Detection and Site Localization of Phosphorylcholine-Modified Peptides by NanoLC-ESI-MS/MS Using Precursor Ion Scanning and Multiple Reaction Monitoring Experiments

NASA Astrophysics Data System (ADS)

Timm, Thomas; Lenz, Christof; Merkel, Dietrich; Sadiffo, Christian; Grabitzki, Julia; Klein, Jochen; Lochnit, Guenter

2015-03-01

Phosphorylcholine (PC)-modified biomolecules like lipopolysaccharides, glycosphingolipids, and (glyco)proteins are widespread, highly relevant antigens of parasites, since this small hapten shows potent immunomodulatory capacity, which allows the establishment of long-lasting infections of the host. Especially for PC-modified proteins, structural data is rare because of the zwitterionic nature of the PC substituent, resulting in low sensitivities and unusual but characteristic fragmentation patterns. We have developed a targeted mass spectrometric approach using hybrid triple quadrupole/linear ion trap (QTRAP) mass spectrometry coupled to nanoflow chromatography for the sensitive detection of PC-modified peptides from complex proteolytic digests, and the localization of the PC-modification within the peptide backbone. In a first step, proteolytic digests are screened using precursor ion scanning for the marker ions of choline ( m/z 104.1) and phosphorylcholine ( m/z 184.1) to establish the presence of PC-modified peptides. Potential PC-modified precursors are then subjected to a second analysis using multiple reaction monitoring (MRM)-triggered product ion spectra for the identification and site localization of the modified peptides. The approach was first established using synthetic PC-modified synthetic peptides and PC-modified model digests. Following the optimization of key parameters, we then successfully applied the method to the detection of PC-peptides in the background of a proteolytic digest of a whole proteome. This methodological invention will greatly facilitate the detection of PC-substituted biomolecules and their structural analysis.

Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

PubMed

Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

2014-05-06

A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

PECAN: library-free peptide detection for data-independent acquisition tandem mass spectrometry data

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

Ting, Ying S.; Egertson, Jarrett D.; Bollinger, James G.

Data-independent acquisition (DIA) is an emerging mass spectrometry (MS)-based technique for unbiased and reproducible measurement of protein mixtures. DIA tandem mass spectrometry spectra are often highly multiplexed, containing product ions from multiple cofragmenting precursors. Detecting peptides directly from DIA data is therefore challenging; most DIA data analyses require spectral libraries. Here we present PECECAN (http://pecan.maccosslab.org), a library-free, peptide-centric tool that robustly and accurately detects peptides directly from DIA data. PECECAN reports evidence of detection based on product ion scoring, which enables detection of low-abundance analytes with poor precursor ion signal. We demonstrate the chromatographic peak picking accuracy and peptide detectionmore » capability of PECECAN, and we further validate its detection with data-dependent acquisition and targeted analyses. Lastly, we used PECECAN to build a plasma proteome library from DIA data and to query known sequence variants.« less

Highly charged ion secondary ion mass spectroscopy

DOEpatents

Hamza, Alex V.; Schenkel, Thomas; Barnes, Alan V.; Schneider, Dieter H.

2001-01-01

A secondary ion mass spectrometer using slow, highly charged ions produced in an electron beam ion trap permits ultra-sensitive surface analysis and high spatial resolution simultaneously. The spectrometer comprises an ion source producing a primary ion beam of highly charged ions that are directed at a target surface, a mass analyzer, and a microchannel plate detector of secondary ions that are sputtered from the target surface after interaction with the primary beam. The unusually high secondary ion yield permits the use of coincidence counting, in which the secondary ion stops are detected in coincidence with a particular secondary ion. The association of specific molecular species can be correlated. The unique multiple secondary nature of the highly charged ion interaction enables this new analytical technique.

Multiple applications of ion chromatography oligosaccharide fingerprint profiles to solve a variety of sugar and sugar-biofuel industry problems

USDA-ARS?s Scientific Manuscript database

Sugar crops contain a broad variety of carbohydrates used for human consumption and the production of biofuels and bioproducts. Ion chromatography with integrated pulsed amperometric detection (IC-IPAD), also known as high performance anion exchange chromatography (HPAEC), can be used to simultaneo...

Infrared laser dissociation of single megadalton polymer ions in a gated electrostatic ion trap: the added value of statistical analysis of individual events.

PubMed

Halim, Mohammad A; Clavier, Christian; Dagany, Xavier; Kerleroux, Michel; Dugourd, Philippe; Dunbar, Robert C; Antoine, Rodolphe

2018-05-07

In this study, we report the unimolecular dissociation mechanism of megadalton SO 3 -containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polymer cations and anions with the aid of infrared multiphoton dissociation coupled to charge detection ion trap mass spectrometry. A gated electrostatic ion trap ("Benner trap") is used to store and detect single gaseous polymer ions generated by positive and negative polarity in an electrospray ionization source. The trapped ions are then fragmented due to the sequential absorption of multiple infrared photons produced from a continuous-wave CO 2 laser. Several fragmentation pathways having distinct signatures are observed. Highly charged parent ions characteristically adopt a distinctive "stair-case" pattern (assigned to the "fission" process) whereas low charge species take on a "funnel like" shape (assigned to the "evaporation" process). Also, the log-log plot of the dissociation rate constants as a function of laser intensity between PAMPS positive and negative ions is significantly different.

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.

Li-ion battery thermal runaway suppression system using microchannel coolers and refrigerant injections

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

Bandhauer, Todd M.; Farmer, Joseph C.

A battery management system with thermally integrated fire suppression includes a multiplicity of individual battery cells in a housing; a multiplicity of cooling passages in the housing within or between the multiplicity of individual battery cells; a multiplicity of sensors operably connected to the individual battery cells, the sensors adapted to detect a thermal runaway event related to one or more of the multiplicity of individual battery cells; and a management system adapted to inject coolant into at least one of the multiplicity of cooling passages upon the detection of the thermal runaway event by the any one of themore » multiplicity of sensors, so that the thermal runaway event is rapidly quenched.« less

The effect of ion-exchange purification on the determination of plutonium at the New Brunswick Laboratory

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

Mitchell, W.G.; Spaletto, M.I.; Lewis, K.

The method of plutonium (Pu) determination at the Brunswick Laboratory (NBL) consists of a combination of ion-exchange purification followed by controlled-potential coulometric analysis (IE/CPC). The present report's purpose is to quantify any detectable Pu loss occurring in the ion-exchange (IE) purification step which would cause a negative bias in the NBL method for Pu analysis. The magnitude of any such loss would be contained within the reproducibility (0.05%) of the IE/CPC method which utilizes a state-of-the-art autocoulometer developed at NBL. When the NBL IE/CPC method is used for Pu analysis, any loss in ion-exchange purification (<0.05%) is confounded with themore » repeatability of the ion-exchange and the precision of the CPC analysis technique (<0.05%). Consequently, to detect a bias in the IE/CPC method due to the IE alone using the IE/CPC method itself requires that many randomized analyses on a single material be performed over time and that statistical analysis of the data be performed. The initial approach described in this report to quantify any IE loss was an independent method, Isotope Dilution Mass Spectrometry; however, the number of analyses performed was insufficient to assign a statistically significant value to the IE loss (<0.02% of 10 mg samples of Pu). The second method used for quantifying any IE loss of Pu was multiple ion exchanges of the same Pu aliquant; the small number of analyses possible per individual IE together with the column-to-column variability over multiple ion exchanges prevented statistical detection of any loss of <0.05%. 12 refs.« less

A simple LC-MS/MS method for determination of deferasirox in human plasma: Troubleshooting of interference from ferric ion in method development and its application.

PubMed

Li, Tengfei; Cui, Zhimin; Wang, Yan; Yang, Wen; Li, Duo; Song, QinXin; Sun, Luning; Ding, Li

2018-03-20

As an orally active iron chelator, deferasirox forms its ion complexes in the prepared plasma samples and LC-MS mobile phase where ferric ion exists, and then comparing with the nominal concentration level, a lower detected concentration level of deferasirox would be obtained after LC-MS analysis, if no proper treatment was adopted. Meanwhile, the phenomenon would be observed that multiple repeat injections of the same deferasirox plasma sample in the same tube would show the lower and lower detected concentration levels of deferasirox, which caused by more and more ferric ions from the injection needle dissolved in the sample solution as multiple repeated injections. The addition of a proper concentration of EDTA in the mobile phase and the sample will competitively inhibit deferasirox from complexing with ferric ion, and prevent the decrease of deferasirox concentration. In this paper, an LC-MS/MS method was developed and validated for the determination of deferasirox in human plasma. To achieve the protein precipitation, the analytes were extracted from aliquots of 200 μL human plasma with acetonitrile. Chromatographic separation was performed on an ODS-C18 column with the mobile phase consisted of methanol and 0.1% formic acid containing 0.04 mM ethylenediamine tetraacetate dihydrate (EDTA) (80:20, v/v) at a flow rate of 0.5 mL/min. Deferasirox and the internal standard (IS, mifepristone) were detected using electrospray ionization in positive ion multiple reaction monitoring mode by monitoring the precursor-to-product ion transitions m/z 374.2 → 108.1 for deferasirox and m/z 430.1 → 372.2 for the IS. The method exhibited good linearity over the concentration range of 0.04-40 μg/mL for deferasirox. The method was successfully applied to a pharmacokinetic study in 10 Chinese healthy volunteers after oral administration of deferasirox. Copyright © 2018 Elsevier B.V. All rights reserved.

Trapped Ion Qubits

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

Maunz, Peter; Wilhelm, Lukas

Qubits can be encoded in clock states of trapped ions. These states are well isolated from the environment resulting in long coherence times [1] while enabling efficient high-fidelity qubit interactions mediated by the Coulomb coupled motion of the ions in the trap. Quantum states can be prepared with high fidelity and measured efficiently using fluorescence detection. State preparation and detection with 99.93% fidelity have been realized in multiple systems [1,2]. Single qubit gates have been demonstrated below rigorous fault-tolerance thresholds [1,3]. Two qubit gates have been realized with more than 99.9% fidelity [4,5]. Quantum algorithms have been demonstrated on systemsmore » of 5 to 15 qubits [6–8].« less

High temperature ion channels and pores

NASA Technical Reports Server (NTRS)

Cheley, Stephen (Inventor); Gu, Li Qun (Inventor); Bayley, Hagan (Inventor); Kang, Xiaofeng (Inventor)

2011-01-01

The present invention includes an apparatus, system and method for stochastic sensing of an analyte to a protein pore. The protein pore may be an engineer protein pore, such as an ion channel at temperatures above 55.degree. C. and even as high as near 100.degree. C. The analyte may be any reactive analyte, including chemical weapons, environmental toxins and pharmaceuticals. The analyte covalently bonds to the sensor element to produce a detectable electrical current signal. Possible signals include change in electrical current. Detection of the signal allows identification of the analyte and determination of its concentration in a sample solution. Multiple analytes present in the same solution may also be detected.

Highly Sensitive and Patchable Pressure Sensors Mimicking Ion-Channel-Engaged Sensory Organs.

PubMed

Chun, Kyoung-Yong; Son, Young Jun; Han, Chang-Soo

2016-04-26

Biological ion channels have led to much inspiration because of their unique and exquisite operational functions in living cells. Specifically, their extreme and dynamic sensing abilities can be realized by the combination of receptors and nanopores coupled together to construct an ion channel system. In the current study, we demonstrated that artificial ion channel pressure sensors inspired by nature for detecting pressure are highly sensitive and patchable. Our ion channel pressure sensors basically consisted of receptors and nanopore membranes, enabling dynamic current responses to external forces for multiple applications. The ion channel pressure sensors had a sensitivity of ∼5.6 kPa(-1) and a response time of ∼12 ms at a frequency of 1 Hz. The power consumption was recorded as less than a few μW. Moreover, a reliability test showed stability over 10 000 loading-unloading cycles. Additionally, linear regression was performed in terms of temperature, which showed no significant variations, and there were no significant current variations with humidity. The patchable ion channel pressure sensors were then used to detect blood pressure/pulse in humans, and different signals were clearly observed for each person. Additionally, modified ion channel pressure sensors detected complex motions including pressing and folding in a high-pressure range (10-20 kPa).

Pulsed Multiple Reaction Monitoring Approach to Enhancing Sensitivity of a Tandem Quadrupole Mass Spectrometer

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

Belov, Mikhail E.; Prasad, Satendra; Prior, David C.

2011-02-23

Liquid chromatography (LC)-triple quadrupole mass spectrometers operating in a Multiple Reaction Monitoring (MRM) mode are increasingly used for quantitative analysis of low abundance analytes in highly complex biochemical matrices. After development and selection of optimum MRM transition, sensitivity and data quality limitations are largely related to mass spectral peak interferences from sample or matrix constituents and statistical limitations at low number of ions reaching the detector. Herein, we report a new approach to enhancing MRM sensitivity by converting the continuous stream of ions from the ion source into a pulsed ion beam through the use of an Ion Funnel Trapmore » (IFT). Evaluation of the pulsed MRM approach was performed with a tryptic digest of Shewanella oneidensis strain MR-1 spiked with several reference peptides. The sensitivity improvement observed with the IFT coupled to the triple quadrupole instrument is based on several unique features. First, ion accumulation in the radio frequency (RF) ion trap facilitates improved droplet desolvation, which is manifested in the reduced background ion noise at the detector. Second, signal amplitude for a given transition is enhanced because of an order-of-magnitude increase in the ion charge density per unit time compared to a continuous mode of operation. Third, signal detection at the full duty cycle is obtained, as the trap use eliminates dead times between transitions, which are inevitable with continuous ion streams. In comparison with the conventional approach, the pulsed MRM signals showed up to 5-fold enhanced peak amplitude and 2-3 fold reduced chemical background, resulting in an improvement in the limit of detection (LOD) by a factor of ~ 4 to ~ 8.« less

Mass Spectrometer Containing Multiple Fixed Collectors

NASA Technical Reports Server (NTRS)

Moskala, Robert; Celo, Alan; Voss, Guenter; Shaffer, Tom

2008-01-01

A miniature mass spectrometer that incorporates features not typically found in prior mass spectrometers is undergoing development. This mass spectrometer is designed to simultaneously measure the relative concentrations of five gases (H2, He, N2, O2, and Ar) in air, over the relative-concentration range from 10(exp -6) to 1, during a sampling time as short as 1 second. It is intended to serve as a prototype of a product line of easy-to-use, portable, lightweight, highspeed, relatively inexpensive instruments for measuring concentrations of multiple chemical species in such diverse applications as detecting explosive or toxic chemicals in air, monitoring and controlling industrial processes, measuring concentrations of deliberately introduced isotopes in medical and biological investigations, and general environmental monitoring. The heart of this mass spectrometer is an integral combination of a circular cycloidal mass analyzer, multiple fixed ion collectors, and two mass-selective ion sources. By circular cycloidal mass analyzer is meant an analyzer that includes (1) two concentric circular cylindrical electrodes for applying a radial electric field and (2) a magnet arranged to impose a magnetic flux aligned predominantly along the cylindrical axis, so that ions, once accelerated into the annulus between the electrodes, move along circular cycloidal trajectories. As in other mass analyzers, trajectory of each ion is determined by its mass-to-charge ratio, and so ions of different species can be collected simultaneously by collectors (Faraday cups) at different locations intersected by the corresponding trajectories (see figure). Unlike in other mass analyzers, the installation of additional collectors to detect additional species does not necessitate increasing the overall size of the analyzer assembly.

Charge multiplication effect in thin diamond films

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

Skukan, N., E-mail: nskukan@irb.hr; Grilj, V.; Sudić, I.

2016-07-25

Herein, we report on the enhanced sensitivity for the detection of charged particles in single crystal chemical vapour deposition (scCVD) diamond radiation detectors. The experimental results demonstrate charge multiplication in thin planar diamond membrane detectors, upon impact of 18 MeV O ions, under high electric field conditions. Avalanche multiplication is widely exploited in devices such as avalanche photo diodes, but has never before been reproducibly observed in intrinsic CVD diamond. Because enhanced sensitivity for charged particle detection is obtained for short charge drift lengths without dark counts, this effect could be further exploited in the development of sensors based on avalanchemore » multiplication and radiation detectors with extreme radiation hardness.« less

Coupled optical resonance laser locking.

PubMed

Burd, S C; du Toit, P J W; Uys, H

2014-10-20

We have demonstrated simultaneous laser frequency stabilization of a UV and IR laser, to coupled transitions of ions in the same spectroscopic sample, by detecting only the absorption of the UV laser. Separate signals for locking the different lasers are obtained by modulating each laser at a different frequency and using lock-in detection of a single photodiode signal. Experimentally, we simultaneously lock a 369 nm and a 935 nm laser to the (2)S(1/2) → (2)(P(1/2) and (2)D(3/2) → (3)D([3/2]1/2) transitions, respectively, of Yb(+) ions generated in a hollow cathode discharge lamp. Stabilized lasers at these frequencies are required for cooling and trapping Yb(+) ions, used in quantum information and in high precision metrology experiments. This technique should be readily applicable to other ion and neutral atom systems requiring multiple stabilized lasers.

A targeted strategy to identify untargeted metabolites from in vitro to in vivo: Rapid and sensitive metabolites profiling of licorice in rats using ultra-high performance liquid chromatography coupled with triple quadrupole-linear ion trap mass spectrometry.

PubMed

Huang, Meilin; Cheng, Zhongzhe; Wang, Lu; Feng, Yulin; Huang, Jiangeng; Du, Zhifeng; Jiang, Hongliang

2018-05-29

It is challenging to conduct in vivo metabolic study for traditional Chinese medicines (TCMs) because of complex components, unpredictable metabolic pathways and low metabolite concentrations. Herein, we proposed a sensitive strategy to characterize TCM metabolites in vivo at an orally clinical dose using ultra-high performance liquid chromatography-triple quadrupole-linear ion trap mass spectrometry (UHPLC-QTRAP-MS). Firstly, the metabolism of individual compounds in rat liver microsomes was studied to obtain the metabolic pathways and fragmentation patterns. The untargeted metabolites in vitro were detected by multiple ion monitoring-enhanced product ion (EPI) and neutral loss-EPI scans. Subsequently, a sensitive multiple reaction monitoring-EPI method was developed according to the in vitro results and predicted metabolites to profile the in vivo metabolites. Licorice as a model herb was used to evaluate and validate our strategy. A clinical dose of licorice water extract was orally administered to rats, then a total of 45 metabolites in urine, 21 metabolites in feces and 35 metabolites in plasma were detected. Among them, 18 minor metabolites have not been reported previously and 6 minor metabolites were first detected in vivo. Several isomeric metabolites were well separated and differentiated in our strategy. These results suggested that this new strategy could be widely used for the detection and characterization of in vivo metabolites of TCMs. Copyright © 2018. Published by Elsevier B.V.

Quantitative Mass Spectrometry by Isotope Dilution and Multiple Reaction Monitoring (MRM).

PubMed

Russo, Paul; Hood, Brian L; Bateman, Nicholas W; Conrads, Thomas P

2017-01-01

Selected reaction monitoring (SRM) is used in molecular profiling to detect and quantify specific known proteins in complex mixtures. Using isotope dilution (Barnidge et al., Anal Chem 75(3):445-451, 2003) methodologies, peptides can be quantified without the need for an antibody-based method. Selected reaction monitoring assays employ electrospray ionization mass spectrometry (ESI-MS) followed by two stages of mass selection: a first stage where the mass of the peptide ion is selected and, after fragmentation by collision-induced dissociation (CID), a second stage (tandem MS) where either a single (e.g., SRM) or multiple (multiple reaction monitoring, MRM) specific peptide fragment ions are transmitted for detection. The MRM experiment is accomplished by specifying the parent masses of the selected endogenous and isotope-labeled peptides for MS/MS fragmentation and then monitoring fragment ions of interest, using their intensities/abundances and relative ratios to quantify the parent protein of interest. In this example protocol, we will utilize isotope dilution MRM-MS to quantify in absolute terms the total levels of the protein of interest, ataxia telangiectasia mutated (ATM) serine/threonine protein kinase. Ataxia telangiectasia mutated (ATM) phosphorylates several key proteins that initiate activation of the DNA damage checkpoint leading to cell cycle arrest.

Metal-assisted SIMS and cluster ion bombardment for ion yield enhancement

NASA Astrophysics Data System (ADS)

Heile, A.; Lipinsky, D.; Wehbe, N.; Delcorte, A.; Bertrand, P.; Felten, A.; Houssiau, L.; Pireaux, J.-J.; De Mondt, R.; Van Vaeck, L.; Arlinghaus, H. F.

2008-12-01

In addition to structural information, a detailed knowledge of the local chemical environment proves to be of ever greater importance, for example for the development of new types of materials as well as for specific modifications of surfaces and interfaces in multiple fields of materials science or various biomedical and chemical applications. But the ongoing miniaturization and therefore reduction of the amount of material available for analysis constitute a challenge to the detection limits of analytical methods. In the case of time-of-flight secondary ion mass spectrometry (TOF-SIMS), several methods of secondary ion yield enhancement have been proposed. This paper focuses on the investigation of the effects of two of these methods, metal-assisted SIMS and polyatomic primary ion bombardment. For this purpose, thicker layers of polystyrene (PS), both pristine and metallized with different amounts of gold, were analyzed using monoatomic (Ar +, Ga +, Xe +, Bi +) and polyatomic (SF 5+, Bi 3+, C 60+) primary ions. It was found that polyatomic ions generally induce a significant increase of the secondary ion yield. On the other hand, with gold deposition, a yield enhancement can only be detected for monoatomic ion bombardment.

Integration of paper-based microarray and time-of-flight secondary ion mass spectrometry (ToF-SIMS) for parallel detection and quantification of molecules in multiple samples automatically.

PubMed

Chu, Kuo-Jui; Chen, Po-Chun; You, Yun-Wen; Chang, Hsun-Yun; Kao, Wei-Lun; Chu, Yi-Hsuan; Wu, Chen-Yi; Shyue, Jing-Jong

2018-04-16

With its low-cost fabrication and ease of modification, paper-based analytical devices have developed rapidly in recent years. Microarrays allow automatic analysis of multiple samples or multiple reactions with minimal sample consumption. While cellulose paper is generally used, its high backgrounds in spectrometry outside of the visible range has limited its application to be mostly colorimetric analysis. In this work, glass-microfiber paper is used as the substrate for a microarray. The glass-microfiber is essentially chemically inert SiO x , and the lower background from this inorganic microfiber can avoid interference from organic analytes in various spectrometers. However, generally used wax printing fails to wet glass microfibers to form hydrophobic barriers. Therefore, to prepare the hydrophobic-hydrophilic pattern, the glass-microfiber paper was first modified with an octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) to make the paper hydrophobic. A hydrophilic microarray was then prepared using a CO 2 laser scriber that selectively removed the OTS layer with a designed pattern. One microliter of aqueous drops of peptides at various concentrations were then dispensed inside the round patterns where OTS SAM was removed while the surrounding area with OTS layer served as a barrier to separate each drop. The resulting specimen of multiple spots was automatically analyzed with a time-of-flight secondary ion mass spectrometer (ToF-SIMS), and all of the secondary ions were collected. Among the various cluster ions that have developed over the past decade, pulsed C 60 + was selected as the primary ion because of its high secondary ion intensity in the high mass region, its minimal alteration of the surface when operating within the static-limit and spatial resolution at the ∼μm level. In the resulting spectra, parent ions of various peptides (in the forms [M+H] + and [M+Na] + ) were readily identified for parallel detection of molecules in a mixture. By normalizing the ion intensity of peptides with respect to the glass-microfiber matrix ([SiOH] + ), a linear calibration curve for each peptide was generated to quantify these components in a mixture. Copyright © 2017 Elsevier B.V. All rights reserved.

DETECTION OF THE AMMONIUM ION IN SPACE

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

Cernicharo, J.; Tercero, B.; Fuente, A.

2013-07-01

We report on the detection of a narrow feature at 262816.73 MHz toward Orion and the cold prestellar core B1-bS which we attribute to the 1{sub 0}-0{sub 0} line of the deuterated ammonium ion, NH{sub 3}D{sup +}. The observations were performed with the IRAM 30 m radio telescope. The carrier has to be a light molecular species as it is the only feature detected over 3.6 GHz of bandwidth. The hyperfine structure is not resolved, indicating a very low value for the electric quadrupolar coupling constant of nitrogen which is expected for NH{sub 3}D{sup +} as the electric field overmore » the N nucleus is practically zero. Moreover, the feature is right at the predicted frequency for the 1{sub 0}-0{sub 0} transition of the ammonium ion, 262817 {+-} 6 MHz (3{sigma}), using rotational constants derived from new infrared data obtained in our laboratory in Madrid. The estimated column density is (1.1 {+-} 0.2) Multiplication-Sign 10{sup 12} cm{sup -2}. Assuming a deuterium enhancement similar to that of NH{sub 2}D, we derive N(NH{sub 4}{sup +}) {approx_equal} 2.6 Multiplication-Sign 10{sup 13} cm{sup -2}, i.e., an abundance for ammonium of a few 10{sup -11}.« less

Ion Mobility Mass Spectrometry Analysis of Isomeric Disaccharide Precursor, Product and Cluster Ions

PubMed Central

Li, Hongli; Bendiak, Brad; Siems, William F.; Gang, David R.; Hill, Herbert H.

2015-01-01

RATIONALE Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and general branching features. The separation of carbohydrate isomers poses a great challenge for current analytical techniques. METHODS The isomeric heterogeneity of disaccharide ions and monosaccharideglycolaldehyde product ions evaluated using electrospray traveling wave ion mobility mass spectrometry (Synapt G2 high definition mass spectrometer) in both positive and negative ion modes investigation. RESULTS The separation of isomeric disaccharide ions was observed but not fully achieved based on their mobility profiles. The mobilities of isomeric product ions, the monosaccharide-glycolaldehydes, derived from different disaccharide isomers were measured. Multiple mobility peaks were observed for both monosaccharide-glycolaldehyde cations and anions, indicating that there was more than one structural configuration in the gas phase as verified by NMR in solution. More importantly, the mobility patterns for isomeric monosaccharide-glycolaldehyde product ions were different, which enabled partial characterization of their respective disaccharide ions. Abundant disaccharide cluster ions were also observed. The Results showed that a majority of isomeric cluster ions had different drift times and, moreover, more than one mobility peak was detected for a number of specific cluster ions. CONCLUSIONS It is demonstrated that ion mobility mass spectrometry is an advantageous method to assess the isomeric heterogeneity of carbohydrate compounds. It is capable of differentiating different types of carbohydrate ions having identical m/z values as well as multiple structural configurations of single compounds. PMID:24591031

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector.

PubMed

Long, Jingming; Furch, Federico J; Durá, Judith; Tremsin, Anton S; Vallerga, John; Schulz, Claus Peter; Rouzée, Arnaud; Vrakking, Marc J J

2017-07-07

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 μm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (10 4 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO 2 ), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector

NASA Astrophysics Data System (ADS)

Long, Jingming; Furch, Federico J.; Durá, Judith; Tremsin, Anton S.; Vallerga, John; Schulz, Claus Peter; Rouzée, Arnaud; Vrakking, Marc J. J.

2017-07-01

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 μm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (104 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO2), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Laser Induced Fluorescence Studies of Electrostatic Double Layers in an Expanding Helicon Plasma

NASA Astrophysics Data System (ADS)

Carr, Jerry, Jr.

We report the first evidence of a laboratory double layer (DL) collapsing in the presence of an instability studied by Chakraborty Thakur et al. 1 with the use of time resolved laser induced fluorescence (LIF) studies. Higher time resolution studies then provided the first statistically validated proof of the correlation between the ion acoustic instability and a DL. Time-frequency analysis in the form of time resolved cross power spectra and continuous wavelet transforms were used to provide insight into beam formation. The implications of this work is that in the creation of strong DLs in expanding plasmas for plasma propulsion or other applications may be self-limited through instability growth. Over the past decade, experimental and theoretical studies have demonstrated the formation of stable, electrostatic, current-free double layers (CFDLs) in plasmas with a strong density gradient; typically a result of a divergent magnetic field. In this work, we present evidence for the formation of multiple double layers within a single divergent magnetic field structure. Downstream of the divergent magnetic field, multiple accelerated ion populations are observed through laser induced fluorescence measurements of the ion velocity distribution function. The formation of the multiple double layer structure is a strong function of the neutral gas pressure in the experiment. The similarity of the accelerated ion populations observed in these laboratory experiments to ion populations observed in reconnection outflow regions in the magnetosphere and in numerical simulations is also described. If ion energization during magnetic reconnection also results solely from acceleration in electric fields, these observations imply a prediction that the ion heating, i.e., the broadening of ion velocity distribution functions, reported in magnetic reconnection experiments is more accurately described by a superposition of differently accelerated ion populations. Therefore, the ion gheatingh rate during reconnection should scale as the square root of the cube of the charge per unit mass (q3/m)1/2 for ions with varying charge-to-mass ratios. A new RFEA probe was benchmarked on the low pressure CFDL plasmas produced in WVU HELIX-LEIA. This work was the result of collaboration between the University of Tromso (UiT) and WVU. LIF was used to confirm the RFEAs ability to detect a beam when one was present. The RFEA was also able to detect the presence of a beam when LIF techniques were limited by metastable quenching. The probefs limitations in dealing with ion focusing are discussed as well.

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

PubMed

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

2018-02-13

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

LC-IMS-MS Feature Finder: detecting multidimensional liquid chromatography, ion mobility and mass spectrometry features in complex datasets.

PubMed

Crowell, Kevin L; Slysz, Gordon W; Baker, Erin S; LaMarche, Brian L; Monroe, Matthew E; Ibrahim, Yehia M; Payne, Samuel H; Anderson, Gordon A; Smith, Richard D

2013-11-01

The addition of ion mobility spectrometry to liquid chromatography-mass spectrometry experiments requires new, or updated, software tools to facilitate data processing. We introduce a command line software application LC-IMS-MS Feature Finder that searches for molecular ion signatures in multidimensional liquid chromatography-ion mobility spectrometry-mass spectrometry (LC-IMS-MS) data by clustering deisotoped peaks with similar monoisotopic mass, charge state, LC elution time and ion mobility drift time values. The software application includes an algorithm for detecting and quantifying co-eluting chemical species, including species that exist in multiple conformations that may have been separated in the IMS dimension. LC-IMS-MS Feature Finder is available as a command-line tool for download at http://omics.pnl.gov/software/LC-IMS-MS_Feature_Finder.php. The Microsoft.NET Framework 4.0 is required to run the software. All other dependencies are included with the software package. Usage of this software is limited to non-profit research to use (see README). rds@pnnl.gov. Supplementary data are available at Bioinformatics online.

An Adaptable Multiple Power Source for Mass Spectrometry and other Scientific Instruments

DOE PAGES

Lin, Tzu-Yung; Anderson, Gordon A.; Norheim, Randolph V.; ...

2015-09-18

Power supplies are commonly used in the operation of many types of scientific equipment, including mass spectrometers and ancillary instrumentation. A generic modern mass spectrometer comprises an ionization source, such as electrospray ionization (ESI), ion transfer devices such as ion funnels and multipole ion guides, and ion signal detection apparatus. Very often such platforms include, or are interfaced with ancillary elements in order to manipulate samples before or after ionization. In order to operate such scientific instruments, numerous direct current (DC) channels and radio frequency (RF) signals are required, along with other controls such as temperature regulation. In particular, DCmore » voltages in the range of ±400 V, along with MHz range RF signals with peak-to-peak amplitudes in the hundreds of volts range are commonly used to transfer ionized samples under vacuum. Additionally, an ESI source requires a high voltage (HV) DC source capable of producing several thousand volts and heaters capable of generating temperatures up to 300°C. All of these signals must be properly synchronized and managed in order to carry out ion trapping, accumulation and detection.« less

A -100 kV Power Supply for Ion Acceleration in Space-based Mass Spectrometers

NASA Astrophysics Data System (ADS)

Gilbert, J. A.; Zurbuchen, T.; Battel, S.

2017-12-01

High voltage power supplies are used in many space-based time-of-flight (TOF) mass spectrometer designs to accelerate incoming ions and increase the probability of their measurement and proper identification. Ions are accelerated in proportion to their charge state, so singly charged ions such as pickup ions are accelerated less than their multiple-charge state solar wind counterparts. This lack of acceleration results in pickup ion measurements with lower resolution and without determinations of absolute energy. Acceleration reduces the effects of angular scattering and energy straggling when ions pass through thin membranes such as carbon foils, and it brings ion energies above the detection threshold of traditional solid state detectors. We have developed a power supply capable of operating at -100 kV for ion acceleration while also delivering up to 10 W of power for the operation of a floating TOF system. We also show results of benchtop calibration and ion beam tests to demonstrate the functionality and success of this approach.

Deep Optical Spectroscopy of Planetary Nebulae: The Search for Neutron-Capture Elements

NASA Astrophysics Data System (ADS)

Sterling, Nicholas C.; Garofali, K.; Dinerstein, H. L.; Hwang, S.; Redfield, S.

2013-01-01

We present deep, high-resolution (R=36,700) optical spectra of five planetary nebulae (PNe), taken with the 2D-coude echelle spectrograph on the 2.7-m Harlan J. Smith Telescope at McDonald Observatory. These observations are part of a larger optical survey of PNe, designed to unambiguously detect emission lines from neutron(n)-capture elements (atomic number Z>30). The abundances of these elements are of particular interest in PNe, since they can be produced by slow n-capture nucleosynthesis (the ``s-process'') during the asymptotic giant branch (AGB) stage of evolution of PN progenitor stars. The first large-scale investigation of n-capture element abundances in PNe (Sterling & Dinerstein 2008, ApJS, 174, 157) surveyed [Kr III] and [Se IV] transitions in the K band spectra of more than 80 PNe. However, the abundances derived from these data relied on ionization corrections that were often large and uncertain due to the detection of only one ion per element. Transitions of other Se and Kr ions, as well as many other trans-iron species, reside at optical wavelengths. High-resolution spectra are essential to unequivocally identify these lines and resolve potential blends with other species. The spectra we present are rich in emission features, with between 125 and 600 distinct lines detected in each PN. Emission from at least one Kr ion is detected in all five objects, and two (Hb 12 and J 900) exhibit emission from multiple Kr ions. We detected multiple Xe ions in J 900, as well as Se, Br, and Rb lines. Hb 12 also exhibits Xe emission, and the first detection of [Se II] in a PN to our knowledge. The spectra display a wealth of other emission lines, including permitted features of second-row elements and forbidden transitions of several iron-peak elements (e.g., Cr, Mn, Fe, Co, Ni, and Cu). Our survey makes it possible to derive more accurate Se and Kr abundances in PNe, and reveals the enrichment of other trans-iron elements. This enables more accurate s-process enrichment factors to be derived for PNe, providing important constraints to models of AGB nucleosynthesis and the chemical evolution of trans-iron nuclides. This research was supported by NSF awards AST-0708425 and AST-901432.

Integrated System Technologies for Modular Trapped Ion Quantum Information Processing

NASA Astrophysics Data System (ADS)

Crain, Stephen G.

Although trapped ion technology is well-suited for quantum information science, scalability of the system remains one of the main challenges. One of the challenges associated with scaling the ion trap quantum computer is the ability to individually manipulate the increasing number of qubits. Using micro-mirrors fabricated with micro-electromechanical systems (MEMS) technology, laser beams are focused on individual ions in a linear chain and steer the focal point in two dimensions. Multiple single qubit gates are demonstrated on trapped 171Yb+ qubits and the gate performance is characterized using quantum state tomography. The system features negligible crosstalk to neighboring ions (< 3e-4), and switching speeds comparable to typical single qubit gate times (< 2 mus). In a separate experiment, photons scattered from the 171Yb+ ion are coupled into an optical fiber with 63% efficiency using a high numerical aperture lens (0.6 NA). The coupled photons are directed to superconducting nanowire single photon detectors (SNSPD), which provide a higher detector efficiency (69%) compared to traditional photomultiplier tubes (35%). The total system photon collection efficiency is increased from 2.2% to 3.4%, which allows for fast state detection of the qubit. For a detection beam intensity of 11 mW/cm 2, the average detection time is 23.7 mus with 99.885(7)% detection fidelity. The technologies demonstrated in this thesis can be integrated to form a single quantum register with all of the necessary resources to perform local gates as well as high fidelity readout and provide a photon link to other systems.

Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

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

Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

2015-05-16

This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS andmore » MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.« less

Compression and neutron and ion beams emission mechanisms within a plasma focus device

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

Yousefi, H. R.; Mohanty, S. R.; Nakada, Y.

This paper reports some results of investigations of the neutron emission from middle energy Mather-type plasma focus. Multiple compressions were observed, and it seems that multiple compression regimes can occur at low pressure, while single compression appeared at higher pressure, which is favorable for neutron production. The multiple compression mechanism can be attributed to the (m=0 type) instability. The m=0 type instability is a necessary condition for fusion activity and x-ray production, but is not sufficient by itself. Accompanying the multiple compressions, multiple deuteron and neutron pulses were detected, which implies that there are different kinds of acceleration mechanisms.

Comparison of single cell sequencing data between two whole genome amplification methods on two sequencing platforms.

PubMed

Chen, DaYang; Zhen, HeFu; Qiu, Yong; Liu, Ping; Zeng, Peng; Xia, Jun; Shi, QianYu; Xie, Lin; Zhu, Zhu; Gao, Ya; Huang, GuoDong; Wang, Jian; Yang, HuanMing; Chen, Fang

2018-03-21

Research based on a strategy of single-cell low-coverage whole genome sequencing (SLWGS) has enabled better reproducibility and accuracy for detection of copy number variations (CNVs). The whole genome amplification (WGA) method and sequencing platform are critical factors for successful SLWGS (<0.1 × coverage). In this study, we compared single cell and multiple cells sequencing data produced by the HiSeq2000 and Ion Proton platforms using two WGA kits and then comprehensively evaluated the GC-bias, reproducibility, uniformity and CNV detection among different experimental combinations. Our analysis demonstrated that the PicoPLEX WGA Kit resulted in higher reproducibility, lower sequencing error frequency but more GC-bias than the GenomePlex Single Cell WGA Kit (WGA4 kit) independent of the cell number on the HiSeq2000 platform. While on the Ion Proton platform, the WGA4 kit (both single cell and multiple cells) had higher uniformity and less GC-bias but lower reproducibility than those of the PicoPLEX WGA Kit. Moreover, on these two sequencing platforms, depending on cell number, the performance of the two WGA kits was different for both sensitivity and specificity on CNV detection. The results can help researchers who plan to use SLWGS on single or multiple cells to select appropriate experimental conditions for their applications.

Magnetic Graphene Nanosheet-Based Microfluidic Device for Homogeneous Real-Time Electronic Monitoring of Pyrophosphatase Activity Using Enzymatic Hydrolysate-Induced Release of Copper Ion.

PubMed

Lin, Youxiu; Zhou, Qian; Li, Juan; Shu, Jian; Qiu, Zhenli; Lin, Yuping; Tang, Dianping

2016-01-05

A novel flow-through microfluidic device based on a magneto-controlled graphene sensing platform was designed for homogeneous electronic monitoring of pyrophosphatase (PPase) activity; enzymatic hydrolysate-induced release of inorganic copper ion (Cu(2+)) from the Cu(2+)-coordinated pyrophosphate ions (Cu(2+)-PPi) complex was assessed to determine enzyme activity. Magnetic graphene nanosheets (MGNS) functionalized with negatively charged Nafion were synthesized by using the wet-chemistry method. The Cu(2+)-PPi complexes were prepared on the basis of the coordination reaction between copper ion and inorganic pyrophosphate ions. Upon target PPase introduction into the detection system, the analyte initially hydrolyzed pyrophosphate ions into phosphate ions and released the electroactive copper ions from Cu(2+)-PPi complexes. The released copper ions could be readily captured through the negatively charged Nafion on the magnetic graphene nanosheets, which could be quantitatively monitored by using the stripping voltammetry on the flow-through detection cell with an external magnet. Under optimal conditions, the obtained electrochemical signal exhibited a high dependence on PPase activity within a dynamic range from 0.1 to 20 mU mL(-1) and allowed the detection at a concentration as low as 0.05 mU mL(-1). Coefficients of variation for reproducibility of the intra-assay and interassay were below 7.6 and 9.8%, respectively. The inhibition efficiency of sodium fluoride (NaF) also received good results in pyrophosphatase inhibitor screening research. In addition, the methodology afforded good specificity and selectivity, simplification, and low cost without the need of sample separations and multiple washing steps, thus representing a user-friendly protocol for practical utilization in a quantitative PPase activity.

Characterization of Harmonic Signal Acquisition with Parallel Dipole and Multipole Detectors

NASA Astrophysics Data System (ADS)

Park, Sung-Gun; Anderson, Gordon A.; Bruce, James E.

2018-04-01

Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is a powerful instrument for the study of complex biological samples due to its high resolution and mass measurement accuracy. However, the relatively long signal acquisition periods needed to achieve high resolution can serve to limit applications of FTICR-MS. The use of multiple pairs of detector electrodes enables detection of harmonic frequencies present at integer multiples of the fundamental cyclotron frequency, and the obtained resolving power for a given acquisition period increases linearly with the order of harmonic signal. However, harmonic signal detection also increases spectral complexity and presents challenges for interpretation. In the present work, ICR cells with independent dipole and harmonic detection electrodes and preamplifiers are demonstrated. A benefit of this approach is the ability to independently acquire fundamental and multiple harmonic signals in parallel using the same ions under identical conditions, enabling direct comparison of achieved performance as parameters are varied. Spectra from harmonic signals showed generally higher resolving power than spectra acquired with fundamental signals and equal signal duration. In addition, the maximum observed signal to noise (S/N) ratio from harmonic signals exceeded that of fundamental signals by 50 to 100%. Finally, parallel detection of fundamental and harmonic signals enables deconvolution of overlapping harmonic signals since observed fundamental frequencies can be used to unambiguously calculate all possible harmonic frequencies. Thus, the present application of parallel fundamental and harmonic signal acquisition offers a general approach to improve utilization of harmonic signals to yield high-resolution spectra with decreased acquisition time. [Figure not available: see fulltext.

Imaging free zinc levels in vivo - what can be learned?

PubMed

De Leon-Rodriguez, Luis; Lubag, Angelo Josue M; Sherry, A Dean

2012-12-01

Our ever-expanding knowledge about the role of zinc in biology includes its role in redox modulation, immune response, neurotransmission, reproduction, diabetes, cancer, and Alzheimers disease is galvanizing interest in detecting and monitoring the various forms of Zn(II) in biological systems. This paper reviews reported strategies for detecting and tracking of labile or "free" unchelated Zn(II) in tissues. While different bound structural forms of Zn(II) have been identified and studied in vitro by multiple techniques, very few molecular imaging methods have successfully tracked the ion in vivo. A number of MRI and optical strategies have now been reported for detection of free Zn(II) in cells and tissues but only a few have been applied successfully in vivo. A recent report of a MRI sensor for in vivo tracking of Zn(II) released from pancreatic β-cells during insulin secretion exemplifies the promise of rational design of new Zn(II) sensors for tracking this biologically important ion in vivo. Such studies promise to provide new insights into zinc trafficking in vivo and the critical role of this ion in many human diseases.

Biomaterial-based Memory Device Development by Conducting Metallic DNA

DTIC Science & Technology

2013-05-28

time. Therefore, we have created a multiple-states memory system . This is the first multi-states resistance memory device by using bio-nanowire of the...world. Based on this achievement, logic device and application will be developed in the near future, too. Moreover, by using Ni-DNA detection system ...ions in DNA can change the resistance of Ni-DNA by applying different polar bias and time. Therefore, we have created a multiple-states memory system

WIMP detection and slow ion dynamics in carbon nanotube arrays.

PubMed

Cavoto, G; Cirillo, E N M; Cocina, F; Ferretti, J; Polosa, A D

2016-01-01

Large arrays of aligned carbon nanotubes (CNTs), open at one end, could be used as target material for the directional detection of weakly interacting dark matter particles (WIMPs). As a result of a WIMP elastic scattering on a CNT, a carbon ion might be injected in the body of the array and propagate through multiple collisions within the lattice. The ion may eventually emerge from the surface with open end CNTs, provided that its longitudinal momentum is large enough to compensate energy losses and its transverse momentum approaches the channeling conditions in a single CNT. Therefore, the angle formed between the WIMP wind apparent orientation and the direction of parallel carbon nanotube axes must be properly chosen. We focus on very low ion recoil kinetic energies, related to low mass WIMPs ([Formula: see text] GeV) where most of the existing experiments have low sensitivity. Relying on some exact results on two-dimensional lattices of circular obstacles, we study the low energy ion motion in the transverse plane with respect to CNT directions. New constraints are obtained on how to devise the CNT arrays to maximize the target channeling efficiency.

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

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

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

2011-05-15

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

HST/COS detection of a Ne VIII absorber towards PG 1407+265: an unambiguous tracer of collisionally ionized hot gas?

NASA Astrophysics Data System (ADS)

Hussain, T.; Muzahid, S.; Narayanan, A.; Srianand, R.; Wakker, B. P.; Charlton, J. C.; Pathak, A.

2015-01-01

We report the detection of Ne VIII in a zabs = 0.599 61 absorber towards the QSO PG1407+265 (zem= 0.94). Besides Ne VIII, absorption from H I Lyman series lines (H I λ1025-λ915), several other low (C II, N II, O II and S II), intermediate (C III, N III, N IV, O III, S IV and S V) and high (S VI, O VI and Ne VIII) ionization metal lines are detected. Disparity in the absorption line kinematics between different ions implies that the absorbing gas comprises of multiple ionization phases. The low and the intermediate ions (except S V) trace a compact (˜410 pc), metal-rich (Z ˜ Z⊙) and overdense (log nH ˜ -2.6) photoionized region that sustained star formation for a prolonged period. The high ions, Ne VIII and O VI, can be explained as arising in a low density (-5.3 ≤ log nH ≤ -5.0), metal-rich (Z ≳ Z⊙) and diffuse (˜180 kpc) photoionized gas. The S V, S VI and C IV [detected in the Faint Object Spectrograph (FOS) spectrum] require an intermediate photoionization phase with -4.2 < log nH < -3.5. Alternatively, a pure collisional ionization model, as used to explain the previous known Ne VIII absorbers, with 5.65 < log T < 5.72, can reproduce the S VI, O VI and Ne VIII column densities simultaneously in a single phase. However, even such models require an intermediate phase to reproduce any observable S V and/or C IV. Therefore, we conclude that when multiple phases are present, the presence of Ne VIII is not necessarily an unambiguous indication of collisionally ionized hot gas.

Extractive electrospray ionization mass spectrometry toward in situ analysis without sample pretreatment.

PubMed

Li, Ming; Hu, Bin; Li, Jianqiang; Chen, Rong; Zhang, Xie; Chen, Huanwen

2009-09-15

A homemade novel nanoextractive electrospray ionization (nanoEESI) source has been characterized for in situ mass spectrometric analysis of ambient samples without sample pretreatment. The primary ions generated using a nanospray emitter interact with the neutral sample plume created by manually nebulizing liquid samples, allowing production of the analyte ions in the spatial cross section of the nanoEESI source. The performance of nanoEESI is experimentally investigated by coupling the nanoEESI source to a commercial LTQ mass spectrometer for rapid analysis of various ambient samples using positive/negative ion detection modes. Compounds of interest in actual samples such as aerosol drug preparations, beverages, milk suspensions, farmland water, and groundwater were unambiguously detected using tandem nanoEESI ion trap mass spectrometry. The limit of detection was low picogram per milliliter levels for the compounds tested. Acceptable relative standard deviation (RSD) values (5-10%) were obtained for direct measurement of analytes in complex matrixes, providing linear dynamic signal responses using manual sample introduction. A single sample analysis was completed within 1.2 s. Requiring no sheath gas for either primary ion production or neutral sample introduction, the nanoEESI has advantages including readiness for miniaturization and integration, simple maintenance, easy operation, and low cost. The experimental data demonstrate that the nanoEESI is a promising tool for high-throughput, sensitive, quantitative, in situ analysis of ambient complex samples, showing potential applications for in situ analysis in multiple disciplines including but not limited to pharmaceutical analysis, food quality control, pesticides residue detection, and homeland security.

Integrated Avalanche Photodiode arrays

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

Harmon, Eric S.

2017-04-18

The present disclosure includes devices for detecting photons, including avalanche photon detectors, arrays of such detectors, and circuits including such arrays. In some aspects, the detectors and arrays include a virtual beveled edge mesa structure surrounded by resistive material damaged by ion implantation and having side wall profiles that taper inwardly towards the top of the mesa structures, or towards the direction from which the ion implantation occurred. Other aspects are directed to masking and multiple implantation and/or annealing steps. Furthermore, methods for fabricating and using such devices, circuits and arrays are disclosed.

Integrated avalanche photodiode arrays

DOEpatents

Harmon, Eric S.

2015-07-07

The present disclosure includes devices for detecting photons, including avalanche photon detectors, arrays of such detectors, and circuits including such arrays. In some aspects, the detectors and arrays include a virtual beveled edge mesa structure surrounded by resistive material damaged by ion implantation and having side wall profiles that taper inwardly towards the top of the mesa structures, or towards the direction from which the ion implantation occurred. Other aspects are directed to masking and multiple implantation and/or annealing steps. Furthermore, methods for fabricating and using such devices, circuits and arrays are disclosed.

An improved pseudotargeted metabolomics approach using multiple ion monitoring with time-staggered ion lists based on ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry.

PubMed

Wang, Yang; Liu, Fang; Li, Peng; He, Chengwei; Wang, Ruibing; Su, Huanxing; Wan, Jian-Bo

2016-07-13

Pseudotargeted metabolomics is a novel strategy integrating the advantages of both untargeted and targeted methods. The conventional pseudotargeted metabolomics required two MS instruments, i.e., ultra-high performance liquid chromatography/quadrupole-time- of-flight mass spectrometry (UHPLC/Q-TOF MS) and UHPLC/triple quadrupole mass spectrometry (UHPLC/QQQ-MS), which makes method transformation inevitable. Furthermore, the picking of ion pairs from thousands of candidates and the swapping of the data between two instruments are the most labor-intensive steps, which greatly limit its application in metabolomic analysis. In the present study, we proposed an improved pseudotargeted metabolomics method that could be achieved on an UHPLC/Q-TOF/MS instrument operated in the multiple ion monitoring (MIM) mode with time-staggered ion lists (tsMIM). Full scan-based untargeted analysis was applied to extract the target ions. After peak alignment and ion fusion, a stepwise ion picking procedure was used to generate the ion lists for subsequent single MIM and tsMIM. The UHPLC/Q-TOF tsMIM MS-based pseudotargeted approach exhibited better repeatability and a wider linear range than the UHPLC/Q-TOF MS-based untargeted metabolomics method. Compared to the single MIM mode, the tsMIM significantly increased the coverage of the metabolites detected. The newly developed method was successfully applied to discover plasma biomarkers for alcohol-induced liver injury in mice, which indicated its practicability and great potential in future metabolomics studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Multiple applications of ion chromatography oligosaccharide fingerprint profiles to solve a variety of sugar and sugar-biofuel industry problems.

PubMed

Eggleston, Gillian; Borges, Eduardo

2015-03-25

Sugar crops contain a broad variety of carbohydrates used for human consumption and the production of biofuels and bioproducts. Ion chromatography with integrated pulsed amperometric detection (IC-IPAD) can be used to simultaneously detect mono-, di-, and oligosaccharides, oligosaccharide isomers, mannitol, and ethanol in complex matrices from sugar crops. By utilizing a strong NaOH/NaOAc gradient method over 45 min, oligosaccharides of at least 2-12 dp can be detected. Fingerprint IC oligosaccharide profiles are extremely selective, sensitive, and reliable and can detect deterioration product metabolites from as low as 100 colony-forming units/mL lactic acid bacteria. The IC fingerprints can also be used to (i) monitor freeze deterioration, (ii) optimize harvesting methods and cut-to-crush times, (iii) differentiate between white refined sugar from sugar cane and from sugar beets, (iv) verify the activities of carbohydrate enzymes, (v) select yeasts for ethanol fermentations, and (vi) isolate and diagnose infections and processing problems in sugar factories.

DEVELOPMENT OF A METHOD FOR THE OBSERVATION OF LIGHTNING IN PROTOPLANETARY DISKS USING ION LINES

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

Muranushi, Takayuki; Akiyama, Eiji; Inutsuka, Shu-ichiro

2015-12-20

In this paper, we propose observational methods for detecting lightning in protoplanetary disks. We do so by calculating the critical electric field strength in the lightning matrix gas (LMG), the parts of the disk where the electric field is strong enough to cause lightning. That electric field accelerates multiple positive ion species to characteristic terminal velocities. In this paper, we present three distinct discharge models with corresponding critical electric fields. We simulate the position–velocity diagrams and the integrated emission maps for the models. We calculate the measure-of-sensitivity values for detection of the models and for distinguishing between the models. Atmore » the distance of TW Hya (54 pc), LMG that occupies 2π in azimuth and has 25 AU < r < 50 AU is detectable at 1200σ to 4000σ. The lower limits of the radii of 5σ-detectable LMG clumps are between 1.6 AU and 5.3 AU, depending on the models.« less

Charge-Transfer Processes in Warm Dense Matter: Selective Spectral Filtering for Laser-Accelerated Ion Beams

NASA Astrophysics Data System (ADS)

Braenzel, J.; Barriga-Carrasco, M. D.; Morales, R.; Schnürer, M.

2018-05-01

We investigate, both experimentally and theoretically, how the spectral distribution of laser accelerated carbon ions can be filtered by charge exchange processes in a double foil target setup. Carbon ions at multiple charge states with an initially wide kinetic energy spectrum, from 0.1 to 18 MeV, were detected with a remarkably narrow spectral bandwidth after they had passed through an ultrathin and partially ionized foil. With our theoretical calculations, we demonstrate that this process is a consequence of the evolution of the carbon ion charge states in the second foil. We calculated the resulting spectral distribution separately for each ion species by solving the rate equations for electron loss and capture processes within a collisional radiative model. We determine how the efficiency of charge transfer processes can be manipulated by controlling the ionization degree of the transfer matter.

Structural characterization by both positive and negative electrospray ion trap mass spectrometry of oligogalacturonates purified by high-performance anion-exchange chromatography.

PubMed

Quéméner, Bernard; Désiré, Cédric; Debrauwer, Laurent; Rathahao, Estelle

2003-01-17

The off-line coupling of high-performance anion-exchange chromatography to electrospray ion trap mass spectrometry (ESI-IT-MS) is described. Two sets of isocratic conditions were optimised for the semi-preparative purification of oligogalacturonates of degree of polymerisation from 4 to 6 by monitoring eluates with either pulsed amperometric detection or evaporative light scattering detection in the presence of an online Dionex Carbohydrate Membrane Desalter (CMD). In these conditions, purified oligogalacturonate solutions were suitable, without further desalting steps, for infusion ESI-IT-MS experiments. This paper provides some interesting features of positive and negative ESI-IT-multiple MS (MSn) of these acidic oligosaccharides. The spectra acquired in both ion modes show characteristic fragments resulting from glycosidic bond and cross-ring cleavages. Under negative ionization conditions, the fragmentation of the singly-charged [M-H]- ions, as well as the Ci-, and Zi-, fragment ions through sequential MSn experiments, was always dominated by product ions from C- and Z-type glycosidic cleavages. All spectra also displayed 0.2 A-type cross-ring cleavage ions which carry linkage information. Collision-induced dissociation (CID) spectra of sodium-cationized species obtained under positive ionization conditions were more complex. Successive MSn experiments also led to the 0.2 A-type cross-ring cleavage ions observed together with B- and Y-type ions. The presence of the 0.2 A ion series was related to Mr 60 (C2H4O2) losses. Combined with the absence of the Mr 30 (CH2O) and the Mr 90 (C3H6O3) ions, these ions were indicative of 1-4 type glycosidic linkage.

Early and Late Chromosome Damages in Human Lymphocytes Induced by Gamma Rays and Fe Ions

NASA Technical Reports Server (NTRS)

Sunagawa, Mayumi; Zhang, Ye; Yeshitla, Samrawit; Kadhim, Munira; Wilson, Bobby; Wu, Honglu

2014-01-01

Chromosomal translocations and inversions are considered stable, and cells containing these types of chromosome aberrations can survive multiple cell divisions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. Detailed analysis of chromosome break ends participating in exchanges revealed a greater fraction of break ends involved in intrachromosome aberrations in the 7- and 14-day samples in comparison to the fraction at first mitosis. In particular, simple inversions were found at 7 and 14 days, but not at the first mitosis, suggesting that some of the aberrations might be formed days post irradiation. In contrast, at the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Comparison between low and high doses of Fe ion irradiation in the induction of late damages will also be discussed.

New detection system and signal processing for the tokamak ISTTOK heavy ion beam diagnostic.

PubMed

Henriques, R B; Nedzelskiy, I S; Malaquias, A; Fernandes, H

2012-10-01

The tokamak ISTTOK havy ion beam diagnostic (HIBD) operates with a multiple cell array detector (MCAD) that allows for the plasma density and the plasma density fluctuations measurements simultaneously at different sampling volumes across the plasma. To improve the capability of the plasma density fluctuations investigations, a new detection system and new signal conditioning amplifier have been designed and tested. The improvements in MCAD design are presented which allow for nearly complete suppression of the spurious plasma background signal by applying a biasing potential onto special electrodes incorporated into MCAD. The new low cost and small size transimpedance amplifiers are described with the parameters of 400 kHz, 10(7) V/A, 0.4 nA of RMS noise, adequate for the plasma density fluctuations measurements.

Detecting negative ions on board small satellites

NASA Astrophysics Data System (ADS)

Lepri, S. T.; Raines, J. M.; Gilbert, J. A.; Cutler, J.; Panning, M.; Zurbuchen, T. H.

2017-04-01

Recent measurements near comets, planets, and their satellites have shown that heavy ions, energetic neutral atoms, molecular ions, and charged dust contain a wealth of information about the origin, evolution, and interaction of celestial bodies with their space environment. Using highly sensitive plasma instruments, positively charged heavy ions have been used to trace exospheric and surface composition of comets, planets, and satellites as well as the composition of interplanetary and interstellar dust. While positive ions dominate throughout the heliosphere, negative ions are also produced from surface interactions. In fact, laboratory experiments have shown that oxygen released from rocky surfaces is mostly negatively charged. Negative ions and negatively charged nanograins have been detected with plasma electron analyzers in several different environments (e.g., by Cassini and Rosetta), though more extensive studies have been challenging without instrumentation dedicated to negative ions. We discuss an adaptation of the Fast Imaging Plasma Spectrometer (FIPS) flown on MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) for the measurement of negatively charged particles. MESSENGER/FIPS successfully measured the plasma environment of Mercury from 2011 until 2015, when the mission ended, and has been used to map multiple ion species (H+ through Na+ and beyond) throughout Mercury's space environment. Modifications to the existing instrument design fits within a 3U CubeSat volume and would provide a low mass, low power instrument, ideal for future CubeSat or distributed sensor missions seeking, for the first time, to characterize the contribution of negative particles in the heliospheric plasmas near the planets, moons, comets, and other sources.

An artificial tongue fluorescent sensor array for identification and quantitation of various heavy metal ions.

PubMed

Xu, Wang; Ren, Changliang; Teoh, Chai Lean; Peng, Juanjuan; Gadre, Shubhankar Haribhau; Rhee, Hyun-Woo; Lee, Chi-Lik Ken; Chang, Young-Tae

2014-09-02

Herein, a small-molecule fluorescent sensor array for rapid identification of seven heavy metal ions was designed and synthesized, with its sensing mechanism mimicking that of a tongue. The photoinduced electron transfer and intramolecular charge transfer mechanism result in combinatorial interactions between sensor array and heavy metal ions, which lead to diversified fluorescence wavelength shifts and emission intensity changes. Upon principle component analysis (PCA), this result renders clear identification of each heavy metal ion on a 3D spatial dispersion graph. Further exploration provides a concentration-dependent pattern, allowing both qualitative and quantitative measurements of heavy metal ions. On the basis of this information, a "safe-zone" concept was proposed, which provides rapid exclusion of versatile hazardous species from clean water samples based on toxicity characteristic leaching procedure standards. This type of small-molecule fluorescent sensor array could open a new avenue for multiple heavy metal ion detection and simplified water quality analysis.

Comparisons of Two Plasma Instruments on the International Space Station

NASA Astrophysics Data System (ADS)

Balthazor, R.; McHarg, M. G.; Minow, J. I.; Chandler, M. O.; Musick, J. D.; Feldmesser, H.; Darrin, M. A.; Osiander, R.

2011-12-01

The United States Air Force Academy's Canary instrument, a low-cost ion spectrometer with integrated charge multiplication, was installed on the International Space Station (ISS) on shuttle flight STS-134. The primary goal of the Canary experiment is to measure ion signals in the wake when ISS is flying in the standard +XVV attitude. However, the instrument is pointed (approximately) into ram and detects ambient Low Earth Orbit ions when the ISS is flying in the -XVV attitude. Simultaneous observations with NASA's Floating Plasma Measurement Unit (FPMU) have been taken during these times, and the results from each instrument are compared, in order to determine the origin of energy variations observed in the Canary ion signal. In addition, insights into the ISS floating plasma potential at the two different instrument locations can be obtained.

Comprehensive identification of mutations induced by heavy-ion beam irradiation in Arabidopsis thaliana.

PubMed

Hirano, Tomonari; Kazama, Yusuke; Ishii, Kotaro; Ohbu, Sumie; Shirakawa, Yuki; Abe, Tomoko

2015-04-01

Heavy-ion beams are widely used for mutation breeding and molecular biology. Although the mutagenic effects of heavy-ion beam irradiation have been characterized by sequence analysis of some restricted chromosomal regions or loci, there have been no evaluations at the whole-genome level or of the detailed genomic rearrangements in the mutant genomes. In this study, using array comparative genomic hybridization (array-CGH) and resequencing, we comprehensively characterized the mutations in Arabidopsis thaliana genomes irradiated with Ar or Fe ions. We subsequently used this information to investigate the mutagenic effects of the heavy-ion beams. Array-CGH demonstrated that the average number of deleted areas per genome were 1.9 and 3.7 following Ar-ion and Fe-ion irradiation, respectively, with deletion sizes ranging from 149 to 602,180 bp; 81% of the deletions were accompanied by genomic rearrangements. To provide a further detailed analysis, the genomes of the mutants induced by Ar-ion beam irradiation were resequenced, and total mutations, including base substitutions, duplications, in/dels, inversions, and translocations, were detected using three algorithms. All three resequenced mutants had genomic rearrangements. Of the 22 DNA fragments that contributed to the rearrangements, 19 fragments were responsible for the intrachromosomal rearrangements, and multiple rearrangements were formed in the localized regions of the chromosomes. The interchromosomal rearrangements were detected in the multiply rearranged regions. These results indicate that the heavy-ion beams led to clustered DNA damage in the chromosome, and that they have great potential to induce complicated intrachromosomal rearrangements. Heavy-ion beams will prove useful as unique mutagens for plant breeding and the establishment of mutant lines. © 2015 The Authors The Plant Journal © 2015 John Wiley & Sons Ltd.

Retention time alignment of LC/MS data by a divide-and-conquer algorithm.

PubMed

Zhang, Zhongqi

2012-04-01

Liquid chromatography-mass spectrometry (LC/MS) has become the method of choice for characterizing complex mixtures. These analyses often involve quantitative comparison of components in multiple samples. To achieve automated sample comparison, the components of interest must be detected and identified, and their retention times aligned and peak areas calculated. This article describes a simple pairwise iterative retention time alignment algorithm, based on the divide-and-conquer approach, for alignment of ion features detected in LC/MS experiments. In this iterative algorithm, ion features in the sample run are first aligned with features in the reference run by applying a single constant shift of retention time. The sample chromatogram is then divided into two shorter chromatograms, which are aligned to the reference chromatogram the same way. Each shorter chromatogram is further divided into even shorter chromatograms. This process continues until each chromatogram is sufficiently narrow so that ion features within it have a similar retention time shift. In six pairwise LC/MS alignment examples containing a total of 6507 confirmed true corresponding feature pairs with retention time shifts up to five peak widths, the algorithm successfully aligned these features with an error rate of 0.2%. The alignment algorithm is demonstrated to be fast, robust, fully automatic, and superior to other algorithms. After alignment and gap-filling of detected ion features, their abundances can be tabulated for direct comparison between samples.

Identification of urinary metabolites of imperatorin with a single run on an LC/Triple TOF system based on multiple mass defect filter data acquisition and multiple data mining techniques.

PubMed

Qiao, Shi; Shi, Xiaowei; Shi, Rui; Liu, Man; Liu, Ting; Zhang, Kerong; Wang, Qiao; Yao, Meicun; Zhang, Lantong

2013-08-01

The detection of drug metabolites, especially for minor metabolites, continues to be a challenge because of the complexity of biological samples. Imperatorin (IMP) is an active natural furocoumarin component originating from many traditional Chinese herbal medicines and is expected to be pursued as a new vasorelaxant agent. In the present study, a generic and efficient approach was developed for the in vivo screening and identification of IMP metabolites using liquid chromatography-Triple TOF mass spectrometry. In this approach, a novel on-line data acquisition method mutiple mass defect filter (MMDF) combined with dynamic background subtraction was developed to trace all probable urinary metabolites of IMP. Comparing with the traditionally intensity-dependent data acquisition method, MMDF method could give the information of low-level metabolites masked by background noise and endogenous components. Thus, the minor metabolites in complex biological matrices could be detected. Then, the sensitive and specific multiple data-mining techniques extracted ion chromatography, mass defect filter, product ion filter, and neutral loss filter were used for the discovery of IMP metabolites. Based on the proposed strategy, 44 phase I and 7 phase II metabolites were identified in rat urine after oral administration of IMP. The results indicated that oxidization was the main metabolic pathway and that different oxidized substituent positions had a significant influence on the fragmentation of the metabolites. Two types of characteristic ions at m/z 203 and 219 can be observed in the MS/MS spectra. This is the first study of IMP metabolism in vivo. The interpretation of the MS/MS spectra of these metabolites and the proposed metabolite pathway provide essential data for further pharmacological studies of other linear-type furocoumarins.

[Analysis of saponins from panax notoginseng using pressurized solvent extraction coupled with liquid chromatography-electrospray mass spectrum].

PubMed

Wan, Jianbo; Li, Changming; Li, Shaopin; Kong, Lingyi; Wang, Yitao

2005-10-01

To establish a method for qualitative analysis of saponins from Panax notoginseng using pressurized solvent extraction coupled with LC-ESI-MS. The PSE technology was applied to the process of extraction for Panax notoginseng, and the negative ion detection and multiple reaction monitoring model were used. The saponins were investigated based on total ion chromatogram (TIC) and MRM chromatogram. According to the fragment character of saponins, the molecular weight and their structures could be identified. The method can be used for qualitative analysis of saponins from Panax notoginseng.

Adsorption of environmental pollutants using magnetic hybrid nanoparticles modified with β-cyclodextrin

NASA Astrophysics Data System (ADS)

Wang, Niejun; Zhou, Lilin; Guo, Jun; Ye, Qiquan; Lin, Jin-Ming; Yuan, Jinying

2014-06-01

Graft through strategy was utilized to coat magnetic Fe3O4 nanoparticles with poly(glycidyl methacrylate) using ordinary radical polymerization and then β-cyclodextrin was linked onto the surface of nanoparticles. With these nanoparticles modified with cyclodextrin groups, adsorption of two model environmental pollutants, bisphenol A and copper ions, was studied. Host-guest interactions between cyclodextrin and aromatic molecules had a great contribution to the adsorption of bisphenol A, while multiple hydroxyls of cyclodextrin also helped the adsorption of copper ions. These magnetic nanoparticles could be applied in the elimination, enrichment and detection of some environmental pollutants.

Laser-assisted atom probe tomography of four paired poly-Si/SiO2 multiple-stacks with each thickness of 10 nm

NASA Astrophysics Data System (ADS)

Kwak, C.-M.; Seol, J.-B.; Kim, Y.-T.; Park, C.-G.

2017-02-01

For the past 10 years, laser-assisted atom probe tomography (APT) analysis has been performed to quantify the near-atomic scale distribution of elements and their local chemical compositions within interfaces that determine the design, processing, and properties of virtually all materials. However, the nature of the occurring laser-induced emission at the surface of needle-shaped sample is highly complex and it has been an ongoing challenge to understand the surface-related interactions between laser-sources and tips containing non-conductive oxides for a robust and reliable analysis of multiple-stacked devices. Here, we find that the APT analysis of four paired poly-Si/SiO2 (conductive/non-conductive) multiple stacks with each thickness of 10 nm is governed by experimentally monitoring three experimental conditions, such as laser-beam energies ranged from 30 to 200 nJ, analysis temperatures varying with 30-100 K, and the inclination of aligned interfaces within a given tip toward analysis direction. Varying with laser-energy and analysis temperature, a drastic compositional ratio of doubly charged Si ions to single charged Si ions within conductive poly-Si layers is modified, as compared with ones detected in the non-conductive layers. Severe distorted APT images of multiple stacks are also inevitable, especially at the conductive layers, and leading to a lowering of the successful analysis yields. This lower throughput has been overcome though changing the inclination of interfaces within a given tip to analysis direction (planar interfaces parallel to the tip axis), but significant deviations in chemical compositions of a conductive layer counted from those of tips containing planar interfaces perpendicular to the tip axis are unavoidable owing to the Si2, SiH2O, and Si2O ions detected, for the first time, within poly-Si layers.

Ruthenium trisbipyridine as a candidate for gas-phase spectroscopic studies in a Fourier transform mass spectrometer

DOE PAGES

Scott, Jill R.; Ham, Jason E.; Durham, Bill; ...

2004-01-01

Metal polypyridines are excellent candidates for gas-phase optical experiments where their intrinsic properties can be studied without complications due to the presence of solvent. The fluorescence lifetimes of [Ru(bpy) 3 ] 1+ trapped in an optical detection cell within a Fourier transform mass spectrometer were obtained using matrix-assisted laser desorption/ionization to generate the ions with either 2,5-dihydroxybenzoic acid (DHB) or sinapinic acid (SA) as matrix. All transients acquired, whether using DHB or SA for ion generation, were best described as approximately exponential decays. The rate constant for transients derived using DHB as matrix was 4×10 7 s −1 , whilemore » the rate constant using SA was 1×10 7 s −1 . Some suggestions of multiple exponential decay were evident although limited by the quality of the signals. Photodissociation experiments revealed that [Ru(bpy) 3 ] 1+ generated using DHB can decompose to [Ru(bpy) 2 ] 1+ , whereas ions generated using SA showed no decomposition. Comparison of the mass spectra with the fluorescence lifetimes illustrates the promise of incorporating optical detection with trapped ion mass spectrometry techniques.« less

Fast ion beta limit measurements by collimated neutron detection in MST plasmas

NASA Astrophysics Data System (ADS)

Capecchi, William; Anderson, Jay; Bonofiglo, Phillip; Kim, Jungha; Sears, Stephanie

2015-11-01

Fast ion orbits in the reversed field pinch (RFP) are well ordered and classically confined despite magnetic field stochasticity generated by multiple tearing modes. Classical TRANSP modeling of a 1MW tangentially injected hydrogen neutral beam in MST deuterium plasmas predicts a core-localized fast ion density that can be up to 25% of the electron density and a fast ion beta of many times the local thermal beta. However, neutral particle analysis of an NBI-driven mode (presumably driven by a fast ion pressure gradient) shows mode-induced transport of core-localized fast ions and a saturated fast ion density. The TRANSP modeling is presumed valid until the onset of the beam-driven mode and gives an initial estimate of the volume-averaged fast ion beta of 1-2% (local core value up to 10%). A collimated neutron detector for fusion product profile measurements will be used to determine the spatial distribution of fast ions, allowing for a first measurement of the critical fast-ion pressure gradient required for mode destabilization. Testing/calibration data and initial fast-ion profiles will be presented. Characterization of both the local and global fast ion beta will be done for deuterium beam injection into deuterium plasmas for comparison to TRANSP predictions. Work supported by US DOE.

Screening and identification of steroidal saponins from Anemarrhena asphodeloides employing UPLC tandem triple quadrupole linear ion trap mass spectrometry.

PubMed

Xia, Yong-Gang; Guo, Xin-Dong; Liang, Jun; Yang, Bing-You; Kuang, Hai-Xue

2017-09-01

This study presents a practical and valid strategy for the screening and structural characterization of Anemarrhena asphodeloides Bge steroidal saponins (SSs) using ultra-high performance liquid chromatography coupled with triple quadrupole linear ion trap mass spectrometry. The whole analytical protocols integrate four-step procedures in the positive mode: (1) rational deduction of mass fragmentation pathways of A. asphodeloides SSs; (2) untargeted screening of potential A. asphodeloides SSs by multiple-ion monitoring-information-dependent-acquiring-enhanced product ion (MIM-IDA-EPI) scan through reverse phase liquid chromatography; (3) comprehensive construction of an ammoniated precursor ion database by combining untargeted MIM-IDA-EPI scans and data literature; and (4) structural interpretation of targeted A. asphodeloides SSs using MIM-IDA-EPI and multiple reaction monitoring (MRM)-IDA-EPI with an energy-resolved technique. The protocols were used to analyze SSs in A. asphodeloides; of the 87 detected SSs that were unambiguously characterized or tentatively identified, 19 compounds were the first to be reported from A. asphodeloides and 13 ones were characterized as potential new compounds. Accuracy of the analytical procedure was demonstrated by structural identification of three SSs by NMR spectroscopy. The proposed schemes hold an excellent promise in the structural prediction and interpretation of complex SSs from plant medicines by mass spectrometry. Copyright © 2017 Elsevier Inc. All rights reserved.

A sensitive mass spectrometric method for hypothesis-driven detection of peptide post-translational modifications: multiple reaction monitoring-initiated detection and sequencing (MIDAS).

PubMed

Unwin, Richard D; Griffiths, John R; Whetton, Anthony D

2009-01-01

The application of a targeted mass spectrometric workflow to the sensitive identification of post-translational modifications is described. This protocol employs multiple reaction monitoring (MRM) to search for all putative peptides specifically modified in a target protein. Positive MRMs trigger an MS/MS experiment to confirm the nature and site of the modification. This approach, termed MIDAS (MRM-initiated detection and sequencing), is more sensitive than approaches using neutral loss scanning or precursor ion scanning methodologies, due to a more efficient use of duty cycle along with a decreased background signal associated with MRM. We describe the use of MIDAS for the identification of phosphorylation, with a typical experiment taking just a couple of hours from obtaining a peptide sample. With minor modifications, the MIDAS method can be applied to other protein modifications or unmodified peptides can be used as a MIDAS target.

Detection, characterization and quantification of salicylic acid conjugates in plant extracts by ESI tandem mass spectrometric techniques.

PubMed

Pastor, Victoria; Vicent, Cristian; Cerezo, Miguel; Mauch-Mani, Brigitte; Dean, John; Flors, Victor

2012-04-01

An approach for the detection and characterization of SA derivatives in plant samples is presented based on liquid chromatography coupled to electrospray ionization (ESI) tandem mass spectrometric techniques. Precursor ion scan methods using an ESI triple quadrupole spectrometer for samples from plants challenged with the virulent Pseudomonas syringae pv tomato DC3000 allowed us to detect two potential SA derivatives. The criterion used to consider a potential SA derivative is based on the detection of analytes in the precursor ion scan chromatogram upon selecting m/z 137 and m/z 93 that correspond to the salicylate and its main product ion, respectively. Product ion spectra of the newly-detected analytes as well as accurate m/z determinations using an ESI Q-time-of-flight instrument were registered as means of characterization and strongly suggest that glucosylated forms of SA at the carboxylic and at the phenol functional groups are present in plant samples. The specific synthesis and subsequent chromatography of salicylic glucosyl ester (SGE) and glucosyl salicylate (SAG) standards confirmed the chemical identity of both peaks that were obtained applying different tandem mass spectrometric techniques and accurate m/z determinations. A multiple reaction monitoring method has been developed and applied to plant samples. The advantages of this LC-ESI-MS/MS methods with respect to the traditional analysis of glucosyl conjugates are also discussed. Preliminary results revealed that SA and the glucosyl conjugates are accumulated in Arabidopsis thaliana in a time dependent manner, accordingly to the up-regulation of SA-dependent defenses following P. syringae infection. This technique applied to plant hormones or fragment ions may be useful to obtain chemical family members of plant metabolites and help identify their contribution in the signaling of plant defenses. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

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.

Scalable entanglement in trapped ions using optimal control of multimode couplings

NASA Astrophysics Data System (ADS)

Debnath, Shantanu; Choi, Taeyoung; Manning, T. Andrew; Figgatt, Caroline; Monroe, Chris

2014-05-01

We perform high fidelity multipartite entanglement of ion subsets in a chain of five Yb+ qubits using optimal pulse shaping. A focused mode-locked laser beam individually addresses qubits to couple them to multiple collective transverse modes of motion to perform entangling phase gates on pairs of adjacent qubits. Pulse shaping by modulating the amplitude and phase of the laser can drive high fidelity gates for certain pulse solutions that are relatively insensitive to detuning errors. We create entangled states in the GHZ class and witness genuine tripartite entanglement using individual state detection. This method of engineering the evolution of multiple modes scales well for large qubit registers by keeping gate times short. This work is supported by grants from the U.S. Army Research Office with funding from the DARPA OLE program, IARPA, and the MURI program; and the NSF Physics Frontier Center at JQI.

Drosophila TRP channels and animal behavior

PubMed Central

Fowler, Melissa A.; Montell, Craig

2012-01-01

Multiple classes of cell surface receptors and ion channels participate in the detection of changes in environmental stimuli, and thereby influence animal behavior. Among the many classes of ion channels, Transient Receptor Potential (TRP) cation channels are notable in contributing to virtually every sensory modality, and in controlling a daunting array of behaviors. TRP channels appear to be conserved in all metazoan organisms including worms, insects and humans. Flies encode 13 TRPs, most of which are expressed and function in sensory neurons, and impact behaviors ranging from phototaxis to thermotaxis, gravitaxis, the avoidance of noxious tastants and smells and proprioception. Multiple diseases result from defects in TRPs, and flies provide an excellent animal model for dissecting the mechanisms underlying “TRPopathies.” Drosophila TRPs also function in the sensation of botanically derived insect repellents, and related TRPs in insect pests are potential targets for the development of improved repellents to combat insect-borne diseases. PMID:22877650

Reconstructing Ion Spectra from Low-Altitude ENAs: Moderate to Large Storms.

NASA Astrophysics Data System (ADS)

LLera, K.; Goldstein, J.; McComas, D. J.; Valek, P. W.

2015-12-01

Two Wide-angle Imaging Neutral-atom Spectrometers (TWINS) Energetic neutral atom (ENA) imagers regularly observe Low-altitude Emission (LAE) intensifications during geomagnetic storm intervals. Since LAEs are produced by the interaction between ions and the near-Earth exosphere (altitudes ~200-800 km), they are a global signature of how the ring current decays in response to solar wind conditions. In this "optically thick" region, an ENA readily becomes reionized, and an ion is readily neutralized. Therefore, emerging ENAs that contribute to the LAE signal (detectable several RE away) have undergone multiple charge exchange and electron stripping interactions. Accounting for the ~36 eV energy loss per interaction, we developed a model to quantify the total energy lost by emergent LAEs. The analytical tool is applied to an ensemble of moderate to large storms (including the recent 17 March and 23 June storms in 2015) to reconstruct the parent ion spectra from TWINS ENA images. We examine the ion spectra energy characteristics among the various storm events.

A hemispherical Langmuir probe array detector for angular resolved measurements on droplet-based laser-produced plasmas

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

Gambino, Nadia, E-mail: gambinon@ethz.ch; Brandstätter, Markus; Rollinger, Bob

2014-09-15

In this work, a new diagnostic tool for laser-produced plasmas (LPPs) is presented. The detector is based on a multiple array of six motorized Langmuir probes. It allows to measure the dynamics of a LPP in terms of charged particles detection with particular attention to droplet-based LPP sources for EUV lithography. The system design permits to temporally resolve the angular and radial plasma charge distribution and to obtain a hemispherical mapping of the ions and electrons around the droplet plasma. The understanding of these dynamics is fundamental to improve the debris mitigation techniques for droplet-based LPP sources. The device hasmore » been developed, built, and employed at the Laboratory for Energy Conversion, ETH Zürich. The experimental results have been obtained on the droplet-based LPP source ALPS II. For the first time, 2D mappings of the ion kinetic energy distribution around the droplet plasma have been obtained with an array of multiple Langmuir probes. These measurements show an anisotropic expansion of the ions in terms of kinetic energy and amount of ion charge around the droplet target. First estimations of the plasma density and electron temperature were also obtained from the analysis of the probe current signals.« less

The new 6 MV multi-nuclide AMS facility at the University of Tsukuba

NASA Astrophysics Data System (ADS)

Sasa, Kimikazu; Takahashi, Tsutomu; Matsumura, Masumi; Matsunaka, Tetsuya; Satou, Yukihiko; Izumi, Daiki; Sueki, Keisuke

2015-10-01

The former accelerator mass spectrometry (AMS) system installed on the 12UD Pelletron tandem accelerator at the University of Tsukuba was completely destroyed by the Great East Japan Earthquake on 11 March 2011. A replacement has been designed and constructed at the university as part of the post-quake reconstruction project. It consists of a 6 MV Pelletron tandem accelerator, two multiple cathode AMS ion sources (MC-SNICSs), and a rare-particle detection system. The 6 MV Pelletron tandem accelerator will be applied not only to AMS, but also to areas such as nanotechnology, ion beam analysis, heavy ion irradiation, and nuclear physics. The rare-particle detection system will be capable of measuring environmental levels of long-lived radioisotopes of 10Be, 14C, 26Al, 36Cl, 41Ca, and 129I. It is also expected to measure other radioisotopes such as 32Si and 90Sr. The 6 MV Pelletron tandem accelerator was installed in the spring of 2014 at the University of Tsukuba. Routine beam delivery and AMS experiments will start in 2015.

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.

Hybrid Ion-Detector/Data-Acquisition System for a TOF-MS

NASA Technical Reports Server (NTRS)

Burton, William D., Jr.; Schultz, J. Albert; Vaughn, Valentine; McCully, Michael; Ulrich, Steven; Egan, Thomas F.

2006-01-01

A modified ion-detector/data-acquisition system has been devised to increase the dynamic range of a time-of-flight mass spectrometer (TOF-MS) that, previously, included a microchannel-plate detector and a data-acquisition system based on counting pulses and time-tagging them by use of a time-to-digital converter (TDC). The dynamic range of the TOF-MS was limited by saturation of the microchannel plate detector, which can handle no more than a few million counts per second. The modified system includes (1) a combined microchannel plate/discrete ion multiplier and (2) a hybrid data-acquisition system that simultaneously performs analog current or voltage measurements and multianode single-ion-pulse-counting time-of-flight measurements to extend the dynamic range of a TDC into the regime in which a mass peak comprises multiple ions arriving simultaneously at the detector. The multianode data are used to determine, in real time, whether the detector is saturated. When saturation is detected, the data-acquisition system selectively enables circuitry that simultaneously determines the ion-peak intensity by measuring the time profile of the analog current or voltage detector-output signal.

Determination of ambroxol in human plasma using LC-MS/MS.

PubMed

Kim, Hohyun; Yoo, Jeong-Yeon; Han, Sang Beom; Lee, Hee Joo; Lee, Kyung Ryul

2003-06-01

A sensitive and selective liquid chromatographic method coupled with tandem mass spectrometry (LC-MS/MS) was developed for the quantification of ambroxol in human plasma. Domperidone was used as internal standard, with plasma samples extracted using diethyl ether under basic condition. A centrifuged upper layer was then evaporated and reconstituted with 200 microl methanol. The reconstituted samples were injected into a C(18) XTerra MS column (2.1 x 30 mm) with 3.5 microm particle size. The analytical column lasted for at least 600 injections. The mobile phase was composed of 20 mM ammonium acetate in 90% acetonitrile (pH 8.8), with flow rate at 250 microl/min. The mass spectrometer was operated in positive ion mode using turbo electrospray ionization. Nitrogen was used as the nebulizer, curtain, collision, and auxiliary gases. Using MS/MS with multiple reaction monitoring (MRM) mode, ambroxol was detected without severe interferences from plasma matrix. Ambroxol produced a protonated precursor ion ([M+H](+)) at m/z 379 and a corresponding product ion at m/z 264. And internal standard (domperidone) produced a protonated precursor ion ([M+H](+)) at m/z 426 and a corresponding product ion at m/z 174. Detection of ambroxol in human plasma was accurate and precise, with quantification limit at 0.2 ng/ml. This method has been successfully applied to a study of ambroxol in human specimens.

mBAND Analysis of Late Chromosome Aberrations in Human Lymphocytes Induced by Gamma Rays and Fe Ions

NASA Technical Reports Server (NTRS)

Sunagawa, Mayumi; Zhang, Ye; Yeshitla, Samrawit; Kadhim, Munira; Wilson, Bobby; Wu, Honglu

2014-01-01

Chromosomal translocations and inversions are considered stable, and cells containing these types of chromosome aberrations can survive multiple cell divisions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. Detailed analysis of chromosome break ends participating in exchanges revealed a greater fraction of break ends involved in intrachromosome aberrations in the 7- and 14-day samples in comparison to the fraction at first mitosis. In particular, simple inversions were found at 7 and 14 days, but not at the first mitosis, suggesting that some of the aberrations might be formed days post irradiation. In contrast, at the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Comparison between low and high doses of Fe ion irradiation in the induction of late damages will also be discussed.

Electrocardiographic Biomarkers for Detection of Drug-Induced Late Sodium Current Block

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

Vicente, Jose; Johannesen, Lars; Hosseini, Meisam

Drugs that prolong the heart rate corrected QT interval (QTc) on the electrocardiogram (ECG) by blocking the hERG potassium channel and also block inward currents (late sodium or L-type calcium) are not associated with torsade de pointes (e.g. ranolazine and verapamil). Furthermore, identifying ECG signs of late sodium current block could aid in the determination of proarrhythmic risk for new drugs. A new cardiac safety paradigm for drug development (the "CiPA" initiative) will involve the preclinical assessment of multiple human cardiac ion channels and ECG biomarkers are needed to determine if there are unexpected ion channel effects in humans.

Electrocardiographic Biomarkers for Detection of Drug-Induced Late Sodium Current Block

DOE PAGES

Vicente, Jose; Johannesen, Lars; Hosseini, Meisam; ...

2016-12-30

Drugs that prolong the heart rate corrected QT interval (QTc) on the electrocardiogram (ECG) by blocking the hERG potassium channel and also block inward currents (late sodium or L-type calcium) are not associated with torsade de pointes (e.g. ranolazine and verapamil). Furthermore, identifying ECG signs of late sodium current block could aid in the determination of proarrhythmic risk for new drugs. A new cardiac safety paradigm for drug development (the "CiPA" initiative) will involve the preclinical assessment of multiple human cardiac ion channels and ECG biomarkers are needed to determine if there are unexpected ion channel effects in humans.

Single-indicator-based Multidimensional Sensing: Detection and Identification of Heavy Metal Ions and Understanding the Foundations from Experiment to Simulation

PubMed Central

Leng, Yumin; Qian, Sihua; Wang, Yuhui; Lu, Cheng; Ji, Xiaoxu; Lu, Zhiwen; Lin, Hengwei

2016-01-01

Multidimensional sensing offers advantages in accuracy, diversity and capability for the simultaneous detection and discrimination of multiple analytes, however, the previous reports usually require complicated synthesis/fabrication process and/or need a variety of techniques (or instruments) to acquire signals. Therefore, to take full advantages of this concept, simple designs are highly desirable. Herein, a novel concept is conceived to construct multidimensional sensing platforms based on a single indicator that has capability of showing diverse color/fluorescence responses with the addition of different analytes. Through extracting hidden information from these responses, such as red, green and blue (RGB) alterations, a triple-channel-based multidimensional sensing platform could consequently be fabricated, and the RGB alterations are further applicable to standard statistical methods. As a proof-of-concept study, a triple-channel sensing platform is fabricated solely using dithizone with assistance of cetyltrimethylammonium bromide (CTAB) for hyperchromicity and sensitization, which demonstrates superior capabilities in detection and identification of ten common heavy metal ions at their standard concentrations of wastewater-discharge of China. Moreover, this sensing platform exhibits promising applications in semi-quantitative and even quantitative analysis individuals of these heavy metal ions with high sensitivity as well. Finally, density functional theory calculations are performed to reveal the foundations for this analysis. PMID:27146105

Improved Multiple-Species Cyclotron Ion Source

NASA Technical Reports Server (NTRS)

Soli, George A.; Nichols, Donald K.

1990-01-01

Use of pure isotope 86Kr instead of natural krypton in multiple-species ion source enables source to produce krypton ions separated from argon ions by tuning cylcotron with which source used. Addition of capability to produce and separate krypton ions at kinetic energies of 150 to 400 MeV necessary for simulation of worst-case ions occurring in outer space.

Simulated space radiation-induced mutants in the mouse kidney display widespread genomic change

PubMed Central

Grygoryev, Dmytro; Lasarev, Michael; Ohlrich, Anna; Rwatambuga, Furaha A.; Johnson, Sorrel; Dan, Cristian; Eckelmann, Bradley; Hryciw, Gwen; Mao, Jian-Hua; Snijders, Antoine M.; Gauny, Stacey; Kronenberg, Amy

2017-01-01

Exposure to a small number of high-energy heavy charged particles (HZE ions), as found in the deep space environment, could significantly affect astronaut health following prolonged periods of space travel if these ions induce mutations and related cancers. In this study, we used an in vivo mutagenesis assay to define the mutagenic effects of accelerated 56Fe ions (1 GeV/amu, 151 keV/μm) in the mouse kidney epithelium exposed to doses ranging from 0.25 to 2.0 Gy. These doses represent fluences ranging from 1 to 8 particle traversals per cell nucleus. The Aprt locus, located on chromosome 8, was used to select induced and spontaneous mutants. To fully define the mutagenic effects, we used multiple endpoints including mutant frequencies, mutation spectrum for chromosome 8, translocations involving chromosome 8, and mutations affecting non-selected chromosomes. The results demonstrate mutagenic effects that often affect multiple chromosomes for all Fe ion doses tested. For comparison with the most abundant sparsely ionizing particle found in space, we also examined the mutagenic effects of high-energy protons (1 GeV, 0.24 keV/μm) at 0.5 and 1.0 Gy. Similar doses of protons were not as mutagenic as Fe ions for many assays, though genomic effects were detected in Aprt mutants at these doses. Considered as a whole, the data demonstrate that Fe ions are highly mutagenic at the low doses and fluences of relevance to human spaceflight, and that cells with considerable genomic mutations are readily induced by these exposures and persist in the kidney epithelium. The level of genomic change produced by low fluence exposure to heavy ions is reminiscent of the extensive rearrangements seen in tumor genomes suggesting a potential initiation step in radiation carcinogenesis. PMID:28683078

Simulated space radiation-induced mutants in the mouse kidney display widespread genomic change.

PubMed

Turker, Mitchell S; Grygoryev, Dmytro; Lasarev, Michael; Ohlrich, Anna; Rwatambuga, Furaha A; Johnson, Sorrel; Dan, Cristian; Eckelmann, Bradley; Hryciw, Gwen; Mao, Jian-Hua; Snijders, Antoine M; Gauny, Stacey; Kronenberg, Amy

2017-01-01

Exposure to a small number of high-energy heavy charged particles (HZE ions), as found in the deep space environment, could significantly affect astronaut health following prolonged periods of space travel if these ions induce mutations and related cancers. In this study, we used an in vivo mutagenesis assay to define the mutagenic effects of accelerated 56Fe ions (1 GeV/amu, 151 keV/μm) in the mouse kidney epithelium exposed to doses ranging from 0.25 to 2.0 Gy. These doses represent fluences ranging from 1 to 8 particle traversals per cell nucleus. The Aprt locus, located on chromosome 8, was used to select induced and spontaneous mutants. To fully define the mutagenic effects, we used multiple endpoints including mutant frequencies, mutation spectrum for chromosome 8, translocations involving chromosome 8, and mutations affecting non-selected chromosomes. The results demonstrate mutagenic effects that often affect multiple chromosomes for all Fe ion doses tested. For comparison with the most abundant sparsely ionizing particle found in space, we also examined the mutagenic effects of high-energy protons (1 GeV, 0.24 keV/μm) at 0.5 and 1.0 Gy. Similar doses of protons were not as mutagenic as Fe ions for many assays, though genomic effects were detected in Aprt mutants at these doses. Considered as a whole, the data demonstrate that Fe ions are highly mutagenic at the low doses and fluences of relevance to human spaceflight, and that cells with considerable genomic mutations are readily induced by these exposures and persist in the kidney epithelium. The level of genomic change produced by low fluence exposure to heavy ions is reminiscent of the extensive rearrangements seen in tumor genomes suggesting a potential initiation step in radiation carcinogenesis.

Development of Ion Chemosensors Based on Porphyrin Analogues.

PubMed

Ding, Yubin; Zhu, Wei-Hong; Xie, Yongshu

2017-02-22

Sensing of metal ions and anions is of great importance because of their widespread distribution in environmental systems and biological processes. Colorimetric and fluorescent chemosensors based on organic molecular species have been demonstrated to be effective for the detection of various ions and possess the significant advantages of low cost, high sensitivity, and convenient implementation. Of the available classes of organic molecules, porphyrin analogues possess inherently many advantageous features, making them suitable for the design of ion chemosensors, with the targeted sensing behavior achieved and easily modulated based on their following characteristics: (1) NH moieties properly disposed for binding of anions through cooperative hydrogen-bonding interactions; (2) multiple pyrrolic N atoms or other heteroatoms for selectively chelating metal ions; (3) variability of macrocycle size and peripheral substitution for modulation of ion selectivity and sensitivity; and (4) tunable near-infrared emission and good biocompatibility. In this Review, design strategies, sensing mechanisms, and sensing performance of ion chemosensors based on porphyrin analogues are described by use of extensive examples. Ion chemosensors based on normal porphyrins and linear oligopyrroles are also briefly described. This Review provides valuable information for researchers of related areas and thus may inspire the development of more practical and effective approaches for designing high-performance ion chemosensors based on porphyrin analogues and other relevant compounds.

Fluorescent Binary Ensemble Based on Pyrene Derivative and Sodium Dodecyl Sulfate Assemblies as a Chemical Tongue for Discriminating Metal Ions and Brand Water.

PubMed

Zhang, Lijun; Huang, Xinyan; Cao, Yuan; Xin, Yunhong; Ding, Liping

2017-12-22

Enormous effort has been put to the detection and recognition of various heavy metal ions due to their involvement in serious environmental pollution and many major diseases. The present work has developed a single fluorescent sensor ensemble that can distinguish and identify a variety of heavy metal ions. A pyrene-based fluorophore (PB) containing a metal ion receptor group was specially designed and synthesized. Anionic surfactant sodium dodecyl sulfate (SDS) assemblies can effectively adjust its fluorescence behavior. The selected binary ensemble based on PB/SDS assemblies can exhibit multiple emission bands and provide wavelength-based cross-reactive responses to a series of metal ions to realize pattern recognition ability. The combination of surfactant assembly modulation and the receptor for metal ions empowers the present sensor ensemble with strong discrimination power, which could well differentiate 13 metal ions, including Cu 2+ , Co 2+ , Ni 2+ , Cr 3+ , Hg 2+ , Fe 3+ , Zn 2+ , Cd 2+ , Al 3+ , Pb 2+ , Ca 2+ , Mg 2+ , and Ba 2+ . Moreover, this single sensing ensemble could be further applied for identifying different brands of drinking water.

Label-free protein quantification using LC-coupled ion trap or FT mass spectrometry: Reproducibility, linearity, and application with complex proteomes.

PubMed

Wang, Guanghui; Wu, Wells W; Zeng, Weihua; Chou, Chung-Lin; Shen, Rong-Fong

2006-05-01

A critical step in protein biomarker discovery is the ability to contrast proteomes, a process referred generally as quantitative proteomics. While stable-isotope labeling (e.g., ICAT, 18O- or 15N-labeling, or AQUA) remains the core technology used in mass spectrometry-based proteomic quantification, increasing efforts have been directed to the label-free approach that relies on direct comparison of peptide peak areas between LC-MS runs. This latter approach is attractive to investigators for its simplicity as well as cost effectiveness. In the present study, the reproducibility and linearity of using a label-free approach to highly complex proteomes were evaluated. Various amounts of proteins from different proteomes were subjected to repeated LC-MS analyses using an ion trap or Fourier transform mass spectrometer. Highly reproducible data were obtained between replicated runs, as evidenced by nearly ideal Pearson's correlation coefficients (for ion's peak areas or retention time) and average peak area ratios. In general, more than 50% and nearly 90% of the peptide ion ratios deviated less than 10% and 20%, respectively, from the average in duplicate runs. In addition, the multiplicity ratios of the amounts of proteins used correlated nicely with the observed averaged ratios of peak areas calculated from detected peptides. Furthermore, the removal of abundant proteins from the samples led to an improvement in reproducibility and linearity. A computer program has been written to automate the processing of data sets from experiments with groups of multiple samples for statistical analysis. Algorithms for outlier-resistant mean estimation and for adjusting statistical significance threshold in multiplicity of testing were incorporated to minimize the rate of false positives. The program was applied to quantify changes in proteomes of parental and p53-deficient HCT-116 human cells and found to yield reproducible results. Overall, this study demonstrates an alternative approach that allows global quantification of differentially expressed proteins in complex proteomes. The utility of this method to biomarker discovery is likely to synergize with future improvements in the detecting sensitivity of mass spectrometers.

Fragmentation of organic ions bearing fixed multiple charges observed in MALDI MS.

PubMed

Lou, Xianwen; Li, Bao; de Waal, Bas F M; Schill, Jurgen; Baker, Matthew B; Bovee, Ralf A A; van Dongen, Joost L J; Milroy, Lech-Gustav; Meijer, E W

2018-01-01

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS) was used to analyze a series of synthetic organic ions bearing fixed multiple charges. Despite the multiple intrinsic charges, only singly charged ions were recorded in each case. In addition to the pseudo-molecular ions formed by counterion adduction, deprotonation and electron capture, a number of fragment ions were also observed. Charge splitting by fragmentation was found to be a viable route for charge reduction leading to the formation of the observed singly charged fragment ions. Unlike multivalent metal ions, organic ions can rearrange and/or fragment during charge reduction. This fragmentation process will evidently complicate the interpretation of the MALDI MS spectrum. Because MALDI MS is usually considered as a soft ionization technique, the fragment ion peaks can easily be erroneously interpreted as impurities. Therefore, the awareness and understanding of the underlying MALDI-induced fragmentation pathways is essential for a proper interpretation of the corresponding mass spectra. Due to the fragment ions generated during charge reduction, special care should be taken in the MALDI MS analysis of multiply charged ions. In this work, the possible mechanisms by which the organic ions bearing fixed multiple charges fragment are investigated. With an improved understanding of the fragmentation mechanisms, MALDI TOF MS should still be a useful technique for the characterization of organic ions with fixed multiple charges. Copyright © 2017 John Wiley & Sons, Ltd.

A novel HPLC-MRM strategy to discover unknown and long-term metabolites of stanozolol for expanding analytical possibilities in doping-control.

PubMed

Wang, Zhe; Zhou, Xinmiao; Liu, Xin; Dong, Ying; Zhang, Jinlan

2017-01-01

Stanozolol is one of the most commonly abused anabolic androgenic steroids (AAS) by athletes and usually detected by its parent drug and major metabolites. However, its metabolic pathway is complex, varied and individually different, it is important to characterize its overall metabolic profiles and discover new and long-term metabolites for the aims of expanding detection windows. High performance liquid chromatography coupled with triple quadrupole mass spectrometer (HPLC-MS/MS) was used to analyze the human urine after oral administration of stanozolol. Multiple reaction monitoring (MRM), one of the scan modes of triple quadrupole mass spectrometer showing extremely high sensitivity was well used to develop a strategy for metabolic profiles characterization and long-term metabolites detection based on typical precursor to product ion transitions of parent drug and its major metabolites. Utilizing the characteristic fragment ions of stanozolol and its major metabolites as the product ions, and speculating unknown precursor ions based on the possible phase I and phase II metabolic reactions in human body, the metabolite profiles of stanozolol could be comprehensively discovered, especially for those unknown and low concentration metabolites in human urine. Then these metabolites were further well structure identified by targeted high resolution MS/MS scan of quadrupole-time of flight mass spectrometry (Q-TOF). Applying this strategy, 27 phase I and 21 phase II metabolites of stanozolol were identified, in which 13 phase I and 14 phase II metabolites have not been reported previously. The 9 out of 48 metabolites could be detected over 15days post drug administration. This strategy could be employed effectively to characterize AAS metabolic profiles and discover unknown and long-term metabolites in sports drug testing. Copyright © 2016 Elsevier B.V. All rights reserved.

Direct large volume injection ultra-high performance liquid chromatography-tandem mass spectrometry determination of artificial sweeteners sucralose and acesulfame in well water.

PubMed

Wu, Minghuo; Qian, Yichao; Boyd, Jessica M; Hrudey, Steve E; Le, X Chris; Li, Xing-Fang

2014-09-12

Acesulfame (ACE) and sucralose (SUC) have become recognized as ideal domestic wastewater contamination indicators. Liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) analysis is commonly used; however, the sensitivity of SUC is more than two orders of magnitude lower than that of ACE, limiting the routine monitoring of SUC. To address this issue, we examined the ESI behavior of both ACE and SUC under various conditions. ACE is ionic in aqueous solution and efficiently produces simple [M-H](-) ions, but SUC produces multiple adduct ions, limiting its sensitivity. The formic acid (FA) adducts of SUC [M+HCOO](-) are sensitively and reproducibly generated under the LC-MS conditions. When [M+HCOO](-) is used as the precursor ion for SUC detection, the sensitivity increases approximately 20-fold compared to when [M-H](-) is the precursor ion. To further improve the limit of detection (LOD), we integrated the large volume injection approach (500μL injection) with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), which reduced the method detection limit (MDL) to 0.2ng/L for ACE and 5ng/L for SUC. To demonstrate the applicability of this method, we analyzed 100 well water samples collected in Alberta. ACE was detected in 24 wells at concentrations of 1-1534ng/L and SUC in 8 wells at concentrations of 65-541ng/L. These results suggest that wastewater is the most likely source of ACE and SUC impacts in these wells, suggesting the need for monitoring the quality of domestic well water. Copyright © 2014 Elsevier B.V. All rights reserved.

Proof of principle of helium-beam radiography using silicon pixel detectors for energy deposition measurement, identification, and tracking of single ions.

PubMed

Gehrke, Tim; Gallas, Raya; Jäkel, Oliver; Martišíková, Maria

2018-02-01

Hadron therapy has the capability to provide a high dose conformation to tumor regions. However, it requires an accurate target positioning. Thus, the precise monitoring of the patient's anatomical positioning during treatment is desirable. For this purpose, hadron-beam radiography with protons (pRad) and ions (iRad) could be an attractive tool complementing the conventional imaging technologies. On the pathway to an envisaged clinical application, several challenges have to be addressed. Among them are achieving the desired spatial resolution in the presence of multiple Coulomb scattering (MCS), performing radiographs with a sufficient thickness resolution at clinically applicable dose levels, and the search for combinations of particularly suitable hadrons and detectors. These topics are investigated in this work for a detection system based on silicon pixel detectors. A method of iRad based on energy deposition measurements in thin layers is introduced. It exploits a detection system consisting of three parallel silicon pixel detectors, which also enables particle tracking and identification. Helium ions, which exhibit less pronounced MCS than protons, were chosen as imaging radiation. A PMMA phantom with a mean water-equivalent thickness (WET) of 192 mm, containing maximal WET-variations of ±6 mm, was imaged with a 173 MeV/u helium ion beam at the Heidelberg Ion-Beam Therapy Center. WET-differences in form of 2.3 mm × 2.3 mm steps were aimed to be visualized and resolved in images of the energy deposition measured behind the phantom. The detection system was placed downstream of the imaged object in order to detect single ions leaving it. The combination of the measured information on energy deposition, ion type, and the track behind the phantom was used for the image formation, employing a self-developed data-processing procedure. It was shown that helium-beam radiography is feasible with the reported detection system. The introduced data preprocessing purified the detector signal from detector artifacts and improved the image quality. Additionally, the rejection of hydrogen ions originating from nuclear interactions was shown to increase the contrast-to-noise ratio (CNR) by at least a factor of 2.5. This enabled the resolution of relative thickness differences of 1.2% at a dose level typical for diagnostic x-ray images. The spatial resolution was improved by taking into account the direction of single helium ions leaving the phantom. A spatial resolution (MTF 10% ) of at least 1.15p mm -1 for the presented experimental set-up was achieved. A successful feasibility study of helium-beam radiography with the introduced detection system was conducted. The methodology of iRad was based on energy deposition measurements in thin silicon layers. The tracking of single ions and the method of the ion identification was shown to be important for helium-beam radiography in terms of spatial resolution and CNR. © 2017 American Association of Physicists in Medicine.

Field-driven ion migration against dead-stop collisional braking

NASA Astrophysics Data System (ADS)

Grzesik, J. A.

1988-02-01

The steady-state migration of ions, driven by a uniform electric field against full-stop collisions, is investigated in some detail. The required phase-space distribution is obtained very easily from Boltzmann's equation together with explicit recognition of energy conservation and population balance for the stagnant ion pool. We go on to decompose this aggregate solution into ion tiers classified by the number of background impacts previously endured. Such a decomposition permits us to detect the presence of Poisson statistics (as to collision number) lurking within the composite, thermalized Maxwellian, and likewise also a multiple-scattering hierarchy having the maiden, first-flight distribution for its natural kernel. Scattering-sequence accounting, in particular, allows a quantitative (even though unwieldy) distinction to be made between ions of varying residence times. A model of this sort is motivated by the technique of ion implantation through sample immersion within a plasma at higher electric potential. Numerical consequences of the solution obtained here reveal that both ion density and average kinetic energy relax to their terminal values within just a few mean free-path lengths. Such modest scaling of plasma-sheath extent evidently carries a beneficial implication for the technological ease with which surface properties (such as metal corrosion resistance and hardness) remain open to improvement via ion bombardment.

Collision-induced fragmentation of negative ions from N-linked glycans derivatized with 2-aminobenzoic acid.

PubMed

Harvey, David J

2005-05-01

N-Linked glycans from bovine ribonuclease B, chicken ovalbumin, bovine fetuin, porcine thyroglobulin and human alpha(1)-acid glycoprotein were derivatized with 2-aminobenzoic acid by reductive amination and their tandem mass spectra were recorded by negative ion electrospray ionization with a quadrupole time-of-flight mass spectrometer. Derivatives were also prepared from 2-amino-5-methyl- and 2-amino-4,5-dimethoxybenzoic acid in order to confirm the identity of fragment ions containing the reducing terminus. Major fragments from the [M - H](-) ions from the neutral glycans retained the derivative (Y-type cleavages) and provided information on sequence and branching. Other major fragments were products of A-type cross-ring cleavages giving information on antenna structure. Singly doubly and triply charged ions were formed from sialylated glycans. They produced major fragments by loss of sialic acid and a series of singly charged ions that were similar to those from the neutral analogues. Doubly charge ions were also produced by the neutral glycans and were fragmented to form product ions with one and two charges. Again, the fragment ions with a single charge were similar to those from the singly charged parents, but branching information was less obvious because of the occurrence of more abundant ions produced by multiple cleavages. Detection limits were around 200 fmol (3 : 1 signal-to-noise ratio). Copyright 2005 John Wiley & Sons, Ltd.

Fault-tolerant quantum error detection.

PubMed

Linke, Norbert M; Gutierrez, Mauricio; Landsman, Kevin A; Figgatt, Caroline; Debnath, Shantanu; Brown, Kenneth R; Monroe, Christopher

2017-10-01

Quantum computers will eventually reach a size at which quantum error correction becomes imperative. Quantum information can be protected from qubit imperfections and flawed control operations by encoding a single logical qubit in multiple physical qubits. This redundancy allows the extraction of error syndromes and the subsequent detection or correction of errors without destroying the logical state itself through direct measurement. We show the encoding and syndrome measurement of a fault-tolerantly prepared logical qubit via an error detection protocol on four physical qubits, represented by trapped atomic ions. This demonstrates the robustness of a logical qubit to imperfections in the very operations used to encode it. The advantage persists in the face of large added error rates and experimental calibration errors.

Multidimensional profiling of components in complex mixtures of natural products for metabolic analysis, proof of concept: application to Quillaja saponins.

PubMed

Bankefors, Johan; Nord, Lars I; Kenne, Lennart

2010-02-01

A method for separation and detection of major and minor components in complex mixtures has been developed, utilising two-dimensional high-performance liquid chromatography (2D-HPLC) combined with electrospray ionisation ion-trap multiple-stage mass spectrometry (ESI-ITMS(n)). Chromatographic conditions were matched with mass spectrometric detection to maximise the number of components that could be separated. The described procedure has proven useful to discern several hundreds of saponin components when applied to Quillaja saponaria Molina bark extracts. The discrimination of each saponin component relies on the fact that three coordinates (x, y, z) for each component can be derived from the retention time of the two chromatographic steps (x, y) and the m/z-values from the multiple-stage mass spectrometry (z(n), n=1, 2, ...). Thus an improved graphical representation was obtained by combining retention times from the two-stage separation with +MS(1) (z(1)) and the additional structural information from the second mass stage +MS(2) (z(2), z(3)) corresponding to the main fragment ions. By this approach three-dimensional plots can be made that reveal both the chromatographic and structural properties of a specific mixture which can be useful in fingerprinting of complex mixtures. 2009 Elsevier B.V. All rights reserved.

A compact E × B filter: A multi-collector cycloidal focusing mass spectrometer

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

Blase, Ryan C., E-mail: rblase@swri.edu; Miller, Greg; Brockwell, Tim

2015-10-15

A compact E × B mass spectrometer is presented. The mass spectrometer presented is termed a “perfect focus” mass spectrometer as the resolution of the device is independent of both the initial direction and energy of the ions (spatial and energy independent). The mass spectrometer is small in size (∼10.7 in.{sup 3}) and weight (∼2 kg), making it an attractive candidate for portability when using small, permanent magnets. A multi-collector Faraday cup design allows for the detection of multiple ion beams in discrete collectors simultaneously; providing the opportunity for isotope ratio monitoring. The mass resolution of the device is aroundmore » 400 through narrow collector slits and the sensitivity of the device follows expected theoretical calculations of the ion current produced in the electron impact ion source. Example mass spectra obtained from the cycloidal focusing mass spectrometer are presented as well as information on mass discrimination based on instrumental parameters and isotope ratio monitoring of certain ion signals in separate Faraday cups.« less

Persistent photoconductivity in oxygen-ion implanted KNbO3 bulk single crystal

NASA Astrophysics Data System (ADS)

Tsuruoka, R.; Shinkawa, A.; Nishimura, T.; Tanuma, C.; Kuriyama, K.; Kushida, K.

2016-12-01

Persistent Photoconductivity (PPC) in oxygen-ion implanted KNbO3 ([001] oriented bulk single crystals; perovskite structure; ferroelectric with a band gap of 3.16 eV)　is studied in air at room temperature to prevent the degradation of its crystallinity caused by the phase transition. The residual hydrogens in un-implanted samples are estimated to be 5×1014 cm-2 from elastic recoil detection analysis (ERDA). A multiple-energy implantation of oxygen ions into KNbO3 is performed using energies of 200, 400, and 600 keV (each ion fluence:1.0×1014 cm-2). The sheet resistance varies from >108 Ω/□ for an un-implanted sample to 1.9×107 Ω/□ for as-implanted one, suggesting the formation of donors due to hydrogen interstitials and oxygen vacancies introduced by the ion implantation. The PPC is clearly observed with ultraviolet and blue LEDs illumination rather than green, red, and infrared, suggesting the release of electrons from the metastable conductive state below the conduction band relating to the charge states of the oxygen vacancy.

Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Marshall, Alan G.

1998-06-01

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

Transmission geometry laserspray ionization vacuum using an atmospheric pressure inlet.

PubMed

Lutomski, Corinne A; El-Baba, Tarick J; Inutan, Ellen D; Manly, Cory D; Wager-Miller, James; Mackie, Ken; Trimpin, Sarah

2014-07-01

This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples.

Transmission Geometry Laserspray Ionization Vacuum Using an Atmospheric Pressure Inlet

PubMed Central

2015-01-01

This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples. PMID:24896880

Simultaneous and Sequential MS/MS Scan Combinations and Permutations in a Linear Quadrupole Ion Trap.

PubMed

Snyder, Dalton T; Szalwinski, Lucas J; Cooks, R Graham

2017-10-17

Methods of performing precursor ion scans as well as neutral loss scans in a single linear quadrupole ion trap have recently been described. In this paper we report methodology for performing permutations of MS/MS scan modes, that is, ordered combinations of precursor, product, and neutral loss scans following a single ion injection event. Only particular permutations are allowed; the sequences demonstrated here are (1) multiple precursor ion scans, (2) precursor ion scans followed by a single neutral loss scan, (3) precursor ion scans followed by product ion scans, and (4) segmented neutral loss scans. (5) The common product ion scan can be performed earlier in these sequences, under certain conditions. Simultaneous scans can also be performed. These include multiple precursor ion scans, precursor ion scans with an accompanying neutral loss scan, and multiple neutral loss scans. We argue that the new capability to perform complex simultaneous and sequential MS n operations on single ion populations represents a significant step in increasing the selectivity of mass spectrometry.

MRM screening/biomarker discovery with linear ion trap MS: a library of human cancer-specific peptides.

PubMed

Yang, Xu; Lazar, Iulia M

2009-03-27

The discovery of novel protein biomarkers is essential in the clinical setting to enable early disease diagnosis and increase survivability rates. To facilitate differential expression analysis and biomarker discovery, a variety of tandem mass spectrometry (MS/MS)-based protein profiling techniques have been developed. For achieving sensitive detection and accurate quantitation, targeted MS screening approaches, such as multiple reaction monitoring (MRM), have been implemented. MCF-7 breast cancer protein cellular extracts were analyzed by 2D-strong cation exchange (SCX)/reversed phase liquid chromatography (RPLC) separations interfaced to linear ion trap MS detection. MS data were interpreted with the Sequest-based Bioworks software (Thermo Electron). In-house developed Perl-scripts were used to calculate the spectral counts and the representative fragment ions for each peptide. In this work, we report on the generation of a library of 9,677 peptides (p < 0.001), representing approximately 1,572 proteins from human breast cancer cells, that can be used for MRM/MS-based biomarker screening studies. For each protein, the library provides the number and sequence of detectable peptides, the charge state, the spectral count, the molecular weight, the parameters that characterize the quality of the tandem mass spectrum (p-value, DeltaM, Xcorr, DeltaCn, Sp, no. of matching a, b, y ions in the spectrum), the retention time, and the top 10 most intense product ions that correspond to a given peptide. Only proteins identified by at least two spectral counts are listed. The experimental distribution of protein frequencies, as a function of molecular weight, closely matched the theoretical distribution of proteins in the human proteome, as provided in the SwissProt database. The amino acid sequence coverage of the identified proteins ranged from 0.04% to 98.3%. The highest-abundance proteins in the cellular extract had a molecular weight (MW)<50,000. Preliminary experiments have demonstrated that putative biomarkers, that are not detectable by conventional data dependent MS acquisition methods in complex un-fractionated samples, can be reliable identified with the information provided in this library. Based on the spectral count, the quality of a tandem mass spectrum and the m/z values for a parent peptide and its most abundant daughter ions, MRM conditions can be selected to enable the detection of target peptides and proteins.

MRM screening/biomarker discovery with linear ion trap MS: a library of human cancer-specific peptides

PubMed Central

2009-01-01

Background The discovery of novel protein biomarkers is essential in the clinical setting to enable early disease diagnosis and increase survivability rates. To facilitate differential expression analysis and biomarker discovery, a variety of tandem mass spectrometry (MS/MS)-based protein profiling techniques have been developed. For achieving sensitive detection and accurate quantitation, targeted MS screening approaches, such as multiple reaction monitoring (MRM), have been implemented. Methods MCF-7 breast cancer protein cellular extracts were analyzed by 2D-strong cation exchange (SCX)/reversed phase liquid chromatography (RPLC) separations interfaced to linear ion trap MS detection. MS data were interpreted with the Sequest-based Bioworks software (Thermo Electron). In-house developed Perl-scripts were used to calculate the spectral counts and the representative fragment ions for each peptide. Results In this work, we report on the generation of a library of 9,677 peptides (p < 0.001), representing ~1,572 proteins from human breast cancer cells, that can be used for MRM/MS-based biomarker screening studies. For each protein, the library provides the number and sequence of detectable peptides, the charge state, the spectral count, the molecular weight, the parameters that characterize the quality of the tandem mass spectrum (p-value, DeltaM, Xcorr, DeltaCn, Sp, no. of matching a, b, y ions in the spectrum), the retention time, and the top 10 most intense product ions that correspond to a given peptide. Only proteins identified by at least two spectral counts are listed. The experimental distribution of protein frequencies, as a function of molecular weight, closely matched the theoretical distribution of proteins in the human proteome, as provided in the SwissProt database. The amino acid sequence coverage of the identified proteins ranged from 0.04% to 98.3%. The highest-abundance proteins in the cellular extract had a molecular weight (MW)<50,000. Conclusion Preliminary experiments have demonstrated that putative biomarkers, that are not detectable by conventional data dependent MS acquisition methods in complex un-fractionated samples, can be reliable identified with the information provided in this library. Based on the spectral count, the quality of a tandem mass spectrum and the m/z values for a parent peptide and its most abundant daughter ions, MRM conditions can be selected to enable the detection of target peptides and proteins. PMID:19327145

Ion mass spectrometer

NASA Technical Reports Server (NTRS)

Neugebauer, M. (Inventor); Clay, D. R.; Goldstein, B. E.; Goldstein, R.

1984-01-01

An ion mass spectrometer is described which detects and indicates the characteristics of ions received over a wide angle, and which indicates the mass to charge ratio, the energy, and the direction of each detected ion. The spectrometer includes a magnetic analyzer having a sector magnet that passes ions received over a wide angle, and an electrostatic analyzer positioned to receive ions passing through the magnetic analyzer. The electrostatic analyzer includes a two dimensional ion sensor at one wall of the analyzer chamber, that senses not only the lengthwise position of the detected ion to indicate its mass to charge ratio, but also detects the ion position along the width of the chamber to indicate the direction in which the ion was traveling.

Higher Energy Plasma Ions found near the Termination Shock: Analyses of Voyager 2 Data in the Heliosheath and in the Outer Heliosphere

NASA Technical Reports Server (NTRS)

Intriligator, Devrie S.; Intriligator, James; Miller, W. David; Webber, William R.; Decker, Robert B.

2010-01-01

We have found in the Voyager 2 (V2) plasma science data in the heliosheath (HS) near the termination shock (TS) high-energy ions (HEIs) in addition to the bulk plasma convective flow ions. The HEI detections temporally coincide with increased V2 plasma wave subsystem (PWS) activity in "event A"h of Gurnett and Kurth. Maxwellian fits to HEI detections indicate the HEIs are moving radially anti -Sunward with a proton speed of 600 km/s, a density of 10(exp -4) (exp -3), and a thermal speed of 10 km/s. The heliosheath bulk convective protons have a speed of 204 km/s, a density of 0.0029 cm(exp -3), and a thermal speed of 26.7 km/s. The HEI flux and ram pressure are approximately 10% and 30% of those of the bulk HS flow. Since the HEI speed is both close to twice the solar wind speed and independent of the heliosheath bulk plasma speed, the HEIs may be detections of pickup protons formed in the solar wind and convected through the TS. The HEIs also are reminiscent of the pickup protons upstream of the Mars bow shock where their energy also was independent of the bulk plasma speed and attributed to multiple reflections off the Mars bow shock. Gurnett and Kurth 's (2008) event A enhanced PWS activity may be generated by a two ]stream instability from the interaction of these HEIs with the heliosheath bulk plasma ions. We present our findings, discuss their implications, and also present alternative interpretations.

AIE active multianalyte fluorescent probe for the detection of Cu2+, Ni2+ and Hg2+ ions.

PubMed

Pannipara, Mehboobali; Al-Sehemi, Abdullah G; Irfan, Ahmad; Assiri, Mohammed; Kalam, Abul; Al-Ammari, Yahya S

2018-08-05

A novel pyrazolyl chromene derivative (Probe 1) displaying aggregation induced emission (AIE) properties that capable of sensing of multiple metal ions has been designed and synthesized. The multi analyte probe exhibits selective sensing for Cu 2+ and Ni 2+ ions via fluorescence turn-off mechanism and ratiometric selectivity for Hg 2+ ions in aqueous media. The extent of binding of the probe with sensitive metal ions has been demonstrated. The experimental results were further investigated by computational means by optimizing the ground state geometries of Probe 1 and its various metal complexes for Probe 1-Ni, Probe 1-Hg and Probe 1-Cu using density functional theory (DFT) at B3LYP/6-31+g(d,p) (LANL2DZ) level. On the basis of binding energies, the stability of metal complexes has been studied. In Probe 1-Ni and Probe 1-Cu complexes, charge transfer has been observed from Probe 1 to metal ions revealing ligand to metal charge transfer (LMCT) while in Probe1-Hg complex LMCT as well as intra-molecular charge tranfer (ICT) within Probe 1. Copyright © 2018 Elsevier B.V. All rights reserved.

A Strategy Combining Higher Energy C-Trap Dissociation with Neutral Loss- and Product Ion-Based MSn Acquisition for Global Profiling and Structure Annotation of Fatty Acids Conjugates

NASA Astrophysics Data System (ADS)

Bi, Qi-rui; Hou, Jin-jun; Yang, Min; Shen, Yao; Qi, Peng; Feng, Rui-hong; Dai, Zhuo; Yan, Bing-peng; Wang, Jian-wei; Shi, Xiao-jian; Wu, Wan-ying; Guo, De-an

2017-03-01

Fatty acids conjugates (FACs) are ubiquitous but found in trace amounts in the natural world. They are composed of multiple unknown substructures and side chains. Thus, FACs are difficult to be analyzed by traditional mass spectrometric methods. In this study, an integrated strategy was developed to global profiling and targeted structure annotation of FACs in complex matrix by LTQ Orbitrap. Dicarboxylic acid conjugated bufotoxins (DACBs) in Venenum bufonis (VB) were used as model compounds. The new strategy (abbreviated as HPNA) combined higher-energy C-trap dissociation (HCD) with product ion- (PI), neutral loss- (NL) based MSn (n ≥ 3) acquisition in both positive-ion mode and negative-ion mode. Several advantages are presented. First, various side chains were found under HCD in negative-ion mode, which included both known and unknown side chains. Second, DACBs with multiple side chains were simultaneously detected in one run. Compared with traditional quadrupole-based mass method, it greatly increased analysis throughput. Third, the fragment ions of side chain and steroids substructure could be obtained by PI- and NL-based MSn acquisition, respectively, which greatly increased the accuracy of the structure annotation of DACBs. In all, 78 DACBs have been discovered, of which 68 were new compounds; 25 types of substructure formulas and seven dicarboxylic acid side chains were found, especially five new side chains, including two saturated dicarboxylic acids [(azelaic acid (C9) and sebacic acid (C10)] and three unsaturated dicarboxylic acids (u-C8, u-C9, and u-C10). All these results greatly enriched the structures of DACBs in VB.

Application of liquid chromatography/electrospray ionization ion trap tandem mass spectrometry for the evaluation of global nucleic acids: methylation in garden cress under exposure to CuO nanoparticles.

PubMed

Alcazar Magana, Armando; Wrobel, Kazimierz; Corrales Escobosa, Alma Rosa; Wrobel, Katarzyna

2016-01-15

A full understanding of the biological impact of nanomaterials demands analytical procedures suitable for the detection/quantification of epigenetic changes that occur in the exposed organisms. Here, the effect of CuO nanoparticles (NPs) on global methylation of nucleic acids in Lepidium sativum was evaluated by liquid chromatography/ion trap mass spectrometry. Enhanced selectivity toward cytosine-containing nucleosides was achieved by using their proton-bound dimers formed in positive electrospray ionization (ESI(+)) as precursor ions for multiple reaction monitoring (MRM) quantification based on one or two ion transitions. Plants were exposed to CuO NPs (0-1000 mg L(-1)); nucleic acid extracts were washed with bathocuproine disulfate; nucleosides were separated on a Luna C18 column coupled via ESI(+) to an AmaZon SL mass spectrometer (Bruker Daltonics). Cytidine, 2´-deoxycytidine, 5-methylcytidine, 5-methyl-2´-deoxycytidine and 5-hydroxymethyl-2´-deoxycytidine were quantified by MRM based on MS(3) ([2M+H](+)/[M+H](+)/[M+H-132](+) or [M+H-116](+)) and MS(2) ([2M+H](+)/[M+H](+) ). Bathocuproine disulfate, added as Cu(I) complexing agent, allowed for elimination of [2M+Cu](+) adducts from the mass spectra. Poorer instrumental detection limits were obtained for MS(3) (20-120 fmol) as compared to MS(2) (9.0-41 fmol); however, two ion transitions helped to eliminate matrix effects in plant extracts. The procedure was tested by analyzing salmon sperm DNA (Sigma) and applied for the evaluation of DNA and RNA methylation in plants; in the absence of NPs, 13.03% and 0.92% methylated cytosines were found in DNA and RNA, respectively; for NPs concentration >50 mg L(-1), DNA hypomethylation was observed with respect to unexposed plants. RNA methylation did not present significant changes upon plant exposure; 5-hydroxymethyl-2´-deoxycytidine was not detected in any sample. The MRM quantification proposed here of cytosine-containing nucleosides using their proton-bound homo-dimers as precursor ions proved its utility for the assessment of global methylation of DNA and RNA in plants under stress imposed by CuO NPs. Detection of copper adducts with cytosine-containing ions, and their elimination by washing extracts with Cu(I) chelator, calls for further investigation. Copyright © 2015 John Wiley & Sons, Ltd.

mBAND Analysis of Early and Late Damages in the Chromosome of Human Lymphocytes after Exposures to Gamma Rays and Fe Ions

NASA Technical Reports Server (NTRS)

Sunagawa, Mayumi; Zhang, Ye; Yeshitla, Samrawit; Kadhim, Munira; Wilson, Bobby; Wu, Honglu

2013-01-01

Stable type chromosome aberrations that survive multiple generations of cell division include translocation and inversions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. At the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Detailed analysis of breaks participating in total chromosome exchanges within the first cell cycle post irradiation revealed a common hotspot located in the 3p21 region, which is a known fragile site corresponding to the band 6 in the mBand analysis. The breakpoint distribution in chromosomes collected at 7 days, but not at 14 days, post irradiation appeared similar to the distribution in cells collected within the first cell cycle post irradiation. The breakpoint distribution for human lymphocytes after radiation exposure was different from the previously published distribution for human mammary epithelial cells, indicating that interphase chromatin folding structures play a role in the distribution of radiation-induced breaks.

Lateral charge transport from heavy-ion tracks in integrated circuit chips

NASA Technical Reports Server (NTRS)

Zoutendyk, J. A.; Schwartz, H. R.; Nevill, L. R.

1988-01-01

A 256K DRAM has been used to study the lateral transport of charge (electron-hole pairs) induced by direct ionization from heavy-ion tracks in an IC. The qualitative charge transport has been simulated using a two-dimensional numerical code in cylindrical coordinates. The experimental bit-map data clearly show the manifestation of lateral charge transport in the creation of adjacent multiple-bit errors from a single heavy-ion track. The heavy-ion data further demonstrate the occurrence of multiple-bit errors from single ion tracks with sufficient stopping power. The qualitative numerical simulation results suggest that electric-field-funnel-aided (drift) collection accounts for single error generated by an ion passing through a charge-collecting junction, while multiple errors from a single ion track are due to lateral diffusion of ion-generated charge.

Uncoupling metallonuclease metal ion binding sites via nudge mutagenesis.

PubMed

Papadakos, Grigorios A; Nastri, Horacio; Riggs, Paul; Dupureur, Cynthia M

2007-05-01

The hydrolysis of phosphodiester bonds by nucleases is critical to nucleic acid processing. Many nucleases utilize metal ion cofactors, and for a number of these enzymes two active-site metal ions have been detected. Testing proposed mechanistic roles for individual bound metal ions has been hampered by the similarity between the sites and cooperative behavior. In the homodimeric PvuII restriction endonuclease, the metal ion dependence of DNA binding is sigmoidal and consistent with two classes of coupled metal ion binding sites. We reasoned that a conservative active-site mutation would perturb the ligand field sufficiently to observe the titration of individual metal ion binding sites without significantly disturbing enzyme function. Indeed, mutation of a Tyr residue 5.5 A from both metal ions in the enzyme-substrate crystal structure (Y94F) renders the metal ion dependence of DNA binding biphasic: two classes of metal ion binding sites become distinct in the presence of DNA. The perturbation in metal ion coordination is supported by 1H-15N heteronuclear single quantum coherence spectra of enzyme-Ca(II) and enzyme-Ca(II)-DNA complexes. Metal ion binding by free Y94F is basically unperturbed: through multiple experiments with different metal ions, the data are consistent with two alkaline earth metal ion binding sites per subunit of low millimolar affinity, behavior which is very similar to that of the wild type. The results presented here indicate a role for the hydroxyl group of Tyr94 in the coupling of metal ion binding sites in the presence of DNA. Its removal causes the affinities for the two metal ion binding sites to be resolved in the presence of substrate. Such tuning of metal ion affinities will be invaluable to efforts to ascertain the contributions of individual bound metal ions to metallonuclease function.

Multiple products monitoring as a robust approach for peptide quantification.

PubMed

Baek, Je-Hyun; Kim, Hokeun; Shin, Byunghee; Yu, Myeong-Hee

2009-07-01

Quantification of target peptides and proteins is crucial for biomarker discovery. Approaches such as selected reaction monitoring (SRM) and multiple reaction monitoring (MRM) rely on liquid chromatography and mass spectrometric analysis of defined peptide product ions. These methods are not very widespread because the determination of quantifiable product ion using either SRM or MRM is a very time-consuming process. We developed a novel approach for quantifying target peptides without such an arduous process of ion selection. This method is based on monitoring multiple product ions (multiple products monitoring: MpM) from full-range MS2 spectra of a target precursor. The MpM method uses a scoring system that considers both the absolute intensities of product ions and the similarities between the query MS2 spectrum and the reference MS2 spectrum of the target peptide. Compared with conventional approaches, MpM greatly improves sensitivity and selectivity of peptide quantification using an ion-trap mass spectrometer.

UPLC-MS/MS determination of ephedrine, methylephedrine, amygdalin and glycyrrhizic acid in Beagle plasma and its application to a pharmacokinetic study after oral administration of Ma Huang Tang.

PubMed

Yan, Tianhua; Fu, Qiang; Wang, Jing; Ma, Shiping

2015-02-01

An ultra performance liquid chromatography-mass spectrometric (UPLC-MS) method was developed to investigate the pharmacokinetic properties of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid after oral gavage of Ma Huang Tang (MHT) in Beagles. Beagle plasma samples were pretreated using liquid-liquid extraction, and chromatographic separation was performed on a C18 column using a linear gradient of water-formic acid mixture (0.1%). The pharmacokinetic parameters of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid from MHT in Beagles were quantitatively determined by UPLC with tandem mass detector. The qualitative detection of the four compounds was accomplished by selected ion monitoring in negative/positive ion modes electrospray ionization-mass spectrometry (ESI-MS). Detection was based on multiple reaction monitoring with the precursor-to-product ion transitions m/z 166.096-116.983 (ephedrine), m/z 179.034-146.087 (methylephedrine), m/z 456.351-323.074 (amygdalin), and m/z 821.606-351.062 (glycyrrhizic acid). The selectivity, sensitivity, linearity, accuracy, precision, extraction recovery, ion suppression, and stability were within the acceptable ranges. The method described was successfully applied to reveal the pharmacokinetic properties of ephedrine, methylephedrine, amygdalin, and glycyrrhizic acid after oral gavage of MHT in Beagles. Copyright © 2014 John Wiley & Sons, Ltd.

A 23Na Multiple-Quantum-Filtered NMR Study of the Effect of the Cytoskeleton Conformation on the Anisotropic Motion of Sodium Ions in Red Blood Cells

NASA Astrophysics Data System (ADS)

Knubovets, Tatyana; Shinar, Hadassah; Eliav, Uzi; Navon, Gil

1996-01-01

Recently, it has been shown that23Na double-quantum-filtered NMR spectroscopy can be used to detect anisotropic motion of bound sodium ions in biological systems. The technique is based on the formation of the second-rank tensor when the quadrupolar interaction is not averaged to zero. Using this method, anisotropic motion of bound sodium in human and dog red blood cells was detected, and the effect was shown to depend on the integrity of the membrane cytoskeleton. In the present study, multiple-quantum-filtered techniques were applied in combination with a quadrupolar echo to measure the transverse-relaxation times,T2fandT2s. Line fitting was performed to obtain the values of the residual quadrupolar interaction, which was measured for sodium in a variety of mammalian erythrocytes of different size, shape, rheological properties, and sodium concentrations. Human unsealed white ghosts were used to study sodium bound at the anisotropic sites on the inner side of the RBC membrane. Modulations of the conformation of the cytoskeleton by the variation of either the ionic strength or pH of the suspending medium caused drastic changes in both the residual quadrupolar interaction andT2fdue to changes in the fraction of bound sodium ions as well as changes in the structure of the binding sites. By combining the two spectroscopic parameters, structural change can be followed. The changes in the structure of the sodium anisotropic binding sites deduced by this method were found to correlate with known conformational changes of the membrane cytoskeleton. Variations of the medium pH affected both the fraction of bound sodium ions and the structure of the anisotropic binding sites. Sodium and potassium were shown to bind to the anisotropic binding sites with the same affinity.

Ion-selective detection by plasticized poly(vinyl chloride) membrane in glass nanopipette with alternating voltage modulation.

PubMed

Deng, Xiao Long; Takami, Tomohide; Son, Jong Wan; Kang, Eun Ji; Kawai, Tomoji; Park, Bae Ho

2013-08-01

An alternating current (AC) voltage modulation was applied to ion-selective observations with plasticized poly(vinyl chloride) membranes in glass nanopipettes. The liquid confronting the membranes in the nanopipettes, the conditioning process, and AC voltage modulation play important roles in the ion-selective detection. In the AC detection system developed by us, where distilled water was used as the liquid within the nanopipettes, potassium ions were selectively detected in the sample solution of sodium and potassium ions because sodium ions were captured at the membrane containing bis(12-crown-4) ionophores, before the saturation of the ionophores. The membrane lost the selectivity after the saturation. On using sodium chloride as the liquid within the nanopipette, the membrane selectively detected potassium and sodium ions before and after the saturation of ionophores, respectively. The ion-selective detection of our system can be explained by the ion extraction-diffusion-dissolution mechanism through the bis(12-crown-4) ionophores with AC voltage modulation.

Simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application in pharmacokinetic study.

PubMed

Zhu, He; Ding, Li; Shakya, Shailendra; Qi, Xiemin; Hu, Linlin; Yang, Xiaolin; Yang, Zhonglin

2011-11-15

A new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method operated in the positive/negative electrospray ionization (ESI) switching mode has been developed and validated for the simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma. After addition of internal standards diazepam (for asperosaponin VI) and glycyrrhetic acid (for hederagenin), the plasma sample was deproteinized with acetonitrile, and separated on a reversed phase C18 column with a mobile phase of methanol (solvent A)-0.05% glacial acetic acid containing 10 mM ammonium acetate and 30 μM sodium acetate (solvent B) using gradient elution. The detection of target compounds was done in multiple reaction monitoring (MRM) mode using a tandem mass spectrometry equipped with positive/negative ion-switching ESI source. At the first segment, the MRM detection was operated in the positive ESI mode using the transitions of m/z 951.5 ([M+Na](+))→347.1 for asperosaponin VI and m/z 285.1 ([M+H](+))→193.1 for diazepam for 4 min, then switched to the negative ESI mode using the transitions of m/z 471.3 ([M-H](-))→471.3 for hederagenin and m/z 469.4 ([M-H](-))→425.4 for glycyrrhetic acid, respectively. The sodiated molecular ion [M+Na](+) at m/z 951.5 was selected as the precursor ion for asperosaponin VI, since it provided better sensitivity compared to the deprotonated and protonated molecular ions. Sodium acetate was added to the mobile phase to make sure that abundant amount of the sodiated molecular ion of asperosaponin VI could be produced, and more stable and intensive mass response of the product ion could be obtained. For the detection of hederagenin, since all of the mass responses of the fragment ions were very weak, the deprotonated molecular ion [M-H](-)m/z 471.3 was employed as both the precursor ion and the product ion. But the collision energy was still used for the MRM, in order to eliminate the influences induced by the interference substances from the rat plasma. The validated method was successfully applied to study the pharmacokinetics of asperosaponin VI and its active metabolite hederagenin in rat plasma after oral administration of asperosaponin VI at a dose of 90 mg/kg. Copyright © 2011 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.

Evaluation of null-point detection methods on simulation data

NASA Astrophysics Data System (ADS)

Olshevsky, Vyacheslav; Fu, Huishan; Vaivads, Andris; Khotyaintsev, Yuri; Lapenta, Giovanni; Markidis, Stefano

2014-05-01

We model the measurements of artificial spacecraft that resemble the configuration of CLUSTER propagating in the particle-in-cell simulation of turbulent magnetic reconnection. The simulation domain contains multiple isolated X-type null-points, but the majority are O-type null-points. Simulations show that current pinches surrounded by twisted fields, analogous to laboratory pinches, are formed along the sequences of O-type nulls. In the simulation, the magnetic reconnection is mainly driven by the kinking of the pinches, at spatial scales of several ion inertial lentghs. We compute the locations of magnetic null-points and detect their type. When the satellites are separated by the fractions of ion inertial length, as it is for CLUSTER, they are able to locate both the isolated null-points, and the pinches. We apply the method to the real CLUSTER data and speculate how common are pinches in the magnetosphere, and whether they play a dominant role in the dissipation of magnetic energy.

Fault-tolerant quantum error detection

PubMed Central

Linke, Norbert M.; Gutierrez, Mauricio; Landsman, Kevin A.; Figgatt, Caroline; Debnath, Shantanu; Brown, Kenneth R.; Monroe, Christopher

2017-01-01

Quantum computers will eventually reach a size at which quantum error correction becomes imperative. Quantum information can be protected from qubit imperfections and flawed control operations by encoding a single logical qubit in multiple physical qubits. This redundancy allows the extraction of error syndromes and the subsequent detection or correction of errors without destroying the logical state itself through direct measurement. We show the encoding and syndrome measurement of a fault-tolerantly prepared logical qubit via an error detection protocol on four physical qubits, represented by trapped atomic ions. This demonstrates the robustness of a logical qubit to imperfections in the very operations used to encode it. The advantage persists in the face of large added error rates and experimental calibration errors. PMID:29062889

N-deethylation and N-oxidation of etamiphylline: identification of etamiphylline-N-oxide in greyhound urine by high performance liquid chromatography-mass spectrometry.

PubMed

Dumasia, M C; Teale, P

2005-01-04

Millophyline-V, (etamiphylline camsylate) was administered intramuscularly to two racing greyhounds at a dose of 10 mg kg(-1). Unhydrolysed pre- and post-administration urine samples were extracted using mixed mode solid phase extraction (SPE) cartridges, the basic isolates derivatised as trimethylsilyl ethers and analysed by positive ion electron ionisation gas chromatography-mass spectrometry (GC/EI+/MS). The parent drug and one metabolite, N-desethyletamiphylline, were detected in urine for up to 72 h. For semi-quantification, urine samples were extracted on-line using a Prospekt sample handler. The analytes retained on the C2 SPE cartridge were eluted by the mobile phase directly on to the analytical high performance liquid chromatography column and analysed by positive ion atmospheric pressure chemical ionisation (LC/APCI+) MS in the multiple selective-ion recording mode. A major peak containing both ions (m/z) 280 and (m/z) 252 was observed. Full scan LC/APCI+/MS of the unknown indicated that the ion at (m/z) 280 was formed by the loss of an oxygen atom [MH+ -->(MH+-O)]. Samples were analysed by positive ion electrospray ionisation LC/MS on two different instruments and the unknown compound was identified as an N-oxide of the tert. nitrogen atom of the 2-(diethylamino)ethyl substituent on N7 of the theophylline nucleus. This compound has not been reported previously either as an in vivo or in vitro metabolite of etamiphylline in any species. Thermal decomposition of the N-oxide could lead to an increase the detection period of the parent drug during routine GC/MS screening of post-competition greyhound urine samples.

A retention-time-shift-tolerant background subtraction and noise reduction algorithm (BgS-NoRA) for extraction of drug metabolites in liquid chromatography/mass spectrometry data from biological matrices.

PubMed

Zhu, Peijuan; Ding, Wei; Tong, Wei; Ghosal, Anima; Alton, Kevin; Chowdhury, Swapan

2009-06-01

A retention-time-shift-tolerant background subtraction and noise reduction algorithm (BgS-NoRA) is implemented using the statistical programming language R to remove non-drug-related ion signals from accurate mass liquid chromatography/mass spectrometry (LC/MS) data. The background-subtraction part of the algorithm is similar to a previously published procedure (Zhang H and Yang Y. J. Mass Spectrom. 2008, 43: 1181-1190). The noise reduction algorithm (NoRA) is an add-on feature to help further clean up the residual matrix ion noises after background subtraction. It functions by removing ion signals that are not consistent across many adjacent scans. The effectiveness of BgS-NoRA was examined in biological matrices by spiking blank plasma extract, bile and urine with diclofenac and ibuprofen that have been pre-metabolized by microsomal incubation. Efficient removal of background ions permitted the detection of drug-related ions in in vivo samples (plasma, bile, urine and feces) obtained from rats orally dosed with (14)C-loratadine with minimal interference. Results from these experiments demonstrate that BgS-NoRA is more effective in removing analyte-unrelated ions than background subtraction alone. NoRA is shown to be particularly effective in the early retention region for urine samples and middle retention region for bile samples, where the matrix ion signals still dominate the total ion chromatograms (TICs) after background subtraction. In most cases, the TICs after BgS-NoRA are in excellent qualitative correlation to the radiochromatograms. BgS-NoRA will be a very useful tool in metabolite detection and identification work, especially in first-in-human (FIH) studies and multiple dose toxicology studies where non-radio-labeled drugs are administered. Data from these types of studies are critical to meet the latest FDA guidance on Metabolite in Safety Testing (MIST). Copyright (c) 2009 John Wiley & Sons, Ltd.

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

PubMed

Liu, Yong-Qiang; Yu, Hong

2017-04-01

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validity of Binary Collision Theory in Ion-Surface Interactions at 50-500 eV

NASA Astrophysics Data System (ADS)

Gordon, Michael; Giapis, Kostas

2003-10-01

Ion-surface interactions in the 50-500 eV regime have become increasingly important in plasma processing. Concerns exist in literature about the validity of the binary collision approximation (BCA) at low impact energies because peculiarities are frequently seen in the scattered ion energy distribution. Sub-surface processes, multiple bouncing, and super-elastic phenomena have all been hypothesized. This talk will explore the usefulness of BCA theory in predicting energy transfer during ion-surface collisions in the 50-500 eV energy range. Well-defined beams of rare gas ions (Ne, Ar, Kr) were scattered off semiconductor (Si, Ge) and metal surfaces (Ag, Au, Ni, Nb) to measure energy loss upon impact. The ion beams were produced from a floating ICP reactor coupled to a small accelerator beamline for transport and mass filtering. Exit channel energies were measured using a 90 gegree electrostatic sector coupled to a quadrupole mass filter with single ion detection capability. Although the BCA presents an over-simplified picture of the collision process, our results demonstrate that it is remarkably accurate in the low energy range for a variety of projectile-target combinations. In addition, reactive ion scattering of O2+ and O+ on inert and reactive surfaces (Au vs. Ag, Pt) suggests there may be rather high energy threshold processes which determine exit channel selectivity.

Frequency-scanning MALDI linear ion trap mass spectrometer for large biomolecular ion detection.

PubMed

Lu, I-Chung; Lin, Jung Lee; Lai, Szu-Hsueh; Chen, Chung-Hsuan

2011-11-01

This study presents the first report on the development of a matrix-assisted laser desorption ionization (MALDI) linear ion trap mass spectrometer for large biomolecular ion detection by frequency scan. We designed, installed, and tested this radio frequency (RF) scan linear ion trap mass spectrometer and its associated electronics to dramatically extend the mass region to be detected. The RF circuit can be adjusted from 300 to 10 kHz with a set of operation amplifiers. To trap the ions produced by MALDI, a high pressure of helium buffer gas was employed to quench extra kinetic energy of the heavy ions produced by MALDI. The successful detection of the singly charged secretory immunoglobulin A ions indicates that the detectable mass-to-charge ratio (m/z) of this system can reach ~385 000 or beyond.

Competitive migration behaviors of multiple ions and their impacts on ion-exchange resin packed microbial desalination cell.

PubMed

Zuo, Kuichang; Yuan, Lulu; Wei, Jincheng; Liang, Peng; Huang, Xia

2013-10-01

Mixed ion-exchange resins packed microbial desalination cell (R-MDC) could stabilize the internal resistance, however, the impacts of multiple ions on R-MDC performance was unclear. This study investigated the desalination performance, multiple ions migration behaviors and their impacts on R-MDCs fed with salt solution containing multiple anions and cations. Results showed that R-MDC removed multiple anions better than multiple cations with desalination efficiency of 99% (effluent conductivity <0.05 ms/cm) at hydraulic retention time of 50 h. Competitive migration order was SO4(2-)>NO3(-)>Cl(-) for anions and Ca(2+)≈Mg(2+)>NH4(+)>Na(+) for cations, jointly affected by both their molar conductivity and exchange selectivity on resins. After long-term operation, the existence of higher concentration Ca(2+) and Mg(2+) caused the electric conductivity of mixed resins decrease and scaling on the surface of cation-exchange membrane adjoined with cathode chamber, suggesting that R-MDC would be more suitable for desalination of water with lower hardness. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ejection of Coulomb Crystals from a Linear Paul Ion Trap for Ion-Molecule Reaction Studies.

PubMed

Meyer, K A E; Pollum, L L; Petralia, L S; Tauschinsky, A; Rennick, C J; Softley, T P; Heazlewood, B R

2015-12-17

Coulomb crystals are being increasingly employed as a highly localized source of cold ions for the study of ion-molecule chemical reactions. To extend the scope of reactions that can be studied in Coulomb crystals-from simple reactions involving laser-cooled atomic ions, to more complex systems where molecular reactants give rise to multiple product channels-sensitive product detection methodologies are required. The use of a digital ion trap (DIT) and a new damped cosine trap (DCT) are described, which facilitate the ejection of Coulomb-crystallized ions onto an external detector for the recording of time-of-flight (TOF) mass spectra. This enables the examination of reaction dynamics and kinetics between Coulomb-crystallized ions and neutral molecules: ionic products are typically cotrapped, thus ejecting the crystal onto an external detector reveals the masses, identities, and quantities of all ionic species at a selected point in the reaction. Two reaction systems are examined: the reaction of Ca(+) with deuterated isotopologues of water, and the charge exchange between cotrapped Xe(+) with deuterated isotopologues of ammonia. These reactions are examples of two distinct types of experiment, the first involving direct reaction of the laser-cooled ions, and the second involving reaction of sympathetically-cooled heavy ions to form a mixture of light product ions. Extensive simulations are conducted to interpret experimental results and calculate optimal operating parameters, facilitating a comparison between the DIT and DCT approaches. The simulations also demonstrate a correlation between crystal shape and image shape on the detector, suggesting a possible means for determining crystal geometry for nonfluorescing ions.

Ion trace detection algorithm to extract pure ion chromatograms to improve untargeted peak detection quality for liquid chromatography/time-of-flight mass spectrometry-based metabolomics data.

PubMed

Wang, San-Yuan; Kuo, Ching-Hua; Tseng, Yufeng J

2015-03-03

Able to detect known and unknown metabolites, untargeted metabolomics has shown great potential in identifying novel biomarkers. However, elucidating all possible liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS) ion signals in a complex biological sample remains challenging since many ions are not the products of metabolites. Methods of reducing ions not related to metabolites or simply directly detecting metabolite related (pure) ions are important. In this work, we describe PITracer, a novel algorithm that accurately detects the pure ions of a LC/TOF-MS profile to extract pure ion chromatograms and detect chromatographic peaks. PITracer estimates the relative mass difference tolerance of ions and calibrates the mass over charge (m/z) values for peak detection algorithms with an additional option to further mass correction with respect to a user-specified metabolite. PITracer was evaluated using two data sets containing 373 human metabolite standards, including 5 saturated standards considered to be split peaks resultant from huge m/z fluctuation, and 12 urine samples spiked with 50 forensic drugs of varying concentrations. Analysis of these data sets show that PITracer correctly outperformed existing state-of-art algorithm and extracted the pure ion chromatograms of the 5 saturated standards without generating split peaks and detected the forensic drugs with high recall, precision, and F-score and small mass error.

{sup 25}Na and {sup 25}Mg fragmentation on {sup 12}C at 9.23 MeV per nucleon at TRIUMF

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

St-Onge, Patrick; Boisjoli, Mark; Fregeau, Marc-Olivier

2012-10-20

HERACLES is a multidetector that is used to study heavy-ion collisions, with ion beams with an energy range between 8 to 15 MeV per nucleon. It has 78 detectors axially distributed around the beam axis in 6 rings allowing detection of multiple charged fragments from nuclear reactions. HERACLES has 4 different types of detectors, BC408/BaF{sub 2} phoswich, Si/CsI(Tl) telescope, BC408/BC444 phoswich and CsI(Tl) detectors. The multidetector has been run with a radioactive {sup 25}Na beam and a stable {sup 25}Mg beam at 9.23 MeV per nucleon on a carbon target.

Linear electronic field time-of-flight ion mass spectrometers

DOEpatents

Funsten, Herbert O.

2010-08-24

Time-of-flight mass spectrometer comprising a first drift region and a second drift region enclosed within an evacuation chamber; a means of introducing an analyte of interest into the first drift region; a pulsed ionization source which produces molecular ions from said analyte of interest; a first foil positioned between the first drift region and the second drift region, which dissociates said molecular ions into constituent atomic ions and emits secondary electrons; an electrode which produces secondary electrons upon contact with a constituent atomic ion in second drift region; a stop detector comprising a first ion detection region and a second ion detection region; and a timing means connected to the pulsed ionization source, to the first ion detection region, and to the second ion detection region.

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

Screening of Carotenoids in Tomato Fruits by Using Liquid Chromatography with Diode Array-Linear Ion Trap Mass Spectrometry Detection.

PubMed

Gentili, Alessandra; Caretti, Fulvia; Ventura, Salvatore; Pérez-Fernández, Virginia; Venditti, Alessandro; Curini, Roberta

2015-08-26

This paper presents an analytical strategy for a large-scale screening of carotenoids in tomato fruits by exploiting the potentialities of the triple quadrupole-linear ion trap hybrid mass spectrometer (QqQLIT). The method involves separation on C30 reversed-phase column and identification by means of diode array detection (DAD) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). The authentic standards of six model compounds were used to optimize the separative conditions and to predict the chromatographic behavior of untargeted carotenoids. An information dependent acquisition (IDA) was performed with (i) enhanced-mass scan (EMS) as the survey scan, (ii) enhanced-resolution (ER) scan to obtain the exact mass of the precursor ions (16-35 ppm), and (iii) enhanced product ion (EPI) scan as dependent scan to obtain structural information. LC-DAD-multiple reaction monitoring (MRM) chromatograms were also acquired for the identification of targeted carotenoids occurring at low concentrations; for the first time, the relative abundance between the MRM transitions (ion ratio) was used as an extra tool for the MS distinction of structural isomers and the related families of geometrical isomers. The whole analytical strategy was high-throughput, because a great number of experimental data could be acquired with few analytical steps, and cost-effective, because only few standards were used; when applied to characterize some tomato varieties ('Tangerine', 'Pachino', 'Datterino', and 'Camone') and passata of 'San Marzano' tomatoes, our method succeeded in identifying up to 44 carotenoids in the 'Tangerine'" variety.

Characterization of the polyphenolic composition of purple loosestrife (Lythrum salicaria).

PubMed

Rauha, J P; Wolfender, J L; Salminen, J P; Pihlaja, K; Hostettmann, K; Vuorela, H

2001-01-01

Phenolic compounds of purple loosestrife (Lythrum salicaria L.) were analysed by the use of liquid chromatography-mass spectrometry (LC/MS) equipped with atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI). The presence of vitexin and orientin as well as their isomers, isovitexin and isoorientin, were confirmed using ion trap multiple stage LC/MS3 analysis. Several phenolic acids and tannins were also detected. Ellagitannins, vescalagin and pedunculagin, are reported from the plant for the first time.

The formation of [M-H]+ ions in N-alkyl-substituted thieno[3,4-c]-pyrrole-4,6-dione derivatives during atmospheric pressure photoionization mass spectrometry.

PubMed

Sioud, Salim; Kharbatia, Najeh; Amad, Maan H; Zhu, Zhiyong; Cabanetos, Clement; Lesimple, Alain; Beaujuge, Pierre

2014-11-30

The formation of ions during atmospheric pressure photoionization (APPI) mass spectrometry in the positive mode usually provides radical cations and/or protonated species. Intriguingly, during the analysis of some N-alkyl-substituted thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives synthesized in our laboratory, unusual [M-H](+) ion peaks were observed. In this work we investigate the formation of [M-H](+) ions observed under APPI conditions. Multiple experimental parameters, including the type of ionization source, the composition of the solvent, the type of dopant, the infusion flow rate, and the length of the alkyl side chain were investigated to determine their effects on the formation of [M-H](+) ions. In addition, a comparison study of the gas-phase tandem mass spectrometric (MS/MS) fragmentation of [M + H](+) vs [M-H](+) ions and computational approaches were used. [M-H](+) ions were observed under APPI conditions. The type of dopant and the length of the alkyl chain affected the formation of these ions. MS/MS fragmentation of [M-H](+) and [M + H](+) ions exhibited completely different patterns. Theoretical calculations revealed that the loss of hydrogen molecules from the [M + H](+) ions is the most favourable condition under which to form [M-H](+) ions. [M-H](+) ions were detected in all the TPD derivatives studied here under the special experimental conditions during APPI, using a halogenated benzene dopant, and TPD containing substituted N-alkyl side chains with a minimum of four carbon atoms. Density functional theory calculations showed that for [M-H](+) ions to be formed under these conditions, the loss of hydrogen molecules from the [M + H](+)  ions is proposed to be necessary. Copyright © 2014 John Wiley & Sons, Ltd.

Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

PubMed

Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

2016-08-17

We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions.

UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Hansen, Christopher S.; Kirk, Benjamin B.; Blanksby, Stephen J.; O'Hair, Richard. A. J.; Trevitt, Adam J.

2013-06-01

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag2 + is compared with a literature spectrum as a further benchmark.

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.

Targeted Data Extraction of the MS/MS Spectra Generated by Data-independent Acquisition: A New Concept for Consistent and Accurate Proteome Analysis*

PubMed Central

Gillet, Ludovic C.; Navarro, Pedro; Tate, Stephen; Röst, Hannes; Selevsek, Nathalie; Reiter, Lukas; Bonner, Ron; Aebersold, Ruedi

2012-01-01

Most proteomic studies use liquid chromatography coupled to tandem mass spectrometry to identify and quantify the peptides generated by the proteolysis of a biological sample. However, with the current methods it remains challenging to rapidly, consistently, reproducibly, accurately, and sensitively detect and quantify large fractions of proteomes across multiple samples. Here we present a new strategy that systematically queries sample sets for the presence and quantity of essentially any protein of interest. It consists of using the information available in fragment ion spectral libraries to mine the complete fragment ion maps generated using a data-independent acquisition method. For this study, the data were acquired on a fast, high resolution quadrupole-quadrupole time-of-flight (TOF) instrument by repeatedly cycling through 32 consecutive 25-Da precursor isolation windows (swaths). This SWATH MS acquisition setup generates, in a single sample injection, time-resolved fragment ion spectra for all the analytes detectable within the 400–1200 m/z precursor range and the user-defined retention time window. We show that suitable combinations of fragment ions extracted from these data sets are sufficiently specific to confidently identify query peptides over a dynamic range of 4 orders of magnitude, even if the precursors of the queried peptides are not detectable in the survey scans. We also show that queried peptides are quantified with a consistency and accuracy comparable with that of selected reaction monitoring, the gold standard proteomic quantification method. Moreover, targeted data extraction enables ad libitum quantification refinement and dynamic extension of protein probing by iterative re-mining of the once-and-forever acquired data sets. This combination of unbiased, broad range precursor ion fragmentation and targeted data extraction alleviates most constraints of present proteomic methods and should be equally applicable to the comprehensive analysis of other classes of analytes, beyond proteomics. PMID:22261725

Application of the MIDAS approach for analysis of lysine acetylation sites.

PubMed

Evans, Caroline A; Griffiths, John R; Unwin, Richard D; Whetton, Anthony D; Corfe, Bernard M

2013-01-01

Multiple Reaction Monitoring Initiated Detection and Sequencing (MIDAS™) is a mass spectrometry-based technique for the detection and characterization of specific post-translational modifications (Unwin et al. 4:1134-1144, 2005), for example acetylated lysine residues (Griffiths et al. 18:1423-1428, 2007). The MIDAS™ technique has application for discovery and analysis of acetylation sites. It is a hypothesis-driven approach that requires a priori knowledge of the primary sequence of the target protein and a proteolytic digest of this protein. MIDAS essentially performs a targeted search for the presence of modified, for example acetylated, peptides. The detection is based on the combination of the predicted molecular weight (measured as mass-charge ratio) of the acetylated proteolytic peptide and a diagnostic fragment (product ion of m/z 126.1), which is generated by specific fragmentation of acetylated peptides during collision induced dissociation performed in tandem mass spectrometry (MS) analysis. Sequence information is subsequently obtained which enables acetylation site assignment. The technique of MIDAS was later trademarked by ABSciex for targeted protein analysis where an MRM scan is combined with full MS/MS product ion scan to enable sequence confirmation.

Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

NASA Astrophysics Data System (ADS)

Ferradas, C. P.; Zhang, J.-C.; Spence, H. E.; Kistler, L. M.; Larsen, B. A.; Reeves, G.; Skoug, R.; Funsten, H.

2016-11-01

We present a case study of the H+, He+, and O+ multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of these ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.

A highly selective and fast-response fluorescent probe based on Cd-MOF for the visual detection of Al3+ ion and quantitative detection of Fe3+ ion

NASA Astrophysics Data System (ADS)

Lv, Rui; Chen, Zhihengyu; Fu, Xin; Yang, Boyi; Li, Hui; Su, Jian; Gu, Wen; Liu, Xin

2018-03-01

A new luminescent Cd(II)-based metal-organic framework, [Cd(PAM)(4-bpdb)1.5]·DMF (Cd-MOF, PAM = 4,4‧-methylenebis(3-hydroxy-2-naphthalene-carboxylic acid) and 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) was successfully synthesized by solvothermal synthesis method. The Cd-MOF reveals excellent luminescence property which can selectively detect Al3+ and Fe3+ ions among other interfering metal ions. The detection limit is 0.56 μM for Al3+ ion in aqueous solutions, and it is obvious lower than the maximum standard of Al3+ ion in drinking water of 7.41 μM which is defined by the WHO. More importantly, the Cd-MOF shows an obvious luminescent color change from yellow to blue under the UV lamp irradiation at 365 nm with the dropping of Al3+ ion, which can make it apply to the visual detection. And, the detection based on the test paper was explored for the first time. In addition, the Cd-MOF can also be used for quantitative detecting Fe3+ ion, and the LOD for Fe3+ ion can be as low as 0.3 μM which is lower than most reported MOFs. It is worth noting that Fe3+ and Al3+ ions can not interfere with each other. These properties make it become an excellent luminescence sensor for the detection of Al3+ and Fe3+ ions.

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.

Diverse wave-particle interactions for energetic ions that traverse Alfvén eigenmodes on their first full orbit [Diverse nonlinear wave-particle interactions for energetic ions that traverse Alfvén eigenmodes on their first full orbit

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

Heidbrink, W. W.; Persico, E. A. D.; Austin, M. E.

2016-02-09

Here, neutral-beam ions that are deflected onto loss orbits by Alfvén eigenmodes (AE) on their first bounce orbit and are detected by a fast-ion loss detector (FILD) satisfy the “local resonance” condition. This theory qualitatively explains FILD observations for a wide variety of AE-particle interactions. When coherent losses are measured for multiple AE, oscillations at the sum and difference frequencies of the independent modes are often observed. The amplitudes of the sum and difference peaks correlate with the amplitudes of the fundamental loss-signal amplitudes but do not correlate with the measured mode amplitudes. In contrast to a simple uniform-plasma theorymore » of the interaction, the loss-signal amplitude at the sum frequency is often larger than the loss-signal amplitude at the difference frequency, indicating a more detailed computation of the orbital trajectories through the mode eigenfunctions is needed.« less

Fire Hose Instability in the Multiple Magnetic Reconnection

NASA Astrophysics Data System (ADS)

Alexandrova, A.; Retino, A.; Divin, A. V.; Le Contel, O.; Matteini, L.; Breuillard, H.; Deca, J.; Catapano, F.; Cozzani, G.; Nakamura, R.; Panov, E. V.; Voros, Z.

2017-12-01

We present observations of multiple reconnection in the Earth's magnetotail. In particular, we observe an ion temperature anisotropy characterized by large temperature along the magnetic field, between the two active X-lines. The anisotropy is associated with right-hand polarized waves at frequencies lower than the ion cyclotron frequency and propagating obliquely to the background magnetic field. We show that the observed anisotropy and the wave properties are consistent with linear kinetic theory of fire hose instability. The observations are in agreement with the particle-in-cell simulations of multiple reconnection. The results suggest that the fire hose instability can develop during multiple reconnection as a consequence of the ion parallel anisotropy that is produced by counter-streaming ions trapped between the X-lines.

MALDI imaging mass spectrometry analysis-A new approach for protein mapping in multiple sclerosis brain lesions.

PubMed

Maccarrone, Giuseppina; Nischwitz, Sandra; Deininger, Sören-Oliver; Hornung, Joachim; König, Fatima Barbara; Stadelmann, Christine; Turck, Christoph W; Weber, Frank

2017-03-15

Multiple sclerosis is a disease of the central nervous system characterized by recurrent inflammatory demyelinating lesions in the early disease stage. Lesion formation and mechanisms leading to lesion remyelination are not fully understood. Matrix Assisted Laser Desorption Ionisation Mass Spectrometry imaging (MALDI-IMS) is a technology which analyses proteins and peptides in tissue, preserves their spatial localization, and generates molecular maps within the tissue section. In a pilot study we employed MALDI imaging mass spectrometry to profile and identify peptides and proteins expressed in normal-appearing white matter, grey matter and multiple sclerosis brain lesions with different extents of remyelination. The unsupervised clustering analysis of the mass spectra generated images which reflected the tissue section morphology in luxol fast blue stain and in myelin basic protein immunohistochemistry. Lesions with low remyelination extent were defined by compounds with molecular weight smaller than 5300Da, while more completely remyelinated lesions showed compounds with molecular weights greater than 15,200Da. An in-depth analysis of the mass spectra enabled the detection of cortical lesions which were not seen by routine luxol fast blue histology. An ion mass, mainly distributed at the rim of multiple sclerosis lesions, was identified by liquid chromatography and tandem mass spectrometry as thymosin beta-4, a protein known to be involved in cell migration and in restorative processes. The ion mass of thymosin beta-4 was profiled by MALDI imaging mass spectrometry in brain slides of 12 multiple sclerosis patients and validated by immunohistochemical analysis. In summary, our results demonstrate the ability of the MALDI-IMS technology to map proteins within the brain parenchyma and multiple sclerosis lesions and to identify potential markers involved in multiple sclerosis pathogenesis and/or remyelination. Copyright © 2016 Elsevier B.V. All rights reserved.

Ion creation, ion focusing, ion/molecule reactions, ion separation, and ion detection in the open air in a small plastic device.

PubMed

Baird, Zane; Wei, Pu; Cooks, R Graham

2015-02-07

A method is presented in which ions are generated and manipulated in the ambient environment using polymeric electrodes produced with a consumer-grade 3D printer. The ability to focus, separate, react, and detect ions in the ambient environment is demonstrated and the data agree well with simulated ion behaviour.

Investigation of Ion Transmission Effects on Intact Protein Quantification in a Triple Quadrupole Mass Spectrometer

NASA Astrophysics Data System (ADS)

Wang, Evelyn H.; Appulage, Dananjaya Kalu; McAllister, Erin A.; Schug, Kevin A.

2017-09-01

Recently, direct intact protein quantitation using triple quadrupole mass spectrometry (QqQ-MS) and multiple reaction monitoring (MRM) was demonstrated (J. Am. Soc. Mass Spectrom. 27, 886-896 (2016)). Even though QqQ-MS is known to provide extraordinary detection sensitivity for quantitative analysis, we found that intact proteins exhibited a less than 5% ion transmission from the first quadrupole to the third quadrupole mass analyzer in the presence of zero collision energy (ZCE). With the goal to enhance intact protein quantitation sensitivity, ion scattering effects, proton transfer effects, and mass filter resolution widths were examined for their contributions to the lost signal. Protein standards myoglobin and ubiquitin along with small molecules reserpine and vancomycin were analyzed together with various collision induced dissociation (CID) gases (N2, He, and Ar) at different gas pressures. Mass resolution settings played a significant role in reducing ion transmission signal. By narrowing the mass resolution window by 0.35 m/z on each side, roughly 75%-90% of the ion signal was lost. The multiply charged proteins experienced additional proton transfer effects, corresponding to 10-fold signal reduction. A study of increased sensitivity of the method was also conducted with various MRM summation techniques. Although the degree of enhancement was analyte-dependent, an up to 17-fold increase in sensitivity was observed for ubiquitin using a summation of multiple MRM transitions. Biological matrix, human urine, and equine plasma were spiked with proteins to demonstrate the specificity of the method. This study provides additional insight into optimizing the use and sensitivity of QqQ-MS for intact protein quantification. [Figure not available: see fulltext.

Comparison of secondary ion intensity enhancement from polymers on silicon and silver substrates by using Au-TOF-SIMS

NASA Astrophysics Data System (ADS)

Kudo, M.; Aimoto, K.; Sunagawa, Y.; Kato, N.; Aoyagi, S.; Iida, S.; Sanada, N.

2008-12-01

The usefulness of the usage of cluster primary ion source together with an Ag substrate and detection of Ag cationized molecular ions was studied from the standpoint to realize high sensitivity TOF-SIMS analysis of organic materials. Although secondary ions from polymer thin films on a Si substrate can be detected in a higher sensitivity with Au 3+ cluster primary ion compared with Ga + ion bombardment, it was clearly observed that the secondary ion intensities from samples on an Ag substrate showed quite a different tendency from that on Si. When monoatomic primary ions, e.g., Au + and Ga +, were used for the measurement of the sample on an Ag substrate, [M+Ag] + ions (M corresponds to polyethylene glycol molecule) were detected in a high sensitivity. On the contrary, when Au 3+ was used, no intensity enhancement of [M+Ag] + ions was observed. The acceleration energy dependence of the detected secondary ions implies the different ionization mechanisms on the different substrates.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Carbohydrate profiling of bacteria by gas chromatography-mass spectrometry and their trace detection in complex matrices by gas chromatography-tandem mass spectrometry.

PubMed

Fox, A

1999-05-28

Bacterial cellular polysaccharides are composed of a variety of sugar monomers. These sugars serve as chemical markers to identify specific species or genera or to determine their physiological status. Some of these markers can also be used for trace detection of bacteria or their constituents in complex clinical or environmental matrices. Analyses are performed, in our hands, employing hydrolysis followed by the alditol acetate derivatization procedure. Substantial improvements have been made to sample preparation including simplification and computer-controlled automation. For characterization of whole cell bacterial hydrolysates, sugars are analyzed by gas chromatography-mass spectrometry (GC-MS). Simple chromatograms are generated using selected ion monitoring (SIM). Using total ion GC-MS, sugars can be readily identified. In more complex clinical and environmental samples, markers for bacteria are present at sufficiently low concentrations that more advanced instrumentation, gas chromatography-tandem mass spectrometry (GC-MS-MS), is preferred for optimal analysis. Using multiple reaction monitoring, MS-MS is used (replacing more conventional SIM) to ignore extraneous chromatographic peaks. Triple quadrupole and ion trap GC-MS-MS instruments have both been used successfully. Absolute chemical identification of sugar markers at trace levels is achieved, using MS-MS, by the product spectrum.

Fail-Safe Design for Large Capacity Lithium-Ion Battery Systems

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

Kim, G. H.; Smith, K.; Ireland, J.

2012-07-15

A fault leading to a thermal runaway in a lithium-ion battery is believed to grow over time from a latent defect. Significant efforts have been made to detect lithium-ion battery safety faults to proactively facilitate actions minimizing subsequent losses. Scaling up a battery greatly changes the thermal and electrical signals of a system developing a defect and its consequent behaviors during fault evolution. In a large-capacity system such as a battery for an electric vehicle, detecting a fault signal and confining the fault locally in the system are extremely challenging. This paper introduces a fail-safe design methodology for large-capacity lithium-ionmore » battery systems. Analysis using an internal short circuit response model for multi-cell packs is presented that demonstrates the viability of the proposed concept for various design parameters and operating conditions. Locating a faulty cell in a multiple-cell module and determining the status of the fault's evolution can be achieved using signals easily measured from the electric terminals of the module. A methodology is introduced for electrical isolation of a faulty cell from the healthy cells in a system to prevent further electrical energy feed into the fault. Experimental demonstration is presented supporting the model results.« less

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

LC-ESI-MS/MS on an ion trap for the determination of LSD, iso-LSD, nor-LSD and 2-oxo-3-hydroxy-LSD in blood, urine and vitreous humor.

PubMed

Favretto, Donata; Frison, Giampietro; Maietti, Sergio; Ferrara, Santo Davide

2007-07-01

A method has been developed for the simultaneous determination of lysergic acid diethylamide (LSD), its epimer iso-LSD, and its main metabolites nor-LSD and 2-oxo-3-hydroxy LSD in blood, urine, and, for the first time, vitreous humor samples. The method is based on liquid/liquid extraction and liquid chromatography-multiple mass spectrometry detection in an ion trap mass spectrometer, in positive ion electrospray ionization conditions. Five microliter of sample are injected and analysis time is 12 min. The method is specific, selective and sensitive, and achieves limits of quantification of 20 pg/ml for both LSD and nor-LSD in blood, urine, and vitreous humor. No significant interfering substance or ion suppression was identified for LSD, iso-LSD, and nor-LSD. The interassay reproducibilities for LSD at 20 pg/ml and 2 ng/ml in urine were 8.3 and 5.6%, respectively. Within-run precision using control samples at 20 pg/ml and 2 ng/ml was 6.9 and 3.9%. Mean recoveries of two concentrations spiked into drug free samples were in the range 60-107% in blood, 50-105% in urine, and 65-105% in vitreous humor. The method was successfully applied to the forensic determination of postmortem LSD levels in the biological fluids of a multi drug abuser; for the first time, LSD could be detected in vitreous humor.

Acquisition of electrical signals using commercial electronic components for detection system of Lead ion in distilled water

NASA Astrophysics Data System (ADS)

Pujiyanto; Yasin, M.; Rusydi, F.

2018-03-01

Development of lead ion detection systems is expected to have an advantage in terms of simplicity of the device and easy for concentration analysis of a lead ion with very high performance. One important part of lead ion detection systems are electrical signal acquisition parts. The electrical signal acquisition part uses the main electronic components: non inverting op-amplifier, instrumentation amplifier, multiplier circuit and logarithmic amplifier. Here will be shown the performance of lead ion detection systems when the existing electrical signal processors use commercial electronic components. The results that can be drawn from this experimental were the lead ion sensor that has been developed can be used to detect lead ions with a sensitivity of 10.48 mV/ppm with the linearity 97.11% and had a measurement range of 0.1 ppm to 80 ppm.

Trade-offs in osmoregulation and parallel shifts in molecular function follow ecological transitions to freshwater in the Alewife

USGS Publications Warehouse

Velotta, Jonathan P.; McCormick, Stephen; Schultz, Eric T.

2015-01-01

Adaptation to freshwater may be expected to reduce performance in seawater because these environments represent opposing selective regimes. We tested for such a trade-off in populations of the Alewife (Alosa pseudoharengus). Alewives are ancestrally anadromous, and multiple populations have been independently restricted to freshwater (landlocked). We conducted salinity challenge experiments, whereby juvenile Alewives from one anadromous and multiple landlocked populations were exposed to freshwater and seawater on acute and acclimation timescales. In response to acute salinity challenge trials, independently derived landlocked populations varied in the degree to which seawater tolerance has been lost. In laboratory-acclimation experiments, landlocked Alewives exhibited improved freshwater tolerance, which was correlated with reductions in seawater tolerance and hypo-osmotic balance, suggesting that trade-offs in osmoregulation may be associated with local adaptation to freshwater. We detected differentiation between life-history forms in the expression of an ion-uptake gene (NHE3), and in gill Na+/K+-ATPase activity. Trade-offs in osmoregulation, therefore, may be mediated by differentiation in ion-uptake and salt-secreting pathways.

Selective and sensitive optical chemosensor for detection of Ag(I) ions based on 2(4-hydroxy pent-3-en-2-ylideneamine) phenol in aqueous samples

NASA Astrophysics Data System (ADS)

Mirzaei, Mohammad; Saeed, Jaber

2011-11-01

A selective and sensitive chemosensor, based on the 2(4-hydroxy pent-3-en-2-ylideneamine) phenol (HPYAP) as chromophore, has been developed for colorimetric and visual detection of Ag(I) ions. HPYAP shows a considerable chromogenic behavior toward Ag(I) ions by changing the color of the solution from pale-yellow to very chromatic-yellow, which can be easily detected with the naked-eye. The chemosensor exhibited selective absorbance enhancement to Ag(I) ions in water samples over other metal ions at 438 nm, with a linear range of 0.4-500 μM ( r2 = 0.999) and a limit of detection 0.07 μM of Ag(I) ions with UV-vis spectrophotometer detection. The relative standard deviation (RSD) for 100 μM Ag(I) ions was 2.05% ( n = 7). The proposed method was applied for the determination Ag(I) ions in water and waste water samples.

Observations of metal concentrations in E-region sporadic thin layers using incoherent-scatter radar

NASA Astrophysics Data System (ADS)

Suzuki, Nobuhiro

This thesis has used incoherent-scatter radar data from the facility at Sondrestrom, Greenland to determine the ion mass values inside thin sporadic-E layers in the lower ionosphere. Metallic positively-charged ions of meteoric origin are deposited in the earth's upper atmosphere over a height range of about 85-120 km. Electric fields and neutral-gas (eg N2, O, O2) winds at high latitudes may produce convergent ion dynamics that results in the re-distribution of the background altitude distribution of the ions to form thin (1-3 km) high-density layers that are detectable with radar. A large database of experimental radar observations has been processed to determine ion mass values inside these thin ion layers. The range resolution of the radar was 600 meters that permitted mass determinations at several altitude steps within the layers. Near the lower edge of the layers the ion mass values were in the range 20-25 amu while at the top portion of the layers the mass values were generally in the range 30-40 amu. The numerical values are consistent with in-situ mass spectrometer data obtained by other researchers that suggest these layers are mainly composed of a mixture or Mg +, Si+, and Fe + ions. The small tendency for heavier ions to reside at the top portion of the layers is consistent with theory. The results have also found new evidence for the existence of complex-shaped multiple layers; the examples studied suggest similar ion mass values in different layers that in some cases are separated in altitude by several km.

Quartz crystal microbalance sensor using ionophore for ammonium ion detection.

PubMed

Kosaki, Yasuhiro; Takano, Kosuke; Citterio, Daniel; Suzuki, Koji; Shiratori, Seimei

2012-01-01

Ionophore-based quartz crystal microbalance (QCM) ammonium ion sensors with a detection limit for ammonium ion concentrations as low as 2.2 microM were fabricated. Ionophores are molecules, which selectively bind a particular ion. In this study, one of the known ionophores for ammonium, nonactin, was used to detect ammonium ions for environmental in-situ monitoring of aquarium water for the first time. To fabricate the sensing films, poly(vinyl chloride) was used as the matrix for the immobilization of nonactin. Furthermore, the anionic additive, tetrakis (4-chlorophenyl) borate potassium salt and the plasticizer dioctyl sebacate were used to enhance the sensor properties. The sensor allowed detecting ammonium ions not only in static solution, but also in flowing water. The sensor showed a nearly linear response with the increase of the ammonium ion concentration. The QCM resonance frequency increased with the increase of ammonium ion concentration, suggesting a decreasing weight of the sensing film. The detailed response mechanism could not be verified yet. However, from the results obtained when using a different plasticizer, nitrophenyl octyl ether, it is considered that this effect is caused by the release of water molecules. Consequently, the newly fabricated sensor detects ammonium ions by discharge of water. It shows high selectivity over potassium and sodium ions. We conclude that the newly fabricated sensor can be applied for detecting ammonium ions in aquarium water, since it allows measuring low ammonium ion concentrations. This sensor will be usable for water quality monitoring and controlling.

Multiple Ion Implantation Effects on Wear and Wet Ability of Polyethylene Based Polymers

NASA Astrophysics Data System (ADS)

Torrisi, L.; Visco, A. M.; Campo, N.

2004-10-01

Polyethylene based polymers were ion implanted with multiple irradiations of different ions (N+, Ar+ and Kr+) at energies between 30 keV and 300 keV and doses ranging between 1013 and 1016 ions/cm2. The ion implantation dehydrogenises the polyethylene inducing cross-link effects in the residual polymer carbons. At high doses the irradiated surface show properties similar to graphite surfaces. The depth of the modified layers depends on the ion range in polyethylene at the incident ion energy. The chemical modification depends on the implanted doses and on the specie of the incident ions. A "pin-on-disc" machine was employed to measure the polymer wear against AISI-316 L stainless steel. A "contact-angle-test" machine was employed to measure the wet ability of the polymer surface for 1 μl pure water drop. Measurements demonstrate that the multiple ion implantation treatments decrease the surface wear and the surface wetting and produce a more resistant polymer surface. The properties of the treated surfaces improves the polymer functionality for many bio-medical applications, such as those relative to the polyethylene friction discs employed in knee and hip prosthesis joints. The possibility to use multiply ion implantations of polymers with traditional ion implanters and with laser ion sources producing plasmas is investigated.

Suppression of stimulated Brillouin instability of a beat-wave of two lasers in multiple-ion-species plasmas

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

Yadav, Pinki; Gupta, D. N., E-mail: dngupta@physics.du.ac.in; Avinash, K.

2016-01-15

Stimulated Brillouin instability of a beat-wave of two lasers in plasmas with multiple-ion-species (negative-ions) was studied. The inclusion of negative-ions affects the growth of ion-acoustic wave in Brillouin scattering. Thus, the growth rate of instability is suppressed significantly by the density of negative-ions. To obey the phase-matching condition, the growth rate of the instability attains a maxima for an appropriate scattering angle (angle between the pump and scattered sideband waves). This study would be technologically important to have diagnostics in low-temperature plasmas.

Development and validation of a QuEChERS based liquid chromatography tandem mass spectrometry method for the determination of multiple mycotoxins in spices.

PubMed

Yogendrarajah, Pratheeba; Van Poucke, Christof; De Meulenaer, Bruno; De Saeger, Sarah

2013-07-05

A reliable and rapid method for the determination of multiple mycotoxins was developed using a QuEChERS (quick, easy, cheap, effective, rugged and safe) based extraction procedure in highly pigmented and complex spice matrices, namely red chilli (Capsicum annum ssp.), black and white pepper (Piper nigrum ssp.). High-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was used for the quantification and confirmation of 17 chemically diversified mycotoxins. Different extraction procedures were studied and optimized in order to obtain better recoveries. Mycotoxins were extracted from the hydrated spices using acidified acetonitrile (1% formic acid), followed by partitioning with NaCl and anhydrous MgSO4; excluding the use of dispersive-solid phase extraction. Significant matrix effect was compensated using the matrix matched calibration curves. Electrospray ionization at positive mode was applied to simultaneously detect all the mycotoxins in a single run time of 20min. Multiple reaction monitoring mode, choosing at least two abundant fragment ions per analyte was applied. Coefficients of determination obtained were in the range of 0.9844-0.9997. Recoveries (ranging from 75% to 117%) were in accordance with the performance criteria required by the European Commission. Intra-day reproducibility ranged from 4% to 22% for most of the mycotoxins. The limit of quantification ranged from 2.3 to 146μgkg(-1). The validated method was finally applied to screen mycotoxins in ten of each spice matrix. Aflatoxins, ochratoxin, fumonisins, sterigmatocystin and citrinin were among the detected analytes. Positive findings were further confirmed using relative ion intensities. The potentiality of the method to be used for confirmatory purposes according to Commission Decision 2002/657/EC was assessed. Copyright © 2013 Elsevier B.V. All rights reserved.

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects.

PubMed

Hack, John; Grills, David C; Miller, John R; Mani, Tomoyasu

2016-02-18

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

PDMS based photonic lab-on-a-chip for the selective optical detection of heavy metal ions.

PubMed

Ibarlucea, Bergoi; Díez-Gil, César; Ratera, Inma; Veciana, Jaume; Caballero, Antonio; Zapata, Fabiola; Tárraga, Alberto; Molina, Pedro; Demming, Stephanie; Büttgenbach, Stephanus; Fernández-Sánchez, César; Llobera, Andreu

2013-02-21

The selective absorbance detection of mercury(II) (Hg(2+)) and lead(II) (Pb(2+)) ions using ferrocene-based colorimetric ligands and miniaturized multiple internal reflection (MIR) systems implemented in a low-cost photonic lab on a chip (PhLoC) is reported. The detection principle is based on the formation of selective stable complexes between the heavy metal ion and the corresponding ligand. This interaction modulates the ligand spectrum by giving rise to new absorbance bands or wavelength shifting of the existing ones. A comparative study for the detection of Hg(2+) was carried out with two MIR-based PhLoC systems showing optical path lengths (OPLs) of 0.64 cm and 1.42 cm as well as a standard cuvette (1.00 cm OPL). Acetonitrile solutions containing the corresponding ligand and increasing concentrations of the heavy metal ion were pumped inside the systems and the absorbance in the visible region of the spectra was recorded. The optical behaviour of all the tested systems followed the expected Beer-Lambert law. Thus, the best results were achieved with the one with the longest OPL, which showed a linear behaviour in a concentration range of 1 μM-90 μM Hg(2+), a sensitivity of 5.6 × 10(-3) A.U. μM(-1) and a LOD of 2.59 μM (0.49 ppm), this being 1.7 times lower than that recorded with a standard cuvette, and using a sample/reagent volume around 190 times smaller. This microsystem was also applied for the detection of Pb(2+) and a linear behaviour in a concentration range of 3-100 μM was obtained, and a sensitivity of 9.59 × 10(-4) A.U. μM(-1) and a LOD of 4.19 μM (0.868 ppm) were achieved. Such a simple analytical tool could be implemented in portable instruments for automatic in-field measurements and, considering the minute sample and reagent volume required, would enable the deployment of high throughput environmental analysis of these pollutants and other related hazardous species.

Negative-ion formation in the explosives RDX, PETN, and TNT using the Reversal Electron Attachment Detection (READ) technique

NASA Technical Reports Server (NTRS)

Chutijian, Ara; Boumsellek, S.; Alajajian, S. H.

1992-01-01

In the search for high sensitivity and direct atmospheric sampling of trace species, techniques have been developed such as atmospheric-sampling, glow-discharge ionization (ASGDI), corona discharge, atmospheric pressure ionization (API), electron-capture detection (ECD), and negative-ion chemical ionization (NICI) that are capable of detecting parts-per-billion to parts-per-trillion concentrations of trace species. These techniques are based on positive- or negative-ion formation via charge-transfer to the target, or electron capture under multiple-collision conditions in a Maxwellian distribution of electron energies at the source temperature. One drawback of the high-pressure, corona- or glow-discharge devices is that they are susceptible to interferences either through indistinguishable product masses, or through undesired ion-molecule reactions. The ASGDI technique is relatively immune from such interferences, since at target concentrations of less than 1 ppm the majority of negative ions arises via electron capture rather than through ion-molecule chemistry. A drawback of the conventional ECD, and possibly of the ASGDI, is that they exhibit vanishingly small densities of electrons with energies in the range 0-10 millielectron volts (meV), as can be seen from a typical Maxwellian electron energy distribution function at T = 300 K. Slowing the electrons to these subthermal (less than 10 meV) energies is crucial, since the cross section for attachment of several large classes of molecules is known to increase to values larger than 10(exp -12) sq cm at near-zero electron energies. In the limit of zero energy these cross sections are predicted to diverge as epsilon(exp -1/2), where epsilon is the electron energy. In order to provide a better 'match' between the electron energy distribution function and attachment cross section, a new concept of attachment in an electrostatic mirror was developed. In this scheme, electrons are brought to a momentary halt by reversing their direction with electrostatic fields. At this turning point the electrons have zero or near-zero energy. A beam of target molecules is introduced, and the resultant negative ions extracted. This basic idea has been recently improved to allow for better reversal geometry, higher electron currents, lower backgrounds, and increased negative-ion extraction efficiency. We present herein application of the so-called reversal electron attachment detector (READ) to the study of negative-ion formation in the explosives molecules RDX, PETN, and TNT under single-collision conditions.

Influence of multiple ion species on low-frequency electromagnetic wave instabilities. [in solar wind

NASA Technical Reports Server (NTRS)

Brinca, Armando L.; Tsurutani, Bruce T.

1989-01-01

The effect of multiple (singly ionized) coexisting newborn ion species on the stability of low-frequency electromagnetic waves was investigated using a plasma model in which solar wind magnetoplasma is made up of isotropic Maxwellian electron and proton populations with a common number density of 4.95/cu cm and temperatures equal to 17.2 eV and 6.9 eV, respectively. It is shown that the effect of multiple ions on wave growth, for given background magnetoplasma conditions and relative densities, depends not only on their mass but also on the physical nature of the wave modes. If the ion masses are disparate, each one of the coexisting ion beams tends to stimulate instabilities without undue influence from the other species. If the masses of newborn ions are similar, they can strongly catalyze wave growth of fluidlike nonresonant modes, but bring about weak growth enhancements in cyclotron resonant instabilities.

Fluorescence spectroscopy of trapped molecular ions

NASA Astrophysics Data System (ADS)

Wright, Kenneth Charles

This thesis describes the development of a unique instrument capable of detecting fluorescence emission from large gas phase molecular ions trapped in a three-dimensional quadrupole ion trap. The hypothesis that has formed the basis of this work is the belief that fluorescence spectroscopy can be combined with ion trap mass spectrometry to probe the structure of gas phase molecular ions. The ion trap provides a rarefied environment where fluorescence experiments can be conducted without interference from solvent molecules or impurities. Although fluorescence was not detected during preliminary experiments, two significant experimental challenges associated with detecting the gas phase fluorescence of ions were discovered. First, gas phase ions were vulnerable to photodissociation and low laser powers were necessary to avoid photodissociation. Since fluorescence emission is directly proportional to laser intensity, a lower laser power limits the fluorescence signal. Second, the fluorescence emission was not significantly Stokes shifted from the excitation. The lack of Stokes shift meant the small fluorescence signal must be detected in the presence of a large amount of background scatter generated by the excitation. Initially, this background was seven orders of magnitude higher than the analytical signal ultimately detected. A specially designed fiber optic probe was inserted between the electrodes of the ion trap to stop light scattered off the outside surfaces of the trap from reaching the detector. The inside surfaces of the ion trap were coated black to further reduce the amount of scattered light collected. These innovations helped reduced the background by six orders of magnitude and fluorescence emission from rhodamine-6G was detected. Pulse counting experiments were used to optimize fluorescence detection. The effects of trapping level, laser power, and irradiation time were investigated and optimized. The instrument developed in this work not only allows for the detection of fluorescent photons, but the sensitivity is high enough for the light to be dispersed and an emission spectrum recorded. The emission spectra of rhodamine-6G and 5-carboxyrhodamine-6G ions reported in this thesis represent the first spectra recorded from large molecular ions confined in a quadrupole ion trap. Finally, anti-Stokes fluorescence from rhodamine-6G was also detected.

A comparison of the determination and speciation of inorganic arsenic using general HPLC methodology with UV, MS and MS/MS detection.

PubMed

Gilmartin, Gregory; Gingrich, Diane

2018-04-15

The determination and speciation of arsenic in natural resources such as drinking water and agricultural soils has been a growing concern in recent years due to its many toxicological effects [1-3]. To speciate and quantitate concentrations of <1 ppm of arsenic, typically an ion chromatograph (IC) interfaced to an inductively coupled plasma mass spectrometer (ICP-MS) is employed [4-9]. This methodology may be very robust and sensitive, but it is expensive and not as ubiquitous as high performance liquid chromatography (HPLC) with ultraviolet (UV) absorbance detection or electrospray ionization mass spectrometry (ESI-MS). Anion exchange chromatography is a well-documented means of speciating arsenite (As(III), As 2 O 3 ) and arsenate (As(V), AsO 4 ) using UV [10], conductivity [11], or ESI-MS detection [12,13]. This paper demonstrates the utilization of common liquid chromatographic instrumentation to speciate and determines inorganic Arsenic compounds using UV or MS via selected ion recording (SIR) or multiple reaction monitoring (MRM) detection. This paper describes the analysis of arsenite and arsenate samples prepared using both deionized and ground water. The limit of quantitation for the techniques described in this paper for samples spiked in ground water were 454 ppb (As(III)) and 562 ppb (As(V)) for UV detection, 45.4 ppb (As(III)) and 56.2 ppb (As(V)) for SIR detection, and 4.54 ppb (As(III)) and 5.62 ppb (As(V)) for MRM detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Determination of imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole in fruits and vegetables by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

PubMed

Pous, X; Ruíz, M J; Picó, Y; Font, G

2001-09-01

Imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole have been simultaneously determined in strawberries, oranges, potatoes, pears, and melons by matrix solid-phase dispersion (MSPD) followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) in positive-ion mode. The samples were homogenized with C8 bonded silica as MSPD sorbent, placed in a glass column, and eluted with dichloromethane. Chromatographic separation of the compounds was achieved on a reversed-phase LC column using a methanol-ammonium formate (50 mmol L(-1)) gradient as a mobile phase. Samples were screened by monitoring the protonated molecular ion at m/z 256 for imidacloprid, 280 for metalaxyl, 289 for myclobutanil, and 202 for thiabendazole, and the main fragment at m/z 138 for propham. Positive samples were confirmed by multiple-ion monitoring. The repeatability (<20%) and recovery (>57%) of the method were good, and limits of detection (<0.05 mg kg(-1)) were adequate.

Approximation of super-ions for single-file diffusion of multiple ions through narrow pores.

PubMed

Kharkyanen, Valery N; Yesylevskyy, Semen O; Berezetskaya, Natalia M

2010-11-01

The general theory of the single-file multiparticle diffusion in the narrow pores could be greatly simplified in the case of inverted bell-like shape of the single-particle energy profile, which is often observed in biological ion channels. There is a narrow and deep groove in the energy landscape of multiple interacting ions in such profiles, which corresponds to the pre-defined optimal conduction pathway in the configurational space. If such groove exists, the motion of multiple ions can be reduced to the motion of single quasiparticle, called the superion, which moves in one-dimensional effective potential. The concept of the superions dramatically reduces the computational complexity of the problem and provides very clear physical interpretation of conduction phenomena in the narrow pores.

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

Field ion spectrometry: a new technology for cocaine and heroin detection

NASA Astrophysics Data System (ADS)

Carnahan, Byron L.; Day, Stephen; Kouznetsov, Viktor; Tarassov, Alexandre

1997-02-01

Field ion spectrometry, also known as transverse field compensation ion mobility spectrometry, is a new technique for trace gas analysis that can be applied to the detection of cocaine and heroin. Its principle is based on filtering ion species according to the functional dependence of their mobilities with electric field strength. Field ion spectrometry eliminates the gating electrodes needed in conventional IMS to pulse ions into the spectrometer; instead, ions are injected in to the spectrometer and reach the detector continuously, resulting in improved sensitivity. The technique enables analyses that are difficult with conventional constant field strength ion mobility spectrometers. We have shown that a filed ion spectrometer can selectively detect the vapors from cocaine and heroin emitted from both their base and hydrochloride forms. The estimated volumetric limits of detection are in the low pptv range, based on testing with standardized drug vapor generation systems. The spectrometer can detect cocaine base in the vapor phase, at concentrations well below its estimated 100 pptv vapor pressure equivalent at 20 degrees C. This paper describes the underlying principles of field ion spectrometry in relation to narcotic drug detection, and recent results obtained for cocaine and heroin. The work has been sponsored in part by the United States Advanced Research Projects Agency under contract DAAB10-95C-0004, for the DOD Counterdrug Technology Development Program.

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

PubMed

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

2016-11-15

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

Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

DOE PAGES

Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.; ...

2016-11-05

Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

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

Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.

Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

Multiple ion beam irradiation for the study of radiation damage in materials

NASA Astrophysics Data System (ADS)

Taller, Stephen; Woodley, David; Getto, Elizabeth; Monterrosa, Anthony M.; Jiao, Zhijie; Toader, Ovidiu; Naab, Fabian; Kubley, Thomas; Dwaraknath, Shyam; Was, Gary S.

2017-12-01

The effects of transmutation produced helium and hydrogen must be included in ion irradiation experiments to emulate the microstructure of reactor irradiated materials. Descriptions of the criteria and systems necessary for multiple ion beam irradiation are presented and validated experimentally. A calculation methodology was developed to quantify the spatial distribution, implantation depth and amount of energy-degraded and implanted light ions when using a thin foil rotating energy degrader during multi-ion beam irradiation. A dual ion implantation using 1.34 MeV Fe+ ions and energy-degraded D+ ions was conducted on single crystal silicon to benchmark the dosimetry used for multi-ion beam irradiations. Secondary Ion Mass Spectroscopy (SIMS) analysis showed good agreement with calculations of the peak implantation depth and the total amount of iron and deuterium implanted. The results establish the capability to quantify the ion fluence from both heavy ion beams and energy-degraded light ion beams for the purpose of using multi-ion beam irradiations to emulate reactor irradiated microstructures.

A multiple hollow fibre liquid-phase microextraction method for the determination of halogenated solvent residues in olive oil.

PubMed

Manso, J; García-Barrera, T; Gómez-Ariza, J L; González, A G

2014-02-01

The present paper describes a method based on the extraction of analytes by multiple hollow fibre liquid-phase microextraction and detection by ion-trap mass spectrometry and electron capture detectors after gas chromatographic separation. The limits of detection are in the range of 0.13-0.67 μg kg(-1), five orders of magnitude lower than those reached with the European Commission Official method of analysis, with three orders of magnitude of linear range (from the quantification limits to 400 μg kg(-1) for all the analytes) and recoveries in fortified olive oils in the range of 78-104 %. The main advantages of the analytical method are the absence of sample carryover (due to the disposable nature of the membranes), high enrichment factors in the range of 79-488, high throughput and low cost. The repeatability of the analytical method ranged from 8 to 15 % for all the analytes, showing a good performance.

Using bacterial inclusion bodies to screen for amyloid aggregation inhibitors.

PubMed

Villar-Piqué, Anna; Espargaró, Alba; Sabaté, Raimon; de Groot, Natalia S; Ventura, Salvador

2012-05-03

The amyloid-β peptide (Aβ42) is the main component of the inter-neuronal amyloid plaques characteristic of Alzheimer's disease (AD). The mechanism by which Aβ42 and other amyloid peptides assemble into insoluble neurotoxic deposits is still not completely understood and multiple factors have been reported to trigger their formation. In particular, the presence of endogenous metal ions has been linked to the pathogenesis of AD and other neurodegenerative disorders. Here we describe a rapid and high-throughput screening method to identify molecules able to modulate amyloid aggregation. The approach exploits the inclusion bodies (IBs) formed by Aβ42 when expressed in bacteria. We have shown previously that these aggregates retain amyloid structural and functional properties. In the present work, we demonstrate that their in vitro refolding is selectively sensitive to the presence of aggregation-promoting metal ions, allowing the detection of inhibitors of metal-promoted amyloid aggregation with potential therapeutic interest. Because IBs can be produced at high levels and easily purified, the method overcomes one of the main limitations in screens to detect amyloid modulators: the use of expensive and usually highly insoluble synthetic peptides.

The effect of ion plated silver and sliding friction on tensile stress-induced cracking in aluminum oxide

NASA Technical Reports Server (NTRS)

Sliney, Harold E.; Spalvins, Talivaldis

1991-01-01

A Hertzian analysis of the effect of sliding friction on contact stresses in alumina is used to predict the critical load for crack generation. The results for uncoated alumina and alumina coated with ion plated silver are compared. Friction coefficient inputs to the analysis are determined experimentally with a scratch test instrument employing an 0.2 mm radius diamond stylus. A series of scratches were made at constant load increments on coated and uncoated flat alumina surfaces. Critical loads for cracking are detected by microscopic examination of cross sections of scratches made at various loads and friction coefficients. Acoustic emission (AE) and friction trends were also evaluated as experimental techniques for determining critical loads for cracking. Analytical predictions correlate well with micrographic evidence and with the lowest load at which AE is detected in multiple scratch tests. Friction/load trends are not good indicators of early crack formation. Lubrication with silver films reduced friction and thereby increased the critical load for crack initiation in agreement with analytical predictions.

Determination of chlorpyrifos and its metabolites in cells and culture media by liquid chromatography-electrospray ionization tandem mass spectrometry.

PubMed

Yang, Xiangkun; Wu, Xian; Brown, Kyle A; Le, Thao; Stice, Steven L; Bartlett, Michael G

2017-09-15

A sensitive method to simultaneously quantitate chlorpyrifos, chlorpyrifos oxon and the detoxified product 3,5,6-trichloro-2-pyridinol (TCP) was developed using either liquid-liquid extraction for culture media samples, or protein precipitation for cell samples. Multiple reaction monitoring in positive ion mode was applied for the detection of chlorpyrifos and chlorpyrifos oxon, and selected ion recording in negative mode was applied to detect TCP. The method provided linear ranges from 5 to 500, 0.2-20 and 20-2000ng/mL for media samples and from 0.5-50, 0.02-2 and 2-200ng/million cells for CPF, CPO and TCP, respectively. The method was validated using selectivity, linearity, precision, accuracy, recovery, stability and dilution tests. All relative standard deviations (RSDs) and relative errors (REs) for QC samples were within 15% (except for LLOQ, within 20%). This method has been successfully applied to study the neurotoxicity and metabolism of chlorpyrifos in a human neuronal model. Copyright © 2017 Elsevier B.V. All rights reserved.

High-resolution mass spectrometric analysis of biomass pyrolysis vapors

DOE PAGES

Christensen, Earl; Evans, Robert J.; Carpenter, Daniel

2017-01-19

Vapors generated from the pyrolysis of lignocellulosic biomass are made up of a complex mixture of oxygenated compounds. Direct analysis of these vapors provides insight into the mechanisms of depolymerization of cellulose, hemicellulose, and lignin as well as insight into reactions that may occur during condensation of pyrolysis vapors into bio-oil. Studies utilizing pyrolysis molecular beam mass spectrometry have provided valuable information regarding the chemical composition of pyrolysis vapors. Mass spectrometers generally employed with these instruments have low mass resolution of approximately a mass unit. The presence of chemical species with identical unit mass but differing elemental formulas cannot bemore » resolved with these instruments and are therefore detected as a single ion. In this study we analyzed the pyrolysis vapors of several biomass sources using a high-resolution double focusing mass spectrometer. High-resolution analysis of pyrolysis vapors allowed for speciation of several compounds that would be detected as a single ion with unit mass resolution. Lastly, these data not only provide greater detail into the composition of pyrolysis vapors but also highlight differences between vapors generated from multiple biomass feedstocks.« less

The effect of ion-plated silver and sliding friction on tensile stress-induced cracking in aluminum oxide

NASA Technical Reports Server (NTRS)

Sliney, Harold E.; Spalvins, Talivaldis

1993-01-01

A Hertzian analysis of the effect of sliding friction on contact stresses in alumina is used to predict the critical load for crack generation. The results for uncoated alumina and alumina coated with ion plated silver are compared. Friction coefficient inputs to the analysis are determined experimentally with a scratch test instrument employing an 0.2 mm radius diamond stylus. A series of scratches were made at constant load increments on coated and uncoated flat alumina surfaces. Critical loads for cracking are detected by microscopic examination of cross sections of scratches made at various loads and friction coefficients. Acoustic emission (AE) and friction trends were also evaluated as experimental techniques for determining critical loads for cracking. Analytical predictions correlate well with micrographic evidence and with the lowest load at which AE is detected in multiple scratch tests. Friction/load trends are not good indicators of early crack formation. Lubrication with silver films reduced friction and thereby increased the critical load for crack initiation in agreement with analytical predictions.

DNAzyme sensors for detection of metal ions in the environment and imaging them in living cells

PubMed Central

McGhee, Claire E.; Loh, Kang Yong

2017-01-01

The on-site and real-time detection of metal ions is important for environmental monitoring and for understanding the impact of metal ions on human health. However, developing sensors selective for a wide range of metal ions that can work in the complex matrices of untreated samples and cells presents significant challenges. To meet these challenges, DNAzymes, an emerging class of metal ion-dependent enzymes selective for almost any metal ion, have been functionalized with fluorophores, nanoparticles and other imaging agents and incorporated into sensors for the detection of metal ions in environmental samples and for imaging the metal ions in living cells. Herein, we highlight the recent developments of DNAzyme-based fluorescent, colorimetric, SERS, electrochemical and electrochemiluminscent sensors for metal ions for these applications. PMID:28458112

Optimization by infusion of multiple reaction monitoring transitions for sensitive quantification of peptides by liquid chromatography/mass spectrometry.

PubMed

Alghanem, Bandar; Nikitin, Frédéric; Stricker, Thomas; Duchoslav, Eva; Luban, Jeremy; Strambio-De-Castillia, Caterina; Muller, Markus; Lisacek, Frédérique; Varesio, Emmanuel; Hopfgartner, Gérard

2017-05-15

In peptide quantification by liquid chromatography/mass spectrometry (LC/MS), the optimization of multiple reaction monitoring (MRM) parameters is essential for sensitive detection. We have compared different approaches to build MRM assays, based either on flow injection analysis (FIA) of isotopically labelled peptides, or on the knowledge and the prediction of the best settings for MRM transitions and collision energies (CE). In this context, we introduce MRMOptimizer, an open-source software tool that processes spectra and assists the user in selecting transitions in the FIA workflow. MS/MS spectral libraries with CE voltages from 10 to 70 V are automatically acquired in FIA mode for isotopically labelled peptides. Then MRMOptimizer determines the optimal MRM settings for each peptide. To assess the quantitative performance of our approach, 155 peptides, representing 84 proteins, were analysed by LC/MRM-MS and the peak areas were compared between: (A) the MRMOptimizer-based workflow, (B1) the SRMAtlas transitions set used 'as-is'; (B2) the same SRMAtlas set with CE parameters optimized by Skyline. 51% of the three most intense transitions per peptide were shown to be common to both A and B1/B2 methods, and displayed similar sensitivity and peak area distributions. The peak areas obtained with MRMOptimizer for transitions sharing either the precursor ion charge state or the fragment ions with the SRMAtlas set at unique transitions were increased 1.8- to 2.3-fold. The gain in sensitivity using MRMOptimizer for transitions with different precursor ion charge state and fragment ions (8% of the total), reaches a ~ 11-fold increase. Isotopically labelled peptides can be used to optimize MRM transitions more efficiently in FIA than by searching databases. The MRMOptimizer software is MS independent and enables the post-acquisition selection of MRM parameters. Coefficients of variation for optimal CE values are lower than those obtained with the SRMAtlas approach (B2) and one additional peptide was detected. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Implantation of sodium ions into germanium

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

Korol', V. M., E-mail: vkorol@ctsnet.ru; Kudriavtsev, Yu.

The donor properties of Na atoms introduced by ion implantation into p-Ge with the resistivity 20-40 {Omega} cm are established for the first time. Na profiles implanted into Ge (the energies 70 and 77 keV and the doses (0.8, 3, 30) Multiplication-Sign 10{sup 14} cm{sup -2}) are studied. The doses and annealing temperatures at which the thermoprobe detects n-type conductivity on the sample surface are established. After implantation, the profiles exhibit an extended tail. The depth of the concentration maximum is in good agreement with the calculated mean projected range of Na ions R{sub p}. Annealing for 30 min atmore » temperatures of 250-700 Degree-Sign C brings about a redistribution of Na atoms with the formation of segregation peaks at a depth, which is dependent on the ion dose, and is accompanied by the diffusion of Na atoms to the surface with subsequent evaporation. After annealing at 700 Degree-Sign C less than 7% of the implanted ions remain in the matrix. The shape of the profile tail portions measured after annealing at temperatures 300-400 Degree-Sign C is indicative of the diffusion of a small fraction of Na atoms into the depth of the sample.« less

Detection of nitro-based and peroxide-based explosives by fast polarity-switchable ion mobility spectrometer with ion focusing in vicinity of Faraday detector.

PubMed

Zhou, Qinghua; Peng, Liying; Jiang, Dandan; Wang, Xin; Wang, Haiyan; Li, Haiyang

2015-05-29

Ion mobility spectrometer (IMS) has been widely deployed for on-site detection of explosives. The common nitro-based explosives are usually detected by negative IMS while the emerging peroxide-based explosives are better detected by positive IMS. In this study, a fast polarity-switchable IMS was constructed to detect these two explosive species in a single measurement. As the large traditional Faraday detector would cause a trailing reactant ion peak (RIP), a Faraday detector with ion focusing in vicinity was developed by reducing the detector radius to 3.3 mm and increasing the voltage difference between aperture grid and its front guard ring to 591 V, which could remove trailing peaks from RIP without loss of signal intensity. This fast polarity-switchable IMS with ion focusing in vicinity of Faraday detector was employed to detect a mixture of 10 ng 2,4,6-trinitrotoluene (TNT) and 50 ng hexamethylene triperoxide diamine (HMTD) by polarity-switching, and the result suggested that [TNT-H](-) and [HMTD+H](+) could be detected in a single measurement. Furthermore, the removal of trailing peaks from RIP by the Faraday detector with ion focusing in vicinity also promised the accurate identification of KClO4, KNO3 and S in common inorganic explosives, whose product ion peaks were fairly adjacent to RIP.

A modular cell-based biosensor using engineered genetic logic circuits to detect and integrate multiple environmental signals

PubMed Central

Wang, Baojun; Barahona, Mauricio; Buck, Martin

2013-01-01

Cells perceive a wide variety of cellular and environmental signals, which are often processed combinatorially to generate particular phenotypic responses. Here, we employ both single and mixed cell type populations, pre-programmed with engineered modular cell signalling and sensing circuits, as processing units to detect and integrate multiple environmental signals. Based on an engineered modular genetic AND logic gate, we report the construction of a set of scalable synthetic microbe-based biosensors comprising exchangeable sensory, signal processing and actuation modules. These cellular biosensors were engineered using distinct signalling sensory modules to precisely identify various chemical signals, and combinations thereof, with a quantitative fluorescent output. The genetic logic gate used can function as a biological filter and an amplifier to enhance the sensing selectivity and sensitivity of cell-based biosensors. In particular, an Escherichia coli consortium-based biosensor has been constructed that can detect and integrate three environmental signals (arsenic, mercury and copper ion levels) via either its native two-component signal transduction pathways or synthetic signalling sensors derived from other bacteria in combination with a cell-cell communication module. We demonstrate how a modular cell-based biosensor can be engineered predictably using exchangeable synthetic gene circuit modules to sense and integrate multiple-input signals. This study illustrates some of the key practical design principles required for the future application of these biosensors in broad environmental and healthcare areas. PMID:22981411

Dual mode ion mobility spectrometer and method for ion mobility spectrometry

DOEpatents

Scott, Jill R [Idaho Falls, ID; Dahl, David A [Idaho Falls, ID; Miller, Carla J [Idaho Falls, ID; Tremblay, Paul L [Idaho Falls, ID; McJunkin, Timothy R [Idaho Falls, ID

2007-08-21

Ion mobility spectrometer apparatus may include an ion interface that is operable to hold positive and negative ions and to simultaneously release positive and negative ions through respective positive and negative ion ports. A first drift chamber is operatively associated with the positive ion port of the ion interface and encloses an electric field therein. A first ion detector operatively associated with the first drift chamber detects positive ions from the first drift chamber. A second drift chamber is operatively associated with the negative ion port of the ion interface and encloses an electric field therein. A second ion detector operatively associated with the second drift chamber detects negative ions from said second drift chamber.

NASA Tech Briefs, January 2006

NASA Technical Reports Server (NTRS)

2006-01-01

Topics covered include: Semiautonomous Avionics-and-Sensors System for a UAV; Biomimetic/Optical Sensors for Detecting Bacterial Species; System Would Detect Foreign-Object Damage in Turbofan Engine; Detection of Water Hazards for Autonomous Robotic Vehicles; Fuel Cells Utilizing Oxygen From Air at Low Pressures; Hybrid Ion-Detector/Data-Acquisition System for a TOF-MS; Spontaneous-Desorption Ionizer for a TOF-MS; Equipment for On-Wafer Testing From 220 to 325 GHz; Computing Isentropic Flow Properties of Air/R-134a Mixtures; Java Mission Evaluation Workstation System; Using a Quadtree Algorithm To Assess Line of Sight; Software for Automated Generation of Cartesian Meshes; Optics Program Modified for Multithreaded Parallel Computing; Programs for Testing Processor-in-Memory Computing Systems; PVM Enhancement for Beowulf Multiple-Processor Nodes; Ion-Exclusion Chromatography for Analyzing Organics in Water; Selective Plasma Deposition of Fluorocarbon Films on SAMs; Water-Based Pressure-Sensitive Paints; System Finds Horizontal Location of Center of Gravity; Predicting Tail Buffet Loads of a Fighter Airplane; Water Containment Systems for Testing High-Speed Flywheels; Vapor-Compression Heat Pumps for Operation Aboard Spacecraft; Multistage Electrophoretic Separators; Recovering Residual Xenon Propellant for an Ion Propulsion System; Automated Solvent Seaming of Large Polyimide Membranes; Manufacturing Precise, Lightweight Paraboloidal Mirrors; Analysis of Membrane Lipids of Airborne Micro-Organisms; Noninvasive Diagnosis of Coronary Artery Disease Using 12-Lead High-Frequency Electrocardiograms; Dual-Laser-Pulse Ignition; Enhanced-Contrast Viewing of White-Hot Objects in Furnaces; Electrically Tunable Terahertz Quantum-Cascade Lasers; Few-Mode Whispering-Gallery-Mode Resonators; Conflict-Aware Scheduling Algorithm; and Real-Time Diagnosis of Faults Using a Bank of Kalman Filters.

Fabrication and characterization of a co-planar detector in diamond for low energy single ion implantation

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

Abraham, John Bishoy Sam; Pacheco, Jose L.; Aguirre, Brandon Adrian

2016-08-09

We demonstrate low energy single ion detection using a co-planar detector fabricated on a diamond substrate and characterized by ion beam induced charge collection. Histograms are taken with low fluence ion pulses illustrating quantized ion detection down to a single ion with a signal-to-noise ratio of approximately 10. We anticipate that this detection technique can serve as a basis to optimize the yield of single color centers in diamond. In conclusion, the ability to count ions into a diamond substrate is expected to reduce the uncertainty in the yield of color center formation by removing Poisson statistics from the implantationmore » process.« less

Microstructured Optical Fiber-based Biosensors: Reversible and Nanoliter-Scale Measurement of Zinc Ions.

PubMed

Heng, Sabrina; McDevitt, Christopher A; Kostecki, Roman; Morey, Jacqueline R; Eijkelkamp, Bart A; Ebendorff-Heidepriem, Heike; Monro, Tanya M; Abell, Andrew D

2016-05-25

Sensing platforms that allow rapid and efficient detection of metal ions would have applications in disease diagnosis and study, as well as environmental sensing. Here, we report the first microstructured optical fiber-based biosensor for the reversible and nanoliter-scale measurement of metal ions. Specifically, a photoswitchable spiropyran Zn(2+) sensor is incorporated within the microenvironment of a liposome attached to microstructured optical fibers (exposed-core and suspended-core microstructured optical fibers). Both fiber-based platforms retains high selectivity of ion binding associated with a small molecule sensor, while also allowing nanoliter volume sampling and on/off switching. We have demonstrated that multiple measurements can be made on a single sample without the need to change the sensor. The ability of the new sensing platform to sense Zn(2+) in pleural lavage and nasopharynx of mice was compared to that of established ion sensing methodologies such as inductively coupled plasma mass spectrometry (ICP-MS) and a commercially available fluorophore (Fluozin-3), where the optical-fiber-based sensor provides a significant advantage in that it allows the use of nanoliter (nL) sampling when compared to ICP-MS (mL) and FluoZin-3 (μL). This work paves the way to a generic approach for developing surface-based ion sensors using a range of sensor molecules, which can be attached to a surface without the need for its chemical modification and presents an opportunity for the development of new and highly specific ion sensors for real time sensing applications.

Neuroaxonal ion dyshomeostasis of the normal-appearing corpus callosum in experimental autoimmune encephalomyelitis.

PubMed

Chen, Chiao-Chi V; Zechariah, Anil; Hsu, Yi-Hua; Chen, Hsiao-Wen; Yang, Li-Chuan; Chang, Chen

2008-04-01

Atrophy of the corpus callosum (CC) is a well-documented observation in clinically definite multiple sclerosis (MS) patients. One recent hypothesis for the neurodegeneration that occurs in MS is that ion dyshomeostasis leads to neuroaxonal damage. To examine whether ion dyshomeostasis occurs in the CC during MS onset, experimental autoimmune encephalomyelitis (EAE) was utilized as an animal MS model to induce autoimmunity-mediated responses. To date, in vivo investigations of neuronal ion homeostasis has not been feasible using traditional neuroscience techniques. Therefore, the current study employed an emerging MRI method, called Mn2+-enhanced MRI (MEMRI). Mn2+ dynamics is closely associated with important neuronal activity events, and is also considered to be a Ca2+ surrogate. Furthermore, when injected intracranially, Mn2+ can be used as a multisynaptic tracer. These features enable MEMRI to detect neuronal ion homeostasis within a multisynaptic circuit that is connected to the injection site. Mn2+ was injected into the visual cortex to trace the CC, and T1-weighted imaging was utilized to observe temporal changes in Mn2+-induced signals in the traced pathways. The results showed that neuroaxonal functional changes associated with ion dyshomeostasis occurred in the CC during an acute EAE attack. In addition, the pathway appeared normal, although EAE-induced immune-cell infiltration was visible around the CC. The findings suggest that ion dyshomeostasis is a major neuronal aberration underlying the deterioration of normal-appearing brain tissues in MS, supporting its involvement in neuroaxonal functioning in MS.

Understanding the detection of carbon in austenitic high-Mn steel using atom probe tomography.

PubMed

Marceau, R K W; Choi, P; Raabe, D

2013-09-01

A high-Mn TWIP steel having composition Fe-22Mn-0.6C (wt%) is considered in this study, where the need for accurate and quantitative analysis of clustering and short-range ordering by atom probe analysis requires a better understanding of the detection of carbon in this system. Experimental measurements reveal that a high percentage of carbon atoms are detected as molecular ion species and on multiple hit events, which is discussed with respect to issues such as optimal experimental parameters, correlated field evaporation and directional walk/migration of carbon atoms at the surface of the specimen tip during analysis. These phenomena impact the compositional and spatial accuracy of the atom probe measurement and thus require careful consideration for further cluster-finding analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Ion detection device and method with compressing ion-beam shutter

DOEpatents

Sperline, Roger P [Tucson, AZ

2009-05-26

An ion detection device, method and computer readable medium storing instructions for applying voltages to shutter elements of the detection device to compress ions in a volume defined by the shutter elements and to output the compressed ions to a collector. The ion detection device has a chamber having an inlet and receives ions through the inlet, a shutter provided in the chamber opposite the inlet and configured to allow or prevent the ions to pass the shutter, the shutter having first and second shutter elements, a collector provided in the chamber opposite the shutter and configured to collect ions passed through the shutter, and a processing unit electrically connected to the first and second shutter elements. The processing unit applies, during a first predetermined time interval, a first voltage to the first shutter element and a second voltage to the second shutter element, the second voltage being lower than the first voltage such that ions from the inlet enter a volume defined by the first and second shutter elements, and during a second predetermined time interval, a third voltage to the first shutter element, higher than the first voltage, and a fourth voltage to the second shutter element, the third voltage being higher than the fourth voltage such that ions that entered the volume are compressed as the ions exit the volume and new ions coming from the inlet are prevented from entering the volume. The processing unit is electrically connected to the collector and configured to detect the compressed ions based at least on a current received from the collector and produced by the ions collected by the collector.

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

Mass Spectrometry Parameters Optimization for the 46 Multiclass Pesticides Determination in Strawberries with Gas Chromatography Ion-Trap Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Fernandes, Virgínia C.; Vera, Jose L.; Domingues, Valentina F.; Silva, Luís M. S.; Mateus, Nuno; Delerue-Matos, Cristina

2012-12-01

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET), maximum excitation energy or " q" value (q), and isolation mass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit. Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

The MR-TOF-MS isobar separator for the TITAN facility at TRIUMF

NASA Astrophysics Data System (ADS)

Jesch, Christian; Dickel, Timo; Plaß, Wolfgang R.; Short, Devin; Ayet San Andres, Samuel; Dilling, Jens; Geissel, Hans; Greiner, Florian; Lang, Johannes; Leach, Kyle G.; Lippert, Wayne; Scheidenberger, Christoph; Yavor, Mikhail I.

2015-11-01

At TRIUMF's Ion Trap for Atomic and Nuclear Science (TITAN) a multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) will extend TITAN's capabilities and facilitate mass measurements and in-trap decay spectroscopy of exotic nuclei that so far have not been possible due to strong isobaric contamination. This MR-TOF-MS will also enable mass measurements of very short-lived nuclides (half-life > 1 ms) that are produced in very low quantities (a few detected ions overall). In order to allow the installation of an MR-TOF-MS in the restricted space on the platform, on which the TITAN facility is located, novel mass spectrometric methods have been developed. Transport, cooling and distribution of the ions inside the device is done using a buffer gas-filled RFQ-based ion beam switchyard. Mass selection is achieved using a dynamic retrapping technique after time-of-flight analysis in an electrostatic isochronous reflector system. Only due to the combination of these novel methods the realization of an MR-TOF-MS based isobar separator at TITAN has become possible. The device has been built, commissioned off-line and is currently under installation at TITAN.

Introducing the concept of centergram. A new tool to squeeze data from separation techniques-mass spectrometry couplings.

PubMed

Erny, Guillaume L; Simó, Carolina; Cifuentes, Alejandro; Esteves, Valdemar I

2014-02-21

In separation techniques hyphenated to mass spectrometry (MS) the bulk from the separation step is continuously flowing into the mass spectrometer where the compounds, arriving at each separation time, are ionized and further separated based on their m/z ratio. An MS detector is recognized as being a universal detector, although it can also be a very selective instrument. In spite of these advantages, classical two dimensional representations from these hyphenated systems, such as those based on the base peak of electropherogram/chromatogram or on the total ion of electropherogram/chromatogram, usually hide a large number of features that if correctly assessed will show the presence of co-migrating species and/or the low abundant ones. The uses of peak picking algorithms to detect and measure as many peaks as possible from a dataset allow extracting much more information. However, a single migrating compound usually produces a multiplicity of ions, making difficult to differentiate peaks generated by the same compound from other peaks due e.g., to closely co-migrating/eluting species. In this work, a new representation is proposed and its usefulness demonstrated with experimental data from capillary electrophoresis-hyphenated to a time of flight mass spectrometer via an electrospray interface. This representation, called centergram, is obtained after using a peak picking methodology that detects electrophoretic peaks of single ions and measure their positions. The centergram is the histogram (i.e. the count of the number of observations that fall into each one of the intervals, known as bins, as determined by the user) of the measured positions. The intensity of the bars in this histogram will indicate the amount of peaks in the whole dataset whose centers are within each interval. As a compound that has been separated and has entered the MS instrument will produce multiple images at the same position along the m/z dimension, the centergram will exhibit a series of intense bars around the migration time. Those bars will allow defining a centergram peak whose area will be proportional to the number of different types of ions that have been generated in the ionization chamber, the position will be equal to the migration/retention time of the parent compounds and the width will depend on the precision in the measurement of the peak positions. The efficiency of this peak is determined to be up to thirty times higher than the equivalent peak in the classical base peak electropherogram allowing detecting easily co-migrating peaks or the presence of compounds at very low abundance. The number of peaks detected by using this new tool called centergram was increased by more than a factor of 3 compared to the standard representations. Copyright © 2014 Elsevier B.V. All rights reserved.

Simultaneous Determination of Oxysterols, Cholesterol and 25-Hydroxy-Vitamin D3 in Human Plasma by LC-UV-MS

PubMed Central

Narayanaswamy, Rohini; Iyer, Vignesh; Khare, Prachi; Bodziak, Mary Lou; Badgett, Darlene; Zivadinov, Robert; Weinstock-Guttman, Bianca; Rideout, Todd C.; Ramanathan, Murali; Browne, Richard W.

2015-01-01

Background Oxysterols are promising biomarkers of neurodegenerative diseases that are linked with cholesterol and vitamin D metabolism. There is an unmet need for methods capable of sensitive, and simultaneous quantitation of multiple oxysterols, vitamin D and cholesterol pathway biomarkers. Methods A method for simultaneous determination of 5 major oxysterols, 25-hydroxy vitamin D3 and cholesterol in human plasma was developed. Total oxysterols were prepared by room temperature saponification followed by solid phase extraction from plasma spiked with deuterated internal standards. Oxysterols were resolved by reverse phase HPLC using a methanol/water/0.1% formic acid gradient. Oxysterols and 25-hydroxy vitamin D3 were detected with atmospheric pressure chemical ionization mass spectrometry in positive ion mode; in-series photodiode array detection at 204nm was used for cholesterol. Method validation studies were performed. Oxysterol levels in 220 plasma samples from healthy control subjects, multiple sclerosis and other neurological disorders patients were quantitated. Results Our method quantitated 5 oxysterols, cholesterol and 25-hydroxy vitamin D3 from 200 μL plasma in 35 minutes. Recoveries were >85% for all analytes and internal standards. The limits of detection were 3-10 ng/mL for oxysterols and 25-hydroxy vitamin D3 and 1 μg/mL for simultaneous detection of cholesterol. Analytical imprecision was <10 %CV for 24(S)-, 25-, 27-, 7α-hydroxycholesterol (HC) and cholesterol and ≤15 % for 7-keto-cholesterol. Multiple Sclerosis and other neurological disorder patients had lower 27-hydroxycholesterol levels compared to controls whereas 7α-hydroxycholesterol was lower specifically in Multiple Sclerosis. Conclusion The method is suitable for measuring plasma oxysterols levels in human health and disease. Analysis of human plasma indicates that the oxysterol, bile acid precursors 7α-hydroxycholesterol and 27-hydroxycholesterol are lower in Multiple Sclerosis and may serve as potential biomarkers of disease. PMID:25875771

Monitoring

DOEpatents

Orr, Christopher Henry; Luff, Craig Janson; Dockray, Thomas; Macarthur, Duncan Whittemore

2004-11-23

The invention provides apparatus and methods which facilitate movement of an instrument relative to an item or location being monitored and/or the item or location relative to the instrument, whilst successfully excluding extraneous ions from the detection location. Thus, ions generated by emissions from the item or location can successfully be monitored during movement. The technique employs sealing to exclude such ions, for instance, through an electro-field which attracts and discharges the ions prior to their entering the detecting location and/or using a magnetic field configured to repel the ions away from the detecting location.

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

PubMed Central

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

DOE PAGES

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; ...

2015-06-11

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemore » of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.« less

Complete structural characterization of ceramides as [M – H]− ions by multiple-stage linear ion trap mass spectrometry

PubMed Central

Hsu, Fong-Fu

2016-01-01

Ceramide is a huge lipid family consisting of diversified structures including various modifications in the fatty acyl chain and the long chain base (LCB). In this contribution, negative-ion ESI linear ion-trap multiple-stage mass spectrometric method (LIT MSn) towards complete structural determination of ceramides in ten major families characterized as the [M – H]− ions is described. Multiple sets of fragment ions reflecting the fatty acyl chain and LCB were observed in the CID MS2 spectrum, while the sequential MS3 and MS4 spectra contain structural information for locating the double bond and the functional groups, permitting realization of the fragmentation processes. Thereby, differentiation of ceramide molecules varied by chain length, the LCB (sphingosine, phytosphigosine, 6-hydroxy-sphingosine), and by the modification (α-hydroxy-, β-hydroxy-, ω-hydroxy-FA) can be achieved; and many isomeric structures in the biological specimen can be revealed in detail. PMID:27523779

Development of multiclass methods for drug residues in eggs: hydrophilic solid-phase extraction cleanup and liquid chromatography/tandem mass spectrometry analysis of tetracycline, fluoroquinolone, sulfonamide, and beta-lactam residues.

PubMed

Heller, David N; Nochetto, Cristina B; Rummel, Nathan G; Thomas, Michael H

2006-07-26

A method was developed for detection of a variety of polar drug residues in eggs via liquid chromatography/tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI). A total of twenty-nine target analytes from four drug classes-sulfonamides, tetracyclines, fluoroquinolones, and beta-lactams-were extracted from eggs using a hydrophilic-lipophilic balance polymer solid-phase extraction (SPE) cartridge. The extraction technique was developed for use at a target concentration of 100 ng/mL (ppb), and it was applied to eggs containing incurred residues from dosed laying hens. The ESI source was tuned using a single, generic set of tuning parameters, and analytes were separated with a phenyl-bonded silica cartridge column using an LC gradient. In a related study, residues of beta-lactam drugs were not found by LC/MS/MS in eggs from hens dosed orally with beta-lactam drugs. LC/MS/MS performance was evaluated on two generations of ion trap mass spectrometers, and key operational parameters were identified for each instrument. The ion trap acquisition methods could be set up for screening (a single product ion) or confirmation (multiple product ions). The lower limit of detection for screening purposes was 10-50 ppb (sulfonamides), 10-20 ppb (fluoroquinolones), and 10-50 ppb (tetracyclines), depending on the drug, instrument, and acquisition method. Development of this method demonstrates the feasibility of generic SPE, LC, and MS conditions for multiclass LC/MS residue screening.

Analyzing slowly exchanging protein conformations by ion mobility mass spectrometry: study of the dynamic equilibrium of prolyl oligopeptidase.

PubMed

López, Abraham; Vilaseca, Marta; Madurga, Sergio; Varese, Monica; Tarragó, Teresa; Giralt, Ernest

2016-07-01

Ion mobility mass spectrometry (IMMS) is a biophysical technique that allows the separation of isobaric species on the basis of their size and shape. The high separation capacity, sensitivity and relatively fast time scale measurements confer IMMS great potential for the study of proteins in slow (µs-ms) conformational equilibrium in solution. However, the use of this technique for examining dynamic proteins is still not generalized. One of the major limitations is the instability of protein ions in the gas phase, which raises the question as to what extent the structures detected reflect those in solution. Here, we addressed this issue by analyzing the conformational landscape of prolyl oligopeptidase (POP) - a model of a large dynamic enzyme in the µs-ms range - by native IMMS and compared the results obtained in the gas phase with those obtained in solution. In order to interpret the experimental results, we used theoretical simulations. In addition, the stability of POP gaseous ions was explored by charge reduction and collision-induced unfolding experiments. Our experiments disclosed two species of POP in the gas phase, which correlated well with the open and closed conformations in equilibrium in solution; moreover, a gas-phase collapsed form of POP was also detected. Therefore, our findings not only support the potential of IMMS for the study of multiple co-existing conformations of large proteins in slow dynamic equilibrium in solution but also stress the need for careful data analysis to avoid artifacts. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Coordination ability determined transition metal ions substitution of Tb in Tb-Asp fluorescent nanocrystals and a facile ions-detection approach.

PubMed

Duan, Jiazhi; Ma, Baojin; Liu, Feng; Zhang, Shan; Wang, Shicai; Kong, Ying; Du, Min; Han, Lin; Wang, Jianjun; Sang, Yuanhua; Liu, Hong

2018-04-26

Although the synthesis and fluorescent properties of lanthanide-amino acid complex nanostructures have been investigated extensively, limited studies have been reported on metal ions' substitution ability for the lanthanide ions in the complex and their effect on the fluorescent property. In this study, taking biocompatible Tb-aspartic acid (Tb-Asp) complex nanocrystals as a model, the substitution mechanism of metal ions, particularly transition metals, for Tb ions in Tb-Asp nanocrystals and the change in the fluorescent property of the Tb-Asp nanocrystals after substitution were systematically investigated. The experimental results illustrated that metal ions with higher electronegativity, higher valence, and smaller radius possess stronger ability for Tb ions' substitution in Tb-Asp nanocrystals. Based on the effect of substituting ions' concentration on the fluorescent property of Tb-Asp, a facile method for copper ions detection with high sensitivity was proposed by measuring the fluorescent intensity of Tb-Asp nanocrystals' suspensions containing different concentrations of copper ions. The good biocompatibility, great convenience of synthesis and sensitive detection ability make Tb-Asp nanocrystals a very low cost and effective material for metal ions detection, which also opens a new door for practical applications of metal-Asp coordinated nanocrystals.

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.

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.

Cassini CAPS-ELS observations of carbon-based anions and aerosol growth in Titan's ionosphere

NASA Astrophysics Data System (ADS)

Desai, Ravindra; Coates, Andrew; Wellbrock, Anne; Kataria, Dhiren; Jones, Geraint; Lewis, Gethyn; Waite, J.

2016-06-01

Cassini observations of Titans ionosphere revealed an atmosphere rich in positively charged ions with masses up to > 350 amu and negatively charged ions and aerosols with mass over charge ratios as high as 13,800 amu/q. The detection of negatively charged molecules by the Cassini CAPS Electron Spectrometer (CAPS-ELS) was particularly surprising and showed how the synthesis of large aerosol-size particles takes place at altitudes much greater than previously thought. Here, we present further analysis into this CAPS-ELS dataset, through an enhanced understanding of the instrument's response function. In previous studies the intrinsic E/E energy resolution of the instrument did not allow specific species to be identified and the detections were classified into broad mass ranges. In this study we use an updated fitting procedure to show how the ELS mass spectrum can be resolved into specific peaks at multiples of carbon-based anions up to > 100 amu/q. The negatively charged ions and aerosols in Titans ionosphere increase in mass with decreasing altitude, the lightest species being observed close to Titan's exobase of ˜1,450km and heaviest species observed at altitudes < 950km. We identify key stages in this apparent growth process and report on key intermediaries which appear to trigger the rapid growth of the larger aerosol-size particles.

FRET-Based Nanobiosensors for Imaging Intracellular Ca²⁺ and H⁺ Microdomains.

PubMed

Zamaleeva, Alsu I; Despras, Guillaume; Luccardini, Camilla; Collot, Mayeul; de Waard, Michel; Oheim, Martin; Mallet, Jean-Maurice; Feltz, Anne

2015-09-23

Semiconductor nanocrystals (NCs) or quantum dots (QDs) are luminous point emitters increasingly being used to tag and track biomolecules in biological/biomedical imaging. However, their intracellular use as highlighters of single-molecule localization and nanobiosensors reporting ion microdomains changes has remained a major challenge. Here, we report the design, generation and validation of FRET-based nanobiosensors for detection of intracellular Ca(2+) and H⁺ transients. Our sensors combine a commercially available CANdot(®)565QD as an energy donor with, as an acceptor, our custom-synthesized red-emitting Ca(2+) or H⁺ probes. These 'Rubies' are based on an extended rhodamine as a fluorophore and a phenol or BAPTA (1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetra-acetic acid) for H⁺ or Ca(2+) sensing, respectively, and additionally bear a linker arm for conjugation. QDs were stably functionalized using the same SH/maleimide crosslink chemistry for all desired reactants. Mixing ion sensor and cell-penetrating peptides (that facilitate cytoplasmic delivery) at the desired stoichiometric ratio produced controlled multi-conjugated assemblies. Multiple acceptors on the same central donor allow up-concentrating the ion sensor on the QD surface to concentrations higher than those that could be achieved in free solution, increasing FRET efficiency and improving the signal. We validate these nanosensors for the detection of intracellular Ca(2+) and pH transients using live-cell fluorescence imaging.

Utility of Higher Harmonics in Electrospray Ionization Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometry.

PubMed

Dziekonski, Eric T; Johnson, Joshua T; McLuckey, Scott A

2017-04-18

Mass resolution (M/ΔM fwhm) is observed to linearly increase with harmonic order in a Fourier transform electrostatic linear ion trap (ELIT) mass spectrometer. This behavior was predicted by Grosshans and Marshall for frequency-multiple detection in a Fourier transform ion cyclotron resonance mass spectrometer only for situations when the prominent mechanism for signal decay is ion ejection from the trap. As the analyzer pressure in our ELIT chamber is relatively high, such that collisional scattering and collision-induced dissociation are expected to underlie much of the ion loss, we sought to explore the relationship between harmonic order and mass resolution. Mass resolutions of 36 900 (fundamental), 75 850 (2nd harmonic), and 108 200 (3rd harmonic) were obtained for GdO + (avg. m/z 173.919) with a transient length of 300 ms. To demonstrate that the mass resolution was truly increasing with harmonic order, the unresolved isotopes at the fundamental distribution of cytochrome c +8 (m/z ∼ 1549) were nearly baseline, resolved at the third harmonic (mass resolution ≈ 23 000) with a transient length of only 200 ms. This experiment demonstrates that, when the ion density is sufficiently low, ions with frequency differences of less than 4 Hz remain uncoalesced. Higher harmonics can be used to increase the effective mass resolution for a fixed transient length and thereby may enable the resolution of closely spaced masses, determination of a protein ion's charge state, and study of the onset of peak coalescence when the resolution at the fundamental frequency is insufficient.

Rapid and Highly Sensitive Detection of Lead Ions in Drinking Water Based on a Strip Immunosensor

PubMed Central

Kuang, Hua; Xing, Changrui; Hao, Changlong; Liu, Liqiang; Wang, Libing; Xu, Chuanlai

2013-01-01

In this study, we have first developed a rapid and sensitive strip immunosensor based on two heterogeneously-sized gold nanoparticles (Au NPs) probes for the detection of trace lead ions in drinking water. The sensitivity was 4-fold higher than that of the conventional LFA under the optimized conditions. The visual limit of detection (LOD) of the amplified method for qualitative detection lead ions was 2 ng/mL and the LOD for semi-quantitative detection could go down to 0.19 ng/mL using a scanning reader. The method suffered from no interference from other metal ions and could be used to detect trace lead ions in drinking water without sample enrichment. The recovery of the test samples ranged from 96% to 103%. As the detection method could be accomplished within 15 min, this method could be used as a potential tool for preliminary monitoring of lead contamination in drinking water. PMID:23539028

Electron Scale Structures and Magnetic Reconnection Signatures in the Turbulent Magnetosheath

NASA Technical Reports Server (NTRS)

Yordanova, E.; Voros, Z.; Varsani, A.; Graham, D. B.; Norgren, C.; Khotyaintsev, Yu. V.; Vaivads, A.; Eriksson, E.; Nakamura, R.; Lindqvist, P.-A.;

Structure and composition of the neutral upper atmosphere of Mars from the MAVEN NGIMS investigation

PubMed Central

Benna, M.; Elrod, M.; Yelle, R. V.; Bougher, S. W.; Stone, S. W.; Jakosky, B. M.

2015-01-01

Abstract The Mars Atmosphere and Volatile EvolutioN (MAVEN) Neutral Gas and Ion Mass Spectrometer (NGIMS) provides sensitive detections of neutral gas and ambient ion composition. NGIMS measurements of nine atomic and molecular neutral species, and their variation with altitude, latitude, and solar zenith angle are reported over several months of operation of the MAVEN mission. Sampling NGIMS signals from multiple neutral species every several seconds reveals persistent and unexpectedly large amplitude density structures. The scale height temperatures are mapped over the course of the first few months of the mission from high down to midlatitudes. NGIMS measurements near the homopause of 40Ar/N2 ratios agree with those reported by the Sample Analysis at Mars investigation and allow the altitude of the homopause for the most abundant gases to be established. PMID:27667873

Survey of pickup ion signatures in the vicinity of Titan using CAPS/IMS

NASA Astrophysics Data System (ADS)

Regoli, L. H.; Coates, A. J.; Thomsen, M. F.; Jones, G. H.; Roussos, E.; Waite, J. H.; Krupp, N.; Cox, G.

2016-09-01

Pickup ion detection at Titan is challenging because ion cyclotron waves are rarely detected in the vicinity of the moon. In this work, signatures left by freshly produced pickup heavy ions (m/q ˜ 16 to m/q ˜ 28) as detected in the plasma data by the Cassini Plasma Spectrometer/Ion Mass Spectrometer (CAPS/IMS) instrument on board Cassini are analyzed. In order to discern whether these correspond to ions of exospheric origin, one of the flybys during which the reported signatures were observed is investigated in detail. For this purpose, ion composition data from time-of-flight measurements and test particle simulations to constrain the ions' origin are used. After being validated, the detection method is applied to all the flybys for which the CAPS/IMS instrument gathered valid data, constraining the region around the moon where the signatures are observed. The results reveal an escape region located in the anti-Saturn direction as expected from the nominal corotation electric field direction. These findings provide new constraints for the area of freshly produced pickup ion escape, giving an approximate escape rate of 3.3-2+3×1023 ions· s-1.

Detection of Large Ions in Time-of-Flight Mass Spectrometry: Effects of Ion Mass and Acceleration Voltage on Microchannel Plate Detector Response

NASA Astrophysics Data System (ADS)

Liu, Ranran; Li, Qiyao; Smith, Lloyd M.

2014-08-01

In time-of-flight mass spectrometry (TOF-MS), ion detection is typically accomplished by the generation and amplification of secondary electrons produced by ions colliding with a microchannel plate (MCP) detector. Here, the response of an MCP detector as a function of ion mass and acceleration voltage is characterized, for singly charged peptide/protein ions ranging from 1 to 290 kDa in mass, and for acceleration voltages from 5 to 25 kV. A nondestructive inductive charge detector (ICD) employed in parallel with MCP detection provides a reliable reference signal to allow accurate calibration of the MCP response. MCP detection efficiencies were very close to unity for smaller ions at high acceleration voltages (e.g., angiotensin, 1046.5 Da, at 25 kV acceleration voltage), but decreased to ~11% for the largest ions examined (immunoglobulin G (IgG) dimer, 290 kDa) even at the highest acceleration voltage employed (25 kV). The secondary electron yield γ (average number of electrons produced per ion collision) is found to be proportional to mv3.1 (m: ion mass, v: ion velocity) over the entire mass range examined, and inversely proportional to the square root of m in TOF-MS analysis. The results indicate that although MCP detectors indeed offer superlative performance in the detection of smaller peptide/protein species, their performance does fall off substantially for larger proteins, particularly under conditions of low acceleration voltage.

Picomolar detection limits with current-polarized Pb2+ ion-selective membranes.

PubMed

Pergel, E; Gyurcsányi, R E; Tóth, K; Lindner, E

2001-09-01

Minor ion fluxes across ion-selective membranes bias submicromolar activity measurements with conventional ion-selective electrodes. When ion fluxes are balanced, the lower limit of detection is expected to be dramatically improved. As proof of principle, the flux of lead ions across an ETH 5435 ionophore-based lead-selective membrane was gradually compensated by applying a few nanoamperes of galvanostatic current. When the opposite ion fluxes were matched, and the undesirable leaching of primary ions was eliminated, Nernstian response down to 3 x 10(-12) M was achieved.

Silver(I) Ions Ultrasensitive Detection at Carbon Electrodes—Analysis of Waters, Tobacco Cells and Fish Tissues

PubMed Central

Krizkova, Sona; Krystofova, Olga; Trnkova, Libuse; Hubalek, Jaromir; Adam, Vojtech; Beklova, Miroslava; Horna, Ales; Havel, Ladislav; Kizek, Rene

2009-01-01

We used carbon paste electrodes and a standard potentiostat to detect silver ions. The detection limit (3 Signal/Noise ratio) was estimated as 0.5 μM. A standard electrochemical instrument microanalysis of silver(I) ions was suggested. As a working electrode a carbon tip (1 mL) or carbon pencil was used. Limits of detection estimated by dilution of a standard were 1 (carbon tip) or 10 nM (carbon pencil). Further we employed flow injection analysis coupled with carbon tip to detect silver(I) ions released in various beverages and mineral waters. During first, second and third week the amount of silver(I) ions releasing into water samples was under the detection limit of the technique used for their quantification. At the end of a thirteen weeks long experiment the content of silver(I) ions was several times higher compared to the beginning of release detected in the third week and was on the order of tens of nanomoles. In subsequent experiments the influence of silver(I) ions (0, 5 and 10 μM) on a plant model system (tobacco BY-2 cells) during a four-day exposition was investigated. Silver(I) ions were highly toxic to the cells, which was revealed by a double staining viability assay. Moreover we investigated the effect of silver(I) ions (0, 0.3, 0.6, 1.2 and 2.5 μM) on guppies (Poecilia reticulata). Content of Ag(I) increased with increasing time of the treatment and applied concentrations in fish tissues. It can be concluded that a carbon tip or carbon pencil coupled with a miniaturized potentiostat can be used for detection of silver(I) ions in environmental samples and thus represents a small, portable, low cost and easy-to-use instrument for such purposes. PMID:22399980

Rapid label-free profiling of oral cancer biomarker proteins using nano-UPLC-Q-TOF ion mobility mass spectrometry.

PubMed

Nassar, Ala F; Williams, Brad J; Yaworksy, Dustin C; Patel, Vyomesh; Rusling, James F

2016-03-01

It has become quite clear that single cancer biomarkers cannot in general provide high sensitivity and specificity for reliable clinical cancer diagnostics. This paper explores the feasibility of rapid detection of multiple biomarker proteins in model oral cancer samples using label-free protein relative quantitation. MS-based label-free quantitative proteomics offer a rapid alternative that bypasses the need for stable isotope containing compounds to chemically bind and label proteins. Total protein content in oral cancer cell culture conditioned media was precipitated, subjected to proteolytic digestion, and then analyzed using a nano-UPLC (where UPLC is ultra-performance liquid chromatography) coupled to a hybrid Q-Tof ion-mobility mass spectrometry (MS). Rapid, simultaneous identification and quantification of multiple possible cancer biomarker proteins was achieved. In a comparative study between cancer and noncancer samples, approximately 952 proteins were identified using a high-throughput 1D ion mobility assisted data independent acquisition (IM-DIA) approach. As we previously demonstrated that interleukin-8 (IL-8) and vascular endothelial growth factor A (VEGF-A) were readily detected in oral cancer cell conditioned media(1), we targeted these biomarker proteins to validate our approach. Target biomarker protein IL-8 was found between 3.5 and 8.8 fmol, while VEGF-A was found at 1.45 fmol in the cancer cell media. Overall, our data suggest that the nano-UPLC-IM-DIA bioassay is a feasible approach to identify and quantify proteins in complex samples without the need for stable isotope labeling. These results have significant implications for rapid tumor diagnostics and prognostics by monitoring proteins such as IL-8 and VEGF-A implicated in cancer development and progression. The analysis in tissue or plasma is not possible at this time, but the subsequent work would be needed for validation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triboelectrification-Enabled Self-Powered Detection and Removal of Heavy Metal Ions in Wastewater.

PubMed

Li, Zhaoling; Chen, Jun; Guo, Hengyu; Fan, Xing; Wen, Zhen; Yeh, Min-Hsin; Yu, Chongwen; Cao, Xia; Wang, Zhong Lin

2016-04-20

A fundamentally new working principle into the field of self-powered heavy-metal-ion detection and removal using the triboelectrification effect is introduced. The as-developed tribo-nanosensors can selectively detect common heavy metal ions. The water-driven triboelectric nanogenerator is taken as a sustainable power source for heavy-metal-ion removal by recycling the kinetic energy from flowing wastewater. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Collection of ions

DOEpatents

Orr, Christopher Henry; Luff, Craig Janson; Dockray, Thomas; Macarthur, Duncan Whittemore; Bounds, John Alan; Koster, James E.

2001-01-01

The apparatus and method provide an improved technique for detecting ions as the area from which ions are attracted to a detector is increased, consequently increasing the number of ions detected. This is achieved by providing the outer electrodes of the detector connected to the electrical potential, together with alternate intermediate electrodes. The other intermediate electrodes and preferably the housing are grounded. The technique renders such detection techniques more sensitive and gives them a lower threshold at which they can function.

System and process for pulsed multiple reaction monitoring

DOEpatents

Belov, Mikhail E

2013-05-17

A new pulsed multiple reaction monitoring process and system are disclosed that uses a pulsed ion injection mode for use in conjunction with triple-quadrupole instruments. The pulsed injection mode approach reduces background ion noise at the detector, increases amplitude of the ion signal, and includes a unity duty cycle that provides a significant sensitivity increase for reliable quantitation of proteins/peptides present at attomole levels in highly complex biological mixtures.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

NASA Astrophysics Data System (ADS)

Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

2016-08-01

Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

A novel fluorescent probe (dtpa-bis(cytosine)) for detection of Eu(III) in rare earth metal ions

NASA Astrophysics Data System (ADS)

Yang, Fan; Ren, Peipei; Liu, Guanhong; Song, Youtao; Bu, Naishun; Wang, Jun

2018-03-01

In this paper, a novel fluorescent probe, dtpa-bis(cytosine), was designed and synthesized for detecting europium (Eu3 +) ion. Upon addition of Eu3 + ions into the dtpa-bis(cytosine) solution, the fluorescence intensity can strongly be enhanced. Conversely, adding other rare earth metal ions, such as Y3 +, Ce3 +, Pr3 +, Nd3 +, Sm3 +, Gd3 +, Tb3 +, Dy3 +, Ho3 +, Er3 +, Yb3 + and Lu3 +, into dtpa-bis(cytosine) solution, the fluorescence intensity is decreased slightly. Some parameters affecting the fluorescence intensity of dtpa-bis(cytosine) solution in the presence of Eu3 + ions were investigated, including solution pH value, Eu3 + ion concentration and interfering substances. The detection mechanism of Eu3 + ion using dtpa-bis(cytosine) as fluorescent probe was proposed. Under optimum conditions, the fluorescence emission intensities of EuIII-dtpa-bis(cytosine) at 375 nm in the concentration range of 0.50 × 10- 5 mol • L- 1-5.00 × 10- 5 mol • L- 1 of Eu3 + ion display a better linear relationship. The limit of detection (LOD) was determined as 8.65 × 10- 7 mol • L- 1 and the corresponding correlation coefficient (R2) of the linear equation is 0.9807. It is wished that the proposed method could be applied for sensitively and selectively detecting Eu3 + ion.

New, high-efficiency ion trap mobility detection system for narcotics and explosives

NASA Astrophysics Data System (ADS)

McGann, William J.; Bradley, V.; Borsody, A.; Lepine, S.

1994-10-01

A new patented Ion Trap Mobility Spectrometer (ITMS) design is presented. Conventional IMS designs typically operate below 0.1% efficiency. This is due primarily to electric field driven, sample ion discharge on a shutter grid. Since 99.9% of the sample ions generated in the reaction region are lost in this discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an `ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a `field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. Many applications for this new detector are now being considered including the detection of narcotics and explosives. Preliminary ion spectra, reduced mobility data and sensitivity data are presented for fifteen narcotics, including cocaine, THC and LSD are reported.

New high-efficiency ion-trap mobility detection system for narcotics

NASA Astrophysics Data System (ADS)

McGann, William J.

1997-02-01

A new patented Ion Trap Mobility Spectrometer design is presented. Conventional IMS designs typically operate below 0.1 percent efficiency. This is due primarily to electric field driven, sample ion discharge on a shutter grid. Since 99.9 percent of the sample ions generated in the reaction region are lost int his discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an 'ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a 'field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. One application for this new detector is now being developed, a portable, hand-held system with switching capability for the detection of drugs and explosives. Preliminary ion spectra and sensitivity data are presented for cocaine and heroin using a hand sniffer configuration.

New high-efficiency ion trap mobility detection system for narcotics and explosives

NASA Astrophysics Data System (ADS)

McGann, William J.; Jenkins, Anthony; Ribiero, K.; Napoli, J.

1994-03-01

A new patented ion trap mobility spectrometer design is presented. Conventional IMS designs typically operate below 0.1% efficiency. This is due primarily to electrical-field-driven, sample ion discharge on a shutter grid. Since 99.9% of the sample ions generated in the reaction region are lost in this discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an `ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a `field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. Many applications for this new detector are now being considered including the detection of narcotics and explosives. Preliminary ion spectra, reduced mobility data and sensitivity data are presented for fifteen narcotics, including cocaine, THC, and LSD are reported.

Hydrodynamic description of an unmagnetized plasma with multiple ion species. I. General formulation

DOE PAGES

Simakov, Andrei Nikolaevich; Molvig, Kim

2016-03-17

A generalization of the Braginskii ion fluid description [S. I. Braginskii, Sov. Phys. JETP 6, 358 (1958)] to the case of an unmagnetized collisional plasma with multiple ion species is presented. An asymptotic expansion in the ion Knudsen number is used to derive the individual ion species continuity, as well as the total ion mass density, momentum, and energy evolution equations accurate through the second order. Expressions for the individual ion species drift velocities with respect to the center of mass reference frame, as well as for the total ion heat flux and viscosity, which are required to close themore » fluid equations, are evaluated in terms of the first-order corrections to the lowest order Maxwellian ion velocity distribution functions. A variational formulation for evaluating such corrections and its relation to the plasma entropy are presented. Employing trial functions for the corrections, written in terms of expansions in generalized Laguerre polynomials, and maximizing the resulting functionals produces two systems of linear equations (for “vector” and “tensor” portions of the corrections) for the expansion coefficients. A general matrix formulation of the linear systems as well as expressions for the resulting transport fluxes are presented in forms convenient for numerical implementation. The general formulation is employed in the companion paper [A. N. Simakov and K. Molvig, Hydrodynamic description of an unmagnetized plasma with multiple ion species. II. Two and three ion species plasmas, submitted to Phys. Plasmas (2015)] to evaluate the individual ion drift velocities and the total ion heat flux and viscosity for specific cases of two and three ion species plasmas.« less

Identification of ion-pair structures in solution by vibrational stark effects

DOE PAGES

Hack, John; Mani, Tomoyasu; Grills, David C.; ...

2016-01-25

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Identification of ion-pair structures in solution by vibrational stark effects

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

Hack, John; Mani, Tomoyasu; Grills, David C.

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

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

PubMed Central

Williams, D. Keith; Muddiman, David C.

2008-01-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Highly sensitive surface enhanced Raman scattering substrates based on Ag decorated Si nanocone arrays and their application in trace dimethyl phthalate detection

NASA Astrophysics Data System (ADS)

Zuo, Zewen; Zhu, Kai; Ning, Lixin; Cui, Guanglei; Qu, Jun; Cheng, Ying; Wang, Junzhuan; Shi, Yi; Xu, Dongsheng; Xin, Yu

2015-01-01

Wafer-scale three-dimensional (3D) surface enhancement Raman scattering (SERS) substrates were prepared using the plasma etching and ion sputtering methods that are completely compatible with well-established silicon device technologies. The substrates are highly sensitive with excellent uniformity and reproducibility, exhibiting an enhancement factor up to 1012 with a very low relative standard deviation (RSD) around 5%. These are attributed mainly to the uniform-distributed, multiple-type high-density hot spots originating from the structural characteristics of Ag nanoparticles (NPs) decorated Si nanocone (NC) arrays. We demonstrate that the trace dimethyl phthalate (DMP) at a concentration of 10-7 M can be well detected using this SERS substrate, showing that the AgNPs-decorated SiNC arrays can serve as efficient SERS substrates for phthalate acid esters (PAEs) detection with high sensitivity.

A Simple, Cost-Effective Sensor for Detecting Lead Ions in Water Using Under-Potential Deposited Bismuth Sub-Layer with Differential Pulse Voltammetry (DPV)

PubMed Central

Dai, Yifan; Liu, Chung Chiun

2017-01-01

This research has developed a simple to use, cost effective sensor system for the detection of lead ions in tap water. An under-potential deposited bismuth sub-layer on a thin gold film based electrochemical sensor was designed, manufactured, and evaluated. Differential pulse voltammetry (DPV) measurement technique was employed in this detection. Tap water from the Cleveland, OH, USA regional water district was the test medium. Concentrations of lead ion in the range of 8 × 10−7 M to 5 × 10−4 M were evaluated, showing a good sensitivity over this concentration range. The calibration curve for the DPV measurements of lead ions in tap water showed excellent reproducibility with R2 value of 0.970. This DPV detection system required 3–6 min to complete the detection measurement. A longer measurement time of 6 min was used for the lower lead ion concentration. The selectivity of this lead ion sensor was very good, and Fe III, Cu II, Ni II, and Mg II at a concentration level of 5 × 10−4 M did not interfere with the lead ion measurement. PMID:28441356

Influence of ligand chemistry on silver nanoparticles for colorimetric detection of Cr3+ and Hg2+ ions

NASA Astrophysics Data System (ADS)

Kailasa, Suresh Kumar; Chandel, Madhurya; Mehta, Vaibhavkumar N.; Park, Tae Jung

2018-04-01

In this work, we describe the role of ligand chemistry on the surfaces of silver nanoparticles (Ag NPs) for tuning their analytical applications. The citrate and melamine (MA) molecules were used as ligands for the surface modification of Ag NPs. The addition of Cr3+ ion in citrate-Ag NPs (Cit-Ag NPs) and of Hg2+ ion in melamine-Ag NPs (MA-Ag NPs) cause Ag NPs aggregation, and are accompanied by a color change and a red-shift. The resulting distinctly visual readouts are favorable for colorimetric detection of Cr3+ and Hg2+ ions. Under optimal conditions, the linear ranges are observed in the concentration ranges of 1.0-50.0 and of 10.0-100.0 μM, and with detection limit of 0.52 and 1.80 μM for Cr3+ and Hg2+ ions. The simultaneous detection of Cr3+ and Hg2+ ion is driven by the changing the ligand chemistry on the surfaces of Ag NPs that allows to tune their specific interactions with target analytes. Finally, the functionalized Ag NPs were successfully applied to detect Cr3+ and Hg2+ ions in water samples with satisfactory recoveries.

Efficient ensemble system based on the copper binding motif for highly sensitive and selective detection of cyanide ions in 100% aqueous solutions by fluorescent and colorimetric changes.

PubMed

Jung, Kwan Ho; Lee, Keun-Hyeung

2015-09-15

A peptide-based ensemble for the detection of cyanide ions in 100% aqueous solutions was designed on the basis of the copper binding motif. 7-Nitro-2,1,3-benzoxadiazole-labeled tripeptide (NBD-SSH, NBD-SerSerHis) formed the ensemble with Cu(2+), leading to a change in the color of the solution from yellow to orange and a complete decrease of fluorescence emission. The ensemble (NBD-SSH-Cu(2+)) sensitively and selectively detected a low concentration of cyanide ions in 100% aqueous solutions by a colorimetric change as well as a fluorescent change. The addition of cyanide ions instantly removed Cu(2+) from the ensemble (NBD-SSH-Cu(2+)) in 100% aqueous solutions, resulting in a color change of the solution from orange to yellow and a "turn-on" fluorescent response. The detection limits for cyanide ions were lower than the maximum allowable level of cyanide ions in drinking water set by the World Health Organization. The peptide-based ensemble system is expected to be a potential and practical way for the detection of submicromolar concentrations of cyanide ions in 100% aqueous solutions.

Stable radiation pressure acceleration of ions by suppressing transverse Rayleigh-Taylor instability with multiple Gaussian pulses

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

Zhou, M. L.; Liu, B.; Hu, R. H.

In the case of a thin plasma slab accelerated by the radiation pressure of an ultra-intense laser pulse, the development of Rayleigh-Taylor instability (RTI) will destroy the acceleration structure and terminate the acceleration process much sooner than theoretical limit. In this paper, a new scheme using multiple Gaussian pulses for ion acceleration in a radiation pressure acceleration regime is investigated with particle-in-cell simulation. We found that with multiple Gaussian pulses, the instability could be efficiently suppressed and the divergence of the ion bunch is greatly reduced, resulting in a longer acceleration time and much more collimated ion bunch with highermore » energy than using a single Gaussian pulse. An analytical model is developed to describe the suppression of RTI at the laser-plasma interface. The model shows that the suppression of RTI is due to the introduction of the long wavelength mode RTI by the multiple Gaussian pulses.« less

Multiple Ions Resonant Heating and Acceleration by Alfven/cyclotron Fluctuations in the Solar Wind

NASA Astrophysics Data System (ADS)

Xie, H.; Ofman, L.

2003-12-01

We study the interaction between protons, and multiple minor ions (O5+, He++) and a given cyclotron resonant spectra in coronal hole plasma. One-dimensional hybrid simulations are performed in initially homogeneous, collisionless, magnetized plasma with waves propagating parallel to the background magnetic field. The self-consistent hybrid simulations are used to study how multiple minor species may affect the resonance interaction between a spectrum of waves and the solar wind protons. The results of the simulations provide a clear picture of wave-particle interaction under various coronal conditions, which can explain 1) how multiple minor ions affect the resonant heating and the temperature anisotropy of the solar wind protons by a given wave spectrum; 2) how energy is distributed and transferred among waves and different ion species; 3) the growth and damping of different beam microinstability modes, including both inward and outward waves; 4) the formation of proton double-peak distribution in the solar wind.

Diverse wave-particle interactions for energetic ions that traverse Alfvén eigenmodes on their first full orbit

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

Heidbrink, W. W.; Persico, E. A. D.; Austin, M. E.

2016-02-15

Neutral-beam ions that are deflected onto loss orbits by Alfvén eigenmodes (AE) on their first bounce orbit and are detected by a fast-ion loss detector (FILD) satisfy the “local resonance” condition proposed by Zhang et al. [Nucl. Fusion 55, 22002 (2015)]. This theory qualitatively explains FILD observations for a wide variety of AE-particle interactions. When coherent losses are measured for multiple AE, oscillations at the sum and difference frequencies of the independent modes are often observed in the loss signal. The amplitudes of the sum and difference peaks correlate weakly with the amplitudes of the fundamental loss-signal amplitudes but domore » not correlate with the measured mode amplitudes. In contrast to a simple uniform-plasma theory of the interaction [Chen et al., Nucl. Fusion 54, 083005 (2014)], the loss-signal amplitude at the sum frequency is often larger than the loss-signal amplitude at the difference frequency, indicating a more detailed computation of the orbital trajectories through the mode eigenfunctions is needed.« less

Iminodiacetic acid functionalised organopolymer monoliths: application to the separation of metal cations by capillary high-performance chelation ion chromatography.

PubMed

Moyna, Áine; Connolly, Damian; Nesterenko, Ekaterina; Nesterenko, Pavel N; Paull, Brett

2013-03-01

Lauryl methacrylate-co-ethylene dimethacrylate monoliths were polymerised within fused silica capillaries and subsequently photo-grafted with varying amounts of glycidyl methacrylate (GMA). The grafted monoliths were then further modified with iminodiacetic acid (IDA), resulting in a range of chelating ion-exchange monoliths of increasing capacity. The IDA functional groups were attached via ring opening of the epoxy group on the poly(GMA) structure. Increasing the amount of attached poly(GMA), via photo-grafting with increasing concentrations of GMA, from 15 to 35%, resulted in a proportional and controlled increase in the complexation capacity of the chelating monoliths. Scanning capacitively coupled contactless conductivity detection (sC(4)D) was used to characterise and verify homogenous distribution of the chelating ligand along the length of the capillaries non-invasively. Chelation ion chromatographic separations of selected transition and heavy metals were carried out, with retention factor data proportional to the concentration of grafted poly(GMA). Average peak efficiencies of close to 5,000 N/m were achieved, with the isocratic separation of Na, Mg(II), Mn(II), Co(II), Cd(II) and Zn(II) possible on a 250-mm-long monolith. Multiple monolithic columns produced to the same recipes gave RSD data for retention factors of <15% (averaged for several metal ions). The monolithic chelating ion-exchanger was applied to the separation of alkaline earth and transition metal ions spiked in natural and potable waters.

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

PubMed Central

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

2008-01-01

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

Detection of reactive metabolites using isotope-labeled glutathione trapping and simultaneous neutral loss and precursor ion scanning with ultra-high-pressure liquid chromatography triple quadruple mass spectrometry.

PubMed

Huang, Ke; Huang, Lingyi; van Breemen, Richard B

2015-04-07

Metabolic activation of drugs to electrophilic species is responsible for over 60% of black box warnings and drug withdrawals from the market place in the United States. Reactive metabolite trapping using glutathione (GSH) and analysis using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) or HPLC with high resolution mass spectrometry (mass defect filtering) have enabled screening for metabolic activation to become routine during drug development. However, current MS-based approaches cannot detect all GSH conjugates present in complex mixtures, especially those present in extracts of botanical dietary supplements. To overcome these limitations, a fast triple quadrupole mass spectrometer-based approach was developed that can detect positively and negatively charged GSH conjugates in a single analysis without the need for advanced knowledge of the elemental compositions of potential conjugates and while avoiding false positives. This approach utilized UHPLC instead of HPLC to shorten separation time and enhance sensitivity, incorporated stable-isotope labeled GSH to avoid false positives, and used fast polarity switching electrospray MS/MS to detect GSH conjugates that form positive and/or negative ions. The general new method was then used to test the licorice dietary supplement Glycyrrhiza glabra, which was found to form multiple GSH conjugates upon metabolic activation. Among the GSH conjugates found in the licorice assay were conjugates with isoliquiritigenin and glabridin, which is an irreversible inhibitor of cytochrome P450 enzymes.

Quaternary ammonium promoted ultra selective and sensitive fluorescence detection of fluoride ion in water and living cells.

PubMed

Li, Long; Ji, Yuzhuo; Tang, Xinjing

2014-10-21

Highly selective and sensitive fluorescent probes with a quaternary ammonium moiety have been rationally designed and developed for fast and sensitive fluorescence detection of fluoride ion (F(-) from NaF, not TBAF) in aqueous solution and living cells. With the sequestration effect of quaternary ammonium, the detection time was less than 2 min and the detection limit of fluoride ion was as low as 0.57 ppm that is among the lowest detection limits in aqueous solutions of many fluoride fluorescence probes in the literature.

Non-destructive state detection for quantum logic spectroscopy of molecular ions.

PubMed

Wolf, Fabian; Wan, Yong; Heip, Jan C; Gebert, Florian; Shi, Chunyan; Schmidt, Piet O

2016-02-25

Precision laser spectroscopy of cold and trapped molecular ions is a powerful tool in fundamental physics--used, for example, in determining fundamental constants, testing for their possible variation in the laboratory, and searching for a possible electric dipole moment of the electron. However, the absence of cycling transitions in molecules poses a challenge for direct laser cooling of the ions, and for controlling and detecting their quantum states. Previously used state-detection techniques based on photodissociation or chemical reactions are destructive and therefore inefficient, restricting the achievable resolution in laser spectroscopy. Here, we experimentally demonstrate non-destructive detection of the quantum state of a single trapped molecular ion through its strong Coulomb coupling to a well controlled, co-trapped atomic ion. An algorithm based on a state-dependent optical dipole force changes the internal state of the atom according to the internal state of the molecule. We show that individual quantum states in the molecular ion can be distinguished by the strength of their coupling to the optical dipole force. We also observe quantum jumps (induced by black-body radiation) between rotational states of a single molecular ion. Using the detuning dependence of the state-detection signal, we implement a variant of quantum logic spectroscopy of a molecular resonance. Our state-detection technique is relevant to a wide range of molecular ions, and could be applied to state-controlled quantum chemistry and to spectroscopic investigations of molecules that serve as probes for interstellar clouds.

Novel approach in LC-MS/MS using MRM to generate a full profile of acyl-CoAs: discovery of acyl-dephospho-CoAs.

PubMed

Li, Qingling; Zhang, Shenghui; Berthiaume, Jessica M; Simons, Brigitte; Zhang, Guo-Fang

2014-03-01

A metabolomic approach to selectively profile all acyl-CoAs was developed using a programmed multiple reaction monitoring (MRM) method in LC-MS/MS and was employed in the analysis of various rat organs. The programmed MRM method possessed 300 mass ion transitions with the mass difference of 507 between precursor ion (Q1) and product ion (Q3), and the precursor ion started from m/z 768 and progressively increased one mass unit at each step. Acyl-dephospho-CoAs resulting from the dephosphorylation of acyl-CoAs were identified by accurate MS and fragmentation. Acyl-dephospho-CoAs were also quantitatively scanned by the MRM method with the mass difference of 427 between Q1 and Q3 mass ions. Acyl-CoAs and dephospho-CoAs were assayed with limits of detection ranging from 2 to 133 nM. The accuracy of the method was demonstrated by assaying a range of concentrations of spiked acyl-CoAs with the results of 80-114%. The distribution of acyl-CoAs reflects the metabolic status of each organ. The physiological role of dephosphorylation of acyl-CoAs remains to be further characterized. The methodology described herein provides a novel strategy in metabolomic studies to quantitatively and qualitatively profile all potential acyl-CoAs and acyl-dephospho-CoAs.

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.

Simultaneous spectrophotometric determination of trace copper, nickel, and cobalt ions in water samples using solid phase extraction coupled with partial least squares approaches

NASA Astrophysics Data System (ADS)

Guo, Yugao; Zhao, He; Han, Yelin; Liu, Xia; Guan, Shan; Zhang, Qingyin; Bian, Xihui

2017-02-01

A simultaneous spectrophotometric determination method for trace heavy metal ions based on solid-phase extraction coupled with partial least squares approaches was developed. In the proposed method, trace metal ions in aqueous samples were adsorbed by cation exchange fibers and desorbed by acidic solution from the fibers. After the ion preconcentration process, the enriched solution was detected by ultraviolet and visible spectrophotometer (UV-Vis). Then, the concentration of heavy metal ions were quantified by analyzing ultraviolet and visible spectrum with the help of partial least squares (PLS) approaches. Under the optimal conditions of operation time, flow rate and detection parameters, the overlapped absorption peaks of mixed ions were obtained. The experimental data showed that the concentration, which can be calculated through chemometrics method, of each metal ion increased significantly. The heavy metal ions can be enriched more than 80-fold. The limits of detection (LOD) for the target analytes of copper ions (Cu2 +), cobalt ions (Co2 +) and nickel ions (Ni2 +) mixture was 0.10 μg L- 1, 0.15 μg L- 1 and 0.13 μg L- 1, respectively. The relative standard deviations (RSD) were less than 5%. The performance of the solid-phase extraction can enrich the ions efficiently and the combined method of spectrophotometric detection and PLS can evaluate the ions concentration accurately. The work proposed here is an interesting and promising attempt for the trace ions determination in water samples and will have much more applied field.

Simultaneous spectrophotometric determination of trace copper, nickel, and cobalt ions in water samples using solid phase extraction coupled with partial least squares approaches.

PubMed

Guo, Yugao; Zhao, He; Han, Yelin; Liu, Xia; Guan, Shan; Zhang, Qingyin; Bian, Xihui

2017-02-15

A simultaneous spectrophotometric determination method for trace heavy metal ions based on solid-phase extraction coupled with partial least squares approaches was developed. In the proposed method, trace metal ions in aqueous samples were adsorbed by cation exchange fibers and desorbed by acidic solution from the fibers. After the ion preconcentration process, the enriched solution was detected by ultraviolet and visible spectrophotometer (UV-Vis). Then, the concentration of heavy metal ions were quantified by analyzing ultraviolet and visible spectrum with the help of partial least squares (PLS) approaches. Under the optimal conditions of operation time, flow rate and detection parameters, the overlapped absorption peaks of mixed ions were obtained. The experimental data showed that the concentration, which can be calculated through chemometrics method, of each metal ion increased significantly. The heavy metal ions can be enriched more than 80-fold. The limits of detection (LOD) for the target analytes of copper ions (Cu 2+ ), cobalt ions (Co 2+ ) and nickel ions (Ni 2+ ) mixture was 0.10μgL -1 , 0.15μgL -1 and 0.13μgL -1 , respectively. The relative standard deviations (RSD) were less than 5%. The performance of the solid-phase extraction can enrich the ions efficiently and the combined method of spectrophotometric detection and PLS can evaluate the ions concentration accurately. The work proposed here is an interesting and promising attempt for the trace ions determination in water samples and will have much more applied field. Copyright © 2016 Elsevier B.V. All rights reserved.

Modified graphene oxide sensors for ultra-sensitive detection of nitrate ions in water.

PubMed

Ren, Wen; Mura, Stefania; Irudayaraj, Joseph M K

2015-10-01

Nitrate ions is a very common contaminant in drinking water and has a significant impact on the environment, necessitating routine monitoring. Due to its chemical and physical properties, it is hard to directly detect nitrate ions with high sensitivity in a simple and inexpensive manner. Herein with amino group modified graphene oxide (GO) as a sensing element, we show a direct and ultra-sensitive method to detect nitrate ions, at a lowest detected concentration of 5 nM in river water samples, much lower than the reported methods based on absorption spectroscopy. Furthermore, unlike the reported strategies based on absorption spectroscopy wherein the nitrate concentration is determined by monitoring an increase in aggregation of gold nanoparticles (GNPs), our method evaluates the concentration of nitrate ions based on reduction in aggregation of GNPs for monitoring in real samples. To improve sensitivity, several optimizations were performed, including the assessment of the amount of modified GO required, concentration of GNPs and incubation time. The detection methodology was characterized by zeta potential, TEM and SEM. Our results indicate that an enrichment of modified GO with nitrate ions contributed to excellent sensitivity and the entire detection procedure could be completed within 75 min with only 20 μl of sample. This simple and rapid methodology was applied to monitor nitrate ions in real samples with excellent sensitivity and minimum pretreatment. The proposed approach paves the way for a novel means to detect anions in real samples and highlights the potential of GO based detection strategy for water quality monitoring. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanism of fat taste perception: Association with diet and obesity.

PubMed

Liu, Dongli; Archer, Nicholas; Duesing, Konsta; Hannan, Garry; Keast, Russell

2016-07-01

Energy homeostasis plays a significant role in food consumption and body weight regulation with fat intake being an area of particular interest due to its palatability and high energy density. Increasing evidence from humans and animal studies indicate the existence of a taste modality responsive to fat via its breakdown product fatty acids. These studies implicate multiple candidate receptors and ion channels for fatty acid taste detection, indicating a complex peripheral physiology that is currently not well understood. Additionally, a limited number of studies suggest a reduced ability to detect fatty acids is associated with obesity and a diet high in fat reduces an individual's ability to detect fatty acids. To support this, genetic variants within candidate fatty acid receptors are also associated with obesity reduced ability to detect fatty acids. Understanding oral peripheral fatty acid transduction mechanisms and the association with fat consumption may provide the basis of novel approaches to control development of obesity. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

New method for comprehensive detection of chemical warfare agents using an electron-cyclotron-resonance ion-source mass spectrometer

NASA Astrophysics Data System (ADS)

Kidera, Masanori; Seto, Yasuo; Takahashi, Kazuya; Enomoto, Shuichi; Kishi, Shintaro; Makita, Mika; Nagamatsu, Tsuyoshi; Tanaka, Tatsuhiko; Toda, Masayoshi

2011-03-01

We developed a detection technology for vapor forms of chemical warfare agents (CWAs) with an element analysis system using an electron cyclotron resonance ion source. After the vapor sample was introduced directly into the ion source, the molecular material was decomposed into elements using electron cyclotron resonance plasma and ionized. The following CWAs and stimulants were examined: diisopropyl fluorophosphonate (DFP), 2-chloroethylethylsulfide (2CEES), cyanogen chloride (CNCl), and hydrogen cyanide (HCN). The type of chemical warfare agents, specifically, whether it was a nerve agent, blister agent, blood agent, or choking agent, could be determined by measuring the quantities of the monatomic ions or CN + using mass spectrometry. It was possible to detect gaseous CWAs that could not be detected by a conventional mass spectrometer. The distribution of electron temperature in the plasma could be closely controlled by adjusting the input power of the microwaves used to generate the electron cyclotron resonance plasma, and the target compounds could be detected as molecular ions or fragment ions, enabling identification of the target agents.

A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms.

PubMed

Bansod, BabanKumar; Kumar, Tejinder; Thakur, Ritula; Rana, Shakshi; Singh, Inderbir

2017-08-15

Heavy metal ions are non-biodegradable and contaminate most of the natural resources occurring in the environment including water. Some of the heavy metals including Lead (Pb), Mercury (Hg), Arsenic (As), Chromium (Cr) and Cadmium (Cd) are considered to be highly toxic and hazardous to human health even at trace levels. This leads to the requirement of fast, accurate and reliable techniques for the detection of heavy metal ions. This review presents various electrochemical detection techniques for heavy metal ions those are user friendly, low cost, provides on-site and real time monitoring as compared to other spectroscopic and optical techniques. The categorization of different electrochemical techniques is done on the basis of different types of detection signals generated due to presence of heavy metal ions in the solution matrix like current, potential, conductivity, electrochemical impedance, and electrochemiluminescence. Also, the recent trends in electrochemical detection of heavy metal ions with various types of sensing platforms including metals, metal films, metal oxides, nanomaterials, carbon nano tubes, polymers, microspheres and biomaterials have been evoked. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrostatic turbulence in the earth's central plasma sheet produced by multiple-ring ion distributions

NASA Technical Reports Server (NTRS)

Huba, J. D.; Chen, J.; Anderson, R. R.

1992-01-01

Attention is given to a mechanism to generate a broad spectrum of electrostatic turbulence in the quiet time central plasma sheet (CPS) plasma. It is shown theoretically that multiple-ring ion distributions can generate short-wavelength (less than about 1), electrostatic turbulence with frequencies less than about kVj, where Vj is the velocity of the jth ring. On the basis of a set of parameters from measurements made in the CPS, it is found that electrostatic turbulence can be generated with wavenumbers in the range of 0.02 and 1.0, with real frequencies in the range of 0 and 10, and with linear growth rates greater than 0.01 over a broad range of angles relative to the magnetic field (5-90 deg). These theoretical results are compared with wave data from ISEE 1 using an ion distribution function exhibiting multiple-ring structures observed at the same time. The theoretical results in the linear regime are found to be consistent with the wave data.

High brightness--multiple beamlets source for patterned X-ray production

DOEpatents

Leung, Ka-Ngo [Hercules, CA; Ji, Qing [Albany, CA; Barletta, William A [Oakland, CA; Jiang, Ximan [El Cerrito, CA; Ji, Lili [Albany, CA

2009-10-27

Techniques for controllably directing beamlets to a target substrate are disclosed. The beamlets may be either positive ions or electrons. It has been shown that beamlets may be produced with a diameter of 1 .mu.m, with inter-aperture spacings of 12 .mu.m. An array of such beamlets, may be used for maskless lithography. By step-wise movement of the beamlets relative to the target substrate, individual devices may be directly e-beam written. Ion beams may be directly written as well. Due to the high brightness of the beamlets from extraction from a multicusp source, exposure times for lithographic exposure are thought to be minimized. Alternatively, the beamlets may be electrons striking a high Z material for X-ray production, thereafter collimated to provide patterned X-ray exposures such as those used in CAT scans. Such a device may be used for remote detection of explosives.

Accurate high-throughput structure mapping and prediction with transition metal ion FRET

PubMed Central

Yu, Xiaozhen; Wu, Xiongwu; Bermejo, Guillermo A.; Brooks, Bernard R.; Taraska, Justin W.

2013-01-01

Mapping the landscape of a protein’s conformational space is essential to understanding its functions and regulation. The limitations of many structural methods have made this process challenging for most proteins. Here, we report that transition metal ion FRET (tmFRET) can be used in a rapid, highly parallel screen, to determine distances from multiple locations within a protein at extremely low concentrations. The distances generated through this screen for the protein Maltose Binding Protein (MBP) match distances from the crystal structure to within a few angstroms. Furthermore, energy transfer accurately detects structural changes during ligand binding. Finally, fluorescence-derived distances can be used to guide molecular simulations to find low energy states. Our results open the door to rapid, accurate mapping and prediction of protein structures at low concentrations, in large complex systems, and in living cells. PMID:23273426

Comparison of Next-Generation Sequencing Systems

PubMed Central

Liu, Lin; Li, Yinhu; Li, Siliang; Hu, Ni; He, Yimin; Pong, Ray; Lin, Danni; Lu, Lihua; Law, Maggie

2012-01-01

With fast development and wide applications of next-generation sequencing (NGS) technologies, genomic sequence information is within reach to aid the achievement of goals to decode life mysteries, make better crops, detect pathogens, and improve life qualities. NGS systems are typically represented by SOLiD/Ion Torrent PGM from Life Sciences, Genome Analyzer/HiSeq 2000/MiSeq from Illumina, and GS FLX Titanium/GS Junior from Roche. Beijing Genomics Institute (BGI), which possesses the world's biggest sequencing capacity, has multiple NGS systems including 137 HiSeq 2000, 27 SOLiD, one Ion Torrent PGM, one MiSeq, and one 454 sequencer. We have accumulated extensive experience in sample handling, sequencing, and bioinformatics analysis. In this paper, technologies of these systems are reviewed, and first-hand data from extensive experience is summarized and analyzed to discuss the advantages and specifics associated with each sequencing system. At last, applications of NGS are summarized. PMID:22829749

Fracto-emission from single fibres of Kevlar

NASA Technical Reports Server (NTRS)

Dickinson, J. T.; Jahan-Latibari, A.; Jensen, L. C.

1985-01-01

Fracto-emission (FE) is the emission of particles (e.g. electrons, ions and photons) during and following fracture. In this paper, we present data on electron emission (EE) and positive ion emission (PIE) from the tensile fracture of Kevlar single fibers. The fibers were initially fractured in pure tension, where a stranded form of fracture was observed, often with multiple peaks spread over several hundred microseconds. The loading condition was then changed by stretching and breaking the fibers over a dull metal edge. With this change in the loading, different forms of fracture were observed, each with distinctive forms of emission curves. When fracture was accompanied by extensive fibril formation, total emission was high and both EE and PIE decay times were long relative to fractures in which little fibril formation occurred. The results of this study suggest that FE has some applicability as a tool for the detection of fracture mechanisms of single fibers.

Serum proteomic MRM identify peptide ions of transferrin as new fibrosis markers in chronic hepatitis B.

PubMed

Xu, Ming-Yi; Qu, Ying; Jia, Xiao-Fang; Wang, Mei-Ling; Liu, Heng; Wang, Xing-Peng; Zhang, Li-Jun; Lu, Lun-Gen

2013-09-01

Because of the limitations of liver biopsy, reliable non-invasive serum biomarkers of liver fibrosis are needed. The aim of this study was to identify such markers by the use of serum proteomics in chronic hepatitis B (CHB). Two-dimensional gel electrophoresis (2-DE) was used to identify differentially expressed protein spots in sera from 40 CHB patients [20 with mild fibrosis (S0-S1) and 20 with severe fibrosis (S3-S4)]. Mass spectrometry (MS) based multiple reaction monitoring (MRM) was used to quantify peptide ions of differential protein spots in another set of sera from 86 CHB patients with different liver fibrosis (S0-S4). Seven differentially expressed protein spots were found by 2-DE. Fourteen peptide ions of seven target protein spots were quantified by MS-based MRM. Summed peak areas ratio (SPAR) values of peptide ions from protein spot 1, 4 and 8, identified as apo serum transferrin, complement component C3c and transferrin, were significantly different from non-fibrosis (S0) to fibrosis stage 4. AUROCs of models established by peptide ions (protein spot 1, 4, 8) and model consisting of a combination of all ions were 0.848∼0.966 (S2-S4 versus S0-S1) and 0.785∼0.875 (S3-S4 versus S0-S2). Only the peptide ions model of transferrin had better sensitivity and specificity for predicting fibrosis stages than did aspartate aminotransferase-to-platelet ratio index (APRI), FIB-4 and Forn's index. Serum peptide ions of transferrin, detected by proteomic MRM, are new and promising biomarkers for staging liver fibrosis in CHB patients. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Prediction of Thorough QT study results using action potential simulations based on ion channel screens.

PubMed

Mirams, Gary R; Davies, Mark R; Brough, Stephen J; Bridgland-Taylor, Matthew H; Cui, Yi; Gavaghan, David J; Abi-Gerges, Najah

2014-01-01

Detection of drug-induced pro-arrhythmic risk is a primary concern for pharmaceutical companies and regulators. Increased risk is linked to prolongation of the QT interval on the body surface ECG. Recent studies have shown that multiple ion channel interactions can be required to predict changes in ventricular repolarisation and therefore QT intervals. In this study we attempt to predict the result of the human clinical Thorough QT (TQT) study, using multiple ion channel screening which is available early in drug development. Ion current reduction was measured, in the presence of marketed drugs which have had a TQT study, for channels encoded by hERG, CaV1.2, NaV1.5, KCNQ1/MinK, and Kv4.3/KChIP2.2. The screen was performed on two platforms - IonWorks Quattro (all 5 channels, 34 compounds), and IonWorks Barracuda (hERG & CaV1.2, 26 compounds). Concentration-effect curves were fitted to the resulting data, and used to calculate a percentage reduction in each current at a given concentration. Action potential simulations were then performed using the ten Tusscher and Panfilov (2006), Grandi et al. (2010) and O'Hara et al. (2011) human ventricular action potential models, pacing at 1Hz and running to steady state, for a range of concentrations. We compared simulated action potential duration predictions with the QT prolongation observed in the TQT studies. At the estimated concentrations, simulations tended to underestimate any observed QT prolongation. When considering a wider range of concentrations, and conventional patch clamp rather than screening data for hERG, prolongation of ≥5ms was predicted with up to 79% sensitivity and 100% specificity. This study provides a proof-of-principle for the prediction of human TQT study results using data available early in drug development. We highlight a number of areas that need refinement to improve the method's predictive power, but the results suggest that such approaches will provide a useful tool in cardiac safety assessment. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Mass cytometry: technique for real time single cell multitarget immunoassay based on inductively coupled plasma time-of-flight mass spectrometry.

PubMed

Bandura, Dmitry R; Baranov, Vladimir I; Ornatsky, Olga I; Antonov, Alexei; Kinach, Robert; Lou, Xudong; Pavlov, Serguei; Vorobiev, Sergey; Dick, John E; Tanner, Scott D

2009-08-15

A novel instrument for real time analysis of individual biological cells or other microparticles is described. The instrument is based on inductively coupled plasma time-of-flight mass spectrometry and comprises a three-aperture plasma-vacuum interface, a dc quadrupole turning optics for decoupling ions from neutral components, an rf quadrupole ion guide discriminating against low-mass dominant plasma ions, a point-to-parallel focusing dc quadrupole doublet, an orthogonal acceleration reflectron analyzer, a discrete dynode fast ion detector, and an 8-bit 1 GHz digitizer. A high spectrum generation frequency of 76.8 kHz provides capability for collecting multiple spectra from each particle-induced transient ion cloud, typically of 200-300 micros duration. It is shown that the transients can be resolved and characterized individually at a peak frequency of 1100 particles per second. Design considerations and optimization data are presented. The figures of merit of the instrument are measured under standard inductively coupled plasma (ICP) operating conditions (<3% cerium oxide ratio). At mass resolution (full width at half-maximum) M/DeltaM > 900 for m/z = 159, the sensitivity with a standard sample introduction system of >1.4 x 10(8) ion counts per second per mg L(-1) of Tb and an abundance sensitivity of (6 x 10(-4))-(1.4 x 10(-3)) (trailing and leading masses, respectively) are shown. The mass range (m/z = 125-215) and abundance sensitivity are sufficient for elemental immunoassay with up to 60 distinct available elemental tags. When <15 elemental tags are used, a higher sensitivity mode at lower resolution (M/DeltaM > 500) can be used, which provides >2.4 x 10(8) cps per mg L(-1) of Tb, at (1.5 x 10(-3))-(5.0 x 10(-3)) abundance sensitivity. The real-time simultaneous detection of multiple isotopes from individual 1.8 microm polystyrene beads labeled with lanthanides is shown. A real time single cell 20 antigen expression assay of model cell lines and leukemia patient samples immuno-labeled with lanthanide-tagged antibodies is presented.

Data Pre-Processing for Label-Free Multiple Reaction Monitoring (MRM) Experiments

PubMed Central

Chung, Lisa M.; Colangelo, Christopher M.; Zhao, Hongyu

2014-01-01

Multiple Reaction Monitoring (MRM) conducted on a triple quadrupole mass spectrometer allows researchers to quantify the expression levels of a set of target proteins. Each protein is often characterized by several unique peptides that can be detected by monitoring predetermined fragment ions, called transitions, for each peptide. Concatenating large numbers of MRM transitions into a single assay enables simultaneous quantification of hundreds of peptides and proteins. In recognition of the important role that MRM can play in hypothesis-driven research and its increasing impact on clinical proteomics, targeted proteomics such as MRM was recently selected as the Nature Method of the Year. However, there are many challenges in MRM applications, especially data pre‑processing where many steps still rely on manual inspection of each observation in practice. In this paper, we discuss an analysis pipeline to automate MRM data pre‑processing. This pipeline includes data quality assessment across replicated samples, outlier detection, identification of inaccurate transitions, and data normalization. We demonstrate the utility of our pipeline through its applications to several real MRM data sets. PMID:24905083

Data Pre-Processing for Label-Free Multiple Reaction Monitoring (MRM) Experiments.

PubMed

Chung, Lisa M; Colangelo, Christopher M; Zhao, Hongyu

2014-06-05

Multiple Reaction Monitoring (MRM) conducted on a triple quadrupole mass spectrometer allows researchers to quantify the expression levels of a set of target proteins. Each protein is often characterized by several unique peptides that can be detected by monitoring predetermined fragment ions, called transitions, for each peptide. Concatenating large numbers of MRM transitions into a single assay enables simultaneous quantification of hundreds of peptides and proteins. In recognition of the important role that MRM can play in hypothesis-driven research and its increasing impact on clinical proteomics, targeted proteomics such as MRM was recently selected as the Nature Method of the Year. However, there are many challenges in MRM applications, especially data pre‑processing where many steps still rely on manual inspection of each observation in practice. In this paper, we discuss an analysis pipeline to automate MRM data pre‑processing. This pipeline includes data quality assessment across replicated samples, outlier detection, identification of inaccurate transitions, and data normalization. We demonstrate the utility of our pipeline through its applications to several real MRM data sets.

Systematic Analysis of Absorbed Anti-Inflammatory Constituents and Metabolites of Sarcandra glabra in Rat Plasma Using Ultra-High-Pressure Liquid Chromatography Coupled with Linear Trap Quadrupole Orbitrap Mass Spectrometry.

PubMed

Li, Xiong; Zhao, Jin; Liu, Jianxing; Li, Geng; Zhao, Ya; Zeng, Xing

2016-01-01

Ultra-high-pressure liquid chromatography (UHPLC) was coupled with linear ion trap quadrupole Orbitrap mass spectrometry (LTQ-Orbitrap) and was used for the first time to systematically analyze the absorbed components and metabolites in rat plasma after oral administration of the water extract of Sarcandra glabra. This extract is a well-known Chinese herbal medicine for the treatment of inflammation and immunity related diseases. The anti-inflammatory activities of the absorbed components were evaluated by measuring nitric oxide (NO) production and proinflammatory genes expression in lipopolysaccharide (LPS)-stimulated murine RAW 264.7 macrophages. As a result, 54 components in Sarcandra glabra were detected in dosed rat plasma, and 36 of them were positively identified. Moreover, 23 metabolites were characterized and their originations were traced. Furthermore, 20 of the 24 studied components showed anti-inflammatory activities. These results provide evidence that this method efficiency detected constituents in plasma based on the anti-inflammatory mechanism of multiple components and would be a useful technique for screening multiple targets for natural medicine research.

Co-immobilization of multiple enzymes by metal coordinated nucleotide hydrogel nanofibers: improved stability and an enzyme cascade for glucose detection.

PubMed

Liang, Hao; Jiang, Shuhui; Yuan, Qipeng; Li, Guofeng; Wang, Feng; Zhang, Zijie; Liu, Juewen

2016-03-21

Preserving enzyme activity and promoting synergistic activity via co-localization of multiple enzymes are key topics in bionanotechnology, materials science, and analytical chemistry. This study reports a facile method for co-immobilizing multiple enzymes in metal coordinated hydrogel nanofibers. Specifically, four types of protein enzymes, including glucose oxidase, Candida rugosa lipase, α-amylase, and horseradish peroxidase, were respectively encapsulated in a gel nanofiber made of Zn(2+) and adenosine monophosphate (AMP) with a simple mixing step. Most enzymes achieved quantitative loading and retained full activity. At the same time, the entrapped enzymes were more stable against temperature variation (by 7.5 °C), protease attack, extreme pH (by 2-fold), and organic solvents. After storing for 15 days, the entrapped enzyme still retained 70% activity while the free enzyme nearly completely lost its activity. Compared to nanoparticles formed with AMP and lanthanide ions, the nanofiber gels allowed much higher enzyme activity. Finally, a highly sensitive and selective biosensor for glucose was prepared using the gel nanofiber to co-immobilize glucose oxidase and horseradish peroxidase for an enzyme cascade system. A detection limit of 0.3 μM glucose with excellent selectivity was achieved. This work indicates that metal coordinated materials using nucleotides are highly useful for interfacing with biomolecules.

Conversion of multiple analyte cation types to a single analyte anion type via ion/ion charge inversion.

PubMed

Hassell, Kerry M; LeBlanc, Yves; McLuckey, Scott A

2009-11-01

Charge inversion ion/ion reactions can convert several cation types associated with a single analyte molecule to a single anion type for subsequent mass analysis. Specifically, analyte ions present with one of a variety of cationizing agents, such as an excess proton, excess sodium ion, or excess potassium ion, can all be converted to the deprotonated molecule, provided that a stable anion can be generated for the analyte. Multiply deprotonated species that are capable of exchanging a proton for a metal ion serve as the reagent anions for the reaction. This process is demonstrated here for warfarin and for a glutathione conjugate. Examples for several other glutathione conjugates are provided as supplementary material to demonstrate the generality of the reaction. In the case of glutathione conjugates, multiple metal ions can be associated with the singly-charged analyte due to the presence of two carboxylate groups. The charge inversion reaction involves the removal of the excess cationizing agent, as well as any metal ions associated with anionic groups to yield a singly deprotonated analyte molecule. The ability to convert multiple cation types to a single anion type is analytically desirable in cases in which the analyte signal is distributed among several cation types, as is common in the electrospray ionization of solutions with relatively high salt contents. For analyte species that undergo efficient charge inversion, such as glutathione conjugates, there is the additional potential advantage for significantly improved signal-to-noise ratios when species that give rise to 'chemical noise' in the positive ion spectrum do not undergo efficient charge inversion.

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

NASA Astrophysics Data System (ADS)

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

1994-11-01

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

Formation of oxidizing species via irradiation of perchlorates using high-energy electrons and D 2 + ions

NASA Astrophysics Data System (ADS)

Crandall, Parker B.; Gillis-Davis, Jeffrey J.; Kaiser, Ralf-Ingo

2016-10-01

The perchlorate ion (ClO4-) has garnered particular interest in recent years following the discovery of perchlorate salts in the Martian regolith at levels of 0.4-0.6 wt% by the Phoenix lander in 2006 and Mars Science Laboratory's Curiosity rover in 2013. Due to their oxidizing properties, perchlorates are suspected to play a contributing role to the surprising lack of organics on the Martian surface. In this study, magnesium perchlorate hexahydrate (Mg(ClO4)2●6H2O) samples were irradiated with monoenergetic beams of 5 keV electrons and D2+ ions separately, sequentially, and simultaneously to simulate the effects of galactic cosmic ray exposure of perchlorates. The irradiation experiments were carried out under ultra-high vacuum conditions at 50 K, after which the samples were slowly heated to 300 K (0.5 K min-1) while desorbing products were monitored by quadrupole mass spectrometry. In all cases, molecular oxygen (O2) was detected upon the onset of irradiation and again during the warmup phase. In the case of simultaneous irradiation, deuterated water (D2O) and deuterium peroxide (D2O2) were also detected as the sample was heated whereas in the D2+ experiment small amounts of D2O2 was found exclusively. When samples were irradiated sequentially, the production of D2O2 was dependent upon the sample being irradiated with D2+ ions prior to electrons. These experiments show that perchlorates are capable of producing multiple oxidizing agents (O2, D2O2) which may also account for the lack of organics on the Martian surface.

Determination of Cloretazine (VNP40101M) and its active metabolite (VNP4090CE) in human plasma by liquid chromatography electrospray tandem mass spectrometry (LC-ESI-MS/MS).

PubMed

Bai, Feng; Minkin, Patton; Fraga, Charles H; O'Shaughnessy, Melinda A; Gururangan, Sri; Stewart, Clinton F

2007-06-15

A sensitive method for the determination of Cloretazine (VNP40101M) and its metabolite (VNP4090CE) with an internal standard (ISTD) in human plasma was developed using high-performance liquid chromatographic separation with tandem mass spectrometric detection. Acidified plasma samples (500 microL) were prepared using solid phase extraction (SPE) columns, and 25 microL of the reconstituted sample was injected onto an Ascentis C18 HPLC column (3 microm, 5 cmx2.1 mm) with an isocratic mobile phase. Analytes were detected with an API-3000 LC-MS/MS System at unit (Q1) and low (Q3) resolution in negative multiple reaction monitoring mode: m/z 249.0 (precursor ion) to m/z 114.9 (product ion) for both Cloretazine (at 3.64 min) and VNP4090CE (at 2.91 min), and m/z 253.0 (precursor ion) to m/z 116.9 (product ion) for the ISTD. The mean recovery for Cloretazine (VNP40101M) and its metabolite (VNP4090CE) was greater than 87% with a lower limit of quantification of 1.0 ng/mL for Cloretazine (S/N=9.7, CV

Triphenylamine based reactive coloro/fluorimetric chemosensors: Structural isomerism and solvent dependent sensitivity and selectivity

NASA Astrophysics Data System (ADS)

Kundu, Anu; Anthony, Savarimuthu Philip

2018-01-01

Triphenyl amine based chemosensors, (2-(((2-(9H-carbazol-9-yl)phenyl)imino)methyl)-5-(diphenylamino)phenol (ortho-CPDP) and 2-(((4-(9H-carbazol-9-yl)phenyl)imino)methyl)-5-(diphenylamino)phenol (para-CPDP), showed solvent and isomerism dependent selective coloro/fluorometric sensing of multiple metal ions (Fe3 +, Al3 + and Zn2 +) with distinguishable responses. In CH3CN, ortho and para-CPDP selectively produced yellow color upon addition of Al3 + and Fe3 + that was slowly disappeared. The yellow color of ortho and para-CPDP in DMF was decolourised selectively by adding Al3 + and Fe3 +. Both ortho and para-CPDP in CH3CN showed nearly similar rate of decolourization for Fe3 + and Al3 +. However, the rate of decolourization of ortho and para-CPDP in DMF was different for Fe3 + (10 μM, 8 min) and Al3 + (5 × 10- 4 M, 40 min) ions. The limit of detection of para-CPDP for Fe3 + is 10 μM and Al3 + 500 μM. The mechanistic studies revealed the imine hydrolysis of ortho and para-CPDP in presence of Lewis acidic Fe3 + and Al3 +. The reactivity based sensing lead to high selectivity for Al3 + and Fe3 + ions. Further, para-CPDP exhibited selective fluorescence turn-on for Zn2 + in DMF (λmax = 513 nm) and detection limit of 6.0 μM. Thus, reactive chemosensors, ortho and para-CPDP, exhibited selective and distinguishable colorimetric sensing of Fe3 + and Al3 + ions and isomerism and solvent dependent fluorescence sensing of Zn2 +.

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Determination of phthalate esters in cleaning and personal care products by dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

PubMed

Viñas, Pilar; Campillo, Natalia; Pastor-Belda, Marta; Oller, Ainhoa; Hernández-Córdoba, Manuel

2015-01-09

Phthalic acid esters (PEs) were preconcentrated from cleaning products, detergents and cosmetics using ultrasound assisted extraction (UAE) in the presence of acetonitrile, and then submitted to dispersive liquid-liquid microextraction (DLLME). For DLLME, 3mL of acetonitrile extract, 150μL carbon tetrachloride and 10mL aqueous solution were used. The enriched organic phase was evaporated, reconstituted with 25μL acetonitrile and injected into a liquid chromatograph with a mobile phase (acetonitrile:10mM ammonium acetate, pH 4) under gradient elution. Detection was carried out using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the multiple reaction monitoring mode (MRM) of the positive fragment ions. Quantification was carried out using matrix-matched standards. Detection limits were in the range 0.04-0.45ngmL(-1) for the six PEs considered. The recoveries obtained were in the 84-124% range, with RSDs lower than 10%. Thirty three different cleaning products were analyzed. The most frequently found compound was diethyl phthalate. Copyright © 2014 Elsevier B.V. All rights reserved.

Relating to ion detection

DOEpatents

Orr, Christopher Henry; Luff, Craig Janson; Dockray, Thomas; Macarthur, Duncan Whittemore

2001-01-01

The apparatus and method provide a technique for improving detection of alpha and/or beta emitting sources on items or in locations using indirect means. The emission forms generate ions in a medium surrounding the item or location and the medium is then moved to a detecting location where the ions are discharged to give a measure of the emission levels. To increase the level of ions generated and render the system particularly applicable for narrow pipes and other forms of conduits, the medium pressure is increased above atmospheric pressure. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

A novel fluorescent probe (dtpa-bis(cytosine)) for detection of Eu(III) in rare earth metal ions.

PubMed

Yang, Fan; Ren, Peipei; Liu, Guanhong; Song, Youtao; Bu, Naishun; Wang, Jun

2018-03-15

In this paper, a novel fluorescent probe, dtpa-bis(cytosine), was designed and synthesized for detecting europium (Eu 3+ ) ion. Upon addition of Eu 3+ ions into the dtpa-bis(cytosine) solution, the fluorescence intensity can strongly be enhanced. Conversely, adding other rare earth metal ions, such as Y 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Yb 3+ and Lu 3+ , into dtpa-bis(cytosine) solution, the fluorescence intensity is decreased slightly. Some parameters affecting the fluorescence intensity of dtpa-bis(cytosine) solution in the presence of Eu 3+ ions were investigated, including solution pH value, Eu 3+ ion concentration and interfering substances. The detection mechanism of Eu 3+ ion using dtpa-bis(cytosine) as fluorescent probe was proposed. Under optimum conditions, the fluorescence emission intensities of Eu III -dtpa-bis(cytosine) at 375nm in the concentration range of 0.50×10 -5 mol∙L -1 -5.00×10 -5 mol∙L -1 of Eu 3+ ion display a better linear relationship. The limit of detection (LOD) was determined as 8.65×10 -7 mol∙L -1 and the corresponding correlation coefficient (R 2 ) of the linear equation is 0.9807. It is wished that the proposed method could be applied for sensitively and selectively detecting Eu 3+ ion. Copyright © 2017 Elsevier B.V. All rights reserved.

ETHYL CYANIDE ON TITAN: SPECTROSCOPIC DETECTION AND MAPPING USING ALMA

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

Cordiner, M. A.; Palmer, M. Y.; Nixon, C. A.

2015-02-10

We report the first spectroscopic detection of ethyl cyanide (C{sub 2}H{sub 5}CN) in Titan’s atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/submillimeter Array (ALMA). The presence of C{sub 2}H{sub 5}CN in Titan’s ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C{sub 2}H{sub 5}CNH{sup +}. Here we report the detection of 27 rotational lines from C{sub 2}H{sub 5}CN (in 19 separate emission features detected at >3σ confidence) in the frequency range 222–241 GHz. Simultaneous detections of multiple emission lines from HC{sub 3}N, CH{sub 3}CN, and CH{sub 3}CCH were alsomore » obtained. In contrast to HC{sub 3}N, CH{sub 3}CN, and CH{sub 3}CCH, which peak in Titan’s northern (spring) hemisphere, the emission from C{sub 2}H{sub 5}CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C{sub 2}H{sub 5}CN. Radiative transfer models show that C{sub 2}H{sub 5}CN is most concentrated at altitudes ≳200 km, suggesting production predominantly in the stratosphere and above. Vertical column densities are found to be in the range (1–5) × 10{sup 14} cm{sup −2}.« less

Ultrasensitive quantum dot fluorescence quenching assay for selective detection of mercury ions in drinking water.

PubMed

Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

2014-07-09

Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg(2+) ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples.

A novel and simple fluorescence probe for detecting main group magnesium ion in HeLa cells and Arabidopsis.

PubMed

Yu, Tingting; Sun, Ping; Hu, Yijie; Ji, Yinggang; Zhou, Hongping; Zhang, Baowei; Tian, Yupeng; Wu, Jieying

2016-12-15

A simple-molecule fluorescence probe L has been designed, synthesized and characterized, which shows high selectivity and sensitivity for the main group magnesium ion through fluorescence "turn-on" response in ethanol solution, and no interference from calcium ion in particular. Detection limit of probe L is 1.47×10(-6) M and the rapid response could reach about 15-20s. The recognition mechanism has been established by fluorescence spectra, (1)H NMR study. Moreover, probe L presents a great photostability, low toxicity and cellular permeability, then we have carried out fluorescent bio-imaging of the probe L for magnesium ions in HeLa cells, which showed that probe L could be utilized to detect the intracellular magnesium ion. Furthermore, it is successfully used as a magnesium ion developer in plant tissues, which shows that it not only can be well tracking the transport of magnesium ion but also make a corresponding fluorescence response to different concentrations magnesium ion. These results would make this probe a great potential application for detecting Mg(2+) in biological system. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultrasensitive Quantum Dot Fluorescence quenching Assay for Selective Detection of Mercury Ions in Drinking Water

PubMed Central

Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

2014-01-01

Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg2+ ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples. PMID:25005836

A high-throughput method for the detection of homoeologous gene deletions in hexaploid wheat

PubMed Central

2010-01-01

Background Mutational inactivation of plant genes is an essential tool in gene function studies. Plants with inactivated or deleted genes may also be exploited for crop improvement if such mutations/deletions produce a desirable agronomical and/or quality phenotype. However, the use of mutational gene inactivation/deletion has been impeded in polyploid plant species by genetic redundancy, as polyploids contain multiple copies of the same genes (homoeologous genes) encoded by each of the ancestral genomes. Similar to many other crop plants, bread wheat (Triticum aestivum L.) is polyploid; specifically allohexaploid possessing three progenitor genomes designated as 'A', 'B', and 'D'. Recently modified TILLING protocols have been developed specifically for mutation detection in wheat. Whilst extremely powerful in detecting single nucleotide changes and small deletions, these methods are not suitable for detecting whole gene deletions. Therefore, high-throughput methods for screening of candidate homoeologous gene deletions are needed for application to wheat populations generated by the use of certain mutagenic agents (e.g. heavy ion irradiation) that frequently generate whole-gene deletions. Results To facilitate the screening for specific homoeologous gene deletions in hexaploid wheat, we have developed a TaqMan qPCR-based method that allows high-throughput detection of deletions in homoeologous copies of any gene of interest, provided that sufficient polymorphism (as little as a single nucleotide difference) amongst homoeologues exists for specific probe design. We used this method to identify deletions of individual TaPFT1 homoeologues, a wheat orthologue of the disease susceptibility and flowering regulatory gene PFT1 in Arabidopsis. This method was applied to wheat nullisomic-tetrasomic lines as well as other chromosomal deletion lines to locate the TaPFT1 gene to the long arm of chromosome 5. By screening of individual DNA samples from 4500 M2 mutant wheat lines generated by heavy ion irradiation, we detected multiple mutants with deletions of each TaPFT1 homoeologue, and confirmed these deletions using a CAPS method. We have subsequently designed, optimized, and applied this method for the screening of homoeologous deletions of three additional wheat genes putatively involved in plant disease resistance. Conclusions We have developed a method for automated, high-throughput screening to identify deletions of individual homoeologues of a wheat gene. This method is also potentially applicable to other polyploidy plants. PMID:21114819

Selective and Sensitive Detection of Heavy Metal Ions in 100% Aqueous Solution and Cells with a Fluorescence Chemosensor Based on Peptide Using Aggregation-Induced Emission.

PubMed

Neupane, Lok Nath; Oh, Eun-Taex; Park, Heon Joo; Lee, Keun-Hyeung

2016-03-15

A fluorescent peptidyl chemosensor for the detection of heavy metal ions in aqueous solution as well as in cells was synthesized on the basis of the peptide receptor for the metal ions using an aggregation-induced emission fluorophore. The peptidyl chemosensor (1) bearing tetraphenylethylene fluorophore showed an exclusively selective turn-on response to Hg(2+) among 16 metal ions in aqueous buffered solution containing NaCl. The peptidyl chemosensor complexed Hg(2+) ions and then aggregated in aqueous buffered solution, resulting in the significant enhancement (OFF-On) of emissions at around 470 nm. The fluorescent sensor showed a highly sensitive response to Hg(2+), and about 1.0 equiv of Hg(2+) was enough for the saturation of the emission intensity change. The detection limit (5.3 nM, R(2) = 0.99) of 1 for Hg(2+) ions was lower than the maximum allowable level of Hg(2+) in drinking water by EPA. Moreover, the peptidyl chemosensor penetrated live cells and detected intracellular Hg(2+) ions by the turn-on response.

Detection of heavy metal ions in drinking water using a high-resolution differential surface plasmon resonance sensor.

PubMed

Forzani, Erica S; Zhang, Haiqian; Chen, Wilfred; Tao, Nongjian

2005-03-01

We have built a high-resolution differential surface plasmon resonance (SPR) sensor for heavy metal ion detection. The sensor surface is divided into a reference and sensing areas, and the difference in the SPR angles from the two areas is detected with a quadrant cell photodetector as a differential signal. In the presence of metal ions, the differential signal changes due to specific binding of the metal ions onto the sensing area coated with properly selected peptides, which provides an accurate real-time measurement and quantification of the metal ions. Selective detection of Cu2+ and Ni2+ in the ppt-ppb range was achieved by coating the sensing surface with peptides NH2-Gly-Gly-His-COOH and NH2-(His)6-COOH. Cu2+ in drinking water was tested using this sensor.

Counting individual ions in the air by tagging them with particles

NASA Astrophysics Data System (ADS)

Gorbunov, B.

2017-07-01

The quantification of ultra-low concentrations of molecules and ions in gases is of fundamental and practical importance for science and technology, for example, the detection of explosives in airports or biomarkers in medical diagnostics. Often the Faraday cup is employed to transfer ion concentrations in an electric current that is then amplified and measured. One of the main challenges is to increase the sensitivity of detection. A novel concept has been developed that enables detection of individual ions in gases by tagging them with neutral nano-objects. The concentration of ionized molecules was measured and a detection limit of 5 cm-3 was observed. It is anticipated that this concept opens doors for advances in detection sensitivity for many applications including security, medical diagnostic, trace chemical analysis.

Anomalous annealing of floating gate errors due to heavy ion irradiation

NASA Astrophysics Data System (ADS)

Yin, Yanan; Liu, Jie; Sun, Youmei; Hou, Mingdong; Liu, Tianqi; Ye, Bing; Ji, Qinggang; Luo, Jie; Zhao, Peixiong

2018-03-01

Using the heavy ions provided by the Heavy Ion Research Facility in Lanzhou (HIRFL), the annealing of heavy-ion induced floating gate (FG) errors in 34 nm and 25 nm NAND Flash memories has been studied. The single event upset (SEU) cross section of FG and the evolution of the errors after irradiation depending on the ion linear energy transfer (LET) values, data pattern and feature size of the device are presented. Different rates of annealing for different ion LET and different pattern are observed in 34 nm and 25 nm memories. The variation of the percentage of different error patterns in 34 nm and 25 nm memories with annealing time shows that the annealing of FG errors induced by heavy-ion in memories will mainly take place in the cells directly hit under low LET ion exposure and other cells affected by heavy ions when the ion LET is higher. The influence of Multiple Cell Upsets (MCUs) on the annealing of FG errors is analyzed. MCUs with high error multiplicity which account for the majority of the errors can induce a large percentage of annealed errors.

Capillary-HPLC with tandem mass spectrometry in analysis of alkaloid dyestuffs - a new approach.

PubMed

Dąbrowski, Damian; Lech, Katarzyna; Jarosz, Maciej

2018-05-01

Development of the identification method of alkaloid compounds in Amur cork tree as well as not examined so far Oregon grape and European Barberry shrubs are presented. The novel approach to separation of alkaloids was applied and the capillary-high-performance liquid chromatography (capillary-HPLC) system was used, which has never previously been reported for alkaloid-based dyestuffs analysis. Its optimization was conducted with three different stationary phases (unmodified octadecylsilane-bonded silica, octadecylsilane modified with polar groups and silica-bonded pentaflourophenyls) as well as with different solvent buffers. Detection of the isolated compounds was carried out using diode-array detector (DAD) and tandem mass spectrometer with electrospray ionization (ESI MS/MS). The working parameters of ESI were optimized, whereas the multiple reactions monitoring (MRM) parameters of MS/MS detection were chosen based on the product ion spectra of the quasi-molecular ions. Calibration curve of berberine has been estimated (y = 1712091x + 4785.03 with the correlation coefficient 0.9999). Limit of detection and limit of quantification were calculated to be 3.2 and 9.7 ng/mL, respectively. Numerous alkaloids (i.e., berberine, jatrorrhizine and magnoflorine, as well as phellodendrine, menisperine and berbamine) were identified in the extracts from alkaloid plants and silk and wool fibers dyed with these dyestuffs, among them their markers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observations and modeling of EMIC wave properties in the presence of multiple ion species as function of magnetic local time

NASA Astrophysics Data System (ADS)

Lee, Justin H.; Angelopoulos, Vassilis

2014-11-01

Electromagnetic ion cyclotron (EMIC) wave generation and propagation in Earth's magnetosphere depend on readily measurable hot (a few to tens of keV) plasma sheet ions, elusive plasmaspheric or ionospheric cold (sub-eV to a few eV) ions, and partially heated warm ions (tens to hundreds of eV). Previous work has assumed all low-energy ions are cold and not considered possible effects of warm ions. Using measurements by multiple Time History of Events and Macroscale Interactions during Substorms spacecraft, we analyze four typical EMIC wave events in the four magnetic local time sectors and consider the properties of both cold and warm ions supplied from previous statistical studies to interpret the wave observations using linear theory. As expected, we find that dusk EMIC waves grow due to the presence of drifting hot anisotropic protons and cold plasmaspheric ions with a dominant cold proton component. Near midnight, EMIC waves are less common because warm heavy ions that suppress wave growth are more abundant there. The waves can grow when cold, plume-like density enhancements are present, however. Dawn EMIC waves, known for their peculiar properties, are generated away from the equator and change polarization during propagation through the warm plasma cloak. Noon EMIC waves can also be generated nonlocally and their properties modified during propagation by a plasmaspheric plume combined with low-energy ions from solar and terrestrial sources. Accounting for multiple ion species, measured wave dispersion, and propagation characteristics can explain previously elusive EMIC wave properties and are therefore important for future studies of EMIC wave effects on energetic particle depletion.

Positron-annihilation-induced ion desorption from TiO2(110)

NASA Astrophysics Data System (ADS)

Tachibana, T.; Hirayama, T.; Nagashima, Y.

2014-05-01

We have investigated the positron-stimulated desorption of ions from a TiO2(110) surface. Desorbed O+ ions were detected in coincidence with the emission of annihilation γ rays. The energy dependence of the ion yields shows that the O+ ions were detected at energies much lower than the previously reported threshold for electron impact desorption corresponding to the excitation energy of Ti(3p) core electrons. These results provide evidence that core-hole creation by positron annihilation with electrons in the core levels leads to ion desorption.

First simultaneous detection of terrestrial ionospheric molecular ions in the Earth's inner magnetosphere and at the Moon

NASA Astrophysics Data System (ADS)

Dandouras, Iannis; Poppe, Andrew R.; Fillingim, Matt O.; Kistler, Lynn M.; Mouikis, Christopher G.; Rème, Henri

2017-04-01

Heavy molecular ions escaping from a planetary atmosphere can contribute to the long-term evolution of its composition. The ARTEMIS (Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun) spacecraft has recently observed outflowing molecular ions at lunar distances in the terrestrial magnetotail (Poppe et al., 2016). Backward particle tracing indicated that these ions should originate from the terrestrial inner magnetosphere. Here we have examined Cluster data acquired by the CIS-CODIF (Cluster Ion Spectrometry-Composition Distribution Function) ion mass spectrometer, obtained in the terrestrial magnetosphere. An event was selected where the orbital conditions were favourable and the Cluster spacecraft were in the high-latitude inner magnetosphere a few hours before the ARTEMIS molecular ion detection. Analysis shows that the CIS-CODIF instrument detected a series of energetic ion species, including not only O+ but also a group of molecular ions around 30 amu. Given the 5-7 m/Δm mass resolution of the instrument, these could include N2+, NO+, or O2+. These ions were detected by Cluster about 14 hours before the ARTEMIS observation in the lunar environment, a time which is compatible with the transfer to lunar distances. The event was during an active period followed by a northward rotation of the IMF. Although energetic heavy molecular ions have been detected in the storm time magnetosphere in the past (e.g. Klecker et al., 1986; Christon et al., 1994), this event constitutes the first coordinated observation in the Earth's inner magnetosphere and at the Moon. Additional events of coordinated outflowing molecular ion observations are currently under analysis. Future missions, as the proposed ESCAPE mission, should investigate in detail the mechanisms of molecular ion acceleration and escape, their link to the solar and magnetospheric activity, and their role in the magnetospheric dynamics and in the long-term evolution of the atmospheric composition.

Instrumentation and methodology for simultaneous excitation/detection of ions in an FTICR mass spectrometer

PubMed

Schmidt; Fiorentino; Arkin; Laude

2000-08-01

A method for direct and continuous detection of ion motion during different perturbation events of the fourier transform ion cyclotron resonance (FTICR) experiment is demonstrated. The modifications necessary to convert an ordinary FTICR cell into one capable of performing simultaneous excitation/detection (SED) using a capacitive network are outlined. With these modifications, a 200-fold reduction in the detection of the coupled excitation signal is achieved. This allows the unique ability not only to observe the response to the perturbation but to observe the perturbation event itself. SED is used successfully to monitor the ion cyclotron transient during single-frequency excitation, remeasurement and exciter-excite experiments.

Aggregation induced emission enhancement (AIEE) characteristics of quinoline based compound - A versatile fluorescent probe for pH, Fe(III) ion, BSA binding and optical cell imaging

NASA Astrophysics Data System (ADS)

Manikandan, Irulappan; Chang, Chien-Huei; Chen, Chia-Ling; Sathish, Veerasamy; Li, Wen-Shan; Malathi, Mahalingam

2017-07-01

Novel benzimidazoquinoline derivative (AVT) was synthesized through a substitution reaction and characterized by various spectral techniques. Analyzing the optical properties of AVT under absorption and emission spectral studies in different environments exclusively with respect to solvents and pH, intriguing characteristics viz. aggregation induced emission enhancement (AIEE) in the THF solvent and 'On-Off' pH sensing were found at neutral pH. Sensing nature of AVT with diverse metal ions and bovine serum albumin (BSA) was also studied. Among the metal ions, Fe3 + ion alone tunes the fluorescence intensity of AVT probe in aqueous medium from ;turn-on; to ;turn-off; through ligand (probe) to metal charge transfer (LMCT) mechanism. The probe AVT in aqueous medium interacts strongly with BSA due to Fluorescence Resonance Energy Transfer (FRET) and the conformational change in BSA was further analyzed using synchronous fluorescence techniques. Docking study of AVT with BSA reveals that the active site of binding is tryptophan residue which is also supported by the experimental results. Interestingly, fluorescent AVT probe in cells was examined through cellular imaging studies using BT-549 and MDA-MB-231 cells. Thus, the single molecule probe based detection of multiple species and stimuli were described.

In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

2016-07-01

We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-09-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Method of detecting luminescent target ions with modified magnetic microspheres

DOEpatents

Shkrob, Ilya A; Kaminski, Michael D

2014-05-13

This invention provides methods of using modified magnetic microspheres to extract target ions from a sample in order to detect their presence in a microfluidic environment. In one or more embodiments, the microspheres are modified with molecules on the surface that allow the target ions in the sample to form complexes with specific ligand molecules on the microsphere surface. In one or more embodiments, the microspheres are modified with molecules that sequester the target ions from the sample, but specific ligand molecules in solution subsequently re-extract the target ions from the microspheres into the solution, where the complexes form independent of the microsphere surface. Once the complexes form, they are exposed to an excitation wavelength light source suitable for exciting the target ion to emit a luminescent signal pattern. Detection of the luminescent signal pattern allows for determination of the presence of the target ions in the sample.

Single-ion adsorption and switching in carbon nanotubes

DOE PAGES

Bushmaker, Adam W.; Oklejas, Vanessa; Walker, Don; ...

2016-01-25

Single-ion detection has, for many years, been the domain of large devices such as the Geiger counter, and studies on interactions of ionized gasses with materials have been limited to large systems. To date, there have been no reports on single gaseous ion interaction with microelectronic devices, and single neutral atom detection techniques have shown only small, barely detectable responses. Here we report the observation of single gaseous ion adsorption on individual carbon nanotubes (CNTs), which, because of the severely restricted one-dimensional current path, experience discrete, quantized resistance increases of over two orders of magnitude. Only positive ions cause changes,more » by the mechanism of ion potentialinduced carrier depletion, which is supported by density functional and Landauer transport theory. Lastly, our observations reveal a new single-ion/CNT heterostructure with novel electronic properties, and demonstrate that as electronics are ultimately scaled towards the one-dimensional limit, atomic-scale effects become increasingly important.« less

Using ion chromatography to monitor haloacetic acids in drinking water: a review of current technologies.

PubMed

Paull, Brett; Barron, Leon

2004-08-13

A review of the application of ion chromatography to the determination of haloacetic acids in drinking water is given. As it requires no sample derivatisation, ion chromatography in its various modes, such as ion-exchange, ion-interaction and ion-exclusion chromatography, is increasingly being investigated as a simpler alternative to gas chromatographic methods for the determination of polar disinfection by-products (DBPs) in drinking waters. Detection limits quoted for the regulated haloacetic acids (HAA5), are commonly in the mid to low microg/L range, however, in most cases analyte preconcentration is still necessary for detection at concentrations commonly found in actual drinking water samples. The coupling of ion chromatography to electrospray mass spectrometry provides a potential future direction, with improved sensitivity and selectivity compared to conductivity based detection, however associated cost and complexity for routine analysis is currently relatively high.

Evaluation of multiple reaction monitoring cubed for the analysis of tachykinin related peptides in rat spinal cord using a hybrid triple quadrupole-linear ion trap mass spectrometer.

PubMed

Pailleux, Floriane; Beaudry, Francis

2014-02-01

Targeted peptide methods generally use HPLC-MS/MRM approaches. Although dependent on the instrumental resolution, interferences may occur while performing analysis of complex biological matrices. HPLC-MS/MRM(3) is a technique, which provides a significantly better selectivity, compared with HPLC-MS/MRM assay. HPLC-MS/MRM(3) allows the detection and quantitation by enriching standard MRM with secondary product ions that are generated within the linear ion trap. Substance P (SP) and neurokinin A (NKA) are tachykinin peptides playing a central role in pain transmission. The objective of this study was to verify whether HPLC-MS/MRM(3) could provide significant advantages over a more traditional HPLC-MS/MRM assay for the quantification of SP and NKA in rat spinal cord. The results suggest that reconstructed MRM(3) chromatograms display significant improvements with the nearly complete elimination of interfering peaks but the sensitivity (i.e. signal-to-noise ratio) was severely reduced. The precision (%CV) observed was between 3.5% and 24.1% using HPLC-MS/MRM and in the range of 4.3-13.1% with HPLC-MS/MRM(3), for SP and NKA. The observed accuracy was within 10% of the theoretical concentrations tested. HPLC-MS/MRM(3) may improve the assay sensitivity to detect difference between samples by reducing significantly the potential of interferences and therefore reduce instrumental errors. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquid crystal based optical platform for the detection of Pb2+ ions using NiFe2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Zehra, Saman; Gul, Iftikhar Hussain; Hussain, Zakir

2018-06-01

A simple, sensitive, selective and real time detection protocol was developed for Pb2+ ions in water using liquid crystals (LCs). In this method, NiFe2O4 nanoparticles were synthesized using chemical co-precipitation method. Crystallite size, morphological, functional groups and magnetization studies were confirmed using X-ray diffraction, Scanning Electron Microscopy, and Fourier transform infrared spectroscopy techniques, respectively. The nanoparticles were mono dispersed with average particle size of 20 ± 2 nm. The surfactant stabilized magnetic nanoparticles were incubated in liquid crystal based sensor system for the detection of Pb+2 ions. The bright to dark transition of LC was observed through optical microscope. When this system was further immersed with a solution containing Pb2+ ions, it caused homeotropic to planar orientation of LC. This interaction is attributed to the presence of abundant hydroxyl groups in such as M-OH, Fe-OH on the surface of spinel ferrites nanoparticles. These groups interact with metal ions at aqueous interface, causing disruption in LCs orientation giving bright texture. This sensor showed higher selectivity towards Pb2+ ions. The detection limit was estimated to be 100 ppb. The cheap and effective protocol reported here should make promising development of LC based sensor for lead ion detection.

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

NASA Astrophysics Data System (ADS)

Graichen, Adam M.; Vachet, Richard W.

2013-06-01

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

A chemosensor for micro- to nano-molar detection of Ag+ and Hg2+ ions in pure aqueous media and its applications in cell imaging.

PubMed

Nandre, Jitendra P; Patil, Samadhan R; Sahoo, Suban K; Pradeep, Chullikkattil P; Churakov, Andrei; Yu, Fabiao; Chen, Lingxin; Redshaw, Carl; Patil, Ashok A; Patil, Umesh D

2017-10-24

The pyridine substituted thiourea derivative PTB-1 was synthesized and characterized by spectroscopic techniques as well as by single crystal X-ray crystallography. The metal ion sensing ability of PTB-1 was explored by various experimental (naked-eye, UV-Vis, fluorescence, mass spectrometry and 1 H NMR spectroscopy) and theoretical (B3LYP/6-31G**/LANL2DZ) methods. PTB-1 exhibited a highly selective naked-eye detectable color change from colorless to dark brown and UV-Vis spectral changes for the detection of Ag + with a detection limit of 3.67 μM in aqueous medium. The detection of Ag + ions was achieved by test paper strip and supported silica methods. In contrast, PTB-1 exhibited a 23-fold enhanced emission at 420 nm in the presence of Hg 2+ ions with a nano-molar detection limit of 0.69 nM. Finally, the sensor PTB-1 was applied successfully for the intracellular detection of Hg 2+ ions in a HepG2 liver cell line, which was monitored by the use of confocal imaging techniques.

Distance-of-Flight Mass Spectrometry: What, Why, and How?

NASA Astrophysics Data System (ADS)

Dennis, Elise A.; Gundlach-Graham, Alexander W.; Ray, Steven J.; Enke, Christie G.; Hieftje, Gary M.

2016-11-01

Distance-of-flight mass spectrometry (DOFMS) separates ions of different mass-to-charge ( m/ z) by the distance they travel in a given time after acceleration. Like time-of-flight mass spectrometry (TOFMS), separation and mass assignment are based on ion velocity. However, DOFMS is not a variant of TOFMS; different methods of ion focusing and detection are used. In DOFMS, ions are driven orthogonally, at the detection time, onto an array of detectors parallel to the flight path. Through the independent detection of each m/ z, DOFMS can provide both wider dynamic range and increased throughput for m/ z of interest compared with conventional TOFMS. The iso-mass focusing and detection of ions is achieved by constant-momentum acceleration (CMA) and a linear-field ion mirror. Improved energy focus (including turn-around) is achieved in DOFMS, but the initial spatial dispersion of ions remains unchanged upon detection. Therefore, the point-source nature of surface ionization techniques could put them at an advantage for DOFMS. To date, three types of position-sensitive detectors have been used for DOFMS: a microchannel plate with a phosphorescent screen, a focal plane camera, and an IonCCD array; advances in detector technology will likely improve DOFMS figures-of-merit. In addition, the combination of CMA with TOF detection has provided improved resolution and duty factor over a narrow m/ z range (compared with conventional, single-pass TOFMS). The unique characteristics of DOFMS can enable the intact collection of large biomolecules, clusters, and organisms. DOFMS might also play a key role in achieving the long-sought goal of simultaneous MS/MS.

In Situ Measurements of Meteoric Ions. Chapter 8

NASA Technical Reports Server (NTRS)

Grebowsky, Joseph M.; Aikin, Arthur C.; Vondrak, Richard R. (Technical Monitor)

2001-01-01

Metal ions found in the atmosphere above 60 km are the result of incoming meteoroid atmospheric ablation. Layers of metal ions are detected by sounding rocket in situ mass spectrometric sampling in the 80 to 130 km region, which coincides with the altitude region where meteors are observed. Enhancements of metal ion concentrations occur during meteor showers. Even outside of shower periods, the metal ion altitude profiles vary from measurement to measurement. Double layers are frequent at middle latitudes. More than 40 different meteoric atomic and molecular ions, including isotopes, have been detected. Atmospheric metal ions on average have an abundance that matches chrondritic material, the same composition as the early solar system. However there are frequently local departures from this composition due to differential ablation, species dependent chemistry and mass dependent ion transport. Metal ions react with atmospheric O2, O, O3, H2O and H2O2 to form oxygenated and hydrogenated ionic compounds. Metal atomic ions at high altitudes have long lifetimes. As a result, these ions, in the presence of Earth's magnetic field, are transported over long distances by upper atmospheric winds and ionospheric electric fields. Satellite measurements have detected metal ions as high as, approximately 1000 km and have revealed circulation of the ions on a global scale.

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

NASA Technical Reports Server (NTRS)

Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

Detection of trace heavy metal ions in water by nanostructured porous Si biosensors.

PubMed

Shtenberg, Giorgi; Massad-Ivanir, Naama; Segal, Ester

2015-07-07

A generic biosensing platform, based on nanostructured porous Si (PSi), Fabry-Pérot thin films, for label-free monitoring of heavy metal ions in aqueous solutions by enzymatic activity inhibition, is described. First, we show a general detection assay by immobilizing horseradish peroxidase (HRP) within the oxidized PSi nanostructure and monitor its catalytic activity in real time by reflective interferometric Fourier transform spectroscopy. Optical studies reveal the high specificity and sensitivity of the HRP-immobilized PSi towards three metal ions (Ag(+) > Pb(2+) > Cu(2+)), with a detection limit range of 60-120 ppb. Next, we demonstrate the concept of specific detection of Cu(2+) ions (as a model heavy metal) by immobilizing Laccase, a multi-copper oxidase, within the oxidized PSi. The resulting biosensor allows for specific detection and quantification of copper ions in real water samples by monitoring the Laccase relative activity. The optical biosensing results are found to be in excellent agreement with those obtained by the gold standard analytical technique (ICP-AES) for all water samples. The main advantage of the presented biosensing concept is the ability to detect heavy metal ions at environmentally relevant concentrations using a simple and portable experimental setup, while the specific biosensor design can be tailored by varying the enzyme type.

Structural distinction of diacyl-, alkylacyl, and alk-1-enylacyl glycerophosphocholines as [M - 15]⁻ ions by multiple-stage linear ion-trap mass spectrometry with electrospray ionization.

PubMed

Hsu, Fong-Fu; Lodhi, Irfan J; Turk, John; Semenkovich, Clay F

2014-08-01

We describe a linear ion-trap (LIT) multiple-stage (MS(n)) mass spectrometric approach towards differentiation of alkylacyl, alk-1-enylacyl- and diacyl-glycerophoscholines (PCs) as the [M - 15]⁻ ions desorbed by electrospray ionization (ESI) in the negative-ion mode. The MS⁴ mass spectra of the [M - 15 - R²'CH = CO]⁻ ions originated from the three PC subfamilies are readily distinguishable, resulting in unambiguous distinction of the lipid classes. This method is applied to two alkyl ether rich PC mixtures isolated from murine bone marrow neutrophils and kidney, respectively, to explore its utility in the characterization of complex PC mixture of biological origin, resulting in the realization of the detailed structures of the PC species, including various classes and many minor isobaric isomers.

Proteomics goes forensic: Detection and mapping of blood signatures in fingermarks.

PubMed

Deininger, Lisa; Patel, Ekta; Clench, Malcolm R; Sears, Vaughn; Sammon, Chris; Francese, Simona

2016-06-01

A bottom up in situ proteomic method has been developed enabling the mapping of multiple blood signatures on the intact ridges of blood fingermarks by Matrix Assisted Laser Desorption Mass Spectrometry Imaging (MALDI-MSI). This method, at a proof of concept stage, builds upon recently published work demonstrating the opportunity to profile and identify multiple blood signatures in bloodstains via a bottom up proteomic approach. The present protocol addresses the limitation of the previously developed profiling method with respect to destructivity; destructivity should be avoided for evidence such as blood fingermarks, where the ridge detail must be preserved in order to provide the associative link between the biometric information and the events of bloodshed. Using a blood mark reference model, trypsin concentration and spraying conditions have been optimised within the technical constraints of the depositor eventually employed; the application of MALDI-MSI and Ion Mobility MS have enabled the detection, confirmation and visualisation of blood signatures directly onto the ridge pattern. These results are to be considered a first insight into a method eventually informing investigations (and judicial debates) of violent crimes in which the reliable and non-destructive detection and mapping of blood in fingermarks is paramount to reconstruct the events of bloodshed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion Fluxes in Giant Excised Cardiac Membrane Patches Detected and Quantified with Ion-selective Microelectrodes

PubMed Central

Kang, Tong Mook; Markin, Vladislav S.; Hilgemann, Donald W.

2003-01-01

We have used ion-selective electrodes (ISEs) to quantify ion fluxes across giant membrane patches by measuring and simulating ion gradients on both membrane sides. Experimental conditions are selected with low concentrations of the ions detected on the membrane side being monitored. For detection from the cytoplasmic (bath) side, the patch pipette is oscillated laterally in front of an ISE. For detection on the extracellular (pipette) side, ISEs are fabricated from flexible quartz capillary tubing (tip diameters, 2–3 microns), and an ISE is positioned carefully within the patch pipette with the tip at a controlled distance from the mouth of the patch pipette. Transport activity is then manipulated by solution changes on the cytoplasmic side. Ion fluxes can be quantified by simulating the ion gradients with appropriate diffusion models. For extracellular (intrapatch pipette) recordings, ion diffusion coefficients can be determined from the time courses of concentration changes. The sensitivity and utility of the methods are demonstrated with cardiac membrane patches by measuring (a) potassium fluxes via ion channels, valinomycin, and Na/K pumps; (b) calcium fluxes mediated by Na/Ca exchangers; (c) sodium fluxes mediated by gramicidin and Na/K pumps; and (d) proton fluxes mediated by an unknown electrogenic mechanism. The potassium flux-to-current ratio for the Na/K pump is approximately twice that determined for potassium channels and valinomycin, as expected for a 3Na/2K pump stoichiometery (i.e., 2K/charge moved). For valinomycin-mediated potassium currents and gramicidin-mediated sodium currents, the ion fluxes calculated from diffusion models are typically 10–15% smaller than expected from the membrane currents. As presently implemented, the ISE methods allow reliable detection of calcium and proton fluxes equivalent to monovalent cation currents <1 pA in magnitude, and they allow detection of sodium and potassium fluxes equivalent to <5 pA currents. The capability to monitor ion fluxes, independent of membrane currents, should facilitate studies of both electrogenic and electroneutral ion–coupled transporters in giant patches. PMID:12668735

Silver-dendrimer nanocomposites as oligonucleotide labels for electrochemical stripping detection of DNA hybridization.

PubMed

Jin, Xin; Zhou, Ling; Zhu, Bo; Jiang, Xue; Zhu, Ningning

2018-06-01

Silver-dendrimer nanocomposites were synthesized and used as oligonucleotide labels for electrochemical stripping detection of DNA hybridization. The synthesized silver-dendrimer nanocomposites were characterized by UV-vis spectrophotometry, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Ratios of silver/dendrimer were optimized in order to obtain stable nanocomposites with maximal silver loading in the interior of a polymeric shell. The silver-dendrimer nanocomposites were attached to sequence-known DNA probes specific to colitoxin, and used to detect probe hybridization by dissolution of the silver nanoparticles in the interior of dendrimer in a diluted nitric acid, followed by measurement of Ag + ions by anodic stripping voltammetry (ASV). Use of differential pulse voltammetry for the stripping step, along with optimization of the ASV conditions, enabled a detection limit of 0.78 pM. The present strategy, in combination with dendrimer-encapsulated copper labeled oligonucleotides probe reported previously, could potentially be used to detect single or multiple DNA targets in one sample. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Human perception of electric fields and ion currents associated with high-voltage DC transmission lines.

PubMed

Blondin, J P; Nguyen, D H; Sbeghen, J; Goulet, D; Cardinal, C; Maruvada, P S; Plante, M; Bailey, W H

1996-01-01

The objective of this study was to assess the ability of humans to detect the presence of DC electric field and ion currents. An exposure chamber simulating conditions present in the vicinity of high-voltage DC (HVDC) lines was designed and built for this purpose. In these experiments, the facility was used to expose observers to DC electric fields up to 50 kV/m and ion current densities up to 120 nA/m2. Forty-eight volunteers (25 women and 23 men) between the ages of 18 and 57 years served as observers. Perception of DC fields was examined by using two psychophysical methods: an adaptive staircase procedure and a rating method derived from signal-detection theory. Subjects completed three different series of observations by using each of these methods; one was conducted without ion currents, and the other two involved various combinations of electric fields and ion currents. Overall, subjects were significantly more likely to detect DC fields as the intensity increased. Observers were able to detect the presence of DC fields alone, but only at high intensities; the average threshold was 45 kV/m. Except in the most sensitive individuals, ion current densities up to 60 nA/m2 did not significantly facilitate the detection of DC fields. However, higher ion current densities were associated with a substantial lowering of sensory thresholds in a large majority of observers. Data analysis also revealed large variations in perceptual thresholds among observers. Normative data indicating DC field and ion current intensities that can be detected by 50% of all observers are provided. In addition, for the most sensitive observers, several other detection proportions were derived from the distribution of individual detection capabilities. These data can form the basis for environmental guidelines relating to the design of HVDC lines.

Multiresponsive polysiloxane bearing spiropyran: synthesis and sensing of pH and metal ions of different valence

NASA Astrophysics Data System (ADS)

Li, Hongqi; Zheng, Tao; Zhao, Yong; Xu, Zhenxiang; Dai, Xuhang; Shao, Zhiyu

2018-03-01

A spiropyran-appended polysiloxane (SP-Si) was synthesized and characterized. The pH-responsive behavior of SP-Si was investigated. It was found that with the decrease of the pH of SP-Si solution the intensity of the absorption peak at 440 nm increased and the color of SP-Si solution turned from colorless to yellow gradually. The polymer serves as chemosensor for colorimetric detection of Ag+ and Fe3+ ions. Addition of Ag+ and Fe3+ ions to SP-Si solution induced color change from colorless to brown and earthy yellow, respectively. Sensing of Ag+ ions by SP-Si was not affected by common competitive metal ions except Hg2+ ions. Based on the transformation from colorless SP-Si solution with negligible absorption at 440 nm to brown SP-Si/Ag+ showing extremely strong absorption at 440 nm by addition of Ag+ ions and subsequent transformation from brown to colorless SP-Si/Ag+/Hg2+ with relatively weak absorption at 440 nm after addition of 1 equivalent of Hg2+ ions, SP-Si/Ag+ system serves as a dual colorimetric and spectroscopic probe for highly selective and sensitive detection of Hg2+ ions. The selective detection of Fe3+ ions by SP-Si is not interfered by common competitive metal ions including Na+, K+, Li+, Hg2+, Ni2+, Fe2+, Zn2+, Co2+, Sr2+, Cu2+, Al3+, Ce3+ and Cr3+. The detection limit of Ag+ and Fe3+ ions is 1.45 × 10-6 M and 3.52 × 10-6 M, respectively.

Rapid LC-MS/MS profiling of protein amino acids and metabolically related compounds for large-scale assessment of metabolic phenotypes.

PubMed

Gu, Liping; Jones, A Daniel; Last, Robert L

2012-01-01

Amino acids extracted from a biological matrix can be resolved and measured using a 6-min per sample method through high-performance liquid chromatography with a short C18 column and rapid gradient using the ion-pairing reagent perfluoroheptanoic acid. LC-tandem mass spectrometry with multiple reaction monitoring (MRM) transitions selective for each compound allows simultaneous quantification of the 20 proteinogenic amino acids and 5 metabolically related compounds. Distinct MRM transitions were also established for selective detection of the isomers leucine/isoleucine and threonine/homoserine.

X-ray emission from high temperature plasmas

NASA Technical Reports Server (NTRS)

Harries, W. L.

1977-01-01

The physical processes occurring in plasma focus devices were investigated with particular emphasis on X-ray emission. Topics discussed include: trajectories of high energy electrons; detection of ion trajectories; spatial distribution of neutron emission; space and time resolved emission of hard X-rays from a plasma focus; the staged plasma focus as a variation of the hypocloidal pinch; formation of current sheets in a staged plasma focus; and X-ray and neutron emission from a staged plasma focus. The possibility of operating dense plasma-focus type devices in multiple arrays beyond the scaling law for a single gun is discussed.

Synchronized Survey Scan Approach Allows for Efficient Discrimination of Isomeric and Isobaric Compounds during LC-MS/MS Analyses

PubMed Central

Masike, Keabetswe

2018-01-01

Liquid chromatography-mass spectrometry- (LC-MS-) based multiple reaction monitoring (MRM) methods have been used to detect and quantify metabolites for years. These approaches rely on the monitoring of various fragmentation pathways of multiple precursors and the subsequent corresponding product ions. However, MRM methods are incapable of confidently discriminating between isomeric and isobaric molecules and, as such, the development of methods capable of overcoming this challenge has become imperative. Due to increasing scanning rates of recent MS instruments, it is now possible to operate MS instruments both in the static and dynamic modes. One such method is known as synchronized survey scan (SSS), which is capable of acquiring a product ion scan (PIS) during MRM analysis. The current study shows, for the first time, the use of SSS-based PIS approach as a feasible identification feature of MRM. To achieve the above, five positional isomers of dicaffeoylquinic acids (diCQAs) were studied with the aid of SSS-based PIS method. Here, the MRM transitions were automatically optimized using a 3,5-diCQA isomer by monitoring fragmentation transitions common to all five isomers. Using the mixture of these isomers, fragmentation spectra of the five isomers achieved with SSS-based PIS were used to identify each isomer based on previously published hierarchical fragmentation keys. The optimized method was also used to detect and distinguish between diCQA components found in Bidens pilosa and their isobaric counterparts found in Moringa oleifera plants. Thus, the method was shown to distinguish (by differences in fragmentation patterns) between diCQA and their isobars, caffeoylquinic acid (CQA) glycosides. In conclusion, SSS allowed the detection and discrimination of isomeric and isobaric compounds in a single chromatographic run by producing a PIS spectrum, triggered in the automatic MS/MS synchronized survey scan mode. PMID:29805830

Detection of heavy metal ions in contaminated water by surface plasmon resonance based optical fibre sensor using conducting polymer and chitosan.

PubMed

Verma, Roli; Gupta, Banshi D

2015-01-01

Optical fibre surface plasmon resonance (SPR) based sensor for the detection of heavy metal ions in the drinking water is designed. Silver (Ag) metal and indium tin oxide (ITO) are used for the fabrication of the SPR probe which is further modified with the coating of pyrrole and chitosan composite. The sensor works on the wavelength interrogation technique and is capable of detecting trace amounts of Cd(2+), Pb(2+), and Hg(2+) heavy metal ions in contaminated water. Four types of sensing probes are fabricated and characterised for heavy metal ions out of these pyrrole/chitosan/ITO/Ag coated probe is found to be highly sensitive among all other probes. Further, the cadmium ions bind strongly to the sensing surface than other ions and due to this the sensor is highly sensitive for Cd(2+) ions. The sensor's performance is best for the low concentrations of heavy metal ions and its sensitivity decreases with the increasing concentration of heavy metal ions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development of a beam ion velocity detector for the heavy ion beam probe

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

Fimognari, P. J., E-mail: PJFimognari@XanthoTechnologies.com; Crowley, T. P.; Demers, D. R.

2016-11-15

In an axisymmetric plasma, the conservation of canonical angular momentum constrains heavy ion beam probe (HIBP) trajectories such that measurement of the toroidal velocity component of secondary ions provides a localized determination of the poloidal flux at the volume where they originated. We have developed a prototype detector which is designed to determine the beam angle in one dimension through the detection of ion current landing on two parallel planes of detecting elements. A set of apertures creates a pattern of ion current on wires in the first plane and solid metal plates behind them; the relative amounts detected bymore » the wires and plates determine the angle which beam ions enter the detector, which is used to infer the toroidal velocity component. The design evolved from a series of simulations within which we modeled ion beam velocity changes due to equilibrium and fluctuating magnetic fields, along with the ion beam profile and velocity dispersion, and studied how these and characteristics such as the size, cross section, and spacing of the detector elements affect performance.« less

Small system for tritium accelerator mass spectrometry

DOEpatents

Roberts, M.L.; Davis, J.C.

1993-02-23

Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and [sup 3]He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.

Small system for tritium accelerator mass spectrometry

DOEpatents

Roberts, Mark L.; Davis, Jay C.

1993-01-01

Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and .sup.3 He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process.

PubMed

Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V

2011-12-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. © The Author(s) 2011. Published by Oxford University Press.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process

PubMed Central

Reshetnikov, Roman V.; Sponer, Jiri; Rassokhina, Olga I.; Kopylov, Alexei M.; Tsvetkov, Philipp O.; Makarov, Alexander A.; Golovin, Andrey V.

2011-01-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. PMID:21893589

Nitrogen doped carbon nanodots as fluorescent probes for selective detection and quantification of Ferric(III) ions

NASA Astrophysics Data System (ADS)

Chin, Suk-Fun; Tan, Shao-Chien; Pang, Suh-Cem; Ng, Sing-Muk

2017-11-01

Nitrogen (N) doped carbon dots (N-CDs) that showed blue fluorescence with quantum yield (QY) of 12.25% were synthesized by one step microwave irradiation of lysine in ortho-phosphoric acid at 1000 W for 5 min. The as-synthesized N-CDs were successfully explored as fluorescent probes for selective detection of ferric (Fe3+) ions in aqueous condition with a linear range from 0.2 to 5.0 mM and a detection limit of 0.074 mM ± 0.081 (S/N = 3). The N-CDs exhibited high selectivity towards the detection of Fe3+ ions even in the presence of interfering ions. The N-CDs also demonstrated the potential of practical application for determining of Fe3+ ions concentration in real samples with high recovery rate and low relative standard deviation error.

Anion-intercalated layered double hydroxides modified test strips for detection of heavy metal ions.

PubMed

Wang, Nan; Sun, Jianchao; Fan, Hai; Ai, Shiyun

2016-01-01

In this work, a novel approach for facile and rapid detection of heavy metal ions using anion-intercalated layered double hydroxides (LDHs) modified test strips is demonstrated. By intercalating Fe(CN)6(4-) or S(2-) anions into the interlayers of LDHs on the filter paper, various heavy metal ions can be easily detected based on the color change before and after reaction between the anions and the heavy metal ions. Upon the dropping of heavy metal ions solutions to the test strips, the colors of the test strips changed instantly, which can be easily observed by naked eyes. With the decrease of the concentration, the color depth changed obviously. The lowest detection concentration can be up to 1×10(-6) mol L(-1). Due to the easily intercalation of anions into the interlayer of the LDHs on test trips, this procedure provides a general method for the construction of LDHs modified test strips for detection of heavy metal ions. The stability of the prepared test strips is investigated. Furthermore, all the results were highly reproducible. The test strips may have potential applications in environmental monitoring fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Ion Acceleration by Double Layers with Multi-Component Ion Species

NASA Astrophysics Data System (ADS)

Good, Timothy; Aguirre, Evan; Scime, Earl; West Virginia University Team

2017-10-01

Current-free double layers (CFDL) models have been proposed to explain observations of magnetic field-aligned ion acceleration in plasmas expanding into divergent magnetic field regions. More recently, experimental studies of the Bohm sheath criterion in multiple ion species plasma reveal an equilibration of Bohm speeds at the sheath-presheath boundary for a grounded plate in a multipole-confined filament discharge. We aim to test this ion velocity effect for CFDL acceleration. We report high resolution ion velocity distribution function (IVDF) measurements using laser induced fluorescence downstream of a CFDL in a helicon plasma. Combinations of argon-helium, argon-krypton, and argon-xenon gases are ionized and measurements of argon or xenon IVDFs are investigated to determine whether ion acceleration is enhanced (or diminished) by the presence of lighter (or heavier) ions in the mix. We find that the predominant effect is a reduction of ion acceleration consistent with increased drag arising from increased gas pressure under all conditions, including constant total gas pressure, equal plasma densities of different ions, and very different plasma densities of different ions. These results suggest that the physics responsible for acceleration of multiple ion species in simple sheaths is not responsible for the ion acceleration observed in these expanding plasmas. Department of Physics, Gettysburg College.

In silico assessment of the conduction mechanism of the Ryanodine Receptor 1 reveals previously unknown exit pathways.

PubMed

Heinz, Leonard P; Kopec, Wojciech; de Groot, Bert L; Fink, Rainer H A

2018-05-02

The ryanodine receptor 1 is a large calcium ion channel found in mammalian skeletal muscle. The ion channel gained a lot of attention recently, after multiple independent authors published near-atomic cryo electron microscopy data. Taking advantage of the unprecedented quality of structural data, we performed molecular dynamics simulations on the entire ion channel as well as on a reduced model. We calculated potentials of mean force for Ba 2+ , Ca 2+ , Mg 2+ , K + , Na + and Cl - ions using umbrella sampling to identify the key residues involved in ion permeation. We found two main binding sites for the cations, whereas the channel is strongly repulsive for chloride ions. Furthermore, the data is consistent with the model that the receptor achieves its ion selectivity by over-affinity for divalent cations in a calcium-block-like fashion. We reproduced the experimental conductance for potassium ions in permeation simulations with applied voltage. The analysis of the permeation paths shows that ions exit the pore via multiple pathways, which we suggest to be related to the experimental observation of different subconducting states.

Consistency between real and synthetic fast-ion measurements at ASDEX Upgrade

NASA Astrophysics Data System (ADS)

Rasmussen, J.; Nielsen, S. K.; Stejner, M.; Geiger, B.; Salewski, M.; Jacobsen, A. S.; Korsholm, S. B.; Leipold, F.; Michelsen, P. K.; Moseev, D.; Schubert, M.; Stober, J.; Tardini, G.; Wagner, D.; The ASDEX Upgrade Team

2015-07-01

Internally consistent characterization of the properties of the fast-ion distribution from multiple diagnostics is a prerequisite for obtaining a full understanding of fast-ion behavior in tokamak plasmas. Here we benchmark several absolutely-calibrated core fast-ion diagnostics at ASDEX Upgrade by comparing fast-ion measurements from collective Thomson scattering, fast-ion {{\\text{D}}α} spectroscopy, and neutron rate detectors with numerical predictions from the TRANSP/NUBEAM transport code. We also study the sensitivity of the theoretical predictions to uncertainties in the plasma kinetic profiles. We find that theory and measurements generally agree within these uncertainties for all three diagnostics during heating phases with either one or two neutral beam injection sources. This suggests that the measurements can be described by the same model assuming classical slowing down of fast ions. Since the three diagnostics in the adopted configurations probe partially overlapping regions in fast-ion velocity space, this is also consistent with good internal agreement among the measurements themselves. Hence, our results support the feasibility of combining multiple diagnostics at ASDEX Upgrade to reconstruct the fast-ion distribution function in 2D velocity space.

Biomimetic heterogeneous multiple ion channels: a honeycomb structure composite film generated by breath figures

NASA Astrophysics Data System (ADS)

Han, Keyu; Heng, Liping; Wen, Liping; Jiang, Lei

2016-06-01

We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields.We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields. Electronic supplementary information (ESI) available: Pore size distribution histograms of the AAO substrates; SEM images of the side view of pure AAO membranes and top view of the flat PI/AAO composite film; the current-time curves of the flat composite film; the current-voltage characteristics curves of pure AAO nanochannels with different mean pore diameters; CA of the two surfaces of the composite PI/AAO film, the structural formula of the polymer polyimide resin (PI), and solid surface zeta potential. See DOI: 10.1039/c6nr02506d

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

Watson, Thomas B.

The Particle-into-Liquid Sampler (PILS) is an aqueous-solution-based online technique for determining bulk chemical composition of ambient aerosol particles. As shown in Figure 1, the instrument consists of two units, briefly described below: 1. An aerosol extraction unit where particles are passed through a growth chamber saturated with water vapor, liquid droplets are grown, and the resulting liquid collected and transferred to the detection system. 2. The detection system that includes ion chromatographs (IC) or a total organic carbon detector (TOC). Ion chromatography is performed using two Metrohm ICs—one for positive ions and one for negative ions—with conductivity detectors. The TOCmore » is detected using a GE TOC analyzer. The instrument can be run in either the ion detection mode or the TOC mode.« less

Transmission measurement based on STM observation to detect the penetration depth of low-energy heavy ions in botanic samples.

PubMed

Liu, Feng; Wang, Yugang; Xue, Jianming; Wang, Sixue; Du, Guanhua; Zhao, Weijiang

2003-02-01

The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2. c2002 Elsevier Science Ltd. All rights reserved.

Transmission measurement based on STM observation to detect the penetration depth of low-energy heavy ions in botanic samples

NASA Technical Reports Server (NTRS)

Liu, Feng; Wang, Yugang; Xue, Jianming; Wang, Sixue; Du, Guanhua; Zhao, Weijiang

2003-01-01

The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2. c2002 Elsevier Science Ltd. All rights reserved.

Co-immobilization of multiple enzymes by metal coordinated nucleotide hydrogel nanofibers: improved stability and an enzyme cascade for glucose detection

NASA Astrophysics Data System (ADS)

Liang, Hao; Jiang, Shuhui; Yuan, Qipeng; Li, Guofeng; Wang, Feng; Zhang, Zijie; Liu, Juewen

2016-03-01

Preserving enzyme activity and promoting synergistic activity via co-localization of multiple enzymes are key topics in bionanotechnology, materials science, and analytical chemistry. This study reports a facile method for co-immobilizing multiple enzymes in metal coordinated hydrogel nanofibers. Specifically, four types of protein enzymes, including glucose oxidase, Candida rugosa lipase, α-amylase, and horseradish peroxidase, were respectively encapsulated in a gel nanofiber made of Zn2+ and adenosine monophosphate (AMP) with a simple mixing step. Most enzymes achieved quantitative loading and retained full activity. At the same time, the entrapped enzymes were more stable against temperature variation (by 7.5 °C), protease attack, extreme pH (by 2-fold), and organic solvents. After storing for 15 days, the entrapped enzyme still retained 70% activity while the free enzyme nearly completely lost its activity. Compared to nanoparticles formed with AMP and lanthanide ions, the nanofiber gels allowed much higher enzyme activity. Finally, a highly sensitive and selective biosensor for glucose was prepared using the gel nanofiber to co-immobilize glucose oxidase and horseradish peroxidase for an enzyme cascade system. A detection limit of 0.3 μM glucose with excellent selectivity was achieved. This work indicates that metal coordinated materials using nucleotides are highly useful for interfacing with biomolecules.Preserving enzyme activity and promoting synergistic activity via co-localization of multiple enzymes are key topics in bionanotechnology, materials science, and analytical chemistry. This study reports a facile method for co-immobilizing multiple enzymes in metal coordinated hydrogel nanofibers. Specifically, four types of protein enzymes, including glucose oxidase, Candida rugosa lipase, α-amylase, and horseradish peroxidase, were respectively encapsulated in a gel nanofiber made of Zn2+ and adenosine monophosphate (AMP) with a simple mixing step. Most enzymes achieved quantitative loading and retained full activity. At the same time, the entrapped enzymes were more stable against temperature variation (by 7.5 °C), protease attack, extreme pH (by 2-fold), and organic solvents. After storing for 15 days, the entrapped enzyme still retained 70% activity while the free enzyme nearly completely lost its activity. Compared to nanoparticles formed with AMP and lanthanide ions, the nanofiber gels allowed much higher enzyme activity. Finally, a highly sensitive and selective biosensor for glucose was prepared using the gel nanofiber to co-immobilize glucose oxidase and horseradish peroxidase for an enzyme cascade system. A detection limit of 0.3 μM glucose with excellent selectivity was achieved. This work indicates that metal coordinated materials using nucleotides are highly useful for interfacing with biomolecules. Electronic supplementary information (ESI) available: Additional methods, IR and XRD spectroscopy, enzyme loading capacity, enzyme kinetic parameters, and enzyme stability data. See DOI: 10.1039/c5nr08734a

Determination of human-use pharmaceuticals in filtered water by direct aqueous injection: high-performance liquid chromatography/tandem mass spectrometry

USGS Publications Warehouse

Furlong, Edward T.; Noriega, Mary C.; Kanagy, Christopher J.; Kanagy, Leslie K.; Coffey, Laura J.; Burkhardt, Mark R.

2014-01-01

This report describes a method for the determination of 110 human-use pharmaceuticals using a 100-microliter aliquot of a filtered water sample directly injected into a high-performance liquid chromatograph coupled to a triple-quadrupole tandem mass spectrometer using an electrospray ionization source operated in the positive ion mode. The pharmaceuticals were separated by using a reversed-phase gradient of formic acid/ammonium formate-modified water and methanol. Multiple reaction monitoring of two fragmentations of the protonated molecular ion of each pharmaceutical to two unique product ions was used to identify each pharmaceutical qualitatively. The primary multiple reaction monitoring precursor-product ion transition was quantified for each pharmaceutical relative to the primary multiple reaction monitoring precursor-product transition of one of 19 isotope-dilution standard pharmaceuticals or the pesticide atrazine, using an exact stable isotope analogue where possible. Each isotope-dilution standard was selected, when possible, for its chemical similarity to the unlabeled pharmaceutical of interest, and added to the sample after filtration but prior to analysis. Method performance for each pharmaceutical was determined for reagent water, groundwater, treated drinking water, surface water, treated wastewater effluent, and wastewater influent sample matrixes that this method will likely be applied to. Each matrix was evaluated in order of increasing complexity to demonstrate (1) the sensitivity of the method in different water matrixes and (2) the effect of sample matrix, particularly matrix enhancement or suppression of the precursor ion signal, on the quantitative determination of pharmaceutical concentrations. Recovery of water samples spiked (fortified) with the suite of pharmaceuticals determined by this method typically was greater than 90 percent in reagent water, groundwater, drinking water, and surface water. Correction for ambient environmental concentrations of pharmaceuticals hampered the determination of absolute recoveries and method sensitivity of some compounds in some water types, particularly for wastewater effluent and influent samples. The method detection limit of each pharmaceutical was determined from analysis of pharmaceuticals fortified at multiple concentrations in reagent water. The calibration range for each compound typically spanned three orders of magnitude of concentration. Absolute sensitivity for some compounds, using isotope-dilution quantitation, ranged from 0.45 to 94.1 nanograms per liter, primarily as a result of the inherent ionization efficiency of each pharmaceutical in the electrospray ionization process. Holding-time studies indicate that acceptable recoveries of pharmaceuticals can be obtained from filtered water samples held at 4 °C for as long as 9 days after sample collection. Freezing samples to provide for storage for longer periods currently (2014) is under evaluation by the National Water Quality Laboratory.

Formation of multiple energy dispersion of H+, He+, and O+ ions in the inner magnetosphere in response to interplanetary shock

NASA Astrophysics Data System (ADS)

Tsuji, H.; Ebihara, Y.; Tanaka, T.

2017-04-01

An interplanetary (IP) shock has a large impact on magnetospheric ions. Satellite observations have shown that soon after arrival of the IP shock, overall intensity of the ions rapidly increases and multiple energy dispersion appears in an energy-time spectrogram of the ions. In order to understand the response of the magnetospheric ions to IP shock, we have performed test particle simulation under the electric and magnetic fields provided by the global magnetohydrodynamic simulation. We reconstructed the differential flux of H+, He+, and O+ ions at (7, 0, 0) Re in GSM coordinates by means of the semi-Lagrangian (phase space mapping) method. Simulation results show that the ions respond to the IP shock in two different ways. First, overall intensity of the flux gradually increases at all pitch angles. As the compressional wave propagates tailward, the magnetic field increases, which accelerates the ions due to the gyrobetatron. Second, multiple energy-time dispersion appears in the reconstructed spectrograms of the ion flux. The energy-time dispersion is caused by the ion moving toward mirror point together with tailward propagating compressional wave at off-equator. The ions are primarily accelerated by the drift betatron under the strong electric field looking dawnward. The dispersion is absent in the spectrogram of equatorially mirroring ions. The dispersion appears at higher energy for heavier ions. These features are consistent with the satellite observations. Because the acceleration depends on bounce phase, the bounce-averaged approximation is probably invalid for the ions during the interval of geomagnetic sudden commencement.