Detection of Posaconazole by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry with Dispersive Liquid-Liquid Microextraction

NASA Astrophysics Data System (ADS)

Lin, Sheng-Yu; Chen, Pin-Shiuan; Chang, Sarah Y.

2015-03-01

A simple, rapid, and sensitive method for the detection of posaconazole using dispersive liquid-liquid microextraction (DLLME) coupled to surface-assisted laser desorption/ionization mass spectrometric detection (SALDI/MS) was developed. After the DLLME, posaconazole was detected using SALDI/MS with colloidal gold and α-cyano-4-hydroxycinnamic acid (CHCA) as the co-matrix. Under optimal extraction and detection conditions, the calibration curve, which ranged from 1.0 to 100.0 nM for posaconazole, was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 0.3 nM for posaconazole. This novel method was successfully applied to the determination of posaconazole in human urine samples.

Photoionization of environmentally polluting aromatic chlorides and nitrides on the water surface by laser and synchrotron radiations.

PubMed

Sato, Miki; Maeda, Yuki; Ishioka, Toshio; Harata, Akira

2017-11-20

The detection limits and photoionization thresholds of polycyclic aromatic hydrocarbons and their chlorides and nitrides on the water surface are examined using laser two-photon ionization and single-photon ionization, respectively. The laser two-photon ionization methods are highly surface-selective, with a high sensitivity for aromatic hydrocarbons tending to accumulate on the water surface in the natural environment due to their highly hydrophobic nature. The dependence of the detection limits of target aromatic molecules on their physicochemical properties (photoionization thresholds relating to excess energy, molar absorptivity, and the octanol-water partition coefficient) is discussed. The detection limit clearly depends on the product of the octanol-water partition coefficient and molar absorptivity, and no clear dependence was found on excess energy. The detection limits of laser two-photon ionization for these types of molecules on the water surface are formulated.

Method for the depth corrected detection of ionizing events from a co-planar grids sensor

DOEpatents

De Geronimo, Gianluigi [Syosset, NY; Bolotnikov, Aleksey E [South Setauket, NY; Carini, Gabriella [Port Jefferson, NY

2009-05-12

A method for the detection of ionizing events utilizing a co-planar grids sensor comprising a semiconductor substrate, cathode electrode, collecting grid and non-collecting grid. The semiconductor substrate is sensitive to ionizing radiation. A voltage less than 0 Volts is applied to the cathode electrode. A voltage greater than the voltage applied to the cathode is applied to the non-collecting grid. A voltage greater than the voltage applied to the non-collecting grid is applied to the collecting grid. The collecting grid and the non-collecting grid are summed and subtracted creating a sum and difference respectively. The difference and sum are divided creating a ratio. A gain coefficient factor for each depth (distance between the ionizing event and the collecting grid) is determined, whereby the difference between the collecting electrode and the non-collecting electrode multiplied by the corresponding gain coefficient is the depth corrected energy of an ionizing event. Therefore, the energy of each ionizing event is the difference between the collecting grid and the non-collecting grid multiplied by the corresponding gain coefficient. The depth of the ionizing event can also be determined from the ratio.

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

PubMed

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

2015-05-19

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

Desalting by crystallization: detection of attomole biomolecules in picoliter buffers by mass spectrometry.

PubMed

Gong, Xiaoyun; Xiong, Xingchuang; Wang, Song; Li, Yanyan; Zhang, Sichun; Fang, Xiang; Zhang, Xinrong

2015-10-06

Sensitive detection of biomolecules in small-volume samples by mass spectrometry is, in many cases, challenging because of the use of buffers to maintain the biological activities of proteins and cells. Here, we report a highly effective desalting method for picoliter samples. It was based on the spontaneous separation of biomolecules from salts during crystallization of the salts. After desalting, the biomolecules were deposited in the tip of the quartz pipet because of the evaporation of the solvent. Subsequent detection of the separated biomolecules was achieved using solvent assisted electric field induced desorption/ionization (SAEFIDI) coupled with mass spectrometry. It allowed for direct desorption/ionization of the biomolecules in situ from the tip of the pipet. The organic component in the assistant solvent inhibited the desorption/ionization of salts, thus assured successful detection of biomolecules. Proteins and peptides down to 50 amol were successfully detected using our method even if there were 3 × 10(5) folds more amount of salts in the sample. The concentration and ion species of the salts had little influence on the detection results.

Selective and comprehensive analysis of organohalogen compounds by GC × GC-HRTofMS and MS/MS.

PubMed

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

2018-03-01

Thousands of organohalogen compounds, including hazardous chemicals such as polychlorinated biphenyls (PCBs) and other persistent organic pollutants (POPs), were selectively and simultaneously detected and identified with simple, or no, purification from environmental sample extracts by using several advanced methods. The methods used were software extraction from two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (GC × GC-HRTofMS) data, measurement by negative chemical ionization with HRTofMS, and neutral loss scanning (NLS) with GC × GC-MS/MS. Global and selective detection of organochlorines and bromines in environmental samples such as sediments and fly ash was achieved by NLS using GC × GC-MS/MS (QQQ), with the expected losses of 35 Cl and 79 Br. We confirmed that negative chemical ionization was effective for sensitive and selective ionization of organohalogens, even using GC × GC-HRTofMS. The 2D total ion chromatograms obtained by using negative chemical ionization and selective extraction of organohalogens using original software from data measured by electron impact ionization were very similar; the software thus functioned well to extract organohalogens. Combining measurements made by using these different methods will help to detect organohalogens selectively and globally. However, to compare the data obtained by individual measurements, the retention times of the peaks on the 2D chromatograms need to match.

A laser-based FAIMS detector for detection of ultra-low concentrations of explosives

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.; Sychev, Alexey V.; Tugaenko, Anton V.; Bogdanov, Artem S.; Perederiy, Anatoly N.; Spitsyn, Eugene M.

2014-06-01

A non-contact method for analyzing of explosives traces from surfaces was developed. The method is based on the laser desorption of analyzed molecules from the surveyed surfaces followed by the laser ionization of air sample combined with the field asymmetric ion mobility spectrometry (FAIMS). The pulsed radiation of the fourth harmonic of a portable GSGG: Cr3+ :Nd3+ laser (λ = 266 nm) is used. The laser desorption FAIMS analyzer have been developed. The detection limit of the analyzer equals 40 pg for TNT. The results of detection of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylenetetranitramine (HMX) are presented. It is shown that laser desorption of nitro-compounds from metals is accompanied by their surface decomposition. A method for detecting and analyzing of small concentrations of explosives in air based on the laser ionization and the FAIMS was developed. The method includes a highly efficient multipass optical scheme of the intracavity fourthharmonic generation of pulsed laser radiation (λ = 266 nm) and the field asymmetric ion mobility (FAIM) spectrometer disposed within a resonator. The ions formation and detection proceed inside a resonant cavity. The laser ion source based on the multi-passage of radiation at λ = 266 nm through the ionization region was elaborated. On the basis of the method the laser FAIMS analyzer has been created. The analyzer provides efficient detection of low concentrations of nitro-compounds in air and shows a detection limit of 10-14 - 10-15 g/cm3 both for RDX and TNT.

High-resolution metabolomics assessment of military personnel: Evaluating analytical strategies for chemical detection

PubMed Central

Liu, Ken H.; Walker, Douglas I.; Uppal, Karan; Tran, ViLinh; Rohrbeck, Patricia; Mallon, Timothy M.; Jones, Dean P.

2016-01-01

Objective To maximize detection of serum metabolites with high-resolution metabolomics (HRM). Methods Department of Defense Serum Repository (DoDSR) samples were analyzed using ultra-high resolution mass spectrometry with three complementary chromatographic phases and four ionization modes. Chemical coverage was evaluated by number of ions detected and accurate mass matches to a human metabolomics database. Results Individual HRM platforms provided accurate mass matches for up to 58% of the KEGG metabolite database. Combining two analytical methods increased matches to 72%, and included metabolites in most major human metabolic pathways and chemical classes. Detection and feature quality varied by analytical configuration. Conclusions Dual chromatography HRM with positive and negative electrospray ionization provides an effective generalized method for metabolic assessment of military personnel. PMID:27501105

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

PubMed

Viidanoja, Jyrki

2015-02-27

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

Determination of Macrolide Antibiotics Using Dispersive Liquid-Liquid Microextraction Followed by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Chen, Kuan-Yu; Yang, Thomas C.; Chang, Sarah Y.

2012-06-01

A novel method for the determination of macrolide antibiotics using dispersive liquid-liquid microextraction coupled to surface-assisted laser desorption/ionization mass spectrometric detection was developed. Acetone and dichloromethane were used as the disperser solvent and extraction solvent, respectively. A mixture of extraction solvent and disperser solvent were rapidly injected into a 1.0 mL aqueous sample to form a cloudy solution. After the extraction, macrolide antibiotics were detected using surface-assisted laser desorption/ionization mass spectrometry (SALDI/MS) with colloidal silver as the matrix. Under optimum conditions, the limits of detection (LODs) at a signal-to-noise ratio of 3 were 2, 3, 3, and 2 nM for erythromycin (ERY), spiramycin (SPI), tilmicosin (TILM), and tylosin (TYL), respectively. This developed method was successfully applied to the determination of macrolide antibiotics in human urine samples.

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

PubMed

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

2015-07-01

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

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

PubMed

Libong, Danielle; Bouchonnet, Stéphane; Ricordel, Ivan

2003-01-01

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

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

NASA Astrophysics Data System (ADS)

Guenther, Sabine; Schäfer, Karl-Christian; Balog, Júlia; Dénes, Júlia; Majoros, Tamás; Albrecht, Katalin; Tóth, Miklós; Spengler, Bernhard; Takáts, Zoltán

2011-11-01

The feasibility of electrospray (ES) ionization of aerosols generated by electrosurgical disintegration methods was investigated. Although electrosurgery itself was demonstrated to produce gaseous ions, post-ionization methods were implemented to enhance the ion yield, especially in those cases when the ion current produced by the applied electrosurgical method is not sufficient for MS analysis. Post-ionization was implemented by mounting an ES emitter onto a Venturi pump, which is used for ion transfer. The effect of various parameters including geometry, high voltage setting, flow parameters, and solvent composition was investigated in detail. Experimental setups were optimized accordingly. ES post-ionization was found to yield spectra similar to those obtained by the REIMS technique, featuring predominantly lipid-type species. Signal enhancement was 20- to 50-fold compared with electrosurgical disintegration in positive mode, while no improvement was observed in negative mode. ES post-ionization was also demonstrated to allow the detection of non-lipid type species in the electrosurgical aerosol, including drug molecules. Since the tissue specificity of the MS data was preserved in the ES post-ionization setup, feasibility of tissue identification was demonstrated using different electrosurgical methods.

Detection of strep throat causing bacterium directly from medical swabs by touch spray-mass spectrometry.

PubMed

Jarmusch, Alan K; Pirro, Valentina; Kerian, Kevin S; Cooks, R Graham

2014-10-07

Strep throat causing Streptococcus pyogenes was detected in vitro and in simulated clinical samples by performing touch spray ionization-mass spectrometry. MS analysis took only seconds to reveal characteristic bacterial and human lipids. Medical swabs were used as the substrate for ambient ionization. This work constitutes the initial step in developing a non-invasive MS-based test for clinical diagnosis of strep throat. It is limited to the single species, S. pyogenes, which is responsible for the vast majority of cases. The method is complementary to and, with further testing, a potential alternative to current methods of point-of-care detection of S. pyogenes.

Real-time detection of hazardous materials in air

NASA Astrophysics Data System (ADS)

Schechter, Israel; Schroeder, Hartmut; Kompa, Karl L.

1994-03-01

A new detection system has been developed for real-time analysis of organic compounds in ambient air. It is based on multiphoton ionization by an unfocused laser beam in a single parallel-plate device. Thus, the ionization volume can be relatively large. The amount of laser created ions is determined quantitatively from the induced total voltage drop between the biased plates (Q equals (Delta) V(DOT)C). Mass information is obtained from computer analysis of the time-dependent signal. When a KrF laser (5 ev) is used, most of the organic compounds can be ionized in a two-photon process, but none of the standard components of atmospheric air are ionized by this process. Therefore, this instrument may be developed as a `sniffer' for organic materials. The method has been applied for benzene analysis in air. The detection limit is about 10 ppb. With a simple preconcentration technique the detection limit can be decreased to the sub-ppb range. Simple binary mixtures are also resolved.

Ultra-performance liquid chromatography/tandem mass spectrometric quantification of structurally diverse drug mixtures using an ESI-APCI multimode ionization source.

PubMed

Yu, Kate; Di, Li; Kerns, Edward; Li, Susan Q; Alden, Peter; Plumb, Robert S

2007-01-01

We report in this paper an ultra-performance liquid chromatography/tandem mass spectrometric (UPLC(R)/MS/MS) method utilizing an ESI-APCI multimode ionization source to quantify structurally diverse analytes. Eight commercial drugs were used as test compounds. Each LC injection was completed in 1 min using a UPLC system coupled with MS/MS multiple reaction monitoring (MRM) detection. Results from three separate sets of experiments are reported. In the first set of experiments, the eight test compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes (ESI+, ESI-, APCI-, and APCI+) during an LC run. Approximately 8-10 data points were collected across each LC peak. This was insufficient for a quantitative analysis. In the second set of experiments, four compounds were analyzed as a single mixture. The mass spectrometer was switching rapidly among four ionization modes during an LC run. Approximately 15 data points were obtained for each LC peak. Quantification results were obtained with a limit of detection (LOD) as low as 0.01 ng/mL. For the third set of experiments, the eight test compounds were analyzed as a batch. During each LC injection, a single compound was analyzed. The mass spectrometer was detecting at a particular ionization mode during each LC injection. More than 20 data points were obtained for each LC peak. Quantification results were also obtained. This single-compound analytical method was applied to a microsomal stability test. Compared with a typical HPLC method currently used for the microsomal stability test, the injection-to-injection cycle time was reduced to 1.5 min (UPLC method) from 3.5 min (HPLC method). The microsome stability results were comparable with those obtained by traditional HPLC/MS/MS.

Apparatus and method for the simultaneous detection of neutrons and ionizing electromagnetic radiation

DOEpatents

Bell, Zane W.

2000-01-01

A sensor for simultaneously detecting neutrons and ionizing electromagnetic radiation comprising: a sensor for the detection of gamma radiation, the sensor defining a sensing head; the sensor further defining an output end in communication with the sensing head; and an exterior neutron-sensitive material configured to form around the sensing head; wherein the neutron-sensitive material, subsequent to the capture of the neutron, fissions into an alpha-particle and a .sup.7 Li ion that is in a first excited state in a majority of the fissions, the first excited state decaying via the emission of a single gamma ray at 478 keV which can in turn be detected by the sensing head; and wherein the sensing head can also detect the ionizing electromagnetic radiation from an incident radiation field without significant interference from the neutron-sensitive material. A method for simultaneously detecting neutrons and ionizing electromagnetic radiation comprising the steps of: providing a gamma ray sensitive detector comprising a sensing head and an output end; conforming an exterior neutron-sensitive material configured to form around the sensing head of the detector; capturing neutrons by the sensing head causing the neutron-sensitive material to fission into an alpha-particle and a .sup.7 Li ion that is in a first excited state in a majority of the fissions, the state decaying via the emission of a single gamma ray at 478 keV; sensing gamma rays entering the detector through the neutron-sensitive material; and producing an output through a readout device coupled to the output end; wherein the detector provides an output which is proportional to the energy of the absorbed ionizing electromagnetic radiation.

High pressure xenon ionization detector

DOEpatents

Markey, J.K.

1989-11-14

A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

High pressure xenon ionization detector

DOEpatents

Markey, John K.

1989-01-01

A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

Development of methods to monitor ionization modification from dosing vehicles and phospholipids in study samples.

PubMed

Chang, Min; Li, Yongchao; Angeles, Reginald; Khan, Samina; Chen, Lian; Kaplan, Julia; Yang, Liyu

2011-08-01

Two approaches to monitor the matrix effect on ionization in study samples were described. One approach is the addition of multiple reaction monitoring transitions to the bioanalytical methods to monitor the presence of known ionization modification-causing components of the matrix, for example, m/z 184→125 (or m/z 184→184) and m/z 133→89 may be used for phospholipids and polyethylene oxide containing surfactants, respectively. This approach requires no additional equipment and can be readily adapted for most method. The approach detects only the intended interfering compounds and provides little quantitative indication if the matrix effect is within the tolerable range (±15%). The other approach requires the addition of an infusion pump and identifies an appropriate surrogate of the analyte to be infused for the determination of modification on the ionization of the analyte. The second approach detects interferences in the sample regardless of the sources (i.e., dosing vehicle components, co-administrated drugs, their metabolites, phospholipids, plasticizers and endogenous components introduced due to disease stage).

A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

PubMed Central

2009-01-01

Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI) compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA)) and small polar molecules (e.g., jasmonic acid (JA), salicylic acid (SA)) containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the molecules must contain at least one free carboxyl group. PMID:19939243

A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

NASA Astrophysics Data System (ADS)

Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

2011-01-01

A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

Determination of glucosinolates in rapeseed and Thlaspi caerulescens plants by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

PubMed

Tolrà, R P; Alonso, R; Poschenrieder, C; Barceló, D; Barceló, J

2000-08-11

Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry was used to identify glucosinolates in plant extracts. Optimization of the analytical conditions and the determination of the method detection limit was performed using commercial 2-propenylglucosinolate (sinigrin). Optimal values for the following parameters were determined: nebulization pressure, gas temperature, flux of drying gas, capillar voltage, corona current and fragmentor conditions. The method detection limit for sinigrin was 2.85 ng. For validation of the method the glucosinolates in reference material (rapeseed) from the Community Bureau of Reference Materials (BCR) were analyzed. The method was applied for the determination of glucosinolates in Thlaspi caerulescens plants.

Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization.

PubMed

Ovchinnikova, Olga S; Van Berkel, Gary J

2010-06-30

An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

Iron oxide nanomatrix facilitating metal ionization in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Obena, Rofeamor P; Lin, Po-Chiao; Lu, Ying-Wei; Li, I-Che; del Mundo, Florian; Arco, Susan dR; Nuesca, Guillermo M; Lin, Chung-Chen; Chen, Yu-Ju

2011-12-15

The significance and epidemiological effects of metals to life necessitate the development of direct, efficient, and rapid method of analysis. Taking advantage of its simple, fast, and high-throughput features, we present a novel approach to metal ion detection by matrix-functionalized magnetic nanoparticle (matrix@MNP)-assisted MALDI-MS. Utilizing 21 biologically and environmentally relevant metal ion solutions, the performance of core and matrix@MNP against conventional matrixes in MALDI-MS and laser desorption ionization (LDI) MS were systemically tested to evaluate the versatility of matrix@MNP as ionization element. The matrix@MNPs provided 20- to >100-fold enhancement on detection sensitivity of metal ions and unambiguous identification through characteristic isotope patterns and accurate mass (<5 ppm), which may be attributed to its multifunctional role as metal chelator, preconcentrator, absorber, and reservoir of energy. Together with the comparison on the ionization behaviors of various metals having different ionization potentials (IP), we formulated a metal ionization mechanism model, alluding to the role of exciton pooling in matrix@MNP-assisted MALDI-MS. Moreover, the detection of Cu in spiked tap water demonstrated the practicability of this new approach as an efficient and direct alternative tool for fast, sensitive, and accurate determination of trace metal ions in real samples.

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

PubMed Central

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

2015-01-01

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

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

DOEpatents

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

2015-09-01

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

Detection of strep throat causing bacterium directly from medical swabs by touch spray - mass spectrometry

PubMed Central

Jarmusch, Alan K.; Pirro, Valentina; Kerian, Kevin S.; Cooks, Graham

2014-01-01

Strep throat causing Streptococcus pyogenes was detected in vitro and in simulated clinical samples by performing touch spray ionization - mass spectrometry. MS analysis took only seconds to reveal characteristic bacterial and human lipids. Medical swabs were used as the substrate for ambient ionization. This work constitutes the initial step in developing a noninvasive MS-based test for clinical diagnosis of strep throat. It is limited to the single species, S. pyogenes, which is responsible for the vast majority of cases. The method is complementary to and, with further testing, a potential alternative to current methods of point-of-care detection of S. pyogenes. PMID:25102079

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

PubMed

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

2006-11-10

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

The great importance of normalization of LC-MS data for highly-accurate non-targeted metabolomics.

PubMed

Mizuno, Hajime; Ueda, Kazuki; Kobayashi, Yuta; Tsuyama, Naohiro; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

2017-01-01

The non-targeted metabolomics analysis of biological samples is very important to understand biological functions and diseases. LC combined with electrospray ionization-based MS has been a powerful tool and widely used for metabolomic analyses. However, the ionization efficiency of electrospray ionization fluctuates for various unexpected reasons such as matrix effects and intraday variations of the instrument performances. To remove these fluctuations, normalization methods have been developed. Such techniques include increasing the sensitivity, separating co-eluting components and normalizing the ionization efficiencies. Normalization techniques allow simultaneously correcting of the ionization efficiencies of the detected metabolite peaks and achieving quantitative non-targeted metabolomics. In this review paper, we focused on these normalization methods for non-targeted metabolomics by LC-MS. Copyright © 2016 John Wiley & Sons, Ltd.

Method for quantifying NSAIDs and clofibric acid in aqueous samples, lumpfish (Cyclopterus lumpus) roe, and zebrafish (Danio rerio) eleutheroembryos and evaluation of their bioconcentration in zebrafish eleutheroembryos.

PubMed

Molina-Fernandez, N; Perez-Conde, C; Rainieri, S; Sanz-Landaluze, J

2017-04-01

Pharmaceuticals such as nonsteroidal anti-inflammatory drugs (NSAIDs) and lipid regulators are being repeatedly detected at low concentrations (pg · mL -1 -ng · mL -1 ) in the environment. A large fraction of these compounds are ionizable. Ionized compounds show different physico-chemical properties and environmental behavior in comparison to their neutral analogs; as a consequence, the quantification methods currently available, based on the neutral molecules, might not be suitable to detect the corresponding ionized compounds. To overcome this problem, we developed a specific analytical method to quantify NSAIDs and lipid regulators (i.e., ibuprofen, diclofenac, naproxen, and clofibric acid) and their ionized compounds. This method is based on three steps: (1) the extraction of the organic compounds with an organic solvent assisted with an ultrasonic probe, (2) the cleaning of the extracts with a dispersive SPE with C 18 , and (3) the determination of the chemical compounds by GC-MS (prior derivatization of the analytes). We demonstrated that the proposed method can successfully quantify the pharmaceuticals and their ionized compounds in aqueous samples, lumpfish eggs, and zebrafish eleutheroembryos. Additionally, it allows the extraction and the cleanup of extracts from small samples (0.010 g of wet weight in pools of 20 larvae) and complex matrixes (due to high lipid content) and can be used as a basis for bioaccumulation assays performed with zebrafish eleutheroembryos in alternative to OECD test 305.

Utilizing two detectors in the measurement of trichloroacetic acid in human urine by reaction headspace gas chromatography.

PubMed

Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

2018-05-16

A reaction headspace gas chromatography (HS-GC) technique was investigated for quantitatively analyzing trichloroacetic acid in human urine. This method is based on the decomposition reaction of trichloroacetic acid under high-temperature conditions. The carbon dioxide and chloroform formed from the decomposition reaction can be respectively detected by the thermal conductivity detection HS-GC and flame ionization detection HS-GC. The reaction can be completed in 60 min at 90°C. This method was used to quantify 25 different human urine samples, which had a range of trichloroacetic acid from 0.52 to 3.47 mg/L. It also utilized two different detectors, the thermal conductivity detector and the flame ionization detector. The present reaction HS-GC method is accurate, reliable and well suitable for batch detection of trichloroacetic acid in human urine. Copyright © 2018 John Wiley & Sons, Ltd.

Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

2015-08-01

A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

High-Resolution Metabolomics Assessment of Military Personnel: Evaluating Analytical Strategies for Chemical Detection.

PubMed

Liu, Ken H; Walker, Douglas I; Uppal, Karan; Tran, ViLinh; Rohrbeck, Patricia; Mallon, Timothy M; Jones, Dean P

2016-08-01

The aim of this study was to maximize detection of serum metabolites with high-resolution metabolomics (HRM). Department of Defense Serum Repository (DoDSR) samples were analyzed using ultrahigh resolution mass spectrometry with three complementary chromatographic phases and four ionization modes. Chemical coverage was evaluated by number of ions detected and accurate mass matches to a human metabolomics database. Individual HRM platforms provided accurate mass matches for up to 58% of the KEGG metabolite database. Combining two analytical methods increased matches to 72% and included metabolites in most major human metabolic pathways and chemical classes. Detection and feature quality varied by analytical configuration. Dual chromatography HRM with positive and negative electrospray ionization provides an effective generalized method for metabolic assessment of military personnel.

Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: ionization.

PubMed

Raro, M; Portolés, T; Sancho, J V; Pitarch, E; Hernández, F; Marcos, J; Ventura, R; Gómez, C; Segura, J; Pozo, O J

2014-06-01

The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection of all AAS is currently afforded by the combination of these strategies. Alternative ionization techniques can minimize these drawbacks and help in the implementation of a single method for the detection of AAS. In the present work, a new atmospheric pressure chemical ionization (APCI) source commercialized for gas chromatography coupled to a quadrupole time-of-flight analyzer has been tested to evaluate the ionization of 60 model AAS. Underivatized and trimethylsylil (TMS)-derivatized compounds have been investigated. The use of GC-APCI-MS allowed for the ionization of all AAS assayed irrespective of their structure. The presence of water in the source as modifier promoted the formation of protonated molecules ([M+H](+)), becoming the base peak of the spectrum for the majority of studied compounds. Under these conditions, [M+H](+), [M+H-H2O](+) and [M+H-2·H2O](+) for underivatized AAS and [M+H](+), [M+H-TMSOH](+) and [M+H-2·TMSOH](+) for TMS-derivatized AAS were observed as main ions in the spectra. The formed ions preserve the intact steroid skeleton, and, therefore, they might be used as specific precursors in MS/MS-based methods. Additionally, a relationship between the relative abundance of these ions and the AAS structure has been established. This relationship might be useful in the structural elucidation of unknown metabolites. Copyright © 2014 John Wiley & Sons, Ltd.

Laser Ablation-Aerosol Mass Spectrometry-Chemical Ionization Mass Spectrometry for Ambient Surface Imaging

DOE PAGES

Berry, Jennifer L.; Day, Douglas A.; Elseberg, Tim; ...

2018-02-20

Mass spectrometry imaging is becoming an increasingly common analytical technique due to its ability to provide spatially resolved chemical information. In this paper, we report a novel imaging approach combining laser ablation with two mass spectrometric techniques, aerosol mass spectrometry and chemical ionization mass spectrometry, separately and in parallel. Both mass spectrometric methods provide the fast response, rapid data acquisition, low detection limits, and high-resolution peak separation desirable for imaging complex samples. Additionally, the two techniques provide complementary information with aerosol mass spectrometry providing near universal detection of all aerosol molecules and chemical ionization mass spectrometry with a heated inletmore » providing molecular-level detail of both gases and aerosols. The two techniques operate with atmospheric pressure interfaces and require no matrix addition for ionization, allowing for samples to be investigated in their native state under ambient pressure conditions. We demonstrate the ability of laser ablation-aerosol mass spectrometry-chemical ionization mass spectrometry (LA-AMS-CIMS) to create 2D images of both standard compounds and complex mixtures. Finally, the results suggest that LA-AMS-CIMS, particularly when combined with advanced data analysis methods, could have broad applications in mass spectrometry imaging applications.« less

Laser Ablation-Aerosol Mass Spectrometry-Chemical Ionization Mass Spectrometry for Ambient Surface Imaging

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

Berry, Jennifer L.; Day, Douglas A.; Elseberg, Tim

Mass spectrometry imaging is becoming an increasingly common analytical technique due to its ability to provide spatially resolved chemical information. In this paper, we report a novel imaging approach combining laser ablation with two mass spectrometric techniques, aerosol mass spectrometry and chemical ionization mass spectrometry, separately and in parallel. Both mass spectrometric methods provide the fast response, rapid data acquisition, low detection limits, and high-resolution peak separation desirable for imaging complex samples. Additionally, the two techniques provide complementary information with aerosol mass spectrometry providing near universal detection of all aerosol molecules and chemical ionization mass spectrometry with a heated inletmore » providing molecular-level detail of both gases and aerosols. The two techniques operate with atmospheric pressure interfaces and require no matrix addition for ionization, allowing for samples to be investigated in their native state under ambient pressure conditions. We demonstrate the ability of laser ablation-aerosol mass spectrometry-chemical ionization mass spectrometry (LA-AMS-CIMS) to create 2D images of both standard compounds and complex mixtures. Finally, the results suggest that LA-AMS-CIMS, particularly when combined with advanced data analysis methods, could have broad applications in mass spectrometry imaging applications.« less

Comparative study of fourteen alkaloids from Uncaria rhynchophylla hooks and leaves using HPLC-diode array detection-atmospheric pressure chemical ionization/MS method.

PubMed

Qu, Jialin; Gong, Tianxing; Ma, Bin; Zhang, Lin; Kano, Yoshihiro; Yuan, Dan

2012-01-01

The purpose of the study is to compare alkaloid profile of Uncaria rhynchophylla hooks and leaves. Ten oxindole alkaloids and four glycosidic indole alkaloids were identified using HPLC-diode array detection (DAD) or LC-atmospheric pressure chemical ionization (APCI)-MS method, and a HPLC-UV method for simultaneous quantification of major alkaloids was validated. The hooks are characterized by high levels of four oxindole alkaloids rhynchophylline (R), isorhynchophylline (IR), corynoxeine (C) and isocorynoxeine (IC), while the leaves contained high level of two glycosidic indole alkaloids vincoside lactam (VL) and strictosidine (S). The presented methods have proven its usefulness in chemical characterization of U. rhynchophylla hooks and leaves.

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

PubMed

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

2012-12-15

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

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

PubMed

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

2012-04-21

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

Mass spectrometry imaging for visualizing organic analytes in food.

PubMed

Handberg, Eric; Chingin, Konstantin; Wang, Nannan; Dai, Ximo; Chen, Huanwen

2015-01-01

The demand for rapid chemical imaging of food products steadily increases. Mass spectrometry (MS) is featured by excellent molecular specificity of analysis and is, therefore, a very attractive method for chemical profiling. MS for food imaging has increased significantly over the past decade, aided by the emergence of various ambient ionization techniques that allow direct and rapid analysis in ambient environment. In this article, the current status of food imaging with MSI is reviewed. The described approaches include matrix-assisted laser desorption/ionization (MALDI), but emphasize desorption atmospheric pressure photoionization (DAPPI), electrospray-assisted laser desorption/ionization (ELDI), probe electrospray ionization (PESI), surface desorption atmospheric pressure chemical ionization (SDAPCI), and laser ablation flowing atmospheric pressure afterglow (LA-FAPA). The methods are compared with regard to spatial resolution; analysis speed and time; limit of detection; and technical aspects. The performance of each method is illustrated with the description of a related application. Specific requirements in food imaging are discussed. © 2014 Wiley Periodicals, Inc.

Method and apparatus for detecting combustion instability in continuous combustion systems

DOEpatents

Benson, Kelly J.; Thornton, Jimmy D.; Richards, George A.; Straub, Douglas L.

2006-08-29

An apparatus and method to sense the onset of combustion stability is presented. An electrode is positioned in a turbine combustion chamber such that the electrode is exposed to gases in the combustion chamber. A control module applies a voltage potential to the electrode and detects a combustion ionization signal and determines if there is an oscillation in the combustion ionization signal indicative of the occurrence of combustion stability or the onset of combustion instability. A second electrode held in a coplanar but spaced apart manner by an insulating member from the electrode provides a combustion ionization signal to the control module when the first electrode fails. The control module broadcasts a notice if the parameters indicate the combustion process is at the onset of combustion instability or broadcasts an alarm signal if the parameters indicate the combustion process is unstable.

Silver-109-based laser desorption/ionization mass spectrometry method for detection and quantification of amino acids.

PubMed

Arendowski, Adrian; Nizioł, Joanna; Ruman, Tomasz

2018-04-01

A new methodology applicable for both high-resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging of amino acids is presented. The matrix-assisted laser desorption ionization-type target containing monoisotopic cationic 109 Ag nanoparticles ( 109 AgNPs) was used for rapid mass spectrometry measurements of 11 amino acids of different chemical properties. Amino acids were directly tested in 100,000-fold concentration change conditions ranging from 100 μg/mL to 1 ng/mL which equates to 50 ng to 500 fg of amino acid per measurement spot. Limit of detection values obtained suggest that presented method/target system is among the fastest and most sensitive ones in laser mass spectrometry. Mass spectrometry imaging of spots of human blood plasma spiked with amino acids showed their surface distribution allowing optimization of quantitative measurements. Copyright © 2018 John Wiley & Sons, Ltd.

Dark matter candidates and methods for detecting them

NASA Technical Reports Server (NTRS)

Raffelt, G. G.

1992-01-01

A number of experiments employing Ge and Si ionization detectors have excluded large regions in the plane of masses and scattering cross-sections for weakly-interacting dark matter (DM) candidates. It is judged that, before a realistic detection experiment for supersymmetric DM candidates can be conducted, significant development efforts will have to be completed for suitable cryogenic or ionization detectors. Pilot experiments have demonstrated the feasibility of axion searches with microwave cavities, but these are at least two orders of magnitude too low in sensitivity.

Parallel Study of HEND, RAD, and DAN Instrument Response to Martian Radiation and Surface Conditions

NASA Technical Reports Server (NTRS)

Martiniez Sierra, Luz Maria; Jun, Insoo; Litvak, Maxim; Sanin, Anton; Mitrofanov, Igor; Zeitlin, Cary

2015-01-01

Nuclear detection methods are being used to understand the radiation environment at Mars. JPL (Jet Propulsion Laboratory) assets on Mars include: Orbiter -2001 Mars Odyssey [High Energy Neutron Detector (HEND)]; Mars Science Laboratory Rover -Curiosity [(Radiation Assessment Detector (RAD); Dynamic Albedo Neutron (DAN))]. Spacecraft have instruments able to detect ionizing and non-ionizing radiation. Instrument response on orbit and on the surface of Mars to space weather and local conditions [is discussed] - Data available at NASA-PDS (Planetary Data System).

Sensitive ion detection device and method for analysis of compounds as vapors in gases

DOEpatents

Denton, M. Bonner; Sperline, Roger P.

2015-09-15

An ion mobility spectrometer (IMS) for the detection of trace gaseous molecular compounds dissolved or suspended in a carrier gas, particularly in ambient air, without preconcentration or the trapping of analyte particles. The IMS of the invention comprises an ionization volume of greater than 5 cm.sup.3 and preferably greater than 100 cm.sup.3. The larger size ionizers of this invention enable analysis of trace (<1 ppb) of sample compounds in the gas phase. To facilitate efficient ion motion through the large volume ionization and reaction regions of the IMS, an electric field gradient can be provided in the ionization region or in both the ionization and reaction regions. The systems can be implemented with radioactive ionization sources, corona discharge ion sources or ions can be formed by photoionization. In specific embodiments, particularly when the sample gas is ambient air, the sample gas is heater prior to entry into the instrument, the instrument is run at temperatures above ambient, and the instrument can be heated by contact with heated sample gas exiting the instrument.

Sensitive ion detection device and method for analysis of compounds as vapors in gases

DOEpatents

Denton, M. Bonner; Sperline, Roger P

2014-02-18

An ion mobility spectrometer (IMS) for the detection of trace gaseous molecular compounds dissolved or suspended in a carrier gas, particularly in ambient air, without preconcentration or the trapping of analyte particles. The IMS of the invention comprises an ionization volume of greater than 5 cm.sup.3 and preferably greater than 100 cm.sup.3. The larger size ionizers of this invention enable analysis of trace (<1 ppb) of sample compounds in the gas phase. To facilitate efficient ion motion through the large volume ionization and reaction regions of the IMS, an electric field gradient can be provided in the ionization region or in both the ionization and reaction regions. The systems can be implemented with radioactive ionization sources, corona discharge ion sources or ions can be formed by photoionization. In specific embodiments, particularly when the sample gas is ambient air, the sample gas is heater prior to entry into the instrument, the instrument is run at temperatures above ambient, and the instrument can be heated by contact with heated sample gas exiting the instrument.

OVERVIEW OF A NEW EPA METHOD: DETERMINATION OF PERCHLORATE IN DRINKING WATER, GROUNDWATER AND HIGH SALINITY WATER BY ION CHROMATOGRAPHY, SUPPRESSED CONDUCTIVITY WITH ELECTROSPRAY IONIZATION MASS SPECTROMETRIC DETECTION

EPA Science Inventory

In this presentation the analytical instrumentation and procedures necessary to qualitatively and quantitatively determine low levels of perchlorate (ClO4-) in drinking waters using ion chromatography with electrolytic conductivity suppression, electrospray ionization mass spec...

A new method for differentiating adducts of common drinking water DBPs from higher molecular weight DBPs in electrospray ionization-mass spectrometry analysis.

PubMed

Zhai, Hongyan; Zhang, Xiangru

2009-05-01

With the presence of bromide in source waters, numerous brominated disinfection byproducts (DBPs) are formed during chlorination. Many of them are polar/highly polar DBPs and thus hard to be detected by gas chromatography mass spectrometry. Electrospray ionization triple quadrupole mass spectrometry (ESI-MS/MS) is reported to be an effective method in finding polar brominated DBPs by setting precursor ion scans of m/z 79 and 81. But as a soft ionization technique, ESI could form adducts of common DBPs, which may complicate ESI-MS/MS spectra and hinder the efforts in finding new brominated DBPs. In this paper, a new method was developed for differentiating adducts of common DBPs from higher molecular weight DBPs. This method was based on the ESI-MS/MS precursor ion scans of the fragments that correspond to the molecular ions of common DBPs. Adducts of common DBPs were selectively detected in the ESI-MS/MS spectra of a simulated drinking water sample. Moreover, the structures of several new brominated DBPs in the sample were tentatively proposed.

Direct antigen detection from immunoprecipitated beads using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry; a new method for immunobeads-mass spectrometry (iMS).

PubMed

Shimada, Takashi; Toyama, Atsuhiko; Aoki, Chikage; Aoki, Yutaka; Tanaka, Koichi; Sato, Taka-Aki

2011-12-15

One-step detection of biological molecules is one of the principal techniques for clinical diagnosis, and the potential of mass spectrometry for biomarker detection has been a promising new approach in the field of medical sciences. We demonstrate here a new and high-sensitivity method that we termed immunobeads-mass spectrometry (iMS), which combines conventional immunoprecipitation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The key feature of iMS is the MS-compatible condition of immunoprecipitation using detergents with a monosaccaride-C8 alkyl chain or a disaccharide-C10 alkyl chain, and the minimized number of steps required for high-sensitivity detection of target peptides in serum or biological fluid. This was achieved by optimizing the wash buffer and subjecting the immunobeads directly to MALDI-TOF MS analysis. Using this method, we showed that 1 fmol of amyloid beta peptide spiked in serum was readily detectable, demonstrating the powerful tool of iMS as a biomarker detection method. Copyright © 2011 John Wiley & Sons, Ltd.

Residual Agar Determination in Bacterial Spores by Electrospray Ionization Mass Spectrometry

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

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

2010-02-15

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

Development of liquid chromatographic methods for the determination of phytosterols in Standard Reference Materials containing saw palmetto.

PubMed

Bedner, Mary; Schantz, Michele M; Sander, Lane C; Sharpless, Katherine E

2008-05-23

Liquid chromatographic (LC) methods using atmospheric pressure chemical ionization/mass spectrometric (APCI-MS) detection were developed for the separation and analysis of the phytosterols campesterol, cycloartenol, lupenone, lupeol, beta-sitosterol, and stigmasterol. Brassicasterol and cholesterol were also included for investigation as internal standards. The methods were used to identify and quantify the phytosterols in each of two Serenoa repens (saw palmetto) Standard Reference Materials (SRMs) developed by the National Institute of Standards and Technology (NIST). Values obtained by LC-MS were compared to those obtained using the more traditional approach of gas chromatography with flame ionization detection. This is the first reported use of LC-MS to determine phytosterols in saw palmetto dietary supplement materials.

Electrical Versus Optical: Comparing Methods for Detecting Terahertz Radiation Using Neon Lamps

NASA Astrophysics Data System (ADS)

Slocombe, L. L.; Lewis, R. A.

2018-05-01

Terahertz radiation impinging on a lit neon tube causes additional ionization of the encapsulated gas. As a result, the electrical current flowing between the electrodes increases and the glow discharge in the tube brightens. These dual phenomena suggest two distinct modes of terahertz sensing. The electrical mode simply involves measuring the electrical current. The optical mode involves monitoring the brightness of the weakly ionized plasma glow discharge. Here, we directly compare the two detection modes under identical experimental conditions. We measure 0.1-THz radiation modulated at frequencies in the range 0.1-10 kHz, for lamp currents in the range 1-10 mA. We find that electrical detection provides a superior signal-to-noise ratio while optical detection has a faster response. Either method serves as the basis of a compact, robust, and inexpensive room-temperature detector of terahertz radiation.

Method and apparatus for time dispersive spectroscopy

DOEpatents

Tarver, III, Edward E.; Siems, William F.

2003-06-17

Methods and apparatus are described for time dispersive spectroscopy. In particular, a modulated flow of ionized molecules of a sample are introduced into a drift region of an ion spectrometer. The ions are subsequently detected by an ion detector to produce an ion detection signal. The ion detection signal can be modulated to obtain a signal useful in assaying the chemical constituents of the sample.

Detection and identification of immobilized low-volatility organophosphates by desorption ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Hagan, Nathan A.; Cornish, Timothy J.; Pilato, Robert S.; van Houten, Kelly A.; Antoine, Miquel D.; Lippa, Timothy P.; Becknell, Alan F.; Demirev, Plamen A.

2008-12-01

Two desorption ionization mass spectrometry (MS) techniques - ultraviolet laser desorption/ionization (LDI) and desorption electrospray ionization (DESI) - have been used to detect and identify low-volatility organophosphates when deposited on surfaces or loaded into the pore volume of porous inorganic or polymeric organic powders. The insecticides malathion and dicrotophos were chosen for this study as simulants of low vapor pressure chemical warfare agents which are inherently difficult to detect directly by traditional methods. Both liquid and powdered forms of either insecticide were readily detected by LDI or DESI MS. LDI MS was performed on a miniaturized home-built time-of-flight (TOF) mass spectrometer and a commercial TOF/TOF instrument. For DESI MS, a home-built ion source was interfaced to a commercial quadrupole ion trap. In LDI, intact molecular ion signatures could be acquired by using an appropriate cationizing agent and powder additive in positive ion mode. Tandem MS was used to confirm the identity of each analyte based on the observed characteristic fragmentation pattern. In DESI, less than 100 pg of the liquid insecticides spotted on clean surfaces were detected, while detection limits for the powder-loaded preparations were lower than 1 [mu]g. The effects of sample surface, salt additives, nanoparticle admixtures, and analyte solubility on the LDI and DESI MS sensitivity have been investigated as well.

Challenges for Detecting Valproic Acid in a Nontargeted Urine Drug Screening Method.

PubMed

Pope, Jeffrey D; Black, Marion J; Drummer, Olaf H; Schneider, Hans G

2017-08-01

Valproic acid (VPA) is a widely prescribed medicine, and acute toxicity is possible. As such, it should be included in any nontargeted urine drug screening method. In many published liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS/MS) methods, VPA is usually measured using a pseudo-multiple reaction monitoring (MRM) transition. We investigate a simple ultra-high-performance liquid chromatography-quadrupole time-of-flight (QTof) approach to detect the presence of VPA with more confidence. Three commercially sourced VPA metabolites were characterized and added to a nontargeted high-resolution MS urine drug screening method. All analyses were performed on a Waters Xevo G2-XS LC-QTof in negative electrospray ionization mode. The mass detector was operated in MS mode, and data were processed with UNIFI software. Sixty-eight patient urine samples, which were previously identified by a well-established gas chromatography-MS method as containing VPA, were analyzed on the Waters Xevo G2-XS LC-QTof, to validate this approach. VPA metabolite standards were characterized, and their detection data were added to the broad drug screening library. VPA metabolites were readily detectable in the urine of patients taking VPA. The inclusion of characterized VPA metabolites provides a simple and reliable method enabling the detection of VPA in nontargeted urine drug screening.

A simple and sensitive quantitation of N,N-dimethyltryptamine by gas chromatography with surface ionization detection.

PubMed

Ishii, A; Seno, H; Suzuki, O; Hattori, H; Kumazawa, T

1997-01-01

A simple and sensitive method for determination of N,N-dimethyltryptamine (DMT) by gas chromatography (GC) with surface ionization detection (SID) is presented. Whole blood or urine, containing DMT and gramine (internal standard), was subjected to solid-phase extraction with a Sep-Pak C18 cartridge before analysis by GC-SID. The calibration curve was linear in the DMT range of 1.25-20 ng/mL blood or urine. The detection limit of DMT was about 0.5 ng/mL (10 pg on-column). The recovery of both DMT and gramine spiked in biological fluids was above 86%.

On the SIMS Ionization Probability of Organic Molecules.

PubMed

Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

2017-06-01

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract .

Development of an apparatus for obtaining molecular beams in the energy range from 2 to 200 eV

NASA Technical Reports Server (NTRS)

Clapier, R.; Devienne, F. M.; Roustan, A.; Roustan, J. C.

1985-01-01

The formation and detection of molecular beams obtained by charge exchange from a low-energy ion source is discussed. Dispersion in energy of the ion source was measured and problems concerning detection of neutral beams were studied. Various methods were used, specifically secondary electron emissivity of a metallic surface and ionization of a gas target with a low ionization voltage. The intensities of neutral beams as low as 10 eV are measured by a tubular electron multiplier and a lock-in amplifier.

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Portable Intelligent Tritium in Air Monitor

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

Purghel, L.; Calin, M.R.; Bartos, D.

2005-07-15

The tritium detection method used for this monitor is original, patented in Romania. The detection unit consists of a single ionization chamber, a special fast preamplifier and a dedicated software associated to the detection unit, for signals processing. Some results concerning the tritium in relative strong gamma-ray fields are presented.

Analysis of volatile compounds by open-air ionization mass spectrometry.

PubMed

Meher, Anil Kumar; Chen, Yu-Chie

2017-05-08

This study demonstrates a simple method for rapid and in situ identification of volatile and endogenous compounds in culinary spice samples through mass spectrometry (MS). This method only requires a holder for solid spice sample (2-3 mm) that is placed close to a mass spectrometer inlet, which is applied with a high voltage. Volatile species responsible for the aroma of the spice samples can be readily detected by the mass spectrometer. Sample pretreatment is not required prior to MS analysis, and no solvent was used during MS analysis. The high voltage applied to the inlet of the mass spectrometer induces the ionization of volatile compounds released from the solid spice samples. Furthermore, moisture in the air also contributes to the ionization of volatile compounds. Dried spices including cinnamon and cloves are used as the model sample to demonstrate this straightforward MS analysis, which can be completed within few seconds. Furthermore, we also demonstrate the suitability of the current method for rapid screening of cinnamon quality through detection of the presence of a hepatotoxic agent, i.e. coumarin. Copyright © 2017 Elsevier B.V. All rights reserved.

High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

PubMed

Hourani, Nadim; Kuhnert, Nikolai

2012-10-15

High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

Assessing the Potential of Metal-Assisted Imaging Mass Spectrometry in Cancer Research.

PubMed

Dufresne, M; Patterson, N H; Lauzon, N; Chaurand, P

2017-01-01

In the last decade, imaging mass spectrometry (IMS) has been the primary tool for biomolecular imaging. While it is possible to map a wide range of biomolecules using matrix-assisted laser desorption/ionization IMS ranging from high-molecular-weight proteins to small metabolites, more often than not only the most abundant easily ionisable species are detected. To better understand complex diseases such as cancer more specific and sensitive methods need to be developed to enable the detection of lower abundance molecules but also molecules that have yet to be imaged by IMS. In recent years, a big shift has occurred in the imaging community from developing wide reaching methods to developing targeted ones which increases sensitivity through the use of more specific sample preparations. This has been primarily marked by the advent of solvent-free matrix deposition methods for polar lipids, chemical derivatization for hormones and metabolites, and the use of alternative ionization agents for neutral lipids. In this chapter, we discuss two of the latest sample preparations which exploit the use of alternative ionization agents to enable the detection of certain classes of neutral lipids along with free fatty acids by high-sensitivity IMS as demonstrated within our lab. © 2017 Elsevier Inc. All rights reserved.

Signal enhancement of carboxylic acids by inclusion with β-cyclodextrin in negative high-voltage-assisted laser desorption ionization mass spectrometry.

PubMed

Ren, Xinxin; Liu, Jia; Zhang, Chengsen; Sun, Jiamu; Luo, Hai

2014-01-15

It is difficult to directly analyze carboxylic acids in complex mixtures by ambient high-voltage-assisted laser desorption ionization mass spectrometry (HALDI-MS) in negative ion mode due to the low ionization efficiency of carboxylic acids. A method for the rapid detection of carboxylic acids in negative HALDI-MS has been developed based on their inclusion with β-cyclodextrin (β-CD). The negative HALDI-MS signal-to-noise ratios (S/Ns) of aliphatic, aromatic and hetero atom-containing carboxylic acids can all be significantly improved by forming 1:1 complexes with β-CD. These complexes are mainly formed by specific inclusion interactions which are verified by their collision-induced dissociation behaviors in comparison with that of their corresponding maltoheptaose complexes. A HALDI-MS/MS method has been successfully developed for the detection of α-lipoic acid in complex cosmetics and ibuprofen in a viscous drug suspension. The negative HALDI-MS S/Ns of carboxylic acids can be improved up to 30 times via forming non-covalent complexes with β-CD. The developed method shows the advantages of being rapid and simple, and is promising for rapid detection of active ingredients in complex samples or fast screening of drugs and cosmetics. Copyright © 2013 John Wiley & Sons, Ltd.

Study of detecting mechanism of carbon nanotubes gas sensor based on multi-stable stochastic resonance model.

PubMed

Jingyi, Zhu

2015-01-01

The detecting mechanism of carbon nanotubes gas sensor based on multi-stable stochastic resonance (MSR) model was studied in this paper. A numerically stimulating model based on MSR was established. And gas-ionizing experiment by adding electronic white noise to induce 1.65 MHz periodic component in the carbon nanotubes gas sensor was performed. It was found that the signal-to-noise ratio (SNR) spectrum displayed 2 maximal values, which accorded to the change of the broken-line potential function. The experimental results of gas-ionizing experiment demonstrated that periodic component of 1.65 MHz had multiple MSR phenomena, which was in accordance with the numerical stimulation results. In this way, the numerical stimulation method provides an innovative method for the detecting mechanism research of carbon nanotubes gas sensor.

Direct identification of prohibited substances in cosmetics and foodstuffs using ambient ionization on a miniature mass spectrometry system.

PubMed

Ma, Qiang; Bai, Hua; Li, Wentao; Wang, Chao; Li, Xinshi; Cooks, R Graham; Ouyang, Zheng

2016-03-17

Significantly simplified work flows were developed for rapid analysis of various types of cosmetic and foodstuff samples by employing a miniature mass spectrometry system and ambient ionization methods. A desktop Mini 12 ion trap mass spectrometer was coupled with paper spray ionization, extraction spray ionization and slug-flow microextraction for direct analysis of Sudan Reds, parabens, antibiotics, steroids, bisphenol and plasticizer from raw samples with complex matrices. Limits of detection as low as 5 μg/kg were obtained for target analytes. On-line derivatization was also implemented for analysis of steroid in cosmetics. The developed methods provide potential analytical possibility for outside-the-lab screening of cosmetics and foodstuff products for the presence of illegal substances. Copyright © 2016 Elsevier B.V. All rights reserved.

A review of the processes by which ultrasound is generated through the interaction of ionizing radiation and irradiated materials: some possible applications.

PubMed

Baily, N A

1992-01-01

The production of acoustic waves following the absorption of energy deposited by ionizing radiation, with a consequent production of localized thermal spikes has been confirmed by a number of papers published in the physics literature. This paper reviews the basic theory and presents most of the supporting experimental data. Some of the experimental methods used and the results obtained are summarized. In addition to the rather straightforward and routine use of acoustic phenomena produced by ionizing radiation for the detection and measurements of such radiation, there are some special applications that appear to be especially attractive for medical physics. Some of these are unique to ionizing radiation in that the amplitude of the ultrasound wave is proportional to the energy deposited in small volumes at localized sites of these interactions, while others derive from methodologies already in use with nonionizing radiations. The detection and measurement of this ultrasonic radiation could possibly lead to methods for the study of such fundamental phenomenon as track structure, precision localization of therapeutic treatment beams, and even the possible imaging of internal anatomic structures to provide on-line portal images.

Use of matrix-assisted laser desorption ionization-time of flight mass spectrometry for caspofungin susceptibility testing of Candida and Aspergillus species.

PubMed

De Carolis, Elena; Vella, Antonietta; Florio, Ada R; Posteraro, Patrizia; Perlin, David S; Sanguinetti, Maurizio; Posteraro, Brunella

2012-07-01

Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was evaluated for testing susceptibility to caspofungin of wild-type and fks mutant isolates of Candida and Aspergillus. Complete essential agreement was observed with the CLSI reference method, with categorical agreement for 94.1% of the Candida isolates tested. Thus, MALDI-TOF MS is a reliable and accurate method to detect fungal isolates with reduced caspofungin susceptibility.

Inkjet-printed gold nanoparticle surfaces for the detection of low molecular weight biomolecules by laser desorption/ionization mass spectrometry.

PubMed

Marsico, Alyssa L M; Creran, Brian; Duncan, Bradley; Elci, S Gokhan; Jiang, Ying; Onasch, Timothy B; Wormhoudt, Joda; Rotello, Vincent M; Vachet, Richard W

2015-11-01

Effective detection of low molecular weight compounds in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is often hindered by matrix interferences in the low m/z region of the mass spectrum. Here, we show that monolayer-protected gold nanoparticles (AuNPs) can serve as alternate matrices for the very sensitive detection of low molecular weight compounds such as amino acids. Amino acids can be detected at low fmol levels with minimal interferences by properly choosing the AuNP deposition method, density, size, and monolayer surface chemistry. By inkjet-printing AuNPs at various densities, we find that AuNP clusters are essential for obtaining the greatest sensitivity. Graphical Abstract ᅟ.

MALDI-MS analysis and theoretical evaluation of olanzapine as a UV laser desorption ionization (LDI) matrix.

PubMed

Musharraf, Syed Ghulam; Ameer, Mariam; Ali, Arslan

2017-01-05

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) being soft ionization technique, has become a method of choice for high-throughput analysis of proteins and peptides. In this study, we have explored the potential of atypical anti-psychotic drug olanzapine (OLZ) as a matrix for MALDI-MS analysis of peptides aided with the theoretical studies. Seven small peptides were employed as target analytes to check performance of olanzapine and compared with conventional MALDI matrix α-cyano-4-hydroxycinnamic acid (HCCA). All peptides were successfully detected when olanzapine was used as a matrix. Moreover, peptides angiotensin Ι and angiotensin ΙΙ were detected with better S/N ratio and resolution with this method as compared to their analysis by HCCA. Computational studies were performed to determine the thermochemical properties of olanzapine in order to further evaluate its similarity to MALDI matrices which were found in good agreement with the data of existing MALDI matrices. Copyright © 2016. Published by Elsevier B.V.

Beyond Naphthenic Acids: Environmental Screening of Water from Natural Sources and the Athabasca Oil Sands Industry Using Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Barrow, Mark P; Peru, Kerry M; Fahlman, Brian; Hewitt, L Mark; Frank, Richard A; Headley, John V

2015-09-01

There is a growing need for environmental screening of natural waters in the Athabasca region of Alberta, Canada, particularly in the differentiation between anthropogenic and naturally-derived organic compounds associated with weathered bitumen deposits. Previous research has focused primarily upon characterization of naphthenic acids in water samples by negative-ion electrospray ionization methods. Atmospheric pressure photoionization is a much less widely used ionization method, but one that affords the possibility of observing low polarity compounds that cannot be readily observed by electrospray ionization. This study describes the first usage of atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (in both positive-ion and negative-ion modes) to characterize and compare extracts of oil sands process water, river water, and groundwater samples from areas associated with oil sands mining activities. When comparing mass spectra previously obtained by electrospray ionization and data acquired by atmospheric pressure photoionization, there can be a doubling of the number of components detected. In addition to polar compounds that have previously been observed, low-polarity, sulfur-containing compounds and hydrocarbons that do not incorporate a heteroatom were detected. These latter components, which are not amenable to electrospray ionization, have potential for screening efforts within monitoring programs of the oil sands.

Determination of Total Petroleum Hydrocarbons in Australian Groundwater Through the Improvised Gas Chromatography-Flame Ionization Detection Technique.

PubMed

Faustorilla, Maria Vilma; Chen, Zuliang; Dharmarajan, Rajarathnam; Naidu, Ravendra

2017-09-01

Assessment of total petroleum hydrocarbons (TPHs) from contaminated sites demands routine and reliable measurement at trace levels. However, the detection limits of these methods need to be improved. This study developed the programmable temperature vaporization-large volume injection (PTV-LVI) method to quantify TPHs through gas chromatography-flame ionization detection. This configuration enhances the method sensitivity for trace level detections through large volume injections and pre-concentration of analytes along the injection liner. The method was evaluated for the three commonly observed hydrocarbon fractions: C10-C14, C15-C28 and C29-C36. In comparison with conventional injection methods (splitless and pulsed splitless), PTV-LVI showed R2 values > 0.999 with enhanced limits of detection and limits of quantification values. The method was applied to real samples for routine environmental monitoring of TPHs in an Australian contaminated site characterized by refueling station. Analysis of groundwater samples in the area showed a wide range of TPH concentrations as follows: 66-1,546,000 (C10-C14), 216-22,762 (C15-C28) and 105-2,103 (C29-C36) μg/L. This method has detected trace levels, thereby measuring a wider concentration range of TPHs. These more accurate measurements can lead to the appropriate application of risk assessments and remediation techniques. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Ultrananocrystalline Diamond Membranes for Detection of High-Mass Proteins

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

PubMed

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

2017-09-15

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

Optimization and Comparison of ESI and APCI LC-MS/MS Methods: A Case Study of Irgarol 1051, Diuron, and their Degradation Products in Environmental Samples

NASA Astrophysics Data System (ADS)

Maragou, Niki C.; Thomaidis, Nikolaos S.; Koupparis, Michael A.

2011-10-01

A systematic and detailed optimization strategy for the development of atmospheric pressure ionization (API) LC-MS/MS methods for the determination of Irgarol 1051, Diuron, and their degradation products (M1, DCPMU, DCPU, and DCA) in water, sediment, and mussel is described. Experimental design was applied for the optimization of the ion sources parameters. Comparison of ESI and APCI was performed in positive- and negative-ion mode, and the effect of the mobile phase on ionization was studied for both techniques. Special attention was drawn to the ionization of DCA, which presents particular difficulty in API techniques. Satisfactory ionization of this small molecule is achieved only with ESI positive-ion mode using acetonitrile in the mobile phase; the instrumental detection limit is 0.11 ng/mL. Signal suppression was qualitatively estimated by using purified and non-purified samples. The sample preparation for sediments and mussels is direct and simple, comprising only solvent extraction. Mean recoveries ranged from 71% to 110%, and the corresponding (%) RSDs ranged between 4.1 and 14%. The method limits of detection ranged between 0.6 and 3.5 ng/g for sediment and mussel and from 1.3 to 1.8 ng/L for sea water. The method was applied to sea water, marine sediment, and mussels, which were obtained from marinas in Attiki, Greece. Ion ratio confirmation was used for the identification of the compounds.

Development of gas chromatographic methods for the analyses of organic carbonate-based electrolytes

NASA Astrophysics Data System (ADS)

Terborg, Lydia; Weber, Sascha; Passerini, Stefano; Winter, Martin; Karst, Uwe; Nowak, Sascha

2014-01-01

In this work, novel methods based on gas chromatography (GC) for the investigation of common organic carbonate-based electrolyte systems are presented, which are used in lithium ion batteries. The methods were developed for flame ionization detection (FID), mass spectrometric detection (MS). Further, headspace (HS) sampling for the investigation of solid samples like electrodes is reported. Limits of detection are reported for FID. Finally, the developed methods were applied to the electrolyte system of commercially available lithium ion batteries as well as on in-house assembled cells.

Sensitive screening of abused drugs in dried blood samples using ultra-high-performance liquid chromatography-ion booster-quadrupole time-of-flight mass spectrometry.

PubMed

Chepyala, Divyabharathi; Tsai, I-Lin; Liao, Hsiao-Wei; Chen, Guan-Yuan; Chao, Hsi-Chun; Kuo, Ching-Hua

2017-03-31

An increased rate of drug abuse is a major social problem worldwide. The dried blood spot (DBS) sampling technique offers many advantages over using urine or whole blood sampling techniques. This study developed a simple and efficient ultra-high-performance liquid chromatography-ion booster-quadrupole time-of-flight mass spectrometry (UHPLC-IB-QTOF-MS) method for the analysis of abused drugs and their metabolites using DBS. Fifty-seven compounds covering the most commonly abused drugs, including amphetamines, opioids, cocaine, benzodiazepines, barbiturates, and many other new and emerging abused drugs, were selected as the target analytes of this study. An 80% acetonitrile solvent with a 5-min extraction by Geno grinder was used for sample extraction. A Poroshell column was used to provide efficient separation, and under optimal conditions, the analytical times were 15 and 5min in positive and negative ionization modes, respectively. Ionization parameters of both electrospray ionization source and ion booster (IB) source containing an extra heated zone were optimized to achieve the best ionization efficiency of the investigated abused drugs. In spite of their structural diversity, most of the abused drugs showed an enhanced mass response with the high temperature ionization from an extra heated zone of IB source. Compared to electrospray ionization, the ion booster (IB) greatly improved the detection sensitivity for 86% of the analytes by 1.5-14-fold and allowed the developed method to detect trace amounts of compounds on the DBS cards. The validation results showed that the coefficients of variation of intra-day and inter-day precision in terms of the signal intensity were lower than 19.65%. The extraction recovery of all analytes was between 67.21 and 115.14%. The limits of detection of all analytes were between 0.2 and 35.7ngmL -1 . The stability study indicated that 7% of compounds showed poor stability (below 50%) on the DBS cards after 6 months of storage at room temperature and -80°C. The reported method provides a new direction for abused drug screening using DBS. Copyright © 2017 Elsevier B.V. All rights reserved.

Fast quantitative detection of cocaine in beverages using nanoextractive electrospray ionization tandem mass spectrometry.

PubMed

Hu, Bin; Peng, Xuejiao; Yang, Shuiping; Gu, Haiwei; Chen, Huanwen; Huan, Yanfu; Zhang, Tingting; Qiao, Xiaolin

2010-02-01

Without any sample pretreatment, effervescent beverage fluids were manually sprayed into the primary ion plume created by using a nanoelectrospray ionization source for direct ionization, and the analyte ions of interest were guided into an ion trap mass spectrometer for tandem mass analysis. Functional ingredients (e.g., vitamins, taurine, and caffeine, etc.) and spiked impurity (e.g., cocaine) in various beverages, such as Red Bull energy drink, Coco-cola, and Pepsi samples were rapidly identified within 1.5 s. The limit of detection was found to be 7-15 fg (S/N = 3) for cocaine in different samples using the characteristic fragment (m/z 150) observed in the MS(3) experiments. Typical relative standard deviation and recovery of this method were 6.9%-8.6% and 104%-108% for direct analysis of three actual samples, showing that nanoextractive electrospray ionization tandem mass spectrometry is a useful technique for fast screening cocaine presence in beverages. 2010. Published by Elsevier Inc.

Identification of volatiles by headspace gas chromatography with simultaneous flame ionization and mass spectrometric detection.

PubMed

Tiscione, Nicholas B; Yeatman, Dustin Tate; Shan, Xiaoqin; Kahl, Joseph H

2013-10-01

Volatiles are frequently abused as inhalants. The methods used for identification are generally nonspecific if analyzed concurrently with ethanol or require an additional analytical procedure that employs mass spectrometry. A previously published technique utilizing a capillary flow technology splitter to simultaneously quantitate and confirm ethyl alcohol by flame ionization and mass spectrometric detection after headspace sampling and gas chromatographic separation was evaluated for the detection of inhalants. Methanol, isopropanol, acetone, acetaldehyde, toluene, methyl ethyl ketone, isoamyl alcohol, isobutyl alcohol, n-butyl alcohol, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane (Norflurane, HFC-134a), chloroethane, trichlorofluoromethane (Freon®-11), dichlorodifluoromethane (Freon®-12), dichlorofluoromethane (Freon®-21), chlorodifluoromethane (Freon®-22) and 1,2-dichlorotetrafluoroethane (Freon®-114) were validated for qualitative identification by this method. The validation for qualitative identification included evaluation of matrix effects, sensitivity, carryover, specificity, repeatability and ruggedness/robustness.

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

PubMed

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

2017-10-01

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

Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

PubMed

Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

2016-02-12

Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51). Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of C6-C10 aromatic hydrocarbons in water by purge-and-trap capillary gas chromatography

USGS Publications Warehouse

Eganhouse, R.P.; Dorsey, T.F.; Phinney, C.S.; Westcott, A.M.

1993-01-01

A method is described for the determination of the C6-C10 aromatic hydrocarbons in water based on purge-and-trap capillary gas chromatography with flame ionization and mass spectrometric detection. Retention time data and 70 eV mass spectra were obtained for benzene and all 35 C7-C10 aromatic hydrocarbons. With optimized chromatographic conditions and mass spectrometric detection, benzene and 33 of the 35 alkylbenzenes can be identified and measured in a 45-min run. Use of a flame ionization detector permits the simultaneous determination of benzene and 26 alkylbenzenes.

Molecular orbital imaging via above-threshold ionization with circularly polarized pulses.

PubMed

Zhu, Xiaosong; Zhang, Qingbin; Hong, Weiyi; Lu, Peixiang; Xu, Zhizhan

2011-07-18

Above-threshold ionization (ATI) for aligned or orientated linear molecules by circularly polarized laser pulsed is investigated. It is found that the all-round structural information of the molecular orbital is extracted with only one shot by the circularly polarized probe pulse rather than with multi-shot detections in a linearly polarized case. The obtained photoelectron momentum spectrum directly depicts the symmetry and electron distribution of the occupied molecular orbital, which results from the strong sensitivity of the ionization probability to these structural features. Our investigation indicates that the circularly polarized probe scheme would present a simple method to study the angle-dependent ionization and image the occupied electronic orbital.

Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution

NASA Astrophysics Data System (ADS)

Andrianova, Anastasia A.; DiProspero, Thomas; Geib, Clayton; Smoliakova, Irina P.; Kozliak, Evguenii I.; Kubátová, Alena

2018-05-01

The capability to characterize lignin, lignocellulose, and their degradation products is essential for the development of new renewable feedstocks. Electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR TOF-MS) method was developed expanding the lignomics toolkit while targeting the simultaneous detection of low and high molecular weight (MW) lignin species. The effect of a broad range of electrolytes and various ionization conditions on ion formation and ionization effectiveness was studied using a suite of mono-, di-, and triarene lignin model compounds as well as kraft alkali lignin. Contrary to the previous studies, the positive ionization mode was found to be more effective for methoxy-substituted arenes and polyphenols, i.e., species of a broadly varied MW structurally similar to the native lignin. For the first time, we report an effective formation of multiply charged species of lignin with the subsequent mass spectrum deconvolution in the presence of 100 mmol L-1 formic acid in the positive ESI mode. The developed method enabled the detection of lignin species with an MW between 150 and 9000 Da or higher, depending on the mass analyzer. The obtained M n and M w values of 1500 and 2500 Da, respectively, were in good agreement with those determined by gel permeation chromatography. Furthermore, the deconvoluted ESI mass spectrum was similar to that obtained with matrix-assisted laser desorption/ionization (MALDI)-HR TOF-MS, yet featuring a higher signal-to-noise ratio. The formation of multiply charged species was confirmed with ion mobility ESI-HR Q-TOF-MS. [Figure not available: see fulltext.

Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution

NASA Astrophysics Data System (ADS)

Andrianova, Anastasia A.; DiProspero, Thomas; Geib, Clayton; Smoliakova, Irina P.; Kozliak, Evguenii I.; Kubátová, Alena

2018-03-01

The capability to characterize lignin, lignocellulose, and their degradation products is essential for the development of new renewable feedstocks. Electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR TOF-MS) method was developed expanding the lignomics toolkit while targeting the simultaneous detection of low and high molecular weight (MW) lignin species. The effect of a broad range of electrolytes and various ionization conditions on ion formation and ionization effectiveness was studied using a suite of mono-, di-, and triarene lignin model compounds as well as kraft alkali lignin. Contrary to the previous studies, the positive ionization mode was found to be more effective for methoxy-substituted arenes and polyphenols, i.e., species of a broadly varied MW structurally similar to the native lignin. For the first time, we report an effective formation of multiply charged species of lignin with the subsequent mass spectrum deconvolution in the presence of 100 mmol L-1 formic acid in the positive ESI mode. The developed method enabled the detection of lignin species with an MW between 150 and 9000 Da or higher, depending on the mass analyzer. The obtained M n and M w values of 1500 and 2500 Da, respectively, were in good agreement with those determined by gel permeation chromatography. Furthermore, the deconvoluted ESI mass spectrum was similar to that obtained with matrix-assisted laser desorption/ionization (MALDI)-HR TOF-MS, yet featuring a higher signal-to-noise ratio. The formation of multiply charged species was confirmed with ion mobility ESI-HR Q-TOF-MS. [Figure not available: see fulltext.

Rapid detection of meticillin-resistant Staphylococcus aureus bacteraemia using combined three-hour short-incubation matrix-assisted laser desorption/ionization time-of-flight MS identification and Alere Culture Colony PBP2a detection test.

PubMed

Delport, Johannes Andries; Mohorovic, Ivor; Burn, Sandi; McCormick, John Kenneth; Schaus, David; Lannigan, Robert; John, Michael

2016-07-01

Meticillin-resistant Staphylococcus aureus (MRSA) bloodstream infection is responsible for significant morbidity, with mortality rates as high as 60 % if not treated appropriately. We describe a rapid method to detect MRSA in blood cultures using a combined three-hour short-incubation BRUKER matrix-assisted laser desorption/ionization time-of-flight MS BioTyper protocol and a qualitative immunochromatographic assay, the Alere Culture Colony Test PBP2a detection test. We compared this combined method with a molecular method detecting the nuc and mecA genes currently performed in our laboratory. One hundred and seventeen S. aureus blood cultures were tested of which 35 were MRSA and 82 were meticillin-sensitive S. aureus (MSSA). The rapid combined test correctly identified 100 % (82/82) of the MSSA and 85.7 % (30/35) of the MRSA after 3 h. There were five false negative results where the isolates were correctly identified as S. aureus, but PBP2a was not detected by the Culture Colony Test. The combined method has a sensitivity of 87.5 %, specificity of 100 %, a positive predictive value of 100 % and a negative predictive value of 94.3 % with the prevalence of MRSA in our S. aureus blood cultures. The combined rapid method offers a significant benefit to early detection of MRSA in positive blood cultures.

Collison nebulizer as a new soft ionization source for mass spectrometry

NASA Astrophysics Data System (ADS)

Pervukhin, V. V.; Sheven', D. G.; Kolomiets, Yu. N.

2016-08-01

We have proposed that a Collison-type nebulizer be used as an ionization source for mass spectrometry with ionization under atmospheric pressure. This source does not require the use of electric voltage, radioactive sources, heaters, or liquid pumps. It has been shown that the number of ions produced by the 63Ni radioactive source is three to four times larger than the number of ions produced by acoustic ionization sources. We have considered the possibility of using a Collison-type nebulizer in combination with a vortex focusing system as an ion source for extractive ionization of compounds under atmospheric pressure. The ionization of volatile substances in crossflows of a charged aerosol and an analyte (for model compounds of the amine class, viz., diethylaniline, triamylamine, and cocaine) has been investigated. It has been shown that the limit of detecting cocaine vapor by this method is on the level of 4.6 × 10-14 g/cm3.

Rapid Microcystin Determination Using a Paper Spray Ionization Method with a Time-of-Flight Mass Spectrometry System.

PubMed

Zhu, Xiaoqiang; Huang, Zhengxu; Gao, Wei; Li, Xue; Li, Lei; Zhu, Hui; Mo, Ting; Huang, Bao; Zhou, Zhen

2016-07-13

The eutrophication of surface water sources and climate changes have resulted in an annual explosion of cyanobacterial blooms in many irrigating and drinking water resources. To decrease health risks to the public, a rapid real time method for the synchronous determination of two usually harmful microcystins (MC-RR and MC-LR) in environmental water samples was built by employing a paper spray ionization method coupled with a time-of-flight mass spectrometer system. With this approach, direct analysis of microcystin mixtures without sample preparation has been achieved. Rapid detection was performed, simulating the release process of microcystins in reservoir water samples, and the routine detection frequency was every three minutes. The identification time of microcystins was reduced from several hours to a few minutes. The limit of detection is 1 μg/L, and the limit of quantitation is 3 μg/L. This method displays the ability for carrying out rapid, direct, and high-throughput experiments for determination of microcystins, and it would be of significant interest for environmental and food safety applications.

Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

PubMed

Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

2016-06-21

Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the ion source is compact, can be powered with a 10 V battery, and is tolerant of complex mixtures.

Comparison of ESI- and APCI-LC-MS/MS methods: A case study of levonorgestrel in human plasma.

PubMed

Wang, Rulin; Zhang, Lin; Zhang, Zunjian; Tian, Yuan

2016-12-01

Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) techniques for liquid chromatography-tandem mass spectrometry (LC-MS/MS) determination of levonorgestrel were evaluated. In consideration of difference in ionization mechanism, the two ionization sources were compared in terms of LC conditions, MS parameters and performance of method. The sensitivity for detection of levonorgestrel with ESI was 0.25 ng/mL which was lower than 1 ng/mL with APCI. Matrix effects were evaluated for levonorgestrel and canrenone (internal standard, IS) in human plasma, and the results showed that APCI source appeared to be slightly less liable to matrix effect than ESI source. With an overall consideration, ESI was chosen as a better ionization technique for rapid and sensitive quantification of levonorgestrel. The optimized LC-ESI-MS/MS method was validated for a linear range of 0.25-50 ng/mL with a correlation coefficient ≥0.99. The intra- and inter-batch precision and accuracy were within 11.72% and 6.58%, respectively. The application of this method was demonstrated by a bioequivalence study following a single oral administration of 1.5 mg levonorgestrel tablets in 21 Chinese healthy female volunteers.

Trace analysis of impurities in bulk gases by gas chromatography-pulsed discharge helium ionization detection with "heart-cutting" technique.

PubMed

Weijun, Yao

2007-10-12

A method has been developed for the detection of low-nL/L-level impurities in bulk gases such as H(2), O(2), Ar, N(2), He, methane, ethylene and propylene, respectively. The solution presented here is based upon gas chromatography-pulsed discharge helium ionization detection (GC-PDHID) coupled with three two-position valves, one two-way solenoid valve and four packed columns. During the operation, the moisture and heavy compounds are first back-flushed via a pre-column. Then the trace impurities (except CO(2) which is diverted to a separate analytical column for separation and detection) together with the matrix enter onto a main column, followed by the heart-cut of the impurities onto a longer analytical column for complete separation. Finally the detection is performed by PDHID. This method has been applied to different bulk gases and the applicability of detecting impurities in H(2), Ar, and N(2) are herewith demonstrated. As an example, the resulting detection limit of 100 nL/L and a dynamic range of 100-1000 nL/L have been obtained using an Ar sample containing methane.

Simultaneous determination of carboprost methylate and its active metabolite carboprost in dog plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application to a pharmacokinetic study.

PubMed

Yin, Lei; Meng, Xiangjun; Zhou, Xiaotong; Zhang, Tinglan; Sun, Heping; Yang, Zhichao; Yang, Bo; Xiao, Ning; Fawcett, J Paul; Yang, Yan; Gu, Jingkai

2015-08-15

A liquid chromatography-tandem mass spectrometric (LC-MS/MS) method using positive/negative electrospray ionization (ESI) switching for the simultaneous quantitation of carboprost methylate and carboprost in dog plasma has been developed and validated. After screening, the esterase inhibitor, dichlorvos was added to the whole blood at a ratio of 1:99 (v/v) to stabilize carboprost methylate during blood collection, sample storage and LLE. Indomethacin was added to plasma to inhibit prostaglandins synthesis after sampling. After liquid-liquid extraction of 500μL plasma with ethyl ether-dichloromethane (75:25, v/v), analytes and internal standard (IS), alprostadil-d4, were chromatographed on a CAPCELL PAK Phenyl column (150×2.0mm, 5μm) using acetonitrile-5mM ammonium acetate as mobile phase. Carboprost methylate was detected by positive ion electrospray ionization followed by multiple reaction monitoring (MRM) of the transition at m/z 400.5→329.3; the carboprost and IS were detected by negative ion electrospray ionization followed by MRM of the transitions at m/z 367.2→323.2, and 357.1→321.2, respectively. The method was linear for both analytes in the concentration range 0.05-30ng/mL with intra- and inter-day precisions (as relative standard deviation) of ≤6.75% and accuracy (as relative error) of ≤7.21% and limit of detection (LOD) values were 10 and 20pg/mL, respectively. The method was successfully applied to a pharmacokinetic study of the analytes in beagle dogs after intravaginal administration of a suppository containing 0.5mg carboprost methylate. Copyright © 2015 Elsevier B.V. All rights reserved.

Multi-dimensional TOF-SIMS analysis for effective profiling of disease-related ions from the tissue surface.

PubMed

Park, Ji-Won; Jeong, Hyobin; Kang, Byeongsoo; Kim, Su Jin; Park, Sang Yoon; Kang, Sokbom; Kim, Hark Kyun; Choi, Joon Sig; Hwang, Daehee; Lee, Tae Geol

2015-06-05

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) emerges as a promising tool to identify the ions (small molecules) indicative of disease states from the surface of patient tissues. In TOF-SIMS analysis, an enhanced ionization of surface molecules is critical to increase the number of detected ions. Several methods have been developed to enhance ionization capability. However, how these methods improve identification of disease-related ions has not been systematically explored. Here, we present a multi-dimensional SIMS (MD-SIMS) that combines conventional TOF-SIMS and metal-assisted SIMS (MetA-SIMS). Using this approach, we analyzed cancer and adjacent normal tissues first by TOF-SIMS and subsequently by MetA-SIMS. In total, TOF- and MetA-SIMS detected 632 and 959 ions, respectively. Among them, 426 were commonly detected by both methods, while 206 and 533 were detected uniquely by TOF- and MetA-SIMS, respectively. Of the 426 commonly detected ions, 250 increased in their intensities by MetA-SIMS, whereas 176 decreased. The integrated analysis of the ions detected by the two methods resulted in an increased number of discriminatory ions leading to an enhanced separation between cancer and normal tissues. Therefore, the results show that MD-SIMS can be a useful approach to provide a comprehensive list of discriminatory ions indicative of disease states.

Multi-dimensional TOF-SIMS analysis for effective profiling of disease-related ions from the tissue surface

PubMed Central

Park, Ji-Won; Jeong, Hyobin; Kang, Byeongsoo; Kim, Su Jin; Park, Sang Yoon; Kang, Sokbom; Kim, Hark Kyun; Choi, Joon Sig; Hwang, Daehee; Lee, Tae Geol

2015-01-01

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) emerges as a promising tool to identify the ions (small molecules) indicative of disease states from the surface of patient tissues. In TOF-SIMS analysis, an enhanced ionization of surface molecules is critical to increase the number of detected ions. Several methods have been developed to enhance ionization capability. However, how these methods improve identification of disease-related ions has not been systematically explored. Here, we present a multi-dimensional SIMS (MD-SIMS) that combines conventional TOF-SIMS and metal-assisted SIMS (MetA-SIMS). Using this approach, we analyzed cancer and adjacent normal tissues first by TOF-SIMS and subsequently by MetA-SIMS. In total, TOF- and MetA-SIMS detected 632 and 959 ions, respectively. Among them, 426 were commonly detected by both methods, while 206 and 533 were detected uniquely by TOF- and MetA-SIMS, respectively. Of the 426 commonly detected ions, 250 increased in their intensities by MetA-SIMS, whereas 176 decreased. The integrated analysis of the ions detected by the two methods resulted in an increased number of discriminatory ions leading to an enhanced separation between cancer and normal tissues. Therefore, the results show that MD-SIMS can be a useful approach to provide a comprehensive list of discriminatory ions indicative of disease states. PMID:26046669

Direct Standard-Free Quantitation of Tamiflu® and Other Pharmaceutical Tablets using Clustering Agents with Electrospray Ionization Mass Spectrometry

PubMed Central

Flick, Tawnya G.; Leib, Ryan D.; Williams, Evan R.

2010-01-01

Accurate and rapid quantitation is advantageous to identify counterfeit and substandard pharmaceutical drugs. A standard-free electrospray ionization mass spectrometry method is used to directly determine the dosage in the prescription and over-the-counter drugs, Tamiflu®, Sudafed®, and Dramamine®. A tablet of each drug was dissolved in aqueous solution, filtered, and introduced into solutions containing a known concentration of either L-tryptophan, L-phenylalanine or prednisone as clustering agents. The active ingredient(s) incorporates statistically into large clusters of the clustering agent where effects of differential ionization/detection are substantially reduced. From the abundances of large clusters, the dosages of the active ingredients in each of the tablets were determined to typically better than 20% accuracy even when the ionization/detection efficiency of the individual components differed by over 100×. Although this unorthodox method for quantitation is not as accurate as using conventional standards, it has the advantages that it is fast, it can be applied to mixtures where the identities of the analytes are unknown, and it can be used when suitable standards may not be readily available, such as schedule I or II controlled substances or new designer drugs that have not previously been identified. PMID:20092258

Matrix-assisted laser desorption/ionization mass spectrometric imaging for the rapid segmental analysis of methamphetamine in a single hair using umbelliferone as a matrix.

PubMed

Wang, Hang; Wang, Ying

2017-07-04

Segmental hair analysis offers a longer period for retrospective drug detection than blood or urine. Hair is a keratinous fiber and is strongly hydrophobic. The embedding of drugs in hydrophobic hair at low concentrations makes it difficult for extraction and detection with matrix-assisted laser desorption/ionization (MALDI) coupled with mass spectrometric imaging (MSI). In this study, a single scalp hair was longitudinally cut with a cryostat section to a length of 4 mm and fixed onto a stainless steel MALDI plate. Umbelliferone was used as a new hydrophobic matrix to enrich and assist the ionization efficiency of methamphetamine in the hair sample. MALDI-Fourier transform ion cyclotron resonance (FTICR)-MS profiling and imaging were performed for direct detection and mapping of methamphetamine on the longitudinal sections of the single hair sample in positive ion mode. Using MALDI-MSI, the distribution of methamphetamine was observed throughout five longitudinally sectioned hair samples from a drug abuser. The changes of methamphetamine were also semi-quantified by comparing the ratios of methamphetamine/internal standard (I.S). This method improves the detection sensitivity of target drugs embedded in a hair matrix for imaging with mass spectrometry. The method could provide a detection level of methamphetamine down to a nanogram per milligram incorporated into hair. The results were also compared with the conventional high performance liquid chromatography -tandem mass spectrometry (HPLC-MS/MS) method. Changes in the imaging results over time by the MSI method showed good semi-quantitative correlation to the results from the HPLC-MS/MS method. This study provides a powerful tool for drug abuse control and forensic medicine analysis in a narrow time frame, and a reduction in the sample amount required. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of the Discharge Parameters on the Efficiency and Stability of Ambient Metastable-Induced Desorption Ionization

NASA Astrophysics Data System (ADS)

Zhang, Xiaotian; Chen, Chilai; Liu, Youjiang; Wang, Hongwei; Zhang, Lehua; Kong, Deyi; Mario, Chavarria

2015-12-01

Ionization efficiency is an important factor for ion sources in mass spectrometry and ion mobility spectrometry. Using helium as the discharge gas, acetone as the sample, and high-field asymmetric ion mobility spectrometry (FAIMS) as the ion detection method, this work investigates in detail the effects of discharge parameters on the efficiency of ambient metastable-induced desorption ionization (AMDI) at atmospheric pressure. The results indicate that the discharge power and gas flow rate are both significantly correlated with the ionization efficiency. Specifically, an increase in the applied discharge power leads to a rapid increase in the ionization efficiency, which gradually reaches equilibrium due to ion saturation. Moreover, when the discharge voltage is fixed at 2.1 kV, a maximum efficiency can be achieved at the flow rate of 9.0 m/s. This study provides a foundation for the design and application of AMDI for on-line detection with mass spectrometry and ion mobility spectrometry. supported by National Natural Science Foundation of China (No. 61374016), the Changzhou Science and Technology Support Program, China (No. CE20120081) and the External Cooperation Program of Chinese Academy of Sciences (No. GJHZ1218)

Modeling ionization and recombination from low energy nuclear recoils in liquid argon

DOE PAGES

Foxe, M.; Hagmann, C.; Jovanovic, I.; ...

2015-03-27

Coherent elastic neutrino-nucleus scattering (CENNS) is an as-yet undetected, flavor-independent neutrino interaction predicted by the Standard Model. Detection of CENNS could offer benefits for detection of supernova and solar neutrinos in astrophysics, or for detection of antineutrinos for nuclear reactor monitoring and nuclear nonproliferation. One challenge with detecting CENNS is the low energy deposition associated with a typical CENNS nuclear recoil. In addition, nuclear recoils result in lower ionization yields than those produced by electron recoils of the same energy. While a measurement of the nuclear recoil ionization yield in liquid argon in the keV energy range has been recentlymore » reported, a corresponding model for low-energy ionization yield in liquid argon does not exist. For this reason, a Monte Carlo simulation has been developed to predict the ionization yield at sub-10 keV energies. The model consists of two distinct components: (1) simulation of the atomic collision cascade with production of ionization, and (2) the thermalization and drift of ionization electrons in an applied electric field including local recombination. As an application of our results we report updated estimates of detectable ionization in liquid argon from CENNS at a nuclear reactor.« less

The development of a super-fine-grained nuclear emulsion

NASA Astrophysics Data System (ADS)

Asada, Takashi; Naka, Tatsuhiro; Kuwabara, Ken-ichi; Yoshimoto, Masahiro

2017-06-01

A nuclear emulsion with micronized crystals is required for the tracking detection of submicron ionizing particles, which are one of the targets of dark-matter detection and other techniques. We found that a new production method, called the PVA—gelatin mixing method (PGMM), could effectively control crystal size from 20 nm to 50 nm. We called the two types of emulsion produced with the new method the nano imaging tracker and the ultra-nano imaging tracker. Their composition and spatial resolution were measured, and the results indicate that these emulsions detect extremely short tracks.

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

NASA Technical Reports Server (NTRS)

Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

1995-01-01

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

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

PubMed

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

2015-02-03

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

Real-time explosive particle detection using a cyclone particle concentrator.

PubMed

Hashimoto, Yuichiro; Nagano, Hisashi; Takada, Yasuaki; Kashima, Hideo; Sugaya, Masakazu; Terada, Koichi; Sakairi, Minoru

2014-06-30

There is a need for more rapid methods for the detection of explosive particles. We have developed a novel real-time analysis technique for explosive particles that uses a cyclone particle concentrator. This technique can analyze sample surfaces for the presence of particles from explosives such as TNT and RDX within 3 s, which is much faster than is possible by conventional methods. Particles are detached from the sample surface with air jet pulses, and then introduced into a cyclone particle concentrator with a high pumping speed of about 80 L/min. A vaporizer placed at the bottom of the cyclone particle concentrator immediately converts the particles into a vapor. The vapor is then ionized in the atmospheric pressure chemical ionization (APCI) source of a linear ion trap mass spectrometer. An online connection between the vaporizer and a mass spectrometer enables high-speed detection within a few seconds, compared with the conventional off-line heating method that takes more than 10 s to raise the temperature of a sample filter unit. Since the configuration enriched the number density of explosive particles by about 80 times compared with that without the concentrator, a sub-ng amount of TNT particles on a surface was detectable. The detection limit of our technique is comparable with that of an explosives trace detector using ion mobility spectrometry. The technique will be beneficial for trace detection in security applications, because it detects explosive particles on the surface more speedily than conventional methods. Copyright © 2014 John Wiley & Sons, Ltd.

Liquid chromatography/electrospray ionization tandem mass spectrometry analysis of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

PubMed

Pan, Xiaoping; Zhang, Baohong; Tian, Kang; Jones, Lindsey E; Liu, Jun; Anderson, Todd A; Wang, Jia-Sheng; Cobb, George P

2006-01-01

A quantitative liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method was developed for the analysis of the explosive, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). In negative ionization mode, HMX forms an acetate adduct ion [M + CH(3)COO](-), m/z 355, in the presence of a small amount of acetic acid in the mobile phase. The ESI collision-induced dissociation (CID) spectrum of m/z 355 was acquired and the transitions m/z 355 --> 147 and m/z 355 --> 174 were chosen for the determination of HMX in samples. Using this quantification technique, the method detection limit was 1.57 microg/L and good linearity was achieved in the range 5-500 microg/L. This method will help to unambiguously analyze environmentally relevant concentrations of HMX. Copyright (c) 2006 John Wiley & Sons, Ltd.

Rapid Analysis of Ingredients in Cream Using Ultrasonic Mist-Direct Analysis in Real-Time Time-of-Flight Mass Spectrometry

NASA Astrophysics Data System (ADS)

Shimada, Haruo; Maeno, Katsuyuki; Kinoshita, Kazumasa; Shida, Yasuo

2017-07-01

A novel method for the simultaneous detection of ingredients in pharmaceutical applications such as creams and lotions was developed. An ultrasonic atomizer has been used to produce a mist containing ingredients. The analyte molecules in the mist can be ionized by using direct analysis in real time (DART) at lower temperature than traditionally used, and we thus solved the problem of normal DART-MS measurement using a high-temperature gas. Thereby, molecular-related ions of heat-unstable components and nonvolatile components became detectable. The deprotonated molecular ion of glycyrrhizic acid (m/z 821), which is unstable at high temperatures, was detected without pyrolysis by ultrasonic mist-DART-MS using unheated helium gas, although it was not detected by normal DART-MS using heated helium gas. The cationized molecular ions of derivatives of polyethylene glycol fatty acid monoesters, which are nonvolatile compounds, were also detected as m/z peaks observed from 800 to 2300. Although the protonated molecular ion of tocopherol acetate was not detected in ionization by ultrasonic mist, it was detected by ultrasonic mist-DART-MS even in the emulsion. It was not necessary to dissolve a sample completely to detect its ions. This method enabled us to obtain the composition of pharmaceutical applications simply and rapidly.

Tunable Ionization Modes of a Flowing Atmospheric-Pressure Afterglow (FAPA) Ambient Ionization Source.

PubMed

Badal, Sunil P; Michalak, Shawn D; Chan, George C-Y; You, Yi; Shelley, Jacob T

2016-04-05

Plasma-based ambient desorption/ionization sources are versatile in that they enable direct ionization of gaseous samples as well as desorption/ionization of analytes from liquid and solid samples. However, ionization matrix effects, caused by competitive ionization processes, can worsen sensitivity or even inhibit detection all together. The present study is focused on expanding the analytical capabilities of the flowing atmospheric-pressure afterglow (FAPA) source by exploring additional types of ionization chemistry. Specifically, it was found that the abundance and type of reagent ions produced by the FAPA source and, thus, the corresponding ionization pathways of analytes, can be altered by changing the source working conditions. High abundance of proton-transfer reagent ions was observed with relatively high gas flow rates and low discharge currents. Conversely, charge-transfer reagent species were most abundant at low gas flows and high discharge currents. A rather nonpolar model analyte, biphenyl, was found to significantly change ionization pathway based on source operating parameters. Different analyte ions (e.g., MH(+) via proton-transfer and M(+.) via charge-transfer) were formed under unique operating parameters demonstrating two different operating regimes. These tunable ionization modes of the FAPA were used to enable or enhance detection of analytes which traditionally exhibit low-sensitivity in plasma-based ADI-MS analyses. In one example, 2,2'-dichloroquaterphenyl was detected under charge-transfer FAPA conditions, which were difficult or impossible to detect with proton-transfer FAPA or direct analysis in real-time (DART). Overall, this unique mode of operation increases the number and range of detectable analytes and has the potential to lessen ionization matrix effects in ADI-MS analyses.

MALDI versus ESI: The Impact of the Ion Source on Peptide Identification.

PubMed

Nadler, Wiebke Maria; Waidelich, Dietmar; Kerner, Alexander; Hanke, Sabrina; Berg, Regina; Trumpp, Andreas; Rösli, Christoph

2017-03-03

For mass spectrometry-based proteomic analyses, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) are the commonly used ionization techniques. To investigate the influence of the ion source on peptide detection in large-scale proteomics, an optimized GeLC/MS workflow was developed and applied either with ESI/MS or with MALDI/MS for the proteomic analysis of different human cell lines of pancreatic origin. Statistical analysis of the resulting data set with more than 72 000 peptides emphasized the complementary character of the two methods, as the percentage of peptides identified with both approaches was as low as 39%. Significant differences between the resulting peptide sets were observed with respect to amino acid composition, charge-related parameters, hydrophobicity, and modifications of the detected peptides and could be linked to factors governing the respective ion yields in ESI and MALDI.

Saturated fatty acid determination method using paired ion electrospray ionization mass spectrometry coupled with capillary electrophoresis.

PubMed

Lee, Ji-Hyun; Kim, Su-Jin; Lee, Sul; Rhee, Jin-Kyu; Lee, Soo Young; Na, Yun-Cheol

2017-09-01

A sensitive and selective capillary electrophoresis-mass spectrometry (CE-MS) method for determination of saturated fatty acids (FAs) was developed by using dicationic ion-pairing reagents forming singly charged complexes with anionic FAs. For negative ESI detection, 21 anionic FAs at pH 10 were separated using ammonium formate buffer containing 40% acetonitrile modifier in normal polarity mode in CE by optimizing various parameters. This method showed good separation efficiency, but the sensitivity of the method to short-chain fatty acids was quite low, causing acetic and propionic acids to be undetectable even at 100 mgL -1 in negative ESI-MS detection. Out of the four dicationic ion-pairing reagents tested, N,N'-dibutyl 1,1'-pentylenedipyrrolidium infused through a sheath-liquid ion source during CE separation was the best reagent regarding improved sensitivity and favorably complexed with anionic FAs for detection in positive ion ESI-MS. The monovalent complex showed improved ionization efficiency, providing the limits of detection (LODs) for 15 FAs ranging from 0.13 to 2.88 μg/mL and good linearity (R 2  > 0.99) up to 150 μg/mL. Compared to the negative detection results, the effect was remarkable for the detection of short- and medium-chain fatty acids. The optimized CE-paired ion electrospray (PIESI)-MS method was utilized for the determination of FAs in cheese and coffee with simple pretreatment. This method may be extended for sensitive analysis of unsaturated fatty acids. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic materials and devices for detecting ionizing radiation

DOEpatents

Doty, F Patrick [Livermore, CA; Chinn, Douglas A [Livermore, CA

2007-03-06

A .pi.-conjugated organic material for detecting ionizing radiation, and particularly for detecting low energy fission neutrons. The .pi.-conjugated materials comprise a class of organic materials whose members are intrinsic semiconducting materials. Included in this class are .pi.-conjugated polymers, polyaromatic hydrocarbon molecules, and quinolates. Because of their high resistivities (.gtoreq.10.sup.9 ohmcm), these .pi.-conjugated organic materials exhibit very low leakage currents. A device for detecting and measuring ionizing radiation can be made by applying an electric field to a layer of the .pi.-conjugated polymer material to measure electron/hole pair formation. A layer of the .pi.-conjugated polymer material can be made by conventional polymer fabrication methods and can be cast into sheets capable of covering large areas. These sheets of polymer radiation detector material can be deposited between flexible electrodes and rolled up to form a radiation detector occupying a small volume but having a large surface area. The semiconducting polymer material can be easily fabricated in layers about 10 .mu.m to 100 .mu.m thick. These thin polymer layers and their associated electrodes can be stacked to form unique multi-layer detector arrangements that occupy small volume.

Recent advances in CE-MS coupling: Instrumentation, methodology, and applications.

PubMed

Týčová, Anna; Ledvina, Vojtěch; Klepárník, Karel

2017-01-01

This review focuses on the latest development of microseparation electromigration methods in capillaries and microfluidic devices coupled with MS for detection and identification of important analytes. It is a continuation of the review article on the same topic by Kleparnik (Electrophoresis 2015, 36, 159-178). A wide selection of 161 relevant articles covers the literature published from June 2014 till May 2016. New improvements in the instrumentation and methodology of MS interfaced with capillary or microfluidic versions of zone electrophoresis, isotachophoresis, and isoelectric focusing are described in detail. The most frequently implemented MS ionization methods include electrospray ionization, matrix-assisted desorption/ionization and inductively coupled plasma ionization. Although the main attention is paid to the development of instrumentation and methodology, representative examples illustrate also applications in the proteomics, glycomics, metabolomics, biomarker research, forensics, pharmacology, food analysis, and single-cell analysis. The combinations of MS with capillary versions of electrochromatography, and micellar electrokinetic chromatography are not included. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cross sections for ionization of tetrahydrofuran by protons at energies between 300 and 3000 keV

NASA Astrophysics Data System (ADS)

Wang, Mingjie; Rudek, Benedikt; Bennett, Daniel; de Vera, Pablo; Bug, Marion; Buhr, Ticia; Baek, Woon Yong; Hilgers, Gerhard; Rabus, Hans

2016-05-01

Double-differential cross sections for ionization of tetrahydrofuran by protons with energies from 300 to 3000 keV were measured at the Physikalisch-Technische Bundesanstalt ion accelerator facility. The electrons emitted at angles between 15∘ and 150∘ relative to the ion-beam direction were detected with an electrostatic hemispherical electron spectrometer. Single-differential and total ionization cross sections have been derived by integration. The experimental results are compared to the semiempirical Hansen-Kocbach-Stolterfoht model as well as to the recently reported method based on the dielectric formalism. The comparison to the latter showed good agreement with experimental data in a broad range of emission angles and energies of secondary electrons. The scaling property of ionization cross sections for tetrahydrofuran was also investigated. Compared to molecules of different size, the ionization cross sections of tetrahydrofuran were found to scale with the number of valence electrons at large impact parameters.

Dosimeter and method for using the same

DOEpatents

Warner, Benjamin P.; Johns, Deidre M.

2003-06-24

A very sensitive dosimeter that detects ionizing radiation is described. The dosimeter includes a breakable sealed container. A solution of a reducing agent is inside the container. The dosimeter has an air-tight dosimeter body with a transparent portion and an opaque portion. The transparent portion includes a transparent chamber that holds the breakable container with the reducing agent. The opaque portion includes an opaque chamber that holds an emulsion of silver salt (AgX) selected from silver chloride, silver bromide, silver iodide, and combinations of them. A passageway in the dosimeter provides fluid communication between the transparent chamber and the opaque chamber. The dosimeter may also include a chemical pH indicator in the breakable container that provides a detectable color change to the solution for a pH of about 3-10. The invention also includes a method of detecting ionizing radiation that involves producing the dosimeter, breaking the breakable container, allowing the solution to flow through the passageway and contact the emulsion, detecting any color change in the solution and using the color change to determine a radiation dosage.

Detection of antimicrobial resistance-associated proteins by titanium dioxide-facilitated intact bacteria mass spectrometry† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc04089j

PubMed Central

Zhu, Yingdi; Gasilova, Natalia; Jović, Milica; Qiao, Liang; Liu, Baohong; Lovey, Lysiane Tissières; Pick, Horst

2018-01-01

Titanium dioxide-modified target plates were developed to enhance intact bacteria analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The plates were designed to photocatalytically destroy the bacterial envelope structure and improve the ionization efficiency of intracellular components, thereby promoting the measurable mass range and the achievable detection sensitivity. Accordingly, a method for rapid detection of antimicrobial resistance-associated proteins, conferring bacterial resistance against antimicrobial drugs, was established by mass spectrometric fingerprinting of intact bacteria without the need for any sample pre-treatment. With this method, the variations in resistance proteins’ expression levels within bacteria were quickly measured from the relative peak intensities. This approach of resistance protein detection directly from intact bacteria by mass spectrometry is useful for fast discrimination of antimicrobial-resistant bacteria from their non-resistant counterparts whilst performing species identification. Also, it could be used as a rapid and convenient way for initial determination of the underlying resistance mechanisms. PMID:29719694

Method for detection of dental caries and periodontal disease using optical imaging

DOEpatents

Nathel, Howard; Kinney, John H.; Otis, Linda L.

1996-01-01

A method for detecting the presence of active and inactive caries in teeth and diagnosing periodontal disease uses non-ionizing radiation with techniques for reducing interference from scattered light. A beam of non-ionizing radiation is divided into sample and reference beams. The region to be examined is illuminated by the sample beam, and reflected or transmitted radiation from the sample is recombined with the reference beam to form an interference pattern on a detector. The length of the reference beam path is adjustable, allowing the operator to select the reflected or transmitted sample photons that recombine with the reference photons. Thus radiation scattered by the dental or periodontal tissue can be prevented from obscuring the interference pattern. A series of interference patterns may be generated and interpreted to locate dental caries and periodontal tissue interfaces.

Enrichment of low-molecular-weight proteins from biofluids for biomarker discovery.

PubMed

Chertov, Oleg; Simpson, John T; Biragyn, Arya; Conrads, Thomas P; Veenstra, Timothy D; Fisher, Robert J

2005-01-01

The dramatic progress in mass spectrometry-based methods of protein identification has triggered a new quest for disease-associated biomarkers. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and its variant surface-enhanced laser desorption/ionization mass spectrometry, provide effective means to explore the less studied information slice of the human serum proteome -- low-molecular-weight proteins and peptides. These low-molecular-weight proteins and peptides are promising for the detection of important biomarkers. Due to the significant experimental problems imposed by high-abundance and high-molecular-weight proteins, it is important to effectively remove these species prior to mass spectrometry analysis of the low-molecular-weight serum and plasma proteomes. In this review, the advantages afforded by recently introduced methods for prefractionation of serum, as they pertain to the detection and identification of biomarkers, will be discussed.

Separation and identification of neutral cereal lipids by normal phase high-performance liquid chromatography, using evaporative light-scattering and electrospray mass spectrometry for detection.

PubMed

Rocha, João M; Kalo, Paavo J; Ollilainen, Velimatti; Malcata, F Xavier

2010-04-30

A novel method was developed for the analysis of molecular species in neutral lipid classes, using separation by normal phase high-performance liquid chromatography, followed by detection by evaporative light-scattering and electrospray ionization tandem mass spectrometry. Monoacid standards, i.e. sterol esters, triacylglycerols, fatty acids, diacylglycerols, free sterols and monoacylglycerols, were separated to baseline on microbore 3 microm-silica gel columns. Complete or partial separation of molecular species in each lipid class permitted identification by automatic tandem mass spectrometry of ammonium adducts, produced via positive electrospray ionization. After optimization of the method, separation and identification of molecular species of various lipid classes was comprehensively tested by analysis of neutral lipids from the free lipid extract of maize flour. 2010 Elsevier B.V. All rights reserved.

Rapid identification of regulated organic chemical compounds in toys using ambient ionization and a miniature mass spectrometry system.

PubMed

Guo, Xiangyu; Bai, Hua; Lv, Yueguang; Xi, Guangcheng; Li, Junfang; Ma, Xiaoxiao; Ren, Yue; Ouyang, Zheng; Ma, Qiang

2018-04-01

Rapid, on-site analysis was achieved through significantly simplified operation procedures for a wide variety of toy samples (crayon, temporary tattoo sticker, finger paint, modeling clay, and bubble solution) using a miniature mass spectrometry system with ambient ionization capability. The labor-intensive analytical protocols involving sample workup and chemical separation, traditionally required for MS-based analysis, were replaced by direct sampling analysis using ambient ionization methods. A Mini β ion trap miniature mass spectrometer was coupled with versatile ambient ionization methods, e.g. paper spray, extraction spray and slug-flow microextraction nanoESI for direct identification of prohibited colorants, carcinogenic primary aromatic amines, allergenic fragrances, preservatives and plasticizers from raw toy samples. The use of paper substrates coated with Co 3 O 4 nanoparticles allowed a great increase in sensitivity for paper spray. Limits of detection as low as 5μgkg -1 were obtained for target analytes. The methods being developed based on the integration of ambient ionization with miniature mass spectrometer represent alternatives to current in-lab MS analysis operation, and would enable fast, outside-the-lab screening of toy products to ensure children's safety and health. Copyright © 2017 Elsevier B.V. All rights reserved.

Mass Spectrometry in the Home and Garden

NASA Astrophysics Data System (ADS)

Pulliam, Christopher J.; Bain, Ryan M.; Wiley, Joshua S.; Ouyang, Zheng; Cooks, R. Graham

2015-02-01

Identification of active components in a variety of chemical products used directly by consumers is described at both trace and bulk levels using mass spectrometry. The combination of external ambient ionization with a portable mass spectrometer capable of tandem mass spectrometry provides high chemical specificity and sensitivity as well as allowing on-site monitoring. These experiments were done using a custom-built portable ion trap mass spectrometer in combination with the ambient ionization methods of paper spray, leaf spray, and low temperature plasma ionization. Bactericides, garden chemicals, air fresheners, and other products were examined. Herbicide applied to suburban lawns was detected in situ on single leaves 5 d after application.

Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry applied to virus identification

PubMed Central

Calderaro, Adriana; Arcangeletti, Maria-Cristina; Rodighiero, Isabella; Buttrini, Mirko; Gorrini, Chiara; Motta, Federica; Germini, Diego; Medici, Maria-Cristina; Chezzi, Carlo; De Conto, Flora

2014-01-01

Virus detection and/or identification traditionally rely on methods based on cell culture, electron microscopy and antigen or nucleic acid detection. These techniques are good, but often expensive and/or time-consuming; furthermore, they not always lead to virus identification at the species and/or type level. In this study, Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) was tested as an innovative tool to identify human polioviruses and to identify specific viral protein biomarkers in infected cells. The results revealed MALDI-TOF MS to be an effective and inexpensive tool for the identification of the three poliovirus serotypes. The method was firstly applied to Sabin reference strains, and then to isolates from different clinical samples, highlighting its value as a time-saving, sensitive and specific technique when compared to the gold standard neutralization assay and casting new light on its possible application to virus detection and/or identification. PMID:25354905

Polysiloxane scintillator composition

DOEpatents

Walker, J.K.

1992-05-05

A plastic scintillator useful for detecting ionizing radiation comprising a matrix which comprises an optically transparent polysiloxane having incorporated therein at least one ionizing radiation-hard fluor capable of converting electromagnetic energy produced in the polysiloxane upon absorption of ionizing radiation to detectable light.

Polysiloxane scintillator composition

DOEpatents

Walker, James K.

1992-01-01

A plastic scintillator useful for detecting ionizing radiation comprising a matrix which comprises an optically transparent polysiloxane having incorporated therein at least one ionizing radiation-hard fluor capable of converting electromagnetic energy produced in the polysiloxane upon absorption of ionizing radiation to detectable light.

Ethanol analysis by headspace gas chromatography with simultaneous flame-ionization and mass spectrometry detection.

PubMed

Tiscione, Nicholas B; Alford, Ilene; Yeatman, Dustin Tate; Shan, Xiaoqin

2011-09-01

Ethanol is the most frequently identified compound in forensic toxicology. Although confirmation involving mass spectrometry is desirable, relatively few methods have been published to date. A novel technique utilizing a Dean's Switch to simultaneously quantitate and confirm ethyl alcohol by flame-ionization (FID) and mass spectrometric (MS) detection after headspace sampling and gas chromatographic separation is presented. Using 100 μL of sample, the limits of detection and quantitation were 0.005 and 0.010 g/dL, respectively. The zero-order linear range (r(2) > 0.990) was determined to span the concentrations of 0.010 to 1.000 g/dL. The coefficient of variation of replicate analyses was less than 3.1%. Quantitative accuracy was within ±8%, ±6%, ±3%, and ±1.5% at concentrations of 0.010, 0.025, 0.080, and 0.300 g/dL, respectively. In addition, 1,1-difluoroethane was validated for qualitative identification by this method. The validated FID-MS method provides a procedure for the quantitation of ethyl alcohol in blood by FID with simultaneous confirmation by MS and can also be utilized as an identification method for inhalants such as 1,1-difluoroethane.

A positive chemical ionization GC/MS method for the determination of airborne ethylene glycol and propylene glycols in non-occupational environments.

PubMed

Zhu, Jiping; Feng, Yong-Lai; Aikawa, Bio

2004-11-01

An analytical method for ethylene glycol and propylene glycols has been developed for measuring airborne levels of these chemicals in non-occupational environments such as residences and office buildings. The analytes were collected on charcoal tubes, solvent extracted, and analyzed by gas chromatography-mass spectrometry using a positive chemical ionization technique. The method had a method detection limit of 0.07 microg m(-3) for ethylene glycol and 0.03 microg m(-3) for 1,2- and 1,3-propylene glycols, respectively, based on a 1.44 m3 sampling volume. Indoor air samples of several residential homes and other indoor environments have been analyzed. The median concentrations of ethylene glycol and 1,2-propylene glycol in nine residential indoor air samples were 53 microg m(-3) and 13 microg m(-3) respectively with maximum values of 223 microg m(-3) and 25 microg m(-3) detected for ethylene glycol and 1,2-propylene glycol respectively. The concentrations of these two chemicals in one office and two laboratories were at low microg m(-3) levels. The maximum concentration of 1,3-propylene glycol detected in indoor air was 0.1 microg m(-3).

Subcellular analysis by laser ablation electrospray ionization mass spectrometry

DOEpatents

Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

2014-12-02

In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

Method for registration of solar cosmic rays by detecting neutrons

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

Andreev, A. V.; Mordovskoy, M. V., E-mail: mvmordovsk@mail.ru; Skorkin, V. M.

2016-12-15

We consider a method of detecting the ionizing component of solar cosmic rays (SCRs) with energy from tens of MeV to tens of GeV by measuring the energy loss of SCR protons and light nuclei in scintillators and the multiplicity of the local neutron generation in a converter. Scintillation detectors based on stilbene, lithium glass, and solid-state photomultiplier tubes are capable of detecting fast neutrons with a temporal resolution of 10 ns and rejecting the gamma-ray background in the measuring system. The method will allow investigating the nucleon components of primary SCRs in circumterrestrial space.

First results on Ge resonant laser photoionization in hollow cathode lamp

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

Scarpa, Daniele, E-mail: daniele.scarpa@lnl.infn.it; Andrighetto, Alberto; Barzakh, Anatoly

2016-02-15

In the framework of the research and development activities of the SPES project regarding the optimization of the radioactive beam production, a dedicated experimental study has been recently started in order to investigate the possibility of in-source ionization of germanium using a set of tunable dye lasers. Germanium is one of the beams to be accelerated by the SPES ISOL facility, which is under construction at Legnaro INFN Laboratories. The three-step, two color ionization schemes have been tested using a Ge hollow cathode lamp. The slow and the fast optogalvanic signals were detected and averaged by an oscilloscope as amore » proof of the laser ionization inside the lamp. As a result, several wavelength scans across the resonances of ionization schemes were collected with the fast optogalvanic signal. Some comparisons of ionization efficiency for different ionization schemes were made. Furthermore, saturation curves of the first excitation transitions have been obtained. This investigation method and the setup built in the laser laboratory of the SPES project can be applied for the photo-ionization scheme studies also for the other possible radioactive elements.« less

High Sensitivity and High Detection Specificity of Gold-Nanoparticle-Grafted Nanostructured Silicon Mass Spectrometry for Glucose Analysis.

PubMed

Tsao, Chia-Wen; Yang, Zhi-Jie

2015-10-14

Desorption/ionization on silicon (DIOS) is a high-performance matrix-free mass spectrometry (MS) analysis method that involves using silicon nanostructures as a matrix for MS desorption/ionization. In this study, gold nanoparticles grafted onto a nanostructured silicon (AuNPs-nSi) surface were demonstrated as a DIOS-MS analysis approach with high sensitivity and high detection specificity for glucose detection. A glucose sample deposited on the AuNPs-nSi surface was directly catalyzed to negatively charged gluconic acid molecules on a single AuNPs-nSi chip for MS analysis. The AuNPs-nSi surface was fabricated using two electroless deposition steps and one electroless etching step. The effects of the electroless fabrication parameters on the glucose detection efficiency were evaluated. Practical application of AuNPs-nSi MS glucose analysis in urine samples was also demonstrated in this study.

Comparison of electrospray ionization and atmospheric pressure photoionization liquid chromatography mass spectrometry methods for analysis of ergot alkaloids from endophyte-infected sleepygrass (Achnatherum robustum).

PubMed

Jarmusch, Alan K; Musso, Ashleigh M; Shymanovich, Tatsiana; Jarmusch, Scott A; Weavil, Miranda J; Lovin, Mary E; Ehrmann, Brandie M; Saari, Susanna; Nichols, David E; Faeth, Stanley H; Cech, Nadja B

2016-01-05

Ergot alkaloids are mycotoxins with an array of biological effects. With this study, we investigated for the first time the application of atmospheric pressure photoionization (APPI) as an ionization method for LC-MS analysis of ergot alkaloids, and compared its performance to that of the more established technique of electrospray ionization (ESI). Samples of the grass Achnatherum robustum infected with the ergot producing Epichloë fungus were extracted using cold methanol and subjected to reserved-phase HPLC-ESI-MS and HPLC-APPI-MS analysis. The ergot alkaloids ergonovine and lysergic acid amide were detected in these samples, and quantified via external calibration. Validation parameters were recorded in accordance with ICH guidelines. A triple quadrupole MS operated in multiple reaction monitoring yielded the lowest detection limits. The performance of APPI and ESI methods was comparable. Both methods were subject to very little matrix interference, with percent recoveries ranging from 82% to 100%. As determined with HPLC-APPI-MS quantification, lysergic acid amide and ergonovine were extracted from an A. robustum sample infected with the Epichloë fungus at concentrations of 1.143±0.051 ppm and 0.2822±0.0071 ppm, respectively. There was no statistically significant difference between these concentrations and those determined using ESI for the same samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Harris, Glenn A.

Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in Chapter 1. Chapter 2 presents the first investigations into the atmospheric pressure ion transport phenomena during DART analysis. Chapter 3 provides a comparison on the internal energy deposition processes during DART and pneumatically assisted-ESI. Chapter 4 investigates the complex spatially-dependent sampling sensitivity, dynamic range and ion suppression effects present in most DART experiments. New implementations and applications with DART are shown in Chapters 5 and 6. In Chapter 5, DART is coupled to multiplexed drift tube ion mobility spectrometry as a potential fieldable platform for the detection of toxic industrial chemicals and chemical warfare agents simulants. In Chapter 6, transmission-mode DART is shown to be an effective method for reproducible sampling from materials which allow for gas to flow through it. Also, Chapter 6 provides a description of a MS imaging platform coupling infrared laser ablation and DART-like phenomena. Finally, in Chapter 7 I will provide perspective on the work completed with DART and the tasks and goals that future studies should focus on.

Assisted inhibition effect of acetylcholinesterase with n-octylphosphonic acid and application in high sensitive detection of organophosphorous pesticides by matrix-assisted laser desorption/ionization Fourier transform mass spectrometry.

PubMed

Cai, Tingting; Zhang, Li; Wang, Haoyang; Zhang, Jing; Guo, Yinlong

2011-11-14

A simple and practical approach to improve the sensitivity of acetylcholinesterase (AChE)-inhibited method has been developed for monitoring organophosphorous (OP) pesticide residues. In this work, matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS) was used to detect AChE activity. Due to its good salt-tolerance and low sample consumption, MALDI-FTMS facilitates rapid and high-throughput screening of OP pesticides. Here we describe a new method to obtain low detection limits via employing external reagents. Among candidate compounds, n-octylphosphonic acid (n-Octyl-PA) displays assistant effect to enhance AChE inhibition by OP pesticides. In presence of n-Octyl-PA, the percentages of AChE inhibition still kept correlation with OP pesticide concentrations. The detection limits were improved significantly even by 10(2)-10(3) folds in comparison with conventional enzyme-inhibited methods. Different detection limits of OP pesticides with different toxicities were as low as 0.005 μg L(-1) for high toxic pesticides and 0.05 μg L(-1) for low toxic pesticides. Besides, the reliability of results from this method to analyze cowpea samples had been demonstrated by liquid-chromatography tandem mass spectrometry (LC-MS/MS). The application of this commercial available assistant agent shows great promise to detect OP compounds in complicated biological matrix and broadens the mind for high sensitivity detection of OP pesticide residues in agricultural products. Copyright © 2011 Elsevier B.V. All rights reserved.

Chemical composition and antioxidant activity of Lippia alba essential oil obtained by supercritical CO2 and hydrodistillation

USDA-ARS?s Scientific Manuscript database

Lippia alba extracts from Mexico were obtained by hydrodistillation (HD) and supercritical fluid (SFE) extraction methods. The extracts were analyzed by gas chromatography using flame ionization and mass spectrometric detections. Antioxidant activity was tested by two methods (DPPH and ABTS) and tot...

Developing analytical approaches to explore the connectionbetween endocrine-active pharmaceuticals in waterto effects in fish

EPA Science Inventory

The emphasis of this research project was to develop, and optimize, a solid-phase extraction (SPE) method and high performance liquid chromatography-electrospray ionization- mass spectrometry (LC-MS/MS) method, such that a linkage between the detection of endocrine active pharma...

Methods for Creation and Detection of Ultra-Strong Artificial Ionization in the Upper Atmosphere (Invited)

NASA Astrophysics Data System (ADS)

Bernhardt, P. A.; Siefring, C. L.; Briczinski, S. J.; Kendall, E. A.; Watkins, B. J.; Bristow, W. A.; Michell, R.

2013-12-01

The High Frequency Active Auroral Research Program (HAARP) transmitter in Alaska has been used to produce localized regions of artificial ionization at altitudes between 150 and 250 km. High power radio waves tuned near harmonics of the electron gyro frequency were discovered by Todd Pederson of the Air Force Research Laboratory to produce ionosonde traces that looked like artificial ionization layers below the natural F-region. The initial regions of artificial ionization (AI) were not stable but had moved down in altitude over a period of 15 minutes. Recently, artificial ionization has been produced by the 2nd, 3rd, 4th and 6th harmonics transmissions by the HAARP. In march 2013, the artificial ionization clouds were sustained for more the 5 hours using HAARP tuned to the 4 fce at the full power of 3.6 Mega-Watts with a twisted-beam antenna pattern. Frequency selection with narrow-band sweeps and antenna pattern shaping has been employed for optimal generation of AI. Recent research at HAARP has produced the longest lived and denser artificial ionization clouds using HF transmissions at the harmonics of the electron cyclotron frequency and ring-shaped radio beams tailored to prevent the descent of the clouds. Detection of artificial ionization employs (1) ionosonde echoes, (2) coherent backscatter from the Kodiak SuperDARN radar, (3) enhanced ion and plasma line echoes from the HAARP MUIR radar at 400 MHz, (4) high resolution optical image from ground sites, and (5) unique stimulated electromagnetic emissions, and (6) strong UHF and L-Band scintillation induced into trans-ionospheric signals from satellite radio beacons. Future HAARP experiments will determine the uses of long-sustained AI for enhanced HF communications.

Broad-Range Detection of Microorganisms Directly from Bronchoalveolar Lavage Specimens by PCR/Electrospray Ionization-Mass Spectrometry

PubMed Central

Ullberg, Måns; Lüthje, Petra; Mölling, Paula; Strålin, Kristoffer

2017-01-01

The clinical demand on rapid microbiological diagnostic is constantly increasing. PCR coupled to electrospray ionization-mass spectrometry, PCR/ESI-MS, offers detection and identification of over 750 bacteria and Candida species directly from clinical specimens within 6 hours. In this study, we investigated the clinical performance of the IRIDICA BAC LRT Assay for detection of bacterial pathogens in 121 bronchoalveolar lavage (BAL) samples that were received consecutively at our bacterial laboratory for BAL culture. Commensal or pathogenic microorganisms were detected in 118/121 (98%) BAL samples by PCR/ESI-MS, while in 104/121 (86%) samples by routine culture (P<0.01). Detection of potentially pathogenic microorganisms by PCR/ESI-MS was evaluated in comparison with conventional culture-based or molecular methods. The agreement between positive findings was overall good. Most Staphylococcus aureus-positive PCR/ESI-MS results were confirmed by culture or species-specific PCR (27/33, 82%). The identity of Streptococcus pneumoniae could however be confirmed for only 6/17 (35%) PCR/ESI-MS-positive samples. Non-cultivable and fastidious pathogens, which were not covered by standard culture procedures were readily detected by PCR/ESI-MS, including Legionella pneumophila, Bordetella pertussis, Norcadia species and Mycoplasma pneumoniae. In conclusion, PCR/ESI-MS detected a broad range of potential pathogens with equal or superior sensitivity compared to conventional methods within few hours directly from BAL samples. This novel method might thus provide a relevant tool for diagnostics in critically ill patients. PMID:28085931

Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry.

PubMed

Feng, Dan; Xia, Yan

2018-07-19

Covalent organic framework (COF) was explored as a novel matrix with a high desorption/ionization efficiency for direct detection of small molecules by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). By using COF as an LDI MS matrix, we could detect not only biological micro molecules such as amino acids and fatty acids, but also emerging environmental pollutants like bisphenol S (BPS) and pyrene. With COF as the matrix, higher desorption/ionization efficiency, and less background interference were achieved than the conventional organic matrices. Good salt tolerance (as high as 500 mM NaCl) and repeatability allowed the detection limit of amino acids was 90 fmol. In addition, COF matrix performed well for amino acids analysis in the honey sample. The ionization mechanism was also discussed. These results demonstrate that COF is a powerful matrix for small molecules analysis in real samples by MS. Copyright © 2018 Elsevier B.V. All rights reserved.

[Simultaneous determination of sixteen perfluorinated organic compounds in surface water by solid phase extraction and ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry].

PubMed

Zhang, Ming; Tang, Fangliang; Yu, Yayun; Chen, Feng; Xu, Jianfen; Ye, Yonggen

2014-05-01

A high-throughput detection method has been developed for the determination of sixteen perfluorinated organic compounds (PFCs) in surface water by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI-MS/MS). The water samples were concentrated and purified through WAX solid phase extraction cartridges. The UPLC separation was performed on an ACQUITY UPLC BEH C18 column utilizing a gradient elution program of methanol (containing 2 mmol/L ammonium acetate) and water (containing 2 mmol/L ammonium acetate) as the mobile phases at a flow rate of 0.4 mL/min. The MS/MS detection was performed under negative electrospray ionization ( ESI ) in multiple reaction monitoring (MRM) mode. Good linearities were observed in the range of 0.5-100 gg/L or 1.0 - 100 microg/L with correlation coefficients from 0.998 7 to 0.999 9. The limits of detection (LODs) for the sixteen perfluorinated organic compounds were in the range of 0.06-0.46 ng/L. The recoveries ranged from 67.6% to 103% with the relative standard deviations between 2.94% and 12.0%. This method was characterized by high sensitivity and precision, extensive range and high speed, and can be applied for the analysis of PFC contaminants in surface water.

Ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of natural steroid hormones in sea lamprey (Petromyzon marinus) plasma and tissues.

PubMed

Wang, Huiyong; Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Weiming

2016-01-15

This study aims to provide a rapid, sensitive and precise UPLC-MS/MS method for target steroid quantitation in biological matrices. We developed and validated an UPLC-MS/MS method to simultaneously determine 16 steroids in plasma and tissue samples. Ionization sources of Electrospray Ionization (ESI) and Atmospheric Pressure Chemical Ionization (APCI) were compared in this study by testing their spectrometry performances at the same chromatographic conditions, and the ESI source was found up to five times more sensitive than the APCI. Different sample preparation techniques were investigated for an optimal extraction of steroids from the biological matrices. The developed method exhibited excellent linearity for all analytes with regression coefficients higher than 0.99 in broad concentration ranges. The limit of detection (LOD) was from 0.003 to 0.1ng/mL. The method was validated according to FDA guidance and applied to determine steroids in sea lamprey plasma and tissues (fat and testes) by the developed method. Copyright © 2015. Published by Elsevier B.V.

Trace determination of 13 haloacetamides in drinking water using liquid chromatography triple quadrupole mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Chu, Wenhai; Gao, Naiyun; Yin, Daqiang; Krasner, Stuart W; Templeton, Michael R

2012-04-27

The haloacetamides (HAcAms) are disinfection by-products (DBPs) in drinking water which are currently receiving increased scientific attention due to their elevated toxicity relative to regulated disinfection by-products. A simultaneous determination method of 13 HAcAms, combining solid-phase extraction (SPE) enrichment, liquid chromatographic (LC) separation, and triple quadrupole mass spectrometry (tqMS) detection with atmospheric pressure chemical ionization (APCI) using selective reaction monitoring in positive mode, was developed to measure HAcAms, including chlorinated, brominated, and iodinated analogs. Ammonium chloride and Oasis HLB were selected as the dechlorinating reagent and polymeric SPE sorbent of HAcAm samples. The used tqMS apparatus showed higher sensitivity for the studied HAcAms in the APCI mode than electrospray ionization. 13 HAcAms were separated by LC in 9.0 min, and the detection limits ranged from 7.6 to 19.7 ng/L. The SPE-LC/tqMS method was successfully applied to quantify 13 HAcAms in drinking water samples for the first time, and first indentified tribromoacetamide and chloroiodoacetamide as DBPs in drinking water. Copyright © 2012 Elsevier B.V. All rights reserved.

Water cluster fragmentation probed by pickup experiments

NASA Astrophysics Data System (ADS)

Huang, Chuanfu; Kresin, Vitaly V.; Pysanenko, Andriy; Fárník, Michal

2016-09-01

Electron ionization is a common tool for the mass spectrometry of atomic and molecular clusters. Any cluster can be ionized efficiently by sufficiently energetic electrons, but concomitant fragmentation can seriously obstruct the goal of size-resolved detection. We present a new general method to assess the original neutral population of the cluster beam. Clusters undergo a sticking collision with a molecule from a crossed beam, and the velocities of neat and doped cluster ion peaks are measured and compared. By making use of longitudinal momentum conservation, one can reconstruct the sizes of the neutral precursors. Here this method is applied to H2O and D2O clusters in the detected ion size range of 3-10. It is found that water clusters do fragment significantly upon electron impact: the deduced neutral precursor size is ˜3-5 times larger than the observed cluster ions. This conclusion agrees with beam size characterization by another experimental technique: photoionization after Na-doping. Abundant post-ionization fragmentation of water clusters must therefore be an important factor in the interpretation of experimental data; interestingly, there is at present no detailed microscopic understanding of the underlying fragmentation dynamics.

Characterization of Nitrated Sugar Alcohols by Atmospheric-Pressure Chemical-Ionization Mass Spectrometry

DTIC Science & Technology

2016-07-27

disclosed here will benefit the area of explosives trace detection for counterterrorism and forensics . INTRODUCTION The military-grade...plasticizer formulation.[4] As a result, methods to detect MHN, SHN, and XPN should be pursued for the same security and forensics applications as...with ion mobility mass spectrometry (IMS) provide direct detection of molecular ions,[8] and thus are preferred for most security and forensic

Near Infrared Imaging as a Diagnostic Tool for Detecting Enamel Demineralization: An in vivo Study

NASA Astrophysics Data System (ADS)

Lucas, Seth Adam

Background and Objectives: For decades there has been an effort to develop alternative optical methods of imaging dental decay utilizing non-ionizing radiation methods. The purpose of this in-vivo study was to demonstrate whether NIR can be used as a diagnostic tool to evaluate dental caries and to compare the sensitivity and specificity of this method with that of conventional methods, including bitewing x-rays and visual inspection. Materials and Methods: 31 test subjects (n=31) from the UCSF orthodontic clinic undergoing orthodontic treatment with planned premolar extractions were recruited. Calibrated examiners performed caries detection examinations using conventional methods: bitewing radiographs and visual inspection. These findings were compared with the results from NIR examinations: transillumination and reflectance. To confirm the results found in the two different detection methods, a gold standard was used. After teeth were extracted, polarized light microscopy and transverse microradiography were performed. Results: A total of 87 premolars were used in the study. NIR identified the occlusal lesions with a sensitivity of 71% and a specificity of 77%, whereas, the visual examination had a sensitivity of only 40% and a specifity of 39%. For interproximal lesions halfway to DEJ, specificity remained constant, but sensitivity improved to 100% for NIR and 75% for x-rays. Conclusions: The results of this preliminary study demonstrate that NIR is just as effective at detecting enamel interproximal lesions as standard dental x-rays. NIR was more effective at detecting occlusal lesions than visual examination alone. NIR shows promise as an alternative diagnostic tool to the conventional methods of x-rays and visual examination and provides a non-ionizing radiation technique.

Measuring the effects of Coulomb repulsion via signal decay in an atmospheric pressure laser ionization ion mobility spectrometer.

PubMed

Ihlenborg, Marvin; Schuster, Ann-Kathrin; Grotemeyer, Juergen; Gunzer, Frank

2018-01-01

Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

Heralded ions via ionization coincidence

NASA Astrophysics Data System (ADS)

McCulloch, A. J.; Speirs, R. W.; Wissenberg, S. H.; Tielen, R. P. M.; Sparkes, B. M.; Scholten, R. E.

2018-04-01

We demonstrate a method for the deterministic production of single ions by exploiting the correlation between an electron and associated ion following ionization. Coincident detection and feedback in combination with Coulomb-driven particle selection allows for high-fidelity heralding of ions at a high repetition rate. Extension of the scheme beyond time-correlated feedback to position- and momentum-correlated feedback will provide a general and powerful means to optimize the ion beam brightness for the development of next-generation focused ion beam technologies.

Analysis of the extracts of Isatis tinctoria by new analytical approaches of HPLC, MS and NMR.

PubMed

Zhou, Jue; Qu, Fan

2011-01-01

The methods of extraction, separation and analysis of alkaloids and indole glucosinolates (GLs) ofIsatis tinctoria were reviewed. Different analytical approaches such as High-pressure Liquid Chromatography (HPLC), Liquid Chromatography with Electrospray Ionization Mass Spectrometry (LC/ESI/MS), Electrospray Ionization Time-Of-Flight Mass Spectrometry (ESI-TOF-MS), and Nuclear Magnetic Resonance (NMR) were used to validate and identity of these constituents. These methods provide rapid separation, identification and quantitative measurements of alkaloids and GLs of Isatis tinctoria. By connection with different detectors to HPLC such as PDA, ELSD, ESI- and APCI-MS in positive and negative ion modes, complicated compounds could be detected with at least two independent detection modes. The molecular formula can be derived in a second step of ESI-TOF-MS data. But for some constituents, UV and MS cannot provide sufficient structure identification. After peak purification, NMR by semi-preparative HPLC can be used as a complementary method.

Fully correcting the meteor speed distribution for radar observing biases

NASA Astrophysics Data System (ADS)

Moorhead, Althea V.; Brown, Peter G.; Campbell-Brown, Margaret D.; Heynen, Denis; Cooke, William J.

2017-09-01

Meteor radars such as the Canadian Meteor Orbit Radar (CMOR) have the ability to detect millions of meteors, making it possible to study the meteoroid environment in great detail. However, meteor radars also suffer from a number of detection biases; these biases must be fully corrected for in order to derive an accurate description of the meteoroid population. We present a bias correction method for patrol radars that accounts for the full form of ionization efficiency and mass distribution. This is an improvement over previous methods such as that of Taylor (1995), which requires power-law distributions for ionization efficiency and a single mass index. We apply this method to the meteor speed distribution observed by CMOR and find a significant enhancement of slow meteors compared to earlier treatments. However, when the data set is severely restricted to include only meteors with very small uncertainties in speed, the fraction of slow meteors is substantially reduced, indicating that speed uncertainties must be carefully handled.

Polysialylated N-Glycans Identified in Human Serum Through Combined Developments in Sample Preparation, Separations and Electrospray ionization-mass spectrometry

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

Kronewitter, Scott R.; Marginean, Ioan; Cox, Jonathan T.

The N-glycan diversity of human serum glycoproteins, i.e. the human blood serum N-glycome, is complex due to the range of glycan structures potentially synthesizable by human glycosylation enzymes. The reported glycome, however, is limited by methods of sample preparation, available analytical platforms, e.g., based upon electrospray ionization-mass spectrometry (ESI-MS), and software tools for data analysis. In this report, several improvements have been implemented in sample preparation and analysis to extend ESI-MS glycan characterization and to provide an improved view of glycan diversity. Sample preparation improvements include acidified, microwave-accelerated, PNGase F N-glycan release, and sodium borohydride reduction were optimized to improvemore » quantitative yields and conserve the number of glycoforms detected. Two-stage desalting (during solid phase extraction and on the analytical column) increased the sensitivity by reducing analyte signal division between multiple reducing-end-forms or cation adducts. On-line separations were improved by using extended length graphitized carbon columns and adding TFA as an acid modifier to a formic acid/reversed phase gradient which provides additional resolving power and significantly improved desorption of both large and heavily sialylated glycans. To improve MS sensitivity and provide gentler ionization conditions at the source-MS interface, subambient pressure ionization with nanoelectrospray (SPIN) has been utilized. When method improvements are combined together with the Glycomics Quintavariate Informed Quantification (GlyQ-IQ) recently described1 these technologies demonstrate the ability to significantly extend glycan detection sensitivity and provide expanded glycan coverage. We demonstrate application of these advances in the context of the human serum glycome, and for which our initial observations include detection of a new class of heavily sialylated N-glycans, including polysialylated N-glycans.« less

Ionization detector, electrode configuration and single polarity charge detection method

DOEpatents

He, Z.

1998-07-07

An ionization detector, an electrode configuration and a single polarity charge detection method each utilize a boundary electrode which symmetrically surrounds first and second central interlaced and symmetrical electrodes. All of the electrodes are held at a voltage potential of a first polarity type. The first central electrode is held at a higher potential than the second central or boundary electrodes. By forming the first and second central electrodes in a substantially interlaced and symmetrical pattern and forming the boundary electrode symmetrically about the first and second central electrodes, signals generated by charge carriers are substantially of equal strength with respect to both of the central electrodes. The only significant difference in measured signal strength occurs when the charge carriers move to within close proximity of the first central electrode and are received at the first central electrode. The measured signals are then subtracted and compared to quantitatively measure the magnitude of the charge. 10 figs.

Ionization detector, electrode configuration and single polarity charge detection method

DOEpatents

He, Zhong

1998-01-01

An ionization detector, an electrode configuration and a single polarity charge detection method each utilize a boundary electrode which symmetrically surrounds first and second central interlaced and symmetrical electrodes. All of the electrodes are held at a voltage potential of a first polarity type. The first central electrode is held at a higher potential than the second central or boundary electrodes. By forming the first and second central electrodes in a substantially interlaced and symmetrical pattern and forming the boundary electrode symmetrically about the first and second central electrodes, signals generated by charge carriers are substantially of equal strength with respect to both of the central electrodes. The only significant difference in measured signal strength occurs when the charge carriers move to within close proximity of the first central electrode and are received at the first central electrode. The measured signals are then subtracted and compared to quantitatively measure the magnitude of the charge.

Method for detection of dental caries and periodontal disease using optical imaging

DOEpatents

Nathel, H.; Kinney, J.H.; Otis, L.L.

1996-10-29

A method is disclosed for detecting the presence of active and inactive caries in teeth and diagnosing periodontal disease uses non-ionizing radiation with techniques for reducing interference from scattered light. A beam of non-ionizing radiation is divided into sample and reference beams. The region to be examined is illuminated by the sample beam, and reflected or transmitted radiation from the sample is recombined with the reference beam to form an interference pattern on a detector. The length of the reference beam path is adjustable, allowing the operator to select the reflected or transmitted sample photons that recombine with the reference photons. Thus radiation scattered by the dental or periodontal tissue can be prevented from obscuring the interference pattern. A series of interference patterns may be generated and interpreted to locate dental caries and periodontal tissue interfaces. 7 figs.

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

PubMed

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

2016-11-01

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

Feasibility of atmospheric pressure desorption/ionization on silicon mass spectrometry in analysis of drugs.

PubMed

Huikko, K; Ostman, P; Sauber, C; Mandel, F; Grigoras, K; Franssila, S; Kotiaho, T; Kostiainen, R

2003-01-01

The feasibility of atmospheric pressure desorption/ionization on silicon mass spectrometry (AP-DIOS-MS) for drug analysis was investigated. It was observed that only compounds with relative high proton affinity are efficiently ionized under AP-DIOS conditions. The limits of detection (LODs) achieved in MS mode with midazolam, propranolol, and angiotensin II were 80 fmol, 20 pmol, and 1 pmol, respectively. In MS/MS mode the LODs for midazolam and propranolol were 10 fmol and 5 pmol, respectively. The good linearity (r(2) > 0.991), linear dynamic range of 3 orders of magnitude, and reasonable repeatability showed that the method is suitable for quantitative analysis. Copyright 2003 John Wiley & Sons, Ltd.

Simultaneous determination of eighteen nitro-polyaromatic hydrocarbons in PM2.5 by atmospheric pressure gas chromatography-tandem mass spectrometry.

PubMed

Zhang, Yanhao; Li, Ruijin; Fang, Jing; Wang, Chen; Cai, Zongwei

2018-05-01

A new atmospheric pressure gas chromatography-tandem mass spectrometry (APGC-MS/MS) was developed to simultaneously separate, identify and quantify 18 nitro-polyaromatic hydrocarbons (NPAHs) in air fine particulate matter (PM 2.5 ). Compared with traditional negative chemical ionization (NCI) or electron impact ionization (EI)-MS/MS methods, APGC-MS/MS equipped with an atmospheric pressure chemical ionization (APCI) source provided better sensitivity and selectivity for NPAHs analysis in PM 2.5 .18 NPAHs were completely separated, and satisfactory linear response (R 2  > 0.99), low instrumental detection limits (0.20-2.18 pg mL -1 ) and method detection limits (0.001-0.015 pg m -3 ) were achieved. Due to the reliable performance of the instrument, only minimal sample pretreatment is needed. It ensured the satisfactory method recovery (70%-120%) and qualified repeatability (RSD: 1.1%-17.2%), which met the requirement of trace analysis of NAPHs in the real environmental PM 2.5 . Using the developed method, the actual PM 2.5 samples collected from Taiyuan, China in both summer and winter were analyzed, and 17 NPAHs but 2-nitrofluorene were detected and quantified. According to the obtained NAPH concentration results, the generation mechanism of NPAHs in PM 2.5 and the effects on NPAHs formation caused by some ambient air pollutants were preliminarily discussed: secondary photochemical reaction might be the dominant source of NPAHs in PM 2.5 collected from Taiyuan in both summer and winter; ambient air pollutants (NO 2 , SO 2 , CO) had more contribution on the NPAHs secondary formation of PM 2.5 in winter. Copyright © 2018 Elsevier Ltd. All rights reserved.

The MARIACHI Project: Mixed Apparatus for Radio Investigation of Atmospheric Cosmic Rays of High Ionization

NASA Astrophysics Data System (ADS)

Inglis, M. D.; Takai, H.; Warasia, R.; Sundermier, J.

2005-12-01

Extreme Energy Cosmic Rays are nuclei that have been accelerated to kinetic energies in excess of 1020 eV. Where do they come from? How are they produced? Are they survivors of the early universe? Are they remnants of supernovas? MARIACHI, a unique collaboration between scientists, physics teachers and students, is an innovative technique that allows us to detect and study them. The Experiment MARIACHI is a unique research experiment that seeks the detection of extreme energy cosmic rays (EECRs), with E >1020 eV. It is an exciting project with many aspects: Research: It investigates an unconventional way of detecting EECRs based upon a method successfully used to detect meteors entering the upper atmosphere. The method was developed by planetary astronomers listening to radio signals reflected off the ionization trail. MARIACHI seeks to listen to TV signals reflected off the ionization trail of an EECR. The unique experiment topology will also permit the study of meteors, exotic forms of lightning, and atmospheric science. Computing and Technology: It uses radio detection stations, along with mini shower arrays hooked up to GPS clocks. Teachers and students build the arrays. It implements the Internet and the GRID as means of communication, data transfer, data processing, and for hosting a public educational outreach web site. Outreach and Education: It is an open research project with the active participation of a wide audience of astronomers, physicists, college professors, high school teachers and students. Groups representing high schools, community colleges and universities all collaborate in the project. The excitement of a real experiment motivates the science and technology classroom, and incorporates several high school physical science topics along with material from other disciplines such as astronomy, electronics, radio, optics.

The Phobos neutral and ionized torus

NASA Astrophysics Data System (ADS)

Poppe, A. R.; Curry, S. M.; Fatemi, S.

2016-05-01

Charged particle sputtering, micrometeoroid impact vaporization, and photon-stimulated desorption are fundamental processes operating at airless surfaces throughout the solar system. At larger bodies, such as Earth's Moon and several of the outer planet moons, these processes generate tenuous surface-bound exospheres that have been observed by a variety of methods. Phobos and Deimos, in contrast, are too gravitationally weak to keep ejected neutrals bound and, thus, are suspected to generate neutral tori in orbit around Mars. While these tori have not yet been detected, the distribution and density of both the neutral and ionized components are of fundamental interest. We combine a neutral Monte Carlo model and a hybrid plasma model to investigate both the neutral and ionized components of the Phobos torus. We show that the spatial distribution of the neutral torus is highly dependent on each individual species (due to ionization rates that span nearly 4 orders of magnitude) and on the location of Phobos with respect to Mars. Additionally, we present the flux distribution of torus pickup ions throughout the Martian system and estimate typical pickup ion fluxes. We find that the predicted pickup ion fluxes are too low to perturb the ambient plasma, consistent with previous null detections by spacecraft around Mars.

Classical vs. evolved quenching parameters and procedures in scintillation measurements: The importance of ionization quenching

NASA Astrophysics Data System (ADS)

Bagán, H.; Tarancón, A.; Rauret, G.; García, J. F.

2008-07-01

The quenching parameters used to model detection efficiency variations in scintillation measurements have not evolved since the decade of 1970s. Meanwhile, computer capabilities have increased enormously and ionization quenching has appeared in practical measurements using plastic scintillation. This study compares the results obtained in activity quantification by plastic scintillation of 14C samples that contain colour and ionization quenchers, using classical (SIS, SCR-limited, SCR-non-limited, SIS(ext), SQP(E)) and evolved (MWA-SCR and WDW) parameters and following three calibration approaches: single step, which does not take into account the quenching mechanism; two steps, which takes into account the quenching phenomena; and multivariate calibration. Two-step calibration (ionization followed by colour) yielded the lowest relative errors, which means that each quenching phenomenon must be specifically modelled. In addition, the sample activity was quantified more accurately when the evolved parameters were used. Multivariate calibration-PLS also yielded better results than those obtained using classical parameters, which confirms that the quenching phenomena must be taken into account. The detection limits for each calibration method and each parameter were close to those obtained theoretically using the Currie approach.

Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

PubMed

Zhang, Wei; Huang, Guangming

2015-11-15

Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

Ionization imaging—A new method to search for 0- ν ββ decay

NASA Astrophysics Data System (ADS)

Chinowski, W.; Goldschmidt, A.; Nygren, D.; Bernstein, A.; Heffner, M.; Millaud, J.

2007-10-01

We present a new method to search for 0- ν ββ decay in 136Xe, the Ionization Imaging Chamber. This concept is based on 3-D track reconstruction by detection of ionization, without avalanche gain, in a novel time projection chamber (TPC) geometry. The rejection efficiency of external charged particle backgrounds is optimized by the realization of a maximal, fully active, closed, and ex post facto variable fiducial surface. Event localization within the fiducial volume and detailed event reconstruction mitigate external neutral particle backgrounds; larger detectors offer higher rejection efficiencies. Energy resolution at the Q-value of 2.5 MeV is expected to be better than 1% FWHM, reducing the potential impact of allowed 2- ν ββ decays. Scaling from ˜25 kg prototype to 1000+ kg target mass is graceful. A new possible methodology for the identification of the daughter barium nucleus is also described.

Effects of Ionizing Radiation on the Heart

PubMed Central

Boerma, Marjan; Sridharan, Vijayalakshmi; Mao, Xiao-Wen; Nelson, Gregory A.; Cheema, Amrita K.; Koturbash, Igor; Singh, Sharda P.; Tackett, Alan J.; Hauer-Jensen, Martin

2016-01-01

This article provides an overview of studies addressing effects of ionizing radiation on the heart. Clinical studies have identified early and late manifestations of radiation-induced heart disease, a side effect of radiation therapy to tumors in the chest when all or part of the heart is situated in the radiation field. Studies in preclinical animal models have contributed to our understanding of the mechanisms by which radiation may injure the heart. More recent observations in human subjects suggest that ionizing radiation may have cardiovascular effects at lower doses than was previously thought. This has led to examinations of low-dose photons and low-dose charged particle irradiation in animal models. Lastly, studies have started to identify noninvasive methods for detection of cardiac radiation injury and interventions that may prevent or mitigate these adverse effects. Altogether, this ongoing research should increase our knowledge of biological mechanisms of cardiovascular radiation injury, identify non-invasive biomarkers for early detection, and potential interventions that may prevent or mitigate these adverse effects. PMID:27919338

Quantum dots assisted laser desorption/ionization mass spectrometric detection of carbohydrates: qualitative and quantitative analysis.

PubMed

Bibi, Aisha; Ju, Huangxian

2016-04-01

A quantum dots (QDs) assisted laser desorption/ionization mass spectrometric (QDA-LDI-MS) strategy was proposed for qualitative and quantitative analysis of a series of carbohydrates. The adsorption of carbohydrates on the modified surface of different QDs as the matrices depended mainly on the formation of hydrogen bonding, which led to higher MS intensity than those with conventional organic matrix. The effects of QDs concentration and sample preparation method were explored for improving the selective ionization process and the detection sensitivity. The proposed approach offered a new dimension to the application of QDs as matrices for MALDI-MS research of carbohydrates. It could be used for quantitative measurement of glucose concentration in human serum with good performance. The QDs served as a matrix showed the advantages of low background, higher sensitivity, convenient sample preparation and excellent stability under vacuum. The QDs assisted LDI-MS approach has promising application to the analysis of carbohydrates in complex biological samples. Copyright © 2016 John Wiley & Sons, Ltd.

Direct analysis of psychoactive tryptamine and harmala alkaloids in the Amazonian botanical medicine ayahuasca by liquid chromatography-electrospray ionization-tandem mass spectrometry.

PubMed

McIlhenny, Ethan H; Pipkin, Kelly E; Standish, Leanna J; Wechkin, Hope A; Strassman, Rick; Barker, Steven A

2009-12-18

A direct injection/liquid chromatography-electrospray ionization-tandem mass spectrometry procedure has been developed for the simultaneous quantitation of 11 compounds potentially found in the increasingly popular Amazonian botanical medicine and religious sacrament ayahuasca. The method utilizes a deuterated internal standard for quantitation and affords rapid detection of the alkaloids by a simple dilution assay, requiring no extraction procedures. Further, the method demonstrates a high degree of specificity for the compounds in question, as well as low limits of detection and quantitation despite using samples for analysis that had been diluted up to 200:1. This approach also appears to eliminate potential matrix effects. Method bias for each compound, examined over a range of concentrations, was also determined as was inter- and intra-assay variation. Its application to the analysis of three different ayahuasca preparations is also described. This method should prove useful in the study of ayahuasca in clinical and ethnobotanical research as well as in forensic examinations of ayahuasca preparations.

Liquid chromatography-electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato.

PubMed

Andrade, G C R M; Monteiro, S H; Francisco, J G; Figueiredo, L A; Botelho, R G; Tornisielo, V L

2015-05-15

A quick and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method, using dynamic multiple reaction monitoring and a 1.8-μm particle size analytical column, was developed to determine 57 pesticides in tomato in a 13-min run. QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for samples preparations and validations was carried out in compliance with EU SANCO guidelines. The method was applied to 58 tomato samples. More than 84% of the compounds investigated showed limits of detection equal to or lower than 5 mg kg(-1). A mild (<20%), medium (20-50%), and strong (>50%) matrix effect was observed for 72%, 25%, and 3% of the pesticides studied, respectively. Eighty-one percent of the pesticides showed recoveries ranging between 70% and 120%. Twelve pesticides were detected in 35 samples, all below the maximum residue levels permitted in the Brazilian legislation; 15 samples exceeded the maximum residue levels established by the EU legislation for methamidophos; and 10 exceeded limits for acephate and four for bromuconazole. Copyright © 2014 Elsevier Ltd. All rights reserved.

Analysis of Compounds Dissolved in Nonpolar Solvents by Electrospray Ionization on Conductive Nanomaterials

NASA Astrophysics Data System (ADS)

Xia, Bing; Gao, Yuanji; Ji, Baocheng; Ma, Fengwei; Ding, Lisheng; Zhou, Yan

2018-03-01

Electrospray ionization mass spectrometry (ESI-MS) technique has limitations in analysis of compounds that are dissolved in nonpolar solvents. In this study, ambient ionization of compounds in solvents that are not "friendly" to electrospray ionization, such as n-hexane, is achieved by conductive nanomaterials spray ionization (CNMSI) on nanomaterial emitters, including carbon nanotubes paper and mesodendritic silver covered metal, which applies high voltages to emitters made of these materials without the assistance of polar solvents. Although the time intensity curves (TIC) commonly vary from 4.5% to 23.7% over analyses, protonated molecular ions were found to be the most abundant species, demonstrating good reproducibility of the technique in terms of ionized species. Higher mass spectrometric responses are observed in analyzing nonpolar systems than polar systems. 2-Methoxyacetophenone, 4-methylacetophenone, benzothiazole, quinolone, and cycloheptanone as low as 2 pg in n-hexane can be directly detected using the developed method. The developed technique expands the analysis capability of ESI-MS for direct, online analysis of nonpolar systems, such as low polarity extracts, normal phase liquid chromatography eluates, and synthetic mixtures. [Figure not available: see fulltext.

Detection of protein modifications and counterfeit protein pharmaceuticals using isotope tags for relative and absolute quantification and matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry: studies of insulins.

PubMed

Ye, Hongping; Hill, John; Kauffman, John; Gryniewicz, Connie; Han, Xianlin

2008-08-15

Isotope tags for relative and absolute quantification (iTRAQ) reagent coupled with matrix-assisted laser desorption/ionization tandem time-of-flight (MALDI-TOF/TOF) mass spectrometric analysis has been evaluated as both a qualitative and quantitative method for the detection of modifications to active pharmaceutical ingredients derived from recombinant DNA technologies and as a method to detect counterfeit drug products. Five types of insulin (human, bovine, porcine, Lispro, and Lantus) were used as model products in the study because of their minor variations in amino acid sequence. Several experiments were conducted in which each insulin variant was separately digested with Glu-C, and the digestate was labeled with one of four different iTRAQ reagents. All digestates were then combined for desalting and MALDI-TOF/TOF mass spectrometric analysis. When the digestion procedure was optimized, the insulin sequence coverage was 100%. Five different types of insulin were readily differentiated, including human insulin (P28K29) and Lispro insulin (K28P29), which differ only by the interchange of two contiguous residues. Moreover, quantitative analyses show that the results obtained from the iTRAQ method agree well with those determined by other conventional methods. Collectively, the iTRAQ method can be used as a qualitative and quantitative technique for the detection of protein modification and counterfeiting.

A Comparison of Alternating Current and Direct Current Electrospray Ionization for Mass Spectrometry

PubMed Central

Sarver, Scott A.; Gartner, Carlos A.; Chetwani, Nishant; Go, David B.; Dovichi, Norman J.

2014-01-01

A series of studies comparing the performance of alternating current electrospray ionization (AC ESI) mass spectrometry (MS) and direct current electrospray ionization (DC ESI) MS has been conducted, exploring the absolute signal intensity and signal-to-background ratios produced by both methods using caffeine and a model peptide as targets. Because the high-voltage AC signal was more susceptible to generating gas discharges, the operating voltage range of AC ESI was significantly smaller than that for DC ESI, such that the absolute signal intensities produced by DC ESI at peak voltages were 1 - 2 orders of magnitude greater than those for AC ESI. Using an electronegative nebulizing gas, sulfur hexafluoride (SF6), instead of nitrogen (N2) increased the operating range of AC ESI by ~50%, but did not appreciably improve signal intensities. While DC ESI generated far greater signal intensities, both ionization methods produced comparable signal-to-background noise, with AC ESI spectra appearing qualitatively cleaner. A quantitative calibration analysis was performed for two analytes, caffeine and the peptide MRFA. AC ESI utilizing SF6 outperforms all other techniques for the detection of MRFA, producing chromatographic limits of detection nearly one order of magnitude lower than that of DC ESI utilizing N2, and one half that of DC ESI utilizing SF6. However, DC ESI outperforms AC ESI for the analysis of caffeine, indicating improvements in spectral quality may benefit certain compounds, or classes of compounds, on an individual basis. PMID:24464359

Ultrafast multiphoton ionization dynamics and control of NaK molecules

NASA Astrophysics Data System (ADS)

Davidsson, Jan; Hansson, Tony; Mukhtar, Emad

1998-12-01

The multiphoton ionization dynamics of NaK molecules is investigated experimentally using one-color pump-probe femtosecond spectroscopy at 795 nm and intermediate laser field strengths (about 10 GW/cm2). Both NaK+ and Na+ ions are detected as a function of pulse separation time, pulse intensities, and strong pulse-weak pulse order. To aid in the analysis, the potential energy curves of the two lowest electronic states of NaK+ and the electronic transition dipole moment between them are calculated by the GAUSSIAN94 UCIS method. Different ionization pathways are identified by Franck-Condon analysis, and vibrational dynamics in the A 1Σ+ and 3 1Π states, as well as in the ground state, is observed. Further, the existence of a highly excited (above the adiabatic ionization limit) neutral state of NaK is proposed. By changing the strong pulse-weak pulse order of the pulses, the ionization pathways for production of both ions can be varied and thus controlled.

Multi-detection of preservatives in cheeses by liquid chromatography-tandem mass spectrometry.

PubMed

Fuselli, Fabio; Guarino, Chiara; La Mantia, Alessandro; Longo, Lucia; Faberi, Angelo; Marianella, Rosa Maria

2012-10-01

The incorrect use of preservatives in cheeses may compromise food safety and damage consumers. According to the law, more than one preservative may be contemporarily used in cheeses. So a method for their contemporary detection may be useful for both manufacturers and control agencies quality control. In this research a liquid chromatography-tandem mass spectrometric with electrospray ionization method for the multi-determination of seven preservatives (benzoic acid, citric acid, hexamethylenetetramine, lysozyme, natamycin, nisin and sorbic acid) in cheese was developed. The preservatives were contemporarily extracted from cheese by a single procedure, and analyzed by RP-LC/ESI-MS/MS (Ion Trap) in positive ionization mode, with single reaction monitoring (SRM) acquisition. Three sample types (hard, pasta filata and fresh cheese) were used for method evaluation. Recoveries were mostly higher than 90%; MDLs ranged from 0.02 to 0.26 mgkg(-1), and MQLs were included between 0.07 and 0.88 mgkg(-1). Due to matrix effect, quantitation was performed by referring to a matrix matched calibration curve, for each cheese typology. This method was also applied to commercial cheese samples, with good results. It appears fast, reliable and suitable for both screening and confirmation of the presence and quantitation of the preservatives in a single, multi-detection analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Headspace gas chromatography with flame ionization detection (HS-GC-FID) for the determination of dissolved methane in wastewater.

PubMed

Beale, D J; Tjandraatmadja, G; Toifl, M; Goodman, N

2014-01-01

There is currently a need for a simple, accurate and reproducible method that quantifies the amount of dissolved methane in wastewater in order to realize the potential methane that can be recovered and account for any emissions. This paper presents such a method, using gas chromatography with flame ionization detection fitted with a GS-Gas PRO column coupled with a headspace auto sampler. A practical limit of detection for methane of 0.9 mg L(-1), with a retention time of 1.24 min, was obtained. It was found that the reproducibility and accuracy of the method increased significantly when samples were collected using an in-house constructed bailer sampling device and with the addition of 100 μL hydrochloric acid (HCl) and 25% sodium chloride (NaCl) and sonication for 30 min prior to analysis. Analysis of wastewater samples and wastewater sludge collected from a treatment facility were observed to range from 12.51 to 15.79 mg L(-1) (relative standard deviation (RSD) 8.1%) and 17.56 to 18.67 mg L(-1) (RSD 3.4%) respectively. The performance of this method was validated by repeatedly measuring a mid-level standard (n=8; 10 mg L(-1)), with an observed RSD of 4.6%.

Rapid screening of basic colorants in processed vegetables through mass spectrometry using an interchangeable thermal desorption electrospray ionization source.

PubMed

Chao, Yu-Ying; Chen, Yen-Ling; Lin, Hong-Yi; Huang, Yeou-Lih

2018-06-20

Thermal desorption electrospray ionization/mass spectrometry (TD-ESI-MS) employing a quickly interchangeable ionization source is a relatively new ambient ionization mass spectrometric technique that has had, to date, only a limited number of applications related to food safety control. With reallocation of resources, this direct-analysis technique has had wider use in food analysis when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to an ambient ionization source from a traditional atmospheric pressure ionization source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants in processed vegetables (PVs), as a proof-of-concept for the detection of basic colorants. While TD-ESI can offer direct qualitative screening analyses for PVs with detection capabilities lower than those provided with liquid chromatography/UV detection within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous food matrices. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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

2012-12-30

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

Rapid analysis of Δ-9-tetrahydrocannabinol in hair using direct analysis in real time ambient ionization orbitrap mass spectrometry.

PubMed

Duvivier, Wilco F; van Beek, Teris A; Pennings, Ed J M; Nielen, Michel W F

2014-04-15

Forensic hair analysis methods are laborious, time-consuming and provide only a rough retrospective estimate of the time of drug intake. Recently, hair imaging methods using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were reported, but these methods require the application of MALDI matrix and are performed under vacuum. Direct analysis of entire locks of hair without any sample pretreatment and with improved spatial resolution would thus address a need. Hair samples were attached to stainless steel mesh screens and scanned in the X-direction using direct analysis in real time (DART) ambient ionization orbitrap MS. The DART gas temperature and the accuracy of the probed hair zone were optimized using Δ-9-tetrahydrocannabinol (THC) as a model compound. Since external contamination is a major issue in forensic hair analysis, sub-samples were measured before and after dichloromethane decontamination. The relative intensity of the THC signal in spiked blank hair versus that of quinine as the internal standard showed good reproducibility (26% RSD) and linearity of the method (R(2)  = 0.991). With the DART hair scan THC could be detected in hair samples from different chronic cannabis users. The presence of THC was confirmed by quantitative liquid chromatography/tandem mass spectrometry. Zones with different THC content could be clearly distinguished, indicating that the method might be used for retrospective timeline assessments. Detection of THC in decontaminated drug user hair showed that the DART hair scan not only probes THC on the surface of hair, but penetrates deeply enough to measure incorporated THC. A new approach in forensic hair analysis has been developed by probing complete locks of hair using DART-MS. Longitudinal scanning enables detection of incorporated compounds and can be used as pre-screening for THC without sample preparation. The method could also be adjusted for the analysis of other drugs of abuse. Copyright © 2014 John Wiley & Sons, Ltd.

Establishment of analysis method for methane detection by gas chromatography

NASA Astrophysics Data System (ADS)

Liu, Xinyuan; Yang, Jie; Ye, Tianyi; Han, Zeyu

2018-02-01

The study focused on the establishment of analysis method for methane determination by gas chromatography. Methane was detected by hydrogen flame ionization detector, and the quantitative relationship was determined by working curve of y=2041.2x+2187 with correlation coefficient of 0.9979. The relative standard deviation of 2.60-6.33% and the recovery rate of 96.36%∼105.89% were obtained during the parallel determination of standard gas. This method was not quite suitable for biogas content analysis because methane content in biogas would be over the measurement range in this method.

Comparison of Ambient and Atmospheric Pressure Ion Sources for Cystic Fibrosis Exhaled Breath Condensate Ion Mobility-Mass Spectrometry Metabolomics

NASA Astrophysics Data System (ADS)

Zang, Xiaoling; Pérez, José J.; Jones, Christina M.; Monge, María Eugenia; McCarty, Nael A.; Stecenko, Arlene A.; Fernández, Facundo M.

2017-08-01

Cystic fibrosis (CF) is an autosomal recessive disorder caused by mutations in the gene that encodes the cystic fibrosis transmembrane conductance regulator (CFTR) protein. The vast majority of the mortality is due to progressive lung disease. Targeted and untargeted CF breath metabolomics investigations via exhaled breath condensate (EBC) analyses have the potential to expose metabolic alterations associated with CF pathology and aid in assessing the effectiveness of CF therapies. Here, transmission-mode direct analysis in real time traveling wave ion mobility spectrometry time-of-flight mass spectrometry (TM-DART-TWIMS-TOF MS) was tested as a high-throughput alternative to conventional direct infusion (DI) electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) methods, and a critical comparison of the three ionization methods was conducted. EBC was chosen as the noninvasive surrogate for airway sampling over expectorated sputum as EBC can be collected in all CF subjects regardless of age and lung disease severity. When using pooled EBC collected from a healthy control, ESI detected the most metabolites, APCI a log order less, and TM-DART the least. TM-DART-TWIMS-TOF MS was used to profile metabolites in EBC samples from five healthy controls and four CF patients, finding that a panel of three discriminant EBC metabolites, some of which had been previously detected by other methods, differentiated these two classes with excellent cross-validated accuracy.

Determination of coumarin, vanillin, and ethyl vanillin in vanilla extract products: liquid chromatography mass spectrometry method development and validation studies.

PubMed

de Jager, Lowri S; Perfetti, Gracia A; Diachenko, Gregory W

2007-03-23

A LC-MS method was developed for the determination of coumarin, vanillin, and ethyl vanillin in vanilla products. Samples were analyzed using LC-electrospray ionization (ESI)-MS in the positive ionization mode. Limits of detection for the method ranged from 0.051 to 0.073 microg mL(-1). Using the optimized method, 24 vanilla products were analyzed. All samples tested negative for coumarin. Concentrations ranged from 0.38 to 8.59 mg mL(-1) (x =3.73) for vanillin and 0.33 to 2.27 mg mL(-1) (x =1.03) for ethyl vanillin. The measured concentrations are compared to values calculated using UV monitoring and to results reported in a similar survey in 1988. Analytical results, method precision, and accuracy data are presented.

MALDI, AP/MALDI and ESI techniques for the MS detection of amyloid [beta]-peptides

NASA Astrophysics Data System (ADS)

Grasso, Giuseppe; Mineo, Placido; Rizzarelli, Enrico; Spoto, Giuseppe

2009-04-01

Amyloid [beta]-peptides (A[beta]s) are involved in several neuropathological conditions such as Alzheimer's disease and considerable experimental evidences have emerged indicating that different proteases play a major role in regulating the accumulation of A[beta]s in the brain. Particularly, insulin-degrading enzyme (IDE) has been shown to degrade A[beta]s at different cleavage sites, but the experimental results reported in the literature and obtained by mass spectrometry methods are somehow fragmentary. The detection of A[beta]s is often complicated by solubility issues, oxidation artifacts and spontaneous aggregation/cleavage and, in order to rationalize the different reported results, we analyzed A[beta]s solutions by three different MS approaches: matrix assisted laser desorption ionization-time of flight (MALDI-TOF), atmospheric pressure (AP) MALDI ion trap and electrospray ionization (ESI) ion trap. Differences in the obtained results are discussed and ESI is chosen as the most suitable MS method for A[beta]s detection. Finally, cleavage sites produced by interaction of A[beta]s with IDE are identified, two of which had never been reported in the literature.

Determination of benzothiazole and benzotriazole derivates in tire and clothing textile samples by high performance liquid chromatography-electrospray ionization tandem mass spectrometry.

PubMed

Avagyan, Rozanna; Sadiktsis, Ioannis; Thorsén, Gunnar; Östman, Conny; Westerholm, Roger

2013-09-13

A high performance liquid chromatography-tandem mass spectrometry method utilizing electrospray ionization in positive and negative mode has been developed for the separation and detection of benzothiazole and benzotriazole derivates. Ultra-sonication assisted solvent extraction of these compounds has also been developed and the overall method demonstrated on a selected clothing textile and an automobile tire sample. Matrix effects and extraction recoveries, as well as linearity and limits of detection have been evaluated. The calibration curves spanned over more than two orders of magnitude with coefficients of correlation R(2)>0.99 and the limits of detection and the limits of quantification were in the range 1.7-58pg injected and 18-140pg/g, respectively. The extraction recoveries ranged between 69% and 102% and the matrix effects between 75% and 101%. Benzothiazole and benzotriazole derivates were determined in the textile sample and benzothiazole derivatives determined in the tire sample with good analytical performance. Copyright © 2013 Elsevier B.V. All rights reserved.

Gain Switching for a Detection System to Accommodate a Newly Developed MALDI-Based Quantification Method

NASA Astrophysics Data System (ADS)

Ahn, Sung Hee; Hyeon, Taeghwan; Kim, Myung Soo; Moon, Jeong Hee

2017-09-01

In matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF), matrix-derived ions are routinely deflected away to avoid problems with ion detection. This, however, limits the use of a quantification method that utilizes the analyte-to-matrix ion abundance ratio. In this work, we will show that it is possible to measure this ratio by a minor instrumental modification of a simple form of MALDI-TOF. This involves detector gain switching. [Figure not available: see fulltext.

A Miniaturized Linear Wire Ion Trap with Electron Ionization and Single Photon Ionization Sources

NASA Astrophysics Data System (ADS)

Wu, Qinghao; Tian, Yuan; Li, Ailin; Andrews, Derek; Hawkins, Aaron R.; Austin, Daniel E.

2017-05-01

A linear wire ion trap (LWIT) with both electron ionization (EI) and single photon ionization (SPI) sources was built. The SPI was provided by a vacuum ultraviolet (VUV) lamp with the ability to softly ionize organic compounds. The VUV lamp was driven by a pulse amplifier, which was controlled by a pulse generator, to avoid the detection of photons during ion detection. Sample gas was introduced through a leak valve, and the pressure in the system is shown to affect the signal-to-noise ratio and resolving power. Under optimized conditions, the limit of detection (LOD) for benzene was 80 ppbv using SPI, better than the LOD using EI (137 ppbv). System performance was demonstrated by distinguishing compounds in different classes from gasoline.

The mechanism of detection of air pollution by an ionization chamber.

PubMed

Novković, D; Vukanac; Milosević, Z

2000-01-01

The mechanism of detection of chemical vapors in air by an ionization chamber supplied by DC and AC voltage has been described. The theoretical explanation is based on numerical solutions of the differential equations of the cylindrical ionization chamber. The current of the ionization chamber operating in the AC regime has two components: a conductive component, caused by the ions drifts, and a capacitive component, caused by the distortion of the electric field. The ionization chamber operating in the DC regime has only the first component; hence the AC supplied chamber has larger response than the DC supplied chamber.

Detection of creatinine in exhaled breath of humans with chronic kidney disease by extractive electrospray ionization mass spectrometry.

PubMed

Zeng, Qian; Li, Penghui; Cai, Yunfeng; Zhou, Wei; Wang, Haidong; Luo, Jiao; Ding, Jianhua; Chen, Huanwen

2016-02-09

Exhaled breath contains chemicals that have a diagnostic value in human pathologies. Here in vivo breath analysis of creatinine has been demonstrated by constructing a novel platform based on extractive electrospray ionization mass spectrometry (EESI-MS) without sample pretreatment. Under optimized experimental conditions, the limit of creatinine detection in breath was 30.57 ng L(-1), and the linear range of detection was from 0.3 μg L(-1) to 100 μg L(-1). The concentration range of creatinine in the exhaled breath of 50 volunteers with chronic kidney disease was from 42 pptv to 924 pptv, and the range of the relative standard deviations was from 9.3% to 19.2%. The method provides high sensitivity, high specificity and high speed for semi-quantitative analysis of creatinine in exhaled human breath.

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

PubMed

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

2018-05-09

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

[Study for the revision of analytical method for tris (2,3-dibromopropyl) phosphate with restriction in textiles].

PubMed

Mimura, Mayumi; Nakashima, Harunobu; Yoshida, Jin; Yoshida, Toshiaki; Kawakami, Tsuyoshi; Isama, Kazuo

2014-01-01

The official analytical method for tris(2,3-dibromopropyl)phosphate (TDBPP), which is banned from use in textile products by the "Act on Control of Household Products Containing Harmful Substances", requires revision. This study examined an analytical method for TDBPP by GC/MS using a capillary column. Thermal decomposition of TDBPP was observed by GC/MS measurement using capillary column, unlike in the case of gas chromatography/flame photometric detector (GC/FPD) measurement based on a direct injection method using a capillary megabore column. A quadratic curve, Y=2572X(1.416), was obtained for the calibration curve of GC/FPD in the concentration range 2.0-100 μg/mL. The detection limit was 1.0 μg/mL under S/N=3. The reproducibility for repetitive injections was satisfactory. A pretreatment method was established using methanol extraction, followed by liquid-liquid partition and purification with a florisil cartridge column. The recovery rate of this method was ～100%. TDBPP was not detected in any of the five commercial products that this study analyzed. To understand the cause of TDBPP decomposition during GC/MS (electron ionization; EI) measurement using capillary column, GC/MS (chemical ionization; CI), GC/FPD, and gas chromatography/flame ionization detector (GC/FID) measurements were conducted. It was suggested that TDBPP might thermally decompose both during GC injection, especially through a splitless injection method, and in the column or ion sources. To attempt GC/MS measurement, an injection part comprising quartz liner was used and the column length was halved (15 m); thus, only one peak could be obtained.

Solvent jet desorption capillary photoionization-mass spectrometry.

PubMed

Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2015-03-17

A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper.

Enhanced signal generation for use in the analysis of synthetic pyrethroids using chemical ionization tandem quadrupole ion trap mass spectrometry.

PubMed

Sichilongo, Kwenga

2004-12-01

Synthetic pyrethroids fragment extensively under electron ionization (EI) conditions to give low mass ions, most of them with the same m/z ratios. This fragmentation is primarily due to the labile ester linkage found in these compounds. In this research we established the best gas chromatography (GC) conditions in the EI mode that served as a benchmark in the development of a chemical ionization (CI) protocol for ten selected synthetic pyrethroids. Based on proton affinity data, several reagent gases were evaluated in the positive CI ionization mode. Methanol was found to produce higher average ion counts relative to the other gases evaluated, which led to the development of an optimized method consisting of selective ejection chemical ionization (SECI) and MS/MS. Standard stainless steel ion trap electrodes produced significant degradation of chromatographic performance on late eluting compounds, which was attributed to electrode surface chemistry. A dramatic improvement in signal-to-noise (S/N) ratios was observed when the chromatographically inert Silcosteel coated electrodes were used. The resulting method, that has significant S/N ratio improvements resulting from a combination of septum programmable injections (SPI), optimized CI and inert Silcosteel-coated electrodes, was used to determine instrument detection limits.

Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

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

Ovchinnikova, Olga S; Kertesz, Vilmos; Van Berkel, Gary J

This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of thismore » coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.« less

First detection of winds in red giants by microwave continuum techniques

NASA Technical Reports Server (NTRS)

Drake, S. A.; Linsky, J. L.

1983-01-01

Eight red giants and supergiants have been observed at 4885 MHz (6 cm) with the Very Large Array in an attempt to detect continuum emission. The bright giant Alpha-1 Her (M5 II) was detected at an average flux density of 0.9 + or - 0.13 mJy. Since the likely source of this emission is an ionized, optically thick component of a stellar wind, this detection implies a mass loss rate of 2 x 10 to the -9th solar masses per yr for the ionized gas. The fraction of the outflow in Alpha-1 Her that is ionized (0.002-0.02) seems to be similar to that previously found for Alpha Ori and Alpha Sco A. Alpha Boo (K2 IIIp) and Beta Gem (K0 III) are probable and definite detections, respectively. The derived ionized mass loss rates for these two stars are about 1 x 10 to the -10th solar masses per yr, implying in the case of Alpha Boo that the wind is largely ionized.

The photobase generator nifedipine as a novel matrix for the detection of polyphenols in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Nguyen, Huu-Nghi; Tanaka, Mitsuru; Komabayashi, Genki; Matsui, Toshiro

2016-10-01

Matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) is widely used for the detection and analysis of ionizable compounds. However, the method has less potential for the analysis of neutral compounds, such as polyphenols, owing to their lack of favorable proton-attachment or -removal groups. In this study, we reported for the first time that nifedipine (2,6-dimethyl-3,5-dicarbomethoxy-4-(2-nitrophenyl)-1,4-dihydropyridine), which is a strong photobase generator commonly used in polymerization, can abstract protons from neutral compounds in negative mode-MALDI experiments. When nifedipine (5 mg/ml) was used as a matrix reagent, the limit of detection (LOD) for epigallocatechin-3-O-gallate (EGCG) was determined to be 100 fmol/spot, which constitutes >50-fold improvement compared to the LOD obtained when trans-3-indoleacrylic acid, a matrix reagent previously reported for polyphenol detection, was used. Of the dihydropyridines investigated, only nifedipine facilitated the detection of EGCG, suggesting that the nitrosophenyl pyridine derivative of nifedipine formed by photoreduction under laser irradiation at 355 nm plays a crucial role in detecting polyphenols in negative mode. Reduced MS detection of 5-O-methylnaringenin indicated that nifedipine may preferably remove a proton from the 5-position OH group in the A ring of the flavonoid skeleton. The significant MS detection by nifedipine was extensively observed for polyphenols including flavones, flavonones, chalcones, stilbenoids and phenolic acids. In conclusion, nifedipine can act as a novel matrix for improving polyphenol detection by MALDI-MS in negative mode. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Rapid Trace Detection and Isomer Quantitation of Pesticide Residues via Matrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wu, Xinzhou; Li, Weifeng; Guo, Pengran; Zhang, Zhixiang; Xu, Hanhong

2018-04-18

Matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) has been applied for rapid, sensitive, undisputed, and quantitative detection of pesticide residues on fresh leaves with little sample pretreatment. Various pesticides (insecticides, bactericides, herbicides, and acaricides) are detected directly in the complex matrix with excellent limits of detection down to 4 μg/L. FTICR-MS could unambiguously identify pesticides with tiny mass differences (∼0.017 75 Da), thereby avoiding false-positive results. Remarkably, pesticide isomers can be totally discriminated by use of diagnostic fragments, and quantitative analysis of pesticide isomers is demonstrated. The present results expand the horizons of the MALDI-FTICR-MS platform in the reliable determination of pesticides, with integrated advantages of ultrahigh mass resolution and accuracy. This method provides growing evidence for the resultant detrimental effects of pesticides, expediting the identification and evaluation of innovative pesticides.

Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research

NASA Astrophysics Data System (ADS)

Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F. C.; Geske, M.; Taha, A.; Pelzer, K.; Schlögl, R.

2006-05-01

A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000°C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100μm sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10ms. A detection time resolution of up to 20ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N2 and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N2 to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250°C on a Pt catalyst are presented. The detection of CH3• radicals is successfully demonstrated.

Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research

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

Horn, R.; Ihmann, K.; Ihmann, J.

2006-05-15

A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000 deg. C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100 {mu}m sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecularmore » beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10 ms. A detection time resolution of up to 20 ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N{sub 2} and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N{sub 2} to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250 deg. C on a Pt catalyst are presented. The detection of CH{sub 3}{center_dot} radicals is successfully demonstrated.« less

Critical factors determining the quantification capability of matrix-assisted laser desorption/ionization– time-of-flight mass spectrometry

PubMed Central

Wang, Chia-Chen; Lai, Yin-Hung; Ou, Yu-Meng; Chang, Huan-Tsung; Wang, Yi-Sheng

2016-01-01

Quantitative analysis with mass spectrometry (MS) is important but challenging. Matrix-assisted laser desorption/ionization (MALDI) coupled with time-of-flight (TOF) MS offers superior sensitivity, resolution and speed, but such techniques have numerous disadvantages that hinder quantitative analyses. This review summarizes essential obstacles to analyte quantification with MALDI-TOF MS, including the complex ionization mechanism of MALDI, sensitive characteristics of the applied electric fields and the mass-dependent detection efficiency of ion detectors. General quantitative ionization and desorption interpretations of ion production are described. Important instrument parameters and available methods of MALDI-TOF MS used for quantitative analysis are also reviewed. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644968

Attachment of chloride anion to sugars: mechanistic investigation and discovery of a new dopant for efficient sugar ionization/detection in mass spectrometers.

PubMed

Boutegrabet, Lemia; Kanawati, Basem; Gebefügi, Istvan; Peyron, Dominique; Cayot, Philippe; Gougeon, Régis D; Schmitt-Kopplin, Philippe

2012-10-08

A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum model (PCM) for calculations in solution at the high B3LYP/6-31+G(d,p)//B3LYP/6-311+G(2d,p) level of theory. In all optimized geometries of identified [M+Cl](-) anions, a non-covalent interaction exists. Differences were revealed between monodentate and bidentate complex anions, with the latter having noticeably higher binding energies. The calculated affinity of glucose and galactose toward the chloride anion in the gas phase and their chloride anion binding energies in solution are in excellent agreement with glucose and galactose [M+Cl](-) experimental intensity profiles that are represented as a function of the chloride ion concentration. Density functional calculations of gas-phase affinities toward chloride anion were also performed for the studied disaccharides sucrose and gentiobiose. All calculations are in excellent agreement with the experimental data. An example is introduced wherein HCl was used to effectively ionize sugars and form chlorinated adduct anions to detect sugars and glycosylated metabolites (anthocyanins) in real biological systems (Vitis vinifera grape extracts and wines), whereas they would not have been easily detectable under standard infusion electrospray mass spectrometry conditions as deprotonated species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of making a scintillator waveguide

DOEpatents

Bliss, Mary; Craig, Richard A.; Reeder, Paul L.

2000-01-01

The present invention is an apparatus for detecting ionizing radiation, having: a waveguide having a first end and a second end, the waveguide formed of a scintillator material wherein the therapeutic ionizing radiation isotropically generates scintillation light signals within the waveguide. This apparatus provides a measure of radiation dose. The apparatus may be modified to permit making a measure of location of radiation dose. Specifically, the scintillation material is segmented into a plurality of segments; and a connecting cable for each of the plurality of segments is used for conducting scintillation signals to a scintillation detector.

The kinetic energy spectrum of protons produced by the dissociative ionization of H2 by electron impact

NASA Technical Reports Server (NTRS)

Khakoo, M. A.; Srivastava, S. K.

1985-01-01

The kinetic energy spectra of protons resulting from the dissociative ionization of H2 by electron impact have been measured for electron impact energies from threshold (approximately 17 eV) to 160 eV at 90 deg and 30 deg detection angles, using a crossed-beam experimental arrangement. To check reliability, two separate proton energy analysis methods have been employed, i.e., a time-of-flight proton energy analysis and an electrostatic hemispherical energy analyzer. The present results are compared with previous measurements.

Pulsed helium ionization detection system

DOEpatents

Ramsey, R.S.; Todd, R.A.

1985-04-09

A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

Pulsed helium ionization detection system

DOEpatents

Ramsey, Roswitha S.; Todd, Richard A.

1987-01-01

A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

The ionized gas at the centre of IC 10: a possible localized chemical pollution by Wolf-Rayet stars

NASA Astrophysics Data System (ADS)

López-Sánchez, Á. R.; Mesa-Delgado, A.; López-Martín, L.; Esteban, C.

2011-03-01

We present results from integral field spectroscopy with the Potsdam Multi-Aperture Spectrograph at the 3.5-m telescope at Calar Alto Observatory of the intense star-forming region [HL90] 111 at the centre of the starburst galaxy IC 10. We have obtained maps with a spatial sampling of 1 × 1 arcsec2= 3.9× 3.9 pc2 of different emission lines and analysed the extinction, physical conditions, nature of the ionization and chemical abundances of the ionized gas, as well determined locally the age of the most recent star formation event. By defining several apertures, we study the main integrated properties of some regions within [HL90] 111. Two contiguous spaxels show an unambiguous detection of the broad He IIλ4686 emission line, this feature seems to be produced by a single late-type WN star. We also report a probable N and He enrichment in the precise spaxels where the Wolf-Rayet (WR) features are detected. The enrichment pattern is roughly consistent with that expected for the pollution of the ejecta of a single or a very small number of WR stars. Furthermore, this chemical pollution is very localized (˜2 arcsec ˜7.8 pc) and it should be difficult to detect in star-forming galaxies beyond the Local Volume. We also discuss the use of the most common empirical calibrations to estimate the oxygen abundances of the ionized gas in nearby galaxies from 2D spectroscopic data. The ionization degree of the gas plays an important role when applying these empirical methods, as they tend to give lower oxygen abundances with increasing ionization degree. Based on observations collected at the Centro Astrónomico Hispano Alemán (CAHA) at Calar Alto, operated jointly by the Max-Plank Institut für Astronomie and the Instituto de Astrofísica de Andalucía (CSIC).Visiting Astronomer at the Instituto de Astrofísica de Canarias.

In situ mass analysis of particles by surface ionization mass spectrometry

NASA Technical Reports Server (NTRS)

Lassiter, W. S.; Moen, A. L.

1974-01-01

A qualitative study of the application of surface ionization and mass spectrometry to the in situ detection and constituent analysis of atmospheric particles was conducted. The technique consists of mass analysis of ions formed as a result of impingement of a stream of particles on a hot filament where, it is presumed, surface ionization takes place. Laboratory air particles containing K, Ca, and possibly hydrocarbons were detected. Other known particles such as Al2O3, Pb(NO3)2, and Cr2O3 were analyzed by detecting the respective metal atoms making up the particles. In some cases, mass numbers indicative of compounds making up the particles were detected showing surface ionization of particles sometimes leads to chemical analysis as well as to elemental analysis. Individual particles were detected, and it was shown that the technique is sensitive to Al2O3 particles with a mass of a few nanograms.

Mass spectroscopic apparatus and method

DOEpatents

Bomse, David S.; Silver, Joel A.; Stanton, Alan C.

1991-01-01

The disclosure is directed to a method and apparatus for ionization modulated mass spectrometric analysis. Analog or digital data acquisition and processing can be used. Ions from a time variant source are detected and quantified. The quantified ion output is analyzed using a computer to provide a two-dimensional representation of at least one component present within an analyte.

Method for detecting radiation dose utilizing thermoluminescent material

DOEpatents

Miller, Steven D.; McDonald, Joseph C.; Eichner, Fred N.; Durham, James S.

1992-01-01

The amount of ionizing radiation to which a thermoluminescent material has been exposed is determined by first cooling the thermoluminescent material and then optically stimulating the thermoluminescent material by exposure to light. Visible light emitted by the thermoluminescent material as it is allowed to warm up to room temperature is detected and counted. The thermoluminescent material may be annealed by exposure to ultraviolet light.

Method for detecting radiation dose utilizing thermoluminescent material

DOEpatents

Miller, S.D.; McDonald, J.C.; Eichner, F.N.; Durham, J.S.

1992-08-04

The amount of ionizing radiation to which a thermoluminescent material has been exposed is determined by first cooling the thermoluminescent material and then optically stimulating the thermoluminescent material by exposure to light. Visible light emitted by the thermoluminescent material as it is allowed to warm up to room temperature is detected and counted. The thermoluminescent material may be annealed by exposure to ultraviolet light. 5 figs.

Kinematically complete study of low-energy electron-impact ionization of argon: Internormalized cross sections in three-dimensional kinematics

NASA Astrophysics Data System (ADS)

Ren, Xueguang; Amami, Sadek; Zatsarinny, Oleg; Pflüger, Thomas; Weyland, Marvin; Dorn, Alexander; Madison, Don; Bartschat, Klaus

2016-06-01

As a further test of advanced theoretical methods to describe electron-impact single-ionization processes in complex atomic targets, we extended our recent work on Ne (2 p ) ionization [X. Ren, S. Amami, O. Zatsarinny, T. Pflüger, M. Weyland, W. Y. Baek, H. Rabus, K. Bartschat, D. Madison, and A. Dorn, Phys. Rev. A 91, 032707 (2015), 10.1103/PhysRevA.91.032707] to Ar (3 p ) ionization at the relatively low incident energy of E0=66 eV. The experimental data were obtained with a reaction microscope, which can cover nearly the entire 4 π solid angle for the secondary electron emission. We present experimental data for detection angles of 10, 15, and 20∘ for the faster of the two outgoing electrons as a function of the detection angle of the secondary electron with energies of 3, 5, and 10 eV, respectively. Comparison with theoretical predictions from a B -spline R -matrix (BSR) with pseudostates approach and a three-body distorted-wave (3DW) approach, for detection of the secondary electron in three orthogonal planes as well as the entire solid angle, shows overall satisfactory agreement between experiment and the BSR results, whereas the 3DW approach faces difficulties in predicting some of the details of the angular distributions. These findings are different from our earlier work on Ne (2 p ), where both the BSR and 3DW approaches yielded comparable levels of agreement with the experimental data.

[C ii] 158 μm line detection of the warm ionized medium in the Scutum-Crux spiral arm tangency

NASA Astrophysics Data System (ADS)

Velusamy, T.; Langer, W. D.; Pineda, J. L.; Goldsmith, P. F.

2012-05-01

Context. The Herschel HIFI GOT C+ Galactic plane [C ii] spectral survey has detected strong emission at the spiral arm tangencies. Aims: We use the unique viewing geometry of the Scutum-Crux (S-C) tangency nearl = 30° to detect the warm ionized medium (WIM) component traced by [CII] and to study the effects of spiral density waves on Interstellar Medium (ISM) gas. Methods: We compare [C ii] velocity features with ancillary H i, 12CO and 13CO data near tangent velocities at each longitude to separate the cold neutral medium and the warm neutral + ionized components in the S-C tangency, then we identify [C ii] emission at the highest velocities without any contribution from 12CO clouds, as WIM. Results: We present the GOT C+ results for the S-C tangency. We interpret the diffuse and extended excess [C ii] emission at and above the tangent velocities as arising in the electron-dominated warm ionized gas in the WIM. We derive an electron density in the range of 0.2-0.9 cm-3 at each longitude, a factor of several higher than the average value from Hα and pulsar dispersion. Conclusions: We interpret the excess [C ii] in S-C tangency as shock compression of the WIM induced by the spiral density waves. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

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

PubMed

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

2015-11-10

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

Rapid determination of the isomeric truxillines in illicit cocaine via capillary gas chromatography/flame ionization detection and their use and implication in the determination of cocaine origin and trafficking routes.

PubMed

Mallette, Jennifer R; Casale, John F

2014-10-17

The isomeric truxillines are a group of minor alkaloids present in all illicit cocaine samples. The relative amount of truxillines in cocaine is indicative of the variety of coca used for cocaine processing, and thus, is useful in source determination. Previously, the determination of isomeric truxillines in cocaine was performed with a gas chromatography/electron capture detection method. However, due to the tedious sample preparation as well as the expense and maintenance required of electron capture detectors, the protocol was converted to a gas chromatography/flame-ionization detection method. Ten truxilline isomers (alpha-, beta-, delta-, epsilon-, gamma-, omega, zeta-, peri-, neo-, and epi-) were quantified relative to a structurally related internal standard, 4',4″-dimethyl-α-truxillic acid dimethyl ester. The method was shown to have a linear response from 0.001 to 1.00 mg/mL and a lower detection limit of 0.001 mg/mL. In this method, the truxillines are directly reduced with lithium aluminum hydride and then acylated with heptafluorobutyric anhydride prior to analysis. The analysis of more than 100 cocaine hydrochloride samples is presented and compared to data obtained by the previous methodology. Authentic cocaine samples obtained from the source countries of Colombia, Bolivia, and Peru were also analyzed, and comparative data on more than 23,000 samples analyzed over the past 10 years with the previous methodology is presented. Published by Elsevier B.V.

Proportional counter device for detecting electronegative species in an air sample

DOEpatents

Allman, Steve L.; Chen, Fang C.; Chen, Chung-Hsuan

1994-01-01

Apparatus for detecting an electronegative species comprises an analysis chamber, an inlet communicating with the analysis chamber for admitting a sample containing the electronegative species and an ionizable component, a radioactive source within the analysis chamber for emitting radioactive energy for ionizing a component of the sample, a proportional electron detector within the analysis chamber for detecting electrons emitted from the ionized component, and a circuit for measuring the electrons and determining the presence of the electronegative species by detecting a reduction in the number of available electrons due to capture of electrons by the electronegative species.

Proportional counter device for detecting electronegative species in an air sample

DOEpatents

Allman, S.L.; Chen, F.C.; Chen, C.H.

1994-03-08

Apparatus for detecting an electronegative species comprises an analysis chamber, an inlet communicating with the analysis chamber for admitting a sample containing the electronegative species and an ionizable component, a radioactive source within the analysis chamber for emitting radioactive energy for ionizing a component of the sample, a proportional electron detector within the analysis chamber for detecting electrons emitted from the ionized component, and a circuit for measuring the electrons and determining the presence of the electronegative species by detecting a reduction in the number of available electrons due to capture of electrons by the electronegative species. 2 figures.

Analysis of Intrinsic Peptide Detectability via Integrated Label-Free and SRM-Based Absolute Quantitative Proteomics.

PubMed

Jarnuczak, Andrew F; Lee, Dave C H; Lawless, Craig; Holman, Stephen W; Eyers, Claire E; Hubbard, Simon J

2016-09-02

Quantitative mass spectrometry-based proteomics of complex biological samples remains challenging in part due to the variability and charge competition arising during electrospray ionization (ESI) of peptides and the subsequent transfer and detection of ions. These issues preclude direct quantification from signal intensity alone in the absence of a standard. A deeper understanding of the governing principles of peptide ionization and exploitation of the inherent ionization and detection parameters of individual peptides is thus of great value. Here, using the yeast proteome as a model system, we establish the concept of peptide F-factor as a measure of detectability, closely related to ionization efficiency. F-factor is calculated by normalizing peptide precursor ion intensity by absolute abundance of the parent protein. We investigated F-factor characteristics in different shotgun proteomics experiments, including across multiple ESI-based LC-MS platforms. We show that F-factors mirror previously observed physicochemical predictors as peptide detectability but demonstrate a nonlinear relationship between hydrophobicity and peptide detectability. Similarly, we use F-factors to show how peptide ion coelution adversely affects detectability and ionization. We suggest that F-factors have great utility for understanding peptide detectability and gas-phase ion chemistry in complex peptide mixtures, selection of surrogate peptides in targeted MS studies, and for calibration of peptide ion signal in label-free workflows. Data are available via ProteomeXchange with identifier PXD003472.

Matrix-assisted laser-desorption/ionization mass spectrometric imaging of olanzapine in a single hair using esculetin as a matrix.

PubMed

Wang, Hang; Wang, Ying; Wang, Ge; Hong, Lizhi

2017-07-15

Matrix-assisted laser desorption/ionization-mass spectrometric imaging (MALDI-MSI) for the analysis of intact hair is a powerful tool for monitoring changes in drug consumption. The embedding of a low drug concentration in the hydrophobic hair matrix makes it difficult to extract and detect, and requires an improved method to increase detection sensitivity. In this study, an MSI method using MALDI-Fourier transform ion cyclotron resonance was developed for direct identification and imaging of olanzapine in hair samples using the positive ion mode. Following decontamination, scalp hair samples from an olanzapine user were scraped from the proximal to the distal end three times, and 5mm hair sections were fixed onto an Indium-Tin-Oxide (ITO)-coated microscopic glass slide. Esculetin (6,7-dihydroxy-2H-chromen-2-one) was used as a new hydrophobic matrix to increase the affinity, extraction and ionization efficiency of olanzapine in the hair samples. The spatial distribution of olanzapine was observed using five single hairs from the same drug user. This matrix improves the affinity of olanzapine in hair for molecular imaging with mass spectrometry. This method may provide a detection power for olanzapine to the nanogram level per 5mm hair. Time course changes in the MSI results were also compared with quantitative HPLC-MS/MS for each 5mm segment of single hair shafts selected from the MALDI target. MALDI imaging intensities in single hairs showed good semi-quantitative correlation with the results from conventional HPLC-MS/MS. MALDI-MSI is suitable for monitoring drug intake with a high time resolution. Copyright © 2017 Elsevier B.V. All rights reserved.

Method for Continuous Monitoring of Electrospray Ion Formation

NASA Astrophysics Data System (ADS)

Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

2017-10-01

A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes. [Figure not available: see fulltext.

Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

NASA Technical Reports Server (NTRS)

Boumsellek, S.; Alajajian, S. H.; Chutjian, A.

1992-01-01

First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

Analysis of the cyanolichen Lichina pygmaea metabolites using in situ DART-MS: from detection to thermochemistry of mycosporine serinol.

PubMed

Le Pogam, Pierre; Legouin, Béatrice; Le Lamer, Anne-Cécile; Boustie, Joël; Rondeau, David

2015-03-01

Direct Analysis in Real Time DART-HRMS is here first applied to the detection of molecules from a lichen, Lichina pygmaea. The aim was to propose an innovative method of in situ detection of lichen secondary metabolites using the possibilities of elemental composition determination available when a DART source is interfaced with a TOF analyzer. Three kinds of samples have been submitted to DART ionization, i.e. an intact thallus, a powder obtained from the crushed lichen and an aqueous extract. In situ analysis of crushed lichen, yields an extensive chemical profile, comparable to what is obtained from the aqueous extract, comprising both major polar metabolites described in literature along with some other signals that could correspond to potentially unknown metabolites. One of the detected secondary metabolites, mycosporine serinol, underwent a dehydration reaction prior to its transfer in the gas-phase by DART ionization. The consideration of the thermal transfers involved in the DART ionization process and the possibility to record time-dependent mass spectra through the use of the TOF analyzer allowed establishing Arrhenius plots of this water molecule loss to obtain associated thermodynamic quantities. The low values of corresponding activation enthalpy (Δr‡Hm° of the order of 25 kJ mol(-1)) enabled formulating some assumption regarding a possible role of such metabolites in the lichen. Copyright © 2015 John Wiley & Sons, Ltd.

Hydrazinonicotinic acid derivatization for selective ionization and improved glycan structure characterization by MALDI-MS.

PubMed

Jiao, Jing; Yang, Lijun; Zhang, Ying; Lu, Haojie

2015-08-21

The analysis of glycan is important for understanding cell biology and disease processes because the glycans play a key role in many important biological behaviors, such as cell division, cellular localization, tumor immunology and inflammation. Nevertheless, it is still hard work to analyze glycans by MALDI-MS, which generally stems from the inherent low abundance and the low ionization efficiency of glycans. Moreover, the difficulty in generating informative fragmentations further hinders glycans structure characterization. In this work, hydrazinonicotinic acid (HYNIC) was used as a novel derivatized reagent for improved and selective detection of glycans. Through tagging the reducing terminus of glycans with the diazanyl group of HYNIC, significant enhancement of the ionization efficiency of glycans was achieved. After derivatization, the signal to noise ratio (S/N) of the maltoheptaose was improved by more than one order of magnitude in positive mode. HYNIC derivatization also allowed the sensitive detection of sialylated glycan in negative mode, with a 15 fold enhancement of S/N. Interestingly, it is noteworthy that the HYNIC reagent not only effectively labeled the reducing end of glycans in the presence of tryptic peptides, but also suppressed the ionization of peptides, enabling the direct detection of glycans from glycoprotein without separation. Therefore, analysis of glycans became easier due to the omission of a pre-separation step. Importantly, by using different acid reagents as the catalyst, derivatized product signals corresponding to [M + Na](+) or [M + H](+) were obtained respectively, which yield complementary fragmentation patterns for the structure elucidation of glycans. Finally, more than 40 N-glycans were successfully detected in 10 μL human serum using this method.

Determination of volatile compounds in wine by gas chromatography-flame ionization detection: comparison between the U.S. Environmental Protection Agency 3sigma approach and Hubaux-Vos calculation of detection limits using ordinary and bivariate least squares.

PubMed

Caruso, Rosario; Scordino, Monica; Traulo, Pasqualino; Gagliano, Giacomo

2012-01-01

A capillary GC-flame ionization detection (FID) method to determine volatile compounds (ethyl acetate, 1,1-diethoxyethane, methyl alcohol, 1-propanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-butanol, and 2-butanol) in wine was investigated in terms of calculation of detection limits and calibration method. The main objectives were: (1) calculation of regression coefficient parameters by ordinary least-squares (OLS) and bivariate least-squares (BLS) regression models, taking into account errors in both axes; (2) estimation of linear dynamic range (LDR) according to International Conference on Harmonization recommendations; (3) performance evaluation of a method by using three different internal standards (ISs) such as acetonitrile, acetone, and 1-pentanol; (4) evaluation of LODs according to the U.S. Environmental Protection Agency (EPA) 3sigma approach and the Hubaux-Vos (H-V) method; (5) application of H-V theory to a gas chromatographic analytical method and to a food matrix; and (6) accuracy assessment of the method relative to methyl alcohol content through a Unione Italiana Vini (UIV) interlaboratory proficiency test. Calibration curves calculated via BLS and OLS show similar slopes, while intercepts are closer to zero in the first case, independent of the chosen IS. The studied ISs show a substantially equivalent behavior, even though the IS closer to the analyte retention time seems to be more appropriate in terms of LDR and LOD. Results indicate an underestimation of LODs using the EPA 3sigma approach instead of the more realistic H-V method, both with OLS and BLS regression models. Methanol contents compared with UIV average values indicate recovery between 90 and 110%.

Real time analysis of brain tissue by direct combination of ultrasonic surgical aspiration and sonic spray mass spectrometry.

PubMed

Schäfer, Karl-Christian; Balog, Júlia; Szaniszló, Tamás; Szalay, Dániel; Mezey, Géza; Dénes, Júlia; Bognár, László; Oertel, Matthias; Takáts, Zoltán

2011-10-15

Direct combination of cavitron ultrasonic surgical aspirator (CUSA) and sonic spray ionization mass spectrometry is presented. A commercially available ultrasonic surgical device was coupled to a Venturi easy ambient sonic-spray ionization (V-EASI) source by directly introducing liquified tissue debris into the Venturi air jet pump. The Venturi air jet pump was found to efficiently nebulize the suspended tissue material for gas phase ion production. The ionization mechanism involving solely pneumatic spraying was associated with that of sonic spray ionization. Positive and negative ionization spectra were obtained from brain and liver samples reflecting the primary application areas of the surgical device. Mass spectra were found to feature predominantly complex lipid-type constituents of tissues in both ion polarity modes. Multiply charged peptide anions were also detected. The influence of instrumental settings was characterized in detail. Venturi pump geometry and flow parameters were found to be critically important in ionization efficiency. Standard solutions of phospholipids and peptides were analyzed in order to test the dynamic range, sensitivity, and suppression effects. The spectra of the intact tissue specimens were found to be highly specific to the histological tissue type. The principal component analysis (PCA) and linear discriminant analysis (LDA) based data analysis method was developed for real-time tissue identification in a surgical environment. The method has been successfully tested on post-mortem and ex vivo human samples including astrocytomas, meningeomas, metastatic brain tumors, and healthy brain tissue. © 2011 American Chemical Society

Total 25-Hydroxyvitamin D Determination by an Entry Level Triple Quadrupole Instrument: Comparison between Two Commercial Kits

PubMed Central

Cocci, Andrea; Zuppi, Cecilia; Persichilli, Silvia

2013-01-01

Objective. 25-hydroxyvitamin D2/D3 (25-OHD2/D3) determination is a reliable biomarker for vitamin D status. Liquid chromatography-tandem mass spectrometry was recently proposed as a reference method for vitamin D status evaluation. The aim of this work is to compare two commercial kits (Chromsystems and PerkinElmer) for 25-OHD2/D3 determination by our entry level LC-MS/MS. Design and Methods. Chromsystems kit adds an online trap column to an HPLC column and provides atmospheric pressure chemical ionization, isotopically labeled internal standard, and 4 calibrator points. PerkinElmer kit uses a solvent extraction and protein precipitation method. This kit can be used with or without derivatization with, respectively, electrospray and atmospheric pressure chemical ionization. For each analyte, there are isotopically labeled internal standards and 7 deuterated calibrator points. Results. Performance characteristics are acceptable for both methods. Mean bias between methods calculated on 70 samples was 1.9 ng/mL. Linear regression analysis gave an R 2 of 0.94. 25-OHD2 is detectable only with PerkinElmer kit in derivatized assay option. Conclusion. Both methods are suitable for routine. Chromsystems kit minimizes manual sample preparation, requiring only protein precipitation, but, with our system, 25-OHD2 is not detectable. PerkinElmer kit without derivatization does not guarantee acceptable performance with our LC-MS/MS system, as sample is not purified online. Derivatization provides sufficient sensitivity for 25-OHD2 detection. PMID:23555079

Direct Detection of Pharmaceuticals and Personal Care Products from Aqueous Samples with Thermally-Assisted Desorption Electrospray Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Campbell, Ian S.; Ton, Alain T.; Mulligan, Christopher C.

2011-07-01

An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

Evaluation of malodor for automobile air conditioner evaporator by using laboratory-scale test cooling bench.

PubMed

Kim, Kyung Hwan; Kim, Sun Hwa; Jung, Young Rim; Kim, Man Goo

2008-09-12

As one of the measures to improve the environment in an automobile, malodor caused by the automobile air-conditioning system evaporator was evaluated and analyzed using laboratory-scale test cooling bench. The odor was simulated with an evaporator test cooling bench equipped with an airflow controller, air temperature and relative humidity controller. To simulate the same odor characteristics that occur from automobiles, one previously used automobile air conditioner evaporator associated with unpleasant odors was selected. The odor was evaluated by trained panels and collected with aluminum polyester bags. Collected samples were analyzed by thermal desorption into a cryotrap and subsequent gas chromatographic separation, followed by simultaneous olfactometry, flame ionization detector and identified by atomic emission detection and mass spectrometry. Compounds such as alcohols, aldehydes, and organic acids were identified as responsible odor-active compounds. Gas chromatography/flame ionization detection/olfactometry combined sensory method with instrumental analysis was very effective as an odor evaluation method in an automobile air-conditioning system evaporator.

Glycan profiling of monoclonal antibodies using zwitterionic-type hydrophilic interaction chromatography coupled with electrospray ionization mass spectrometry detection.

PubMed

Mauko, Lea; Nordborg, Anna; Hutchinson, Joseph P; Lacher, Nathan A; Hilder, Emily F; Haddad, Paul R

2011-01-15

We present a new method for the analysis of glycans enzymatically released from monoclonal antibodies (MAbs) employing a zwitterionic-type hydrophilic interaction chromatography (ZIC-HILIC) column coupled with electrospray ionization mass spectrometry (ESI-MS). Both native and reduced glycans were analyzed, and the developed procedure was compared with a standard HILIC procedure used in the pharmaceutical industry whereby fluorescent-labeled glycans are analyzed using a TSK Amide-80 column coupled with fluorescence detection. The separation of isobaric alditol oligosaccharides present in monoclonal antibodies and ribonuclease B is demonstrated, and ZIC-HILIC is shown to have good capability for structural recognition. Glycan profiles obtained with the ZIC-HILIC column and ESI-MS provided detailed information on MAb glycosylation, including identification of some less abundant glycan species, and are consistent with the profiles generated with the standard procedure. This new ZIC-HILIC method offers a simpler and faster approach for glycosylation analysis of therapeutic antibodies. Copyright © 2010 Elsevier Inc. All rights reserved.

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

Watson, Thomas B.

The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H 3O +), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-chargemore » ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.« less

The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

PubMed

Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail А; Pod'yachev, Sergey P

2014-06-01

A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct detection of pharmaceuticals and personal care products from aqueous samples with thermally-assisted desorption electrospray ionization mass spectrometry.

PubMed

Campbell, Ian S; Ton, Alain T; Mulligan, Christopher C

2011-07-01

An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

Mass spectrometry of selective androgen receptor modulators.

PubMed

Thevis, Mario; Schänzer, Wilhelm

2008-07-01

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

Chemical analysis of raw and processed Fructus arctii by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry

PubMed Central

Qin, Kunming; Liu, Qidi; Cai, Hao; Cao, Gang; Lu, Tulin; Shen, Baojia; Shu, Yachun; Cai, Baochang

2014-01-01

Background: In traditional Chinese medicine (TCM), raw and processed herbs are used to treat the different diseases. Fructus Arctii, the dried fruits of Arctium lappa l. (Compositae), is widely used in the TCM. Stir-frying is the most common processing method, which might modify the chemical compositions in Fructus Arctii. Materials and Methods: To test this hypothesis, we focused on analysis and identification of the main chemical constituents in raw and processed Fructus Arctii (PFA) by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry. Results: The results indicated that there was less arctiin in stir-fried materials than in raw materials. however, there were higher levels of arctigenin in stir-fried materials than in raw materials. Conclusion: We suggest that arctiin reduced significantly following the thermal conversion of arctiin to arctigenin. In conclusion, this finding may shed some light on understanding the differences in the therapeutic values of raw versus PFA in TCM. PMID:25422559

Ambient diode laser desorption dielectric barrier discharge ionization mass spectrometry of nonvolatile chemicals.

PubMed

Gilbert-López, Bienvenida; Schilling, Michael; Ahlmann, Norman; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan F; Franzke, Joachim

2013-03-19

In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface.

Quantitative analysis of the eight major compounds in the Samsoeum using a high-performance liquid chromatography coupled with diode array detection and electrospray ionization mass spectrometer

PubMed Central

Weon, Jin Bae; Yang, Hye Jin; Lee, Bohyoung; Ma, Jin Yeul; Ma, Choong Je

2015-01-01

Background: Samsoeum was traditionally used for treatment of a respiratory disease. Objective: The simultaneous determination of eight major compounds, ginsenoside Rg3, caffeic acid, puerarin, costunolide, hesperidin, naringin, glycyrrhizin, and 6-gingerol in the Samsoeum using a high-performance liquid chromatography (HPLC) coupled with diode array detection (DAD) and an electrospray ionization mass spectrometer was developed for an accurate and reliable quality assessment. Materials and Methods: Eight compounds were qualitative identified based on their mass spectra and by comparing with standard compounds and quantitative analyzed by HPLC-DAD. Separation of eight compounds was carried out on a LUNA C18 column (S-5 μm, 4.6 mm i.d. ×250 mm) with gradient elution composed of acetonitrile and 0.1% trifluoroacetic acid. Results: The data showed good linearity (R2 > 0.9996). The limits of detection and the limits of quantification were <0.53 μg and 1.62 μg, respectively. Inter- and Intra-day precisions (expressed as relative standard deviation values) were within 1.94% and 1.91%, respectively. The recovery of the method was in the range of 94.24–107.90%. Conclusion: The established method is effective and could be applied to quality control of Samsoeum. PMID:25829771

Dual enzyme activities assay by quantitative electrospray ionization quadrupole-time-of-flight mass spectrometry.

PubMed

Cai, Tingting; Zhang, Li; Wang, Haoyang; Zhang, Jing; Wang, Rong; Zhang, Yurong; Guo, Yinlong

2012-01-01

A practical and rapid method based on electrospray ionization quadrupole-time of flight mass spectrometry (ESI-Q-ToF MS) was developed for detecting activities of both acetylcholinesterase IAChEI and glutathione S-transferase (GST). The simultaneous study of these two enzyme activities is significant for studying human bio-functions, especially for those who take in toxic compounds and have a risk of disease. Here, the enzyme activities were represented by the conversion of enzymatic substrates and determined by quantitatively analyzing enzymatic substrates. Different internal standards were used to quantify each enzymatic substrate and the good linearity of calibration curves demonstrated the feasibility of the internal standards. The Michaelis-Menten constants (Km) of both GST and AChE were measured by this method and were consistent with values previously reported. Furthermore, we applied this approach to detect GST and AChE activities of whole bloods from four deceased and healthy people. The variation in enzyme activity was in accord with information from gas chromatography mass spectrometry [GC/MS). The screening of AChE and GST provided reliable results and strong forensic evidence. This method offers an alternative choice for detecting enzyme activities and is anticipated to have wide applications in pharmaceutical research and prevention in toxic compounds.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

PubMed

Abdelhamid, Hani Nasser

2018-03-01

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

Combined electrophoresis-electrospray interface and method

DOEpatents

Smith, Richard D.; Udseth, Harold R.; Barinaga, Charles J.

1995-01-01

An improvement to the system and method for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity.

Detection of DNA–protein crosslinks (DPCs) by novel direct fluorescence labeling methods: distinct stabilities of aldehyde and radiation-induced DPCs

PubMed Central

Shoulkamy, Mahmoud I.; Nakano, Toshiaki; Ohshima, Makiko; Hirayama, Ryoichi; Uzawa, Akiko; Furusawa, Yoshiya; Ide, Hiroshi

2012-01-01

Proteins are covalently trapped on DNA to form DNA–protein crosslinks (DPCs) when cells are exposed to DNA-damaging agents. DPCs interfere with many aspects of DNA transactions. The current DPC detection methods indirectly measure crosslinked proteins (CLPs) through DNA tethered to proteins. However, a major drawback of such methods is the non-linear relationship between the amounts of DNA and CLPs, which makes quantitative data interpretation difficult. Here we developed novel methods of DPC detection based on direct CLP measurement, whereby CLPs in DNA isolated from cells are labeled with fluorescein isothiocyanate (FITC) and quantified by fluorometry or western blotting using anti-FITC antibodies. Both formats successfully monitored the induction and elimination of DPCs in cultured cells exposed to aldehydes and mouse tumors exposed to ionizing radiation (carbon-ion beams). The fluorometric and western blotting formats require 30 and 0.3 μg of DNA, respectively. Analyses of the isolated genomic DPCs revealed that both aldehydes and ionizing radiation produce two types of DPC with distinct stabilities. The stable components of aldehyde-induced DPCs have half-lives of up to days. Interestingly, that of radiation-induced DPCs has an infinite half-life, suggesting that the stable DPC component exerts a profound effect on DNA transactions over many cell cycles. PMID:22730301

Publications - GMC 14 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 14 Publication Details Title: Total organic carbon and flame ionization detectable carbon Unknown, 1979, Total organic carbon and flame ionization detectable carbon analyses cuttings from on-shore

New diagnostic methods for laser plasma- and microwave-enhanced combustion

PubMed Central

Miles, Richard B; Michael, James B; Limbach, Christopher M; McGuire, Sean D; Chng, Tat Loon; Edwards, Matthew R; DeLuca, Nicholas J; Shneider, Mikhail N; Dogariu, Arthur

2015-01-01

The study of pulsed laser- and microwave-induced plasma interactions with atmospheric and higher pressure combusting gases requires rapid diagnostic methods that are capable of determining the mechanisms by which these interactions are taking place. New rapid diagnostics are presented here extending the capabilities of Rayleigh and Thomson scattering and resonance-enhanced multi-photon ionization (REMPI) detection and introducing femtosecond laser-induced velocity and temperature profile imaging. Spectrally filtered Rayleigh scattering provides a method for the planar imaging of temperature fields for constant pressure interactions and line imaging of velocity, temperature and density profiles. Depolarization of Rayleigh scattering provides a measure of the dissociation fraction, and multi-wavelength line imaging enables the separation of Thomson scattering from Rayleigh scattering. Radar REMPI takes advantage of high-frequency microwave scattering from the region of laser-selected species ionization to extend REMPI to atmospheric pressures and implement it as a stand-off detection method for atomic and molecular species in combusting environments. Femtosecond laser electronic excitation tagging (FLEET) generates highly excited molecular species and dissociation through the focal zone of the laser. The prompt fluorescence from excited molecular species yields temperature profiles, and the delayed fluorescence from recombining atomic fragments yields velocity profiles. PMID:26170432

A simple, fast and sensitive screening LC-ESI-MS/MS method for antibiotics in fish.

PubMed

Guidi, Letícia Rocha; Santos, Flávio Alves; Ribeiro, Ana Cláudia S R; Fernandes, Christian; Silva, Luiza H M; Gloria, Maria Beatriz A

2017-01-15

The objective of this study was to develop and validate a fast, sensitive and simple liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method for the screening of six classes of antibiotics (aminoglycosides, beta-lactams, macrolides, quinolones, sulfonamides and tetracyclines) in fish. Samples were extracted with trichloroacetic acid. LC separation was achieved on a Zorbax Eclipse XDB C18 column and gradient elution using 0.1% heptafluorobutyric acid in water and acetonitrile as mobile phase. Analysis was carried out in multiple reaction monitoring mode via electrospray interface operated in the positive ionization mode, with sulfaphenazole as internal standard. The method was suitable for routine screening purposes of 40 antibiotics, according to EC Guidelines for the Validation of Screening Methods for Residues of Veterinary Medicines, taking into consideration threshold value, cut-off factor, detection capability, limit of detection, sensitivity and specificity. Real fish samples (n=193) from aquaculture were analyzed and 15% were positive for enrofloxacin (quinolone), one of them at a higher concentration than the level of interest (50µgkg -1 ), suggesting possible contamination or illegal use of that antibiotic. Copyright © 2016 Elsevier B.V. All rights reserved.

Validation and Application of a Simple UHPLC–MS-MS Method for the Enantiospecific Determination of Warfarin in Human Urine

PubMed Central

Alshogran, Osama Y.; Ocque, Andrew J.; Leblond, François A.; Pichette, Vincent; Nolin, Thomas D.

2016-01-01

A simple and rapid liquid chromatographic–tandem mass spectrometric method has been developed and validated for the enantiospecific determination of R- and S-warfarin in human urine. Warfarin enantiomers were extracted from urine using methyl tert-butyl ether. Chromatographic separation of warfarin enantiomers and the internal standard d5-warfarin was achieved using a Astec Chirobiotic V column with gradient mobile phase at a flow rate of 400 µL/min over 10 min. Detection was performed on a TSQ Quantum Ultra triple quadrupole mass spectrometer equipped with a heated electrospray ionization source. Analytes were detected in negative ionization mode using selected reaction monitoring. Calibration curves were linear with a correlation coefficient of ≥0.996 for both enantiomers over a concentration range of 5–500 ng/mL. The intra- and interday accuracy and precision for both analytes were within ±9.0%. Excellent extraction efficiency and negligible matrix effects were observed. The applicability of the method was demonstrated by successful measurement of warfarin enantiomers in urine of patients with kidney disease. The method is simple, accurate and reproducible and is currently being used to support warfarin pharmacokinetic studies. PMID:26657732

Method for detecting radiation dose utilizing thermoluminescent material

DOEpatents

Miller, Steven D.; McDonald, Joseph C.; Eichner, Fred N.; Tomeraasen, Paul L.

1991-01-01

The amount of ionizing radiation to which a thermoluminescent material has been exposed is determined by first cooling the thermoluminescent material to a cryogenic temperature. The thermoluminescent material is then optically stimulated by exposure to ultraviolet light. Visible light emitted by the thermoluminescent material as it is allowed to warm up to room temperature is detected and counted. The thermoluminescent material may be annealed by exposure to ultraviolet light.

Method for detecting and distinguishing between specific types of environmental radiation using a high pressure ionization chamber with pulse-mode readout

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

Degtiarenko, Pavel V.

An environmental radiation detector for detecting and distinguishing between all types of environmental radiation, including photons, charged particles, and neutrons. A large volume high pressure ionization chamber (HPIC) includes BF.sub.3 gas at a specific concentration to render the radiation detector sensitive to the reactions of neutron capture in Boron-10 isotope. A pulse-mode readout is connected to the ionization chamber capable of measuring both the height and the width of the pulse. The heavy charged products of the neutron capture reaction deposit significant characteristic energy of the reaction in the immediate vicinity of the reaction in the gas, producing a signalmore » with a pulse height proportional to the reaction energy, and a narrow pulse width corresponding to the essentially pointlike energy deposition in the gas. Readout of the pulse height and the pulse width parameters of the signals enables distinguishing between the different types of environmental radiation, such as gamma (x-rays), cosmic muons, and neutrons.« less

Toward single-cell analysis by plume collimation in laser ablation electrospray ionization mass spectrometry.

PubMed

Stolee, Jessica A; Vertes, Akos

2013-04-02

Ambient ionization methods for mass spectrometry have enabled the in situ and in vivo analysis of biological tissues and cells. When an etched optical fiber is used to deliver laser energy to a sample in laser ablation electrospray ionization (LAESI) mass spectrometry, the analysis of large single cells becomes possible. However, because in this arrangement the ablation plume expands in three dimensions, only a small portion of it is ionized by the electrospray. Here we show that sample ablation within a capillary helps to confine the radial expansion of the plume. Plume collimation, due to the altered expansion dynamics, leads to greater interaction with the electrospray plume resulting in increased ionization efficiency, reduced limit of detection (by a factor of ~13, reaching 600 amol for verapamil), and extended dynamic range (6 orders of magnitude) compared to conventional LAESI. This enhanced sensitivity enables the analysis of a range of metabolites from small cell populations and single cells in the ambient environment. This technique has the potential to be integrated with flow cytometry for high-throughput metabolite analysis of sorted cells.

Advances in biological dosimetry

NASA Astrophysics Data System (ADS)

Ivashkevich, A.; Ohnesorg, T.; Sparbier, C. E.; Elsaleh, H.

2017-01-01

Rapid retrospective biodosimetry methods are essential for the fast triage of persons occupationally or accidentally exposed to ionizing radiation. Identification and detection of a radiation specific molecular ‘footprint’ should provide a sensitive and reliable measurement of radiation exposure. Here we discuss conventional (cytogenetic) methods of detection and assessment of radiation exposure in comparison to emerging approaches such as gene expression signatures and DNA damage markers. Furthermore, we provide an overview of technical and logistic details such as type of sample required, time for sample preparation and analysis, ease of use and potential for a high throughput analysis.

Targeted Multiplex Imaging Mass Spectrometry in Transmission Geometry for Subcellular Spatial Resolution

PubMed Central

Lavenant, Gwendoline Thiery; Zavalin, Andrey I.; Caprioli, Richard M.

2013-01-01

Targeted multiplex Imaging Mass Spectrometry utilizes several different antigen-specific primary antibodies, each directly labeled with a unique photocleavable mass tag, to detect multiple antigens in a single tissue section. Each photocleavable mass tag bound to an antibody has a unique molecular weight and can be readily ionized by laser desorption ionization mass spectrometry. This manuscript describes a mass spectrometry method that allows imaging of targeted single cells within tissue using transmission geometry laser desorption ionization mass spectrometry. Transmission geometry focuses the laser beam on the back side of the tissue placed on a glass slide, providing a 2 μm diameter laser spot irradiating the biological specimen. This matrix-free method enables simultaneous localization at the sub-cellular level of multiple antigens using specific tagged antibodies. We have used this technology to visualize the co-expression of synaptophysin and two major hormones peptides, insulin and somatostatin, in duplex assays in beta and delta cells contained in a human pancreatic islet. PMID:23397138

Targeted Multiplex Imaging Mass Spectrometry in Transmission Geometry for Subcellular Spatial Resolution

NASA Astrophysics Data System (ADS)

Thiery-Lavenant, Gwendoline; Zavalin, Andre I.; Caprioli, Richard M.

2013-04-01

Targeted multiplex imaging mass spectrometry utilizes several different antigen-specific primary antibodies, each directly labeled with a unique photocleavable mass tag, to detect multiple antigens in a single tissue section. Each photocleavable mass tag bound to an antibody has a unique molecular weight and can be readily ionized by laser desorption ionization mass spectrometry. This article describes a mass spectrometry method that allows imaging of targeted single cells within tissue using transmission geometry laser desorption ionization mass spectrometry. Transmission geometry focuses the laser beam on the back side of the tissue placed on a glass slide, providing a 2 μm diameter laser spot irradiating the biological specimen. This matrix-free method enables simultaneous localization at the sub-cellular level of multiple antigens using specific tagged antibodies. We have used this technology to visualize the co-expression of synaptophysin and two major hormones peptides, insulin and somatostatin, in duplex assays in beta and delta cells contained in a human pancreatic islet.

Development of quantitative laser ionization mass spectrometry (LIMS). Final report, 1 Aug 87-1 Jan 90

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

Odom, R.W.

1991-06-04

The objective of the research was to develop quantitative microanalysis methods for dielectric thin films using the laser ionization mass spectrometry (LIMS) technique. The research involved preparation of thin (5,000 A) films of SiO2, Al2O3, MgF2, TiO2, Cr2O3, Ta2O5, Si3N4, and ZrO2, and doping these films with ion implant impurities of 11B, 40Ca, 56Fe, 68Zn, 81Br, and 121Sb. Laser ionization mass spectrometry (LIMS), secondary ion mass spectrometry (SIMS) and Rutherford backscattering spectrometry (RBS) were performed on these films. The research demonstrated quantitative LIMS analysis down to detection levels of 10-100 ppm, and led to the development of (1) a compoundmore » thin film standards product line for the performing organization, (2) routine LIMS analytical methods, and (3) the manufacture of high speed preamplifiers for time-of-flight mass spectrometry (TOF-MS) techniques.« less

Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-07-01

An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of iodinated haloacetic acids in drinking water by reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry with large volume direct aqueous injection.

PubMed

Li, Yongtao; Whitaker, Joshua S; McCarty, Christina L

2012-07-06

A large volume direct aqueous injection method was developed for the analysis of iodinated haloacetic acids in drinking water by using reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry in the negative ion mode. Both the external and internal standard calibration methods were studied for the analysis of monoiodoacetic acid, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid in drinking water. The use of a divert valve technique for the mobile phase solvent delay, along with isotopically labeled analogs used as internal standards, effectively reduced and compensated for the ionization suppression typically caused by coexisting common inorganic anions. Under the optimized method conditions, the mean absolute and relative recoveries resulting from the replicate fortified deionized water and chlorinated drinking water analyses were 83-107% with a relative standard deviation of 0.7-11.7% and 84-111% with a relative standard deviation of 0.8-12.1%, respectively. The method detection limits resulting from the external and internal standard calibrations, based on seven fortified deionized water replicates, were 0.7-2.3 ng/L and 0.5-1.9 ng/L, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Tip-Enhanced Photoinduced Electron Transfer and Ionization on Vertical Silicon Nanowires.

PubMed

Chen, Xiaoming; Wang, Tao; Lin, Leimiao; Wo, Fangjie; Liu, Yaqin; Liang, Xiao; Ye, Hui; Wu, Jianmin

2018-05-02

Nanostructured semiconductors are one of the most potent candidates for matrix-free laser desorption/ionization mass spectrometric (LDI-MS) analysis of low-molecular-weight molecules. Herein, the enhanced photoinduced electron transfer and LDI on the tip of a vertical silicon nanowire (SiNW) array were investigated. Theoretical simulation and LDI detection of indigo and isatin molecules in negative ion mode revealed that the electric field can be enhanced on the tip end of SiNWs, thereby promoting the energy and electron transfer to the analytes adsorbed on the tip of SiNWs. On the basis of this finding, a tip-contact sampling method coupled with LDI-MS detection was established. In this strategy, the tip of SiNWs can be regarded as microextraction heads for the sampling of molecules when they come in contact with analytes. Impression of skin, tissue, and pericarp on the vertical SiNW array can effectively transfer endogenous metabolites or exogenous substances onto the tip. Upon laser irradiation, the adsorbed molecules on the SiNW tip can be efficiently ionized and detected in negative ion mode because of the tip-enhanced electron transfer and LDI effect. We believe this work may significantly expand the application of LDI-MS in various fields.

The CGL1 (HeLa × Normal Skin Fibroblast) Human Hybrid Cell Line: A History of Ionizing Radiation Induced Effects on Neoplastic Transformation and Novel Future Directions in SNOLAB.

PubMed

Pirkkanen, Jake S; Boreham, Douglas R; Mendonca, Marc S

2017-10-01

Cellular transformation assays have been utilized for many years as powerful in vitro methods for examining neoplastic transformation potential/frequency and mechanisms of carcinogenesis for both chemical and radiological carcinogens. These mouse and human cell based assays are labor intensive but do provide quantitative information on the numbers of neoplastically transformed foci produced after carcinogenic exposure and potential molecular mechanisms involved. Several mouse and human cell systems have been generated to undertake these studies, and they vary in experimental length and endpoint assessment. The CGL1 human cell hybrid neoplastic model is a non-tumorigenic pre-neoplastic cell that was derived from the fusion of HeLa cervical cancer cells and a normal human skin fibroblast. It has been utilized for the several decades to study the carcinogenic/neoplastic transformation potential of a variety of ionizing radiation doses, dose rates and radiation types, including UV, X ray, gamma ray, neutrons, protons and alpha particles. It is unique in that the CGL1 assay has a relatively short assay time of 18-21 days, and rather than relying on morphological endpoints to detect neoplastic transformation utilizes a simple staining method that detects the tumorigenic marker alkaline phosphatase on the neoplastically transformed cells cell surface. In addition to being of human origin, the CGL1 assay is able to detect and quantify the carcinogenic potential of very low doses of ionizing radiation (in the mGy range), and utilizes a neoplastic endpoint (re-expression of alkaline phosphatase) that can be detected on both viable and paraformaldehyde fixed cells. In this article, we review the history of the CGL1 neoplastic transformation model system from its initial development through the wide variety of studies examining the effects of all types of ionizing radiation on neoplastic transformation. In addition, we discuss the potential of the CGL1 model system to investigate the effects of near zero background radiation levels available within the radiation biology lab we have established in SNOLAB.

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.

Holographic particle detection

NASA Technical Reports Server (NTRS)

Bowen, Theodore

1988-01-01

The feasibility was studied of developing a novel particle track detector based on the detection of 1p-1s emission radiation from electron bubbles in liquid helium. The principles, design, construction, and initial testing of the detection system have been described in previous reports. The main obstacle encountered was the construction of the liquid-helium tight infrared windows. Despite numerous efforts in testing and redesigning the windows, the problem of window leakage at low temperature persisted. Due to limited time and resources, attention was switched to investigating the possibility of using room-temperature liquid as the detection medium. A possible mechanism was the detection of de-excitation radiation emitted from localized electrons in common liquids where electrons exhibit low mobilities, as suggested in the previous report. The purity of the liquid is critical in this method as the dissolved impurities (such as oxygen), even in trace amounts, will act as scavengers of electrons. Another mechanism is discussed whereby the formation of the superoxide ions by electron scavenging behavior of dissolved oxygen is exploited to detect the track of ionizing particles. An experiment to measure the ionization current produced in a liquid by a pulsed X-ray beam in order to study propertiies of the ions is also reported.

Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-12-01

Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a microcartridge technique for the measurement of atmospheric carbonyls and emissions from plants and a new analytical technique for the measurement of argon as a passive tracer

NASA Astrophysics Data System (ADS)

Skaggs, Rhonda Lynn

A new cartridge sampling and derivatization technique was developed for the determination of aldehydes and ketones in air that allows measurement of sub-ppbv mixing ratios using sampling times of ten minutes or less. This thesis describes the development and evaluation of the analytical technique and a preliminary survey of carbonyl emissions from wounded plants. Also described is the development of an analytical technique for the measurement of argon, a passive biogeochemical tracer. Carbonyl compounds are sampled onto high pressure cartridges containing particles coated with 2,4- dinitrophenylhydrazine where they react to form hydrazones. The entire sample is eluted and transferred to the head of a high performance liquid chromatograph (HPLC) for separation and detection by UV absorbance. The method is demonstrated to be approximately two orders of magnitude more sensitive than the conventional DNPH technique in which only a small fraction of the hydrazones are transferred to the column. It was found that two calibration methods gave different sensitivities resulting from the formation of different ratios of syn and anti isomers of the hydrazones. These results suggest that many measurements of atmospheric carbonyls reported in the literature may have significant errors if syn and anti isomers were unresolved. A chamber method was used to study the emissions of aldehydes and ketones from a variety of wounded plants. 2-E-Hexenal and acetaldehyde were detected in the wound response emissions of all six plants examined. Enhanced concentrations of methylethyl ketone (MEK) in addition to acetaldehyde and 2-E-hexenal were detected following wounding of clover, and the emissions of 2-E-hexenal and MEK in response to wounding displayed different temporal release patterns. A novel application of a commercial photionization detector for the quantification of argon is described and applied to the headspace analysis of water. Argon is measured indirectly by its effect on an ionizable gas (nitric oxide) present in the detection cell. By varying the amount of nitric oxide added to the detection cell, two modes of operation were demonstrated: a competitive absorbance mode and a Penning ionization mode. Optimized Penning ionization detection with a nitric oxide concentration of ~940 ppmv was used to analyze air and the headspace of water samples. The limit of detection was determined to be 14 pmol Ar s-1.

Characterization of constituents in Stellera chamaejasme L. by rapid-resolution liquid chromatography-diode array detection and electrospray ionization time-of-flight mass spectrometry.

PubMed

Zhao, Liang; Lou, Zi-Yang; Zhu, Zhen-Yu; Zhang, Guo-Qing; Chai, Yi-Feng

2008-01-01

A reliable and rapid method based on rapid-resolution liquid chromatography-diode array detection (RRLC-DAD) and electrospray ionization time-of-flight mass spectrometry (ESI-TOF/MS) has been developed for the isolation and characterization of multiple constituents in the root of Stellera chamaejasme L., which was extracted by sonication with methanol in an optimized procedure. Separation of the multiple constituents was achieved on an Agilent Zorbax XDB-C18 (50x3.0 mm i.d.; 1.8 microm) column using a gradient elution at a flow rate of 0.4 mL/min. The detection wavelength was 210 nm. Mass spectra were acquired in both positive and negative modes. A formula database of the known chemical constituents in the root of Stellera chamaejasme L. was established by an Agilent software. Twenty-two obvious peaks appeared in the total ion chromatogram and nine of them were characterized by TOF/MS. The RRLC-DAD and ESI-TOF/MS method with ultrasonic extraction would be useful for rapid and effective characterization of chemical constituents in the root of Stellera chamaejasme L. Copyright (c) 2007 John Wiley & Sons, Ltd.

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

PubMed

Chen, Yisheng; Schwack, Wolfgang

2014-02-28

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

Passive particle dosimetry. [silver halide crystal growth

NASA Technical Reports Server (NTRS)

Childs, C. B.

1977-01-01

Present methods of dosimetry are reviewed with emphasis on the processes using silver chloride crystals for ionizing particle dosimetry. Differences between the ability of various crystals to record ionizing particle paths are directly related to impurities in the range of a few ppm (parts per million). To understand the roles of these impurities in the process, a method for consistent production of high purity silver chloride, and silver bromide was developed which yields silver halides with detectable impurity content less than 1 ppm. This high purity silver chloride was used in growing crystals with controlled doping. Crystals were grown by both the Czochalski method and the Bridgman method, and the Bridgman grown crystals were used for the experiments discussed. The distribution coefficients of ten divalent cations were determined for the Bridgman crystals. The best dosimeters were made with silver chloride crystals containing 5 to 10 ppm of lead; other impurities tested did not produce proper dosimeters.

Detection of explosives using negative ion mobility spectrometry in air based on dopant-assisted thermal ionization.

PubMed

Shahraki, Hassan; Tabrizchi, Mahmoud; Farrokhpor, Hossein

2018-05-26

The ionization source is an essential component of most explosive detectors based on negative ion mobility spectrometry. Conventional ion sources suffer from such inherent limitations as special safety regulations on radioactive sources or generating interfering ions (for non-radioactive sources) such as corona discharge operating in the air. In this study, a new negative ion source is introduced for ion mobility spectrometry that is based on thermal ionization and operates in the air, applicable to explosives detection. Our system consists of a heating filament powered by an isolated power supply connected to negative high voltage. The ionization is assisted by doping chlorinated compounds in the gas phase using chlorinated hydrocarbons in contact with the heating element to yield Cl - reactant ions. Several chlorinated hydrocarbons are evaluated as the reagent chemicals for providing Cl- reactant ions, of which CCl 4 is identified as the best ionizing reagent. The ion source is evaluated by recording the ion mobility spectra of common explosives, including TNT, RDX, and PETN in the air. A detection limit of 150 pg is obtained for TNT. Compared to other ionization sources, the new source is found to be low-cost, simple, and long-lived, making it suited to portable explosives detection devices. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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

2005-07-15

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

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

NASA Astrophysics Data System (ADS)

Laudien, Robert; Schultze, Rainer; Wieser, Jochen

2010-10-01

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

Systems and methods for detecting nuclear radiation in the presence of backgrounds

DOEpatents

Bross, Alan D.; Mellott, Kerry L.; Pla-Dalmau, Anna

2005-06-21

Systems and methods for the simultaneous detection and identification of radiation species, including neutrons, gammas/x-rays and minimum ionizing particles (MIPs). A plurality of rectangular and/or triangularly shaped radiation sensitive scintillators can be configured from a plurality of nano-sized particles, dopants and an extruded plastic material. A wavelength-shifting fiber can then be located within a central hole of each extruded scintillator, wherein the wavelength-shifting fiber absorbs scintillation light and re-emits the light at a longer wavelength, thereby piping the light to a photodetector whose response to the light indicates the presence of radiation The resulting method and system can simultaneously detect neutrons, gamma rays, x-rays and cosmic rays (MIPs) and identify each.

NMT - A new individual ion counting method: Comparison to a Faraday cup

NASA Astrophysics Data System (ADS)

Burton, Michael; Gorbunov, Boris

2018-03-01

Two sample detectors used to analyze the emission from Gas Chromatography (GC) columns are the Flame Ionization Detector (FID) and the Electron Capture Detector (ECD). Both of these detectors involve ionization of the sample molecules and then measuring electric current in the gas using a Faraday cup. In this paper a newly discovered method of ion counting, Nanotechnology Molecular Tagging (NMT) is tested as a replacement to the Faraday cup in GCs. In this method the effective physical volume of individual molecules is enlarged up to 1 billion times enabling them to be detected by an optical particle counter. It was found that the sensitivity of NMT was considerably greater than the Faraday cup. The background in the NMT was circa 200 ions per cm3, corresponding to an extremely low electric current ∼10-17 A.

Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

PubMed

He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

2016-09-01

Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix.

Novel Electrosorption-Enhanced Solid-Phase Microextraction Device for Ultrafast In Vivo Sampling of Ionized Pharmaceuticals in Fish.

PubMed

Qiu, Junlang; Wang, Fuxin; Zhang, Tianlang; Chen, Le; Liu, Yuan; Zhu, Fang; Ouyang, Gangfeng

2018-01-02

Decreasing the tedious sample preparation duration is one of the most important concerns for the environmental analytical chemistry especially for in vivo experiments. However, due to the slow mass diffusion paths for most of the conventional methods, ultrafast in vivo sampling remains challenging. Herein, for the first time, we report an ultrafast in vivo solid-phase microextraction (SPME) device based on electrosorption enhancement and a novel custom-made CNT@PPY@pNE fiber for in vivo sampling of ionized acidic pharmaceuticals in fish. This sampling device exhibited an excellent robustness, reproducibility, matrix effect-resistant capacity, and quantitative ability. Importantly, the extraction kinetics of the targeted ionized pharmaceuticals were significantly accelerated using the device, which significantly improved the sensitivity of the SPME in vivo sampling method (limits of detection ranged from 0.12 ng·g -1 to 0.25 ng·g -1 ) and shorten the sampling time (only 1 min). The proposed approach was successfully applied to monitor the concentrations of ionized pharmaceuticals in living fish, which demonstrated that the device and fiber were suitable for ultrafast in vivo sampling and continuous monitoring. In addition, the bioconcentration factor (BCF) values of the pharmaceuticals were derived in tilapia (Oreochromis mossambicus) for the first time, based on the data of ultrafast in vivo sampling. Therefore, we developed and validated an effective and ultrafast SPME sampling device for in vivo sampling of ionized analytes in living organisms and this state-of-the-art method provides an alternative technique for future in vivo studies.

High efficiency direct detection of ions from resonance ionization of sputtered atoms

DOEpatents

Gruen, Dieter M.; Pellin, Michael J.; Young, Charles E.

1986-01-01

A method and apparatus are provided for trace and other quantitative analysis with high efficiency of a component in a sample, with the analysis involving the removal by ion or other bombardment of a small quantity of ion and neutral atom groups from the sample, the conversion of selected neutral atom groups to photoions by laser initiated resonance ionization spectroscopy, the selective deflection of the photoions for separation from original ion group emanating from the sample, and the detection of the photoions as a measure of the quantity of the component. In some embodiments, the original ion group is accelerated prior to the RIS step for separation purposes. Noise and other interference are reduced by shielding the detector from primary and secondary ions and deflecting the photoions sufficiently to avoid the primary and secondary ions.

High efficiency direct detection of ions from resonance ionization of sputtered atoms

DOEpatents

Gruen, D.M.; Pellin, M.J.; Young, C.E.

1985-01-16

A method and apparatus are provided for trace and other quantitative analysis with high efficiency of a component in a sample, with the analysis involving the removal by ion or other bombardment of a small quantity of ion and neutral atom groups from the sample, the conversion of selected neutral atom groups to photoions by laser initiated resonance ionization spectroscopy, the selective deflection of the photoions for separation from original ion group emanating from the sample, and the detection of the photoions as a measure of the quantity of the component. In some embodiments, the original ion group is accelerated prior to the RIS step for separation purposes. Noise and other interference are reduced by shielding the detector from primary and secondary ions and deflecting the photoions sufficiently to avoid the primary and secondary ions.

Direct detection of the plant pathogens Burkholderia glumae, Burkholderia gladioli pv. gladioli, and Erwinia chrysanthemi pv. zeae in infected rice seedlings using matrix assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Kajiwara, Hideyuki

2016-01-01

The plant pathogens Burkholderia glumae, Burkholderia gladioli pv. gladioli, and Erwinia chrysanthemi pv. zeae were directly detected in extracts from infected rice seedlings by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). This method did not require culturing of the pathogens on artificial medium. In the MALDI-TOF MS analysis, peaks originating from bacteria were found in extracts from infected rice seedlings. The spectral peaks showed significantly high scores, in spite of minor differences in spectra. The spectral peaks originating from host plant tissues did not affect this direct MALDI-TOF MS analysis for the rapid identification of plant pathogens. Copyright © 2015 Elsevier B.V. All rights reserved.

New phenolic components and chromatographic profiles of green and fermented teas

USDA-ARS?s Scientific Manuscript database

A standardized profiling method based on liquid chromatography with diode array and electrospray ionization/mass spectrometric detection (LC-DAD-ESI/MS) was applied to establish the phenolic profiles of 41 green teas and 25 fermented teas. More than 80 phenolic compounds were either identified that ...

A systematic approach to the identification of common hydroxycinnamoylquinic acids in plant materials

USDA-ARS?s Scientific Manuscript database

A standardized profiling method based on liquid chromatography with diode array and electrospray ionization/mass spectrometric detection (LC-DAD-ESI/MS) was used to separate and identify the phenolic components of arnica flowers (Arnica montana L.), burdock roots (Artium lappa L.), coffee beans (Cof...

Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams

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

He, Yunteng; Zhang, Jie; Li, Yang

2015-08-15

We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He{sub 2}{sup +} and He{sub 4}{sup +}, which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl{sub 4} doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He){sub n}C{sup +}, (He){sub n}Cl{sup +}, and (He){sub n}CCl{sup +}. Usingmore » both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets.« less

Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of friction modifier additives analyzed directly from base oil solutions.

PubMed

Widder, Lukas; Brennerb, Josef; Huttera, Herbert

2014-01-01

To develop new products and to apply measures of quality control quick and simple accessibility of additive composition in automo- tive lubrication is important. The aim of this study was to investigate the possibility of analyzing organic friction modifier additives by means of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry [AP-MALDI-MS] from lubricant solu- tions without the use of additional separation techniques. Analyses of selected friction modifier ethoxylated tallow amines and oleic acid amide were compared using two ionization methods, positive-ion electrospray ionization (ESI) and AP-MALDI, using a LTQ Orbitrap mass spectrometer. Pure additives were characterized from solvent solutions, as well as from synthetic and mineral base oil mixtures. Detected ions of pure additive samples consisted mainly of [M + H]+, but also alkaLi metal adducts [M + Na]+ and [M + K]+ could be seen. Characterizations of blends of both friction modifiers from the base oil mixtures were carried out as well and showed significant inten- sities for several additive peaks. Thus, this work shows a method to directly analyze friction modifier additives used in the automotive industry from an oil blend via the use of AP-MALDI without any further separation steps. The method presented will further simplify the acquisition of data on lubricant composition and additives. Furthermore, it allows the perspective of analyzing additive reaction products directly from formulated oil blends.

Evidence for a Hard Ionizing Spectrum from a z = 6.11 Stellar Population

NASA Astrophysics Data System (ADS)

Mainali, Ramesh; Kollmeier, Juna A.; Stark, Daniel P.; Simcoe, Robert A.; Walth, Gregory; Newman, Andrew B.; Miller, Daniel R.

2017-02-01

We present the Magellan/FIRE detection of highly ionized C IV λ1550 and O III]λ1666 in a deep infrared spectrum of the z = 6.11 gravitationally lensed low-mass galaxy RXC J2248.7-4431-ID3, which has previously known Lyα. No corresponding emission is detected at the expected location of He II λ1640. The upper limit on He II, paired with detection of O III] and C IV, constrains possible ionization scenarios. Production of C IV and O III] requires ionizing photons of 2.5-3.5 Ryd, but once in that state their multiplet emission is powered by collisional excitation at lower energies (˜0.5 Ryd). As a pure recombination line, He II emission is powered by 4 Ryd ionizing photons. The data therefore require a spectrum with significant power at 3.5 Ryd but a rapid drop toward 4.0 Ryd. This hard spectrum with a steep drop is characteristic of low-metallicity stellar populations, and less consistent with soft AGN excitation, which features more 4 Ryd photons and hence higher He II flux. The conclusions based on ratios of metal line detections to helium non-detection are strengthened if the gas metallicity is low. RXJ2248-ID3 adds to the growing handful of reionization-era galaxies with UV emission line ratios distinct from the general z=2{--}3 population in a way that suggests hard ionizing spectra that do not necessarily originate in AGNs.

Theoretical investigation of low detection sensitivity for underivatized carbohydrates in ESI and MALDI.

PubMed

Chen, Jien-Lian; Lee, Chuping; Lu, I-Chung; Chien, Chia-Lung; Lee, Yuan-Tseh; Hu, Wei-Ping; Ni, Chi-Kung

2016-12-01

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mainly generate protonated ions from peptides and proteins but sodiated (or potassiated) ions from carbohydrates. The ion intensities of sodiated (or potassiated) carbohydrates generated by ESI and MALDI are generally lower than those of protonated peptides and proteins. Ab initio calculations and transition state theory were used to investigate the reasons for the low detection sensitivity for underivatized carbohydrates. We used glucose and cellobiose as examples and showed that the low detection sensitivity is partly attributable to the following factors. First, glucose exhibits a low proton affinity. Most protons generated by ESI or MALDI attach to water clusters and matrix molecules. Second, protonated glucose and cellobiose can easily undergo dehydration reactions. Third, the sodiation affinities of glucose and cellobiose are small. Some sodiated glucose and cellobiose dissociate into the sodium cations and neutral carbohydrates during ESI or MALDI process. The increase of detection sensitivity of carbohydrates in mass spectrometry by various methods can be rationalized according to these factors. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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

PubMed

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

2009-05-01

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

A promising new mechanism of ionizing radiation detection for positron emission tomography: Modulation of optical properties

PubMed Central

Tao, Li; Daghighian, Henry M.; Levin, Craig S.

2016-01-01

Using conventional scintillation detection, the fundamental limit in positron emission tomography (PET) time resolution is strongly dependent on the inherent temporal variances generated during the scintillation process, yielding an intrinsic physical limit for the coincidence time resolution of around 100 ps. On the other hand, modulation mechanisms of the optical properties of a material exploited in the optical telecommunications industry can be orders of magnitude faster. In this paper we borrow from the concept of optics pump-probe measurement to for the first time study whether ionizing radiation can produce modulations of optical properties, which can be utilized as a novel method for radiation detection. We show that a refractive index modulation of approximately 5 × 10−6 is induced by interactions in a cadmium telluride (CdTe) crystal from a 511 keV photon source. Furthermore, using additional radionuclide sources, we show that the amplitude of the optical modulation signal varies linearly with both the detected event rate and average photon energy of the radiation source. PMID:27716640

Combined electrophoresis-electrospray interface and method

DOEpatents

Smith, R.D.; Udseth, H.R.; Barinaga, C.J.

1995-06-13

An improvement to the system and method is disclosed for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity. 10 figs.

Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Rezaee Aghdam, Samaneh; Nouri, Nina; Bamorrowat, Mahdi

2016-12-01

In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice. Copyright © 2016 Elsevier Ltd. All rights reserved.

A comprehensive library-based, automated screening procedure for 46 synthetic cannabinoids in serum employing liquid chromatography-quadrupole ion trap mass spectrometry with high-temperature electrospray ionization.

PubMed

Huppertz, Laura M; Kneisel, Stefan; Auwärter, Volker; Kempf, Jürgen

2014-02-01

Considering the vast variety of synthetic cannabinoids and herbal mixtures - commonly known as 'Spice' or 'K2' - on the market and the resulting increase of severe intoxications related to their consumption, there is a need in clinical and forensic toxicology for comprehensive up-to-date screening methods. The focus of this project aimed at developing and implementing an automated screening procedure for the detection of synthetic cannabinoids in serum using a liquid chromatography-ion trap-MS (LC-MS(n)) system and a spectra library-based approach, currently including 46 synthetic cannabinoids and 8 isotope labelled analogues. In the process of method development, a high-temperature ESI source (IonBooster(TM), Bruker Daltonik) and its effects on the ionization efficiency of the investigated synthetic cannabinoids were evaluated and compared to a conventional ESI source. Despite their structural diversity, all investigated synthetic cannabinoids benefitted from high-temperature ionization by showing remarkably higher MS intensities compared to conventional ESI. The employed search algorithm matches retention time, MS and MS(2)/MS(3) spectra. With the utilization of the ionBooster source, limits for the automated detection comparable to cut-off values of routine MRM methods were achieved for the majority of analytes. Even compounds not identified when using a conventional ESI source were detected using the ionBooster-source. LODs in serum range from 0.1 ng/ml to 0.5 ng/ml. The use of parent compounds as analytical targets offers the possibility of instantly adding new emerging compounds to the library and immediately applying the updated method to serum samples, allowing the rapid adaptation of the screening method to ongoing forensic or clinical requirements. The presented approach can also be applied to other specimens, such as oral fluid or hair, and herbal mixtures and was successfully applied to authentic serum samples. Quantitative MRM results of samples with analyte concentrations above the determined LOD were confirmed as positive findings by the presented method. Copyright © 2014 John Wiley & Sons, Ltd.

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

USGS Publications Warehouse

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

2004-01-01

Commonly used prescription and over-the-counter pharmaceuticals are possibly present in surface- and ground-water samples at ambient concentrations less than 1 μg/L. In this report, the performance characteristics of a combined solid-phase extraction isolation and high-performance liquid chromatography–electrospray ionization mass spectrometry (HPLC–ESI-MS) analytical procedure for routine determination of the presence and concentration of human-health pharmaceuticals are described. This method was developed and used in a recent national reconnaissance of pharmaceuticals in USA surface waters. The selection of pharmaceuticals evaluated for this method was based on usage estimates, resulting in a method that contains compounds from diverse chemical classes, which presents challenges and compromises when applied as a single routine analysis. The method performed well for the majority of the 22 pharmaceuticals evaluated, with recoveries greater than 60% for 12 pharmaceuticals. The recoveries of angiotensin-converting enzyme inhibitors, a histamine (H2) receptor antagonist, and antihypoglycemic compound classes were less than 50%, but were retained in the method to provide information describing the potential presence of these compounds in environmental samples and to indicate evidence of possible matrix enhancing effects. Long-term recoveries, evaluated from reagent-water fortifications processed over 2 years, were similar to initial method performance. Method detection limits averaged 0.022 μg/L, sufficient for expected ambient concentrations. Compound-dependent matrix effects on HPLC/ESI-MS analysis, including enhancement and suppression of ionization, were observed as a 20–30% increase in measured concentrations for three compounds and greater than 50% increase for two compounds. Changing internal standard and more frequent ESI source maintenance minimized matrix effects. Application of the method in the national survey demonstrates that several pharmaceuticals are routinely detected at 0.010–0.100 μg/L concentrations.

Relative spectral response calibration using Ti plasma lines

NASA Astrophysics Data System (ADS)

Teng, FEI; Congyuan, PAN; Qiang, ZENG; Qiuping, WANG; Xuewei, DU

2018-04-01

This work introduces the branching ratio (BR) method for determining relative spectral responses, which are needed routinely in laser induced breakdown spectroscopy (LIBS). Neutral and singly ionized Ti lines in the 250–498 nm spectral range are investigated by measuring laser-induced micro plasma near a Ti plate and used to calculate the relative spectral response of an entire LIBS detection system. The results are compared with those of the conventional relative spectral response calibration method using a tungsten halogen lamp, and certain lines available for the BR method are selected. The study supports the common manner of using BRs to calibrate the detection system in LIBS setups.

Rapid, in situ detection of cocaine residues based on paper spray ionization coupled with ion mobility spectrometry.

PubMed

Li, Ming; Zhang, Jingjing; Jiang, Jie; Zhang, Jing; Gao, Jing; Qiao, Xiaolin

2014-04-07

In this paper, a novel approach based on paper spray ionization coupled with ion mobility spectrometry (PSI-IMS) was developed for rapid, in situ detection of cocaine residues in liquid samples and on various surfaces (e.g. glass, marble, skin, wood, fingernails), without tedious sample pretreatment. The obvious advantages of PSI are its low cost, easy operation and simple configuration without using nebulizing gas or discharge gas. Compared with mass spectrometry, ion mobility spectrometry (IMS) takes advantage of its low cost, easy operation, and simple configuration without requiring a vacuum system. Therefore, IMS is a more congruous detection method for PSI in the case of rapid, in situ analysis. For the analysis of cocaine residues in liquid samples, dynamic responses from 5 μg mL(-1) to 200 μg mL(-1) with a linear coefficient (R(2)) of 0.992 were obtained. In this case, the limit of detection (LOD) was calculated to be 2 μg mL(-1) as signal to noise (S/N) was 3 with a relative standard deviation (RSD) of 6.5% for 11 measurements (n = 11). Cocaine residues on various surfaces such as metal, glass, marble, wood, skin, and fingernails were also directly analyzed before wiping the surfaces with a piece of paper. The LOD was calculated to be as low as 5 ng (S/N = 3, RSD = 6.3%, n = 11). This demonstrates the capability of the PSI-IMS method for direct detection of cocaine residues at scenes of cocaine administration. Our results show that PSI-IMS is a simple, sensitive, rapid and economical method for in situ detection of this illicit drug, which could help governments to combat drug abuse.

[Special application of matrix-assisted laser desorption ionization time-of-flight mass spectrometry in clinical microbiological diagnostics].

PubMed

Nagy, Erzsébet; Abrók, Marianna; Bartha, Noémi; Bereczki, László; Juhász, Emese; Kardos, Gábor; Kristóf, Katalin; Miszti, Cecilia; Urbán, Edit

2014-09-21

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry as a new possibility for rapid identification of bacteria and fungi revolutionized the clinical microbiological diagnostics. It has an extreme importance in the routine microbiological laboratories, as identification of the pathogenic species rapidly will influence antibiotic selection before the final determination of antibiotic resistance of the isolate. The classical methods for identification of bacteria or fungi, based on biochemical tests, are influenced by many environmental factors. The matrix-assisted laser desorption ionization time-of-flight mass spectrometry is a rapid method which is able to identify a great variety of the isolated bacteria and fungi based on the composition of conserved ribosomal proteins. Recently several other applications of the method have also been investigated such as direct identification of pathogens from the positive blood cultures. There are possibilities to identify bacteria from the urine samples in urinary tract infection or from other sterile body fluids. Using selective enrichment broth Salmonella sp from the stool samples can be identified more rapidly, too. The extended spectrum beta-lactamase or carbapenemase production of the isolated bacteria can be also detected by this method helping the antibiotic selection in some cases. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry based methods are suitable to investigate changes in deoxyribonucleic acid or ribonucleic acid, to carry out rapid antibiotic resistance determination or other proteomic analysis. The aim of this paper is to give an overview about present possibilities of using this technique in the clinical microbiological routine procedures.

Electroless plating of silver nanoparticles on porous silicon for laser desorption/ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Yan, Hong; Xu, Ning; Huang, Wen-Yi; Han, Huan-Mei; Xiao, Shou-Jun

2009-03-01

An improved DIOS (desorption ionization on porous silicon) method for laser desorption/ionization mass spectrometry (LDI MS) by electroless plating of silver nanoparticles (AgNPs) on porous silicon (PSi) was developed. By addition of 4-aminothiophenol (4-ATP) into the AgNO3 plating solution, the plating speed can be slowed down and simultaneously 4-ATP self-assembled monolayers (SAMs) on AgNPs (4-ATP/AgNPs) were formed. Both AgNPs and 4-ATP/AgNPs coated PSi substrates present much higher stability, sensitivity and reproducibility for LDI MS than the un-treated porous silicon ones. Their shelf life in air was tested for several weeks to a month and their mass spectra still displayed the same high quality and sensitivity as the freshly prepared ones. And more 4-ATP SAMs partly play a role of matrix to increase the ionization efficiency. A small organic molecule of tetrapyridinporphyrin (TPyP), oligomers of polyethylene glycol (PEG 400 and 2300), and a peptide of oxytocin were used as examples to demonstrate the feasibility of the silver-plated PSi as a matrix-free-like method for LDI MS. This approach can obtain limits of detection to femtomoles for TPyP, subpicomoles for oxytocin, and picomoles for PEG 400 and 2300, comparable to the traditional matrix method and much better than the DIOS method. It simplifies the sample preparation as a matrix-free-like method without addition of matrix molecules and homogenizes the sample spread over the spot for better and more even mass signals.

In-injection port thermal desorption for explosives trace evidence analysis.

PubMed

Sigman, M E; Ma, C Y

1999-10-01

A gas chromatographic method utilizing thermal desorption of a dry surface wipe for the analysis of explosives trace chemical evidence has been developed and validated using electron capture and negative ion chemical ionization mass spectrometric detection. Thermal desorption was performed within a split/splitless injection port with minimal instrument modification. Surface-abraded Teflon tubing provided the solid support for sample collection and desorption. Performance was characterized by desorption efficiency, reproducibility, linearity of the calibration, and method detection and quantitation limits. Method validation was performed with a series of dinitrotoluenes, trinitrotoluene, two nitroester explosives, and one nitramine explosive. The method was applied to the sampling of a single piece of debris from an explosion containing trinitrotoluene.

Annotation of the human serum metabolome by coupling three liquid chromatography methods to high-resolution mass spectrometry.

PubMed

Boudah, Samia; Olivier, Marie-Françoise; Aros-Calt, Sandrine; Oliveira, Lydie; Fenaille, François; Tabet, Jean-Claude; Junot, Christophe

2014-09-01

This work aims at evaluating the relevance and versatility of liquid chromatography coupled to high resolution mass spectrometry (LC/HRMS) for performing a qualitative and comprehensive study of the human serum metabolome. To this end, three different chromatographic systems based on a reversed phase (RP), hydrophilic interaction chromatography (HILIC) and a pentafluorophenylpropyl (PFPP) stationary phase were used, with detection in both positive and negative electrospray modes. LC/HRMS platforms were first assessed for their ability to detect, retain and separate 657 metabolite standards representative of the chemical families occurring in biological fluids. More than 75% were efficiently retained in either one LC-condition and less than 5% were exclusively retained by the RP column. These three LC/HRMS systems were then evaluated for their coverage of serum metabolome. The combination of RP, HILIC and PFPP based LC/HRMS methods resulted in the annotation of about 1328 features in the negative ionization mode, and 1358 in the positive ionization mode on the basis of their accurate mass and precise retention time in at least one chromatographic condition. Less than 12% of these annotations were shared by the three LC systems, which highlights their complementarity. HILIC column ensured the greatest metabolome coverage in the negative ionization mode, whereas PFPP column was the most effective in the positive ionization mode. Altogether, 192 annotations were confirmed using our spectral database and 74 others by performing MS/MS experiments. This resulted in the formal or putative identification of 266 metabolites, among which 59 are reported for the first time in human serum. Copyright © 2014 Elsevier B.V. All rights reserved.

Diamond, titanium dioxide, titanium silicon oxide, and barium strontium titanium oxide nanoparticles as matrixes for direct matrix-assisted laser desorption/ionization mass spectrometry analysis of carbohydrates in plant tissues.

PubMed

Gholipour, Yousef; Giudicessi, Silvana L; Nonami, Hiroshi; Erra-Balsells, Rosa

2010-07-01

Nanoparticles (NPs) of diamond, titanium dioxide, titanium silicon oxide, barium strontium titanium oxide, and silver (Ag) were examined for their potential as MALDI matrixes for direct laser desorption/ionization of carbohydrates, especially fructans, from plant tissue. Two sample preparation methods including solvent-assisted and solvent-free (dry) NPs deposition were performed and compared. All examined NPs except for Ag could desorb/ionize standard sucrose and fructans in positive and in negative ion mode. Ag NPs yielded good signals only for nonsalt-doped samples that were measured in the negative ion mode. In the case of in vivo studies, except for Ag, all NPs studied could desorb/ionize carbohydrates from tissue in both the positive and negative ion modes. Furthermore, compared to the results obtained with soluble sugars extracted from plant tissues, fructans with higher molecular weight intact molecular ions could be detected when the plant tissues were directly profiled. The limit of detection (LOD) of fructans and the ratios between signal intensities and fructan concentrations were analyzed. NPs had similar LODs for standard fructan triose (1-kestose) in the positive ion mode and better LODs in the negative ion mode when compared with the common crystalline organic MALDI matrixes used for carbohydrates (2,5-dihydroxybenzoic acid and nor-harmane) or carbon nanotubes. Solvent-free NP deposition on tissues partially improves the signal acquisition. Although lower signal-to-noise ratio sugar signals were acquired from the tissues when compared to the solvent-assisted method, the reproducibility averaged over all sample was more uniform.

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

PubMed

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

2016-09-21

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

Fragmentation pathways and structural characterization of organophosphorus compounds related to the Chemical Weapons Convention by electron ionization and electrospray ionization tandem mass spectrometry.

PubMed

Hosseini, Seyed Esmaeil; Saeidian, Hamid; Amozadeh, Ali; Naseri, Mohammad Taghi; Babri, Mehran

2016-12-30

For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Surface analysis under ambient conditions using plasma-assisted desorption/ionization mass spectrometry.

PubMed

Ratcliffe, Lucy V; Rutten, Frank J M; Barrett, David A; Whitmore, Terry; Seymour, David; Greenwood, Claire; Aranda-Gonzalvo, Yolanda; Robinson, Steven; McCoustra, Martin

2007-08-15

A novel plasma-assisted desorption/ionization (PADI) method that can be coupled with atmospheric pressure sampling mass spectrometry to yield mass spectral information under ambient conditions of pressure and humidity from a range of surfaces without the requirement for sample preparation or additives is reported. PADI is carried out by generating a nonthermal plasma which interacts directly with the surface of the analyte. Desorption and ionization then occur at the surface, and ions are sampled by the mass spectrometer. The PADI technique is demonstrated and compared with desorption electrospray ionization (DESI) for the detection of active ingredients in a range of over-the-counter and prescription pharmaceutical formulations, including nonsterodial anti-inflammatory drugs (mefenamic acid, Ibugel, and ibuprofen), analgesics (paracetamol, Anadin Extra), and Beecham's "all in one" cold and flu remedy. PADI has also been successfully applied to the analysis of nicotine in tobacco and thiosulfates in garlic. PADI experiments have been performed using a prototype source interfaced with a Waters Platform LCZ single-quadrupole mass spectrometer with limited modifications and a Hiden Analytical HPR-60 molecular beam mass spectrometer (MBMS). The ability of PADI to rapidly detect active ingredients in pharmaceuticals without the need for prior sample preparation, solvents, or exposed high voltages demonstrates the potential of the technique for high-throughput screening in a pharmaceutical or forensic environment.

Quantitative Profiling of Major Neutral Lipid Classes in Human Meibum by Direct Infusion Electrospray Ionization Mass Spectrometry

PubMed Central

Chen, Jianzhong; Green, Kari B.; Nichols, Kelly K.

2013-01-01

Purpose. The purpose of this investigation was to better understand lipid composition in human meibum. Methods. Intact lipids in meibum samples were detected by direct infusion electrospray ionization mass spectrometry (ESI-MS) analysis in positive detection mode using sodium iodide (NaI) as an additive. The peak intensities of all major types of lipid species, that is, wax esters (WEs), cholesteryl esters (CEs), and diesters (DEs) were corrected for peak overlapping and isotopic distribution; an additional ionization efficiency correction was performed for WEs and CEs, which was simplified by the observation that the corresponding ionization efficiency was primarily dependent on the specific lipid class and saturation degree of the lipids while independent of the carbon chain length. A set of WE and CE standards was spiked in meibum samples for ionization efficiency determination and absolute quantitation. Results. The absolute amount (μmol/mg) for each of 51 WEs and 31 CEs in meibum samples was determined. The summed masses for 51 WEs and 31 CEs accounted for 48 ± 4% and 40 ± 2%, respectively, of the total meibum lipids. The mass percentages of saturated and unsaturated species were determined to be 75 ± 2% and 25 ± 1% for CEs and 14 ± 1% and 86 ± 1% for WEs. The profiles for two types of DEs were also obtained, which include 42 α,ω Type II DEs, and 21 ω Type I-St DEs. Conclusions. Major neutral lipid classes in meibum samples were quantitatively profiled by ESI-MS analysis with NaI additive. PMID:23847307

Commercial silicon-on-insulator (SOI) wafers as a versatile substrate for laser desorption/ionization mass spectrometry.

PubMed

Kim, Shin Hye; Kim, Jeongkwon; Moon, Dae Won; Han, Sang Yun

2013-01-01

We report here that a commercial silicon-on-insulator (SOI) wafer offers an opportunity for laser desorption/ionization (LDI) of peptide molecules, which occurs directly from its flat surface without requiring special surface preparation. The LDI-on-SOI exhibits intact ionization of peptides with a good detection limit of lower than 20 fmol, of which the mass range is demonstrated up to insulin with citric acid additives. The LDI process most likely arises from laser-induced surface heating promoted by two-dimensional thermal confinement in the thin Si surface layer of the SOI wafer. As a consequence of the thermal process, the LDI-on-SOI method is also capable of creating post-source decay (PSD) of the resulting peptide LDI ions, which is suitable for peptide sequencing using conventional TOF/TOF mass spectrometry.

Sensitive determination of RDX, nitroso-RDX metabolites, and other munitions in ground water by solid-phase extraction and isotope dilution liquid chromatography-atmospheric pressure electro-spray [correction of chemical] ionization mass spectrometry.

PubMed

Cassada, D A; Monson, S J; Snow, D D; Spalding, R F

1999-06-04

Recent improvements in the LC-MS interface have increased the sensitivity and selectivity of this instrument in the analysis of polar and thermally-labile aqueous constituents. Determination of RDX, nitroso-RDX metabolites, and other munitions was enhanced using LC-MS with solid-phase extraction, 15N3-RDX internal standard, and electrospray ionization (ESI) in negative ion mode. ESI produced a five-fold increase in detector response over atmospheric pressure chemical ionization (APCI) for the nitramine compounds, while the more energetic APCI produced more than twenty times the ESI response for nitroaromatics. Method detection limits in ESI for nitramines varied from 0.03 microgram l-1 for MNX to 0.05 microgram l-1 for RDX.

Interstellar matter in Shapley-Ames elliptical galaxies. II. The distribution of dust and ionized gas

NASA Astrophysics Data System (ADS)

Goudfrooij, P.; Hansen, L.; Jorgensen, H. E.; Norgaard-Nielsen, H. U.

1994-06-01

We present results of deep optical CCD imaging for a complete, optical magnitude-limited sample of 56 elliptical galaxies from the RSA catalog. For each galaxy we have obtained broad-band images (in B, V, and I) and narrow-band images using interference filters isolating the Hα+[NII] emission lines to derive the amount and morphology of dust and ionized gas. Detailed consideration of systematic errors due to effects of sky background subtraction and removal of stellar continuum light from the narrow-band images is described. The flux calibration of the narrow-band images is performed by deconvolving actually measured spectral energy distributions with the filter transmission curves. We also present optical long-slit spectroscopy to determine the [NII]/Hα intensity ratio of the ionized gas. Dust lanes and/or patches have been detected in 23 galaxies (41%) from this sample using both colour-index images and division by purely elliptical model images. We achieved a detection limit for dust absorption of A_B_~0.02. Accounting for selection effects, the true fraction of elliptical galaxies containing dust is estimated to be of order 80%. This detection rate is comparable to that of the IRAS satellite, and significantly larger than results of previous optical studies. Ionized gas has been detected in 32 galaxies (57%). The spectroscopic data confirm the presence and distribution of ionized gas as seen in the direct imaging. All elliptical galaxies in our sample in which a number of emission lines is detected show very similar emission-line intensity ratios, which are typical of LINER nuclei. The amounts of detectable dust and ionized gas are generally small--of order 10^4^-10^5^Msun_ of dust and 10^3^-10^4^Msun_ of ionized gas. The dust and ionized gas show a wide variety of distributions-extended along either the apparent major axis, or the minor axis, or a skewed axis, indicating that triaxiality is in general required as a galaxy figure. In some cases (NGC 1275, NGC 2325, NGC 3136, NGC 3962, NGC 4696, NGC 5018, NGC 5044, NGC 5813, IC 1459) the interstellar matter has a patchy or filamentary distribution, suggestive of a recent interaction event. The distributions of dust and ionized gas are consistent with being physically associated with each other.

Generation of polypeptide-templated gold nanoparticles using ionizing radiation.

PubMed

Walker, Candace Rae; Pushpavanam, Karthik; Nair, Divya Geetha; Potta, Thrimoorthy; Sutiyoso, Caesario; Kodibagkar, Vikram D; Sapareto, Stephen; Chang, John; Rege, Kaushal

2013-08-13

Ionizing radiation, including γ rays and X-rays, are high-energy electromagnetic radiation with diverse applications in nuclear energy, astrophysics, and medicine. In this work, we describe the use of ionizing radiation and cysteine-containing elastin-like polypeptides (C(n)ELPs, where n = 2 or 12 cysteines in the polypeptide sequence) for the generation of gold nanoparticles. In the presence of C(n)ELPs, ionizing radiation doses higher than 175 Gy resulted in the formation of maroon-colored gold nanoparticle dispersions, with maximal absorbance at 520 nm, from colorless metal salts. Visible color changes were not observed in any of the control systems, indicating that ionizing radiation, gold salt solution, and C(n)ELPs were all required for nanoparticle formation. The hydrodynamic diameters of nanoparticles, determined using dynamic light scattering, were in the range of 80-150 nm, while TEM imaging indicated the formation of gold cores 10-20 nm in diameter. Interestingly, C2ELPs formed 1-2 nm diameter gold nanoparticles in the absence of radiation. Our results describe a facile method of nanoparticle formation in which nanoparticle size can be tailored based on radiation dose and C(n)ELP type. Further improvements in these polypeptide-based systems can lead to colorimetric detection of ionizing radiation in a variety of applications.

Ionization detection system for aerosols

DOEpatents

Jacobs, Martin E.

1977-01-01

This invention relates to an improved smoke-detection system of the ionization-chamber type. In the preferred embodiment, the system utilizes a conventional detector head comprising a measuring ionization chamber, a reference ionization chamber, and a normally non-conductive gas triode for discharging when a threshold concentration of airborne particulates is present in the measuring chamber. The improved system utilizes a measuring ionization chamber which is modified to minimize false alarms and reductions in sensitivity resulting from changes in ambient temperature. In the preferred form of the modification, an annular radiation shield is mounted about the usual radiation source provided to effect ionization in the measuring chamber. The shield is supported by a bimetallic strip which flexes in response to changes in ambient temperature, moving the shield relative to the source so as to vary the radiative area of the source in a manner offsetting temperature-induced variations in the sensitivity of the chamber.

In Situ Geochemical Analysis and Age Dating of Rocks Using Laser Ablation-Miniature Mass Spectrometer

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva P.; Hecht, Michael H.; Hurowitz, Joel A.

2012-01-01

A miniaturized instrument for performing chemical and isotopic analysis of rocks has been developed. The rock sample is ablated by a laser and the neutral species produced are analyzed using the JPL-invented miniature mass spectrometer. The direct sampling of neutral ablated material and the simultaneous measurement of all the elemental and isotopic species are the novelties of this method. In this laser ablation-miniature mass spectrometer (LA-MMS) method, the ablated neutral atoms are led into the electron impact ionization source of the MMS, where they are ionized by a 70-eV electron beam. This results in a secondary ion pulse typically 10-100 microsecond wide, compared to the original 5-10-nanosecond laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer and measured in parallel by a modified CCD (charge-coupled device) array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LAMMS offers a more quantitative assessment of elemental composition than techniques that detect laser-ionized species produced directly in the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the laser beam, and the ionization energies of the elements. The measurement of high-precision isotopic ratios and elemental composition of different rock minerals by LAMMS method has been demonstrated. The LA-MMS can be applied for the absolute age determination of rocks. There is no such instrument available presently in a miniaturized version that can be used for NASA space missions. Work is in progress in the laboratory for geochronology of rocks using LA-MMS that is based on K-Ar radiogenic dating technique.

Combined Determination of Poly-β-Hydroxyalkanoic and Cellular Fatty Acids in Starved Marine Bacteria and Sewage Sludge by Gas Chromatography with Flame Ionization or Mass Spectrometry Detection

PubMed Central

Odham, Göran; Tunlid, Anders; Westerdahl, Gunilla; Mårdén, Per

1986-01-01

Extraction of lipids from bacterial cells or sewage sludge samples followed by simple and rapid extraction procedures and room temperature esterification with pentafluorobenzylbromide allowed combined determinations of poly-β-hydroxyalkanoate constituents and fatty acids. Capillary gas chromatography and flame ionization or mass spectrometric detection was used. Flame ionization permitted determination with a coefficient of variation ranging from 10 to 27% at the picomolar level, whereas quantitative chemical ionization mass spectrometry afforded sensitivities for poly-β-hydroxyalkanoate constituuents in the attomolar range. The latter technique suggests the possibility of measuring such components in bacterial assemblies with as few as 102 cells. With the described technique using flame ionization detection, it was possible to study the rapid formation of poly-β-hydroxyalkanoate during feeding of a starved marine bacterium isolate with a complex medium or glucose and correlate the findings to changes in cell volumes. Mass spectrometric detection of short β-hydroxy acids in activated sewage sludge revealed the presence of 3-hydroxybutyric, 3-hydroxyhexanoic, and 3-hydroxyoctanoic acids in the relative proportions of 56, 5 and 39%, respectively. No odd-chain β-hydroxy acids were found. PMID:16347181

Detection, characterization and identification of phenolic acids in Danshen using high-performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry.

PubMed

Liu, Ai-Hua; Guo, Hui; Ye, Min; Lin, Yan-Hua; Sun, Jiang-Hao; Xu, Man; Guo, De-An

2007-08-17

By using HPLC-diode array detection-electrospray ion trap tandem mass spectrometry (HPLC-DAD-ESI-MS(n)) in negative ion mode, we have analyzed the fragmentation pathways of 11 phenolic acids which were isolated from Danshen. Then the extract of Danshen was analyzed, and a total of 42 phenolic acids, including sixteen new minor constituents, were identified or tentatively identified for the first time. A new solid-phase extraction (SPE) method, new HPLC separation method, new liquid chromatography (LC)-MS and LC-MS(n) (n=3-5) data and proposed fragmentation pathways, LC retention time for phenolic acids are reported.

Neutron-detecting apparatuses and methods of fabrication

DOEpatents

Dahal, Rajendra P.; Huang, Jacky Kuan-Chih; Lu, James J. Q.; Danon, Yaron; Bhat, Ishwara B.

2015-10-06

Neutron-detecting structures and methods of fabrication are provided which include: a substrate with a plurality of cavities extending into the substrate from a surface; a p-n junction within the substrate and extending, at least in part, in spaced opposing relation to inner cavity walls of the substrate defining the plurality of cavities; and a neutron-responsive material disposed within the plurality of cavities. The neutron-responsive material is responsive to neutrons absorbed for releasing ionization radiation products, and the p-n junction within the substrate spaced in opposing relation to and extending, at least in part, along the inner cavity walls of the substrate reduces leakage current of the neutron-detecting structure.

A Versatile Integrated Ambient Ionization Source Platform.

PubMed

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-30

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.

A Versatile Integrated Ambient Ionization Source Platform

NASA Astrophysics Data System (ADS)

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-01

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. [Figure not available: see fulltext.

Surface-assisted laser desorption ionization mass spectrometry techniques for application in forensics.

PubMed

Guinan, Taryn; Kirkbride, Paul; Pigou, Paul E; Ronci, Maurizio; Kobus, Hilton; Voelcker, Nicolas H

2015-01-01

Matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is an excellent analytical technique for the rapid and sensitive analysis of macromolecules (>700 Da), such as peptides, proteins, nucleic acids, and synthetic polymers. However, the detection of smaller organic molecules with masses below 700 Da using MALDI-MS is challenging due to the appearance of matrix adducts and matrix fragment peaks in the same spectral range. Recently, nanostructured substrates have been developed that facilitate matrix-free laser desorption ionization (LDI), contributing to an emerging analytical paradigm referred to as surface-assisted laser desorption ionization (SALDI) MS. Since SALDI enables the detection of small organic molecules, it is rapidly growing in popularity, including in the field of forensics. At the same time, SALDI also holds significant potential as a high throughput analytical tool in roadside, work place and athlete drug testing. In this review, we discuss recent advances in SALDI techniques such as desorption ionization on porous silicon (DIOS), nano-initiator mass spectrometry (NIMS) and nano assisted laser desorption ionization (NALDI™) and compare their strengths and weaknesses with particular focus on forensic applications. These include the detection of illicit drug molecules and their metabolites in biological matrices and small molecule detection from forensic samples including banknotes and fingerprints. Finally, the review highlights recent advances in mass spectrometry imaging (MSI) using SALDI techniques. © 2014 Wiley Periodicals, Inc.

Anticodeine aptamer immobilized on a Whatman cellulose paper for thin-film microextraction of codeine from urine followed by electrospray ionization ion mobility spectrometry.

PubMed

Hashemian, Zahra; Khayamian, Taghi; Saraji, Mohammad

2015-02-01

A combination of thin-film microextaction based on an aptamer immobilized on modified Whatman cellulose paper followed by electrospray ionization ion mobility spectrometry has been developed for the analysis of codeine in urine samples. The immobilization is based on the covalent linking of an amino-modified anticodeine aptamer to aldehyde groups of the oxidized cellulose paper. The covalent bonds were examined by infrared spectroscopy and elemental analysis. The effect of the extraction parameters, including the elution conditions (solvent type and volume), extraction time, and extraction temperature, on the extraction efficiency were investigated. Under the optimized conditions, the linear dynamic range was found to be 10-300 ng/mL with a detection limit of 3.4 ng/mL for codeine in urine. The relative standard deviation was 6.8% for three replicate measurements of codeine at 100 ng/mL in urine. Furthermore, the samples were analyzed with a standard method for the analysis of codeine using high-performance liquid chromatography with ultraviolet detection. The comparison of the results validates the accuracy of the proposed method as an alternative method for the analysis of codeine in urine samples.

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.

Effects of Ionizing Radiation on Biological Molecules—Mechanisms of Damage and Emerging Methods of Detection

PubMed Central

Reisz, Julie A.; Bansal, Nidhi; Qian, Jiang; Zhao, Weiling

2014-01-01

Abstract Significance: The detrimental effects of ionizing radiation (IR) involve a highly orchestrated series of events that are amplified by endogenous signaling and culminating in oxidative damage to DNA, lipids, proteins, and many metabolites. Despite the global impact of IR, the molecular mechanisms underlying tissue damage reveal that many biomolecules are chemoselectively modified by IR. Recent Advances: The development of high-throughput “omics” technologies for mapping DNA and protein modifications have revolutionized the study of IR effects on biological systems. Studies in cells, tissues, and biological fluids are used to identify molecular features or biomarkers of IR exposure and response and the molecular mechanisms that regulate their expression or synthesis. Critical Issues: In this review, chemical mechanisms are described for IR-induced modifications of biomolecules along with methods for their detection. Included with the detection methods are crucial experimental considerations and caveats for their use. Additional factors critical to the cellular response to radiation, including alterations in protein expression, metabolomics, and epigenetic factors, are also discussed. Future Directions: Throughout the review, the synergy of combined “omics” technologies such as genomics and epigenomics, proteomics, and metabolomics is highlighted. These are anticipated to lead to new hypotheses to understand IR effects on biological systems and improve IR-based therapies. Antioxid. Redox Signal. 21: 260–292. PMID:24382094

Human exposure to Bisphenol A and liver health status: Quantification of urinary and circulating levels by LC-MS/MS.

PubMed

Nicolucci, Carla; Errico, Sonia; Federico, Alessandro; Dallio, Marcello; Loguercio, Carmelina; Diano, Nadia

2017-06-05

A selective and highly sensitive analytical methodology for determination of Bisphenol A in human plasma was developed and validated. The method was based on selective liquid/solid extraction, combined with liquid chromatography-electrospray ionization tandem mass spectrometry in the multiple reaction monitoring mode and negative ionization. The linearity of the detector response was verified in human plasma over the concentration range 0.100-200ngmL -1 . The detection limit was 0.03ngmL -1 and the quantification limit was 0.100ngmL -1 . The analytical features of the proposed in-house validated method were satisfactory: precision was <10% and recoveries were around 84-104%. The matrix effect was studied and compensated using deuterated labeled standard. The applicability of the proposed method was demonstrated analyzing human plasma samples from individuals affected by non-alcoholic fatty liver disease. Bisphenol A was detected above the detection limit in all samples. The data show a persistence of unconjugated Bisphenol A levels in plasma and indicate a chronic Bisphenol A exposure of the target organ, suggesting an association between liver health status and Bisphenol A exposure. The results from our study are valuable for further investigation with large sample size and longitudinal study designs, necessary to confirm the observed association. Copyright © 2017 Elsevier B.V. All rights reserved.

Deep eutectic solvent based gas-assisted dispersive liquid-phase microextraction combined with gas chromatography and flame ionization detection for the determination of some pesticide residues in fruit and vegetable samples.

PubMed

Farajzadeh, Mir Ali; Sattari Dabbagh, Masoumeh; Yadeghari, Adeleh

2017-05-01

In this study, a gas-assisted dispersive liquid-phase microextraction method using a deep eutectic solvent as the extraction solvent combined with gas chromatography and flame ionization detection was developed for the extraction and determination of some pesticide residues in vegetable and fruit juice samples. In this method, choline chloride and 4-chlorophenol at a molar ratio of 1:2 were mixed. By heating and vortexing, a clear, water-immiscible, and homogeneous liquid was formed. The obtained deep eutectic solvent was added to an aqueous solution of the analytes in a conical test tube. Air was bubbled into the aqueous solution and a cloudy solution was obtained. During this step, the analytes were extracted into the fine droplets of the extraction solvent. After centrifugation, an aliquot of the settled phase was injected into the separation system. Under the optimum extraction conditions, enrichment factors, and extraction recoveries were obtained in the ranges of 247-355 and 49-71%, respectively. The obtained values for the limits of detection and quantification were in the ranges of 0.24-1.4 and 0.71-4.2 μg/L, respectively. The proposed method is simple, fast, efficient, and inexpensive. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of lower tropospheric responses to solar energetic particles at midlatitudes.

PubMed

Nicoll, K A; Harrison, R G

2014-06-06

Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon's trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere's weather-generating regions.

Ultra High Mass Range Mass Spectrometer System

DOEpatents

Reilly, Peter T. A. [Knoxville, TN

2005-12-06

Applicant's present invention comprises mass spectrometer systems that operate in a mass range from 1 to 10.sup.16 DA. The mass spectrometer system comprising an inlet system comprising an aerodynamic lens system, a reverse jet being a gas flux generated in an annulus moving in a reverse direction and a multipole ion guide; a digital ion trap; and a thermal vaporization/ionization detector system. Applicant's present invention further comprises a quadrupole mass spectrometer system comprising an inlet system having a quadrupole mass filter and a thermal vaporization/ionization detector system. Applicant's present invention further comprises an inlet system for use with a mass spectrometer system, a method for slowing energetic particles using an inlet system. Applicant's present invention also comprises a detector device and a method for detecting high mass charged particles.

Quantitation of phlorizin and phloretin using an ultra high performance liquid chromatography-electrospray ionization tandem mass spectrometric method.

PubMed

Lijia, Xu; Guo, Jianru; Chen, QianQian; Baoping, Jiang; Zhang, Wei

2014-06-01

A sensitive and selective ultra high performance liquid chromatography-tandem mass spectrometric (UHPLC-MS/MS) method for the determination of phlorizin and phloretin in human plasma has been firstly developed. Samples were prepared after protein precipitation and analyzed on a C18 column interfaced with a triple quadrupole tandem mass spectrometer. Negative electrospray ionization was employed as the ionization source. The mobile phase consisted of acetonitrile-water (0.02% formic acid), using a gradient procedure. The analytes and internal standard dihydroquercetin were both detected by use of multiple reaction monitoring mode. The method was linear in the concentration range of 2.5-1000.0 ng/mL. The lower limit of quantification (LLOQ) was 2.5 ng/mL. The intra- and inter-day relative standard deviation across three validation runs over the entire concentration range was less than 9.2%. The accuracy determined at three concentrations was within ± 7.3% in terms of relative error. The total run time was 12.0 min. This assay offers advantages in terms of expediency, and suitability for the analysis of phlorizin and phloretin in various biological fluids. Copyright © 2014 Elsevier B.V. All rights reserved.

Computerized analysis of sonograms for the detection of breast lesions

NASA Astrophysics Data System (ADS)

Drukker, Karen; Giger, Maryellen L.; Horsch, Karla; Vyborny, Carl J.

2002-05-01

With a renewed interest in using non-ionizing radiation for the screening of high risk women, there is a clear role for a computerized detection aid in ultrasound. Thus, we are developing a computerized detection method for the localization of lesions on breast ultrasound images. The computerized detection scheme utilizes two methods. Firstly, a radial gradient index analysis is used to distinguish potential lesions from normal parenchyma. Secondly, an image skewness analysis is performed to identify posterior acoustic shadowing. We analyzed 400 cases (757 images) consisting of complex cysts, solid benign lesions, and malignant lesions. The detection method yielded an overall sensitivity of 95% by image, and 99% by case at a false-positive rate of 0.94 per image. In 51% of all images, only the lesion itself was detected, while in 5% of the images only the shadowing was identified. For malignant lesions these numbers were 37% and 9%, respectively. In summary, we have developed a computer detection method for lesions on ultrasound images of the breast, which may ultimately aid in breast cancer screening.

Extraction and preconcentration of residual solvents in pharmaceuticals using dynamic headspace-liquid phase microextraction and their determination by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Dehghani, Hamideh; Yadeghari, Adeleh; Khoshmaram, Leila

2017-02-01

The present study describes a microextraction and determination method for analyzing residual solvents in pharmaceutical products using dynamic headspace-liquid phase microextraction technique followed by gas chromatography-flame ionization detection. In this method dimethyl sulfoxide (μL level) placed into a GC liner-shaped extraction vessel is used as a collection/extraction solvent. Then the liner is exposed to the headspace of a vial containing the sample solution. The effect of different parameters influencing the microextraction procedure including collection/extraction solvent type and its volume, ionic strength, extraction time, extraction temperature and concentration of NaOH solution used in dissolving the studied pharmaceuticals are investigated and optimized. Under the optimum extraction conditions, the method showed wide linear ranges between 0.5 and 5000 mg L -1 . The other analytical parameters were obtained in the following ranges: enrichment factors 240-327, extraction recoveries 72-98% and limits of detection 0.1-0.8 mg L -1 in solution and 0.6-3.2 μg g -1 in solid. Relative standard deviations for the extraction of 100 mg L -1 of each analyte were obtained in the ranges of 4-7 and 5-8% for intra-day (n = 6) and inter-day (n = 4) respectively. Finally the target analytes were determined in different samples such as erythromycin, azithromycin, cefalexin, amoxicillin and co-amoxiclav by the proposed method. Copyright © 2016 John Wiley & Sons, Ltd.

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

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

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

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

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish.

PubMed

Alaee, M; Sergeant, D B; Ikonomou, M G; Luross, J M

2001-09-01

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.

High Sensitivity Analysis of Nanoliter Volumes of Volatile and Nonvolatile Compounds using Matrix Assisted Ionization (MAI) Mass Spectrometry

NASA Astrophysics Data System (ADS)

Hoang, Khoa; Pophristic, Milan; Horan, Andrew J.; Johnston, Murray V.; McEwen, Charles N.

2016-10-01

First results are reported using a simple, fast, and reproducible matrix-assisted ionization (MAI) sample introduction method that provides substantial improvements relative to previously published MAI methods. The sensitivity of the new MAI methods, which requires no laser, high voltage, or nebulizing gas, is comparable to those reported for MALDI-TOF and n-ESI. High resolution full acquisition mass spectra having low chemical background are acquired from low nanoliters of solution using only a few femtomoles of analyte. The limit-of-detection for angiotensin II is less than 50 amol on an Orbitrap Exactive mass spectrometer. Analysis of peptides, including a bovine serum albumin digest, and drugs, including drugs in urine without a purification step, are reported using a 1 μL zero dead volume syringe in which only the analyte solution wetting the walls of the syringe needle is used in the analysis.

Quantification of lipoic acid in plasma by high-performance liquid chromatography-electrospray ionization mass spectrometry.

PubMed

Chen, Jun; Jiang, Wenming; Cai, Jia; Tao, Weixing; Gao, Xiaoling; Jiang, Xinguo

2005-09-25

A sensitive and specific liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) method has been developed and validated for the identification and quantification of lipoic acid (LA) in human plasma. LA and the internal standard, naproxen, were extracted from a 500 microl plasma sample by one-step deproteination using acetonitrile. Chromatographic separation was performed on a Zorbax SB-C(18) Column (100 mmx3.0mm i.d. with 3.5 microm particle size) with the mobile phase consisting of acetonitrile and 0.1% acetic acid (pH 4, adjusted with ammonia solution) (65:35, v/v), and the flow rate was set at 0.3 ml/min. Detection was performed on a single quadrupole mass spectrometer by selected ion monitoring (SIM) mode via electrospray ionization (ESI) source. The method was linear over the concentration range of 5-10,000 ng/ml for LA. The intra- and inter-day precisions were less than 7% and accuracy ranged from -7.87 to 9.74% at the LA concentrations tested. The present method provides a relatively simple and sensitive assay with short turn-around time. The method has been successfully applied to a clinical pharmacokinetic study of LA in 10 healthy subjects.

Validation and Application of a Simple UHPLC-MS-MS Method for the Enantiospecific Determination of Warfarin in Human Urine.

PubMed

Alshogran, Osama Y; Ocque, Andrew J; Leblond, François A; Pichette, Vincent; Nolin, Thomas D

2016-04-01

A simple and rapid liquid chromatographic-tandem mass spectrometric method has been developed and validated for the enantiospecific determination of R- and S-warfarin in human urine. Warfarin enantiomers were extracted from urine using methyl tert-butyl ether. Chromatographic separation of warfarin enantiomers and the internal standard d5-warfarin was achieved using a Astec Chirobiotic V column with gradient mobile phase at a flow rate of 400 µL/min over 10 min. Detection was performed on a TSQ Quantum Ultra triple quadrupole mass spectrometer equipped with a heated electrospray ionization source. Analytes were detected in negative ionization mode using selected reaction monitoring. Calibration curves were linear with a correlation coefficient of ≥0.996 for both enantiomers over a concentration range of 5-500 ng/mL. The intra- and interday accuracy and precision for both analytes were within ±9.0%. Excellent extraction efficiency and negligible matrix effects were observed. The applicability of the method was demonstrated by successful measurement of warfarin enantiomers in urine of patients with kidney disease. The method is simple, accurate and reproducible and is currently being used to support warfarin pharmacokinetic studies. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Characterization of the components of meleumycin by liquid chromatography with photo-diode array detection and electrospray ionization tandem mass spectrometry.

PubMed

Wang, Ming-Juan; Li, Ya-Ping; Wang, Yan; Li, Jin; Hu, Chang-Qin; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin

2013-10-01

Reversed-phase liquid chromatography coupled with photo-diode array (PDA) detection and electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to characterize the components of meleumycin, a 16-membered macrolide antibiotic produced by fermentation. In total 31 components were characterized in commercial samples, including 12 impurities that had never been reported before and 12 others that were partially characterized. The structures of these unknown compounds were deduced by comparison of their fragmentation patterns with those of known components. Their ultraviolet spectra and chromatographic behavior were used to confirm the proposed structures: e.g. λmax shift from 232 nm to 282 nm would indicate the presence of an α-, β-, γ-, δ-unsaturated ketone instead of a normal α-, β-, γ-, δ-unsaturated alcohol in the 16-membered ring of the examined components. Compared to other methods, this LC/MS(n) method is particularly advantageous to characterize minor components at trace levels in multi-components antibiotics, in terms of sensitivity and efficiency. Copyright © 2013 Elsevier B.V. All rights reserved.

[Determination of acetanilide herbicide residues in tea by gas chromatography-mass spectrometry with two different ionization techniques].

PubMed

Shen, Weijian; Xu, Jinzhong; Yang, Wenquan; Shen, Chongyu; Zhao, Zengyun; Ding, Tao; Wu, Bin

2007-09-01

An analytical method of solid phase extraction-gas chromatography-mass spectrometry with two different ionization techniques was established for simultaneous determination of 12 acetanilide herbicide residues in tea-leaves. Herbicides were extracted from tea-leaf samples with ethyl acetate. The extract was cleaned-up on an active carbon SPE column connected to a Florisil SPE column. Analytical screening was determined by the technique of gas chromatography (GC)-mass spectrometry (MS) in the selected ion monitoring (SIM) mode with either electron impact ionization (EI) or negative chemical ionization (NCI). It is reliable and stable that the recoveries of all herbicides were in the range from 50% to 110% at three spiked levels, 10 microg/kg, 20 microg/kg and 40 microg/kg, and the relative standard deviations (RSDs) were no more than 10.9%. The two different ionization techniques are complementary as more ion fragmentation information can be obtained from the EI mode while more molecular ion information from the NCI mode. By comparison of the two techniques, the selectivity of NCI-SIM was much better than that of EI-SIM method. The sensitivities of the both techniques were high, the limit of quantitative (LOQ) for each herbicide was no more than 2.0 microg/kg, and the limit of detection (LOD) with NCI-SIM technique was much lower than that of EI-SIM when analyzing herbicides with several halogen atoms in the molecule.

Measuring ionizing radiation with a mobile device

NASA Astrophysics Data System (ADS)

Michelsburg, Matthias; Fehrenbach, Thomas; Puente León, Fernando

2012-02-01

In cases of nuclear disasters it is desirable to know one's personal exposure to radioactivity and the related health risk. Usually, Geiger-Mueller tubes are used to assess the situation. Equipping everyone with such a device in a short period of time is very expensive. We propose a method to detect ionizing radiation using the integrated camera of a mobile consumer device, e.g., a cell phone. In emergency cases, millions of existing mobile devices could then be used to monitor the exposure of its owners. In combination with internet access and GPS, measured data can be collected by a central server to get an overview of the situation. During a measurement, the CMOS sensor of a mobile device is shielded from surrounding light by an attachment in front of the lens or an internal shutter. The high-energy radiation produces free electrons on the sensor chip resulting in an image signal. By image analysis by means of the mobile device, signal components due to incident ionizing radiation are separated from the sensor noise. With radioactive sources present significant increases in detected pixels can be seen. Furthermore, the cell phone application can make a preliminary estimate on the collected dose of an individual and the associated health risks.

High Energy Electron and Gamma - Ray Detection with ATIC

NASA Technical Reports Server (NTRS)

Chang, J.; Schmidt, W. K. H.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

The Advanced Thin Ionization Calorimeter (ATIC) balloon borne ionization calorimeter is well suited to record and identify high energy cosmic ray electrons, and at very high energies gamma-ray photons as well. We have simulated the performance of the instrument, and compare the simulations with actual high energy electron exposures at the CERN accelerator. Simulations and measurements do not compare exactly, in detail, but overall the simulations have predicted actual measured behavior quite well. ATIC has had its first 16 day balloon flight at the turn of the year over Antarctica, and first results obtained using the analysis methods derived from simulations and calibrations will be reported.

Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection

PubMed Central

Matisová, Eva; Hrouzková, Svetlana

2012-01-01

Endocrine disrupting chemicals, among them many pesticides, alter the normal functioning of the endocrine system of both wildlife and humans at very low concentration levels. Therefore, the importance of method development for their analysis in food and the environment is increasing. This also covers contributions in the field of ultra-trace analysis of multicomponent mixtures of organic pollutants in complex matrices. With this fact conventional capillary gas chromatography (CGC) and fast CGC with mass spectrometric detection (MS) has acquired a real importance in the analysis of endocrine disrupting pesticide (EDP) residues. This paper provides an overview of GC methods, including sample preparation steps, for analysis of EDPs in a variety of matrices at ultra-trace concentration levels. Emphasis is put on separation method, mode of MS detection and ionization and obtained limits of detection and quantification. Analysis time is one of the most important aspects that should be considered in the choice of analytical methods for routine analysis. Therefore, the benefits of developed fast GC methods are important. PMID:23202677

Systems and methods for cylindrical hall thrusters with independently controllable ionization and acceleration stages

DOEpatents

Diamant, Kevin David; Raitses, Yevgeny; Fisch, Nathaniel Joseph

2014-05-13

Systems and methods may be provided for cylindrical Hall thrusters with independently controllable ionization and acceleration stages. The systems and methods may include a cylindrical channel having a center axial direction, a gas inlet for directing ionizable gas to an ionization section of the cylindrical channel, an ionization device that ionizes at least a portion of the ionizable gas within the ionization section to generate ionized gas, and an acceleration device distinct from the ionization device. The acceleration device may provide an axial electric field for an acceleration section of the cylindrical channel to accelerate the ionized gas through the acceleration section, where the axial electric field has an axial direction in relation to the center axial direction. The ionization section and the acceleration section of the cylindrical channel may be substantially non-overlapping.

Targeted analyte detection by standard addition improves detection limits in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Toghi Eshghi, Shadi; Li, Xingde; Zhang, Hui

2012-09-18

Matrix-assisted laser desorption/ionization (MALDI) has proven an effective tool for fast and accurate determination of many molecules. However, the detector sensitivity and chemical noise compromise the detection of many invaluable low-abundance molecules from biological and clinical samples. To challenge this limitation, we developed a targeted analyte detection (TAD) technique. In TAD, the target analyte is selectively elevated by spiking a known amount of that analyte into the sample, thereby raising its concentration above the noise level, where we take advantage of the improved sensitivity to detect the presence of the endogenous analyte in the sample. We assessed TAD on three peptides in simple and complex background solutions with various exogenous analyte concentrations in two MALDI matrices. TAD successfully improved the limit of detection (LOD) of target analytes when the target peptides were added to the sample in a concentration close to optimum concentration. The optimum exogenous concentration was estimated through a quantitative method to be approximately equal to the original LOD for each target. Also, we showed that TAD could achieve LOD improvements on an average of 3-fold in a simple and 2-fold in a complex sample. TAD provides a straightforward assay to improve the LOD of generic target analytes without the need for costly hardware modifications.

Multiplexed electronically programmable multimode ionization detector for chromatography

DOEpatents

Wise, M.B.; Buchanan, M.V.

1988-05-19

Method and apparatus for detecting and differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated in a plurality of multiplexed electronically programmable operating modes to alter the detector response during a single sampling cycle to acquire multiple simultaneous chromatograms corresponding to each of the different operating modes. The cell is held at a constant subatmospheric pressure while the electron collection bias voltage applied to the cell is modulated electronically to allow acquisition of multiple chromatograms for a single sample elution from a chromatograph representing three distinctly different response modes. A system is provided which automatically controls the programmed application of bias pulses at different intervals and/or amplitudes to switch the detector from an ionization mode to the electron capture mode and various degrees therebetween to provide an improved means of tuning an ECD for multimode detection and improved specificity. 6 figs.

Multiplexed electronically programmable multimode ionization detector for chromatography

DOEpatents

Wise, Marcus B.; Buchanan, Michelle V.

1989-01-01

Method and apparatus for detecting and differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated in a plurality of multiplexed electroncially programmable operating modes to alter the detector response during a single sampling cycle to acquire multiple simultaneous chromatograms corresponding to each of the different operating modes. The cell is held at a constant subatmospheric pressure while the electron collection bias voltage applied to the cell is modulated electronically to allow acquisition of multiple chromatograms for a single sample elution from a chromatograph representing three distinctly different response modes. A system is provided which automatically controls the programmed application of bias pulses at different intervals and/or amplitudes to switch the detector from an ionization mode to the electron capture mode and various degrees therebetween to provide an improved means of tuning an ECD for multimode detection and improved specificity.

Determination of selected fatty acids in dried sweat spot using gas chromatography with flame ionization detection.

PubMed

Kanďár, Roman; Drábková, Petra; Andrlová, Lenka; Kostelník, Adam; Čegan, Alexander

2016-11-01

A method is described for the determination of fatty acids in dried sweat spot and plasma samples using gas chromatography with flame ionization detection. Plasma and dried sweat spot samples were obtained from a group of blood donors. The sweat was collected from each volunteer during exercise. Sweat was spotted onto collection paper containing butylated hydroxytoluene. Fatty acids were derivatized with acetyl chloride in methanol to form methyl esters of fatty acids. The fatty acids in dried sweat spot samples treated with butylated hydroxytoluene and stored at -20°C were stable for 3 months. Our results indicate that sweat contains, among fatty acids with short chain, also fatty acids with long chain and unsaturated fatty acids. Linear relationships between percentage content of selected fatty acids in dried sweat spot and plasma were observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of the Species of Origin for Meat Products by Rapid Evaporative Ionization Mass Spectrometry.

PubMed

Balog, Julia; Perenyi, Dora; Guallar-Hoyas, Cristina; Egri, Attila; Pringle, Steven D; Stead, Sara; Chevallier, Olivier P; Elliott, Chris T; Takats, Zoltan

2016-06-15

Increasingly abundant food fraud cases have brought food authenticity and safety into major focus. This study presents a fast and effective way to identify meat products using rapid evaporative ionization mass spectrometry (REIMS). The experimental setup was demonstrated to be able to record a mass spectrometric profile of meat specimens in a time frame of <5 s. A multivariate statistical algorithm was developed and successfully tested for the identification of animal tissue with different anatomical origin, breed, and species with 100% accuracy at species and 97% accuracy at breed level. Detection of the presence of meat originating from a different species (horse, cattle, and venison) has also been demonstrated with high accuracy using mixed patties with a 5% detection limit. REIMS technology was found to be a promising tool in food safety applications providing a reliable and simple method for the rapid characterization of food products.

Characterization of Hydrophobic Peptides in the Presence of Detergent by Photoionization Mass Spectrometry

PubMed Central

Bagag, Aïcha; Jault, Jean-Michel; Sidahmed-Adrar, Nazha; Réfrégiers, Matthieu; Giuliani, Alexandre; Le Naour, François

2013-01-01

The characterization of membrane proteins is still challenging. The major issue is the high hydrophobicity of membrane proteins that necessitates the use of detergents for their extraction and solubilization. The very poor compatibility of mass spectrometry with detergents remains a tremendous obstacle in studies of membrane proteins. Here, we investigated the potential of atmospheric pressure photoionization (APPI) for mass spectrometry study of membrane proteins. This work was focused on the tetraspanin CD9 and the multidrug transporter BmrA. A set of peptides from CD9, exhibiting a broad range of hydropathicity, was investigated using APPI as compared to electrospray ionization (ESI). Mass spectrometry experiments revealed that the most hydrophobic peptides were hardly ionized by ESI whereas all peptides, including the highly hydrophobic one that corresponds to the full sequence of the first transmembrane domain of CD9, were easily ionized by APPI. The native protein BmrA purified in the presence of the non-ionic detergent beta-D-dodecyl maltoside (DDM) was digested in-solution using trypsin. The resulting peptides were investigated by flow injection analysis of the mixture followed by mass spectrometry. Upon ESI, only detergent ions were detected and the ionic signals from the peptides were totally suppressed. In contrast, APPI allowed many peptides distributed along the sequence of the protein to be detected. Furthermore, the parent ion corresponding to the first transmembrane domain of the protein BmrA was detected under APPI conditions. Careful examination of the APPI mass spectrum revealed a-, b-, c- and y- fragment ions generated by in-source fragmentation. Those fragment ions allowed unambiguous structural characterization of the transmembrane domain. In conclusion, APPI–MS appears as a versatile method allowing the ionization and fragmentation of hydrophobic peptides in the presence of detergent. PMID:24236085

Ambient aerodynamic ionization source for remote analyte sampling and mass spectrometric analysis.

PubMed

Dixon, R Brent; Sampson, Jason S; Hawkridge, Adam M; Muddiman, David C

2008-07-01

The use of aerodynamic devices in ambient ionization source development has become increasingly prevalent in the field of mass spectrometry. In this study, an air ejector has been constructed from inexpensive, commercially available components to incorporate an electrospray ionization emitter within the exhaust jet of the device. This novel aerodynamic device, herein termed remote analyte sampling, transport, and ionization relay (RASTIR) was used to remotely sample neutral species in the ambient and entrain them into an electrospray plume where they were subsequently ionized and detected using a linear ion trap Fourier transform mass spectrometer. Two sets of experiments were performed in the ambient environment to demonstrate the device's utility. The first involved the remote (approximately 1 ft) vacuum collection of pure sample particulates (i.e., dry powder) from a glass slide, entrainment and ionization at the ESI emitter, and mass spectrometric detection. The second experiment involved the capture (vacuum collection) of matrix-assisted laser desorbed proteins followed by entrainment in the ESI emitter plume, multiple charging, and mass spectrometric detection. This approach is in principle a RASTIR-assisted matrix-assisted laser desorption electrospray ionization source (Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. J. Am. Soc. Mass Spectrom. 2006, 17, 1712-1716; Rapid Commun. Mass Spectrom. 2007, 21, 1150-1154.). A detailed description of the device construction, operational parameters, and preliminary small molecule and protein data are presented.

Determination of residual 1,4-dioxane in surfactants and cleaning agents using headspace single-drop microextraction followed by gas chromatography-flame ionization detection.

PubMed

Saraji, M; Shirvani, N

2017-02-01

Polyethoxylated surfactants are widely used in the formulation of different cleaning agents such as shampoo, dish washing and hand washing products and lotion formulation. During the production of polyethoxylated surfactants, 1,4-dioxane as a toxic and carcinogenic by-product is formed. A simple low-cost method based on headspace single-drop microextraction combined with gas chromatography-flame ionization detection was developed for the determination of 1,4-dioxane in surfactants and cleaning agents. In this method, 1,4-dioxane was extracted from 8.0 mL sample solution into a microdrop of an organic solvent, and then, it was injected to gas chromatography. The effects of such parameters as the solvent type, salt addition, microdrop volume, stirring rate, equilibrium time, extraction time and the temperature of sample solution on the extraction performance were studied and optimized. An ethoxylated surfactant containing 1,4-dioxane was used as the sample for the optimization of the extraction parameters. The linear range, determination coefficient, limit of detection and relative standard deviation of the method were 0.5-100 μg g -1 , 0.9977, 0.4 μg g -1 and 7.2% (n = 5), respectively. Different real samples including sodium lauryl ether sulphate, sodium lauryl sulphate (SLS), four brands of shampoo, and hand washing and dish washing liquids were analysed by the method. 1,4-Dioxane was detected at the concentration range of 2.4-201 μg g -1 in the samples, except dish washing liquid and SLS. A new method with the merits of simplicity, low cost, low organic solvent consumption, short analysis time, good repeatability and suitable detection limit was developed for the analysis of 1,4-dioxane in surfactants and cleaning agents. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Identification of gamma-irradiated papaya, melon and watermelon

NASA Astrophysics Data System (ADS)

Marín-Huachaca, Nélida S.; Mancini-Filho, Jorge; Delincée, Henry; Villavicencio, Anna Lúcia C. H.

2004-09-01

Ionizing radiation can be used to control spoilage microorganisms and to increase the shelf life of fresh fruits and vegetables in replacement for the treatment with chemical fumigants. In order to enforce labelling regulations, methods for detecting the irradiation treatment directly in the produce are required. Recently, a number of detection methods for irradiated food have been adopted by the Codex Comission. A rapid screening method for qualitative detection of irradiation is the DNA Comet Assay. The applicability of the DNA Comet Assay for distinguishing irradiated papaya, melon, and watermelon was evaluated. The samples were treated in a 60Co facility at dose levels of 0.0, 0.5, 0.75, and 1.0kGy. The irradiated samples showed typical DNA fragmentation whereas cells from non-irradiated ones appeared intact. In addition to the DNA Comet Assay also the half-embryo test was applied in melon and watermelon to detect the irradiation treatment.

Electrospun fibrous thin film microextraction coupled with desorption corona beam ionization-mass spectrometry for rapid analysis of antidepressants in human plasma.

PubMed

Chen, Di; Hu, Yu-Ning; Hussain, Dilshad; Zhu, Gang-Tian; Huang, Yun-Qing; Feng, Yu-Qi

2016-05-15

Appropriate sample preparations prior to analysis can significantly enhance the sensitivity of ambient ionization techniques, especially during the enrichment or purification of analytes in the presence of complex biological matrix. Here in, we developed a rapid analysis method by the combination of thin film microextraction (TFME) and desorption corona beam ionization (DCBI) for the determination of antidepressants in human plasma. Thin films used for extraction consisted of sub-micron sized highly ordered mesoporous silica-carbon composite fibers (OMSCFs), simply prepared by electrospinning and subsequent carbonization. Typically, OMSCFs thin film was immersed into the diluted plasma for extraction of target analytes and then directly subjected to the DCBI-MS for detection. Size-exclusion effect of mesopores contributed to avoid of the protein precipitation step prior to extraction. Mass transfer was benefited from high surface-to-volume ratio which is attributed to macroporous network and ordered mesostructures. Moreover, the OMSCFs provided mixed-mode hydrophobic/ion-exchange interactions towards target analytes. Thus, the detection sensitivity was greatly improved due to effective enrichment of the target analytes and elimination of matrix interferences. After optimization of several parameters related to extraction performance, the proposed method was eventually applied for the determination of three antidepressants in human plasma. The calibration curves were plotted in the range of 5-1000 ng/mL with acceptable linearity (R(2) >0.983). The limits of detection (S/N=3) of three antidepressants were in ranges of 0.3-1 ng/mL. Reproducibility was achieved with RSD less than 17.6% and the relative recoveries were in ranges of 83.6-116.9%. Taken together, TFME-DCBI-MS method offers a powerful capacity for rapid analysis to achieve much-improved sensitivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluating the Aging of Multiple Emulsions Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

PubMed

Tsuda, Yukihiro; Uchimura, Tomohiro

2016-01-01

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry was applied to measurements of multiple emulsions with no pretreatment; a method for the quantitative evaluation of aging was proposed. We prepared water-in-oil-in-water (W/O/W) multiple emulsions containing toluene and m-phenylenediamine. The samples were measured immediately following both preparation and after having been stirred for 24 h. Time profiles of the peak areas for each analyte species were obtained, and several intense spikes for toluene could be detected from each sample after stirring, which suggests that the concentration of toluene in the middle phase had increased during stirring. On the other hand, in the case of a W/O/W multiple emulsion containing phenol and m-phenylenediamine, spikes for m-phenylenediamine, rather than phenol, were detected after stirring. In the present study, the time-profile data were converted into a scatter plot in order to quantitatively evaluate the aging. As a result, the ratio of the plots where strong signal intensities of toluene were detected increased from 8.4% before stirring to 33.2% after stirring for 24 h. The present method could be a powerful tool for evaluating multiple emulsions, such as studies on the kinetics of the encapsulation and release of active ingredients.

Detection of intact ricin in crude and purified extracts from castor beans using matrix-assisted laser desorption ionization mass spectrometry.

PubMed

Brinkworth, Craig S; Pigott, Eloise J; Bourne, David J

2009-02-15

Ricin is a highly toxic protein from the seeds of the castor bean plant. Crude extracts from castor beans are toxic by several routes, and there is international concern about the use of these extracts by terrorist organizations. Lethality in aerosolized form has spurred the development of methods for the rapid detection of this protein from air samples that is critical in determining the illicit use of this material. Matrix-assisted laser desorption ionization (MALDI) mass measurement with an automated laser firing sequence was used to detect intact ricin from solutions containing less than 4 microg/mL of ricin in the presence of other endogenous seed proteins. This sensitivity was attained with the addition of 0.01% Tween 80 to the extracts that greatly enhanced the ricin signal. Importantly, this treatment substantially reduces the interference from the castor bean seed storage proteins. Commonly the ricin signal can be completely obscured by the oligomers of seed storage proteins, and this treatment reveals the ricin molecular ion, allowing the analyst to make a judgment as to the ricin content of the extract. This method provides for sensitive and rapid identification of intact ricin from aqueous samples with little sample preparation and is amenable to automatic acquisition.

Improvement of mineral oil saturated and aromatic hydrocarbons determination in edible oil by liquid-liquid-gas chromatography with dual detection.

PubMed

Zoccali, Mariosimone; Barp, Laura; Beccaria, Marco; Sciarrone, Danilo; Purcaro, Giorgia; Mondello, Luigi

2016-02-01

Mineral oils, which are mainly composed of saturated hydrocarbons and aromatic hydrocarbons, are widespread food contaminants. Liquid chromatography coupled to gas chromatography with flame ionization detection represents the method of choice to determine these two families. However, despite the high selectivity of this technique, the presence of olefins (particularly squalene and its isomers) in some samples as in olive oils, does not allow the correct quantification of the mineral oil aromatic hydrocarbons fraction, requiring additional off-line tools to eliminate them. In the present research, a novel on-line liquid chromatography coupled to gas chromatography method is described for the determination of hydrocarbon contamination in edible oils. Two different liquid chromatography columns, namely a silica one (to retain the bulk of the matrix) and a silver-ion one (which better retains the olefins), were coupled in series to obtain the mineral oil aromatic hydrocarbons hump free of interfering peaks. Furthermore, the use of a simultaneous dual detection, flame ionization detector and triple quadrupole mass spectrometer allowed us not only to quantify the mineral oil contamination, but also to evaluate the presence of specific markers (i.e. hopanes) to confirm the petrogenic origin of the contamination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection limits of organic compounds achievable with intense, short-pulse lasers.

PubMed

Miles, Jordan; De Camillis, Simone; Alexander, Grace; Hamilton, Kathryn; Kelly, Thomas J; Costello, John T; Zepf, Matthew; Williams, Ian D; Greenwood, Jason B

2015-06-21

Many organic molecules have strong absorption bands which can be accessed by ultraviolet short pulse lasers to produce efficient ionization. This resonant multiphoton ionization scheme has already been exploited as an ionization source in time-of-flight mass spectrometers used for environmental trace analysis. In the present work we quantify the ultimate potential of this technique by measuring absolute ion yields produced from the interaction of 267 nm femtosecond laser pulses with the organic molecules indole and toluene, and gases Xe, N2 and O2. Using multiphoton ionization cross sections extracted from these results, we show that the laser pulse parameters required for real-time detection of aromatic molecules at concentrations of one part per trillion in air and a limit of detection of a few attomoles are achievable with presently available commercial laser systems. The potential applications for the analysis of human breath, blood and tissue samples are discussed.

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

PubMed

Burton, Casey; Shi, Honglan; Ma, Yinfa

2013-11-19

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

IR Fine-Structure Line Signatures of Central Dust-Bounded Nebulae in Luminous Infrared Galaxies

NASA Technical Reports Server (NTRS)

Fischer, J.; Allen, R.; Dudley, C. C.; Satyapal, S.; Luhman, M.; Wolfire, M.; Smith, H. A.

2004-01-01

To date, the only far-infrared spectroscopic observations of ultraluminous infrared galaxies have been obtained with the European Space Agency s Infrared Space Observatory Long Wavelength Spectrometer. The spectra of these galaxies are characterized by molecular absorption lines and weak emission lines from photodissociation regions (PDRs), but no far-infrared (greater than 40 microns) lines from ionized regions have been detected. ESA s Herschel Space Observatory, slated for launch in 2007, will likely be able to detect these lines in samples of local and moderate redshift ultra luminous galaxies and to enable measurement of the ionization parameters, the slope of the ionizing continuum, and densities present in the ionized regions of these galaxies. The higher spatial resolution of proposed observatories discussed in this workshop will enable isolation of the central regions of local galaxies and detection of these lines in high-redshift galaxies for study of the evolution of galaxies. Here we discuss evidence for the e.ects of absorption by dust within ionized regions and present the spectroscopic signatures predicted by photoionization modeling of dust-bounded regions.

Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry.

PubMed

Setner, Bartosz; Rudowska, Magdalena; Klem, Ewelina; Cebrat, Marek; Szewczuk, Zbigniew

2014-10-01

Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1-azabicyclo[2.2.2]octane (ABCO) or 1,4-diazabicyclo[2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI-MS) and longer retention times on the reverse-phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision-induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a- and b-type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision-induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI-MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.

Instantaneous characterization of vegetable oils via TAG and FFA profiles by easy ambient sonic-spray ionization mass spectrometry.

PubMed

Simas, Rosineide C; Catharino, Rodrigo R; Cunha, Ildenize B S; Cabral, Elaine C; Barrera-Arellano, Daniel; Eberlin, Marcos N; Alberici, Rosana M

2010-04-01

A fast and reliable method is presented for the analysis of vegetable oils. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to efficiently desorb and ionize the main oil constituents from an inert surface under ambient conditions and to provide comprehensive triacylglyceride (TAG) and free fatty acid (FFA) profiles detected mainly as either [TAG + Na](+) or [FFA-H](-) ions. EASI(+/-)-MS analysis is simple, easily implemented, requires just a tiny droplet of the oil and is performed without any pre-separation or chemical manipulation. It also causes no fragmentation of TAG ions hence diacylglyceride (DAG) and monoacylglyceride (MAG) profiles and contents can also be measured. The EASI(+/-)-MS profiles of TAG and FFA permit authentication and quality control and can be used, for instance, to access levels of adulteration, acidity, oxidation or hydrolysis of vegetable oils in general.

Desorption atmospheric pressure photoionization.

PubMed

Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Arvola, Ville; Kotiaho, Tapio; Ketola, Raimo A; Franssila, Sami; Kauppila, Tiina J; Kostiainen, Risto

2007-10-15

An ambient ionization technique for mass spectrometry, desorption atmospheric pressure photoionization (DAPPI), is presented, and its application to the rapid analysis of compounds of various polarities on surfaces is demonstrated. The DAPPI technique relies on a heated nebulizer microchip delivering a heated jet of vaporized solvent, e.g., toluene, and a photoionization lamp emitting 10-eV photons. The solvent jet is directed toward sample spots on a surface, causing the desorption of analytes from the surface. The photons emitted by the lamp ionize the analytes, which are then directed into the mass spectrometer. The limits of detection obtained with DAPPI were in the range of 56-670 fmol. Also, the direct analysis of pharmaceuticals from a tablet surface was successfully demonstrated. A comparison of the performance of DAPPI with that of the popular desorption electrospray ionization method was done with four standard compounds. DAPPI was shown to be equally or more sensitive especially in the case of less polar analytes.

Ionization of Local Interstellar Gas Based on STIS and FUSE spectra of Nearby Stars

NASA Astrophysics Data System (ADS)

Redfield, Seth; Linsky, J. L.

2009-01-01

The ultraviolet contains many resonance line transitions that are sensitive to a range of ionization stages of ions present in the local interstellar medium (LISM). We couple observations of high resolution ultraviolet spectrographs, STIS and GHRS on the Hubble Space Telescope (HST) and the Far-Ultraviolet Spectroscopic Explorer (FUSE) in order to make a comprehensive survey of the ionization structure of the local interstellar medium. In particular, we focus on the sight line toward G191-B2B, a nearby (69 pc) white dwarf. We present interstellar detections of highly ionized elements (e.g., SiIII, CIII, CIV, etc) and compare them directly to neutral or singly ionized LISM detections (e.g., SiII, CII, etc). The extensive observations of G191-B2B provides an opportunity for a broad study of ionization stages of several elements, while a survey of several sight lines provides a comprehensive look at the ionization structure of the LISM. We acknowledge support for this project through NASA FUSE Grant NNX06AD33G.

Detection and characterization of a new metabolite of 17alpha-methyltestosterone.

PubMed

Pozo, Oscar J; Van Eenoo, Peter; Deventer, Koen; Lootens, Leen; Van Thuyne, Wim; Parr, Maria K; Schänzer, Wilhelm; Sancho, Juan V; Hernández, Felix; Meuleman, Philip; Leroux-Roels, Geert; Delbeke, Frans T

2009-11-01

The misuse of the anabolic steroid methyltestosterone is currently routinely monitored in doping control laboratories by gas chromatography-mass spectrometry (GC-MS) of two of its metabolites: 17alpha-methyl-5beta-androstane-3alpha,17beta-diol and 17alpha-methyl-5alpha-androstane-3alpha,17beta-diol. Because of the absence of any easy ionizable moiety, these metabolites are poorly detectable using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). In this study, the metabolism of methyltestosterone has been reinvestigated by the use of a precursor ion scan method in LC-ESI-MS/MS. Two metabolites have been detected using this method. Both compounds have been confirmed in postadministration urine samples of an urokinase plasminogen activator-severe combined immunodeficiency (uPA-SCID) mouse with humanized liver and were characterized by LC-MS/MS and GC-MS using both quadrupole and time of flight analyzers. From the detailed study of the fragmentation, these metabolites were proposed to be epimethyltestosterone and a dehydrogenated compound. Epimethyltestosterone has previously been described as a minor metabolite, whereas the occurrence of the oxidized metabolite has not been reported. Comparison with the synthesized reference revealed that the structure of the dehydrogenated metabolite is 6-ene-epimethyltestosterone. A selected reaction monitoring method including three transitions for each metabolite has been developed and applied to samples from an excretion study and to samples declared positive after GC-MS analysis. 6-Ene-epimethyltestosterone was found in all samples, showing its applicability in the detection of methyltestosterone misuse.

Semiconductor radiation detector

DOEpatents

Bell, Zane W.; Burger, Arnold

2010-03-30

A semiconductor detector for ionizing electromagnetic radiation, neutrons, and energetic charged particles. The detecting element is comprised of a compound having the composition I-III-VI.sub.2 or II-IV-V.sub.2 where the "I" component is from column 1A or 1B of the periodic table, the "II" component is from column 2B, the "III" component is from column 3A, the "IV" component is from column 4A, the "V" component is from column 5A, and the "VI" component is from column 6A. The detecting element detects ionizing radiation by generating a signal proportional to the energy deposited in the element, and detects neutrons by virtue of the ionizing radiation emitted by one or more of the constituent materials subsequent to capture. The detector may contain more than one neutron-sensitive component.

Development and validation of LC-MS/MS methods for the determination of mirabegron and its metabolites in human plasma and their application to a clinical pharmacokinetic study.

PubMed

Teijlingen, Raymond van; Meijer, John; Takusagawa, Shin; Gelderen, Marcel van; Beld, Cas van den; Usui, Takashi

2012-03-01

Mirabegron is being developed for the treatment of overactive bladder. To support the development of mirabegron, including pharmacokinetic studies, liquid chromatography/tandem mass spectrometry methods for mirabegron and eight metabolites (M5, M8, M11-M16) were developed and validated for heparinized human plasma containing sodium fluoride. Four separate bioanalytical methods were developed for the analysis of: (1) mirabegron; (2) M5 and M16; (3) M8; and (4) M11-M15. Either solid-phase extraction or liquid-liquid extraction was used to extract the analytes of interest from matrix constituents. For mirabegron, an Inertsil C₈-3 analytical column was used and detection was performed using a triple-quad mass spectrometer equipped with an atmospheric pressure chemical ionization interface. For the metabolite assays, chromatographic separation was performed through a Phenomenex Synergi Fusion-RP C₁₈ analytical column and detection was performed using a triple-quad mass spectrometer equipped with a Heated Electrospray Ionization interface. The validation results demonstrated that the developed liquid chromatography/tandem mass spectrometry methods were precise, accurate, and selective for the determination of mirabegron and its metabolites in human plasma. All methods were successfully applied in evaluating the pharmacokinetic parameters of mirabegron and metabolites in human plasma. Copyright © 2012 Elsevier B.V. All rights reserved.

The Pillars of Creation revisited with MUSE: gas kinematics and high-mass stellar feedback traced by optical spectroscopy

NASA Astrophysics Data System (ADS)

McLeod, A. F.; Dale, J. E.; Ginsburg, A.; Ercolano, B.; Gritschneder, M.; Ramsay, S.; Testi, L.

2015-06-01

Integral field unit (IFU) data of the iconic Pillars of Creation in M16 are presented. The ionization structure of the pillars was studied in great detail over almost the entire visible wavelength range, and maps of the relevant physical parameters, e.g. extinction, electron density, electron temperature, line-of-sight velocity of the ionized and neutral gas are shown. In agreement with previous authors, we find that the pillar tips are being ionized and photoevaporated by the massive members of the nearby cluster NGC 6611. They display a stratified ionization structure where the emission lines peak in a descending order according to their ionization energies. The IFU data allowed us to analyse the kinematics of the photoevaporative flow in terms of the stratified ionization structure, and we find that, in agreement with simulations, the photoevaporative flow is traced by a blueshift in the position-velocity profile. The gas kinematics and ionization structure have allowed us to produce a sketch of the 3D geometry of the Pillars, positioning the pillars with respect to the ionizing cluster stars. We use a novel method to detect a previously unknown bipolar outflow at the tip of the middle pillar and suggest that it has an embedded protostar as its driving source. Furthermore we identify a candidate outflow in the leftmost pillar. With the derived physical parameters and ionic abundances, we estimate a mass-loss rate due to the photoevaporative flow of 70 M⊙ Myr-1 which yields an expected lifetime of approximately 3 Myr.

[Determination of 27 industrial dyes in juice and wine using ultra performance liquid chromatography with electrospray ionization tandem quadrupole mass spectrometry].

PubMed

Zhao, Shan; Zhang, Jing; Yang, Yi; Shao, Bing

2010-04-01

A method for the determination of 27 industrial dyes in juice and wine has been developed using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/ MS). Acetonitrile was used as extraction solvent, and sodium chloride was added to salt out the analytes from the samples. Chromatographic separation was performed on a C18 column with the gradient elution and the mass spectrometric acquisition was carried out under the mode of multiple reaction monitoring (MRM). Twenty-four of the 27 dyes were detected under positive ionization mode using the mobile phase of acetonitrile and water containing 0.1% formic acid. The other 3 dyes were analyzed under negative ionization mode with the mobile phase of acetonitrile and water. As a result, the average recoveries of 27 dyes spiked in juice ranged from 57.0% to 117.7% with the relative standard deviations (RSDs) of 2.4%-17.7%, and the average recoveries of 27 dyes spiked in wine ranged from 40.8% to 109.4% with the RSDs of 1.6%-17.9%. The limits of quantification (LOQs) of 27 dyes spiked in juice were in the range of 0.1-50 microg/kg, and 0.2-50 microg/kg for those spiked in wine. This method can be applied to rapid detection of illegally added dyes in soft drinks due to its simplicity and high sensitivity.

Schinus terebinthifolius scale-up countercurrent chromatography (Part I): High performance countercurrent chromatography fractionation of triterpene acids with off-line detection using atmospheric pressure chemical ionization mass spectrometry.

PubMed

Vieira, Mariana Neves; Costa, Fernanda das Neves; Leitão, Gilda Guimarães; Garrard, Ian; Hewitson, Peter; Ignatova, Svetlana; Winterhalter, Peter; Jerz, Gerold

2015-04-10

'Countercurrent chromatography' (CCC) is an ideal technique for the recovery, purification and isolation of bioactive natural products, due to the liquid nature of the stationary phase, process predictability and the possibility of scale-up from analytical to preparative scale. In this work, a method developed for the fractionation of Schinus terebinthifolius Raddi berries dichloromethane extract was thoroughly optimized to achieve maximal throughput with minimal solvent and time consumption per gram of processed crude extract, using analytical, semi-preparative and preparative 'high performance countercurrent chromatography' (HPCCC) instruments. The method using the biphasic solvent system composed of n-heptane-ethyl acetate-methanol-water (6:1:6:1, v/v/v/v) was volumetrically scaled up to increase sample throughput up to 120 times, while maintaining separation efficiency and time. As a fast and specific detection alternative, the fractions collected from the CCC-separations were injected to an 'atmospheric pressure chemical ionization mass-spectrometer' (APCI-MS/MS) and reconstituted molecular weight MS-chromatograms of the APCI-ionizable compounds from S. terebinthifolius were obtained. This procedure led to the direct isolation of tirucallane type triterpenes such as masticadienonic and 3β-masticadienolic acids. Also oleanonic and moronic acids have been identified for the first time in the species. In summary, this approach can be used for other CCC scale-up processes, enabling MS-target-guided isolation procedures. Copyright © 2015 Elsevier B.V. All rights reserved.

Enhancement of concentration range of chromatographically detectable components with array detector mass spectrometry

DOEpatents

Enke, Christie

2013-02-19

Methods and instruments for high dynamic range analysis of sample components are described. A sample is subjected to time-dependent separation, ionized, and the ions dispersed with a constant integration time across an array of detectors according to the ions m/z values. Each of the detectors in the array has a dynamically adjustable gain or a logarithmic response function, producing an instrument capable of detecting a ratio of responses or 4 or more orders of magnitude.

Analysis of anabolic steroids in urine by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry with chlorobenzene as dopant.

PubMed

Hintikka, Laura; Haapala, Markus; Kuuranne, Tiia; Leinonen, Antti; Kostiainen, Risto

2013-10-18

A gas chromatography-microchip atmospheric pressure photoionization-tandem mass spectrometry (GC-μAPPI-MS/MS) method was developed for the analysis of anabolic androgenic steroids in urine as their trimethylsilyl derivatives. The method utilizes a heated nebulizer microchip in atmospheric pressure photoionization mode (μAPPI) with chlorobenzene as dopant, which provides high ionization efficiency by producing abundant radical cations with minimal fragmentation. The performance of GC-μAPPI-MS/MS was evaluated with respect to repeatability, linearity, linear range, and limit of detection (LOD). The results confirmed the potential of the method for doping control analysis of anabolic steroids. Repeatability (RSD<10%), linearity (R(2)≥0.996) and sensitivity (LODs 0.05-0.1ng/mL) were acceptable. Quantitative performance of the method was tested and compared with that of conventional GC-electron ionization-MS, and the results were in good agreement. Copyright © 2013 Elsevier B.V. All rights reserved.

Laser Desorption 7.87 eV Postionization Mass Spectrometry of Antibiotics in Staphylococcus epidermidis Bacterial Biofilms

PubMed Central

Gasper, Gerald L.; Carlson, Ross; Akhmetov, Artem; Moore, Jerry F.; Hanley, Luke

2010-01-01

This paper describes the development of laser desorption 7.87 eV vacuum ultraviolet postionization mass spectrometry (LDPI-MS) to detect antibiotics within intact bacterial colony biofilms. As >99% of the molecules ejected by laser desorption are neutrals, vacuum ultraviolet (VUV) photoionization of these neutrals can provide significantly increased signal compared to detection of directly emitted ions. Postionization with VUV radiation from the molecular fluorine laser single photon ionizes laser desorbed neutrals with ionization potentials below the 7.87 eV photon energy. Antibiotics with structures indicative of sub-7.87 eV ionization potentials were examined for their ability to be detected by 7.87 eV LDPI-MS. Tetracycline, sulfadiazine, and novobiocin were successfully detected neat as dried films physisorbed on porous silicon oxide substrates. Tetracycline and sulfadiazine were then detected within intact Staphylococcus epidermidis colony biofilms, the former with LOD in the micromolar concentration range. PMID:18704905

Is electrospray emission really due to columbic forces?

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

Aliotta, Francesco, E-mail: aliotta@ipcf.cnr.it; Ponterio, Rosina C.; Salvato, Gabriele

2014-09-15

Electrospray ionization (ESI) is a widely adopted soft ionization method for mass spectroscopy (MS). In spite of the undeniable success of the technique, its mechanisms are difficult to be analytically modelled because the process is characterized by non-equilibrium conditions. The common belief is that the formation of gas-phase ions takes place at the apex of the Taylor cone via electrophoretic charging. The charge balance implies that a conversion of electrons to ions should occur at the metal-liquid interface of the injector needle. We have detected that the above description is based on unproved assumptions which are not consistent with themore » correct evaluation of the problem. The comparison between experiments performed under the usual geometry and observations obtained under symmetric field configurations suggests that the emitted droplets cannot be significantly charged or, at least, that any possible ionization mechanism is so poorly efficient to ensure that columbic forces cannot play a major role in jet formation, even in cases where the liquid consists of a solution of ionic species. Further work is required to clearly understand how ionization occurs in ESI-MS.« less

Application of the desulfurization of phenothiazines for a sensitive detection method by high-performance liquid chromatography.

PubMed

Shimada, K; Mino, T; Nakajima, M; Wakabayashi, H; Yamato, S

1994-11-04

A simple and sensitive high-performance liquid chromatographic (HPLC) method for the determination of phenothiazine (PHE) is described. PHE is converted to diphenylamine (DIP) by desulfurization with Raney nickel catalyst. DIP is highly sensitive to electrochemical detection. The calibration graph for PHE quantification after desulfurization was linear between 0.1 and 2.0 ng per injection. The detection limit (signal-to-noise ratio = 3) of PHE after desulfurization was 10 pg, which is twenty times higher than that of the parent compound PHE. The proposed desulfurization technique was applied to other PHE-related compounds. The structural confirmation of the desulfurized product of PHE was carried out by LC-MS using atmospheric pressure chemical ionization.

Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

2017-04-01

Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (<200 ppt). We report on the effect of atmospheric water vapor and oxygen concentrations on instrument response for isoprene and a wide range of monoterpenes and sesquiterpenes. To gain mechanistic insight into the ion-molecule reactions and the role of water vapor and oxygen, we compare our measured sensitivities with a computational analysis of the charge distribution between the analyte, reagent ion and water molecules in the gas phase. These parameters provide insight on the ionization mechanism and provide parameters for quantification of organic molecules measured during field campaigns. References Kim, M. J., M. C. Zoerb, N. R. Campbell, K. J. Zimmermann, B. W. Blomquist, B. J. Huebert, and T. H. Bertram (2016), Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

Comparison of PCR/electron spray ionization-time-of-flight-mass spectrometry versus traditional clinical microbiology for active surveillance of organisms contaminating high-use surfaces in a burn intensive care unit, an orthopedic ward and healthcare workers.

PubMed

Yun, Heather C; Kreft, Rachael E; Castillo, Mayra A; Ehrlich, Garth D; Guymon, Charles H; Crouch, Helen K; Chung, Kevin K; Wenke, Joseph C; Hsu, Joseph R; Spirk, Tracy L; Costerton, J William; Mende, Katrin; Murray, Clinton K

2012-10-10

Understanding nosocomial pathogen transmission is restricted by culture limitations. Novel platforms, such as PCR-based electron spray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS), may be useful as investigational tools. Traditional clinical microbiology (TCM) and PCR/ESI-TOF-MS were used to recover and detect microorganisms from the hands and personal protective equipment of 10 burn intensive care unit (ICU) healthcare workers providing clinical care at a tertiary care military referral hospital. High-use environmental surfaces were assessed in 9 burn ICU and 10 orthopedic patient rooms. Clinical cultures during the study period were reviewed for pathogen comparison with investigational molecular diagnostic methods. From 158 samples, 142 organisms were identified by TCM and 718 by PCR/ESI-TOF-MS. The molecular diagnostic method detected more organisms (4.5 ± 2.1 vs. 0.9 ± 0.8, p < 0.01) from 99% vs. 67% of samples (p < 0.01). TCM detected S. aureus in 13 samples vs. 21 by PCR/ESI-TOF-MS. Gram-negative organisms were less commonly identified than gram-positive by both methods; especially by TCM. Among all detected bacterial species, similar percentages were typical nosocomial pathogens (18-19%) for TCM vs. PCR/ESI-TOF-MS. PCR/ESI-TOF-MS also detected mecA in 112 samples, vanA in 13, and KPC-3 in 2. MecA was associated (p < 0.01) with codetection of coagulase negative staphylococci but not S. aureus. No vanA was codetected with enterococci; one KPC-3 was detected without Klebsiella spp. In this pilot study, PCR/ESI-TOF-MS detected more organisms, especially gram-negatives, compared to TCM, but the current assay format is limited by the number of antibiotic resistance determinants it covers. Further large-scale assessments of PCR/ESI-TOF-MS for hospital surveillance are warranted.

Detection of Amyloid Beta (Aβ) Oligomeric Composition Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry (MALDI MS)

NASA Astrophysics Data System (ADS)

Wang, Jasmine S.-H.; Whitehead, Shawn N.; Yeung, Ken K.-C.

2018-02-01

The use of MALDI MS as a fast and direct method to detect the Aβ oligomers of different masses is examined in this paper. Experimental results suggest that Aβ oligomers are ionized and detected as singly charged ions, and thus, the resulting mass spectrum directly reports the oligomer size distribution. Validation experiments were performed to verify the MS data against artifacts. Mass spectra collected from modified Aβ peptides with different propensities for aggregation were compared. Generally, the relative intensities of multimers were higher from samples where oligomerization was expected to be more favorable, and vice versa. MALDI MS was also able to detect the differences in oligomeric composition before and after the incubation/oligomerization step. Such differences in sample composition were also independently confirmed with an in vitro Aβ toxicity study on primary rat cortical neurons. An additional validation was accomplished through removal of oligomers from the sample using molecular weight cutoff filters; the resulting MS data correctly reflected the removal at the expected cutoff points. The results collectively validated the ability of MALDI MS to assess the monomeric/multimeric composition of Aβ samples. [Figure not available: see fulltext.

System level latchup mitigation for single event and transient radiation effects on electronics

DOEpatents

Kimbrough, J.R.; Colella, N.J.

1997-09-30

A ``blink`` technique, analogous to a person blinking at a flash of bright light, is provided for mitigating the effects of single event current latchup and prompt pulse destructive radiation on a micro-electronic circuit. The system includes event detection circuitry, power dump logic circuitry, and energy limiting measures with autonomous recovery. The event detection circuitry includes ionizing radiation pulse detection means for detecting a pulse of ionizing radiation and for providing at an output terminal thereof a detection signal indicative of the detection of a pulse of ionizing radiation. The current sensing circuitry is coupled to the power bus for determining an occurrence of excess current through the power bus caused by ionizing radiation or by ion-induced destructive latchup of a semiconductor device. The power dump circuitry includes power dump logic circuitry having a first input terminal connected to the output terminal of the ionizing radiation pulse detection circuitry and having a second input terminal connected to the output terminal of the current sensing circuitry. The power dump logic circuitry provides an output signal to the input terminal of the circuitry for opening the power bus and the circuitry for shorting the power bus to a ground potential to remove power from the power bus. The energy limiting circuitry with autonomous recovery includes circuitry for opening the power bus and circuitry for shorting the power bus to a ground potential. The circuitry for opening the power bus and circuitry for shorting the power bus to a ground potential includes a series FET and a shunt FET. The invention provides for self-contained sensing for latchup, first removal of power to protect latched components, and autonomous recovery to enable transparent operation of other system elements. 18 figs.

System level latchup mitigation for single event and transient radiation effects on electronics

DOEpatents

Kimbrough, Joseph Robert; Colella, Nicholas John

1997-01-01

A "blink" technique, analogous to a person blinking at a flash of bright light, is provided for mitigating the effects of single event current latchup and prompt pulse destructive radiation on a micro-electronic circuit. The system includes event detection circuitry, power dump logic circuitry, and energy limiting measures with autonomous recovery. The event detection circuitry includes ionizing radiation pulse detection means for detecting a pulse of ionizing radiation and for providing at an output terminal thereof a detection signal indicative of the detection of a pulse of ionizing radiation. The current sensing circuitry is coupled to the power bus for determining an occurrence of excess current through the power bus caused by ionizing radiation or by ion-induced destructive latchup of a semiconductor device. The power dump circuitry includes power dump logic circuitry having a first input terminal connected to the output terminal of the ionizing radiation pulse detection circuitry and having a second input terminal connected to the output terminal of the current sensing circuitry. The power dump logic circuitry provides an output signal to the input terminal of the circuitry for opening the power bus and the circuitry for shorting the power bus to a ground potential to remove power from the power bus. The energy limiting circuitry with autonomous recovery includes circuitry for opening the power bus and circuitry for shorting the power bus to a ground potential. The circuitry for opening the power bus and circuitry for shorting the power bus to a ground potential includes a series FET and a shunt FET. The invention provides for self-contained sensing for latchup, first removal of power to protect latched components, and autonomous recovery to enable transparent operation of other system elements.

Donald Glaser, the Bubble Chamber, and Elementary Particles

Science.gov Websites

Effects of Ionizing Radiation on the Formation of Bubbles in Liquids Physical Review, Vol. 87, Issue 4 , 665, August 15, 1952 Characteristics of Bubble Chambers Physical Review, Vol. 97, Issue 2, 474-479 Chambers Physical Review, Vol. 102, Issue 6, 1653-1658, June 15, 1956 Methods of Particle Detection for

Detecting breast microcalcifications using super-resolution ultrasound imaging: a clinical study

NASA Astrophysics Data System (ADS)

Huang, Lianjie; Labyed, Yassin; Hanson, Kenneth; Sandoval, Daniel; Pohl, Jennifer; Williamson, Michael

2013-03-01

Imaging breast microcalcifications is crucial for early detection and diagnosis of breast cancer. It is challenging for current clinical ultrasound to image breast microcalcifications. However, new imaging techniques using data acquired with a synthetic-aperture ultrasound system have the potential to significantly improve ultrasound imaging. We recently developed a super-resolution ultrasound imaging method termed the phase-coherent multiple-signal classification (PC-MUSIC). This signal subspace method accounts for the phase response of transducer elements to improve image resolution. In this paper, we investigate the clinical feasibility of our super-resolution ultrasound imaging method for detecting breast microcalcifications. We use our custom-built, real-time synthetic-aperture ultrasound system to acquire breast ultrasound data for 40 patients whose mammograms show the presence of breast microcalcifications. We apply our super-resolution ultrasound imaging method to the patient data, and produce clear images of breast calcifications. Our super-resolution ultrasound PC-MUSIC imaging with synthetic-aperture ultrasound data can provide a new imaging modality for detecting breast microcalcifications in clinic without using ionizing radiation.

Biosynthesis of staphylococcal enterotoxin A by genetic engineering technology and determination of staphylococcal enterotoxin A in water by HPLC-ESI-TOF.

PubMed

Li, Hong-Na; Yuan, Fei; Luo, Yun-Jing; Wang, Jian-Feng; Zhang, Chuan-Bin; Zhou, Wei-E; Ren, Zhi-Qin; Wu, Wen-Jie; Zhang, Feng

2017-08-01

Staphylococcal enterotoxin A (SEA) was the major virulence factor of Staphylococcus aureus and a biomarker of S. aureus. To establish a fast, low cost, high accuracy, reliable, and simple method for detecting S. aureus, SEA was analyzed by HPLC-ESI-TOF. SEA was not yet commercially available in universal, so SEA was prepared before it was analyzed by HPLC-ESI-TOF. The result showed that high purified SEA was successfully prepared and SEA has normal distribution in mass spectra. A large amount of recombinant SEA (rSEA) was obtained by engineering technology and was purified by Ni affinity chromatography column, and the expression and purity of rSEA and SEA were analyzed by SDS-PAGE. The factors effected on ionization of SEA were studied, and the qualitative analysis of SEA by HPLC-ESI-TOF. The result showed that large amount of SEs expressed within a short time at 28 °C or thereabouts, and there was no impurity bands in electrophorogram after rSEA was purified by Ni affinity chromatography column. In addition, the SEA which had homologous AA sequence with wild SEA was made by rSEA. The retention of SEA in column and ionization of SEA in ESI-TOF were studied for qualitative analysis of S. aureus. The result showed that the content of formic acid in mobile phase was an important factor for ionization of SEs in ESI-TOF. And the result provided theoretical foundation for qualitative detection of S. aureus. [SEs + nH + + mNH 4 + ] n+m+ was shown on ESI-TOF spectra when SEA was detected by ESI-TOF in positive ion mode, and the numerical value of n+m was less than or equal to the number of basic amino acids in SEs. This method was applied to determine SEA in water samples preliminarily, and the detection limit of SEA in spiked water sample was 3 mg/kg. The limit of detection of 3 mg/kg was low sensitivity for low molecular weight matters, but it was high sensitivity for SEA which had a high molecular weight of 27 kDa. Of SEA, 3 mg/kg was equivalent to 10 -4  mmol/kg of SEA. This study can provide evidence for establishing method to determine SEA in real samples.

ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT, EXPLOSIVES DETECTION TECHNOLOGY, SRI INSTRUMENTS, MODEL 8610C, GAS CHROMATOGRAPH/THERMIONIC IONIZATION DETECTION

EPA Science Inventory

The SRI Model 86 1 OC gas chromatograph (GC) is a transportable instrument that can provide on-site analysis of soils for explosives. Coupling this transportable gas chromatograph with a thermionic ionization detector (TID) allows for the determination of explosives in soil matri...

The Beta Pictoris circumstellar disk. XV - Highly ionized species near Beta Pictoris

NASA Technical Reports Server (NTRS)

Deleuil, M.; Gry, C.; Lagrange-Henri, A.-M.; Vidal-Madjar, A.; Beust, H.; Ferlet, R.; Moos, H. W.; Livengood, T. A.; Ziskin, D.; Feldman, P. D.

1993-01-01

Temporal variations of the Fe II, Mg II, and Al III circumstellar lines towards Beta Pictoris have been detected and monitored since 1985. However, the unusual presence of Al III ions is still puzzling, since the UV stellar flux from an A5V star such as Beta Pic is insufficient to produce such an ion. In order to better define the origin of such a phenomenon, new observations have been carried out to detect faint signatures of other highly ionized species in the short UV wavelength range, where the stellar continuum flux is low. These observations reveal variations not only near the C IV doublet lines, but also in C I and Al II lines, two weakly ionized species, not clearly detectable until now. In the framework of an infalling body scenario, highly ionized species would be created in the tail, far from the comet head, by collisions with ambient gas surrounding the star, or a weak stellar wind. Spectral changes have also been detected near a CO molecular band location, which, if confirmed, would provide the first molecular signature around Beta Pictoris.

Ultra trace determination of 31 pesticides in water samples by direct injection-rapid resolution liquid chromatography-electrospray tandem mass spectrometry.

PubMed

Díaz, Laura; Llorca-Pórcel, Julio; Valor, Ignacio

2008-08-22

A liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based method for the detection of pesticides in tap and treated wastewater was developed and validated according to the ISO/IEC 17025:1999. Key features of this method include direct injection of 100 microL of sample, an 11 min separation by means of a rapid resolution liquid chromatography system with a 4.6 mm x 50 mm, 1.8 microm particle size reverse phase column and detection by electrospray ionization (ESI) MS-MS. The limits of detection were below 15 ng L(-1) and correlation coefficients for the calibration curves in the range of 30-2000 ng L(-1) were higher than 0.99. Precision was always below 20% and accuracy was confirmed by external evaluation. The main advantages of this method are direct injection of sample without preparative procedures and low limits of detection that fulfill the requirements established by the current European regulations governing pesticide detection.

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

PubMed

Santa, Tomofumi

2011-01-01

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

Amorphous silicon ionizing particle detectors

DOEpatents

Street, Robert A.; Mendez, Victor P.; Kaplan, Selig N.

1988-01-01

Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation.

Approaches for the Analysis of Chlorinated Lipids

PubMed Central

Wang, Wen-yi; Albert, Carolyn J.; Ford, David A.

2013-01-01

Leukocytes are key cellular mediators of human diseases through their role in inflammation. Identifying unique molecules produced by leukocytes may provide new biomarkers and mechanistic insights into the role of leukocytes in disease. Chlorinated lipids are generated as a result of myeloperoxidase-containing leukocyte-derived hypochlorous acid targeting the vinyl ether bond of plasmalogens. The initial product of this reaction is α-chlorofatty aldehyde. α -Chlorofatty aldehyde is both oxidized to α-chlorofatty acid and reduced to α-chlorofatty alcohol by cellular metabolism. This review focuses on the separation techniques and quantitative analysis for these chlorinated lipids. For α-chlorofatty acid the negative charge of carboxylic acids is exploited to detect the chlorinated lipid species of these acids by electrospray ionization mass spectrometry in the negative ion mode. In contrast, α-chlorofatty aldehyde and α-chlorofatty alcohol are converted to pentafluorobenzyl oxime and pentafluorobenzoyl ester derivatives, which are detected by negative ion-chemical ionization mass spectrometry. These two detection methods coupled with the use of stable isotope internal standards and either liquid chromatography or gas chromatography provide highly sensitive analytical approaches to measure these novel lipids. PMID:24056259

Negative electrospray ionization on porous supporting tips for mass spectrometric analysis: electrostatic charging effect on detection sensitivity and its application to explosive detection.

PubMed

Wong, Melody Yee-Man; Man, Sin-Heng; Che, Chi-Ming; Lau, Kai-Chung; Ng, Kwan-Ming

2014-03-21

The simplicity and easy manipulation of a porous substrate-based ESI-MS technique have been widely applied to the direct analysis of different types of samples in positive ion mode. However, the study and application of this technique in negative ion mode are sparse. A key challenge could be due to the ease of electrical discharge on supporting tips upon the application of negative voltage. The aim of this study is to investigate the effect of supporting materials, including polyester, polyethylene and wood, on the detection sensitivity of a porous substrate-based negative ESI-MS technique. By using nitrobenzene derivatives and nitrophenol derivatives as the target analytes, it was found that the hydrophobic materials (i.e., polyethylene and polyester) with a higher tendency to accumulate negative charge could enhance the detection sensitivity towards nitrobenzene derivatives via electron-capture ionization; whereas, compounds with electron affinities lower than the cut-off value (1.13 eV) were not detected. Nitrophenol derivatives with pKa smaller than 9.0 could be detected in the form of deprotonated ions; whereas polar materials (i.e., wood), which might undergo competitive deprotonation with the analytes, could suppress the detection sensitivity. With the investigation of the material effects on the detection sensitivity, the porous substrate-based negative ESI-MS method was developed and applied to the direct detection of two commonly encountered explosives in complex samples.

Improving quantitative gas chromatography-electron ionization mass spectrometry results using a modified ion source: demonstration for a pharmaceutical application.

PubMed

D'Autry, Ward; Wolfs, Kris; Hoogmartens, Jos; Adams, Erwin; Van Schepdael, Ann

2011-07-01

Gas chromatography-mass spectrometry is a well established analytical technique. However, mass spectrometers with electron ionization sources may suffer from signal drifts, hereby negatively influencing quantitative performance. To demonstrate this phenomenon for a real application, a static headspace-gas chromatography method in combination with electron ionization-quadrupole mass spectrometry was optimized for the determination of residual dichloromethane in coronary stent coatings. Validating the method, the quantitative performance of an original stainless steel ion source was compared to that of a modified ion source. Ion source modification included the application of a gold coating on the repeller and exit plate. Several validation aspects such as limit of detection, limit of quantification, linearity and precision were evaluated using both ion sources. It was found that, as expected, the stainless steel ion source suffered from signal drift. As a consequence, non-linearity and high RSD values for repeated analyses were obtained. An additional experiment was performed to check whether an internal standard compound would lead to better results. It was found that the signal drift patterns of the analyte and internal standard were different, consequently leading to high RSD values for the response factor. With the modified ion source however, a more stable signal was observed resulting in acceptable linearity and precision. Moreover, it was also found that sensitivity improved compared to the stainless steel ion source. Finally, the optimized method with the modified ion source was applied to determine residual dichloromethane in the coating of coronary stents. The solvent was detected but found to be below the limit of quantification. Copyright © 2011 Elsevier B.V. All rights reserved.

Coupling frontal elution paper chromatography with desorption corona beam ionization mass spectrometry for rapid analysis of chlorphenamine in herbal medicines and dietary supplements.

PubMed

Huang, Yun-Qing; You, Jing-Qing; Zhang, Junsheng; Sun, Wenjian; Ding, Li; Feng, Yu-Qi

2011-10-14

We developed a convenient method by coupling frontal elution paper chromatography with desorption corona beam ionization mass spectrometry (DCBI-MS) for rapid determination of chlorphenamine added in herbal medicines or dietary supplements. In this method, the ethanol extract of the herbal products was spotted directly onto an isosceles triangular filter paper sheet, and then the paper sheet was developed under strong elution condition with the sample zone migrating at the solvent front. The analyte was finally condensed at the V-shaped tip which could then be placed under the visible plasma beam of DCBI for ionization. The overall procedure took less than 5 min. The frontal elution paper chromatography on a triangular plate used in this work improved the signal intensity of chlorphenamine by 30-fold due to the analyte condensing at the tip and the reduction of the background suppression. Furthermore, the paper sheet also functioned as a filter in the analysis of solid or powder samples, which can increase the analytical throughput by omitting the step of centrifugation. The proposed method in current study was successfully applied in the determination of chlorphenamine in herbal medicines. Chlorphenamine was detected in four of the twelve types of herbal medicines examined in this study. The limit of detection was 200 ng/mL (2.0 ng absolute) in full-scan positive-ion mode and the linear range was from 5.0 μg/mL to 50 μg/mL with satisfactory linear coefficient (R(2) (the square of the correlation coefficient)=0.895). Good reproducibility was achieved with relative standard deviations (RSDs) less than 15.0% and the recoveries of chlorphenamine ranged from 84.3 to 90.6%. Copyright © 2011 Elsevier B.V. All rights reserved.

Development and Validation of a Method for Alcohol Analysis in Brain Tissue by Headspace Gas Chromatography with Flame Ionization Detector

PubMed Central

Chun, Hao-Jung; Poklis, Justin L.; Poklis, Alphonse; Wolf, Carl E.

2016-01-01

Ethanol is the most widely used and abused drug. While blood is the preferred specimen for analysis, tissue specimens such as brain serve as alternative specimens for alcohol analysis in post-mortem cases where blood is unavailable or contaminated. A method was developed using headspace gas chromatography with flame ionization detection (HS-GC-FID) for the detection and quantification of ethanol, acetone, isopropanol, methanol and n-propanol in brain tissue specimens. Unfixed volatile-free brain tissue specimens were obtained from the Department of Pathology at Virginia Commonwealth University. Calibrators and controls were prepared from 4-fold diluted homogenates of these brain tissue specimens, and were analyzed using t-butanol as the internal standard. The chromatographic separation was performed with a Restek BAC2 column. A linear calibration was generated for all analytes (mean r2 > 0.9992) with the limits of detection and quantification of 100–110 mg/kg. Matrix effect from the brain tissue was determined by comparing the slopes of matrix prepared calibration curves with those of aqueous calibration curves; no significant differences were observed for ethanol, acetone, isopropanol, methanol and n-propanol. The bias and the CVs for all volatile controls were ≤10%. The method was also evaluated for carryover, selectivity, interferences, bench-top stability and freeze-thaw stability. The HS-GC-FID method was determined to be reliable and robust for the analysis of ethanol, acetone, isopropanol, methanol and n-propanol concentrations in brain tissue, effectively expanding the specimen options for post-mortem alcohol analysis. PMID:27488829

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

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

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

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

Observations of extended and counterrotating disks of ionized gas in S0 galaxies

NASA Technical Reports Server (NTRS)

Dettmar, Ralf-Juergen; Jullien-Dettmar, Marlies; Barteldrees, Andreas

1990-01-01

While many E/S0 galaxies have been found to show emission line spectra in their nuclear regions, the question of the presence and nature of extended disks of ionized gas in these galaxies has been addressed only in recent years. Typically the ionized gas is detected in the inner region on a scale of approx. 1 kpc (e.g., Phillips et al. 1986, Caldwell 1984). Here researchers present evidence that the disks of ionized gas of at least some S0 galaxies are much more extended than previously believed. In addition, with the detection of the counterrotation of gas and stars in NGC 7007 they strengthen the basis for arguments that the source of gas in S0 galaxies is external

Amorphous silicon ionizing particle detectors

DOEpatents

Street, R.A.; Mendez, V.P.; Kaplan, S.N.

1988-11-15

Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation. 15 figs.

Circular dichroism in photo-single-ionization of unoriented atoms.

PubMed

Feagin, James M

2002-01-28

We predict circular dichroism in photo-single-ionization angular distributions from spherically symmetric atomic states if the ionized electron is detected using two-slit interferometry. We demonstrate that the resulting electron interference pattern captures phase information on quadrupole corrections to the photoionization amplitude lost in conventional angular distributions.

Radiation sensitive devices and systems for detection of radioactive materials and related methods

DOEpatents

Kotter, Dale K

2014-12-02

Radiation sensitive devices include a substrate comprising a radiation sensitive material and a plurality of resonance elements coupled to the substrate. Each resonance element is configured to resonate responsive to non-ionizing incident radiation. Systems for detecting radiation from a special nuclear material include a radiation sensitive device and a sensor located remotely from the radiation sensitive device and configured to measure an output signal from the radiation sensitive device. In such systems, the radiation sensitive device includes a radiation sensitive material and a plurality of resonance elements positioned on the radiation sensitive material. Methods for detecting a presence of a special nuclear material include positioning a radiation sensitive device in a location where special nuclear materials are to be detected and remotely interrogating the radiation sensitive device with a sensor.

On-Site Detection as a Countermeasure to Chemical Warfare/Terrorism.

PubMed

Seto, Y

2014-01-01

On-site monitoring and detection are necessary in the crisis and consequence management of wars and terrorism involving chemical warfare agents (CWAs) such as sarin. The analytical performance required for on-site detection is mainly determined by the fatal vapor concentration and volatility of the CWAs involved. The analytical performance for presently available on-site technologies and commercially available on-site equipment for detecting CWAs interpreted and compared in this review include: classical manual methods, photometric methods, ion mobile spectrometry, vibrational spectrometry, gas chromatography, mass spectrometry, sensors, and other methods. Some of the data evaluated were obtained from our experiments using authentic CWAs. We concluded that (a) no technologies perfectly fulfill all of the on-site detection requirements and (b) adequate on-site detection requires (i) a combination of the monitoring-tape method and ion-mobility spectrometry for point detection and (ii) a combination of the monitoring-tape method, atmospheric pressure chemical ionization mass spectrometry with counterflow introduction, and gas chromatography with a trap and special detectors for continuous monitoring. The basic properties of CWAs, the concept of on-site detection, and the sarin gas attacks in Japan as well as the forensic investigations thereof, are also explicated in this article. Copyright © 2014 Central Police University.

Real-time breath analysis with active capillary plasma ionization-ambient mass spectrometry.

PubMed

Bregy, Lukas; Sinues, Pablo Martinez-Lozano; Nudnova, Maryia M; Zenobi, Renato

2014-06-01

On-line analysis of exhaled human breath is a growing area in analytical science, for applications such as fast and non-invasive medical diagnosis and monitoring. In this work, we present a novel approach based on ambient ionization of compounds in breath and subsequent real-time mass spectrometric analysis. We introduce a plasma ionization source for this purpose, which has no need for additional gases, is very small, and is easily interfaced with virtually any commercial atmospheric pressure ionization mass spectrometer (API-MS) without major modifications. If an API-MS instrument exists in a laboratory, the cost to implement this technology is only around [Formula: see text]500, far less than the investment for a specialized mass spectrometric system designed for volatile organic compounds (VOCs) analysis. In this proof-of-principle study we were able to measure mass spectra of exhaled human breath and found these to be comparable to spectra obtained with other electrospray-based methods. We detected over 100 VOCs, including relevant metabolites like fatty acids, with molecular weights extending up to 340 Da. In addition, we were able to monitor the time-dependent evolution of the peaks and show the enhancement of the metabolism after a meal. We conclude that this approach may complement current methods to analyze breath or other types of vapors, offering an affordable option to upgrade any pre-existing API-MS to a real-time breath analyzer.

Identification of Sialic Acid Linkages on Intact Glycopeptides via Differential Chemical Modification Using IntactGIG-HILIC

NASA Astrophysics Data System (ADS)

Yang, Shuang; Wu, Wells W.; Shen, Rong-Fong; Bern, Marshall; Cipollo, John

2018-04-01

Mass spectrometric analysis of intact glycopeptides can reveal detailed information about glycosite, glycan structural features, and their heterogeneity. Sialyl glycopeptides can be positively, negatively, or neutrally charged depending on pH of their buffer solution and ionization conditions. To detect sialoglycopeptides, a negative-ion mode mass spectrometry may be applied with a minimal loss of sialic acids, although the positively charged or neutral glycopeptides may be excluded. Alternatively, the sialyl glycopeptides can be identified using positive-ion mode analysis by doping a high concentration of sodium salts to the analytes. Although manipulation of unmodified sialoglycopeptides can be useful for analysis of samples, less than optimal ionization, facile loss of sialyl and unfavorable ionization of accompanying non-sialyl peptides make such strategies suboptimal. Currently available chemical derivatization methods, while stabilizing for sialic acid, mask sialic acid linkage configuration. Here, we report the development of a novel approach to neutralize sialic acids via sequentially chemical modification that also reveals their linkage configuration, often an important determinant in biological function. This method utilizes several components to facilitate glycopeptide identification. These include the following: solid phase derivatization, enhanced ionization of sialoglycopeptides, differentiation of sialic acid linkage, and enrichment of the modified glycopeptides by hydrophilic interaction liquid chromatography. This technology can be used as a tool for quantitative analysis of protein sialylation in diseases with determination of sialic acid linkage configuration. [Figure not available: see fulltext.

Salivary hormone measurement using LC/MS/MS: specific and patient-friendly tool for assessment of endocrine function.

PubMed

Higashi, Tatsuya

2012-01-01

Saliva has recently been attracting attention as a patient-friendly available bio-fluid and an alternative to serum/plasma for hormone tests. LC coupled with atmospheric pressure ionization-MS/MS, especially electrospray ionization (ESI)-MS/MS, has been recently valued as a highly specific method in the analysis of salivary hormones. In this article, LC/ESI-MS/MS assays for salivary hormones are overviewed according to the papers that have been published during the last 5 years. Practical derivatization to enhance the detectabilities of hormones in ESI-MS/MS is also discussed, because a major disadvantage of using saliva is low hormone concentrations.

Space charge dosimeters for extremely low power measurements of radiation in shipping containers

DOEpatents

Britton, Jr., Charles L.; Buckner, Mark A [Oak Ridge, TN; Hanson, Gregory R [Clinton, TN; Bryan, William L [Knoxville, TN

2011-05-03

Methods and apparatus are described for space charge dosimeters for extremely low power measurements of radiation in shipping containers. A method includes insitu polling a suite of passive integrating ionizing radiation sensors including reading-out dosimetric data from a first passive integrating ionizing radiation sensor and a second passive integrating ionizing radiation sensor, where the first passive integrating ionizing radiation sensor and the second passive integrating ionizing radiation sensor remain situated where the dosimetric data was integrated while reading-out. Another method includes arranging a plurality of ionizing radiation sensors in a spatially dispersed array; determining a relative position of each of the plurality of ionizing radiation sensors to define a volume of interest; collecting ionizing radiation data from at least a subset of the plurality of ionizing radiation sensors; and triggering an alarm condition when a dose level of an ionizing radiation source is calculated to exceed a threshold.

Space charge dosimeters for extremely low power measurements of radiation in shipping containers

DOEpatents

Britton, Jr; Charles, L [Alcoa, TN; Buckner, Mark A [Oak Ridge, TN; Hanson, Gregory R [Clinton, TN; Bryan, William L [Knoxville, TN

2011-04-26

Methods and apparatus are described for space charge dosimeters for extremely low power measurements of radiation in shipping containers. A method includes in situ polling a suite of passive integrating ionizing radiation sensors including reading-out dosimetric data from a first passive integrating ionizing radiation sensor and a second passive integrating ionizing radiation sensor, where the first passive integrating ionizing radiation sensor and the second passive integrating ionizing radiation sensor remain situated where the dosimetric data was integrated while reading-out. Another method includes arranging a plurality of ionizing radiation sensors in a spatially dispersed array; determining a relative position of each of the plurality of ionizing radiation sensors to define a volume of interest; collecting ionizing radiation data from at least a subset of the plurality of ionizing radiation sensors; and triggering an alarm condition when a dose level of an ionizing radiation source is calculated to exceed a threshold.

Trace analysis of selected hormones and sterols in river sediments by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

PubMed

Matić, Ivana; Grujić, Svetlana; Jauković, Zorica; Laušević, Mila

2014-10-17

In this paper, development and optimization of new LC-MS method for determination of twenty selected hormones, human/animal and plant sterols in river sediments were described. Sediment samples were prepared using ultrasonic extraction and clean up with silica gel/anhydrous sodium sulphate cartridge. Extracts were analyzed by liquid chromatography-linear ion trap-tandem mass spectrometry, with atmospheric pressure chemical ionization. The optimized extraction parameters were extraction solvent (methanol), weight of the sediment (2 g) and time of ultrasonic extraction (3× 10 min). Successful chromatographic separation of hormones (estriol and estrone, 17α- and 17β-estradiol) and four human/animal sterols (epicoprostanol, coprostanol, α-cholestanol and β-cholestanol) that have identical fragmentation reactions was achieved. The developed and optimized method provided high recoveries (73-118%), low limits of detection (0.8-18 ng g(-1)) and quantification (2.5-60 ng g(-1)) with the RSDs generally lower than 20%. Applicability of the developed method was confirmed by analysis of six river sediment samples. A widespread occurrence of human/animal and plant sterols was found. The only detected hormone was mestranol in just one sediment sample. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical analysis of pharmaceuticals and explosives in fingermarks using matrix-assisted laser desorption ionization/time-of-flight mass spectrometry.

PubMed

Kaplan-Sandquist, Kimberly; LeBeau, Marc A; Miller, Mark L

2014-02-01

Chemical analysis of latent fingermarks, "touch chemistry," has the potential of providing intelligence or forensically relevant information. Matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI/TOF MS) was used as an analytical platform for obtaining mass spectra and chemical images of target drugs and explosives in fingermark residues following conventional fingerprint development methods and MALDI matrix processing. There were two main purposes of this research: (1) develop effective laboratory methods for detecting drugs and explosives in fingermark residues and (2) determine the feasibility of detecting drugs and explosives after casual contact with pills, powders, and residues. Further, synthetic latent print reference pads were evaluated as mimics of natural fingermark residue to determine if the pads could be used for method development and quality control. The results suggest that artificial amino acid and sebaceous oil residue pads are not suitable to adequately simulate natural fingermark chemistry for MALDI/TOF MS analysis. However, the pads were useful for designing experiments and setting instrumental parameters. Based on the natural fingermark residue experiments, handling whole or broken pills did not transfer sufficient quantities of drugs to allow for definitive detection. Transferring drugs or explosives in the form of powders and residues was successful for preparing analytes for detection after contact with fingers and deposition of fingermark residue. One downfall to handling powders was that the analyte particles were easily spread beyond the original fingermark during development. Analyte particles were confined in the original fingermark when using transfer residues. The MALDI/TOF MS was able to detect procaine, pseudoephedrine, TNT, and RDX from contact residue under laboratory conditions with the integration of conventional fingerprint development methods and MALDI matrix. MALDI/TOF MS is a nondestructive technique which provides chemical information in both the mass spectra and chemical images. Published by Elsevier Ireland Ltd.

Ionized magnesium in plasma and erythrocytes for the assessment of low magnesium status in alcohol dependent patients.

PubMed

Ordak, Michal; Maj-Zurawska, Magdalena; Matsumoto, Halina; Bujalska-Zadrozny, Magdalena; Kieres-Salomonski, Ilona; Nasierowski, Tadeusz; Muszynska, Elzbieta; Wojnar, Marcin

2017-09-01

Studies on the homeostasis of magnesium in alcohol-dependent patients have often been characterized by low hypomagnesemia detection rates. This may be due to the fact that the content of magnesium in blood serum constitutes only 1% of the average magnesium level within the human body. However, the concentration of ionized magnesium is more physiologically important and makes up 67% of the total magnesium within a human organism. There are no data concerning the determination of the ionized fraction of magnesium in patients addicted to alcohol and its influence on mental health status. This study included 100 alcohol-dependent patients and 50 healthy subjects. The free magnesium fraction was determined using the potentiometric method by means of using ion-selective electrodes. The total magnesium level was determined by using a biochemical Indiko Plus analyzer. In this study, different psychometric scales were applied. Our results confirm the usefulness of ionized magnesium concentrations in erythrocytes and plasma as a diagnostic parameter of low magnesium status in alcohol-dependent patients. The lower the concentration of ionized magnesium, the worse the quality of life an alcohol-dependent person might experience. In the case of total magnesium, no such correlation was determined. Copyright © 2017 Elsevier B.V. All rights reserved.

New developments of the in-source spectroscopy method at RILIS/ISOLDE

NASA Astrophysics Data System (ADS)

Marsh, B. A.; Andel, B.; Andreyev, A. N.; Antalic, S.; Atanasov, D.; Barzakh, A. E.; Bastin, B.; Borgmann, Ch.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Dehairs, M.; Derkx, X.; De Witte, H.; Fedorov, D. V.; Fedosseev, V. N.; Focker, G. J.; Fink, D. A.; Flanagan, K. T.; Franchoo, S.; Ghys, L.; Huyse, M.; Imai, N.; Kalaninova, Z.; Köster, U.; Kreim, S.; Kesteloot, N.; Kudryavtsev, Yu.; Lane, J.; Lecesne, N.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Molkanov, P. L.; Nicol, T.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Schweikhard, L.; Seliverstov, M. D.; Sels, S.; Sjödin, A. M.; Truesdale, V.; Van Beveren, C.; Van Duppen, P.; Wendt, K.; Wienholtz, F.; Wolf, R. N.; Zemlyanoy, S. G.

2013-12-01

At the CERN ISOLDE facility, long isotope chains of many elements are produced by proton-induced reactions in target materials such as uranium carbide. The Resonance Ionization Laser Ion Source (RILIS) is an efficient and selective means of ionizing the reaction products to produce an ion beam of a chosen isotope. Coupling the RILIS with modern ion detection techniques enables highly sensitive studies of nuclear properties (spins, electromagnetic moments and charge radii) along an isotope chain, provided that the isotope shifts and hyperfine structure splitting of the atomic transitions can be resolved. At ISOLDE the campaign to measure the systematics of isotopes in the lead region (Pb, Bi, Tl and Po) has been extended to include the gold and astatine isotope chains. Several developments were specifically required for the feasibility of the most recent measurements: new ionization schemes (Po, At); a remote controlled narrow line-width mode of operation for the RILIS Ti:sapphire laser (At, Au, Po); isobar free ionization using the Laser Ion Source Trap, LIST (Po); isobar selective particle identification using the multi-reflection time-of-flight mass separator (MR-ToF MS) of ISOLTRAP (Au, At). These are summarized as part of an overview of the current status of the in-source resonance ionization spectroscopy setup at ISOLDE.

Analysis of antibiotic fungicide kasugamycin in irrigation water by high performance liquid chromatography.

PubMed

Sheu, Ceshing; Chen, Shu-Chuan; Lo, Chi-Chu

2010-07-01

A high performance liquid chromatographic (HPLC) analysis method with an ultraviolet (UV) detector and an Aqua C18 (250 x 4.6 mm, Phenomenex) column were applied to analyze the antibiotic fungicide kasugamycin in water. An aromatic sulfonic acid spe column (Backerbond, J. T. Backer) was used to remove the interfering materials from irrigation water. A good linear relation existed between the concentration of the fungicide and the peak area, and correlation coefficient of linearity from 0.1 to 10.2 microg/mL was 0.998. The accuracies expressed as the recoveries of kasugamycin from irrigation water ranged from 112.2 to 111.7 %. The precisions expressed as relative standard deviations (RSD) were found to be below 7.0 %. The quantitative detection limit (LOQ) of kasugamycin in irrigation water was set at 2.2 microg/mL which was 2-times higher than the method detection limit (MDL) 1.03 microg/mL. Electrospray ionization-mass (ESI-MS) and fast-atom bombardment-mass (FAB-MS) were applied to compare the ability of identifying the component of the eluent peak from HPLC, and the result indicated that electrospray ionization-mass (ESI-MS) was more sensitive than fast-atom bombardment-mass (FAB-MS) in the detection of kasugamycin. There was no kasugamycin residue detected in irrigation water samples collected from paddyfields at Wufong, indicated that the residues of kasugamycin in water were less than 2.2 microg/mL, and the risk of water contamination was very low.

Mass Spectrometry Vapor Analysis for Improving Explosives Detection Canine Proficiency

DTIC Science & Technology

2017-02-10

ionization (SESI), 8,19-21 dielectric barrier discharge ionization (DBDI), 21,22 selected-ion-flow-tube (SIFT), 23,24 and proton transfer reaction...handled only with wood- en or Teflon® spatulas to prevent static discharge . Using these precautions, we never experienced an accidental detonation...ionization (SESI) and dielectric barrier discharge ionization (DBDI) sources were used for vapor ioni- zation. Source temperature was held at 100 o C

Simultaneous analysis of ten phytohormones in Sargassum horneri by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry.

PubMed

Li, Yan; Zhou, Chengxu; Yan, Xiaojun; Zhang, Jinrong; Xu, Jilin

2016-05-01

Phytohormones have attracted wide attention due to their important biological functions. However, their detection is still a challenge because of their complex composition, low abundance and diverse sources. In this study, a novel method of high-performance liquid chromatography with electrospray ionization tandem mass spectrometry was developed and validated for the simultaneous determination of ten phytohormones including indole-3-acetic acid, isopentenyladenine, isopentenyl adenosine, trans-zeatin riboside, zeatin, strigolactones, abscisic acid, salicylic acid, gibberellin A3, and jasmonic acid in Sargassum horneri (S. horneri). The phytohormones were extracted from freeze-dried S. horneri with methanol/water/methanoic acid (15:4:1, v/v/v) analyzed on a Hypersil Gold C18 column and detected by electrospray ionization tandem triple quadrupole mass spectrometry in the multiple reaction monitoring mode. The experimental conditions for the extraction and analysis of phytohormones were optimized and validated in terms of reproducibility, linearity, sensitivity, recovery, accuracy, and stability. Distributions of the phytohormones in the stems, blades, and gas bladder of the S. horneri in drift, fixed, and semi-fixed growing states were investigated for the first time. The observed contents of the phytohormones in S. horneri range from not detected to 5066.67 ng/g (fresh weight). Most phytohormones are distributed mainly in the stems of S. horneri in drift and semi-fixed states. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser ablation-miniature mass spectrometer for elemental and isotopic analysis of rocks.

PubMed

Sinha, M P; Neidholdt, E L; Hurowitz, J; Sturhahn, W; Beard, B; Hecht, M H

2011-09-01

A laser ablation-miniature mass spectrometer (LA-MMS) for the chemical and isotopic measurement of rocks and minerals is described. In the LA-MMS method, neutral atoms ablated by a pulsed laser are led into an electron impact ionization source, where they are ionized by a 70 eV electron beam. This results in a secondary ion pulse typically 10-100 μs wide, compared to the original 5-10 ns laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer (MMS) and measured in parallel by a modified CCD array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LA-MMS offers a more quantitative assessment of elemental composition than techniques that detect ions directly generated by the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the wavelength of the laser beam, and the not well characterized ionization efficiencies of the elements in the process. The above problems attendant to the direct ion analysis has been minimized in the LA-MMS by analyzing the ablated neutral species after their post-ionization by electron impaction. These neutral species are much more abundant than the directly ablated ions in the ablated vapor plume and are, therefore, expected to be characteristic of the chemical composition of the solid. Also, the electron impact ionization of elements is well studied and their ionization cross sections are known and easy to find in databases. Currently, the LA-MMS limit of detection is 0.4 wt.%. Here we describe LA-MMS elemental composition measurements of various minerals including microcline, lepidolite, anorthoclase, and USGS BCR-2G samples. The measurements of high precision isotopic ratios including (41)K/(39)K (0.077 ± 0.004) and (29)Si/(28)Si (0.052 ± 0.006) in these minerals by LA-MMS are also described. The LA-MMS has been developed as a prototype instrument system for space applications for geochemical and geochronological measurements on the surface of extraterrestrial bodies. © 2011 American Institute of Physics

Simultaneous quantification of 25 active constituents in the total flavonoids extract from Herba Desmodii Styracifolii by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry.

PubMed

Guo, Panpan; Yan, Wenying; Han, Qingjie; Wang, Chunying; Zhang, Zijian

2015-04-01

A sensitive and selective high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry method has been developed and validated for the simultaneous determination of 25 active constituents, including 21 flavonoids and four phenolic acids in the total flavonoids extract from Herba Desmodii Styracifolii for the first time. Among the 25 compounds, seven compounds including caffeic acid, acacetin, genistein, genistin, diosmetin, diosmin and hesperidin were identified and quantified for the first time in Herba Desmodii Styracifolii. Chromatographic separation was accomplished on a ZORBAX SB-C18 (250 mm×4.6 mm, 5.0 μm) column using gradient elution of methanol and 0.1‰ acetic acid v/v at a flow rate of 1.0 mL/min. The identification and quantification of the analytes were achieved using negative electrospray ionization mass spectrometry in multiple-reaction monitoring mode. The method was fully validated in terms of limits of detection and quantification, linearity, precision and accuracy. The results indicated that the developed method is simple, rapid, specific and reliable. Furthermore, the developed method was successfully applied to quantify the 25 active components in six batches of total flavonoids extract from Herba Desmodii Styracifolii. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of PCR/Electron spray Ionization-Time-of-Flight-Mass Spectrometry versus Traditional Clinical Microbiology for active surveillance of organisms contaminating high-use surfaces in a burn intensive care unit, an orthopedic ward and healthcare workers

PubMed Central

2012-01-01

Background Understanding nosocomial pathogen transmission is restricted by culture limitations. Novel platforms, such as PCR-based electron spray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS), may be useful as investigational tools. Methods Traditional clinical microbiology (TCM) and PCR/ESI-TOF-MS were used to recover and detect microorganisms from the hands and personal protective equipment of 10 burn intensive care unit (ICU) healthcare workers providing clinical care at a tertiary care military referral hospital. High-use environmental surfaces were assessed in 9 burn ICU and 10 orthopedic patient rooms. Clinical cultures during the study period were reviewed for pathogen comparison with investigational molecular diagnostic methods. Results From 158 samples, 142 organisms were identified by TCM and 718 by PCR/ESI-TOF-MS. The molecular diagnostic method detected more organisms (4.5 ± 2.1 vs. 0.9 ± 0.8, p < 0.01) from 99% vs. 67% of samples (p < 0.01). TCM detected S. aureus in 13 samples vs. 21 by PCR/ESI-TOF-MS. Gram-negative organisms were less commonly identified than gram-positive by both methods; especially by TCM. Among all detected bacterial species, similar percentages were typical nosocomial pathogens (18-19%) for TCM vs. PCR/ESI-TOF-MS. PCR/ESI-TOF-MS also detected mecA in 112 samples, vanA in 13, and KPC-3 in 2. MecA was associated (p < 0.01) with codetection of coagulase negative staphylococci but not S. aureus. No vanA was codetected with enterococci; one KPC-3 was detected without Klebsiella spp. Conclusions In this pilot study, PCR/ESI-TOF-MS detected more organisms, especially gram-negatives, compared to TCM, but the current assay format is limited by the number of antibiotic resistance determinants it covers. Further large-scale assessments of PCR/ESI-TOF-MS for hospital surveillance are warranted. PMID:23050585

Theoretical considerations on the optogalvanic detection of laser induced fluorescence in atmospheric pressure atomizers

NASA Astrophysics Data System (ADS)

Omenetto, N.; Smith, B. W.; Winefordner, J. D.

1989-01-01

Several theoretical considerations are given on the potential and practical capabilities of a detector of fluorescence radiation whose operating principle is based on a multi-step excitation-ionization scheme involving the fluorescence photons as the first excitation step. This detection technique, which was first proposed by MATVEEVet al. [ Zh. Anal Khim.34, 846 (1979)], combines two independent atomizers, one analytical cell for the excitation of the sample fluorescence and one cell, filled with pure analyte atomic vapor, acting as the ionization detector. One laser beam excites the analyte fluorescence in the analytical cell and one (or two) laser beams are used to ionize the excited atoms in the detector. Several different causes of signal and noise are evaluated, together with a discussion on possible analytical atom reservoirs (flames, furnaces) and laser sources which could be used with this approach. For properly devised conditions, i.e. optical saturation of the fluorescence and unity ionization efficiency, detection limits well below pg/ml in solution and well below femtograms as absolute amounts in furnaces can be predicted. However, scattering problems, which are absent in a conventional laser-enhanced ionization set-up, may be important in this approach.

Development of soft ionization using direct current pulse glow discharge plasma source in mass spectrometry for volatile organic compounds analysis

NASA Astrophysics Data System (ADS)

Nunome, Yoko; Kodama, Kenji; Ueki, Yasuaki; Yoshiie, Ryo; Naruse, Ichiro; Wagatsuma, Kazuaki

2018-01-01

This study describes an ionization source for mass analysis, consisting of glow discharge plasma driven by a pulsed direct-current voltage for soft plasma ionization, to detect toxic volatile organic compounds (VOCs) rapidly and easily. The novelty of this work is that a molecular adduct ion, in which the parent molecule attaches with an NO+ radical, [M + NO]+, can be dominantly detected as a base peak with little or no fragmentation of them in an ambient air plasma at a pressure of several kPa. Use of ambient air as the discharge plasma gas is suitable for practical applications. The higher pressure in an ambient air discharge provided a stable glow discharge plasma, contributing to the soft ionization of organic molecules. Typical mass spectra of VOCs toluene, benzene, o-xylene, chlorobenzene and n-hexane were observed as [M + NO]+ adduct ion whose peaks were detected at m/z 122, 108, 136, 142 and 116, respectively. The NO generation was also confirmed by emission bands of NO γ-system. The ionization reactions were suggested, such that NO+ radical formed in an ambient air discharge could attach with the analyte molecule.

Validation of lipolysis product extraction from aqueous/biological samples, separation and quantification by thin-layer chromatography with flame ionization detection analysis using O-cholesteryl ethylene glycol as a new internal standard.

PubMed

Cavalier, Jean-François; Lafont, Dominique; Boullanger, Paul; Houisse, David; Giallo, Jacqueline; Ballester, Jean-Michel; Carrière, Frédéric

2009-09-11

A general and easily accessible method for the extraction followed by the simultaneous separation and quantitative determination of triacylglycerols, diacylglycerols, monoacylglycerols and free fatty acids has been improved and optimized based on existing protocols using liquid-phase extraction and thin-layer chromatography coupled to flame ionization detection (TLC/FID Iatroscan). After lipid extraction in the presence of a suitable new synthetic internal standard, namely CholE1, a single elution step using n-heptane/diethyl ether/formic acid (55:45:1, v/v/v) was applied. This method was validated in line with international bioanalytical method validation guidelines using two different matrix systems: purified water and human gastro-intestinal fluid. Overall, the assay was found to have high levels of precision with coefficients of variation ranging from 1.48% to 11.0% and accuracy ranging from -13.3% to +5.79% RE. The confidence limits of the lipid mean recovery rates varied between 89.9% and 104%. This method is therefore highly suitable for quantifying the lipolysis products generated in vitro during the hydrolysis of various fats and oils by digestive lipases, as well as those collected from the gastro-intestinal tract in the course of human clinical studies on lipid digestion.

High-throughput and simultaneous analysis of eight central-acting muscle relaxants in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry in the positive and negative ionization modes.

PubMed

Ogawa, Tadashi; Hattori, Hideki; Kaneko, Rina; Ito, Kenjiro; Iwai, Masae; Mizutani, Yoko; Arinobu, Tetsuya; Ishii, Akira; Seno, Hiroshi

2011-06-01

In this report, a high-throughput and sensitive method for analysis of eight central-acting muscle relaxants in human plasma by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) in the positive and negative ionization modes using tolbutamide as internal standard is presented. After pretreatment of a plasma sample by solid-phase extraction with an Oasis HLB cartridge, muscle relaxants were analyzed by UPLC with Acquity UPLC BEH C(18) column and Acquity TQD tandem quadrupole mass spectrometer equipped with an electrospray ionization interface. The calibration curves for muscle relaxants spiked into human plasma equally showed good linearities in the nanogram per milliliter order range. The detection limits (signal-to-noise ratio = 3) was as low as 0.1-2 ng/mL. The method gave satisfactory recovery rates, accuracy, and precision for quality control samples spiked with muscle relaxants. To further validate the present method, 250 mg of chlorphenesin carbamate was orally administered to a healthy male volunteer, and the concentrations of chlorphenesin carbamate in plasma were measured 0.5, 1, 2, 4, 6, and 8 h after dosing; their concentrations in human plasma were between 0.62 and 2.44 μg/mL. To our knowledge, this is the first report describing simultaneous analysis of over more than two central-acting muscle relaxants by liquid chromatography-tandem mass spectrometry. This has been realized by the capability of our instrument for simultaneous multiple reaction monitoring of the target compounds in both positive and negative ionization modes. Therefore, the present method seems very useful in forensic and clinical toxicology and pharmacokinetic studies.

Novel liquid chromatography-electrospray ionization mass spectrometry method for the quantification in human urine of microbial aromatic acid metabolites derived from dietary polyphenols.

PubMed

Gonthier, Marie-Paule; Rios, Laurent Y; Verny, Marie- Anne; Rémésy, Christian; Scalbert, Augustin

2003-06-15

An HPLC-ESI-MS-MS method was developed to quantify in human urine fourteen aromatic acids known as metabolites of dietary polyphenols. These metabolites were determined simultaneously in a single 20-min chromatographic analysis with multiple reaction monitoring detection. The inter- and intra-day precisions, calculated from quality control samples were 8.8 and 5.3%, respectively, and the mean accuracy was 2.3%. The method was tested on urine samples collected from one healthy volunteer who consumed a polyphenol-rich diet for 3 days. Increased levels of several aromatic acid metabolites were observed, demonstrating that the method can be used to detect changes in the excretion of microbial metabolites induced by the consumption of polyphenol-containing foods in humans.

Detection of trace ink compounds in erased handwritings using electrospray-assisted laser desorption ionization mass spectrometry.

PubMed

Kao, Yi-Ying; Cheng, Sy-Chyi; Cheng, Chu-Nian; Shiea, Jentaie; Ho, Hsiu-O

2014-06-01

Writings made with erasable pens on paper surfaces can either be rubbed off with an eraser or rendered invisible by changing the temperature of the ink. However, trace ink compounds still remain in the paper fibers even after rubbing or rendering. The detection of these ink compounds from erased handwritings will be helpful in knowing the written history of the paper. In this study, electrospray-assisted laser desorption ionization/mass spectrometry was used to characterize trace ink compounds remaining in visible and invisible ink lines. The ink compounds were desorbed from the paper surface by irradiating the handwritings with a pulsed laser beam; the desorbed analytes were subsequently ionized in an electrospray plume and detected by a quadrupole time-of-flight mass spectrometry mass analyzer. Because of the high spatial resolution of the laser beam, electrospray-assisted laser desorption ionization/mass spectrometry analysis resulted in minimal damage to the sample documents. Copyright © 2014 John Wiley & Sons, Ltd.

Detection of the H92α recombination line from NGC 4945

NASA Astrophysics Data System (ADS)

Roy, A. L.; Oosterloo, T.; Goss, W. M.; Anantharamaiah, K. R.

2010-07-01

Context. Hydrogen ionized by young, high-mass stars in starburst galaxies radiates radio recombination lines (RRLs), whose strength can be used as a diagnostic of the ionization rate, conditions and gas dynamics in the starburst region, without problems of dust obscuration. However, the lines are weak and only few extragalactic starburst systems have been detected. Aims: We aimed to increase the number of known starburst systems with detectable RRLs for detailed studies, and we used the line properties to study the gas properties and dynamics. Methods: We searched for the RRLs H91α and H92α with rest frequencies of 8.6 GHz and 8.3 GHz in the nearby southern Seyfert galaxy NGC 4945 using the Australia Telescope Compact Array with resolution of 3”. This yielded a detection from which we derived conditions in the starburst regions. Results: We detected RRLs from the nucleus of NGC 4945 with a peak line strength integrated over the source of 17.8 mJy, making it the strongest extragalactic RRL emitter known at this frequency. The line and continuum emission from NGC 4945 can be matched by a model consisting of a collection of 10 to 300 H II regions with temperatures of 5000 K, densities of 103 cm-3 to 104 cm-3 and a total effective diameter of 2 pc to 100 pc. The Lyman continuum production rate required to maintain the ionization is 6 × 1052 s-1 to 3 × 1053 s-1, which requires 2000 to 10 000 O5 stars to be produced in the starburst, inferring a star formation rate of 2 M_⊙ yr-1 to 8 M_⊙ yr-1. We resolved the rotation curve within the central 70 pc region and this is well described by a set of rotating rings that were coplanar and edge on. We found no reason to depart from a simple flat rotation curve. The rotation speed of 120 km s-1 within the central 1” (19 pc) radius infers an enclosed mass of 3 × 107 M⊙, and an average surface density with the central 19 pc of 25 000 pc-2, which exceeds the threshold gas surface density for star formation. Conclusions: We discovered RRLs from NGC 4945. It is the strongest known extragalactic RRL emitter and is suited to high-quality spectroscopic study. We resolved the dynamics of the ionized gas in the central 70 pc and derived conditions and star formation rates in the ionized gas.

Microliter-sized ionization device and method

NASA Technical Reports Server (NTRS)

Simac, Robert M. (Inventor); Wernlund, Roger F. (Inventor); Cohen, Martin J. (Inventor)

1999-01-01

A microliter-sized metastable ionization device with a cavity, a sample gas inlet, a corona gas inlet and a gas outlet. A first electrode has a hollow and disposed in the cavity and is in fluid communication with the sample gas inlet. A second electrode is in fluid communication with the corona gas inlet and is disposed around the first electrode adjacent the hollow end thereof. A gap forming means forms a corona gap between the first and second electrodes. A first power supply is connected to the first electrode and the second power supply is connected to the second electrode for generating a corona discharge across the corona gap. A collector has a hollow end portion disposed in the cavity which is in fluid communications with the gas outlet for the outgassing and detection of ionized gases. The first electrode can be a tubular member aligned concentrically with a cylindrical second electrode. The gap forming means can be in annular disc projecting radially inwardly from the cylindrical second electrode. The collector can have a tubular opening aligned coaxially with the first electrode and has an end face spaced a short distance from an end face of the first electrode forming a small active volume therebetween for the generation and detection of small quantities of trace analytes.

Direct analysis of in-gel proteins by carbon nanotubes-modified paper spray ambient mass spectrometry.

PubMed

Han, Feifei; Yang, Yuhan; Ouyang, Jin; Na, Na

2015-02-07

The in situ and direct extraction, desorption and ionization of in-gel intact proteins after electrophoresis has been achieved by carbon nanotubes (CNTs)-modified paper spray mass spectrometry at ambient conditions. Characteristics of CNTs (including larger surface area, smaller pore diameter and enhanced conductivity) were endowed to the porous filter paper substrate by uniformly dispersing the CNTs on the filter paper. Upon applying electric potential to the CNTs-modified paper, the in-gel proteins were extracted from the gel and subsequently migrated to the tip of the filter paper by electrophoresis-like behavior for paper spray ionization, which was monitored by extracted ion chronograms. The characterizations of modified filter papers and CNTs nanoparticles further confirmed the role of CNTs in in-gel protein extraction, protein migration as well as spray ionization at the paper tip. Under optimized conditions, a mixture of cytochrome c, lysozyme and myoglobin was successfully separated by native electrophoresis and subsequently analysed by the present method, showing a limit of detection of 10 ng per gel band. The present strategy offers a new pathway for the direct detection of in-gel intact proteins at ambient conditions without any pre-treatment (e.g. digestion, chemical extraction and desalting), which exhibits potential applications in top-down proteomics.

Carbon based sample supports and matrices for laser desorption/ ionization mass spectrometry.

PubMed

Rainer, Matthias; Najam-ul-Haq, Muhammad; Huck, Christian W; Vallant, Rainer M; Heigl, Nico; Hahn, Hans; Bakry, Rania; Bonn, Günther K

2007-01-01

Laser desorption/ionization mass spectrometry (LDI-MS) is a widespread and powerful technique for mass analysis allowing the soft ionization of molecules such as peptides, proteins and carbohydrates. In many applications, an energy absorbing matrix has to be added to the analytes in order to protect them from being fragmented by direct laser beam. LDI-MS in conjunction with matrix is commonly referred as matrix-assisted LDI (MALDI). One of the striking disadvantages of this method is the desorption of matrix molecules, which causes interferences originating from matrix background ions in lower mass range (< 1000 Da). This has been led to the development of a variety of different carbon based LDI sample supports, which are capable of absorbing laser light and simultaneously transfering energy to the analytes for desorption. Furthermore carbon containing sample supports are used as carrier materials for the specific binding and preconcentration of molecules out of complex samples. Their subsequent analysis with MALDI mass spectrometry allows performing studies in metabolomics and proteomics. Finally a thin layer of carbon significantly improves sensitivity concerning detection limit. Analytes in low femtomole and attomole range can be detected in this regard. In the present article, these aspects are reviewed from patents where nano-based carbon materials are comprehensively utilized.

Film Vetoes for Alpha Background Rejection in Bolometer Detectors

NASA Astrophysics Data System (ADS)

Deporzio, Nicholas; Bucci, Carlo; Canonica, Lucia; Divacri, Marialaura; Cuore Collaboration; Absurd Team

2015-04-01

This study characterizes the effectiveness of encasing bolometer detectors in scintillator, metal ionization, and more exotic films to veto alpha radiation background. Bolometers are highly susceptible to alpha background and a successful veto should boost the statistical strength, speed, and signal-background ratio of bolometer particle searches. Plastic scintillator films are cooled to bolometer temperatures and bombarded with 1.4 MeV to 6.0 MeV alpha particles representative of detector conditions. Photomultipliers detect the keV range scintillation light and produce a veto signal. Also, layered films of a primary metal, dielectric, and secondary metal, such as gold-polyethylene-gold films, are cooled to milli-kelvin temperatures and biased with 0.1V to 100V to produce a current signal when incident 1.4 MeV to 6.0 MeV alpha particles ionize conduction paths through the film. Veto signals are characterized by their affect on bolometer detection of 865 keV target signals. Similar methods are applied to more exotic films. Early results show scintillator films raise target signal count rate and suppress counts above target energy by at least a factor of 10. This indicates scintillation vetoes are effective and that metal ionization and other films under study will also be effective.

Sampling and analyte enrichment strategies for ambient mass spectrometry.

PubMed

Li, Xianjiang; Ma, Wen; Li, Hongmei; Ai, Wanpeng; Bai, Yu; Liu, Huwei

2018-01-01

Ambient mass spectrometry provides great convenience for fast screening, and has showed promising potential in analytical chemistry. However, its relatively low sensitivity seriously restricts its practical utility in trace compound analysis. In this review, we summarize the sampling and analyte enrichment strategies coupled with nine modes of representative ambient mass spectrometry (desorption electrospray ionization, paper vhspray ionization, wooden-tip spray ionization, probe electrospray ionization, coated blade spray ionization, direct analysis in real time, desorption corona beam ionization, dielectric barrier discharge ionization, and atmospheric-pressure solids analysis probe) that have dramatically increased the detection sensitivity. We believe that these advances will promote routine use of ambient mass spectrometry. Graphical abstract Scheme of sampling stretagies for ambient mass spectrometry.

Electronic drive and acquisition system for mass spectrometry

NASA Technical Reports Server (NTRS)

Schaefer, Rembrandt Thomas (Inventor); Chutjian, Ara (Inventor); Tran, Tuan (Inventor); Madzunkov, Stojan M. (Inventor); Thomas, John L. (Inventor); Mojarradi, Mohammad (Inventor); MacAskill, John (Inventor); Blaes, Brent R. (Inventor); Darrach, Murray R. (Inventor); Burke, Gary R. (Inventor)

2010-01-01

The present invention discloses a mixed signal RF drive electronics board that offers small, low power, reliable, and customizable method for driving and generating mass spectra from a mass spectrometer, and for control of other functions such as electron ionizer, ion focusing, single-ion detection, multi-channel data accumulation and, if desired, front-end interfaces such as pumps, valves, heaters, and columns.

QUANTITATION OF PERCHLORATE ION BY ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS) USING STABLE ASSOCIATION COMPLEXES WITH ORGANIC CATIONS AND BASES TO ENHANCE SELECTIVITY

EPA Science Inventory

Quantitation of trace levels of perchlorate ion in water has become a key issue since this species was discovered in water supplies around the United States. Although ion chromatographic methods presently offer the lowest limit of detection, =40 nm (4ngm1-1), chromatographic ret...

Characterization of physalins and fingerprint analysis for the quality evaluation of Physalis alkekengi L. var. franchetii by ultra-performance liquid chromatography combined with diode array detection and electrospray ionization tandem mass spectrometry.

PubMed

Zheng, Yunliang; Luan, Lianjun; Chen, Yong; Ren, Yiping; Wu, Yongjiang

2012-12-01

Physalins are important bioactive compounds from genus Physalis. They often occur as isomers, which makes the structural elucidation difficult. In the present study, the fragmentation behavior and UV characteristics of seven physalins from genus Physalis were firstly investigated using electrospray ionization tandem mass spectrometry (ESI-MS/MS) and diode array detection (DAD). Combined with ultra-performance liquid chromatography (UPLC) and DAD, the established approach to the structural identification of physalins by ESI-MS/MS was then applied to the analysis of Physalis alkekengi L. According to the UPLC retention behavior, the diagnostic UV spectra and the molecular structural information provided by MS/MS spectra, about 19 fingerprint peaks were identified, including 14 physalins and 5 other compounds. Finally, the established fingerprint method was applied to the analysis of 31 P. alkekengi L. samples collected from different locations, which reflected their similar chemical constituent properties. The proposed method provides a scientific and technical platform to the herbal industry for quality control and safety assurance of herbal preparations that contain this class of physalins. Copyright © 2012 Elsevier B.V. All rights reserved.

A simple and selective method for the measurement of azadirachtin and related azadirachtoid levels in fruits and vegetables using liquid chromatography electrospray ionization tandem mass spectrometry.

PubMed

Sarais, Giorgia; Caboni, Pierluigi; Sarritzu, Erika; Russo, Mariateresa; Cabras, Paolo

2008-05-14

Neem-based insecticides containing azadirachtin and related azadirachtoids are widely used in agriculture. Here, we report an analytical method for the rapid and accurate quantification of the insecticide azadirachtin A and B and other azadirachtoids such as salannin, nimbin, and their deacetylated analogues on tomatoes and peaches. Azadirachtoids were extracted from fruits and vegetables with acetonitrile. Using high-performance liquid chromatography/electrospray ionization tandem mass spectrometer, azadirachtoids were selectively detected monitoring the multiple reaction transitions of sodium adduct precursor ions. For azadirachtin A, calibration was linear over a working range of 1-1000 microg/L with r > 0.996. The limit of detection and limit of quantification for azadirachtin A were 0.4 and 0.8 microg/kg, respectively. The presence of interfering compounds in the peach and tomato extracts was evaluated and found to be minimal. Because of the linear behavior, it was concluded that the multiple reaction transitions of sodium adduct ions can be used for analytical purposes, that is, for the identification and quantification of azadirachtin A and B and related azadirachtoids in fruit and vegetable extracts at trace levels.

Direct detection of carbapenemase-associated proteins of Acinetobacter baumannii using nanodiamonds coupled with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Chang, Kai-Chih; Chung, Chin-Yi; Yeh, Chen-Hsing; Hsu, Kuo-Hsiu; Chin, Ya-Ching; Huang, Sin-Siang; Liu, Bo-Rong; Chen, Hsi-An; Hu, Anren; Soo, Po-Chi; Peng, Wen-Ping

2018-04-01

The appearance and spread of carbapenem-resistant Acinetobacter baumannii (CRAB) pose a challenge for optimization of antibiotic therapies and outbreak preventions. The carbapenemase production can be detected through culture-based methods (e.g. Modified Hodge Test-MHT) and DNA based methods (e.g. Polymerase Chain Reaction-PCR). The culture-based methods are time-consuming, whereas those of PCR assays need only a few hours but due to its specificity, can only detect known genetic targets encoding carbapenem-resistance genes. Therefore, new approaches to detect carbapenemase-producing A. baumannii are of great importance. Here, we have developed a rapid and novel method using detonation nanodiamonds (DNDs) as a platform for concentration and extraction of A. baumannii carbapenemase-associated proteins prior to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF-MS) analysis. To concentrate and extract the A. baumannii carbapenemase-associated proteins, we tested several protein precipitation conditions and found a 0.5% trifluoroacetic acid (TFA) solution within the bacterial suspension could result in strong ion signals with DNDs. A total of 66 A. baumannii clinical-isolates including 51 carbapenem-resistant strains and 15 carbapenem-susceptible strains were tested. Our result showed that among the 51 carbapenem-resistant strains 49 strains had a signal at m/z ~40,279 (±87); among the 15 carbapenem-susceptible strains, 4 strains showed a signal at m/z ~40,279. With on-diamond digestion, we confirmed that the captured protein at m/z ~40,279 was related to ADC family extended-spectrum class C beta-lactamase, from A. baumannii. Using this ADC family protein as a biomarker (m/z ~ 40,279) for carbapenem susceptibility testing of A. baumannii, the sensitivity and the specificity could reach 96% and 73% as compared to traditional imipenem susceptibility testing (MIC results). However, the sensitivity and specificity of this method reached 100% as compared to polymerase chain reaction (PCR) result. Our approach could directly detect the carbapenemase-associated proteins of A. baumannii within 90 min and does not require addition of carbapenemase substrate which is required in the MHT or other mass spectrometric methods. For future applications, our method could be efficiently used in the detection of other carbapenemase-producing bacteria. Copyright © 2018 Elsevier B.V. All rights reserved.

Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

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

Waltman, Melanie J.

2010-05-01

Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionizedmore » through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.« less

Quantitative Detection of Trace Malachite Green in Aquiculture Water Samples by Extractive Electrospray Ionization Mass Spectrometry

PubMed Central

Fang, Xiaowei; Yang, Shuiping; Chingin, Konstantin; Zhu, Liang; Zhang, Xinglei; Zhou, Zhiquan; Zhao, Zhanfeng

2016-01-01

Exposure to malachite green (MG) may pose great health risks to humans; thus, it is of prime importance to develop fast and robust methods to quantitatively screen the presence of malachite green in water. Herein the application of extractive electrospray ionization mass spectrometry (EESI-MS) has been extended to the trace detection of MG within lake water and aquiculture water, due to the intensive use of MG as a biocide in fisheries. This method has the advantage of obviating offline liquid-liquid extraction or tedious matrix separation prior to the measurement of malachite green in native aqueous medium. The experimental results indicate that the extrapolated detection limit for MG was ~3.8 μg·L−1 (S/N = 3) in lake water samples and ~0.5 μg·L−1 in ultrapure water under optimized experimental conditions. The signal intensity of MG showed good linearity over the concentration range of 10–1000 μg·L−1. Measurement of practical water samples fortified with MG at 0.01, 0.1 and 1.0 mg·L−1 gave a good validation of the established calibration curve. The average recoveries and relative standard deviation (RSD) of malachite green in lake water and Carassius carassius fish farm effluent water were 115% (6.64% RSD), 85.4% (9.17% RSD) and 96.0% (7.44% RSD), respectively. Overall, the established EESI-MS/MS method has been demonstrated suitable for sensitive and rapid (<2 min per sample) quantitative detection of malachite green in various aqueous media, indicating its potential for online real-time monitoring of real life samples. PMID:27529262

Quantitative Detection of Trace Malachite Green in Aquiculture Water Samples by Extractive Electrospray Ionization Mass Spectrometry.

PubMed

Fang, Xiaowei; Yang, Shuiping; Chingin, Konstantin; Zhu, Liang; Zhang, Xinglei; Zhou, Zhiquan; Zhao, Zhanfeng

2016-08-11

Exposure to malachite green (MG) may pose great health risks to humans; thus, it is of prime importance to develop fast and robust methods to quantitatively screen the presence of malachite green in water. Herein the application of extractive electrospray ionization mass spectrometry (EESI-MS) has been extended to the trace detection of MG within lake water and aquiculture water, due to the intensive use of MG as a biocide in fisheries. This method has the advantage of obviating offline liquid-liquid extraction or tedious matrix separation prior to the measurement of malachite green in native aqueous medium. The experimental results indicate that the extrapolated detection limit for MG was ~3.8 μg·L(-1) (S/N = 3) in lake water samples and ~0.5 μg·L(-1) in ultrapure water under optimized experimental conditions. The signal intensity of MG showed good linearity over the concentration range of 10-1000 μg·L(-1). Measurement of practical water samples fortified with MG at 0.01, 0.1 and 1.0 mg·L(-1) gave a good validation of the established calibration curve. The average recoveries and relative standard deviation (RSD) of malachite green in lake water and Carassius carassius fish farm effluent water were 115% (6.64% RSD), 85.4% (9.17% RSD) and 96.0% (7.44% RSD), respectively. Overall, the established EESI-MS/MS method has been demonstrated suitable for sensitive and rapid (<2 min per sample) quantitative detection of malachite green in various aqueous media, indicating its potential for online real-time monitoring of real life samples.

Efficient Detection of Carbapenemase Activity in Enterobacteriaceae by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry in Less Than 30 Minutes.

PubMed

Lasserre, Camille; De Saint Martin, Luc; Cuzon, Gaelle; Bogaerts, Pierre; Lamar, Estelle; Glupczynski, Youri; Naas, Thierry; Tandé, Didier

2015-07-01

The recognition of carbapenemase-producing Enterobacteriaceae (CPE) isolates is a major laboratory challenge, and their inappropriate or delayed detection may have negative impacts on patient management and on the implementation of infection control measures. We describe here a matrix-assisted laser desorption ionization-time of flight (MALDI-TOF)-based method to detect carbapenemase activity in Enterobacteriaceae. After a 20-min incubation of the isolate with 0.5 mg/ml imipenem at 37°C, supernatants were analyzed by MALDI-TOF in order to identify peaks corresponding to imipenem (300 Da) and an imipenem metabolite (254 Da). A total of 223 strains, 77 CPE (OXA-48 variants, KPC, NDM, VIM, IMI, IMP, and NMC-A) and 146 non-CPE (cephalosporinases, extended-spectrum β-lactamases [ESBLs], and porin defects), were tested and used to calculate a ratio of imipenem hydrolysis: mass spectrometry [MS] ratio = metabolite/(imipenem + metabolite). An MS ratio cutoff was statistically determined to classify strains as carbapenemase producers (MS ratio of ≥0.82). We validated this method first by testing 30 of our 223 isolates (15 CPE and 15 non-CPE) 10 times to calculate an intraclass correlation coefficient (ICC of 0.98), showing the excellent repeatability of the method. Second, 43 strains (25 CPE and 18 non-CPE) different from the 223 strains used to calculate the ratio cutoff were used as external controls and blind tested. They yielded sensitivity and specificity of 100%. The total cost per test is <0.10 U.S. dollars (USD). This easy-to-perform assay is time-saving, cost-efficient, and highly reliable and might be used in any routine laboratory, given the availability of mass spectrometry, to detect CPE. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Application of gas chromatography/flame ionization detector-based metabolite fingerprinting for authentication of Asian palm civet coffee (Kopi Luwak).

PubMed

Jumhawan, Udi; Putri, Sastia Prama; Yusianto; Bamba, Takeshi; Fukusaki, Eiichiro

2015-11-01

Development of authenticity screening for Asian palm civet coffee, the world-renowned priciest coffee, was previously reported using metabolite profiling through gas chromatography/mass spectrometry (GC/MS). However, a major drawback of this approach is the high cost of the instrument and maintenance. Therefore, an alternative method is needed for quality and authenticity evaluation of civet coffee. A rapid, reliable and cost-effective analysis employing a universal detector, GC coupled with flame ionization detector (FID), and metabolite fingerprinting has been established for discrimination analysis of 37 commercial and non-commercial coffee beans extracts. gas chromatography/flame ionization detector (GC/FID) provided higher sensitivity over a similar range of detected compounds than GC/MS. In combination with multivariate analysis, GC/FID could successfully reproduce quality prediction from GC/MS for differentiation of commercial civet coffee, regular coffee and coffee blend with 50 wt % civet coffee content without prior metabolite details. Our study demonstrated that GC/FID-based metabolite fingerprinting can be effectively actualized as an alternative method for coffee authenticity screening in industries. Copyright © 2015. Published by Elsevier B.V.

Minimizing thermal degradation in gas chromatographic quantitation of pentaerythritol tetranitrate.

PubMed

Lubrano, Adam L; Field, Christopher R; Newsome, G Asher; Rogers, Duane A; Giordano, Braden C; Johnson, Kevin J

2015-05-15

An analytical method for establishing calibration curves for the quantitation of pentaerythriol tetranitrate (PETN) from sorbent-filled thermal desorption tubes by gas chromatography with electron capture detection (TDS-GC-ECD) was developed. As PETN has been demonstrated to thermally degrade under typical GC instrument conditions, peaks corresponding to both PETN degradants and molecular PETN are observed. The retention time corresponding to intact PETN was verified by high-resolution mass spectrometry with a flowing atmospheric pressure afterglow (FAPA) ionization source, which enabled soft ionization of intact PETN eluting the GC and subsequent accurate-mass identification. The GC separation parameters were transferred to a conventional GC-ECD instrument where analytical method-induced PETN degradation was further characterized and minimized. A method calibration curve was established by direct liquid deposition of PETN standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Two local, linear relationships between detector response and PETN concentration were observed, with a total dynamic range of 0.25-25ng. Published by Elsevier B.V.

A microwave-mediated saponification of galactosylceramide and galactosylceramide I3-sulfate and identification of their lyso-compounds by delayed extraction matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

PubMed

Taketomi, T; Hara, A; Uemura, K; Kurahashi, H; Sugiyama, E

1996-07-16

Small amounts of galactosylceramide (cerebroside) and galactosylceramide I3-sulfate (sulfatide) obtained from porcine spinal cord and equine kidney were deacylated by a rapid method of microwave-mediated saponification to prepare their lyso-compounds. Mass spectra of their protonated or deprotonated molecular ion peaks were detected by recently developed new technology of a delayed extraction matrix-assisted laser desorption ionization time-of-flight mass spectrometer with reflector detector in positive or negative ion mode. Long chain bases of lysocerebroside and lysosulfatide were different between porcine spinal cord and equine kidney, but similar to each other in the same organ, suggesting their common synthetic pathway. It is noted that the new rapid method can be similarly applied to the deacylation of both cerebroside and sulfatide in contrast to our classical method which was able to be applied to cerebroside, but not to sulfatide.

Quantitative analysis of glycosaminoglycans, chondroitin/dermatan sulfate, hyaluronic acid, heparan sulfate, and keratan sulfate by liquid chromatography-electrospray ionization-tandem mass spectrometry.

PubMed

Osago, Harumi; Shibata, Tomoko; Hara, Nobumasa; Kuwata, Suguru; Kono, Michihaya; Uchio, Yuji; Tsuchiya, Mikako

2014-12-15

We developed a method using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) with a selected reaction monitoring (SRM) mode for simultaneous quantitative analysis of glycosaminoglycans (GAGs). Using one-shot analysis with our MS/MS method, we demonstrated the simultaneous quantification of a total of 23 variously sulfated disaccharides of four GAG classes (8 chondroitin/dermatan sulfates, 1 hyaluronic acid, 12 heparan sulfates, and 2 keratan sulfates) with a sensitivity of less than 0.5 pmol within 20 min. We showed the differences in the composition of GAG classes and the sulfation patterns between porcine articular cartilage and yellow ligament. In addition to the internal disaccharides described above, some saccharides derived from the nonreducing terminal were detected simultaneously. The simultaneous quantification of both internal and nonreducing terminal saccharides could be useful to estimate the chain length of GAGs. This method would help to establish comprehensive "GAGomic" analysis of biological tissues. Copyright © 2014 Elsevier Inc. All rights reserved.

Simple method to assess stability of immobilized peptide ligands against proteases.

PubMed

Giudicessi, Silvana L; Salum, María L; Saavedra, Soledad L; Martínez-Ceron, María C; Cascone, Osvaldo; Erra-Balsells, Rosa; Camperi, Silvia A

2017-09-01

Although peptides are used as affinity chromatography ligands, they could be digested by proteases. Usually, peptide stability is evaluated in solution, which differs from the resin-bounded peptide behavior. Furthermore, the study of the degradation products requires purification steps before analysis. Here, we describe an easy method to assess immobilized peptide stability. Sample peptides were synthesized on hydroxymethylbenzamide-ChemMatrix resin. Peptidyl-resin beads were then incubated with solutions containing proteases. Peptides were detached from the solid support with ammonia vapor and analyzed by matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometry, allowing the detection of the whole peptides as well as their C-terminal degradation products. The method allowed a fast evaluation of peptide ligand stability in solid phase towards proteases that may be present in the crude sample before their use as ligands in affinity chromatography. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.

El medio interestelar en los alrededores de la region HII Sh2-183

NASA Astrophysics Data System (ADS)

Cichowolski, S.; Cappa, C. E.; Blanco, A.; Eppens, L.; Ertini, K.; Leiva, M. M.

2017-10-01

We present a multiwavelength study of the HII region Sh2-183, located at (,) = (123.3,+3.0) at a distance of 7.0 1.5 kpc from the Sun. Based on the radio continuum data we estimated the amount of ionized gas, the electronic density, and the number of ionizing photons needed to keep the region ionized, which is important since the star/s responsible of the region was/were not detected yet. On the other hand, based on IRAS data we have analyzed the dust temperature and distribution. The Hi line data allowed the detection of a shell-like structure surrounding the ionized gas and the CO data revealed the presence of 6 molecular clouds probably related to Sh2-183, which harbor several young stellar object candidates.

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

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

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

1981-01-01

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

Quantitative determination of the hydrolysis products of nitrogen mustards in human urine by liquid chromatography-electrospray ionization tandem mass spectrometry.

PubMed

Lemire, Sharon W; Ashley, David L; Calafat, Antonia M

2003-01-01

Nitrogen mustards are a public health concern because of their extreme vesicant properties and the possible exposure of workers during the destruction of chemical stockpiles. A sensitive, rapid, accurate, and precise analysis for the quantitation of ultratrace levels of N-ethyldiethanolamine (EDEA) and N-methyldiethanolamine (MDEA) in human urine as a means of assessing recent exposure to the nitrogen mustards bis(2-chloroethyl)ethylamine and bis(2-chloroethyl)methylamine, respectively, was developed. The method was based on solid-phase extraction, followed by analysis of the urine extract using isotope-dilution high-performance liquid chromatography-mass spectrometry with TurbolonSpray ionization and multiple-reaction monitoring. The method limits of detection were 0.41 ng/mL for EDEA and 0.96 ng/mL for MDEA in 1 mL of urine with coefficients of variation < 10% for both compounds.

Use of ground radar to detect reentering debris

NASA Technical Reports Server (NTRS)

Crews, J. L.

1985-01-01

The velocity of the particles is required to identify the type of particles producing the ionization trails. A method of approximating the velocity of a meteor from radar data was developed. The method requires the time between the spacings of the Fresnel interference fringes, the range to the ionization trail, and the wavelength of the radar system. The orbital mechanics of the problem are evaluated, if the particles originate with the shuttle, the orbital mechanics will substantiate the relative position of the particles with the position of the shuttle. A program to determine spacecraft orbital decay due to perturbations is utilized for a preliminary evaluation of the orbital mechanics of the problem. Many assumptions concerning the size, shape, density, etc. of the particles are necessary for the preliminary evaluation. The results do not negate the possibility that the events observed by the radar are reentering particles originating from the shuttle.

[Simultaneous determination of nine perfluorinated compound precursors in atmospheric precipitation by solid phase extraction and ultra performance liquid chromatography with tandem mass spectrometry].

PubMed

Zhang, Ming; Tang, Fangliang; Xu, Jianfen; Yu, Bo; Zhang, Wei; Yao, Jianliang; Hu, Minhua

2017-10-08

A high-throughput detection method has been developed for the determination of nine perfluorinated compound precursors (PFCPs) in atmospheric precipitation by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI-MS/MS). The atmospheric precipitation samples were concentrated and purified with HLB solid phase extraction cartridges. The UPLC separation was performed on an HSS T 3 column (100 mm×2.1 mm, 1.7 μm) utilizing a gradient elution program of methanol and water as the mobile phases at a flow rate of 0.2 mL/min. The MS/MS detection was performed under negative electrospray ionization (ESI - ) in multiple reaction monitoring (MRM) mode. Good linearity was observed in the range of 0.05-5.00 μg/L, 0.50-50.0 μg/L or 5.00-500 μg/L with correlation coefficients from 0.9921 to 0.9995. The limits of detection (LODs) for the nine perfluorinated compound precursors were in the ranges of 0.05-7.9 ng/L. The recoveries ranged from 76.0% to 106% with the relative standard deviations between 0.72% and 13.7%. This method is characterized by high sensitivity and precision, extensive analytical range and quick analytical rate, and can be applied for the analysis of perfluorinated compound precursors in atmospheric precipitation.

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

PubMed

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

2014-09-05

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

Analysis of wastewater samples by direct combination of thin-film microextraction and desorption electrospray ionization mass spectrometry.

PubMed

Strittmatter, Nicole; Düring, Rolf-Alexander; Takáts, Zoltán

2012-09-07

An analysis method for aqueous samples by the direct combination of C18/SCX mixed mode thin-film microextraction (TFME) and desorption electrospray ionization mass spectrometry (DESI-MS) was developed. Both techniques make analytical workflow simpler and faster, hence the combination of the two techniques enables considerably shorter analysis time compared to the traditional liquid chromatography mass spectrometry (LC-MS) approach. The method was characterized using carbamazepine and triclosan as typical examples for pharmaceuticals and personal care product (PPCP) components which draw increasing attention as wastewater-derived environmental contaminants. Both model compounds were successfully detected in real wastewater samples and their concentrations determined using external calibration with isotope labeled standards. Effects of temperature, agitation, sample volume, and exposure time were investigated in the case of spiked aqueous samples. Results were compared to those of parallel HPLC-MS determinations and good agreement was found through a three orders of magnitude wide concentration range. Serious matrix effects were observed in treated wastewater, but lower limits of detection were still found to be in the low ng L(-1) range. Using an Orbitrap mass spectrometer, the technique was found to be ideal for screening purposes and led to the detection of various different PPCP components in wastewater treatment plant effluents, including beta-blockers, nonsteroidal anti-inflammatory drugs, and UV filters.

Detection of lysergic acid diethylamide (LSD) in urine by gas chromatography-ion trap tandem mass spectrometry.

PubMed

Sklerov, J H; Kalasinsky, K S; Ehorn, C A

1999-10-01

A confirmatory method for the detection and quantitation of lysergic acid diethylamide (LSD) is presented. The method employs gas chromatography-tandem mass spectrometry (GC-MS-MS) using an internal ionization ion trap detector for sensitive MS-MS-in-time measurements of LSD extracted from urine. Following a single-step solid-phase extraction of 5 mL of urine, underivatized LSD can be measured with limits of quantitation and detection of 80 and 20 pg/mL, respectively. Temperature-programmed on-column injections of urine extracts were linear over the concentration range 20-2000 pg/mL (r2 = 0.999). Intraday and interday coefficients of variation were < 6% and < 13%, respectively. This procedure has been applied to quality-control specimens and LSD-positive samples in this laboratory. Comparisons with alternate GC-MS methods and extraction procedures are discussed.

Composite scintillators for detection of ionizing radiation

DOEpatents

Dai, Sheng [Knoxville, TN; Stephan, Andrew Curtis [Knoxville, TN; Brown, Suree S [Knoxville, TN; Wallace, Steven A [Knoxville, TN; Rondinone, Adam J [Knoxville, TN

2010-12-28

Applicant's present invention is a composite scintillator having enhanced transparency for detecting ionizing radiation comprising a material having optical transparency wherein said material comprises nano-sized objects having a size in at least one dimension that is less than the wavelength of light emitted by the composite scintillator wherein the composite scintillator is designed to have selected properties suitable for a particular application.

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

NASA Astrophysics Data System (ADS)

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

1993-12-01

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

Easy ambient sonic-spray ionization mass spectrometry combined with thin-layer chromatography.

PubMed

Haddad, Renato; Milagre, Humberto M S; Catharino, Rodrigo Ramos; Eberlin, Marcos N

2008-04-15

On-spot detection and analyte characterization on thin-layer chromatography (TLC) plates is performed via ambient desorption/ionization and (tandem) mass spectrometry detection, that is, via easy ambient sonic spray ionization mass spectrometry (EASI-MS). As proof-of-principle cases, mixtures of semipolar nitrogenated compounds as well as pharmaceutical drugs and vegetable oils have been tested. The technique has also been applied to monitor a chemical reaction of synthetic importance. EASI is the simplest and gentlest ambient ionization technique currently available, assisted solely by N2 (or air). It uses no voltages, no electrical discharges; no UV or laser beams, and no high temperature and is most easily implemented in all API mass spectrometers. TLC is also the simplest, fastest, and most easily performed chromatographic technique. TLC plus EASI-MS therefore provide a simple and advantageous combination of chromatographic separation and sensitive detection of the TLC spots as well as on-spot MS or MS/MS characterization. The favorable characteristics of TLC-EASI-MS indicate advantageous applications in several areas such as drug and oil analysis, phytochemistry and synthetic chemistry, forensics via reliable counterfeit detection, and quality control.

Authenticity analysis of pear juice employing chromatographic fingerprinting.

PubMed

Willems, Jamie L; Low, Nicholas H

2014-12-03

Pear juice is predominately composed of carbohydrates/polyols (>95% of the total soluble solids), making it susceptible to adulteration by the addition of less expensive commercial sweeteners. In this research, the major carbohydrate and polyol (fructose, glucose, sucrose, and sorbitol) content of 32 pure pear juices representing five world producing regions and three years of production was determined. Additionally, methods employing oligosaccharide profiling to detect the debasing of these samples with four commercial sweeteners (HFCS 55 and 90, TIS, and HIS) were developed using capillary gas chromatography with flame ionization detection (CGC-FID) and high-performance liquid chromatography with pulsed amperometric detection (HPAE-PAD). Detection limits for the four commercial sweeteners ranged from 0.5 to 5.0% (v/v). In addition, the developed CGC-FID method could be used to (a) detect the addition of pear to apple juice via arbutin detection and (b) determine if a pear juice was produced using enzymatic liquefaction via the presence of O-β-d-glucopyranosyl-(1→4)-d-glucopyranose (cellobiose), all within a single chromatographic analysis.

Seasonal variation of gastroprotective terpenoids in Maytenus robusta (Celastraceae) quantified by gas chromatography-flame ionization detection (GC-FID).

PubMed

Zermiani, Tailyn; Junior, Antonio A S; Ferreira, Renê A; Wagner, Theodoro M; Machado, Marina S; Cechinel-Filho, Valdir; Niero, Rivaldo

2016-11-01

The triterpenes friedelin (1), β-friedelinol (2) and 3,15-dioxo-21α-hydroxyfriedelane (3) in the aerial parts of Maytenus robusta, a Brazilian medicinal plant with antiulcer potential, were seasonally quantified by gas chromatography flame-ionization detection (GC-FID) using an external standard. The method was found to be linear, precise and sensitive. Compounds 1 and 2 were found in M. robusta leaves and branches, with highest concentrations in the leaves collected in autumn, i.e. 3.21 ± 0.16 and 12.60 ± 1.49 mg g-1 dry weight of 1 and 2, respectively. On the other hand, compound 3 was found only in the branches, with the highest concentrations in winter and autumn (0.21 ± 0.01 and 0.20 ± 0.02 mg g-1). The results allow to define the optimal season and plant parts for the collection of M. robusta as a phytotherapeutic drug.

Crosslinking of polysaccharides in room temperature ionic liquids by ionizing radiation

NASA Astrophysics Data System (ADS)

Kimura, Atsushi; Nagasawa, Naotsugu; Shimada, Akihiko; Taguchi, Mitsumasa

2016-07-01

Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis. Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations, and its gel fraction increased with the dose and reached 86% at 60 kGy.

Detection of bacteria from biological mixtures using immunomagnetic separation combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

USGS Publications Warehouse

Madonna, A.J.; Basile, F.; Furlong, E.; Voorhees, K.J.

2001-01-01

A rapid method for identifying specific bacteria from complex biological mixtures using immunomagnetic separation coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been developed. The technique employs commercially available magnetic beads coated with polycolonal antibodies raised against specific bacteria and whole cell analysis by MALDI-MS. A suspension of a bacterial mixture is mixed with the immunomagnetic beads specific for the target microorganism. After a short incubation period (20 mins) the bacteria captured by the beads are washed, resuspended in deionized H2O and directly applied onto a MALDI probe. Liquid suspensions containing bacterial mixtures can be screened within 1 h total analysis time. Positive tests result in the production of a fingerprint mass spectrum primarily consisting of protein biomarkers characteristic of the targeted microorganism. Using this procedure, Salmonella choleraesuis was isolated and detected from standard bacterial mixtures and spiked samples of river water, human urine, and chicken blood. Copyright ?? 2001 John Wiley & Sons, Ltd.

Sensitivity enhancement for nitrophenols using cationic surfactant-modified activated carbon for solid-phase extraction surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Chen, Y C; Tsai, M F

2000-01-01

Previous work has demonstrated that a combination of solid-phase extraction with surface-assisted laser desorption/ionization (SPE-SALDI) mass spectrometry can be applied to the determination of trace nitrophenols in water. An improved method to lower the detection limit of this hyphenated technique is described in this present study. Activated carbon powder is used as both the SPE adsorbent and the SALDI solid in the analysis by SPE-SALDI. The surface of the activated carbon is modified by passing an aqueous solution of a cationic surfactant through the SPE cartridge. The results demonstrate that the sensitivity for nitrophenols in the analysis by SPE-SALDI can be improved by using cationic surfactants to modify the surface of the activated carbon. The detection limit for nitrophenols is about 25 ppt based on a signal-to-noise ratio of 3 by sampling from 100 mL of solution. Copyright 2000 John Wiley & Sons, Ltd.

Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

PubMed

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

2016-04-01

The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.

Influence of Culture Media on Detection of Carbapenem Hydrolysis by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

PubMed

Ramos, Ana Carolina; Carvalhaes, Cecília Godoy; Cordeiro-Moura, Jhonatha Rodrigo; Rockstroh, Anna Carolina; Machado, Antonia Maria Oliveira; Gales, Ana Cristina

2016-07-01

In this study, we evaluated the influence of distinct bacterial growth media on detection of carbapenemase hydrolysis by matrix-assisted laser desorption ionization-time of flight mass spectrometry. False-negative results were observed for OXA-25-, OXA-26-, and OXA-72-producing Acinetobacter baumannii isolates grown on MacConkey agar medium. The other culture media showed 100% sensitivity and 100% specificity for detecting carbapenemase. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

PubMed

Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

2012-06-04

Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry. Copyright © 2012 Elsevier B.V. All rights reserved.

Improving low-level plasma protein mass spectrometry-based detection for candidate biomarker discovery and validation

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

Page, Jason S.; Kelly, Ryan T.; Camp, David G.

2008-09-01

Methods. To improve the detection of low abundance protein candidate biomarker discovery and validation, particularly in complex biological fluids such as blood plasma, increased sensitivity is desired using mass spectrometry (MS)-based instrumentation. A key current limitation on the sensitivity of electrospray ionization (ESI) MS is due to the fact that many sample molecules in solution are never ionized, and the vast majority of the ions that are created are lost during transmission from atmospheric pressure to the low pressure region of the mass analyzer. Two key technologies, multi-nanoelectrospray emitters and the electrodynamic ion funnel have recently been developed and refinedmore » at Pacific Northwest National Laboratory (PNNL) to greatly improve the ionization and transmission efficiency of ESI MS based analyses. Multi-emitter based ESI enables the flow from a single source (typically a liquid chromatography [LC] column) to be divided among an array of emitters (Figure 1). The flow rate delivered to each emitter is thus reduced, allowing the well-documented benefits of nanoelectrospray 1 for both sensitivity and quantitation to be realized for higher flow rate separations. To complement the increased ionization efficiency afforded by multi-ESI, tandem electrodynamic ion funnels have also been developed at PNNL, and shown to greatly improve ion transmission efficiency in the ion source interface.2, 3 These technologies have been integrated into a triple quadrupole mass spectrometer for multiple reaction monitoring (MRM) of probable biomarker candidates in blood plasma and show promise for the identification of new species even at low level concentrations.« less

Non-volatile analysis in fruits by laser resonant ionization spectrometry: application to resveratrol (3,5,4'-trihydroxystilbene) in grapes

NASA Astrophysics Data System (ADS)

Montero, C.; Orea, J. M.; Soledad Muñoz, M.; Lobo, R. F. M.; González Ureña, A.

A laser desorption (LD) coupled with resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass spectrometry (TOFMS) technique for non-volatile trace analysis compounds is presented. Essential features are: (a) an enhanced desorption yield due to the mixing of metal powder with the analyte in the sample preparation, (b) a high resolution, great sensitivity and low detection limit due to laser resonant ionisation and mass spectrometry detection. Application to resveratrol content in grapes demonstrated the capability of the analytical method with a sensitivity of 0.2 pg per single laser shot and a detection limit of 5 ppb.

Direct Detection of Fungal Siderophores on Bats with White-Nose Syndrome via Fluorescence Microscopy-Guided Ambient Ionization Mass Spectrometry

PubMed Central

Mascuch, Samantha J.; Moree, Wilna J.; Hsu, Cheng-Chih; Turner, Gregory G.; Cheng, Tina L.; Blehert, David S.; Kilpatrick, A. Marm; Frick, Winifred F.; Meehan, Michael J.; Dorrestein, Pieter C.; Gerwick, Lena

2015-01-01

White-nose syndrome (WNS) caused by the pathogenic fungus Pseudogymnoascus destructans is decimating the populations of several hibernating North American bat species. Little is known about the molecular interplay between pathogen and host in this disease. Fluorescence microscopy ambient ionization mass spectrometry was used to generate metabolic profiles from the wings of both healthy and diseased bats of the genus Myotis. Fungal siderophores, molecules that scavenge iron from the environment, were detected on the wings of bats with WNS, but not on healthy bats. This work is among the first examples in which microbial molecules are directly detected from an infected host and highlights the ability of atmospheric ionization methodologies to provide direct molecular insight into infection. PMID:25781976

Direct detection of fungal siderophores on bats with white-nose syndrome via fluorescence microscopy-guided ambient ionization mass spectrometry

USGS Publications Warehouse

Mascuch, Samantha J.; Moree, Wilna J.; Cheng-Chih Hsu, Cheng-Chih; Turner, Gregory G.; Cheng, Tina L.; Blehert, David S.; Kilpatrick, A. Marm; Frick, Winifred F.; Meehan, Michael J.; Dorrestein, Pieter C.; Gerwick, Lena

2015-01-01

White-nose syndrome (WNS) caused by the pathogenic fungus Pseudogymnoascus destructans is decimating the populations of several hibernating North American bat species. Little is known about the molecular interplay between pathogen and host in this disease. Fluorescence microscopy ambient ionization mass spectrometry was used to generate metabolic profiles from the wings of both healthy and diseased bats of the genus Myotis. Fungal siderophores, molecules that scavenge iron from the environment, were detected on the wings of bats with WNS, but not on healthy bats. This work is among the first examples in which microbial molecules are directly detected from an infected host and highlights the ability of atmospheric ionization methodologies to provide direct molecular insight into infection.

First Detections of the [NII] 122 Micrometer Line at High Redshift: Demonstrating the Utility of the Line for Studying Galaxies in the Early Universe

NASA Technical Reports Server (NTRS)

Ferkinhoff, Carl; Brisbin, Drew; Nikola, Thomas; Parshley, Stephen C.; Stacey, Gordon J.; Phillips, Thomas G.; Falgarone, Edith; Benford, Dominic J.; Staguhn, Johannes G.; Tucker, Carol E.

2011-01-01

We report the first detections of the [NIl] 122 {\\mu} m line from a high redshift galaxy. The line was strongly (> 6{\\sigma}) detected from SMMJ02399-0136, and HI413+ 117 (the Cloverleaf QSO) using the Redshift(z) and Early Universe Spectrometer (ZEUS) on the CSO. The lines from both sources are quite bright with line-to-FIR continuum luminosity ratios that are approx.7.0x10(exp -4) (Cloverleaf) and 2.1x10(exp -3) (SMMJ02399). With ratios 2-10 times larger than the average value for nearby galaxies, neither source exhibits the line-to-continuum deficits seen in nearby sources. The line strengths also indicate large ionized gas fractions, approx.8 to 17% of the molecular gas mass. The [OIII]/[NII] line ratio is very sensitive to the effective temperature of ionizing stars and the ionization parameter for emission arising in the narrow-line region (NLR) of an AGN. Using our previous detection of the [01II] 88 {\\mu}m line, the [OIII]/ [NIl] line ratio for SMMJ02399-0136 indicates the dominant source of the line emission is either stellar HII regions ionized by 09.5 stars, or the NLR of the AGN with ionization parameter 10g(U) = -3.3 to -4.0. A composite system, where 30 to 50% of the FIR lines arise in the NLR also matches the data. The Cloverleaf is best modeled by a superposition of approx.200 M82like starbursts accounting for all of the FIR emission and 43% of the [NIl] line. The remainder may come from the NLR. This work demonstrates the utility of the [NIl] and [OIII] lines in constraining properties of the ionized medium.

A Comparison of Tissue Spray and Lipid Extract Direct Injection Electrospray Ionization Mass Spectrometry for the Differentiation of Eutopic and Ectopic Endometrial Tissues

NASA Astrophysics Data System (ADS)

Chagovets, Vitaliy; Wang, Zhihao; Kononikhin, Alexey; Starodubtseva, Natalia; Borisova, Anna; Salimova, Dinara; Popov, Igor; Kozachenko, Andrey; Chingin, Konstantin; Chen, Huanwen; Frankevich, Vladimir; Adamyan, Leila; Sukhikh, Gennady

2018-02-01

Recent research revealed that tissue spray mass spectrometry enables rapid molecular profiling of biological tissues, which is of great importance for the search of disease biomarkers as well as for online surgery control. However, the payback for the high speed of analysis in tissue spray analysis is the generally lower chemical sensitivity compared with the traditional approach based on the offline chemical extraction and electrospray ionization mass spectrometry detection. In this study, high resolution mass spectrometry analysis of endometrium tissues of different localizations obtained using direct tissue spray mass spectrometry in positive ion mode is compared with the results of electrospray ionization analysis of lipid extracts. Identified features in both cases belong to three lipid classes: phosphatidylcholines, phosphoethanolamines, and sphingomyelins. Lipids coverage is validated by hydrophilic interaction liquid chromatography with mass spectrometry of lipid extracts. Multivariate analysis of data from both methods reveals satisfactory differentiation of eutopic and ectopic endometrium tissues. Overall, our results indicate that the chemical information provided by tissue spray ionization is sufficient to allow differentiation of endometrial tissues by localization with similar reliability but higher speed than in the traditional approach relying on offline extraction.

SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

PubMed

Klink, Dennis; Schmitz, Oliver Johannes

2016-01-05

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

Method and apparatus to monitor a beam of ionizing radiation

DOEpatents

Blackburn, Brandon W.; Chichester, David L.; Watson, Scott M.; Johnson, James T.; Kinlaw, Mathew T.

2015-06-02

Methods and apparatus to capture images of fluorescence generated by ionizing radiation and determine a position of a beam of ionizing radiation generating the fluorescence from the captured images. In one embodiment, the fluorescence is the result of ionization and recombination of nitrogen in air.

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

Lipidomic analysis of glycerolipid and cholesteryl ester autooxidation products.

PubMed

Kuksis, Arnis; Suomela, Jukka-Pekka; Tarvainen, Marko; Kallio, Heikki

2009-06-01

Thin-layer chromatography (TLC), gas chromatography (GC), and liquid chromatography (LC) in combination with mass spectrometry (MS) have been adopted for the isolation and identification of oxolipids and for determining their functionality. TLC provides a rapid separation and access to most oxolipids as intact molecules and has recently been effectively interfaced with time-of-flight (TOF) MS (TOF-MS). GC with flame ionization (FI) (GC/FI) and electron impact (EI) MS (GC/EI-MS) has been extensively utilized in the analysis of isoprostanes and other low-molecular-weight oxolipids, although these methods require derivatization of the analytes. In contrast, LC with ultraviolet (UV) absorption (LC/UV) or evaporate light scattering detection (ELSD) (LC/ELSD) as well as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) MS (LC/ESI-MS) or LC/APCI-MS has proven to be well suited for the analysis of intact oxolipids and their conjugates without or with minimal derivatization. Nevertheless, kit-based colorimetric and fluorescent procedures continue to serve as sensitive indicators of the presence of hydroperoxides and aldehydes.

DMSO Assisted Electrospray Ionization for the Detection of Small Peptide Hormones in Urine by Dilute-and-Shoot-Liquid-Chromatography-High Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Judák, Péter; Grainger, Janelle; Goebel, Catrin; Van Eenoo, Peter; Deventer, Koen

2017-08-01

The mobile phase additive (DMSO) has been described as a useful tool to enhance electrospray ionization (ESI) of peptides and proteins. So far, this technique has mainly been used in proteomic/peptide research, and its applicability in a routine clinical laboratory setting (i.e., doping control analysis) has not been described yet. This work provides a simple, easy to implement screening method for the detection of doping relevant small peptides (GHRPs, GnRHs, GHS, and vasopressin-analogues) with molecular weight less than 2 kDa applying DMSO in the mobile phase. The gain in sensitivity was sufficient to inject the urine samples after a 2-fold dilution step omitting a time consuming sample preparation. The employed analytical procedure was validated for the qualitative determination of 36 compounds, including 13 metabolites. The detection limits (LODs) ranged between 50 and 1000 pg/mL and were compliant with the 2 ng/mL minimum detection level required by the World Anti-Doping Agency (WADA) for all the target peptides. To demonstrate the feasibility of the work, urine samples obtained from patients who have been treated with desmopressin or leuprolide and urine samples that have been declared as adverse analytical findings were analyzed.

Lyman-continuum leakage as dominant source of diffuse ionized gas in the Antennae galaxy

NASA Astrophysics Data System (ADS)

Weilbacher, Peter M.; Monreal-Ibero, Ana; Verhamme, Anne; Sandin, Christer; Steinmetz, Matthias; Kollatschny, Wolfram; Krajnović, Davor; Kamann, Sebastian; Roth, Martin M.; Erroz-Ferrer, Santiago; Marino, Raffaella Anna; Maseda, Michael V.; Wendt, Martin; Bacon, Roland; Dreizler, Stefan; Richard, Johan; Wisotzki, Lutz

2018-04-01

The Antennae galaxy (NGC 4038/39) is the closest major interacting galaxy system and is therefore often studied as a merger prototype. We present the first comprehensive integral field spectroscopic dataset of this system, observed with the MUSE instrument at the ESO VLT. We cover the two regions in this system which exhibit recent star formation: the central galaxy interaction and a region near the tip of the southern tidal tail. In these fields, we detect HII regions and diffuse ionized gas to unprecedented depth. About 15% of the ionized gas was undetected by previous observing campaigns. This newly detected faint ionized gas is visible everywhere around the central merger, and shows filamentary structure. We estimate diffuse gas fractions of about 60% in the central field and 10% in the southern region. We are able to show that the southern region contains a significantly different population of HII regions, showing fainter luminosities. By comparing HII region luminosities with the HST catalog of young star clusters in the central field, we estimate that there is enough Lyman-continuum leakage in the merger to explain the amount of diffuse ionized gas that we detect. We compare the Lyman-continuum escape fraction of each HII region against emission line ratios that are sensitive to the ionization parameter. While we find no systematic trend between these properties, the most extreme line ratios seem to be strong indicators of density bounded ionization. Extrapolating the Lyman-continuum escape fractions to the southern region, we conclude that simply from the comparison of the young stellar populations to the ionized gas there is no need to invoke other ionization mechanisms than Lyman-continuum leaking HII regions for the diffuse ionized gas in the Antennae. FITS images and Table of HII regions are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/611/A95 and at http://muse-vlt.eu/science/antennae/

Impact desolvation of electrosprayed microdroplets--a new ionization method for mass spectrometry of large biomolecules.

PubMed

Aksyonov, S A; Williams, P

2001-01-01

Impact desolvation of electrosprayed microdroplets (IDEM) is a new method for producing gas-phase ions of large biomolecules. Analytes are dissolved in an electrolyte solution which is electrosprayed in vacuum, producing highly charged micron and sub-micron sized droplets (microdroplets). These microdroplets are accelerated through potential differences approximately 5 - 10 kV to velocities of several km/s and allowed to impact a target surface. The energetic impacts vaporize the droplets and release desolvated gas-phase ions of the analyte molecules. Oligonucleotides (2- to 12-mer) and peptides (bradykinin, neurotensin) yield singly and doubly charged molecular ions with no detectable fragmentation. Because the extent of multiple charging is significantly less than in atmospheric pressure electrospray ionization, and the method produces ions largely free of adducts from solutions of high ionic strength, IDEM has some promise as a method for coupling to liquid chromatographic techniques and for mixture analysis. Ions are produced in vacuum at a flat equipotential surface, potentially allowing efficient ion extraction. Copyright 2001 John Wiley & Sons, Ltd.

Rapid Detection and Identification of Candidemia by Direct Blood Culturing on Solid Medium by Use of Lysis-Centrifugation Method Combined with Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS).

PubMed

Idelevich, Evgeny A; Grünastel, Barbara; Becker, Karsten

2017-01-01

Candida sepsis is a life-threatening condition with increasing prevalence. In this study, direct blood culturing on solid medium using a lysis-centrifugation procedure enabled successful Candida species identification by matrix-assisted laser desorption-ionization time of flight mass spectrometry on average 3.8 h (Sabouraud agar) or 7.4 h (chocolate agar) before the positivity signal for control samples in Bactec mycosis-IC/F or Bactec Plus aerobic/F bottles, respectively. Direct culturing on solid medium accelerated candidemia diagnostics compared to that with automated broth-based systems. Copyright © 2016 American Society for Microbiology.

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

Development of an iterative reconstruction method to overcome 2D detector low resolution limitations in MLC leaf position error detection for 3D dose verification in IMRT.

PubMed

Visser, R; Godart, J; Wauben, D J L; Langendijk, J A; Van't Veld, A A; Korevaar, E W

2016-05-21

The objective of this study was to introduce a new iterative method to reconstruct multi leaf collimator (MLC) positions based on low resolution ionization detector array measurements and to evaluate its error detection performance. The iterative reconstruction method consists of a fluence model, a detector model and an optimizer. Expected detector response was calculated using a radiotherapy treatment plan in combination with the fluence model and detector model. MLC leaf positions were reconstructed by minimizing differences between expected and measured detector response. The iterative reconstruction method was evaluated for an Elekta SLi with 10.0 mm MLC leafs in combination with the COMPASS system and the MatriXX Evolution (IBA Dosimetry) detector with a spacing of 7.62 mm. The detector was positioned in such a way that each leaf pair of the MLC was aligned with one row of ionization chambers. Known leaf displacements were introduced in various field geometries ranging from  -10.0 mm to 10.0 mm. Error detection performance was tested for MLC leaf position dependency relative to the detector position, gantry angle dependency, monitor unit dependency, and for ten clinical intensity modulated radiotherapy (IMRT) treatment beams. For one clinical head and neck IMRT treatment beam, influence of the iterative reconstruction method on existing 3D dose reconstruction artifacts was evaluated. The described iterative reconstruction method was capable of individual MLC leaf position reconstruction with millimeter accuracy, independent of the relative detector position within the range of clinically applied MU's for IMRT. Dose reconstruction artifacts in a clinical IMRT treatment beam were considerably reduced as compared to the current dose verification procedure. The iterative reconstruction method allows high accuracy 3D dose verification by including actual MLC leaf positions reconstructed from low resolution 2D measurements.

Broad-range PCR coupled with mass-spectrometry for the detection of Mycobacterium tuberculosis drug resistance

PubMed Central

Florea, Dragoş; Oţelea, Dan; Olaru, Ioana D.; Hristea, Adriana

2016-01-01

Background The need to limit the spread of drug-resistant Mycobacterium tuberculosis requires rapid detection of resistant strains. The present study aimed to evaluate a commercial assay using broad-range PCR coupled with electrospray ionization mass spectrometry (PCR/ESI-MS) for the rapid detection of isoniazid (INH) and rifampin (RIF) resistance in M. tuberculosis strains isolated from Romanian patients with pulmonary tuberculosis. Methods PCR/ESI-MS was used to detect genotypic resistance to RIF and INH in a panel of 63 M. tuberculosis isolates phenotypically characterized using the absolute concentration method on Löwenstein-Jensen medium. Results Thirty-eight (60%) strains were susceptible to both drugs, 22 (35%) were RIF and INH resistant, one was INH mono-resistant and two were RIF mono-resistant. The sensitivity for INH and RIF resistance mutations detection were 100% and 92% respectively, with a specificity of more than 95% for each drug. Conclusion PCR/ESI-MS is a good method for the detection of RIF and INH resistance and might represent an alternative to other rapid diagnostic tests for the detection of genetic markers of resistance in M. tuberculosis isolates. PMID:27019827

Matrix Assisted Ionization Vacuum (MAIV), a New Ionization Method for Biological Materials Analysis Using Mass Spectrometry*

PubMed Central

Inutan, Ellen D.; Trimpin, Sarah

2013-01-01

The introduction of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) for the mass spectrometric analysis of peptides and proteins had a dramatic impact on biological science. We now report that a wide variety of compounds, including peptides, proteins, and protein complexes, are transported directly from a solid-state small molecule matrix to gas-phase ions when placed into the vacuum of a mass spectrometer without the use of high voltage, a laser, or added heat. This ionization process produces ions having charge states similar to ESI, making the method applicable for high performance mass spectrometers designed for atmospheric pressure ionization. We demonstrate highly sensitive ionization using intermediate pressure MALDI and modified ESI sources. This matrix and vacuum assisted soft ionization method is suitable for the direct surface analysis of biological materials, including tissue, via mass spectrometry. PMID:23242551

Graphene oxide-based dispersive micro-solid phase extraction for separation and preconcentration of nicotine from biological and environmental water samples followed by gas chromatography-flame ionization detection.

PubMed

Mahpishanian, Shokouh; Sereshti, Hassan

2014-12-01

Graphene oxide (GO) has showed great potential to use as an adsorbent in sample preparation procedures. In this research, GO was used as an effective adsorbent in a simple GO-based dispersive micro-solid phase extraction (GO-D-µ-SPE) method for isolation and preconcentration of nicotine prior to gas chromatography-flame ionization detection (GC-FID). The prepared GO was characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), thermogravimetric analysis/differential thermal analysis (TGA/DTA), and ultraviolet-visible (UV-vis) absorption spectroscopy techniques. Various experimental parameters affecting the extraction recovery, including the amount of GO, extraction time, pH of the sample solution, salt concentration, and desorption conditions were investigated and optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 5-2000 ng mL(-1) with a determination coefficient of 0.9987. The limit of detection (LOD) of the method at a signal to noise ratio of 3 was 1.5 ng mL(-1). The linearity was in the concentration range of 5-2000 ng mL(-1) with a determination coefficient of 0.9987. Intraday and inter-day precisions were obtained equal to 2.7% and 5.2%, respectively. The method was successfully applied to the nicotine analysis in biological and water samples with the recoveries in the range of 88.7-109.7%. Copyright © 2014 Elsevier B.V. All rights reserved.

Short-lived Rn-222 daughters in cryogenic liquids

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

Pelczar, Krzysztof; Frodyma, Nikodem; Wójcik, Marcin

In this paper a detection method of α emitters from {sup 222}Rn decay chain, present in cryogenic liquids, using bare Si-PIN diodes immersed in the liquids is presented. Properties of ionized {sup 222}Rn daughters deduced from conducted measurements are outlined. Life-time of positive ions was found to be of the order of 10 s, and nonzero content of electronegative ions was observed.

Development of a fast screening and confirmatory method by liquid chromatography-quadrupole-time-of-flight mass spectrometry for glucuronide-conjugated methyltestosterone metabolite in tilapia.

PubMed

Amarasinghe, Kande; Chu, Pak-Sin; Evans, Eric; Reimschuessel, Renate; Hasbrouck, Nicholas; Jayasuriya, Hiranthi

2012-05-23

This paper describes the development of a fast method to screen and confirm methyltestosterone 17-O-glucuronide (MT-glu) in tilapia bile. The method consists of solid-phase extraction (SPE) followed by high-performance liquid chromatography-mass spectrometry. The system used was an Agilent 6530 Q-TOF with an Agilent Jet stream electrospray ionization interface. The glucuronide detected in the bile was characterized as MT-glu by comparison with a chemically synthesized standard. MT-glu was detected in bile for up to 7 days after dosing. Semiquantification was done with matrix-matched calibration curves, because MT-glu showed signal suppression due to matrix effects. This method provides a suitable tool to monitor the illegal use of methyltestosterone in tilapia culture.

Identification of Three Kinds of Citri Reticulatae Pericarpium Based on Deoxyribonucleic Acid Barcoding and High-performance Liquid Chromatography-diode Array Detection-electrospray Ionization/Mass Spectrometry/Mass Spectrometry Combined with Chemometric Analysis

PubMed Central

Yu, Xiaoxue; Zhang, Yafeng; Wang, Dongmei; Jiang, Lin; Xu, Xinjun

2018-01-01

Background: Citri Reticulatae Pericarpium is the dried mature pericarp of Citrus reticulata Blanco which can be divided into “Chenpi” and “Guangchenpi.” “Guangchenpi” is the genuine Chinese medicinal material in Xinhui, Guangdong province; based on the greatest quality and least amount, it is most expensive among others. Hesperidin is used as the marker to identify Citri Reticulatae Pericarpium described in the Chinese Pharmacopoeia 2010. However, both “Chenpi” and “Guangchenpi” contain hesperidin so that it is impossible to differentiate them by measuring hesperidin. Objective: Our study aims to develop an efficient and accurate method to separate and identify “Guangchenpi” from other Citri Reticulatae Pericarpium. Materials and Methods: The genomic deoxyribonucleic acid (DNA) of all the materials was extracted and then the internal transcribed spacer 2 was amplified, sequenced, aligned, and analyzed. The secondary structures were created in terms of the database and website established by Jörg Schultz et al. High-performance liquid chromatography-diode array detection-electrospray Ionization/mass spectrometry (HPLC-DAD-ESI-MS)/MS coupled with chemometric analysis was applied to compare the differences in chemical profiles of the three kinds of Citri Reticulatae Pericarpium. Results: A total of 22 samples were classified into three groups. The results of DNA barcoding were in accordance with principal component analysis and hierarchical cluster analysis. Eight compounds were deduced from HPLC-DAD-ESI-MS/MS. Conclusions: This method is a reliable and effective tool to differentiate the three Citri Reticulatae Pericarpium. SUMMARY The internal transcribed spacer 2 regions and the secondary structure among three kinds of Citri Reticulatae Pericarpium varied considerablyAll the 22 samples were analyzed by high-performance liquid chromatography (HPLC) to obtain the chemical profilesPrincipal component analysis and hierarchical cluster analysis were used in the chemometric analysisdeoxyribonucleic acid barcoding and HPLC-diode array detection-electrospray ionization/mass spectrometry/MS coupled with chemometric analysis provided an accurate and strong proof to identify these three herbs. Abbreviations used: CTAB: Hexadecyltrimethylammonium bromide, DNA: Deoxyribonucleic acid, ITS2: Internal transcribed spacer 2, PCR: Polymerase chain reaction. PMID:29576703

Metal oxide nanoparticles for latent fingerprint visualization and analysis of small drug molecules using surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Amin, Mohamed O; Madkour, Metwally; Al-Hetlani, Entesar

2018-05-17

We explored the applicability of different metal oxide nanoparticles (NPs; ZnO, TiO 2 , Fe 2 O 3 , and CeO 2 ) for the optical imaging and mass spectrometric determination of small drug molecules in latent fingerprints (LFPs). Optical imaging was achieved using a dry method-simply dusting the LFPs with a minute amount of NP powder-and still images were captured using a digital microscope and a smartphone camera. Mass spectrometric determination was performed using the NPs as substrates for surface-assisted laser desorption ionization/mass spectrometry (SALDI-MS), which enabled the detection of small drug molecules with high signal intensities. The reproducibility of the results was studied by calculating the % error, SD, and RSD in the results obtained with the various metal oxide NPs. Collectively, the findings showed that using NPs can boost the intensity of the detected signal while minimizing background noise which is an issue predominantly associated with conventional organic matrices of MALDI-MS. Among the four metal oxide NPs, utilization of the Fe 2 O 3 NPs led to the best SALDI performance and the highest detection sensitivity for the analytes of interest. The study was then extended by investigating the influence of time elapsed since the generation of the LFP on the detection of drug molecules in the LFP. The results demonstrated that this method allows the analysis of drug molecules after as long as one week at low and intermediate temperatures (0 and 25 °C). Therefore, the SALDI analysis of small molecules using inorganic NPs, which can be implemented in forensic laboratories for screening and detection purposes, as a powerful alternative to the use of organic matrices. Graphical abstract ᅟ.

Ionization processes in combined high-voltage nanosecond - laser discharges in inert gas

NASA Astrophysics Data System (ADS)

Starikovskiy, Andrey; Shneider, Mikhail; PU Team

2016-09-01

Remote control of plasmas induced by laser radiation in the atmosphere is one of the challenging issues of free space communication, long-distance energy transmission, remote sensing of the atmosphere, and standoff detection of trace gases and bio-threat species. Sequences of laser pulses, as demonstrated by an extensive earlier work, offer an advantageous tool providing access to the control of air-plasma dynamics and optical interactions. The avalanche ionization induced in a pre-ionized region by infrared laser pulses where investigated. Pre-ionization was created by an ionization wave, initiated by high-voltage nanosecond pulse. Then, behind the front of ionization wave extra avalanche ionization was initiated by the focused infrared laser pulse. The experiment was carried out in argon. It is shown that the gas pre-ionization inhibits the laser spark generation under low pressure conditions.

Potential mapping with charged-particle beams

NASA Technical Reports Server (NTRS)

Robinson, J. W.; Tillery, D. G.

1979-01-01

Experimental methods of mapping the equipotential surfaces near some structure of interest rely on the detection of charged particles which have traversed the regions of interest and are detected remotely. One method is the measurement of ion energies for ions created at a point of interest and expelled from the region by the fields. The ion energy at the detector in eV corresponds to the potential where the ion was created. An ionizing beam forms the ions from background neutrals. The other method is to inject charged particles into the region of interest and to locate their exit points. A set of several trajectories becomes a data base for a systematic mapping technique. An iterative solution of a boundary value problem establishes concepts and limitations pertaining to the mapping problem.

Determination of CMPO using HPLC -UV

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

Gracy Elias; Gary S. Groenewold; Bruce J. Mincher

Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) is an extractant proposed for selective separation of radionuclide metals from used nuclear fuel solutions using solvent extraction. Radiolysis reactions can degrade CMPO and reduce separation performance and hence methods for measuring concentration of CMPO and identifying degradation products are needed. A novel high performance liquid chromatography (HPLC) method employing ultraviolet detection (UV) was developed to detect and quantitate CMPO in dodecane. Some radiolysis products in gamma and alpha irradiated CMPO solutions were identified using HPLC/electrospray ionization-mass spectrometry (ESI-MS). Validation data indicated that the HPLC-UV method for CMPO determination provided good linearity, sensitivity, procedure accuracy and systemmore » precision. CMPO-nitric acid complexes were also identified, that account for the apparent loss of CMPO in acidic environment, independent of irradiation.« less

Identification of process related trace level impurities in the actinide decorporation agent 3,4,3-LI(1,2-HOPO): Nozzle–skimmer fragmentation via ESI LC–QTOFMS

DOE PAGES

Panyala, Nagender R.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2014-08-12

We report that 3,4,3-LI(1,2-HOPO) is a chelating ligand and decorporation agent that can remove radioactive lanthanides and actinides from the body. Identification of trace impurities in drug samples is gaining much interest due to their significant influence on drug activity. In this study, trace impurities were detected in manufactured lots of 3,4,3-LI(1,2-HOPO) by a developed method of Liquid Chromatography coupled with photo-diode array UV detection and Electrospray Ionization-Quadrupole Time of Flight Mass spectrometry (LC-QTOFMS), via induced-in-source or collision-induced mass fragmentation (Nozzle-Skimmer Fragmentation). Molecular ions were fragmented within the nozzle-skimmer region of electrospray ionization (ESI) mass spectrometer equipped with a Timemore » of Flight detector. Eight major (detected at levels higher than a 0.1% threshold) and seven minor trace impurities were identified. The respective structures of these impurities were elucidated via analysis of the generated fragment ions using mass fragmentation and elemental composition software. Proposed structures of impurities were further confirmed via isotopic modeling.« less

A Mass Spectrometric Analysis Method Based on PPCA and SVM for Early Detection of Ovarian Cancer.

PubMed

Wu, Jiang; Ji, Yanju; Zhao, Ling; Ji, Mengying; Ye, Zhuang; Li, Suyi

2016-01-01

Background. Surfaced-enhanced laser desorption-ionization-time of flight mass spectrometry (SELDI-TOF-MS) technology plays an important role in the early diagnosis of ovarian cancer. However, the raw MS data is highly dimensional and redundant. Therefore, it is necessary to study rapid and accurate detection methods from the massive MS data. Methods. The clinical data set used in the experiments for early cancer detection consisted of 216 SELDI-TOF-MS samples. An MS analysis method based on probabilistic principal components analysis (PPCA) and support vector machine (SVM) was proposed and applied to the ovarian cancer early classification in the data set. Additionally, by the same data set, we also established a traditional PCA-SVM model. Finally we compared the two models in detection accuracy, specificity, and sensitivity. Results. Using independent training and testing experiments 10 times to evaluate the ovarian cancer detection models, the average prediction accuracy, sensitivity, and specificity of the PCA-SVM model were 83.34%, 82.70%, and 83.88%, respectively. In contrast, those of the PPCA-SVM model were 90.80%, 92.98%, and 88.97%, respectively. Conclusions. The PPCA-SVM model had better detection performance. And the model combined with the SELDI-TOF-MS technology had a prospect in early clinical detection and diagnosis of ovarian cancer.

Studies on laser-assisted Penning ionization by the optogalvanic effect in Ne/Eu hollow cathode discharge.

PubMed

Saini, V K; Kumar, P; Dixit, S K; Nakhe, S V

2015-02-01

Laser-assisted Penning ionization (LAPI) is detected in a Ne/Eu hollow cathode (HC) discharge lamp using the pulsed optogalvanic (OG) method. In the Ne/Eu discharge, doubly ionized europium excited energy levels Eu[4f(7)(P(7/2,5/2)6)] lie within the thermal limit (∼kT) from the laser-excited neon's energy level [2p(5)(P3/202)3p or 2p(8) (in Paschen notation)] lying at 149,848  cm(-1). Therefore, Penning ionization (PI) of europium atoms likely to occur into its highly excited ionic states is investigated. To probe the PI of europium, the temporal profiles of its counterpart neon OG signal are studied as a function of discharge current for the transitions (1s(4)→2p(8)) and (1s(2)→2p(2)), corresponding to 650.65 and 659.89 nm wavelengths, respectively. It is observed that PI of europium alters the overall discharge characteristics significantly and, hence, modifies the temporal profile of the OG signals accordingly. The quasi-resonant ionizing energy transfer collisions between laser-excited Ne 2p(8) atoms and electronically excited europium P(9/2)10 atoms are used to explain the LAPI mechanism. Such LAPI studies carried out in HC discharge could be useful for the discharge of a metal-vapor laser with appropriate Penning mixtures.

Superbasic alkyl-substituted bisphosphazene proton sponges: a new class of deprotonating matrices for negative ion matrix-assisted ionization/laser desorption mass spectrometry of low molecular weight hardly ionizable analytes.

PubMed

Calvano, C D; Cataldi, T R I; Kögel, J F; Monopoli, A; Palmisano, F; Sundermeyer, J

2016-07-30

Here hardly ionizable and low molecular weight compounds are detected in negative ion mode by using novel superbasic proton sponges based on 1,8-bisphosphazenylnaphthalene (PN) as MALDI matrices. Among the selected proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) has shown the best behaviour as matrix since it allows the direct detection of intact cholesterol without derivatization also in real challenging samples. Very weakly acidic compounds such as sterols, steroids, fatty alcohols and saccharides were detected in reflectron negative ion mode by a MALDI TOF/TOF system equipped with a neodymium-doped yttrium lithium fluoride (Nd:YLF) laser (345 nm) with typical mass accuracy of 10 ppm. MS/MS experiments were performed by using ambient air as the collision gas. Contrary to traditional MALDI matrices, superbasic proton sponges allowed the easy deprotonation of an alcohol functional group without a previous chemical derivatization step. Experimental evidence indicates that analyte deprotonation is achieved in the condensed phase, i.e. PN superbasic proton sponges operate according to a recently proposed model named matrix assisted ionization/laser desorption (MAILD). A detection limit of 3 pmol/spot of cholesterol (model compound) with a signal-to-noise ratio ≥ 10 was typically obtained. For the first time, the usefulness of novel superbasic proton sponges is demonstrated for MALDI detection of hardly ionizable compounds such as sterols, steroids, fatty alcohols and saccharides. The leading candidate TPPN has been successfully applied for negative ion MAILD-MS analysis of cholesterol, fatty acids and phospholipids in egg yolk and brain tissue extracts. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Deep Fabry-Perot Hα observations of two Sculptor group galaxies, NGC 247 and 300

NASA Astrophysics Data System (ADS)

Hlavacek-Larrondo, J.; Marcelin, M.; Epinat, B.; Carignan, C.; de Denus-Baillargeon, M.-M.; Daigle, O.; Hernandez, O.

2011-09-01

It has been suggested that diffuse ionized gas can extend all the way to the end of the H I disc, and even beyond, such as in the case of the warped galaxyNGC 253 (Bland-Hawthorn et al.). Detecting ionized gas at these radii could carry significant implications as to the distribution of dark matter in galaxies. With the aim of detecting this gas, we carried out a deep Hα kinematical analysis of two Sculptor group galaxies, NGC 247 and 300. The Fabry-Perot data were taken at the 36-cm Marseille Telescope in La Silla, Chile, offering a large field of view. With almost 20 hours of observations for each galaxy, very faint diffuse emission is detected. Typical emission measures of 0.1 cm-6 pc are reached. For NGC 247, emission extending up to a radius comparable with that of the H I disc (r˜ 13 arcmin) is found, but no emission is seen beyond the H I disc. For NGC 300, we detect ionized gas on the entirety of our field of view (rmax˜ 14 arcmin), and find that the bright H II regions are embedded in a diffuse background. Using the deep data, extended optical rotation curves are obtained, as well as mass models. These are the most extended optical rotation curves thus far for these galaxies. We find no evidence suggesting that NGC 247 has a warped disc, and to account for our non-detection of Hα emission beyond its H I disc, as opposed to the warped galaxy NGC 253, our results favour the model in which, only through a warp, ionization by hot young stars in the central region of a galaxy can let photons escape and ionize the interstellar medium in the outer parts.

Radial arrays of nano-electrospray ionization emitters and methods of forming electrosprays

DOEpatents

Kelly, Ryan T [West Richland, WA; Tang, Keqi [Richland, WA; Smith, Richard D [Richland, WA

2010-10-19

Electrospray ionization emitter arrays, as well as methods for forming electrosprays, are described. The arrays are characterized by a radial configuration of three or more nano-electrospray ionization emitters without an extractor electrode. The methods are characterized by distributing fluid flow of the liquid sample among three or more nano-electrospray ionization emitters, forming an electrospray at outlets of the emitters without utilizing an extractor electrode, and directing the electrosprays into an entrance to a mass spectrometry device. Each of the nano-electrospray ionization emitters can have a discrete channel for fluid flow. The nano-electrospray ionization emitters are circularly arranged such that each is shielded substantially equally from an electrospray-inducing electric field.

Conceptual study of a heavy-ion-ERDA spectrometer for energies below 6 MeV

NASA Astrophysics Data System (ADS)

Julin, Jaakko; Sajavaara, Timo

2017-09-01

Elastic recoil detection analysis (ERDA) is a well established technique and it offers unique capabilities in thin film analysis. Simultaneous detection and depth profiling of all elements, including hydrogen, is possible only with time-of-flight ERDA. Bragg ionization chambers or ΔE - E detectors can also be used to identify the recoiling element if sufficiently high energies are used. The chief limitations of time-of-flight ERDA are the beam induced sample damage and the requirement of a relatively large accelerator. In this paper we propose a detector setup, which could be used with 3 MeV to 6 MeV medium heavy beams from either a single ended accelerator (40Ar) or from a tandem accelerator (39K). The detector setup consists of two timing detectors and a gas ionization chamber energy detector. Compared to use of very heavy low energy ions the hydrogen recoils with this beam have sufficient energy to be detected with current gas ionization chamber energy detector. To reduce the beam induced damage the proposed detector setup covers a solid angle larger than 1 msr, roughly an order of magnitude improvement over most time-of-flight ERDA setups. The setup could be used together with a small accelerator to be used for light element analysis of approximately 50 nm films. The concept is tested with 39K beam from a 1.7 MV Pelletron tandem accelerator with the Jyväskylä ToF-ERDA setup. In addition to the measurements effects related to low energies and increase in the solid angle are simulated with Monte Carlo methods.

Bayesian Integration and Characterization of Composition C-4 Plastic Explosives Based on Time-of-Flight Secondary Ion Mass Spectrometry and Laser Ablation-Inductively Coupled Plasma Mass Spectrometry

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

Mahoney, Christine M.; Kelly, Ryan T.; Alexander, M. L.

Key elements regarding the use of non-radioactive ionization sources will be presented as related to explosives detection by mass spectrometry and ion mobility spectrometry. Various non-radioactive ionization sources will be discussed along with associated ionization mechanisms pertaining to specific sample types.

Detection of Staphylococcus aureus by functional gold nanoparticle-based affinity surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Lai, Hong-Zheng; Wang, Sin-Ge; Wu, Ching-Yi; Chen, Yu-Chie

2015-02-17

Staphylococcus aureus is one of the common pathogenic bacteria responsible for bacterial infectious diseases and food poisoning. This study presents an analytical method based on the affinity nanoprobe-based mass spectrometry that enables detection of S. aureus in aqueous samples. A peptide aptamer DVFLGDVFLGDEC (DD) that can recognize S. aureus and methicillin-resistant S. aureus (MRSA) was used as the reducing agent and protective group to generate DD-immobilized gold nanoparticles (AuNPs@DD) from one-pot reactions. The thiol group from cysteine in the peptide aptamer, i.e., DD, can interact with gold ions to generate DD-immobilized AuNPs in an alkaline solution. The generated AuNPs@DD has an absorption maximum at ∼518 nm. The average particle size is 7.6 ± 1.2 nm. Furthermore, the generated AuNPs@DD can selectively bind with S. aureus and MRSA. The conjugates of the target bacteria with AuNPs were directly analyzed by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). The gold ions generated from the AuNPs@DD anchored on the target bacteria were monitored. Gold ions (m/z 197 and 394) were only generated from the conjugates of the target bacterium-AuNP@DD in the SALDI process. Thus, the gold ions could be used as the indicators for the presence of the target bacteria. The detection limit of S. aureus using this method is in the order of a few tens of cells. The low detection limit is due to the ease of generation of gold cluster ion derived from AuNPs under irradiation with a 355 nm laser beam. Apple juice mixed with S. aureus was used as the sample to demonstrate the suitability of the method for real-world application. Because of its low detection limit, this approach can potentially be used to screen the presence of S. aureus in complex samples.

SU-F-T-310: Does a Head-Mounted Ionization Chamber Detect IMRT Errors?

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

Wegener, S; Herzog, B; Sauer, O

2016-06-15

Purpose: The conventional plan verification strategy is delivering a plan to a QA-phantom before the first treatment. Monitoring each fraction of the patient treatment in real-time would improve patient safety. We evaluated how well a new detector, the IQM (iRT Systems, Germany), is capable of detecting errors we induced into IMRT plans of three different treatment regions. Results were compared to an established phantom. Methods: Clinical plans of a brain, prostate and head-and-neck patient were modified in the Pinnacle planning system, such that they resulted in either several percent lower prescribed doses to the target volume or several percent highermore » doses to relevant organs at risk. Unaltered plans were measured on three days, modified plans once, each with the IQM at an Elekta Synergy with an Agility MLC. All plans were also measured with the ArcCHECK with the cavity plug and a PTW semiflex 31010 ionization chamber inserted. Measurements were evaluated with SNC patient software. Results: Repeated IQM measurements of the original plans were reproducible, such that a 1% deviation from the mean as warning and 3% as action level as suggested by the manufacturer seemed reasonable. The IQM detected most of the simulated errors including wrong energy, a faulty leaf, wrong trial exported and a 2 mm shift of one leaf bank. Detection limits were reached for two plans - a 2 mm field position error and a leaf bank offset combined with an MU change. ArcCHECK evaluation according to our current standards also left undetected errors. Ionization chamber evaluation alone would leave most errors undetected. Conclusion: The IQM detected most errors and performed as well as currently established phantoms with the advantage that it can be used throughout the whole treatment. Drawback is that it does not indicate the source of the error.« less

Micromechanical Devices to Reduce 1/f Noise in Magnetic Field and Electric Charge Sensors

NASA Astrophysics Data System (ADS)

Jaramillo, Gerardo

1/f noise is present in every aspect of nature. Sensors and read-out electronics have the ultimate detection limit set by the noise floor of the white noise. In order to increase signal-to-noise ratio (SNR) of low frequency signals buried by high 1/f noise, the signal can be up-converted to a high frequency signal that lies in the lower white noise regime of the sensing device. Mechanical modulation can be employed to move low frequency electronic signals to higher frequency region through the use of microresonators. This thesis has two goals: (1) develop and fabricate a hybrid micromechanical-magnetoresistive magnetic field sensor; and (2) design an electrometer to measure currents collected from air streams containing ionized nano-particles. First, we designed magnetoresistive-microelectromechanical systems (MR-MEMS) hybrid devices based on the monolithic integration of magnetic thin films and silicon-on-insulator (SOI) MEMS fabrication techniques. We used MgO-based magnetic tunnel junctions (MTJ) placed on a bulk micromachined silicon MEMS device to form a hybrid sensing device. The MEMS device was used to mechanically modulate the magnetic field signal detected by the MTJ, thereby reducing the effects of 1/f noise on the MTJ's output. Two actuator designs were investigated: cantilever and electrostatic comb-drive. The second component of the thesis presents a MEMS-based electrometer for the detection of small currents from ionized particles in a particle detection system for air-quality monitoring. One method of particle detection ionizes particles and then feeds a stream of charged particles into a Faraday cup electrometer. We replaced the Faraday cup with a filtering porous mesh sensing-electrode coupled to a MEMS electrometer with a noise floor below 1 fA rms. Experiments were conducted with fA level currents produced by 10 nm diameter particles within an airflow of 1.0 L/min. The MEMS electrometer was compared and calibrated using commercial electrometers and particle counters.

Lipidomics as an important key for the identification of beer-spoilage bacteria.

PubMed

Řezanka, T; Matoulková, D; Benada, O; Sigler, K

2015-06-01

Electrospray ionization-tandem mass spectrometry (ESI-MS/MS) was used for characterizing intact plasmalogen phospholipid molecules in beer-spoilage bacteria. Identification of intact plasmalogens was carried out using collision-induced dissociation and the presence of suitable marker molecular species, both qualitative and quantitative, was determined in samples containing the anaerobic bacteria Megasphaera and Pectinatus. Using selected ion monitoring (SIM), this method had a limit of detection at 1 pg for the standard, i.e. 1-(1Z-octadecenyl)-2-oleoyl-sn-glycero-3-phosphoethanolamine and be linear in the range of four orders of magnitude from 2 pg to 20 ng. This technique was applied to intact plasmalogen extracts from the samples of contaminated and uncontaminated beer without derivatization and resulted in the identification of contamination of beer by Megasphaera and Pectinatus bacteria. The limit of detection was about 830 cells of anaerobic bacteria, i.e. bacteria containing natural cyclopropane plasmalogenes (c-p-19:0/15:0), which is the majority plasmalogen located in both Megasphaera and Pectinatus. The SIM ESI-MS method has been shown to be useful for the analysis of low concentration of plasmalogens in all biological samples, which were contaminated with anaerobic bacteria, e.g. juice, not only in beer. Significance and impact of the study: Electrospray ionization-tandem mass spectrometry (ESI-MS/MS) using collision-induced dissociation was used to characterize intact plasmalogen phospholipid molecules in beer-spoilage anaerobic bacteria Megasphaera and Pectinatus. Using selected ion monitoring (SIM), this method has a detection limit of 1 pg for the standard 1-(1Z-octadecenyl)-2-oleoyl-sn-glycero-3-phosphoethanolamine and is linear within four orders of magnitude (2 pg to 20 ng). The limit of detection was about 830 cells of bacteria containing natural cyclopropane plasmalogen (c-p-19:0/15:0). SIM ESI-MS method is useful for analyzing low concentrations of plasmalogens in biological samples contaminated with anaerobic bacteria, e.g. beer or juice. © 2015 The Society for Applied Microbiology.

Identification and quantification of cardiac glycosides in blood and urine samples by HPLC/MS/MS.

PubMed

Guan, F; Ishii, A; Seno, H; Watanabe-Suzuki, K; Kumazawa, T; Suzuki, O

1999-09-15

Cardiac glycosides (CG) are of forensic importance because of their toxicity and the fact that very limited methods are available for identification of CG in biological samples. In this study, we have developed an identification and quantification method for digoxin, digitoxin, deslanoside, digoxigenin, and digitoxigenin by high-performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS). CG formed abundant [M + NH4]+ ions and much less abundant [M + H]+ ions as observed with electrospray ionization (ESI) source and ammonium formate buffer. Under mild conditions for collision-induced dissociation (CID), each [M + NH4]+ ion fragmented to produce a dominant daughter ion, which was essential to the sensitive method of selected reaction monitoring (SRM) quantification of CG achieved in this study. SRM was compared with selected ion monitoring (SIM) regarding the effects of sample matrixes on the methodology. SRM produced lower detection limits with biological samples than SIM, while both methods produced equal detection limits with CG standards. On the basis of the HPLC/MS/MS results for CG, we have proposed some generalized points for conducting sensitive SRM measurements, in view of the property of analytes as well as instrumental conditions such as the type of HPLC/MS interface and CID parameters. Analytes of which the molecular ion can produce one abundant daughter ion with high yield under CID conditions may be sensitively measured by SRM. ESI is the most soft ionization source developed so far and can afford formation of the fragile molecular ions that are necessary for sensitive SRM detection. Mild CID conditions such as low collision energy and low pressure of collision gas favor production of an abundant daughter ion that is essential to sensitive SRM detection. This knowledge may provide some guidelines for conducting sensitive SRM measurements of very low concentrations of drugs or toxicants in biological samples.

Ultrafast gas chromatography method with direct injection for the quantitative determination of benzene, toluene, ethylbenzene, and xylenes in commercial gasoline.

PubMed

Miranda, Nahieh Toscano; Sequinel, Rodrigo; Hatanaka, Rafael Rodrigues; de Oliveira, José Eduardo; Flumignan, Danilo Luiz

2017-04-01

Benzene, toluene, ethylbenzene, and xylenes are some of the most hazardous constituents found in commercial gasoline samples; therefore, these components must be monitored to avoid toxicological problems. We propose a new routine method of ultrafast gas chromatography coupled to flame ionization detection for the direct determination of benzene, toluene, ethylbenzene, and xylenes in commercial gasoline. This method is based on external standard calibration to quantify each compound, including the validation step of the study of linearity, detection and quantification limits, precision, and accuracy. The time of analysis was less than 3.2 min, with quantitative statements regarding the separation and quantification of all compounds in commercial gasoline samples. Ultrafast gas chromatography is a promising alternative method to official analytical techniques. Government laboratories could consider using this method for quality control. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The requirements for low-temperature plasma ionization support miniaturization of the ion source.

PubMed

Kiontke, Andreas; Holzer, Frank; Belder, Detlev; Birkemeyer, Claudia

2018-06-01

Ambient ionization mass spectrometry (AI-MS), the ionization of samples under ambient conditions, enables fast and simple analysis of samples without or with little sample preparation. Due to their simple construction and low resource consumption, plasma-based ionization methods in particular are considered ideal for use in mobile analytical devices. However, systematic investigations that have attempted to identify the optimal configuration of a plasma source to achieve the sensitive detection of target molecules are still rare. We therefore used a low-temperature plasma ionization (LTPI) source based on dielectric barrier discharge with helium employed as the process gas to identify the factors that most strongly influence the signal intensity in the mass spectrometry of species formed by plasma ionization. In this study, we investigated several construction-related parameters of the plasma source and found that a low wall thickness of the dielectric, a small outlet spacing, and a short distance between the plasma source and the MS inlet are needed to achieve optimal signal intensity with a process-gas flow rate of as little as 10 mL/min. In conclusion, this type of ion source is especially well suited for downscaling, which is usually required in mobile devices. Our results provide valuable insights into the LTPI mechanism; they reveal the potential to further improve its implementation and standardization for mobile mass spectrometry as well as our understanding of the requirements and selectivity of this technique. Graphical abstract Optimized parameters of a dielectric barrier discharge plasma for ionization in mass spectrometry. The electrode size, shape, and arrangement, the thickness of the dielectric, and distances between the plasma source, sample, and MS inlet are marked in red. The process gas (helium) flow is shown in black.

Rapid LC-MS method for the detection of common fragrances in personal care products without sample preparation.

PubMed

Famiglini, Giorgio; Termopoli, Veronica; Palma, Pierangela; Capriotti, Fabiana; Cappiello, Achille

2014-05-01

An LC-MS method for the analysis of personal care and household products without sample preparation is presented. The method takes advantage of the Direct-electron ionization (EI) LC-MS interface for the quantitation of principal components, as well as for the identification of unknown or undeclared ingredients. The technique has proven its inertness toward matrix effects and the electron ionization allows quantitation and library identification. Commercially available products (shower gel, perfume, and hand cream) were diluted with methanol and injected directly into a nano-LC column. Limonene, linalool, and citral were selected as target compounds because of their use as fragrances in toiletry and detergent products. These and all other fragrances are commonly determined with GC-MS analysis, prior to sample cleanup, a procedure that can lead to analytes loss. The selected compounds are not detected with ESI because of their poor or very low response. Figures of merit and validation studies were executed and special attention was devoted to matrix-effects evaluation, because a sample preparation procedure is not involved. No matrix effects were observed, and the repeatability was excellent even after several weeks of operation. Products composition was investigated in full scan mode to determine the presence of unknown or not listed ingredients. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Qualitative and quantitative analysis of hyaluronan oligosaccharides with high performance thin layer chromatography using reagent-free derivatization on amino-modified silica and electrospray ionization-quadrupole time-of-flight mass spectrometry coupling on normal phase.

PubMed

Rothenhöfer, Martin; Scherübl, Rosmarie; Bernhardt, Günther; Heilmann, Jörg; Buschauer, Armin

2012-07-27

Purified oligomers of hyalobiuronic acid are indispensable tools to elucidate the physiological and pathophysiological role of hyaluronan degradation by various hyaluronidase isoenzymes. Therefore, we established and validated a novel sensitive, convenient, rapid, and cost-effective high performance thin layer chromatography (HPTLC) method for the qualitative and quantitative analysis of small saturated hyaluronan oligosaccharides consisting of 2-4 hyalobiuronic acid moieties. The use of amino-modified silica as stationary phase allows a simple reagent-free in situ derivatization by heating, resulting in a very low limit of detection (7-19 pmol per band, depending on the analyzed saturated oligosaccharide). By this derivatization procedure for the first time densitometric quantification of the analytes could be performed by HPTLC. The validated method showed a quantification limit of 37-71 pmol per band and was proven to be superior in comparison to conventional detection of hyaluronan oligosaccharides. The analytes were identified by hyphenation of normal phase planar chromatography to mass spectrometry (TLC-MS) using electrospray ionization. As an alternative to sequential techniques such as high performance liquid chromatography (HPLC) and capillary electrophoresis (CE), the validated HPTLC quantification method can easily be automated and is applicable to the analysis of multiple samples in parallel. Copyright © 2012 Elsevier B.V. All rights reserved.

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

PubMed Central

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-01-01

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate. PMID:28281659

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

NASA Astrophysics Data System (ADS)

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-03-01

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods.

PubMed

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-03-10

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.