifluoperazine (TFZ) was carried out using the experimental FT-IR, FT-Raman and UV-Vis data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the DFT-B3LYP gradient calculations employing 6-31G (d,p) basis set. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. The HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear properties such as first hyperpolarizability of TFZ have been computed using B3LYP quantum chemical calculation. Copyright © 2014 Elsevier B.V. All rights reserved.

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

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

Direct and rapid determination of cotton maturity by FT-Mid-IR technique

USDA-ARS?s Scientific Manuscript database

FT-mid-IR (FT-MIR) spectra of seed and lint cottons were collected to explore the potential for the discrimination of immature cottons from mature ones and also for the determination of actual cotton maturity. Spectral features of immature and mature cottons revealed large differences in the 1200-90...

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.

A new strategy for faster urinary biomarkers identification by Nano-LC-MALDI-TOF/TOF mass spectrometry

PubMed Central

Benkali, K; Marquet, P; Rérolle, JP; Le Meur, Y; Gastinel, LN

2008-01-01

Background LC-MALDI-TOF/TOF analysis is a potent tool in biomarkers discovery characterized by its high sensitivity and high throughput capacity. However, methods based on MALDI-TOF/TOF for biomarkers discovery still need optimization, in particular to reduce analysis time and to evaluate their reproducibility for peak intensities measurement. The aims of this methodological study were: (i) to optimize and critically evaluate each step of urine biomarker discovery method based on Nano-LC coupled off-line to MALDI-TOF/TOF, taking full advantage of the dual decoupling between Nano-LC, MS and MS/MS to reduce the overall analysis time; (ii) to evaluate the quantitative performance and reproducibility of nano-LC-MALDI analysis in biomarker discovery; and (iii) to evaluate the robustness of biomarkers selection. Results A pool of urine sample spiked at increasing concentrations with a mixture of standard peptides was used as a specimen for biological samples with or without biomarkers. Extraction and nano-LC-MS variabilities were estimated by analyzing in triplicates and hexaplicates, respectively. The stability of chromatographic fractions immobilised with MALDI matrix on MALDI plates was evaluated by successive MS acquisitions after different storage times at different temperatures. Low coefficient of variation (CV%: 10–22%) and high correlation (R2 > 0.96) values were obtained for the quantification of the spiked peptides, allowing quantification of these peptides in the low fentomole range, correct group discrimination and selection of "specific" markers using principal component analysis. Excellent peptide integrity and stable signal intensity were found when MALDI plates were stored for periods of up to 2 months at +4°C. This allowed storage of MALDI plates between LC separation and MS acquisition (first decoupling), and between MS and MSMS acquisitions while the selection of inter-group discriminative ions is done (second decoupling). Finally the recording of

Ft. Mojave Smoke Shop Minor NSR Permit Application

EPA Pesticide Factsheets

Tribal Minor New Source Review (NSR) Permit application submitted by Environmental Technology Inc. for soil & groundwater remediation at the Ft. Mojave Smoke Shop, 8501 S. Highway 95 Mojave Valley, AZ 86440.

FT 3 Flight Test Cards for Export

NASA Technical Reports Server (NTRS)

Marston, Michael L.

2015-01-01

These flight test cards will be made available to stakeholders who participated in FT3. NASA entered into the relationship with our stakeholders, including the FAA, to develop requirements that will lead to routine flights of unmanned aircraft systems flying in the national airspace system.

Organic acid component from Taraxacum mongolicum Hand.-Mazz alleviates inflammatory injury in lipopolysaccharide-induced acute tracheobronchitis of ICR mice through TLR4/NF-κB signaling pathway.

PubMed

Yang, Nan; Li, Chao; Tian, Gang; Zhu, Maomao; Bu, Weiquan; Chen, Juan; Hou, Xuefeng; Di, Liuqing; Jia, Xiaobin; Dong, Zibo; Feng, Liang

2016-05-01

Inflammation plays an important role in the pathogenesis of acute tracheobronchitis. Taraxacum mongolicum Hand.-Mazz (TMHM) is a dietic herb for heat-clearing and detoxifying functions as well as swell-reducing and mass-resolving effect in Traditional Chinese Medicine. Studies have shown that its major ingredient organic acid component (OAC) possesses favorable anti-inflammatory activity. However, the protective effect of OAC from TMHM (TMHM-OAC) on inflammatory injury of acute tracheobronchitis and its possible mechanism remains poorly understood. In this study, HPLC-DAD was used to analyze the components of TMHM-OAC. Lipopolysaccharide of 1mg/ml was used to induce respiratory inflammation in ICR mice at the dose of 5mg/kg by intratracheally aerosol administration. Enzyme-linked immunosorbent assay (ELISA) was employed to detect the levels of inflammation factors such as interleukin-6 (IL-6), tumor necrosis factor-α (TNF-α), and nitric oxide in serum and supernatant of trachea tissue. Western blotting (WB) and Immunohistochemistry analysis (IHC) were conducted in parallel to determine TNF-α, IL-6, inducible nitric oxide synthase (iNOS), Toll-like receptors 4(TLR4) protein expressions and nuclear factor-kappa B p65 (NF-κB p65) phosphorylation. Hematoxylin-Eosin staining (HE) was applied to evaluate pathological lesions of trachea tissue. Experimental results showed that TMHM-OAC significantly reduced the levels of the TNF-α, IL-6 and NO in serum and supernatant of tracheal of LPS-induced ICR mice. The protein expression levels of TNF-α, IL-6 and iNOS in tracheal tissue were also down-regulated significantly by the treatment of TMHM-OAC. Moreover, TMHM-OAC downregulated phosphorylation of NF-κB p65 and protein expression of TLR4. Our results indicated that TMHM-OAC could improve LPS-induced histopathological damage of tracheal tissues through the regulation of TLR4/NF-κB signaling pathway and could be beneficial for the treatment of acute tracheobronchitis

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.

SWiFT site atmospheric characterization

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

Kelley, Christopher Lee; Ennis, Brandon Lee

2016-01-01

Historical meteorological tall tower data are analyzed from the Texas Tech University 200 m tower to characterize the atmospheric trends of the Scaled Wind Farm Technologies (SWiFT) site. In this report the data are analyzed to reveal bulk atmospheric trends, temporal trends and correlations of atmospheric variables. Through this analysis for the SWiFT turbines the site International Electrotechnical Commission (IEC) classification is determined to be class III-C. Averages and distributions of atmospheric variables are shown, revealing large fluctuations and the importance of understanding the actual site trends as opposed to simply using averages. The site is significantly directional with themore » average wind speed from the south, and particularly so in summer and fall. Site temporal trends are analyzed from both seasonal (time of the year) to daily (hour of the day) perspectives. Atmospheric stability is seen to vary most with time of day and less with time of year. Turbulence intensity is highly correlated with stability, and typical daytime unstable conditions see double the level of turbulence intensity versus that experienced during the average stable night. Shear, veer and atmospheric stability correlations are shown, where shear and veer are both highest for stable atmospheric conditions. An analysis of the Texas Tech University tower anemometer measurements is performed which reveals the extent of the tower shadow effects and sonic tilt misalignment.« less

FT-IR SOLUTION SPECTRA OF PROPYL SULFIDE, PROPYL SULFOXIDE, AND PROPYL SULFONE

EPA Science Inventory

FT-IR spectra were obtained of 0.5% volumetric solutions of propyl sulfide, propyl sulfoxide, and propyl sulfone in hexane, CCl4, CS2, and CHCl3 to assist in the assignment of FT-IR-PAS spectra of propyl sulfoxide sorbed within the structure of several peats and onto cellulose. T...

Ft1, a novel gene related to ubiquitin-conjugating enzymes, is deleted in the Fused toes mouse mutation.

PubMed

Lesche, R; Peetz, A; van der Hoeven, F; Rüther, U

1997-12-01

The dominant mouse mutation Fused toes is characterized by partial syndactyly of the limbs and thymic hyperplasia. Both morphological abnormalities were shown to be related to impaired regulation of programmed cell death. Ft/Ft embryos die in midgestation showing severe malformations of fore- and midbrain as well as randomized situs. In Ft mice a large chromosomal deletion (about 300 kb) occurred after insertional mutagenesis. In this report we describe the identification of the first gene that has been mutated by Fused toes. The expression of the novel gene Ft1 is reduced in Ft/+ mice and completely absent in Ft/Ft embryos. Analysis of the Ft1 cDNA revealed an open reading frame that could code for a 32-kDa protein with similarities to ubiquitin-conjugating enzymes. Ft1 transcripts with alternative 5' UTR sequences as well as differential usage of polyadenylation sites were found. Interestingly, the 3' parts of the longest Ft1 transcripts are identical to the reverse complement of the 3'-most sequences of the Rb-related p130 gene. Both genes are transcribed in opposite directions and overlap in their 3' UTRs. Despite the close linkage, p130 expression appeared not to be affected by the Ft mutation. In wild type mice, Ft1 expression levels were found to be high in brain, kidney, and testes and detectable in all other adult organs and throughout embryonic development. Finally, we show that Ft1 is conserved among mammals and identify the human homolog.

Overexpression of Arabidopsis FLOWERING LOCUS T (FT) gene improves floral development in cassava (Manihot esculenta, Crantz).

PubMed

Adeyemo, O Sarah; Chavarriaga, Paul; Tohme, Joe; Fregene, Martin; Davis, Seth J; Setter, Tim L

2017-01-01

Cassava is a tropical storage-root crop that serves as a worldwide source of staple food for over 800 million people. Flowering is one of the most important breeding challenges in cassava because in most lines flowering is late and non-synchronized, and flower production is sparse. The FLOWERING LOCUS T (FT) gene is pivotal for floral induction in all examined angiosperms. The objective of the current work was to determine the potential roles of the FT signaling system in cassava. The Arabidopsis thaliana FT gene (atFT) was transformed into the cassava cultivar 60444 through Agrobacterium-mediated transformation and was found to be overexpressed constitutively. FT overexpression hastened flower initiation and associated fork-type branching, indicating that cassava has the necessary signaling factors to interact with and respond to the atFT gene product. In addition, overexpression stimulated lateral branching, increased the prolificacy of flower production and extended the longevity of flower development. While FT homologs in some plant species stimulate development of vegetative storage organs, atFT inhibited storage-root development and decreased root harvest index in cassava. These findings collectively contribute to our understanding of flower development in cassava and have the potential for applications in breeding.

Overexpression of Arabidopsis FLOWERING LOCUS T (FT) gene improves floral development in cassava (Manihot esculenta, Crantz)

PubMed Central

Adeyemo, O. Sarah; Chavarriaga, Paul; Tohme, Joe; Fregene, Martin; Davis, Seth J.

2017-01-01

Cassava is a tropical storage-root crop that serves as a worldwide source of staple food for over 800 million people. Flowering is one of the most important breeding challenges in cassava because in most lines flowering is late and non-synchronized, and flower production is sparse. The FLOWERING LOCUS T (FT) gene is pivotal for floral induction in all examined angiosperms. The objective of the current work was to determine the potential roles of the FT signaling system in cassava. The Arabidopsis thaliana FT gene (atFT) was transformed into the cassava cultivar 60444 through Agrobacterium-mediated transformation and was found to be overexpressed constitutively. FT overexpression hastened flower initiation and associated fork-type branching, indicating that cassava has the necessary signaling factors to interact with and respond to the atFT gene product. In addition, overexpression stimulated lateral branching, increased the prolificacy of flower production and extended the longevity of flower development. While FT homologs in some plant species stimulate development of vegetative storage organs, atFT inhibited storage-root development and decreased root harvest index in cassava. These findings collectively contribute to our understanding of flower development in cassava and have the potential for applications in breeding. PMID:28753668

Thermodynamics and cosmological reconstruction in f(T , B) gravity

NASA Astrophysics Data System (ADS)

Bahamonde, Sebastian; Zubair, M.; Abbas, G.

2018-03-01

Recently, it was formulated a teleparallel theory called f(T , B) gravity which connects both f(T) and f(R) under suitable limits. In this theory, the function in the action is assumed to depend on the torsion scalar T and also on a boundary term related with the divergence of torsion, B = 2∇μTμ. In this work, we study different features of a flat Friedmann-Lemaître-Robertson-Walker (FLRW) cosmology in this theory. First, we show that the FLRW equations can be transformed to the form of Clausius relation TˆhSeff = - dE + WdV, where Tˆh is the horizon temperature and Seff is the entropy which contains contributions both from horizon entropy and an additional entropy term introduced due to the non-equilibrium. We also formulate the constraint for the validity of the generalised second law of thermodynamics (GSLT). Additionally, using a cosmological reconstruction technique, we show that both f(T , B) and - T + F(B) gravity can mimic power-law, de-Sitter and ΛCDM models. Finally, we formulate the perturbed evolution equations and analyse the stability of some important cosmological solutions.

Electron paramagnetic resonance and FT-IR spectroscopic studies of glycine anhydride and betaine hydrochloride

NASA Astrophysics Data System (ADS)

Halim Başkan, M.; Kartal, Zeki; Aydın, Murat

2015-12-01

Gamma irradiated powders of glycine anhydride and betaine hydrochloride have been investigated at room temperature by electron paramagnetic resonance (EPR). In these compounds, the observed paramagnetic species were attributed to the R1 and R2 radicals, respectively. It was determined that the free electron interacted with environmental protons and 14N nucleus in both radicals. The EPR spectra of gamma irradiated powder samples remained unchanged at room temperature for two weeks after irradiation. Also, the Fourier Transform Infrared (FT-IR), FT-Raman and thermal analyses of both compounds were investigated. The functional groups in the molecular structures of glycine anhydride and betaine hydrochloride were identified by vibrational spectroscopies (FT-IR and FT-Raman).

The ICR96 exon CNV validation series: a resource for orthogonal assessment of exon CNV calling in NGS data.

PubMed

Mahamdallie, Shazia; Ruark, Elise; Yost, Shawn; Ramsay, Emma; Uddin, Imran; Wylie, Harriett; Elliott, Anna; Strydom, Ann; Renwick, Anthony; Seal, Sheila; Rahman, Nazneen

2017-01-01

Detection of deletions and duplications of whole exons (exon CNVs) is a key requirement of genetic testing. Accurate detection of this variant type has proved very challenging in targeted next-generation sequencing (NGS) data, particularly if only a single exon is involved. Many different NGS exon CNV calling methods have been developed over the last five years. Such methods are usually evaluated using simulated and/or in-house data due to a lack of publicly-available datasets with orthogonally generated results. This hinders tool comparisons, transparency and reproducibility. To provide a community resource for assessment of exon CNV calling methods in targeted NGS data, we here present the ICR96 exon CNV validation series. The dataset includes high-quality sequencing data from a targeted NGS assay (the TruSight Cancer Panel) together with Multiplex Ligation-dependent Probe Amplification (MLPA) results for 96 independent samples. 66 samples contain at least one validated exon CNV and 30 samples have validated negative results for exon CNVs in 26 genes. The dataset includes 46 exon CNVs in BRCA1 , BRCA2 , TP53 , MLH1 , MSH2 , MSH6 , PMS2 , EPCAM or PTEN , giving excellent representation of the cancer predisposition genes most frequently tested in clinical practice. Moreover, the validated exon CNVs include 25 single exon CNVs, the most difficult type of exon CNV to detect. The FASTQ files for the ICR96 exon CNV validation series can be accessed through the European-Genome phenome Archive (EGA) under the accession number EGAS00001002428.

Differentiation of aflatoxigenic and non-aflatoxigenic strains of Aspergilli by FT-IR spectroscopy.

PubMed

Atkinson, Curtis; Pechanova, Olga; Sparks, Darrell L; Brown, Ashli; Rodriguez, Jose M

2014-01-01

Fourier transform infrared spectroscopy (FT-IR) is a well-established and widely accepted methodology to identify and differentiate diverse microbial species. In this study, FT-IR was used to differentiate 20 strains of ubiquitous and agronomically important phytopathogens of Aspergillus flavus and Aspergillus parasiticus. By analyzing their spectral profiles via principal component and cluster analysis, differentiation was achieved between the aflatoxin-producing and nonproducing strains of both fungal species. This study thus indicates that FT-IR coupled to multivariate statistics can rapidly differentiate strains of Aspergilli based on their toxigenicity.

Do TSH, FT3, and FT4 Impact BAT Visualization of Clinical FDG-PET/CT Images?

PubMed

Nishii, Ryuichi; Nagamachi, Shigeki; Mizutani, Youichi; Terada, Tamasa; Kiyohara, Syogo; Wakamatsu, Hideyuki; Fujita, Seigo; Higashi, Tatsuya; Yoshinaga, Keiichiro; Saga, Tsuneo; Hirai, Toshinori

2018-01-01

We retrospectively analyzed activated BAT visualization on FDG-PET/CT in patients with various conditions and TH levels to clarify the relationships between visualization of BAT on FDG-PET/CT and the effect of TH. Patients who underwent clinical FDG-PET/CT were reviewed and we categorized patients into 5 groups: (i) thyroid hormone withdrawal (THW) group; (ii) recombinant human thyrotropin (rhTSH) group; (iii) hypothyroidism group; (iv) hyperthyroidism group; and (v) BAT group. A total of sixty-two FDG-PET/CT imaging studies in fifty-nine patients were performed. To compare each group, gender; age; body weight; serum TSH, FT3, and FT4 levels; and outside temperature were evaluated. No significant visualization of BAT was noted in any of the images in the THW, rhTSH, hypothyroidism, and hyperthyroidism groups. All patients in the BAT group were in a euthyroid state. When the BAT-negative and BAT-positive patient groups were compared, it was noted that the minimum and maximum temperature on the day of the PET study and maximum temperature of the one day before the PET study were significantly lower in BAT-positive group than in all those of other groups. Elevated TSH condition before RIT, hyperthyroidism, or hypothyroidism did not significantly impact BAT visualization of clinical FDG-PET/CT images.

FTIR, FT-Raman, FT-NMR, UV-visible and quantum chemical investigations of 2-amino-4-methylbenzothiazole.

PubMed

Arjunan, V; Sakiladevi, S; Rani, T; Mythili, C V; Mohan, S

2012-03-01

The FT-IR (4000-400 cm(-1)) and FT-Raman (4000-100 cm(-1)) spectral measurements and complete assignments of the observed spectra of 2-amino-4-methylbenzothiazole (2A4MBT) have been proposed. Ab initio and DFT calculations have been performed and the structural parameters of the compound were determined from the optimised geometry with 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities and Raman activities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO, LUMO and band gap energies were measured by time-dependent DFT (TD-DFT) approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman activities chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. The influences of methyl and amino groups on the skeletal modes and on the proton chemical shifts have been investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Transcript Profile of Flowering Regulatory Genes in VcFT-Overexpressing Blueberry Plants

PubMed Central

Walworth, Aaron E.; Chai, Benli; Song, Guo-qing

2016-01-01

In order to identify genetic components in flowering pathways of highbush blueberry (Vaccinium corymbosum L.), a transcriptome reference composed of 254,396 transcripts and 179,853 gene contigs was developed by assembly of 72.7 million reads using Trinity. Using this transcriptome reference and a query of flowering pathway genes of herbaceous plants, we identified potential flowering pathway genes/transcripts of blueberry. Transcriptome analysis of flowering pathway genes was then conducted on leaf tissue samples of transgenic blueberry cv. Aurora (‘VcFT-Aurora’), which overexpresses a blueberry FLOWERING LOCUS T-like gene (VcFT). Sixty-one blueberry transcripts of 40 genes showed high similarities to 33 known flowering-related genes of herbaceous plants, of which 17 down-regulated and 16 up-regulated genes were identified in ‘VcFT-Aurora’. All down-regulated genes encoded transcription factors/enzymes upstream in the signaling pathway containing VcFT. A blueberry CONSTANS-LIKE 5-like (VcCOL5) gene was down-regulated and associated with five other differentially expressed (DE) genes in the photoperiod-mediated flowering pathway. Three down-regulated genes, i.e., a MADS-AFFECTING FLOWERING 2-like gene (VcMAF2), a MADS-AFFECTING FLOWERING 5-like gene (VcMAF5), and a VERNALIZATION1-like gene (VcVRN1), may function as integrators in place of FLOWERING LOCUS C (FLC) in the vernalization pathway. Because no CONSTAN1-like or FLOWERING LOCUS C-like genes were found in blueberry, VcCOL5 and VcMAF2/VcMAF5 or VRN1 might be the major integrator(s) in the photoperiod- and vernalization-mediated flowering pathway, respectively. The major down-stream genes of VcFT, i.e., SUPPRESSOR of Overexpression of Constans 1-like (VcSOC1), LEAFY-like (VcLFY), APETALA1-like (VcAP1), CAULIFLOWER 1-like (VcCAL1), and FRUITFULL-like (VcFUL) genes were present and showed high similarity to their orthologues in herbaceous plants. Moreover, overexpression of VcFT promoted expression of all

Mass Airflow Cabinet for Control of Airborne Infection of Laboratory Rodents

PubMed Central

McGarrity, Gerard J.; Coriell, Lewis L.

1973-01-01

A mass airflow cabinet for handling and housing of laboratory rodents has been developed and tested. The unit consists of a high-efficiency particulate air filter and uniform distribution of air at a vertical velocity of 19 cm per s. Animals are maintained without bedding in mesh-bottomed cages that rest on rollers for rotation inside the cabinet. There is an air barrier of 90 cm per s separating the cabinet air from room air. Sampling for airborne bacteria yielded an average of 0.03 colony-forming units (CFU) per ft3 of air inside the cabinet, whereas 28.8 CFU per ft3 was simultaneously detected outside the cabinet during housekeeping, a reduction of almost three logs. The efficiency of the air barrier was tested by aerosolization of T3 phage. When phage was aerosolized 5 cm outside the cabinet, no phage could be detected 5 cm inside when the fans were operating; with the fans off an average of 1.6 × 104 plaque-forming units (PFU) per ft3 was detected in six tests. Aerosolization of phage inside the cabinet yielded an average of 9 × 10 PFU per ft3 outside; an average of 4.1 × 106 PFU per ft3 were detected with the fans not in operation, a reduction of more than four logs. In-use studies on effectiveness showed that the cabinet significantly reduced the incidence of mice originally titer-free to Reo-3 virus. Hemagglutination inhibition antibodies to Reo-3 were detected in 9/22 (42%) mice housed in a conventionally ventilated animal laboratory while no seroconversion was detected in any of 22 mice housed in the mass air flow cabinet in the same laboratory. Images PMID:4355261

Mass airflow cabinet for control of airborne infection of laboratory rodents.

PubMed

McGarrity, G J; Coriell, L L

1973-08-01

A mass airflow cabinet for handling and housing of laboratory rodents has been developed and tested. The unit consists of a high-efficiency particulate air filter and uniform distribution of air at a vertical velocity of 19 cm per s. Animals are maintained without bedding in mesh-bottomed cages that rest on rollers for rotation inside the cabinet. There is an air barrier of 90 cm per s separating the cabinet air from room air. Sampling for airborne bacteria yielded an average of 0.03 colony-forming units (CFU) per ft(3) of air inside the cabinet, whereas 28.8 CFU per ft(3) was simultaneously detected outside the cabinet during housekeeping, a reduction of almost three logs. The efficiency of the air barrier was tested by aerosolization of T3 phage. When phage was aerosolized 5 cm outside the cabinet, no phage could be detected 5 cm inside when the fans were operating; with the fans off an average of 1.6 x 10(4) plaque-forming units (PFU) per ft(3) was detected in six tests. Aerosolization of phage inside the cabinet yielded an average of 9 x 10 PFU per ft(3) outside; an average of 4.1 x 10(6) PFU per ft(3) were detected with the fans not in operation, a reduction of more than four logs. In-use studies on effectiveness showed that the cabinet significantly reduced the incidence of mice originally titer-free to Reo-3 virus. Hemagglutination inhibition antibodies to Reo-3 were detected in 9/22 (42%) mice housed in a conventionally ventilated animal laboratory while no seroconversion was detected in any of 22 mice housed in the mass air flow cabinet in the same laboratory.

Inflorescence Development and the Role of LsFT in Regulating Bolting in Lettuce (Lactuca sativa L.).

PubMed

Chen, Zijing; Han, Yingyan; Ning, Kang; Ding, Yunyu; Zhao, Wensheng; Yan, Shuangshuang; Luo, Chen; Jiang, Xiaotang; Ge, Danfeng; Liu, Renyi; Wang, Qian; Zhang, Xiaolan

2017-01-01

Lettuce ( Lactuca sativa L.) is one of the most important leafy vegetable that is consumed during its vegetative growth. The transition from vegetative to reproductive growth is induced by high temperature, which has significant economic effect on lettuce production. However, the progression of floral transition and the molecular regulation of bolting are largely unknown. Here we morphologically characterized the inflorescence development and functionally analyzed the FLOWERING LOCUS T (LsFT) gene during bolting regulation in lettuce. We described the eight developmental stages during floral transition process. The expression of LsFT was negatively correlated with bolting in different lettuce varieties, and was promoted by heat treatment. Overexpression of LsFT could recover the late-flowering phenotype of ft-2 mutant. Knockdown of LsFT by RNA interference dramatically delayed bolting in lettuce, and failed to respond to high temperature. Therefore, this study dissects the process of inflorescence development and characterizes the role of LsFT in bolting regulation in lettuce.

Inflorescence Development and the Role of LsFT in Regulating Bolting in Lettuce (Lactuca sativa L.)

PubMed Central

Chen, Zijing; Han, Yingyan; Ning, Kang; Ding, Yunyu; Zhao, Wensheng; Yan, Shuangshuang; Luo, Chen; Jiang, Xiaotang; Ge, Danfeng; Liu, Renyi; Wang, Qian; Zhang, Xiaolan

2018-01-01

Lettuce (Lactuca sativa L.) is one of the most important leafy vegetable that is consumed during its vegetative growth. The transition from vegetative to reproductive growth is induced by high temperature, which has significant economic effect on lettuce production. However, the progression of floral transition and the molecular regulation of bolting are largely unknown. Here we morphologically characterized the inflorescence development and functionally analyzed the FLOWERING LOCUS T (LsFT) gene during bolting regulation in lettuce. We described the eight developmental stages during floral transition process. The expression of LsFT was negatively correlated with bolting in different lettuce varieties, and was promoted by heat treatment. Overexpression of LsFT could recover the late-flowering phenotype of ft-2 mutant. Knockdown of LsFT by RNA interference dramatically delayed bolting in lettuce, and failed to respond to high temperature. Therefore, this study dissects the process of inflorescence development and characterizes the role of LsFT in bolting regulation in lettuce. PMID:29403510

Zn(II), Cd(II) and Hg(I) complexes of cinnamic acid: FT-IR, FT-Raman, 1H and 13C NMR studies

NASA Astrophysics Data System (ADS)

Kalinowska, M.; Świsłocka, R.; Lewandowski, W.

2011-05-01

The effect of zinc, cadmium(II) and mercury(I) ions on the electronic structure of cinnamic acid (phenylacrylic acid) was studied. In this research many miscellaneous analytical methods, which complement one another, were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance ( 1H, 13C NMR) and quantum mechanical calculations. The spectroscopic studies provide some knowledge on the distribution of the electronic charge in molecule, the delocalization energy of π-electrons and the reactivity of metal complexes. In the series of Zn(II) → Cd(II) → Hg(I) cinnamates: (1) systematic shifts of several bands in the experimental and theoretical IR and Raman spectra and (2) regular chemical shifts for protons 1H and 13C nuclei were observed.

Spectroscopic investigation (FT-IR, FT-Raman), HOMO-LUMO, NBO, and molecular docking analysis of N-ethyl-N-nitrosourea, a potential anticancer agent

NASA Astrophysics Data System (ADS)

Singh, Priyanka; Islam, S. S.; Ahmad, Hilal; Prabaharan, A.

2018-02-01

Nitrosourea plays an important role in the treatment of cancer. N-ethyl-N-nitrosourea, also known as ENU, (chemical formula C3H7N3O2), is a highly potent mutagen. The chemical is an alkylating agent and acts by transferring the ethyl group of ENU to nucleobases (usually thymine) in nucleic acids. The molecular structure of N-ethyl-N-nitrosourea has been elucidated using experimental (FT-IR and FT-Raman) and theoretical (DFT) techniques. APT charges, Mulliken atomic charges, Natural bond orbital, Electrostatic potential, HOMO-LUMO and AIM analysis were performed to identify the reactive sites and charge transfer interactions. Furthermore, to evaluate the anticancer activity of ENU molecular docking studies were carried out against 2JIU protein.

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.

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

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.

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

Detection of Amine Impurity and Quality Assessment of the MALDI Matrix α-Cyano-4-Hydroxy-Cinnamic Acid for Peptide Analysis in the amol Range

NASA Astrophysics Data System (ADS)

Rechthaler, Justyna; Pittenauer, Ernst; Schaub, Tanner M.; Allmaier, Günter

2013-05-01

We have studied sample preparation conditions to increase the reproducibility of positive UV-MALDI-TOF mass spectrometry of peptides in the amol range. By evaluating several α-cyano-4-hydroxy-cinnamic acid (CHCA) matrix batches and preparation protocols, it became apparent that two factors have a large influence on the reproducibility and the quality of the generated peptide mass spectra: (1) the selection of the CHCA matrix, which allows the most sensitive measurements and an easier finding of the "sweet spots," and (2) the amount of the sample volume deposited onto the thin crystalline matrix layer. We have studied in detail the influence of a contaminant, coming from commercial CHCA matrix batches, on sensitivity of generated peptide mass spectra in the amol as well as fmol range of a tryptic peptide mixture. The structure of the contaminant, N, N-dimethylbutyl amine, was determined by applying MALDI-FT-ICR mass spectrometry experiments for elemental composition and MALDI high energy CID experiments utilizing a tandem mass spectrometer (TOF/RTOF). A recrystallization of heavily contaminated CHCA batches that reduces or eliminates the determined impurity is described. Furthermore, a fast and reliable method for the assessment of CHCA matrix batches prior to tryptic peptide MALDI mass spectrometric analyses is presented.

Hepatoprotective effects of litchi (Litchi chinensis) procyanidin A2 on carbon tetrachloride-induced liver injury in ICR mice

PubMed Central

Chen, Lih-Geeng; Chang, Cheng-Wei; Tsay, Jwu-Guh; Weng, Brian Bor-Chun

2017-01-01

Drug tolerance, lacking liver regenerative activity and inconclusive inhibition of steatosis and cirrhosis by silymarin treatment during chronic liver injury have increased the demand for novel alternative or synergistic treatments for liver damage. Litchi fruit is abundant in polyphenolic compounds and is used in traditional Chinese medicine for treatments that include the strengthening of hepatic and pancreatic functions. Unique polyphenolic compounds obtained from litchi pericarp extract (LPE) were studied in vitro and in vivo for hepatoprotection. Epicatechin (EC) and procyanidin A2 (PA2) of LPE were obtained by fractionated-extraction from pulverized litchi pericarps. All fractions, including LPE, were screened against silymarin in carbon tetrachloride (CCl4)-treated murine embryonic liver cell line (BNL). The effects of daily gavage-feeding of LPE, silymarin (200 mg/kg body weight) or H2O in CCl4-intoxicated male ICR mice were evaluated by studying serum chemicals, liver pathology and glutathione antioxidative enzymes. The effects of EC and PA2 on liver cell regenerative activity were investigated using a scratch wound healing assay and flow cytometric cell cycle analysis; the results of which demonstrated that LPE protected BNL from CCl4-intoxication. Gavage-feeding of LPE decreased serum glutamic oxaloacetate transaminase and glutamic pyruvic transaminase levels, and exhibited superior retention of the hexagonal structure of hepatocytes and reduced necrotic cells following liver histopathological examinations in CCl4-intoxicated ICR mice. Glutathione peroxidise and glutathione reductase activities were preserved as the normal control level in LPE groups. EC and PA2 were principle components of LPE. PA2 demonstrated liver cell regenerative activity in scratch wound healing assays and alcohol-induced liver cell injury in vitro. The present findings suggest that litchi pericarp polyphenolic extracts, including EC and PA2, may be a synergistic alternative to

Hepatoprotective effects of litchi (Litchi chinensis) procyanidin A2 on carbon tetrachloride-induced liver injury in ICR mice.

PubMed

Chen, Lih-Geeng; Chang, Cheng-Wei; Tsay, Jwu-Guh; Weng, Brian Bor-Chun

2017-06-01

Drug tolerance, lacking liver regenerative activity and inconclusive inhibition of steatosis and cirrhosis by silymarin treatment during chronic liver injury have increased the demand for novel alternative or synergistic treatments for liver damage. Litchi fruit is abundant in polyphenolic compounds and is used in traditional Chinese medicine for treatments that include the strengthening of hepatic and pancreatic functions. Unique polyphenolic compounds obtained from litchi pericarp extract (LPE) were studied in vitro and in vivo for hepatoprotection. Epicatechin (EC) and procyanidin A2 (PA2) of LPE were obtained by fractionated-extraction from pulverized litchi pericarps. All fractions, including LPE, were screened against silymarin in carbon tetrachloride (CCl 4 )-treated murine embryonic liver cell line (BNL). The effects of daily gavage-feeding of LPE, silymarin (200 mg/kg body weight) or H 2 O in CCl 4 -intoxicated male ICR mice were evaluated by studying serum chemicals, liver pathology and glutathione antioxidative enzymes. The effects of EC and PA2 on liver cell regenerative activity were investigated using a scratch wound healing assay and flow cytometric cell cycle analysis; the results of which demonstrated that LPE protected BNL from CCl 4 -intoxication. Gavage-feeding of LPE decreased serum glutamic oxaloacetate transaminase and glutamic pyruvic transaminase levels, and exhibited superior retention of the hexagonal structure of hepatocytes and reduced necrotic cells following liver histopathological examinations in CCl 4- intoxicated ICR mice. Glutathione peroxidise and glutathione reductase activities were preserved as the normal control level in LPE groups. EC and PA2 were principle components of LPE. PA2 demonstrated liver cell regenerative activity in scratch wound healing assays and alcohol-induced liver cell injury in vitro . The present findings suggest that litchi pericarp polyphenolic extracts, including EC and PA2, may be a synergistic

Circadian egg production by Echinostoma caproni (Digenea: Echinostomatidae) in ICR mice.

PubMed

Platt, Thomas R; Hussey, Gabrielle L; Zelmer, Derek A

2013-04-01

Circadian egg production by Echinostoma caproni was investigated in ICR mice. Four female mice were infected with 25 E. caproni metacercariae, maintained in individual cages on a 12:12 light:dark cycle, and provided food and water ad libitum. Twenty-eight, 51, and 58 days post-infection, mice were transferred to individual, wire-bottomed cages and feces were collected every 2 hr for 24 hr. The feces were weighed and processed immediately to estimate the number of eggs present. Fecal output and egg production were standardized to unit maxima for analysis. Standardized egg count and standardized fecal output followed distinctly circadian patterns and covaried. Egg production was highest from 2200 to 0200 hr and lowest from 1000 to 1800 hr. These correspond to the highest and lowest fecal production, and highest and lowest periods of host activity, respectively. Egg density (eggs/g of feces) covaried weakly with fecal output with an additional peak at 0800-1000 hr, suggesting E. caproni is responding to changes in host physiology in timing of the production and release of eggs into the intestine. The continuous production and release of eggs during the patent period, coupled with the circadian pattern of daily egg release by E. caproni , would result in the widest dispersal of eggs in the host environment and enhance transmission to the first intermediate host.

FT4 Data Analysis Summary (SSI-ARC)

NASA Technical Reports Server (NTRS)

Isaacson, Douglas R.; Gong, Chester; Reardon, Scott Edward; Santiago, Confesor

2016-01-01

Standards for Unmanned Aircraft System (UAS) Detect-and-Avoid (DAA) systems are currently being developed under the auspices of the RTCA Special Committee 228 (SC-228). To support the development of these standards, a series of flight tests has been conducted at NASAs Armstrong Flight Research Center (NASA-AFRC). The fourth in this series of flight test activities (Flight Test 4, or simply FT4) was conducted during the Spring and Summer of 2016. FT4 supported the objectives of numerous organizations working toward UAS DAA Minimum Operational Performance Standards (MOPS) and UAS DAA Radar MOPS. The summary provided herein is limited to the objectives, analysis and conclusions of the NASA Ames Research Center (NASA-ARC) SSI team toward the refinement of UAS DAA MOPS. This document provides a high-level overview of FT4 and the SSI-ARC objectives, a summary of the data analysis methodology and recommendations for UAS DAA MOPS refinements based on the data analysis results. A total of 72 encounters were flown to support SSI-ARC objectives. Test results were generally consistent with acceptable UAS DAA system performance and will be considered in broader SC-228 requirements validation efforts. Observed alert lead times indicated acceptable UAS DAA alerting performance. Effective interoperability between the UAS DAA system and the Traffic Alert and Collision Avoidance System (TCAS) was observed with one notable exception: TCAS Resolutions Advisories (RA) were observed in the absence of any DAA alert on two occasions, indicating the need for alert parameter refinement. Findings further indicated the need for continued work in the areas of DAA Well Clear Recovery logic and alert stability for Mode-C-only intruders. Finally, results demonstrated a high level of compliance with a set of evaluation criteria designed to provide anecdotal evidence of acceptable UAS DAA system performance.

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).

Poliomyelitis in MuLV-infected ICR-SCID mice after injection of basement membrane matrix contaminated with lactate dehydrogenase-elevating virus.

PubMed

Carlson Scholz, Jodi A; Garg, Rohit; Compton, Susan R; Allore, Heather G; Zeiss, Caroline J; Uchio, Edward M

2011-10-01

The arterivirus lactate dehydrogenase-elevating virus (LDV) causes life-long viremia in mice. Although LDV infection generally does not cause disease, infected mice that are homozygous for the Fv1(n) allele are prone to develop poliomyelitis when immunosuppressed, a condition known as age-dependent poliomyelitis. The development of age-dependent poliomyelitis requires coinfection with endogenous murine leukemia virus. Even though LDV is a common contaminant of transplantable tumors, clinical signs of poliomyelitis after inadvertent exposure to LDV have not been described in recent literature. In addition, LDV-induced poliomyelitis has not been reported in SCID or ICR mice. Here we describe the occurrence of poliomyelitis in ICR-SCID mice resulting from injection of LDV-contaminated basement membrane matrix. After exposure to LDV, a subset of mice presented with clinical signs including paresis, which was associated with atrophy of the hindlimb musculature, and tachypnea; in addition, some mice died suddenly with or without premonitory signs. Mice presenting within the first 6 mo after infection had regions of spongiosis, neuronal necrosis and astrocytosis of the ventral spinal cord, and less commonly, brainstem. Axonal degeneration of ventral roots prevailed in more chronically infected mice. LDV was identified by RT-PCR in 12 of 15 mice with typical neuropathology; positive antiLDV immunolabeling was identified in all PCR-positive animals (n = 7) tested. Three of 8 mice with neuropathology but no clinical signs were LDV negative by RT-PCR. RT-PCR yielded murine leukemia virus in spinal cords of all mice tested, regardless of clinical presentation or neuropathology.

Do TSH, FT3, and FT4 Impact BAT Visualization of Clinical FDG-PET/CT Images?

PubMed Central

Nagamachi, Shigeki; Mizutani, Youichi; Terada, Tamasa; Kiyohara, Syogo; Wakamatsu, Hideyuki; Fujita, Seigo; Higashi, Tatsuya; Yoshinaga, Keiichiro; Saga, Tsuneo; Hirai, Toshinori

2018-01-01

Objective We retrospectively analyzed activated BAT visualization on FDG-PET/CT in patients with various conditions and TH levels to clarify the relationships between visualization of BAT on FDG-PET/CT and the effect of TH. Methods Patients who underwent clinical FDG-PET/CT were reviewed and we categorized patients into 5 groups: (i) thyroid hormone withdrawal (THW) group; (ii) recombinant human thyrotropin (rhTSH) group; (iii) hypothyroidism group; (iv) hyperthyroidism group; and (v) BAT group. A total of sixty-two FDG-PET/CT imaging studies in fifty-nine patients were performed. To compare each group, gender; age; body weight; serum TSH, FT3, and FT4 levels; and outside temperature were evaluated. Results No significant visualization of BAT was noted in any of the images in the THW, rhTSH, hypothyroidism, and hyperthyroidism groups. All patients in the BAT group were in a euthyroid state. When the BAT-negative and BAT-positive patient groups were compared, it was noted that the minimum and maximum temperature on the day of the PET study and maximum temperature of the one day before the PET study were significantly lower in BAT-positive group than in all those of other groups. Conclusions Elevated TSH condition before RIT, hyperthyroidism, or hypothyroidism did not significantly impact BAT visualization of clinical FDG-PET/CT images. PMID:29666563

Optimization of Biomass Gasification Process for F-T Bio-Diesel Synthesys

NASA Astrophysics Data System (ADS)

Song, Jae Hun; Sung, Yeon Kyung; Yu, Tae U.; Choi, Young Tae; Lee, Uen Do

The characteristics of biomass steam gasification were investigated to make an optimum syngas for Fischer Tropsch (F-T) synthesis of bio-diesel. Korean pine wood chip was used as a fuel and the experiment was conducted in a lab scale bubbling fluidized bed (0.1m LD. x 3.Omheight). Gas composition was evaluated by changing operating parameters such as gasifier temperature, and steam to fuel ratio. Major syngas was monitored by on-line gas analyzer (ND-IR spectroscopy) and gas chromatography (GC). As the temperature of gasifier increases hydrogen in the syngas increases while CO in the product gas decreases. The low concentration of sulfur compound and nitrogen in the product gas shows the potential advantages in the purification process of the syngas for F-T process. Optimum operating condition of the gasifier was found concerning the following gas cleaning and F-T process; H2-CO ratio and total gas yield increase while decreasing methane and CO2 concentrations in the syngas.

FT-Raman, FT-IR spectra and total energy distribution of 3-pentyl-2,6-diphenylpiperidin-4-one: DFT method.

PubMed

Subashchandrabose, S; Saleem, H; Erdogdu, Y; Rajarajan, G; Thanikachalam, V

2011-11-01

FT-Raman and FT-IR spectra were recorded for 3-pentyl-2,6-diphenylpiperidin-4-one (PDPO) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and the Raman scattering intensities were computed using DFT/6-31G(d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the total energy distribution (TED) of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated and compared with X-ray diffraction data. This comparison was good agreement. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π* transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of the carbon, nitrogen and oxygen were calculated using same level of calculation. Copyright © 2011 Elsevier B.V. All rights reserved.

Negative electrospray ionization mass spectrometry: a method for sequencing and determining linkage position in oligosaccharides from branched hemicelluloses.

PubMed

Quéméner, Bernard; Vigouroux, Jacqueline; Rathahao, Estelle; Tabet, Jean Claude; Dimitrijevic, Aleksandra; Lahaye, Marc

2015-01-01

Xyloglucans of apple, tomato, bilberry and tamarind were hydrolyzed by commercial endo β-1-4-D-endoglucanase. The xylo-gluco-oligosaccharides (XylGos) released were separated on CarboPac PA 200 column in less than 15 min, and, after purification, they were structurally characterized by negative electrospray ionization mass spectrometry using a quadrupole time-of-flight (ESI-Q-TOF), a hybrid linear ion trap (LTQ)/Orbitrap and a hybrid quadrupole Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers. In order to corroborate the fragmentation routes observed on XylGos, some commercial galacto-manno-oligosaccharides (GalMOs) and glucurono-xylo-oligosaccharides were also studied. The fragmentation pathways of the ionized GalMos were similar to those of XylGos ones. The product ion spectra were mainly characterized by prominent double cleavage (D) ions corresponding to the entire inner side chains. The directed fragmentation from the reducing end to the other end was observed for the main glycosylated backbone but also for the side-chains, allowing their complete sequencing. Relevant cross-ring cleavage ions from (0,2)X(j)-type revealed to be diagnostic of the 1-2-linked- glycosyl units from XylGos together with the 1-2-linked glucuronic acid unit from glucuronoxylans. Resonant activation in the LTQ Orbitrap allowed not only determining the type of all linkages but also the O-acetyl group location on fucosylated side-chains. Moreover, the fragmentation of the different side chains using the MS(n) capabilities of the LTQ/Orbitrap analyzer also allowed differentiating terminal arabinosyl and xylosyl substituents inside S and U side-chains of XylGos, respectively. The CID spectra obtained were very informative for distinction of isomeric structures differing only in their substitution pattern. These features together makes the fragmentation in negative ionization mode a relevant and powerful technique useful to highlight the subtle structural changes

The embryotoxic effects of ultrasound exposure in pregnant ICR mice.

PubMed

Kimmel, C A; Stratmeyer, M E; Galloway, W D; Laborde, J B; Brown, N; Pinkavitch, F

1983-04-01

The embryotoxicity of ultrasound exposure during pregnancy was investigated in DUB:(ICR) mice. On day 0 of gestation (day of plug), pregnant mice were assigned to one of five groups: cage control, sham exposed (0 W/cm2), 0.05 W/cm2, 0.50 W/cm2. or 1.00 W/cm2. Females were anesthetized on day 8 of gestation and their abdomens were shaved to assure good acoustic coupling. The animals were strapped on a lucite board and placed vertically into a distilled degassed water bath (30 degrees C) so that the abdomen was fully submerged and centered in the axis of the ultrasonic beam. Insonation was carried out using a PZT transducer with a radius of 1.27 cm and a frequency of 1 MHz under continuous wave conditions. Each animal was placed at a distance of 25 cm from the transducer and exposed to the appropriate intensity for 120 seconds. On day 17 of gestation, the maternal animals were killed, the uterine contents were examined, and live fetuses were weighed and then shipped in cold lactated Ringer's solution from Maryland to Arkansas. Fetuses were examined on the day following maternal sacrifice for external and visceral defects and skeletons were prepared and examined subsequently. Slight but significant differences were detected between the cage control and sham-exposed groups. No statistically significant changes were seen that could be attributed to ultrasound exposure, although there was a slight increase in the incidence of malformed fetuses and the occurrence of multiple malformations in individual fetuses as intensity of the ultrasonic exposure increased.

Diurnal migration of Echinostoma caproni (Digenea: Echinostomatidae) in ICR mice.

PubMed

Platt, Thomas R; Graf, Emily; Kammrath, Anna; Zelmer, Derek A

2010-12-01

Twenty-four female ICR mice, 12 acclimated to a 12 ∶ 12 light-dark cycle and 12 to a 12 ∶ 12 dark-light cycle for 7 days, were each infected with 10 metacercariae of Echinostoma caproni. Infected mice were maintained on their respective lighting regimes for 28 days. Six mice (3 from each group) were necropsied at 4-hr intervals beginning at 0700 hr. The small intestine was removed, opened, and the position of individual worms and worm clusters was measured to the nearest 0.1 cm. Each intestine was subsequently divided into 20 equal segments and individual worms and worm clusters were assigned to the appropriate segment based on the original measurements. All worms were found in the posterior 55% of the intestine (ileum). All posterior segments (10-20), with the exception of segment 18, harbored at least 1 worm at some time. A Monte Carlo simulation of worm abundance in segments 10-17 over all time periods indicated a random distribution, while the same analysis of segments 10-20 indicated a non-random distribution due to large numbers of worms in segment 20 and to the absence of worms in segment 18. To analyze temporal changes in worm distribution, mice were grouped by time of necropsy as follows: night (1900 and 2300 hr), morning (0300 and 0700 hr), and day (1100 and 1500 hr). During the night and morning, E. caproni was heavily concentrated in segments 10-17 and, during the day, worms were located more posteriorly, with a heavy concentration in the last segment (20).

WEREWOLF, a regulator of root hair pattern formation, controls flowering time through the regulation of FT mRNA stability.

PubMed

Seo, Eunjoo; Yu, Jihyeon; Ryu, Kook Hui; Lee, Myeong Min; Lee, Ilha

2011-08-01

A key floral activator, FT, integrates stimuli from long-day, vernalization, and autonomous pathways and triggers flowering by directly regulating floral meristem identity genes in Arabidopsis (Arabidopsis thaliana). Since a small amount of FT transcript is sufficient for flowering, the FT level is strictly regulated by diverse genes. In this study, we show that WEREWOLF (WER), a MYB transcription factor regulating root hair pattern, is another regulator of FT. The mutant wer flowers late in long days but normal in short days and shows a weak sensitivity to vernalization, which indicates that WER controls flowering time through the photoperiod pathway. The expression and double mutant analyses showed that WER modulates FT transcript level independent of CONSTANS and FLOWERING LOCUS C. The histological analysis of WER shows that it is expressed in the epidermis of leaves, where FT is not expressed. Consistently, WER regulates not the transcription but the stability of FT mRNA. Our results reveal a novel regulatory mechanism of FT that is non cell autonomous.

High-definition Fourier Transform Infrared (FT-IR) Spectroscopic Imaging of Human Tissue Sections towards Improving Pathology

PubMed Central

Nguyen, Peter L.; Davidson, Bennett; Akkina, Sanjeev; Guzman, Grace; Setty, Suman; Kajdacsy-Balla, Andre; Walsh, Michael J.

2015-01-01

High-definition Fourier Transform Infrared (FT-IR) spectroscopic imaging is an emerging approach to obtain detailed images that have associated biochemical information. FT-IR imaging of tissue is based on the principle that different regions of the mid-infrared are absorbed by different chemical bonds (e.g., C=O, C-H, N-H) within cells or tissue that can then be related to the presence and composition of biomolecules (e.g., lipids, DNA, glycogen, protein, collagen). In an FT-IR image, every pixel within the image comprises an entire Infrared (IR) spectrum that can give information on the biochemical status of the cells that can then be exploited for cell-type or disease-type classification. In this paper, we show: how to obtain IR images from human tissues using an FT-IR system, how to modify existing instrumentation to allow for high-definition imaging capabilities, and how to visualize FT-IR images. We then present some applications of FT-IR for pathology using the liver and kidney as examples. FT-IR imaging holds exciting applications in providing a novel route to obtain biochemical information from cells and tissue in an entirely label-free non-perturbing route towards giving new insight into biomolecular changes as part of disease processes. Additionally, this biochemical information can potentially allow for objective and automated analysis of certain aspects of disease diagnosis. PMID:25650759

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.

A New N-methoxypyridone from the Co-Cultivation of Hawaiian Endophytic Fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062.

PubMed

Li, Chunshun; Sarotti, Ariel M; Yang, Baojun; Turkson, James; Cao, Shugeng

2017-07-12

A new N -methoxypyridone analog ( 1 ), together with four known compounds, was isolated from the co-culture of Hawaiian endophytic fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062. The structure of the new compound was elucidated as 11 S -hydroxy-1-methoxyfusaricide ( 1 ) by extensive spectroscopic analysis and comparison with the literature. The absolute configuration of 1 was determined by comparison with the experimental and calculated ECD spectra. The absolute configuration of compound 3 was investigated and renamed as (+)-epipyridone by comparison of the optical rotation and CD spectrum with those of 1 . The other known compounds were identified as epicoccarine B ( 2 ), D8646-2-6 ( 4 ), and iso-D8646-2-6 ( 5 ). Compounds 4 and 5 showed modest inhibitory activity towards pathogenic fungi. Epicoccarine B ( 2 ) inhibited A2780 and TK-10 with an IC 50 value of 22 μM.

Automatic Gain Control in Mass Spectrometry using a Jet Disrupter Electrode in an Electrodynamic Ion Funnel

PubMed Central

Page, Jason S.; Bogdanov, Bogdan; Vilkov, Andrey N.; Prior, David C.; Buschbach, Michael A.; Tang, Keqi; Smith, Richard D.

2007-01-01

We report on the use of a jet disrupter electrode in an electrodynamic ion funnel as an electronic valve to regulate the intensity of the ion beam transmitted through the interface of a mass spectrometer in order to perform automatic gain control (AGC). The ion flux is determined by either directly detecting the ion current on the conductance limiting orifice of the ion funnel or using a short mass spectrometry acquisition. Based upon the ion flux intensity, the voltage of the jet disrupter is adjusted to alter the transmission efficiency of the ion funnel to provide a desired ion population to the mass analyzer. Ion beam regulation by an ion funnel is shown to provide control to within a few percent of a targeted ion intensity or abundance. The utility of ion funnel AGC was evaluated using a protein tryptic digest analyzed with liquid chromatography Fourier transform ion cyclotron resonance (LC-FTICR) mass spectrometry. The ion population in the ICR cell was accurately controlled to selected levels, which improved data quality and provided better mass measurement accuracy. PMID:15694774

Spectroscopic (FT-IR, FT-Raman and UV) investigation, NLO, NBO, molecular orbital and MESP analysis of 2-{2-[(2,6-dichlorophenyl)amino]phenyl}acetic acid

NASA Astrophysics Data System (ADS)

Govindasamy, P.; Gunasekaran, S.

2015-02-01

In this work, FT-IR and FT-Raman spectra of 2-{2-[(2,6-dichlorophenyl)amino]phenyl}acetic acid (abbreviated as 2DCPAPAA) have been reported in the regions 4000-450 cm-1 and 4000-50 cm-1, respectively. The molecular structure, geometry optimization, intensities, vibrational frequencies were obtained by the ab initio and DFT levels of theory B3LYP with 6-311++G(d,p) standard basis set and a different scaling of the calculated wave numbers. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using vibrational energy distribution analysis (VEDA 4) program. The harmonic frequencies were calculated and the scaled values were compared with experimental FT-IR and FT-Raman data. The observed and the calculated frequencies are found to be in good agreement. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The thermodynamic properties of the title compound at different temperature reveal the correlations between standard heat capacities (C) standard entropies (S) standard enthalpy changes (ΔH). The important non-linear optical properties such as electric dipole momentum, polarizability and first hyperpolarizability of 2DCPAPAA have been computed using B3LYP/6-311++G(d,p) quantum chemical calculations. The Natural charges, HOMO, LUMO, chemical hardness (η), chemical potential (μ), Electro negativity (χ) and electrophilicity values (ω) are calculated and reported. The oscillator's strength, wave length, and energy calculated by TD-DFT and 2DCPAPAA is approach complement with the experimental findings. The molecular electrostatic potential (MESP) surfaces of the molecule were constructed.

Comparison of tribromoethanol, ketamine/acetylpromazine, Telazol/xylazine, pentobarbital, and methoxyflurane anesthesia in HSD:ICR mice.

PubMed

Gardner, D J; Davis, J A; Weina, P J; Theune, B

1995-04-01

Variation in the duration of surgical anesthesia in mice prompted an evaluation of various commonly used anesthetics. Using biotelemetric technology, we evaluated the effects of six anesthetic regimens (tribromoethanol, ketamine and acetylpromazine in combination, Telazol and xylazine in two combinations, pentobarbital, and methoxyflurane) on temperature and activity. Six groups of four male HSD:ICR mice received one of the anesthetic regimens or an equivalent volume of saline. Induction time (time from anesthetic administration until righting reflex loss) and duration of anesthesia (loss of response to interdigital toe pinch) were evaluated. Methoxyflurane and both doses of Telazol combinations resulted in the shortest and most repeatable induction times. None of the mice in the ketamine/acetylpromazine- and pentobarbital-treated groups lost the interdigital toe pinch reflex. Duration of anesthesia was superior in the two Telazol/xylazine-treated groups. A direct correlation existed between duration of anesthesia and magnitude and duration of temperature reduction. Duration of anesthesia can be used to predict extent of hypothermia.

Spectroscopic characterization of enzymatic flax retting: Factor analysis of FT-IR and FT-Raman data

NASA Astrophysics Data System (ADS)

Archibald, D. D.; Henrikssen, G.; Akin, D. E.; Barton, F. E.

1998-06-01

Flax retting is a chemical, microbial or enzymatic process which releases the bast fibers from the stem matrix so they can be suitable for mechanical processing before spinning into linen yarn. This study aims to determine the vibrational spectral features and sampling methods which can be used to evaluate the retting process. Flax stems were retted on a small scale using an enzyme mixture known to yield good retted flax. Processed stems were harvested at various time points in the process and the retting was evaluated by conventional methods including weight loss, color difference and Fried's test, a visual ranking of how the stems disintegrate in hot water. Spectroscopic measurements were performed on either whole stems or powders of the fibers that were mechanically extracted from the stems. Selected regions of spectra were baseline and amplitude corrected using a variant of the multiplicative signal correction method. Principal component regression and partial least-squares regression with full cross-validation were used to determine the spectral features and rate of spectral transformation by regressing the spectra against the retting time in hours. FT-Raman of fiber powders and FT-IR reflectance of whole stems were the simplest and most precise methods for monitoring the retting transformation. Raman tracks the retting by measuring the decrease in aromatic signal and subtle changes in the C-H stretching vibrations. The IR method uses complex spectral features in the fingerprint and carbonyl region, many of which are due to polysaccharide components. Both spectral techniques monitor the retting process with greater precision than the reference method.

Advantages of TOF-SIMS analysis of hydroxyapatite and fluorapatite in comparison with XRD, HR-TEM and FT-IR.

PubMed

Okazaki, Masayuki; Hirata, Isao; Matsumoto, Takuya; Takahashi, Junzo

2005-12-01

The chemical analysis of hydroxyapatite and fluorapatite was carried out using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Hydroxyapatite and fluorapatite were synthesized at 80 +/- 1 degrees C and pH 7.4 +/- 0.2. Fluorapatite was better crystallized, with its (300) reflection shifted to a slightly higher angle. High-resolution transmission electron microscopy clearly revealed a typical, regular hexagonal cross section perpendicular to the c-axis for fluorapatite and a flattened hexagonal cross section for hydroxyapatite. FT-IR spectra of fluorapatite confirmed the absence of OH absorption peak--which was seen in hydroxyapatite at about 3570 cm(-1). TOF-SIMS mass spectra showed a peak at 40 amu due to calcium. In addition, a peak at 19 amu due to fluorine could be clearly seen, although the intensities of PO, PO2, and PO3 were very low. It was confirmed that TOF-SIMS clearly showed the differences between positive and negative mass spectra of hydroxyapatite and fluorapatite, especially for F-. We concluded that TOF-SIMS exhibited distinct advantages compared with other methods of analysis.

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.

[Study of alkaline lignin from Arundo donax linn based on FT Raman spectroscopy].

PubMed

You, Ting-ting; Ma, Jian-feng; Guo, Si-qin; Xu, Feng

2014-08-01

Arundo donax linn, as a perennial energy crop, has promising application prospect. In the present study, Fourier transform Raman (FT Raman) spectroscopy was applied to determine the structural information of materials, milled wood lignin (MWL), and alkaline lignins (AL, under different treated time) from A. donax stem nondestructively. The results indicated that, extractable compounds in A. donax had negative contribution to the Raman spectra without rising new Raman peaks. FT Raman spectrum of MWL indicated that MWL from A. donax was HGS type lignins. Compared with the spectra of MWL from wood materials, the peak at 1173 cm(-1) was much higher in intensity for the MWL from A. donax stem, which may be assigned to hydroxycinnamic acid by analyzing the standard. With respect to FT Raman spectra of ALs, the relatively highest intensity of 1173 cm(-1) was found in alkaline lignin (AL2), which was treated for 40 min by alkaline. Moreover, the peak of coniferaldehyde/sinapaldehyde (1630 cm(-1)) was lowest in intensity while the band attributed to coniferyl alcohol/sinapyl alcohol (1660 cm(-1)) was almost disappeared in AL2. It could be inferred that AL2 demonstrated a highest content of phenolic acid, which may improve its potential application, such as for antioxidant activity. Furthermore, the results obtained by FT Raman spectra were verified by two dimensional heteronuclear singlequantum coherence nuclear magnetic resonance analyses. Above all, FT Raman spectroscopy provided alternative safe, rapid, accurate, and nondestructive technology for lignin structure determination.

The crowding effect and morphometric variability in Echinostoma caproni (Digenea: Echinostomatidae) from ICR mice.

PubMed

Stillson, Lindsey L; Platt, Thomas R

2007-04-01

Population density, or crowding, was examined to determine its effect on the morphometric variability of Echinostoma caproni (Digenea) in ICR mice. Six mice were infected with 25 and 100 metacercariae, and a single mouse was infected with 300 metacercariae. All mice were infected at necropsy 22 days postinfection with recoveries of 77%, 69%, and 7.3%, respectively. Whole mounts were prepared, and 31 characters were evaluated (25 direct measurements and 6 ratios). Univariate and multivariate statistical analysis revealed significant differences between adult worms from all 3 groups. Twenty-seven of 31 characters showed significant within-group differences, with the primary differences between worms from 25/100 versus 300 metacercariae infections. Discriminant function analysis yielded a 100% correct classification based on infection size, which is consistent with studies on distinct species of Echinostoma. The low recovery from the mouse infected with 300 metacercariae suggests inflammatory expulsion of juvenile worms and the possibility of immunity as a factor in the crowding effect. These results suggest that external factors may affect morphometric variability of digenetic trematodes to a larger degree than previously recognized.

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

Semi-quantitative analysis of FT-IR spectra of humic fractions of nine US soils

USDA-ARS?s Scientific Manuscript database

Fourier Transform Infrared Spectroscopy (FT-IR) is a simple and fast tool for characterizing soil organic matter. However, most FT-IR spectra are only analyzed qualitatively. In this work, we prepared mobile humic acid (MHA) and recalcitrant calcium humate (CaHA) from nine soils collected from six ...

Design, Development & Flight Testing Of The U.S. Army 4200 sq ft Parafoil Recovery System

NASA Technical Reports Server (NTRS)

Bennett, Thomas W.; Fox, Roy

2007-01-01

The purpose of this paper is to describe the design, development and flight testing of the U.S. Army 4200 ft(sup 2) parafoil recovery system built under NASA Contract NAS9-00076. The 4200 ft(sup 2) parafoil described herein was a potential candidate to fulfill the U.S. Army requirement for a 10,000 lb useable payload precision guided recovery system. Design heritage as well as specific features, like lower surface inlets, confluence fitting, upper surface energy modulator design, deployment bag design and 60 ft diameter Ringslot drogue will be discussed. Initial flight test results, ground testing of various components to verify design margin and configuration changes will also be discussed. The 4200 ft(sup 2) parafoil recovery system completed three flight tests during 2003 at payload weights of over 15,000 lbs.

Norepinephrine and thyroxine are predictors of fat mass gain in humans with cold-induced brown adipose tissue activation.

PubMed

Begaye, Brittany; Piaggi, Paolo; Thearle, Marie S; Haskie, Kaitlyn; Walter, Mary; Schlögl, Mathias; Bonfiglio, Susan; Krakoff, Jonathan; Vinales, Karyne L

2018-05-16

In healthy adults with detectable cold-induced brown fat activation (CIBA), the relationships between sympathetic nervous system (SNS) or thyroid activity during energy balance (EBL) with CIBA and body composition change are undetermined. To investigate the relationships between CIBA and thermoneutral catecholamines and thyroid hormones measured during EBL and to determine if CIBA, catecholamines, or thyroid hormones predict body composition changes. Twelve healthy volunteers (7M/5F) with positive CIBA (>2 standardized uptake value (g/mL)) had 24-h energy expenditure (24hEE) assessed during EBL via whole-room indirect calorimetry while residing on a clinical research unit. Positron-emission tomography/computed tomography scans were performed after exposure to 16°C for 2h to quantify CIBA. CIBA, 24hEE during EBL and thermoneutrality with concomitant measurement of urinary catecholamines and plasma free T3 (fT3) and free t4 (fT4). Body composition at baseline and six months by DXA. Lower urinary norepinephrine and fT4 were associated with higher CIBA (r = ‒0.65, p = 0.03 and r = ‒0.75, p<0.01, respectively), but CIBA was not associated with 24hEE at thermoneutrality (p=0.77). Lower CIBA (β = ̶̶ 3.5 kg/SUV, p<0.01) predicted fat mass gain; whereas, higher urinary norepinephrine and fT4 predicted future fat mass gain at 6 months (β = 3.0 kg per two-fold difference in norepinephrine, p=0.03; β = 1.2 kg per 0.1 ng/dL difference in fT4, p=0.03, respectively). Lower SNS and free thyroid measurements at baseline indicate a greater capacity for CIBA, which may be predictive against fat mass gain.

Differentiation of Leishmania species by FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Aguiar, Josafá C.; Mittmann, Josane; Ferreira, Isabelle; Ferreira-Strixino, Juliana; Raniero, Leandro

2015-05-01

Leishmaniasis is a parasitic infectious disease caused by protozoa that belong to the genus Leishmania. It is transmitted by the bite of an infected female Sand fly. The disease is endemic in 88 countries Desjeux (2001) [1] (16 developed countries and 72 developing countries) on four continents. In Brazil, epidemiological data show the disease is present in all Brazilian regions, with the highest incidences in the North and Northeast. There are several methods used to diagnose leishmaniasis, but these procedures have many limitations, are time consuming, have low sensitivity, and are expensive. In this context, Fourier Transform Infrared Spectroscopy (FT-IR) analysis has the potential to provide rapid results and may be adapted for a clinical test with high sensitivity and specificity. In this work, FT-IR was used as a tool to investigate the promastigotes of Leishmaniaamazonensis, Leishmaniachagasi, and Leishmaniamajor species. The spectra were analyzed by cluster analysis and deconvolution procedure base on spectra second derivatives. Results: cluster analysis found four specific regions that are able to identify the Leishmania species. The dendrogram representation clearly indicates the heterogeneity among Leishmania species. The band deconvolution done by the curve fitting in these regions quantitatively differentiated the polysaccharides, amide III, phospholipids, proteins, and nucleic acids. L. chagasi and L. major showed a greater biochemistry similarity and have three bands that were not registered in L. amazonensis. The L. amazonensis presented three specific bands that were not recorded in the other two species. It is evident that the FT-IR method is an indispensable tool to discriminate these parasites. The high sensitivity and specificity of this technique opens up the possibilities for further studies about characterization of other microorganisms.

Study of static wormhole solutions in F(T ,TG) gravity

NASA Astrophysics Data System (ADS)

Sharif, M.; Nazir, Kanwal

2018-06-01

In this paper, we investigate static spherically symmetric wormhole solutions in the background of F(T ,TG) gravity (T is the torsion scalar and TG represents teleparallel equivalent of the Gauss-Bonnet term). We study the wormhole solutions by assuming four different matter contents, a specific redshift function and a particular F(T ,TG) model. The behavior of null/weak energy conditions for these fluids is analyzed graphically. It turns out that wormhole solutions can be obtained in the absence of exotic matter for some particular regions of spacetime. We also explore stability of wormhole solutions through equilibrium condition. It is concluded that there exist physically acceptable wormhole solutions for anisotropic, isotropic and traceless fluids.

FT-IR, FT-Raman, and DFT computational studies of melaminium nitrate molecular-ionic crystal

NASA Astrophysics Data System (ADS)

Tanak, Hasan; Marchewka, Mariusz K.

2013-02-01

The experimental and theoretical vibrational spectra of melaminium nitrate were studied. The Raman and infrared (FT-IR) spectra of the melaminium nitrate and its deuterated analogue were recorded in the solid phase. Molecular geometry and vibrational frequency values of melaminium nitrate in the electronic ground state were calculated using the density functional method (B3LYP) with the 6-31++G(d,p) basis set. The calculated results show that the optimized geometry can well reproduce the crystal structure, and the theoretical vibrational frequency values show good agreement with experimental values. The NBO analysis reveals that the N-H···O and N-H···N intermolecular interactions significantly influence crystal packing in this molecule.

Detection of [O III] at z ∼ 3: A Galaxy Above the Main Sequence, Rapidly Assembling Its Stellar Mass

NASA Astrophysics Data System (ADS)

Vishwas, Amit; Ferkinhoff, Carl; Nikola, Thomas; Parshley, Stephen C.; Schoenwald, Justin P.; Stacey, Gordon J.; Higdon, Sarah J. U.; Higdon, James L.; Weiss, Axel; Güsten, Rolf; Menten, Karl M.

2018-04-01

We detect bright emission in the far-infrared (far-IR) fine structure [O III] 88 μm line from a strong lensing candidate galaxy, H-ATLAS J113526.3-014605, hereafter G12v2.43, at z = 3.127, using the second-generation Redshift (z) and Early Universe Spectrometer (ZEUS-2) at the Atacama Pathfinder Experiment Telescope (APEX). This is only the fifth detection of this far-IR line from a submillimeter galaxy at the epoch of galaxy assembly. The observed [O III] luminosity of 7.1 × 109 ≤ft(\\tfrac{10}{μ }\\right) L ⊙ likely arises from H II regions around massive stars, and the amount of Lyman continuum photons required to support the ionization indicate the presence of (1.2–5.2) × 106 ≤ft(\\tfrac{10}{μ }\\right) equivalent O5.5 or higher stars, where μ would be the lensing magnification factor. The observed line luminosity also requires a minimum mass of ∼2 × 108 ≤ft(\\tfrac{10}{μ }\\right) M ⊙ in ionized gas, that is 0.33% of the estimated total molecular gas mass of 6 × 1010 ≤ft(\\tfrac{10}{μ }\\right) M ⊙. We compile multi-band photometry tracing rest-frame ultraviolet to millimeter continuum emission to further constrain the properties of this dusty high-redshift, star-forming galaxy. Via SED modeling we find G12v2.43 is forming stars at a rate of 916 ≤ft(\\tfrac{10}{μ }\\right) M ⊙ yr‑1 and already has a stellar mass of 8 × 1010 ≤ft(\\tfrac{10}{μ }\\right) M ⊙. We also constrain the age of the current starburst to be ≤slant 5 Myr, making G12v2.43 a gas-rich galaxy lying above the star-forming main sequence at z ∼ 3, undergoing a growth spurt, and it could be on the main sequence within the derived gas depletion timescale of ∼66 Myr.

Spectroscopic (FT-IR, FT-Raman and UV) investigation, NLO, NBO, molecular orbital and MESP analysis of 2-{2-[(2,6-dichlorophenyl)amino]phenyl}acetic acid.

PubMed

Govindasamy, P; Gunasekaran, S

2015-02-05

In this work, FT-IR and FT-Raman spectra of 2-{2-[(2,6-dichlorophenyl)amino]phenyl}acetic acid (abbreviated as 2DCPAPAA) have been reported in the regions 4000-450cm(-1) and 4000-50cm(-1), respectively. The molecular structure, geometry optimization, intensities, vibrational frequencies were obtained by the ab initio and DFT levels of theory B3LYP with 6-311++G(d,p) standard basis set and a different scaling of the calculated wave numbers. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using vibrational energy distribution analysis (VEDA 4) program. The harmonic frequencies were calculated and the scaled values were compared with experimental FT-IR and FT-Raman data. The observed and the calculated frequencies are found to be in good agreement. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The thermodynamic properties of the title compound at different temperature reveal the correlations between standard heat capacities (C) standard entropies (S) standard enthalpy changes (ΔH). The important non-linear optical properties such as electric dipole momentum, polarizability and first hyperpolarizability of 2DCPAPAA have been computed using B3LYP/6-311++G(d,p) quantum chemical calculations. The Natural charges, HOMO, LUMO, chemical hardness (η), chemical potential (μ), Electro negativity (χ) and electrophilicity values (ω) are calculated and reported. The oscillator's strength, wave length, and energy calculated by TD-DFT and 2DCPAPAA is approach complement with the experimental findings. The molecular electrostatic potential (MESP) surfaces of the molecule were constructed. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization and identification of microorganisms by FT-IR microspectrometry

NASA Astrophysics Data System (ADS)

Ngo-Thi, N. A.; Kirschner, C.; Naumann, D.

2003-12-01

We report on a novel FT-IR approach for microbial characterization/identification based on a light microscope coupled to an infrared spectrometer which offers the possibility to acquire IR-spectra of microcolonies containing only few hundred cells. Microcolony samples suitable for FT-IR microspectroscopic measurements were obtained by a replica technique with a stamping device that transfers spatially accurate cells of microcolonies growing on solid culture plates to a special, IR-transparent or reflecting stamping plate. High quality spectra could be recorded either by applying the transmission/absorbance or the reflectance/absorbance mode of the infrared microscope. Signal to noise ratios higher than 1000 were obtained for microcolonies as small as 40 μm in diameter. Reproducibility levels were established that allowed species and strain identification. The differentiation and classification capacity of the FT-IR microscopic technique was tested for different selected microorganisms. Cluster and factor analysis methods were used to evaluate the complex spectral data. Excellent discrimination between bacteria and yeasts, and at the same time Gram-negative and Gram-positive bacterial strains was obtained. Twenty-two selected strains of different species within the genus Staphylococcus were repetitively measured and could be grouped into correct species cluster. Moreover, the results indicated that the method allows also identifications at the subspecies level. Additionally, the new approach allowed spectral mapping analysis of single colonies which provided spatially resolved characterization of growth heterogeneity within complex microbial populations such as colonies.

The spectroscopic (FT-IR, FT-Raman and 1H, 13C NMR) and theoretical studies of cinnamic acid and alkali metal cinnamates

NASA Astrophysics Data System (ADS)

Kalinowska, Monika; Świsłocka, Renata; Lewandowski, Włodzimierz

2007-05-01

The effect of alkali metals (Li → Na → K → Rb → Cs) on the electronic structure of cinnamic acid (phenylacrylic acid) was studied. In this research many miscellaneous analytical methods, which complement one another, were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance ( 1H, 13C NMR) and quantum mechanical calculations. The spectroscopic studies lead to conclusions concerning the distribution of the electronic charge in molecule, the delocalization energy of π-electrons and the reactivity of metal complexes. The change of metal along with the series: Li → Na → K → Rb → Cs caused: (1) the change of electronic charge distribution in cinnamate anion what is seen via the occurrence of the systematic shifts of several bands in the experimental and theoretical IR and Raman spectra of cinnamates, (2) systematic chemical shifts for protons 1H and 13C nuclei.

Movement of 95-ft mobile housing units in Virginia.

DOT National Transportation Integrated Search

1988-01-01

This study was initiated in response to a request to the Virginia Department of Transportation from the Virginia Manufactured Housing Association to permit the movement of 80-ft mobile homes on Virginia highways. Information concerning the movement o...

The protoplanetary disk of FT Tauri: multiwavelength data analysis and modeling

NASA Astrophysics Data System (ADS)

Garufi, A.; Podio, L.; Kamp, I.; Ménard, F.; Brittain, S.; Eiroa, C.; Montesinos, B.; Alonso-Martínez, M.; Thi, W. F.; Woitke, P.

2014-07-01

Context. Investigating the evolution of protoplanetary disks is crucial for our understanding of star and planet formation. There have been several theoretical and observational studies in past decades to advance this knowledge. The launch of satellites operating at infrared wavelengths, such as the Spitzer Space Telescope and the Herschel Space Observatory, has provided important tools for investigating the properties of circumstellar disks. Aims: FT Tauri is a young star in the Taurus star forming region that was included in a number of spectroscopic and photometric surveys. We investigate the properties of the star, the circumstellar disk, and the accretion/ejection processes and propose a consistent gas and dust model also as a reference for future observational studies. Methods: We performed a multiwavelength data analysis to derive the basic stellar and disk properties, as well as mass accretion/outflow rate from TNG/DOLoRes, WHT/LIRIS, NOT/NOTCam, Keck/NIRSpec, and Herschel/PACS spectra. From the literature, we compiled a complete spectral energy distribution. We then performed detailed disk modeling using the MCFOST and ProDiMo codes. Multiwavelength spectroscopic and photometric measurements were compared with the reddened predictions of the codes in order to constrain the disk properties. Results: We have determined the stellar mass (~ 0.3 M⊙), luminosity (~ 0.35 L⊙), and age (~ 1.6 Myr), as well as the visual extinction of the system (1.8 mag). We estimate the mass accretion rate (~ 3 × 10-8 M⊙/yr) to be within the range of accreting objects in Taurus. The evolutionary state and the geometric properties of the disk are also constrained. The radial extent (0.05 to 200 AU), flaring angle (power law with exponent =1.15), and mass (0.02 M⊙) of the circumstellar disk are typical of a young primordial disk. This object can serve as a benchmark for primordial disks with significant mass accretion rate, high gas content, and typical size. Based on

Structure of zirconocene complexes relevant for olefin catalysis: infrared fingerprint of the Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cation in the gas phase.

PubMed

Lagutschenkov, Anita; Springer, Andreas; Lorenz, Ulrich Joseph; Maitre, Philippe; Dopfer, Otto

2010-02-11

Cationic zirconocene complexes are active species in Ziegler-Natta catalysis for olefin polymerization. Their structure and metal-ligand bond strength strongly influence their activity. In the present work, the infrared multiphoton dissociation (IRMPD) spectrum of mass selected Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cations was obtained in the 300-1500 cm(-1) fingerprint range by coupling a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer equipped with an electrospray ionization (ESI) source and the infrared free electron laser (IR-FEL) at the Centre Laser Infrarouge d'Orsay (CLIO). The experimental efforts are complemented by quantum chemical calculations at the MP2 and B3LYP levels using the 6-311G* basis set. Vibrational assignments of transitions observed in the IRMPD spectra to modes of the Zr-O-H, C(5)H(5), and CH(3)CN moieties are based on comparison to calculated linear absorption spectra. Both the experimental data and the calculations provide unprecedented information about structure, metal-ligand bonding, charge distribution, and binding energy of the complex.

Correlation of Body Mass Index (BMI) with Thyroid Function in Euthyroid Pregnant Women in Manipur, India.

PubMed

Kumar, Sumit; Chiinngaihlun, T; Singh, M Rameswar; Punyabati, O

2017-04-01

Body Mass Index (BMI) is significantly increased during pregnancy due to gain of weight with normal progression of pregnancy. The exact influence of thyroid function on BMI are ill defined in euthyroid pregnant women. To correlate serum levels of Free Triiodothyronine (FT3), Free Thyroxine (FT4) and Thyroid Stimulating Hormone (TSH) level with BMI of participant normal pregnant women in all the three trimesters. In this cross-sectional comparative study, total of 210 healthy pregnant women comprising of 70 participants in each trimester, attending Obstetrics Outpatient Department (OPD) for antenatal check-up were consecutively selected. Estimation of serum FT3, FT4 and TSH level was done by ELISA based methods. The correlation of BMI with serum levels of FT3, FT4 and TSH was done using Pearson correlation test (r) by SPSS version 21.0 software. TSH level of participant normal pregnant women showed significant positive correlation with BMI during first (r=0.254 and p=0.034) and second trimester (r=0.263 and p=0.028) of pregnancy. FT4 level showed significant negative correlation in second (r= -0.454 and p<0.001) and third trimester (r= -0.351 and p=0.003) of pregnancy. Correlation between BMI and FT3 level showed no significant association in any of the trimesters. BMI correlates positively with TSH level in first and second trimesters while it correlates negatively with FT4 level in second and third trimesters, but, failed to demonstrate significant association with FT3 level in any of trimesters in euthyroid pregnant women. Serum TSH along with FT4 level appears more useful modality compared to serum TSH alone for targeted thyroid screening particularly in obese pregnant women.

FT-Raman study of dehydrogenation polymer (DHP) lignins

Treesearch

Umesh P. Agarwal; Noritsugu Terashima

2003-01-01

Compared to conventional Raman spectroscopy where samples are excited using visible light lasers, 1064 nm-excited FT-Raman technique has the single most important advantage that the sample-fluorescence is significantly suppressed for samples that are strongly fluorescent. DHPs are difficult to analyze in conventional Raman because small amounts of chromophores present...

Technical Evaluation of the Norwegian Crew Concept Boat (CG-502001) and Comparison to the 41-FT Utility Boat (UTB)

DTIC Science & Technology

1993-11-01

6.36 5.94 6.39 5.99 GMo (ft) 5.07 4.68 4.83 4.60 FSM (ft-lbs) .00 1232.00 1232.00 1232.00 FSC (ft) .00 .02 .02 .02 GMt (ft) 5.07 4.66 4.81 4.58 LCG (ft...mechanical plant , the 502001 can certainly get underway for an emergency response in less than ten minutes of notification, assuming that all crew members are...of the well deck and the stern ramp permit the crew to deploy pollution control booms from the boat. The stern ramp is also useful as a platform and

Attenuated total reflectance-FT-IR spectroscopy for gunshot residue analysis: potential for ammunition determination.

PubMed

Bueno, Justin; Sikirzhytski, Vitali; Lednev, Igor K

2013-08-06

The ability to link a suspect to a particular shooting incident is a principal task for many forensic investigators. Here, we attempt to achieve this goal by analysis of gunshot residue (GSR) through the use of attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FT-IR) combined with statistical analysis. The firearm discharge process is analogous to a complex chemical process. Therefore, the products of this process (GSR) will vary based upon numerous factors, including the specific combination of the firearm and ammunition which was discharged. Differentiation of FT-IR data, collected from GSR particles originating from three different firearm-ammunition combinations (0.38 in., 0.40 in., and 9 mm calibers), was achieved using projection to latent structures discriminant analysis (PLS-DA). The technique was cross (leave-one-out), both internally and externally, validated. External validation was achieved via assignment (caliber identification) of unknown FT-IR spectra from unknown GSR particles. The results demonstrate great potential for ATR-FT-IR spectroscopic analysis of GSR for forensic purposes.

Development of modified FT (MFT) process

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

Jinglai Zhou; Zhixin Zhang; Wenjie Shen

1995-12-31

Two-Stage Modified FT (MFT) process has been developed for producing high-octane gasoline from coal-based syngas. The main R&D are focused on the development of catalysts and technologies process. Duration tests were finished in the single-tube reactor, pilot plant (100T/Y), and industrial demonstration plant (2000T/Y). A series of satisfactory results has been obtained in terms of operating reliability of equipments, performance of catalysts, purification of coal - based syngas, optimum operating conditions, properties of gasoline and economics etc. Further scaling - up commercial plant is being considered.

Wind Turbine - SWiFT southeast - WTGa1 - Reviewed Data

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

Herges, Thomas

Scaled Wind Farm Technology (SWiFT) Facility meteorological tower (MET), turbine, and Technical University of Denmark (DTU) SpinnerLidar data acquired on 20161216 UTC during a neutral atmospheric boundary layer inflow at a single focus distance of 2.5 D (D=27 m).

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.

[Revisiting the chemical diversity in prostatic calculi: a SEM and FT-IR investigation].

PubMed

Dessombz, A; Méria, P; Bazin, D; Foy, E; Rouzière, S; Weil, R; Daudon, M

2011-12-01

Revisiting the chemical diversity of the crystalline phases of prostatic calculi by means of SEM and FT-IR analysis. A set of 32 prostatic calculi has been studied by FT-IR and SEM. FT-IR analysis has determined the chemical composition of each prostatic calculus and the SEM observation has described the morphology of the calculi surfaces and layers. Infrared analysis revealed that 90.7% of the stones were mainly composed of calcium phosphates. However, several mineral phases previously not reported in prostatic calculi were observed, as brushite or octocalcium phosphate pentahydrate. Prostatic calculi exhibited a diversity of crystalline composition and morphology. As previously reported for urinary calculi, relationships between composition and morphology of prostatic stones and étiopathogenic conditions could be of interest in clinical practice. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Development of a Large Field of View Shadowgraph System for a 16 Ft. Transonic Wind Tunnel

NASA Technical Reports Server (NTRS)

Talley, Michael A.; Jones, Stephen B.; Goodman, Wesley L.

2000-01-01

A large field of view shadowgraph flow visualization system for the Langley 16 ft. Transonic Tunnel (16 ft.TT) has been developed to provide fast, low cost, aerodynamic design concept evaluation capability to support the development of the next generation of commercial and military aircraft and space launch vehicles. Key features of the 16 ft. TT shadowgraph system are: (1) high resolution (1280 X 1024) digital snap shots and sequences; (2) video recording of shadowgraph at 30 frames per second; (3) pan, tilt, & zoom to find and observe flow features; (4) one microsecond flash for freeze frame images; (5) large field of view approximately 12 X 6 ft; and (6) a low maintenance, high signal/noise ratio, retro-reflective screen to allow shadowgraph imaging while test section lights are on.

Molecular structure and vibrational study of diprotonated guanazolium using DFT calculations and FT-IR and FT-Raman spectroscopies.

PubMed

Guennoun, L; Zaydoun, S; El Jastimi, J; Marakchi, K; Komiha, N; Kabbaj, O K; El Hajji, A; Guédira, F

2012-11-01

The purpose of this manuscript is to discuss our investigations of diprotonated guanazolium chloride using vibrational spectroscopy and quantum chemical methods. The solid phase FT-IR and FT-Raman spectra were recorded in the regions 4000-400cm(-1) and 3600-50cm(-1) respectively, and the band assignments were supported by deuteration effects. Different sites of diprotonation have been theoretically examined at the B3LYP/6-31G level. The results of energy calculations show that the diprotonation process occurs with the two pyridine-like nitrogen N2 and N4 of the triazole ring. The molecular structure, harmonic vibrational wave numbers, infrared intensities and Raman activities were calculated for this form by DFT/B3LYP methods, using a 6-31G basis set. Both the optimized geometries and the theoretical and experimental spectra for diprotonated guanazolium under a stable form are compared with theoretical and experimental data of the neutral molecule reported in our previous work. This comparison reveals that the diprotonation occurs on the triazolic nucleus, and provide information about the hydrogen bonding in the crystal. The scaled vibrational wave number values of the diprotonated form are in close agreement with the experimental data. The normal vibrations were characterized in terms of potential energy distribution (PED) using the VEDA 4 program. Copyright © 2012 Elsevier B.V. All rights reserved.

Molecular structure and vibrational study of diprotonated guanazolium using DFT calculations and FT-IR and FT-Raman spectroscopies

NASA Astrophysics Data System (ADS)

Guennoun, L.; Zaydoun, S.; El jastimi, J.; Marakchi, K.; Komiha, N.; Kabbaj, O. K.; El Hajji, A.; Guédira, F.

2012-11-01

The purpose of this manuscript is to discuss our investigations of diprotonated guanazolium chloride using vibrational spectroscopy and quantum chemical methods. The solid phase FT-IR and FT-Raman spectra were recorded in the regions 4000-400 cm-1 and 3600-50 cm-1 respectively, and the band assignments were supported by deuteration effects. Different sites of diprotonation have been theoretically examined at the B3LYP/6-31G∗ level. The results of energy calculations show that the diprotonation process occurs with the two pyridine-like nitrogen N2 and N4 of the triazole ring. The molecular structure, harmonic vibrational wave numbers, infrared intensities and Raman activities were calculated for this form by DFT/B3LYP methods, using a 6-31G∗ basis set. Both the optimized geometries and the theoretical and experimental spectra for diprotonated guanazolium under a stable form are compared with theoretical and experimental data of the neutral molecule reported in our previous work. This comparison reveals that the diprotonation occurs on the triazolic nucleus, and provide information about the hydrogen bonding in the crystal. The scaled vibrational wave number values of the diprotonated form are in close agreement with the experimental data. The normal vibrations were characterized in terms of potential energy distribution (PED) using the VEDA 4 program.

Can f(T) gravity theories mimic ΛCDM cosmic history

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

Setare, M.R.; Mohammadipour, N., E-mail: rezakord@ipm.ir, E-mail: N.Mohammadipour@uok.ac.ir

2013-01-01

Recently the teleparallel Lagrangian density described by the torsion scalar T has been extended to a function of T. The f(T) modified teleparallel gravity has been proposed as the natural gravitational alternative for dark energy to explain the late time acceleration of the universe. In order to reconstruct the function f(T) by demanding a background ΛCDM cosmology we assume that, (i) the background cosmic history provided by the flat ΛCDM (the radiation ere with ω{sub eff} = (1/3), matter and de Sitter eras with ω{sub eff} = 0 and ω{sub eff} = −1, respectively) (ii) the radiation dominate in themore » radiation era with Ω{sub 0r} = 1 and the matter dominate during the matter phases when Ω{sub 0m} = 1. We find the cosmological dynamical system which can obey the ΛCDM cosmic history. In each era, we find a critical lines that, the radiation dominated and the matter dominated are one points of them in the radiation and matter phases, respectively. Also, we drive the cosmologically viability condition for these models. We investigate the stability condition with respect to the homogeneous scalar perturbations in each era and we obtain the stability conditions for the fixed points in each eras. Finally, we reconstruct the function f(T) which mimics cosmic expansion history.« less

FT-IR imaging for quantitative determination of liver fat content in non-alcoholic fatty liver.

PubMed

Kochan, K; Maslak, E; Chlopicki, S; Baranska, M

2015-08-07

In this work we apply FT-IR imaging of large areas of liver tissue cross-section samples (∼5 cm × 5 cm) for quantitative assessment of steatosis in murine model of Non-Alcoholic Fatty Liver (NAFLD). We quantified the area of liver tissue occupied by lipid droplets (LDs) by FT-IR imaging and Oil Red O (ORO) staining for comparison. Two alternative FT-IR based approaches are presented. The first, straightforward method, was based on average spectra from tissues and provided values of the fat content by using a PLS regression model and the reference method. The second one – the chemometric-based method – enabled us to determine the values of the fat content, independently of the reference method by means of k-means cluster (KMC) analysis. In summary, FT-IR images of large size liver sections may prove to be useful for quantifying liver steatosis without the need of tissue staining.

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.

Quantum chemical calculation (electronic and topologic) and experimental (FT-IR, FT-Raman and UV) analysis of isonicotinic acid N-oxide

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-04-01

In this work, the molecular conformation, vibrational and electronic analysis of isonicotinic acid N-oxide (iso-NANO) were presented in the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. The geometry optimization and energies associated possible two conformers (Rot-I and Rot-II) were computed. The vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. The obtained structures were analyzed with the Atoms in Molecules (AIMs) methodology. The computational results diagnose the most stable conformer of iso-NANO as the Rot-I form. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (OPDOS) diagrams analysis for the most stable conformer (Rot-I) were calculated using the same method. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated. As a result, the optimized geometry and calculated spectroscopic data show a good agreement with the experimental results.

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.

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

Rotor redesign for a highly loaded 1800 ft/sec tip speed fan, 2

NASA Technical Reports Server (NTRS)

Bolt, C. R.

1980-01-01

Tests were conducted on a 0.5 hub/tip ratio single-stage fan designed to produce a pressure ratio of 2.280 at an efficiency of 83.8 percent with a rotor tip speed of 548.6 m/sec (1800 ft/sec). The rotor was designed utilizing a quasi three dimensional design system and four-part, multiple-circular-arc airfoil sections. The rotor is the third in a series of single-stage fans that have included a precompression airfoil design and a multiple-circular-arc airfoil design. The stage achieved a peak efficiency of 82.8 percent after performance had deteriorated by 0.6 of a point. The design mass flow was achieved at the peak efficiency point, and the stage total pressure ratio was 2.20, which is lower than the design goal of 2.28. The surge margin of 13% from the peak efficiency point exceeded the design goal of 7%.

A new hybrid electrospray Fourier transform mass spectrometer: design and performance characteristics.

PubMed

O'connor, Peter B; Pittman, Jason L; Thomson, Bruce A; Budnik, Bogdan A; Cournoyer, Jason C; Jebanathirajah, Judith; Lin, Cheng; Moyer, Susanne; Zhao, Cheng

2006-01-01

A new hybrid electrospray quadrupole Fourier transform mass spectrometry (FTMS) instrument design is shown and characterized. This instrument involves coupling an electrospray source and mass-resolving quadrupole, ion accumulation, and collision cell linear ion trap system developed by MDS Sciex with a home-built ion guide and ion cyclotron resonance (ICR) cell. The iterative progression of this design is shown. The final design involves a set of hexapole ion guides to transfer the ions from the accumulation/collision trap through the magnetic field gradient and into the cell. These hexapole ion guides are separated by a thin gate valve and two conduction limits to maintain the required <10(-9) mbar vacuum for FTICR. Low-attomole detection limits for a pure peptide are shown, 220 000 resolving power in broadband mode and 820 000 resolving power in narrow-band mode are demonstrated, and mass accuracy in the <2 ppm range is routinely available provided the signal is abundant, cleanly resolved, and internally calibrated. This instrument design provides high experimental flexibility, allowing Q2 CAD, SORI-CAD, IRMPD, and ECD experiments with selected ion accumulation as well as experiments such as nozzle skimmer dissociation. Initial top-down mass spectrometry experiments on a protein is shown using ECD.

Accurate mass screening and identification of emerging contaminants in environmental samples by liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry.

PubMed

Hogenboom, A C; van Leerdam, J A; de Voogt, P

2009-01-16

The European Reach legislation will possibly drive producers to develop newly designed chemicals that will be less persistent, bioaccumulative or toxic. If this innovation leads to an increased use of more hydrophilic chemicals it may result in higher mobilities of chemicals in the aqueous environment. As a result, the drinking water companies may face stronger demands on removal processes as the hydrophilic compounds inherently are more difficult to remove. Monitoring efforts will also experience a shift in focus to more water-soluble compounds. Screening source waters on the presence of (emerging) contaminants is an essential step in the control of the water cycle from source to tap water. In this article, some of our experiences are presented with the hybrid linear ion trap (LTQ) FT Orbitrap mass spectrometer, in the area of chemical water analysis. A two-pronged strategy in mass spectrometric research was employed: (i) exploring effluent, surface, ground- and drinking-water samples searching for accurate masses corresponding to target compounds (and their product ions) known from, e.g. priority lists or the scientific literature and (ii) full-scan screening of water samples in search of 'unknown' or unexpected masses, followed by MS(n) experiments to elucidate the structure of the unknowns. Applications of both approaches to emerging water contaminants are presented and discussed. Results are presented for target analysis search for pharmaceuticals, benzotriazoles, illicit drugs and for the identification of unknown compounds in a groundwater sample and in a polar extract of a landfill soil sample (a toxicity identification evaluation bioassay sample). The applications of accurate mass screening and identification described in this article demonstrate that the LC-LTQ FT Orbitrap MS is well equipped to meet the challenges posed by newly emerging polar contaminants.

Design of an FT-NIR spectrometer for online quality analysis of traditional Chinese medicine manufacturing process

NASA Astrophysics Data System (ADS)

Zhu, Ren; Wu, Lan; Wang, Shiming; Ye, Linhua; Ding, Zhihua

2008-03-01

As a fast, non-destructive analysis method, Fourier transform (FT) near-infrared (NIR) spectroscopy is very suitable and effective for online quality analysis of traditional Chinese medicine (TCM) manufacturing process. In this thesis, the theoretics of FT-NIRS was analyzed and an FT-NIR spectrometer with 4 cm -1 resolution in the 12500-5000 cm -1 frequency range was designed. The spectrometer was based on a Michelson interferometer with Bromine tungsten lamp as the NIR light source and InGaAs detector to collect the interference signal. Each element was designed and chosen to provide maximum sensitivity in the NIR spectral region. A fiber-optic flow cell system was used to realize online analysis of traditional Chinese medicine. The performance of the spectrometer was evaluated and the feasibility of using FT-NIR spectrometer to get absorption spectra of traditional Chinese medicine was demonstrated.

Computer simulation of FT-NMR multiple pulse experiment

NASA Astrophysics Data System (ADS)

Allouche, A.; Pouzard, G.

1989-04-01

Using the product operator formalism in its real form, SIMULDENS expands the density matrix of a scalar coupled nuclear spin system and simulates analytically a large variety of FT-NMR multiple pulse experiments. The observable transverse magnetizations are stored and can be combined to represent signal accumulation. The programming language is VAX PASCAL, but a MacIntosh Turbo Pascal Version is also available.

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.

In-line monitoring of a pharmaceutical blending process using FT-Raman spectroscopy.

PubMed

Vergote, G J; De Beer, T R M; Vervaet, C; Remon, J P; Baeyens, W R G; Diericx, N; Verpoort, F

2004-03-01

FT-Raman spectroscopy (in combination with a fibre optic probe) was evaluated as an in-line tool to monitor a blending process of diltiazem hydrochloride pellets and paraffinic wax beads. The mean square of differences (MSD) between two consecutive spectra was used to identify the time required to obtain a homogeneous mixture. A traditional end-sampling thief probe was used to collect samples, followed by HPLC analysis to verify the Raman data. Large variations were seen in the FT-Raman spectra logged during the initial minutes of the blending process using a binary mixture (ratio: 50/50, w/w) of diltiazem pellets and paraffinic wax beads (particle size: 800-1200 microm). The MSD-profiles showed that a homogeneous mixture was obtained after about 15 min blending. HPLC analysis confirmed these observations. The Raman data showed that the mixing kinetics depended on the particle size of the material and on the mixing speed. The results of this study proved that FT-Raman spectroscopy can be successfully implemented as an in-line monitoring tool for blending processes.

Quantum computational studies, spectroscopic (FT-IR, FT-Raman and UV-Vis) profiling, natural hybrid orbital and molecular docking analysis on 2,4 Dibromoaniline

NASA Astrophysics Data System (ADS)

Abraham, Christina Susan; Prasana, Johanan Christian; Muthu, S.; Rizwana B, Fathima; Raja, M.

2018-05-01

The research exploration will comprise of investigating the molecular structure, vibrational assignments, bonding and anti-bonding nature, nonlinear optical, electronic and thermodynamic nature of the molecule. The research is conducted at two levels: First level employs the spectroscopic techniques - FT-IR, FT-Raman and UV-Vis characterizing techniques; at second level the data attained experimentally is analyzed through theoretical methods using and Density Function Theories which involves the basic principle of solving the Schrodinger equation for many body systems. A comparison is drawn between the two levels and discussed. The probability of the title molecule being bio-active theoretically proved by the electrophilicity index leads to further property analyzes of the molecule. The target molecule is found to fit well with Centromere associated protein inhibitor using molecular docking techniques. Higher basis set 6-311++G(d,p) is used to attain results more concurrent to the experimental data. The results of the organic amine 2, 4 Dibromoaniline is analyzed and discussed.

A study of amber and copal samples using FT-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Brody, Rachel H.; Edwards, Howell G. M.; Pollard, A. Mark

2001-05-01

FT-Raman spectra were collected from fossil resins originating from a variety of geographical locations. The spectral profiles of most of the fossil resins could be related to modern resins containing diterpenoid components with predominantly labdane skeletons. The spectra collected from the fossil resin sample from Borneo differed from other fossil resins and was found to contain triterpenoid components. The differences in the spectral profile of fossil resins containing diterpenoid components are shown to relate to differences in level of maturation rather than geographical origin. FT-Raman spectra of fossil resins cannot be used to distinguish source although the degree of maturation can be used as an indicator to narrow the range of possible geographical origins.

Continuous flow immobilized enzyme reactor-tandem mass spectrometry for screening of AChE inhibitors in complex mixtures.

PubMed

Forsberg, Erica M; Green, James R A; Brennan, John D

2011-07-01

A method is described for identifying bioactive compounds in complex mixtures based on the use of capillary-scale monolithic enzyme-reactor columns for rapid screening of enzyme activity. A two-channel nanoLC system was used to continuously infuse substrate coupled with automated injections of substrate/small molecule mixtures, optionally containing the chromogenic Ellman reagent, through sol-gel derived acetylcholinesterase (AChE) doped monolithic columns. This is the first report of AChE encapsulated in monolithic silica for use as an immobilized enzyme reactor (IMER), and the first use of such IMERs for mixture screening. AChE IMER columns were optimized to allow rapid functional screening of compound mixtures based on changes in the product absorbance or the ratio of mass spectrometric peaks for product and substrate ions in the eluent. The assay had robust performance and produced a Z' factor of 0.77 in the presence of 2% (v/v) DMSO. A series of 52 mixtures consisting of 1040 compounds from the Canadian Compound Collection of bioactives was screened and two known inhibitors, physostigmine and 9-aminoacridine, were identified from active mixtures by manual deconvolution. The activity of the compounds was confirmed using the enzyme reactor format, which allowed determination of both IC(50) and K(I) values. Screening results were found to correlate well with a recently published fluorescence-based microarray screening assay for AChE inhibitors.

FY17 Accomplishments - Testing Facilities and Capabilities at SWiFT, SNL

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

Berg, Jonathan Charles

The Scaled Wind Farm Technologies (SWiFT) facility operated by Sandia National Laboratories (SNL) has, in support of the Atmosphere to electrons (A2e) research program, acquired measurements of wind turbine wake dynamics under various atmospheric conditions and while interacting with a downstream wind turbine. SNL researchers, in collaboration with National Renewable Energy Laboratory (NREL) researchers, installed a customized LIDAR system created by the Technical University of Denmark (DTU) in one of the SWiFT wind turbines (Figure 1) and operated that turbine with intentional yaw-versus-winddirection misalignment to study the behavior of the turbine wake under numerous combinations of atmospheric conditions and turbinemore » yaw offsets. The DTU-customized LIDAR provided detailed measurements of the wake’s shape and location at many distances downwind of the turbine (Figure 2). These measurements will benefit wind energy researchers looking to understand wind turbine wake behavior and improve modeling and simulation of wake dynamics, including the “wake steering” affect that is observed when turbine yaw offset is controlled. During the test campaign, two SWiFT wind turbines were operated at the same time to observe the influence of the turbines on each other as the wake of the upwind turbine was observed sweeping over and interacting with the downwind turbine.« less

Curcumin-β-cyclodextrin inclusion complex: stability, solubility, characterisation by FT-IR, FT-Raman, X-ray diffraction and photoacoustic spectroscopy, and food application.

PubMed

Mangolim, Camila Sampaio; Moriwaki, Cristiane; Nogueira, Ana Claudia; Sato, Francielle; Baesso, Mauro Luciano; Neto, Antônio Medina; Matioli, Graciette

2014-06-15

Curcumin was complexed with β-CD using co-precipitation, freeze-drying and solvent evaporation methods. Co-precipitation enabled complex formation, as indicated by the FT-IR and FT-Raman techniques via the shifts in the peaks that were assigned to the aromatic rings of curcumin. In addition, photoacoustic spectroscopy and X-ray diffraction, with the disappearance of the band related to aromatic rings, by Gaussian fitting, and modifications in the spectral lines, respectively, also suggested complex formation. The possible complexation had an efficiency of 74% and increased the solubility of the pure colourant 31-fold. Curcumin-β-CD complex exhibited a sunlight stability 18% higher than the pure colourant. This material was stable to pH variations and storage at -15 and 4°C. With an isothermal heating at 100 and 150°C for 2h, the material exhibited a colour retention of approximately 99%. The application of curcumin-β-CD complex in vanilla ice creams intensified the colour of the products and produced a great sensorial acceptance. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

CRISPR/Cas9-mediated targeted mutagenesis of GmFT2a delays flowering time in soya bean.

PubMed

Cai, Yupeng; Chen, Li; Liu, Xiujie; Guo, Chen; Sun, Shi; Wu, Cunxiang; Jiang, Bingjun; Han, Tianfu; Hou, Wensheng

2018-01-01

Flowering is an indication of the transition from vegetative growth to reproductive growth and has considerable effects on the life cycle of soya bean (Glycine max). In this study, we employed the CRISPR/Cas9 system to specifically induce targeted mutagenesis of GmFT2a, an integrator in the photoperiod flowering pathway in soya bean. The soya bean cultivar Jack was transformed with three sgRNA/Cas9 vectors targeting different sites of endogenous GmFT2a via Agrobacterium tumefaciens-mediated transformation. Site-directed mutations were observed at all targeted sites by DNA sequencing analysis. T1-generation soya bean plants homozygous for null alleles of GmFT2a frameshift mutated by a 1-bp insertion or short deletion exhibited late flowering under natural conditions (summer) in Beijing, China (N39°58', E116°20'). We also found that the targeted mutagenesis was stably heritable in the following T2 generation, and the homozygous GmFT2a mutants exhibited late flowering under both long-day and short-day conditions. We identified some 'transgene-clean' soya bean plants that were homozygous for null alleles of endogenous GmFT2a and without any transgenic element from the T1 and T2 generations. These 'transgene-clean' mutants of GmFT2a may provide materials for more in-depth research of GmFT2a functions and the molecular mechanism of photoperiod responses in soya bean. They will also contribute to soya bean breeding and regional introduction. © 2017 The Authors. Plant Biotechnology Journal published by Society for Experimental Biology and The Association of Applied Biologists and John Wiley & Sons Ltd.

Spectroscopic (FT-IR, FT-Raman) and quantum mechanical studies of 3t-pentyl-2r,6c-diphenylpiperidin-4-one thiosemicarbazone

NASA Astrophysics Data System (ADS)

Savithiri, S.; Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.; Bharanidharan, S.; Saleem, H.

2015-02-01

In this study, the molecular structure and vibrational spectra of 3t-pentyl2r,6c-diphenylpiperidin-4-one thiosemicarbazone (PDPOTSC) were studied. The ground-state molecular geometry was ascertained by using the density functional theory (DFT)/B3LYP method using 6-31++G(d,p) as a basis set. The vibrational (FT-IR and FT-Raman) spectra of PDPOTSC were computed using DFT/B3LYP and HF methods with 6-31++G(d,p) basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED ⩾ 10%) of the vibrational modes, calculated with scaled quantum mechanics (SQM) methods PQS program. The electrical dipole moment (μ) and first hyperpolarizability (βo) values have been computed using DFT/B3LYP and HF methods. The calculated result (βo) shows that the title molecule might have nonlinear optical (NLO) behavior. Atomic charges of C, N, S and molecular electrostatic potential (MEP) were calculated using B3LYP/6-31G++(d,p). The HOMO-LUMO energies were calculated and natural bonding orbital (NBO) analysis has also been carried out.

Experimental and theoretical studies of (FT-IR, FT-Raman, UV-Visible and DFT) 4-(6-methoxynaphthalen-2-yl) butan-2-one.

PubMed

Govindasamy, P; Gunasekaran, S

2015-01-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-50 cm(-1) and 4000-450 cm(-1) respectively for 4-(6-methoxynaphthalen-2-yl) butan-2-one (abbreviated as 4MNBO) molecule. Theoretical calculations were performed by density functional theory (DFT/B3LYP) method using 6-311G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and calculated wavenumber value of most of the fundamentals were very small. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The UV-Vis spectrum was recorded in the methanol solution. The energy, wavelength and oscillator's strength were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Thermodynamic properties of 4MNBO at different temperature have been calculated. The molecular electrostatic potential surface (MESP) and Frontier molecular orbital's (FMO's) analysis were investigated using theoretical calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

Environmental responses of the FT/TFL1 gene family and their involvement in flower induction in Fragaria × ananassa.

PubMed

Nakano, Yoshihiro; Higuchi, Yohei; Yoshida, Yuichi; Hisamatsu, Tamotsu

2015-04-01

Flowering time control is important for fruit production in Fragaria × ananassa. The flowering inhibition pathway has been extensively elucidated in the woodland strawberry, Fragaria vesca, whereas the factors involved in its promotion remain unclear. In this study, we investigated the environmental responses of F. × ananassa FT and TFL1-like genes, which are considered key floral promoters and repressors in many plants, respectively. A putative floral promoter, FaFT3, was up-regulated in the shoot tip under short-day and/or low growth temperature, in accordance with the result that these treatments promoted flowering. FaFT3 mRNA accumulated before induction of a floral meristem identity gene, FaAP1. FaFT2, a counterpart of FvFT2, expressed in the flower bud of F. vesca, was not induced in the shoot tip differentiating sepal or stamen, suggesting that this gene works at a later stage than stamen formation. In F. vesca, FvFT1 transmits the long-day signal perceived in the leaves to the shoot tip, and induces the potent floral inhibitor FvTFL1. FaFT1 was expressed in the leaves under long-day conditions in F. × ananassa. Expression of FaTFL1 was higher in the shoot tip under long-day than short-day conditions. Independent of day-length, FaTFL1 expression was higher under high temperature than low temperature conditions. These results suggest that FaFT3 induction by short-day or low temperature stimuli is a key step for flowering initiation. As in F. vesca, F. × ananassa floral inhibition pathways depend on FaTFL1 regulation by day-length via FaFT1, and by temperature. Copyright © 2015 Elsevier GmbH. All rights reserved.

The Vaccinium corymbosum FLOWERING LOCUS T-like gene (VcFT): a flowering activator reverses photoperiodic and chilling requirements in blueberry.

PubMed

Song, Guo-qing; Walworth, Aaron; Zhao, Dongyan; Jiang, Ning; Hancock, James F

2013-11-01

The blueberry FLOWERING LOCUS T ( FT )-like gene ( VcFT ) cloned from the cDNA of a tetraploid, northern highbush blueberry ( Vaccinium corymbosum L.) is able to reverse the photoperiodic and chilling requirements and drive early and continuous flowering. Blueberry is a woody perennial bush with a longer juvenile period than annual crops, requiring vernalization to flower normally. Few studies have been reported on the molecular mechanism of flowering in blueberry or other woody plants. Because FLOWERING LOCUS T (FT) from Arabidopsis thaliana plays a multifaceted role in generating mobile molecular signals to regulate plant flowering time, isolation and functional analysis of the blueberry (Vaccinium corymbosum L.) FT-like gene (VcFT) will facilitate the elucidation of molecular mechanisms of flowering in woody plants. Based on EST sequences, a 525-bpVcFT was identified and cloned from the cDNA of a tetraploid, northern highbush blueberry cultivar, Bluecrop. Ectopic expression of 35S:VcFT in tobacco induced flowering an average of 28 days earlier than wild-type plants. Expression of the 35S:VcFT in the blueberry cultivar Aurora resulted in an extremely early flowering phenotype, which flowered not only during in vitro culture, a growth stage when nontransgenic shoots had not yet flowered, but also in 6-10-week old, soil-grown transgenic plants, in contrast to the fact that at least 1 year and 800 chilling hours are required for the appearance of the first flower of both nontransgenic 'Aurora' and transgenic controls with the gusA. These results demonstrate that the VcFT is a functional floral activator and overexpression of the VcFT is able to reverse the photoperiodic and chilling requirements and drive early and continuous flowering.

Stress and salicylic acid induce the expression of PnFT2 in the regulation of the stress-induced flowering of Pharbitis nil.

PubMed

Yamada, Mizuki; Takeno, Kiyotoshi

2014-02-15

Poor nutrition and low temperature stress treatments induced flowering in the Japanese morning glory Pharbitis nil (synonym Ipomoea nil) cv. Violet. The expression of PnFT2, one of two homologs of the floral pathway integrator gene FLOWERING LOCUS T (FT), was induced by stress, whereas the expression of both PnFT1 and PnFT2 was induced by a short-day treatment. There was no positive correlation between the flowering response and the homolog expression of another floral pathway integrator gene SUPPRESSOR OF OVEREXPRESSION OF CO1 and genes upstream of PnFT, such as CONSTANS. In another cultivar, Tendan, flowering and PnFT2 expression were not induced by poor nutrition stress. Aminooxyacetic acid (AOA), a phenylalanine ammonia-lyase inhibitor, inhibited the flowering and PnFT2 expression induced by poor nutrition stress in Violet. Salicylic acid (SA) eliminated the inhibitory effects of AOA. SA enhanced PnFT2 expression under the poor nutrition stress but not under non-stress conditions. These results suggest that SA induces PnFT2 expression, which in turn induces flowering; SA on its own, however, may not be sufficient for induction. Copyright © 2013 Elsevier GmbH. All rights reserved.

14. TIOGA ROAD VIEW NEAR TOULUMNE LODGE AT 9000 FT ...

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

14. TIOGA ROAD VIEW NEAR TOULUMNE LODGE AT 9000 FT ELEVATION MARKER. UNICORN PEAK CENTER DISTANCE. LOOKING SW. GIS: N-37 52.52.6 / W-119 19 31.4 - Tioga Road, Between Crane Flat & Tioga Pass, Yosemite Village, Mariposa County, CA

Rapid detection of talcum powder in tea using FT-IR spectroscopy coupled with chemometrics

PubMed Central

Li, Xiaoli; Zhang, Yuying; He, Yong

2016-01-01

This paper investigated the feasibility of Fourier transform infrared transmission (FT-IR) spectroscopy to detect talcum powder illegally added in tea based on chemometric methods. Firstly, 210 samples of tea powder with 13 dose levels of talcum powder were prepared for FT-IR spectra acquirement. In order to highlight the slight variations in FT-IR spectra, smoothing, normalize and standard normal variate (SNV) were employed to preprocess the raw spectra. Among them, SNV preprocessing had the best performance with high correlation of prediction (RP = 0.948) and low root mean square error of prediction (RMSEP = 0.108) of partial least squares (PLS) model. Then 18 characteristic wavenumbers were selected based on a hybrid of backward interval partial least squares (biPLS) regression, competitive adaptive reweighted sampling (CARS) algorithm and successive projections algorithm (SPA). These characteristic wavenumbers only accounted for 0.64% of the full wavenumbers. Following that, 18 characteristic wavenumbers were used to build linear and nonlinear determination models by PLS regression and extreme learning machine (ELM), respectively. The optimal model with RP = 0.963 and RMSEP = 0.137 was achieved by ELM algorithm. These results demonstrated that FT-IR spectroscopy with chemometrics could be used successfully to detect talcum powder in tea. PMID:27468701

Thermal stability of chemically bonded phases on silica gel by photoacoustic FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Kierys, A.; Pasieczna, S.; Ryczkowski, J.; Goworek, J.

2006-11-01

The temperature resistance of chemically bonded phases on commercial silica gel, LiChrosorb RP 2, RP 8, RP 18 and unmodified Si 60 were tested at different temperatures by photoacoustic FT-IR spectroscopy. The surface characteristics and possible degradation of hydrocarbon phase at higher temperatures were investigated by means of FT-IR/PAS technique. For a series of investigated samples heated up to 423 K, the FT-IR/PAS spectra are similar to those for initial silica samples. The most characteristic band for alkyl modified silica gel, i.e., RP 2, RP 8, and RP 18 was observed between 3200 cm-1 to 2800 cm-1 corresponding to various hydrocarbon species. The bands at 3745 cm-1, 3650 cm-1, and 3430 cm-1 observed in the photoacoustic FT-IR spectra may be ascribed to isolated silanol groups (Si-OH), geminal groups (Si-(OH)2) and hydrogen-bonded Si-OH groups, respectively. For all samples the intensity of the broad band in the region 3800 cm-1 to 3200 cm-1 decreases with the increasing temperature. The additional peak at 3745 cm-1 for chemically bonded long hydrocarbon chain, i.e., C18 and C8 after thermal treatment at 573 K is observed.

The Acceleration of the Barycenter of Solar System Obtained from VLBI Observations and Its Impact on the ICRS

NASA Astrophysics Data System (ADS)

Xu, M. H.

2016-03-01

Since 1998 January 1, instead of the traditional stellar reference system, the International Celestial Reference System (ICRS) has been realized by an ensemble of extragalactic radio sources that are located at hundreds of millions of light years away (if we accept their cosmological distances), so that the reference frame realized by extragalactic radio sources is assumed to be space-fixed. The acceleration of the barycenter of solar system (SSB), which is the origin of the ICRS, gives rise to a systematical variation in the directions of the observed radio sources. This phenomenon is called the secular aberration drift. As a result, the extragalactic reference frame fixed to the space provides a reference standard for detecting the secular aberration drift, and the acceleration of the barycenter with respect to the space can be determined from the observations of extragalactic radio sources. In this thesis, we aim to determine the acceleration of the SSB from astrometric and geodetic observations obtained by Very Long Baseline Interferometry (VLBI), which is a technique using the telescopes globally distributed on the Earth to observe a radio source simultaneously, and with the capacity of angular positioning for compact radio sources at 10-milliarcsecond level. The method of the global solution, which allows the acceleration vector to be estimated as a global parameter in the data analysis, is developed. Through the formal error given by the solution, this method shows directly the VLBI observations' capability to constrain the acceleration of the SSB, and demonstrates the significance level of the result. In the next step, the impact of the acceleration on the ICRS is studied in order to obtain the correction of the celestial reference frame (CRF) orientation. This thesis begins with the basic background and the general frame of this work. A brief review of the realization of the CRF based on the kinematical and the dynamical methods is presented in Chapter 2

Analysis of conifer FLOWERING LOCUS T/TERMINAL FLOWER1-like genes provides evidence for dramatic biochemical evolution in the angiosperm FT lineage.

PubMed

Klintenäs, Maria; Pin, Pierre A; Benlloch, Reyes; Ingvarsson, Pär K; Nilsson, Ove

2012-12-01

In flowering plants, homologs of the Arabidopsis phosphatidylethanolamine-binding protein (PEBP) FLOWERING LOCUS T (FT) are key components in controlling flowering time. We show here that, although FT homologs are found in all angiosperms with completed genome sequences, there is no evidence to date that FT-like genes exist in other groups of plants. Through phylogeny reconstructions and heterologous expression, we examined the biochemical function of the Picea (spruces) and Pinus (pines) PEBP families - two gymnosperm taxa phylogenetically distant from the angiosperms. We have defined a lineage of gymnosperm PEBP genes, termed the FT/TERMINAL FLOWER1 (TFL1)-like genes, that share sequence characteristics with both the angiosperm FT- and TFL1-like clades. When expressed in Arabidopsis, FT/TFL1-like genes repressed flowering, indicating that the proteins are biochemically more similar to the angiosperm TFL1-like proteins than to the FT-like proteins. This suggests that the regulation of the vegetative-to-reproductive switch might differ in gymnosperms compared with angiosperms. Molecular evolution studies suggest that plasticity at exon 4 contributes to the divergence of FT-like function in floral promotion. In addition, the presence of FT-like genes in basal angiosperms indicates that the FT-like function emerged at an early stage during the evolution of flowering plants as a means to regulate flowering time. © 2012 The Authors. New Phytologist © 2012 New Phytologist Trust.

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

Determination of cellulose I crystallinity by FT-Raman spectroscopy

Treesearch

Umesh P. Agarwal; Richard S. Reiner; Sally A. Ralph

2009-01-01

Two new methods based on FT-Raman spectroscopy, one simple, based on band intensity ratio, and the other, using a partial least-squares (PLS) regression model, are proposed to determine cellulose I crystallinity. In the simple method, crystallinity in semicrystalline cellulose I samples was determined based on univariate regression that was first developed using the...

X-15 Model in 7x10 FT Tunnel

NASA Image and Video Library

1959-09-17

X-15 launch techniques were investigated using on-twentieth scale models mounted in the 7x10 FT Tunnel. -- Photograph published in Winds of Change, 75th Anniversary NASA publication (page 67), by James Schultz. -- Photograph also published in Sixty Years of Aeronautical Research 1917-1977 - a NASA publication (page 49), by David A. Anderton.

Surface Meteorological Station - SWiFT southwest - METa1 - Reviewed Data