Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

Science.gov (United States)

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

2017-05-23

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Practical aspects of trapped ion mass spectrometry, 5 applications of ion trapping devices

CERN Document Server

March, Raymond E

2009-01-01

Examines ion/neutral and ion/ion reactions, ion spectroscopy, and the structural characterization of proteins and peptides using quadropole ion trap mass spectrometry, Fourier transform - ion cyclotron resonance (FT-ICR) mass spectrometry, and traveling wave ion mobility mass spectrometry.

Group IIB-VIA semiconductor oxide cluster ions

Science.gov (United States)

Jayasekharan, Thankan

2018-05-01

Metal oxide cluster ions, MnOm± (M = Zn, Cd) and HgnOm- of various stoichiometry have been generated from solid IIB-VIA semiconductor oxides targets, (ZnO(s), CdO(s), and HgO(s)) by using pulse laser desorption ionization time of flight mass spectrometry with a laser of λ = 355 nm. Analysis of mass spectral data indicates the formation of stoichiometric cluster ions viz., (ZnO)n=1-30+ and (CdO)n=1-40+ along with -O bound anions, (ZnO)n=1-30O-, (CdO)n=1-40O- and (HgO)n=1-36O- from their respective solids. Further, metal oxoanions such as ZnOn=2,3-, CdOn=2,3,6-, and HgOn=2,3,6,7- have also been noted signifying the higher coordination ability of both Cd and Hg with O/O2/O3 species.

Secondary Ion Mass Spectrometry SIMS XI

Science.gov (United States)

Gillen, G.; Lareau, R.; Bennett, J.; Stevie, F.

2003-05-01

This volume contains 252 contributions presented as plenary, invited and contributed poster and oral presentations at the 11th International Conference on Secondary Ion Mass Spectrometry (SIMS XI) held at the Hilton Hotel, Walt Disney World Village, Orlando, Florida, 7 12 September, 1997. The book covers a diverse range of research, reflecting the rapid growth in advanced semiconductor characterization, ultra shallow depth profiling, TOF-SIMS and the new areas in which SIMS techniques are being used, for example in biological sciences and organic surface characterization. Papers are presented under the following categories: Isotopic SIMS Biological SIMS Semiconductor Characterization Techniques and Applications Ultra Shallow Depth Profiling Depth Profiling Fundamental/Modelling and Diffusion Sputter-Induced Topography Fundamentals of Molecular Desorption Organic Materials Practical TOF-SIMS Polyatomic Primary Ions Materials/Surface Analysis Postionization Instrumentation Geological SIMS Imaging Fundamentals of Sputtering Ion Formation and Cluster Formation Quantitative Analysis Environmental/Particle Characterization Related Techniques These proceedings provide an invaluable source of reference for both newcomers to the field and experienced SIMS users.

Laser ablation synthesis of arsenic-phosphide Asm Pn clusters from As-P mixtures. Laser desorption ionisation with quadrupole ion trap time-of-flight mass spectrometry: The mass spectrometer as a synthesizer.

Science.gov (United States)

Kubáček, Pavel; Prokeš, Lubomír; Pamreddy, Annapurna; Peña-Méndez, Eladia María; Conde, José Elias; Alberti, Milan; Havel, Josef

2018-05-30

Only a few arsenic phosphides are known. A high potential for the generation of new compounds is offered by Laser Ablation Synthesis (LAS) and when Laser Desorption Ionization (LDI) is coupled with simultaneous Time-Of-Flight Mass Spectrometry (TOFMS), immediate identification of the clusters can be achieved. LAS was used for the generation of arsenic phosphides via laser ablation of phosphorus-arsenic mixtures while quadrupole ion trap time-of-flight mass spectrometry (QIT-TOFMS) was used to acquire the mass spectra. Many new As m P n ± clusters (479 binary and 369 mono-elemental) not yet described in the literature were generated in the gas phase and their stoichiometry determined. The likely structures for some of the observed clusters arbitrary selected (20) were computed by density functional theory (DFT) optimization. LAS is an advantageous approach for the generation of new As m P n clusters, while mass spectrometry was found to be an efficient technique for the determination of cluster stoichiometry. The results achieved might inspire the synthesis of new materials. Copyright © 2018 John Wiley & Sons, Ltd.

Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

Science.gov (United States)

Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

2017-09-08

In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

Cluster ion beam facilities

International Nuclear Information System (INIS)

Popok, V.N.; Prasalovich, S.V.; Odzhaev, V.B.; Campbell, E.E.B.

2001-01-01

A brief state-of-the-art review in the field of cluster-surface interactions is presented. Ionised cluster beams could become a powerful and versatile tool for the modification and processing of surfaces as an alternative to ion implantation and ion assisted deposition. The main effects of cluster-surface collisions and possible applications of cluster ion beams are discussed. The outlooks of the Cluster Implantation and Deposition Apparatus (CIDA) being developed in Guteborg University are shown

Analysis of organic compounds by secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS)

International Nuclear Information System (INIS)

Ewinger, H.P.

1993-05-01

This study is about the use of secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS) as analytical techniques with depth resolution in determining organic components in environmental solid microparticles. The first application of plasma SNMS to organic compounds revealed the spectra to be composed mainly of signals from the atoms of all participating elements, such as C, H, O, N, S, P, and Cl. In addition, signals produced by multi-atomic clusters can be detected, such as CH, C 2 , CH 2 , C 2 H, and C 3 , as well as signals indicating the presence of organic compounds with hetero elements, such as OH, NH, and CN. Their intensity decreases very markedly with increasing numbers of atoms. Among the signals from bi-atomic clusters, those coming from elements with large mass differences are most intense. The use of plasma SNMS with organic compounds has shown that, except for spurious chemical reactions induced by ion bombardment and photodesorption by the photons of the plasma, it is possible to analyze with resolution in depth, elements of organic solids. A more detailed molecular characterization of organic compounds is possible by means of SIMS on the basis of multi-atomic fragments and by comparison with suitable signal patterns. (orig./BBR) [de

Time-of-flight secondary ion mass spectrometry of a range of coal samples: a chemometrics (PCA, cluster, and PLS) analysis

Energy Technology Data Exchange (ETDEWEB)

Lei Pei; Guilin Jiang; Bonnie J. Tyler; Larry L. Baxter; Matthew R. Linford [Brigham Young University, Provo, UT (United States). Department of Chemistry and Biochemistry

2008-03-15

This paper documents time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses of 34 different coal samples. In many cases, the inorganic Na{sup +}, Al{sup +}, Si{sup +}, and K{sup +} ions dominate the spectra, eclipsing the organic peaks. A scores plot of principal component 1 (PC1) versus principal component 2 (PC2) in a principal components analysis (PCA) effectively separates the coal spectra into a triangular pattern, where the different vertices of this pattern come from (I) spectra that have a strong inorganic signature that is dominated by Na{sup +}, (ii) spectra that have a strong inorganic signature that is dominated by Al{sup +}, Si{sup +}, and K{sup +}, and (iii) spectra that have a strong organic signature. Loadings plots of PC1 and PC2 confirm these observations. The spectra with the more prominent inorganic signatures come from samples with higher ash contents. Cluster analysis with the K-means algorithm was also applied to the data. The progressive clustering revealed in the dendrogram correlates extremely well with the clustering of the data points found in the scores plot of PC1 versus PC2 from the PCA. In addition, this clustering often correlates with properties of the coal samples, as measured by traditional analyses. Partial least-squares (PLS), which included the use of interval PLS and a genetic algorithm for variable selection, shows a good correlation between ToF-SIMS spectra and some of the properties measured by traditional means. Thus, ToF-SIMS appears to be a promising technique for the analysis of this important fuel. 33 refs., 9 figs., 5 tabs.

Detection of sputtered molecular doubly charged anions: a comparison of secondary-ion mass spectrometry (SIMS) and accelerator mass spectrometry (AMS)

International Nuclear Information System (INIS)

Gnaser, Hubert; Golser, Robin; Kutschera, Walter; Priller, Alfred; Steier, Peter; Vockenhuber, Christof

2004-01-01

The detection of small molecular dianions by secondary-ion mass spectrometry (SIMS) and by accelerator mass spectrometry (AMS) is compared. In SIMS, the existence of these dianions can be identified safely if the total mass number of the molecule is odd and the dianion is hence detected at a half-integral mass number. The occurrence of fragmentation processes which may interfere with this scheme, is illustrated by means of the energy spectra of singly and doubly charged negative cluster ions. As compared to SIMS, AMS can rely, in addition, on the break-up of molecular species in the stripping process: this allows to monitor the simultaneous arrival of several atomic constituents with a clear energetic pattern in coincidence at the detector. This feature is exemplified for the C 10 2- dianion

Alpha spectrometry and secondary ion mass spectrometry of thorium

International Nuclear Information System (INIS)

Strisovska, Jana; Kuruc, Jozef; Galanda, Dusan; Matel, Lubomir; Velic, Dusan; Aranyosiova, Monika

2009-01-01

A sample of thorium content on steel discs was prepared by electrodeposition with a view to determining the natural thorium isotope. Thorium was determined by alpha spectrometry and by secondary ion mass spectrometry and the results of the two methods were compared

Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke

2011-03-14

The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.

CO2 laser photolysis of clustered ions, (1)

International Nuclear Information System (INIS)

Ikezoe, Yasumasa; Soga, Takeshi; Suzuki, Kazuya; Ohno, Shin-ichi.

1990-09-01

Vibrational excitation and the following decomposition of cluster ions by CO 2 laser photons are studied. Characteristics of the cluster ion and the CO 2 laser photon are summarized in their relation to the photolysis of cluster ions. An apparatus was installed, which is composed of (1) corona discharge-jet expansion section (formation of cluster ions), (2) CO 2 laser section (photolysis of cluster ions), and (3) mass spectrometer section. Experimental results of ammonia cluster ions were described. Effects of repeller voltage, shape of repellers, and adiabatic cooling are examined on the formation of ammonia cluster ions by corona discharge-jet expansion method. Collisional dissociation of cluster ions was observed at high repeller voltages. Size distribution of the ammonia cluster ion is discussed in connection with the temperature of cluster ions. Intensity of CO 2 laser was related to decomposition yield of cluster ions. (author)

Study of shallow junction formation by boron-containing cluster ion implantation of silicon and two-stage annealing

Science.gov (United States)

Lu, Xin-Ming

Shallow junction formation made by low energy ion implantation and rapid thermal annealing is facing a major challenge for ULSI (ultra large scale integration) as the line width decreases down to the sub micrometer region. The issues include low beam current, the channeling effect in low energy ion implantation and TED (transient enhanced diffusion) during annealing after ion implantation. In this work, boron containing small cluster ions, such as GeB, SiB and SiB2, was generated by using the SNICS (source of negative ion by cesium sputtering) ion source to implant into Si substrates to form shallow junctions. The use of boron containing cluster ions effectively reduces the boron energy while keeping the energy of the cluster ion beam at a high level. At the same time, it reduces the channeling effect due to amorphization by co-implanted heavy atoms like Ge and Si. Cluster ions have been used to produce 0.65--2keV boron for low energy ion implantation. Two stage annealing, which is a combination of low temperature (550°C) preannealing and high temperature annealing (1000°C), was carried out to anneal the Si sample implanted by GeB, SiBn clusters. The key concept of two-step annealing, that is, the separation of crystal regrowth, point defects removal with dopant activation from dopant diffusion, is discussed in detail. The advantages of the two stage annealing include better lattice structure, better dopant activation and retarded boron diffusion. The junction depth of the two stage annealed GeB sample was only half that of the one-step annealed sample, indicating that TED was suppressed by two stage annealing. Junction depths as small as 30 nm have been achieved by two stage annealing of sample implanted with 5 x 10-4/cm2 of 5 keV GeB at 1000°C for 1 second. The samples were evaluated by SIMS (secondary ion mass spectrometry) profiling, TEM (transmission electron microscopy) and RBS (Rutherford Backscattering Spectrometry)/channeling. Cluster ion implantation

Temperature-controlled depth profiling in polymeric materials using cluster secondary ion mass spectrometry (SIMS)

Energy Technology Data Exchange (ETDEWEB)

Mahoney, Christine M. [National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371, Gaithersburg, MD, 20899 (United States)]. E-mail: christine.mahoney@nist.gov; Fahey, Albert J. [National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371, Gaithersburg, MD, 20899 (United States); Gillen, Greg [National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371, Gaithersburg, MD, 20899 (United States); Xu Chang [National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371, Gaithersburg, MD, 20899 (United States); Batteas, James D. [National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371, Gaithersburg, MD, 20899 (United States)

2006-07-30

Secondary ion mass spectrometry (SIMS) employing an SF{sub 5} {sup +} polyatomic primary ion source was used to depth profile through poly(methylmethacrylate) (PMMA), poly(lactic acid) (PLA) and polystyrene (PS) thin films at a series of temperatures from -125 deg. C to 150 deg. C. It was found that for PMMA, reduced temperature analysis produced depth profiles with increased secondary ion stability and reduced interfacial widths as compared to analysis at ambient temperature. Atomic force microscopy (AFM) images indicated that this improvement in interfacial width may be related to a decrease in sputter-induced topography. Depth profiling at higher temperatures was typically correlated with increased sputter rates. However, the improvements in interfacial widths and overall secondary ion stability were not as prevalent as was observed at low temperature. For PLA, improvements in signal intensities were observed at low temperatures, yet there was no significant change in secondary ion stability, interface widths or sputter rates. High temperatures yielded a significant decrease in secondary ion stability of the resulting profiles. PS films showed rapid degradation of characteristic secondary ion signals under all temperatures examined.

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

Science.gov (United States)

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.

Proton-bound cluster ions in ion mobility spectrometry

Science.gov (United States)

Ewing, R. G.; Eiceman, G. A.; Stone, J. A.

1999-01-01

Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

A quadrupole ion trap as low-energy cluster ion beam source

CERN Document Server

Uchida, N; Kanayama, T

2003-01-01

Kinetic energy distribution of ion beams was measured by a retarding field energy analyzer for a mass-selective cluster ion beam deposition system that uses a quadrupole ion trap as a cluster ion beam source. The results indicated that the system delivers a cluster-ion beam with energy distribution of approx 2 eV, which corresponded well to the calculation results of the trapping potentials in the ion trap. Using this deposition system, mass-selected hydrogenated Si cluster ions Si sub n H sub x sup + were actually deposited on Si(111)-(7x7) surfaces at impact kinetic energy E sub d of 3-30 eV. Observation by using a scanning tunneling microscope (STM) demonstrated that Si sub 6 H sub x sup + cluster ions landed on the surface without decomposition at E sub d =3 eV, while the deposition was destructive at E sub d>=18 eV. (author)

A novel ion imager for secondary ion mass spectrometry

International Nuclear Information System (INIS)

Matsumoto, Kazuya; Miyata, Kenji; Nakamura, Tsutomu

1993-01-01

This paper describes a new area detector for secondary ion mass spectrometry (SIMS) ion microscope, and its performance. The operational principle is based on detecting the change in potential of a floating photodiode caused by the ion-induced secondary-electron emission and the incoming ion itself. The experiments demonstrated that 10 1 -10 5 aluminum ions per pixel can be detected with good linear response. Moreover, relative ion sensitivities from hydrogen to lead were constant within a factor of 2. The performance of this area detector provides the potential for detection of kiloelectronvolt ion images with current ion microscopy

Binding energies of cluster ions

International Nuclear Information System (INIS)

Parajuli, R.; Matt, S.; Scheier, P.; Echt, O.; Stamatovic, A.; Maerk, T.D.

2002-01-01

The binding energy of charged clusters may be measured by analyzing the kinetic energy released in the metastable decay of mass selected parent ions. Using finite heat bath theory to determine the binding energies of argon, neon, krypton, oxygen and nitrogen from their respective average kinetic energy released were carried out. A high-resolution double focussing two-sector mass spectrometer of reversed Nier-Johnson type geometry was used. MIKE ( mass-analysed ion kinetic energy) were measured to investigate decay reactions of mass-selected ions. For the inert gases neon (Ne n + ), argon (Ar n + ) and krypton (Kr n + ), it is found that the binding energies initially decrease with increasing size n and then level off at a value above the enthalpy of vaporization of the condensed phase. Oxygen cluster ions shown a characteristic dependence on cluster size (U-shape) indicating a change in the metastable fragmentation mechanism when going from the dimer to the decamer ion. (nevyjel)

Detection of gold cluster ions by ion-to-ion conversion using a CsI-converter

International Nuclear Information System (INIS)

Nguyen, V.-T.; Novilkov, A.C.; Obnorskii, V.V.

1997-01-01

Gold cluster ions in the m/z range of 10 4 -2 x 10 6 u were produced by bombarding a thin film of gold with 252 Cf-fission fragments. The gold covering a C-Al substrate formed islets having a mean diameter of 44 A. Their size- and mass-distribution was determined by means of electron microscopy. The main task was to measure the m/z distribution of the cluster ions ejected from the sample surface. For this purpose we built a time-of-flight (TOF) mass spectrometer, which could be used as a linear TOF instrument or, alternatively, as a tandem-TOF instrument being equipped with an ion-to-ion converter. Combining the results obtained in both modes, it turned out that the linear TOF instrument equipped with micro-channel plates had a mean detection efficiency for 20 keV cluster ions of about 40%. In the tandem mode, the cluster ions hit a CsI converter with energies of 40z keV (z = charge state), from where secondary ions - mainly Cs + and (CsI) n Cs + cluster ions - were ejected. These ions were used to measure the TOF spectrum of the gold cluster ions. The detection efficiency of the cluster ions was found to vary in the available mass range from 99.7% to 96.5%. The complete mass distribution between 4 x 10 4 and 4 x 10 6 u was determined and compared with the corresponding mass distribution of the gold islets covering the substrate. (orig.)

Low-energy irradiation effects of gas cluster ion beams

International Nuclear Information System (INIS)

Houzumi, Shingo; Takeshima, Keigo; Mochiji, Kozo; Toyoda, Noriaki; Yamada, Isao

2007-01-01

A cluster-ion irradiation system with cluster-size selection has been developed to study the effects of the cluster size for surface processes using cluster ions. A permanent magnet with a magnetic field of 1.2 T is installed for size separation of large cluster ions. Trace formations at HOPG surface by the irradiation with size-selected Ar-cluster ions under acceleration energy of 30 keV were investigated by a scanning tunneling microscopy. Generation behavior of the crater-like traces is strongly affected by the number of constituent atoms (cluster size) of the irradiating cluster ion. When the incident cluster ion is composed of 100-3000 atoms, crater-like traces are observed on the irradiated surfaces. In contrast, such traces are not observed at all with the irradiation of the cluster-ions composed of over 5000 atoms. Such the behavior is discussed on the basis of the kinetic energy per constituent atom of the cluster ion. To study GCIB irradiation effects against macromolecule, GCIB was irradiated on DNA molecules absorbed on graphite surface. By the GCIB irradiation, much more DNA molecules was sputtered away as compared with the monomer-ion irradiation. (author)

High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

Science.gov (United States)

Swearingen, Kristian E; Moritz, Robert L

2012-10-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

Cluster Ions and Atmospheric Processes

Science.gov (United States)

D'Auria, R.; Turco, R. P.

We investigate the properties and possible roles of naturally occurring ions under at- mospheric conditions. Among other things, the formation of stable charged molecular clusters represents the initial stages of aerosol nucleation [e.g., Keesee and Castle- man, 1982], while the conversion of vapor to aggregates is the first step in certain atmospheric phase transitions [e.g. Hamill and Turco, 2000]. We analyze the stability and size distributions of common ionic clusters by solving the differential equations describing their growth and loss. The necessary reaction rate coefficients are deter- mined using kinetic and thermodynamic data. The latter are derived from direct labo- ratory measurements of equilibrium constants, from the classical charged liquid drop model applied to large aggregates (i.e., the Thomson model [Thomson, 1906]), and from quantum mechanical calculations of the thermodynamic potentials associated with the cluster structures. This approach allows us to characterize molecular clusters across the entire size range from true molecular species to larger aggregates exhibiting macroscopic behavior [D'Auria, 2001]. Cluster systems discussed in this talk include the proton hydrates (PHs) and nitrate-water and nitrate-nitric acid series [D'Auria and Turco, 2001]. These ions have frequently been detected in the stratosphere and tropo- sphere [e.g., Arnold et al., 1977; Viggiano and Arnold, 1981]. We show how the pro- posed hybrid cluster model can be extended to a wide range of ion systems, including non-proton hydrates (NPHs), mixed-ligand clusters such as nitrate-water-nitric acid and sulfate-sulfuric acid-water, as well as more exotic species containing ammonia, pyridine and other organic compounds found on ions [e.g., Eisele, 1988; Tanner and Eisele, 1991]. References: Arnold, F., D. Krankowsky and K. H. Marien, First mass spectrometric measurements of posi- tive ions in the stratosphere, Nature, 267, 30-32, 1977. D'Auria, R., A study of ionic

Fragmentation of cluster ions produced by electron impact ionization

International Nuclear Information System (INIS)

Parajuli, R.

2001-12-01

By studying fragmentation of dimer and cluster ions produced by electron impact ionization of a neutral cluster beam, it is possible to elucidate structure, stability and energetics of these species and the dynamics of the corresponding decay reactions. Fragmentation of carbon cluster ions formed from C 6 0 fullerenes, rare gas cluster ions and dimer ions and simple molecular cluster ions (oxygen and nitrogen) and dimer ions have been studied in this thesis using a high resolution two sector field mass spectrometer of reversed geometry and a NIER type electron impact ion source. Spontaneous decay reactions of triply and quadruply charged C 4 0 z + and C 4 1 z + cluster ions which are formed from C 6 0 fullerenes by electron impact ionization have been analyzed. A new but very weak decay reaction for the even-sized carbon clusters ions is observed, namely loss of C 3 . The odd-sized clusters ions preferentially decay by loss of carbon atoms and, to a lesser degree, trimers. A weak signal due to C 2 loss is observed for C 4 1 3 + ion. These decay channels are discussed in terms of the geometric structure of these metastable, relatively cold cluster ions. Measurements on metastable fragmentation of mass selected rare gas cluster ions (Ne, Ar, Kr) which are produced by electron impact ionization of a neutral rare gas cluster beam have been carried out. From the shape of the fragment ion peaks (MIKE scan technique) information about the distribution of kinetic energy that is released in the decay reaction can be deduced. In this study, the peak shape observed for cluster ions with sizes larger than five is Gaussian and thus from the peak width the mean kinetic energy release of the corresponding decay reactions can be calculated. Using finite heat bath theory, the binding energies of the decaying cluster ions are calculated from these data and have been compared to data in the literature where available. In addition to the decay reactions of cluster ions the metastable

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

Science.gov (United States)

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

1999-10-15

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

Novel radial vanadium pentoxide nanobelt clusters for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Yanping; Zhong, Wenwu [Department of Physics and Electronic Engineering, Taizhou University, Taizhou, Zhejiang 318000 (China); Du, Yinxiao, E-mail: duyinxiao@zzia.edu.cn [Department of Mathematics and Physics, Zhengzhou Institute of Aeronautical Industry Management, Zhengzhou 450015 (China); Yuan, Q.X. [Department of Mathematics and Physics, Zhengzhou Institute of Aeronautical Industry Management, Zhengzhou 450015 (China); Wang, Xu [School of Microelectronics, Key Laboratory of Wide Band-Gap Semiconductor Materials and Devices, Xidian University, Xi' an 710071 (China); Jia, Renxu, E-mail: rxjia@mail.xidian.edu.cn [School of Microelectronics, Key Laboratory of Wide Band-Gap Semiconductor Materials and Devices, Xidian University, Xi' an 710071 (China)

2015-06-05

Highlights: • Radial V{sub 2}O{sub 5} nanobelt clusters were synthesized by a novel hydrothermal process. • The V{sub 2}O{sub 5} clusters are single crystallites with [0 1 0] growth direction. • Specific discharge capacity of V{sub 2}O{sub 5} is 134 mA h/g coupled with good cycle stability. - Abstract: This paper reports the synthesis, characterization and Li-ion intercalation properties of moundlily-like radial vanadium pentoxide (V{sub 2}O{sub 5}) nanobelt clusters. The V{sub 2}O{sub 5} nanobelt clusters was successfully synthesized by a novel soft template assisted hydrothermal process followed by thermal annealing. The as-prepared products were characterized by X-ray diffraction, thermogravimetric analysis, FT-IR spectrometry, scanning electron microscopy and high resolution transmission electron microscopy. The obtained V{sub 2}O{sub 5} possesses a single-crystalline structure with a preferred orientation along the [0 1 0] crystal plane. Electrochemical analysis shows that the specific discharge capacity of the V{sub 2}O{sub 5} nanobelt clusters reaches 134 mA h/g at a current density of 2 A/g coupled with good cycle stability.

Polyatomic ions in inductively coupled plasma-mass spectrometry

International Nuclear Information System (INIS)

Ferguson, Jill Wisnewski; Dudley, Timothy J.; Sears, Kyle C.; McIntyre, Sally M.; Gordon, Mark S.; Houk, R.S.

2009-01-01

Several polyatomic ions in inductively coupled plasma-mass spectrometry are studied experimentally and by computational methods. Novel calculations based on spin-restricted open shell second order perturbation theory (ZAPT2) and coupled cluster (CCSD(T)) theory are performed to determine the energies, structures and partition functions of the ions. These values are combined with experimental data to evaluate a dissociation constant and gas kinetic temperature (T gas ) value. In our opinion, the resulting T gas value can sometimes be interpreted to deduce the location where the polyatomic ion of interest is generated. The dissociation of N 2 H + to N 2 + leads to a calculated T gas of 4550 to 4900 K, depending on the computational data used. The COH + to CO + system yields a similar temperature, which is not surprising considering the similar energies and structures of COH + and N 2 H + . The dissociation of H 2 CO + to HCO + leads to a much lower T gas ( 2 COH + to HCOH + generates a T gas value between those from the other H x CO + ions studied here. All of these measured T gas values correspond to formation of extra polyatomic ion in the interface or extraction region. The computations reveal the existence of isomers such as HCO + and COH + , and H 2 CO + and HCOH + , which have virtually the same m/z values and need to be considered in the interpretation of results.

Fourier transform ion cyclotron resonance mass spectrometry

Science.gov (United States)

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.

Properties of an ionised-cluster beam from a vaporised-cluster ion source

International Nuclear Information System (INIS)

Takagi, T.; Yamada, I.; Sasaki, A.

1978-01-01

A new type of ion source vaporised-metal cluster ion source, has been developed for deposition and epitaxy. A cluster consisting of 10 2 to 10 3 atoms coupled loosely together is formed by adiabatic expansion ejecting the vapour of materials into a high-vacuum region through the nozzle of a heated crucible. The clusters are ionised by electron bombardment and accelerated with neutral clusters toward a substrate. In this paper, mechanisms of cluster formation experimental results of the cluster size (atoms/cluster) and its distribution, and characteristics of the cluster ion beams are reported. The size is calculated from the kinetic equation E = (1/2)mNVsub(ej) 2 , where E is the cluster beam energy, Vsub(ej) is the ejection velocity, m is the mass of atom and N is the cluster size. The energy and the velocity of the cluster are measured by an electrostatic 127 0 energy analyser and a rotating disc system, respectively. The cluster size obtained for Ag is about 5 x 10 2 to 2 x 10 3 atoms. The retarding potential method is used to confirm the results for Ag. The same dependence on cluster size for metals such as Ag, Cu and Pb has been obtained in previous experiments. In the cluster state the cluster ion beam is easily produced by electron bombardment. About 50% of ionised clusters are obtained under typical operation conditions, because of the large ionisation cross sections of the clusters. To obtain a uniform spatial distribution, the ionising electrode system is also discussed. The new techniques are termed ionised-cluster beam deposition (ICBD) and epitaxy (ICBE). (author)

High Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) for Mass Spectrometry-Based Proteomics

Science.gov (United States)

Swearingen, Kristian E.; Moritz, Robert L.

2013-01-01

SUMMARY High field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, we review recent developments in LC-FAIMS-MS and its application to MS-based proteomics. PMID:23194268

Experimental investigations of hydrogen cluster ions

International Nuclear Information System (INIS)

Lumig, H.A. van.

1978-01-01

Experiments to obtain information about the structure and stability of small hydrogen cluster ions have been performed. Attenuation and fragmentation measurements are presented of hydrogen cluster ions colliding with nitrogen, argon, hydrogen and helium over fixed energy ranges. The total collision and differential fragmentation cross sections are tabulated. (C.F.)

Alpha spectrometry and the secondary ion mass spectrometry of thorium

International Nuclear Information System (INIS)

Strisovska, J.; Kuruc, J.; Galanda, D.; Matel, L.; Aranyosiova, M.; Velic, D.

2009-01-01

The main objective of this master thesis was preparation of samples with thorium content on the steel discs by electrodeposition for determination of natural thorium isotope by alpha spectrometry and the secondary ion mass spectrometry and finding out their possible linear correlation between these methods. The samples with electrolytically excluded isotope of 232 Th were prepared by electrodeposition from solution Th(NO 3 ) 4 ·12 H2 O on steel discs in electrodeposition cell with use of solutions Na 2 SO 4 , NaHSO 4 , KOH and (NH 4 ) 2 (C 2 O 4 ) by electric current 0.75 A. Discs were measured by alpha spectrometer. Activity was calculated from the registered impulses for 232 Th and surface's weight. After alpha spectrometry measurements discs were analyzed by TOF-SIMS IV which is installed in the International Laser Centre in Bratislava. Intensities of isotope of 232 Th and ions of ThO + , ThOH + , ThO 2 H + , Th 2 O 4 H + , ThO 2 - , ThO 3 H - , ThH 3 O 3 - and ThN 2 O 5 H - were identified. The linear correlation is between surface's weights of Th and intensities of ions of Th + from SIMS, however the correlation coefficient has relatively low value. We found out with SIMS method that oxidized and hydride forms of thorium are significantly represented in samples with electroplated thorium. (authors)

Some properties of ion and cluster plasma

International Nuclear Information System (INIS)

Gudzenko, L.I.; Derzhiev, V.I.; Yakovlenko, S.I.

1982-01-01

The aggregate of problems connected with the physics of ion and cluster plasma is qualitatively considered. Such a plasma can exist when a dense gas is ionized by a hard ionizer. The conditions for the formation of an ion plasma and the difference between its characteristics and those of an ordinary electron plasma are discussed; a solvated-ion model and the distribution of the clusters with respect to the number of solvated molecules are considered. The recombination rate of the positively and negatively charged clusters is roughly estimated. The parameters of a ball-lightning plasma are estimated on the basis of the cluster model

Ion detection in mass spectrometry

International Nuclear Information System (INIS)

Bolbach, Gerard

2016-03-01

This course aims at providing some elements for a better understanding of ion detectors used in mass spectrometers, of their operations, and of their limitations. A first part addresses the functions and properties of an ideal detector, how to detect ions in gas phase, and particle detectors and ion detectors used in mass spectrometry. The second part proposes an overview of currently used detectors with respect to their operation principle: detection from the ion charge (Faraday cylinder), detection by inductive effects (FTICR, Fourier Transform Ion Cyclotron Resonance), and detection by secondary electron emission. The third part discusses the specificities of secondary electron emission. The fourth one addresses operating modes and parameters related to detectors. The sixth part proposes a prospective view on future detectors by addressing the following issues: cryo-detector, inductive effect and charge detectors, ion detection and nano materials

Properties of clusters in the gas phase: V. Complexes of neutral molecules onto negative ions

International Nuclear Information System (INIS)

Keesee, R.G.; Lee, N.; Castleman, A.W. Jr.

1980-01-01

Ion--molecules association reactions of the form A - (B)/sub n1/-+B=A - (B)/sub n/ were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl - , I - , and NO 2 - with n ranging from one to three or four, and onto SO 2 - and SO 3 - with n equal to one; and (2) carbon dioxide onto Cl - , I - , NO 2 - , CO 3 - , and SO 3 - with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions. For any given ion, the relative order of the addition enthalpies among the neutrals was found to be dependent on the polarizabilities of the neutrals and on the covalency in the ion-neutral bond. Dispersion of charge via covalent bonding was found to affect significantly the succeeding clustering steps

Ion emission in solids bombarded with Aun+ (n = 1 - 9) clusters accelerated within the 0.15 - 1.25 MeV energy range

International Nuclear Information System (INIS)

Wehbe, Nimer

2006-06-01

This experimental work is devoted to the study of the ion emission in solids at the impact of gold clusters of energies within 0.15 to 1.25 MeV range. The physics of ion-solid collisions and the theoretical models of sputtering of solids under ion bombardment are presented in the first chapter. The chapter no. 2 deals with the description of the experimental setup. The study of a gold target allowed to evidence the role of the size and energy of the clusters in determining the emission intensity and the mass distribution of the ions. The 4. chapter gives results from the study of cesium iodide in which the intense emission of CsI clusters could be investigated quantitatively due to multiplicity measurements. Finally, the chapter no. 5 was devoted to the study of a biologic molecule, the phenylalanine, and of a pesticide molecule, chlorosulfuron. This work evidenced the importance of clusters for surface analyses by mass spectrometry

Symposium on fast atom and ion induced mass spectrometry of nonvolatile organic solids

International Nuclear Information System (INIS)

McNeal, C.J.

1982-01-01

The mechanisms of molecular and fragment ion production and the various parameters affecting ion yields were discussed by 6 invited speakers from Europe, Canada, and the US at this symposium. The work reported was almost equally divided between that using low-energy (keV) primary ion (or atom) beams, e.g. fast atom bombardment mass spectrometry (FABMS) and secondary ion mass spectrometry (SIMS) and that using high energy (MeV) particles, e.g. heavy ion induced mass spectrometry (HIIDMS) and 252 Cf-plasma desorption mass spectrometry ( 252 Cf-PDMS). Both theoretical foundations and observed experimental results for both techniques are included

Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

DEFF Research Database (Denmark)

Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka

2017-01-01

Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identi......Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could...... be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for Me......V Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples...

Control of cluster ion sizes for efficient injection heating

International Nuclear Information System (INIS)

Enjoji, Hiroshi; Be, S.H.; Yano, Katsuki; Okamoto, Kosuke

1976-01-01

For heating of plasmas by injection of hydrogen cluster ions, the specific size (N/Z) approximately 10 2 molecules/charge is believed to be most desirable. A fundamental research to develop a practical method for tailoring large cluster ions into small suitable sizes has been carried out by using nitrogen cluster ions of the initial mean specific size (N/Z) 0 approximately 10 5 . The beam of neutral large clusters of total intensity 20 mAsub(eq) was led to an ionizer and then the large cluster ions are accelerated to 8.9 keV before entering the divider which disintegrates them into small fragments by multiple ionization. The mean specific size of disintegrated cluster ions (N/Z)' becomes smaller with increase in ionizing electron current of the divider. (N/Z)' becomes 10 3 approximately 10 4 at an electron current of 140 mA and an accelerating voltage of 680 V of the divider with its efficiency of 20 approximately 60%. Thus, the original large cluster ions are divided into small fragments of which the mean specific size is 1/20 approximately 1/100 of the initial value without much decrease in total intensity of the cluster ion beam

Radiocarbon positive-ion mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Freeman, Stewart P.H.T.; Shanks, Richard P. [Scottish Universities Environmental Research Centre (SUERC), Scottish Enterprise Technology Park, East Kilbride G75 0QF (United Kingdom); Donzel, Xavier; Gaubert, Gabriel [Pantechnik S.A., 13 Rue de la Résistance, 14400 Bayeux (France)

2015-10-15

Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

Radiocarbon positive-ion mass spectrometry

International Nuclear Information System (INIS)

Freeman, Stewart P.H.T.; Shanks, Richard P.; Donzel, Xavier; Gaubert, Gabriel

2015-01-01

Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

Ion beam induced nanosized Ag metal clusters in glass

International Nuclear Information System (INIS)

Mahnke, H.-E.; Schattat, B.; Schubert-Bischoff, P.; Novakovic, N.

2006-01-01

Silver metal clusters have been formed in soda lime glass by high-energy heavy-ion irradiation at ISL. The metal cluster formation was detected with X-ray absorption spectroscopy (EXAFS) in fluorescence mode, and the shape of the clusters was imaged with transmission electron microscopy. While annealing in reducing atmosphere alone, leads to the formation of metal clusters in Ag-containing glasses, where the Ag was introduced by ion-exchange, such clusters are not very uniform in size and are randomly distributed over the Ag-containing glass volume. Irradiation with 600-MeV Au ions followed by annealing, however, results in clusters more uniform in size and arranged in chains parallel to the direction of the ion beam

Dynamic Secondary Ion Mass Spectrometry | Materials Science | NREL

Science.gov (United States)

Ion Mass Spectrometry (SIMS) uses a continuous, focused beam of primary ions to remove material from the surface of a sample by sputtering. The fraction of sputtered material that is ionized is extracted Identifies all elements or isotopes present in a material, from hydrogen to uranium. Different primary-ion

Reference masses for precision mass spectrometry design and implementation of a Pierce geometry to the cluster Ion source at ISOLTRAP

CERN Document Server

Lommen, Jonathan

At the mass spectrometer ISOLTRAP carbon clusters ($^{12}$Cn, 1$\\leqslant$n$\\leqslant$25) are provided as reference masses, which are of particular importance in higher mass ranges (m $\\geqslant$ 200u). In this mass range the measurlment uncertainty is increasingly dominated by the difference of the reference mass and the mass of the ion of interest. Using carbon clusters instead of the common $^{133}$Cs ions, this difference decreases. The carbon clusters are produced in a laser ion source which has been improved in the frame of this thesis. The fluctuations of the count rate have been investigated as a function of the laser energy. Furthermore, the energy density at the target has been increased by implementation of a telescope into the laser beam line, which leads to a more narrow energy distribution of the ions. Through the exact adjustment of timing and length of a pulsed cavity an energy range with constant count rate could be selected. In order to provide ideal starting conditions during and after the ...

Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

2017-01-01

Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

Desalting Protein Ions in Native Mass Spectrometry Using Supercharging Reagents

Science.gov (United States)

Cassou, Catherine A.; Williams, Evan R.

2014-01-01

Effects of the supercharging reagents m-NBA and sulfolane on sodium ion adduction to protein ions formed using native mass spectrometry were investigated. There is extensive sodium adduction on protein ions formed by electrospray ionization from aqueous solutions containing millimolar concentrations of NaCl, which can lower sensitivity by distributing the signal of a given charge state over multiple adducted ions and can reduce mass measuring accuracy for large proteins and non-covalent complexes for which individual adducts cannot be resolved. The average number of sodium ions adducted to the most abundant ion formed from ten small (8.6–29 kDa) proteins for which adducts can be resolved is reduced by 58% or 80% on average, respectively, when 1.5% m-NBA or 2.5% sulfolane are added to aqueous solutions containing sodium compared to without the supercharging reagent. Sulfolane is more effective than m-NBA at reducing sodium ion adduction and at preserving non-covalent protein-ligand and protein-protein interactions. Desalting with 2.5% sulfolane enables detection of several glycosylated forms of 79.7 kDa holo-transferrin and NADH bound to the 146 kDa homotetramer LDH, which are otherwise unresolved due to peak broadening from extensive sodium adduction. Although sulfolane is more effective than m-NBA at protein ion desalting, m-NBA reduces salt clusters at high m/z and can increase the signal-to-noise ratios of protein ions by reducing chemical noise. Desalting is likely a result of these supercharging reagents binding sodium ions in solution, thereby reducing the sodium available to adduct to protein ions. PMID:25133273

Identification of multiply charged proteins and amino acid clusters by liquid nitrogen assisted spray ionization mass spectrometry.

Science.gov (United States)

Kumar Kailasa, Suresh; Hasan, Nazim; Wu, Hui-Fen

2012-08-15

The development of liquid nitrogen assisted spray ionization mass spectrometry (LNASI MS) for the analysis of multiply charged proteins (insulin, ubiquitin, cytochrome c, α-lactalbumin, myoglobin and BSA), peptides (glutathione, HW6, angiotensin-II and valinomycin) and amino acid (arginine) clusters is described. The charged droplets are formed by liquid nitrogen assisted sample spray through a stainless steel nebulizer and transported into mass analyzer for the identification of multiply charged protein ions. The effects of acids and modifier volumes for the efficient ionization of the above analytes in LNASI MS were carefully investigated. Multiply charged proteins and amino acid clusters were effectively identified by LNASI MS. The present approach can effectively detect the multiply charged states of cytochrome c at 400 nM. A comparison between LNASI and ESI, CSI, SSI and V-EASI methods on instrumental conditions, applied temperature and observed charge states for the multiply charged proteins, shows that the LNASI method produces the good quality spectra of amino acid clusters at ambient conditions without applied any electric field and heat. To date, we believe that the LNASI method is the most simple, low cost and provided an alternative paradigm for production of multiply charged ions by LNASI MS, just as ESI-like ions yet no need for applying any electrical field and it could be operated at low temperature for generation of highly charged protein/peptide ions. Copyright © 2012 Elsevier B.V. All rights reserved.

Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry

International Nuclear Information System (INIS)

Laskin, Julia; Futrell, Jean H.

2003-01-01

In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

'Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry'

International Nuclear Information System (INIS)

Laskin, Julia; Futrell, Jean H.

2003-01-01

In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

Formation of positive cluster ions Li(n) Br (n = 2-7) and ionization energies studied by thermal ionization mass spectrometry.

Science.gov (United States)

Veličković, S R; Đustebek, J B; Veljković, F M; Veljković, M V

2012-05-01

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications. Copyright © 2012 John Wiley & Sons, Ltd.

Comprehensive biothreat cluster identification by PCR/electrospray-ionization mass spectrometry.

Directory of Open Access Journals (Sweden)

Rangarajan Sampath

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

Chemical composition of waterfall-induced air ions: Spectrometry vs. simulations

Energy Technology Data Exchange (ETDEWEB)

Parts, T.-E.; Luts, A. [Tartu Univ. (Estonia). Dept. of Environmental Physics; Laakso, L.; Hirsikko, A.; Groenholm, T.; Kulmala, M. [Helsinki Univ. (Finland). Dept. of Physical Sciences

2007-07-01

Our measurements of ion size distributions near a waterfall provided new evidence for a waterfall-induced modification of air ion sizes. The ion size spectrum near a waterfall permanently differs from that in ordinary tropospheric air. In this paper we investigated the near-waterfall air ions chemical nature in detail. We carried out a simulation series of air small negative ion evolution, proposing that falling water, as a new environmental component, increases the concentration of OH{sup -} cluster ions. The produced OH{sup -} ions were employed as an extra input for our ion evolution model. The presence of additional OH{sup -} ions resulted in a decrease of typically model-provided NO{sub 3}{sup -} and/or HSO{sub 4}{sup -} cluster ion concentrations and an increase of the abundance of HCO{sub 3}{sup -} cluster ions. Near the waterfall the latter ions became dominant in our simulations. (orig.)

Solvent Composition-Dependent Signal-Reduction of Molecular Ions Generated from Aromatic Compounds in (+) Atmospheric Pressure Photo Ionization Mass Spectrometry.

Science.gov (United States)

Lee, Seulgidaun; Ahmed, Arif; Kim, Sunghwan

2018-03-30

The ionization process is essential for successful mass spectrometry (MS) analysis because of its influence on selectivity and sensitivity. In particular, certain solvents reduce the ionization of the analyte, thereby reducing the overall sensitivity in APPI. Since the sensitivity varies greatly depending on the solvents, a fundamental understanding of the mechanism is required. Standard solutions were analyzed by (+) Atmospheric pressure photo ionization (APPI) QExactive ion trap mass spectrometer (Thermo Scientific). Each solution was infused directly to the APPI source at a flow rate 100 μl/min and the APPI source temperature was 300 °C. Other operating mass spectrometric parameters were maintained under the same conditions. Quantum mechanical calculations were carried out using the Gaussian 09 suite program. Density functional theory was used to calculate the reaction enthalpies (∆H) of reaction between toluene and other solvents. The experimental and theoretical results showed good agreement. The abundances of analyte ions were well correlated with the calculated ∆H values. Therefore, the results strongly support the suggested signal reduction mechanism. In addition, linear correlations between the abundance of toluene and analyte molecular ions were observed, which also supports the suggested mechanism. A solvent composition-dependent signal reduction mechanism was suggested and evaluated for the (+) atmospheric pressure photo ionization (APPI) mass spectrometry analysis of poly-aromatic hydrocarbons (PAHs) generating mainly molecular ions. Overall, the evidence provided in this work suggests that reactions between solvent cluster(s) and toluene molecular ions are responsible for the observed signal reductions. This article is protected by copyright. All rights reserved.

Behaviour of tetraalkylammonium ions in high-field asymmetric waveform ion mobility spectrometry.

Science.gov (United States)

Aksenov, Alexander A; Kapron, James T

2010-05-30

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an ion-filtering technique recently adapted for use with liquid chromatography/mass spectrometry (LC/MS) to remove interferences during analysis of complex matrices. This is the first systematic study of a series of singly charged tetraalkylammonium ions by FAIMS-MS. The compensation voltage (CV) is the DC offset of the waveform which permits the ion to emerge from FAIMS and it was determined for each member of the series under various conditions. The electrospray ionization conditions explored included spray voltage, vaporizer temperature, and sheath and auxiliary gas pressure. The FAIMS conditions explored included carrier gas flow rate, electrode temperature and composition of the carrier gas. Optimum desolvation was achieved using sufficient carrier gas (flow rate > or = 2 L/min) to ensure stable response. Low-mass ions (m/z 100-200) are more susceptible to changes in electrode temperature and gas composition than high mass ions (m/z 200-700). As a result of this study, ions are reliably analyzed using standard FAIMS conditions (dispersion voltage -5000 V, carrier gas flow rate 3 L/min, 50% helium/50%nitrogen, inner electrode temperature 70 degrees C and outer electrode temperature 90 degrees C). Variation of FAIMS conditions may be of great use for the separation of very low mass tetraalkylammonium (TAA) ions from other TAA ions. The FAIMS conditions do not appear to have a major effect on higher mass ions. Copyright 2010 John Wiley & Sons, Ltd.

Impact of slow gold clusters on various solids

International Nuclear Information System (INIS)

Benguerba, M.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Joret, H.; Beyec, Y. Le; Schweikert, E.A.; Assayag, G.B.; Sudraud, P.

1991-01-01

A liquid metal ion source has been installed on a pulsed ion gun. The time of flight (TOF) spectra of the pulsed beam were recorded. With the gold source several cluster ions (up to 10 atoms in the cluster) and doubly charged ions were identified in the ion beam TOF spectra. With a second pulsation, single cluster ions can be selected as projectiles for secondary ion TOF mass spectrometry. The secondary ion emission induced by cluster impact from a variety of targets (organic, CsI, metallic) was studied. A large enhancement of yield is observed by comparison to single atomic ion impact (e.g., a factor of 30 between Au 3 + and Au + ). The secondary ion yields increase nonlinearly with the number of constituents in the cluster. A comparison with other types of clusters and also fission fragments of 252 Cf has been performed. The rate of secondary emission stimulated by cluster is similar to the secondary ion yield induced by fission fragments. (author) 47 refs., 18 figs., 5 tabs

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

Science.gov (United States)

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.

Ion mobility spectrometry–mass spectrometry studies of ion processes in air at atmospheric pressure and their application to thermal desorption of 2,4,6-trinitrotoluene

International Nuclear Information System (INIS)

Sabo, Martin; Malásková, Michaela; Matejčík, Štefan

2014-01-01

In this study we have investigated the negative reactant ion formation in a negative corona discharge (CD) using the corona discharge ion mobility spectrometry orthogonal acceleration time-of-flight (CD-IMS-oaTOF) technique. The reactant ions were formed in the CD operating in the reverse gas flow mode at an elevated temperature of 363.5 K in synthetic and ambient air. Under these conditions mainly O 2 − and their clusters were formed. We have also studied the influence of CCl 4 admixture to air (dopant gas) on the composition of the reactant ions, which resulted in the formation of Cl − and its clusters with a reduced ion mobility of 3.05 cm 2  V −1  s −1 as a major reactant ion peak. Additional IMS peaks with reduced ion mobilities of 2.49, 2.25 and 2.03 cm 2  V −1  s −1 were detected, and Cl −  · (NO 2 ) and Cl −  · (NO) n (n = 2, 3) anions were identified. The negative reactant ions were used to detect 2,4,6 trinitrotoluene (TNT) using the thermal desorption (TD) technique using a CD-IMS instrument. Using TD sampling and a negative CD ion source doped by CCl 4 we have achieved a limit of detection of 350 pg for direct surface analysis of TNT. (paper)

METI/NEDO Projects on Cluster Ion Beam Process Technology

International Nuclear Information System (INIS)

Yamada, Isao; Matsuo, Jiro; Toyoda, Noriaki

2003-01-01

Since the initial study of gas cluster ion beams (GCIB) was started in the Ion Beam Engineering Experimental Laboratory of Kyoto University, more than 15 years have passed. Some of the results of that study have already been applied for industrial use. Unique characteristics of gas cluster ion bombardment have been found to offer potential for various other industrial applications. The impact of an accelerated cluster ion upon a target surface imparts very high energy densities into the impact area and produces non-linear effects that are not associated with the impacts of atomic ions. Among prospective applications for these effects are included shallow ion implantation, high rate sputtering, surface cleaning and smoothing, and low temperature thin film formation

Separation of different ion structures in atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS).

Science.gov (United States)

Laakia, Jaakko; Adamov, Alexey; Jussila, Matti; Pedersen, Christian S; Sysoev, Alexey A; Kotiaho, Tapio

2010-09-01

This study demonstrates how positive ion atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS) can be used to produce different ionic forms of an analyte and how these can be separated. When hexane:toluene (9:1) is used as a solvent, 2,6-di-tert-butylpyridine (2,6-DtBPyr) and 2,6-di-tert-4-methylpyridine (2,6-DtB-4-MPyr) efficiently produce radical cations [M](+*) and protonated [M + H](+) molecules, whereas, when the sample solvent is hexane, protonated molecules are mainly formed. Interestingly, radical cations drift slower in the drift tube than the protonated molecules. It was observed that an oxygen adduct ion, [M + O(2)](+*), which was clearly seen in the mass spectra for hexane:toluene (9:1) solutions, shares the same mobility with radical cations, [M](+*). Therefore, the observed mobility order is most likely explained by oxygen adduct formation, i.e., the radical cation forming a heavier adduct. For pyridine and 2-tert-butylpyridine, only protonated molecules could be efficiently formed in the conditions used. For 1- and 2-naphthol it was observed that in hexane the protonated molecule typically had a higher intensity than the radical cation, whereas in hexane:toluene (9:1) the radical cation [M](+*) typically had a higher intensity than the protonated molecule [M + H](+). Interestingly, the latter drifts slower than the radical cation [M](+*), which is the opposite of the drift pattern seen for 2,6-DtBPyr and 2,6-DtB-4-MPyr. 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Solar wind dependence of ion parameters in the Earth's magnetospheric region calculated from CLUSTER observations

Directory of Open Access Journals (Sweden)

M. H. Denton

2008-03-01

Full Text Available Moments calculated from the ion distributions (~0–40 keV measured by the Cluster Ion Spectrometry (CIS instrument are combined with data from the Cluster Flux Gate Magnetometer (FGM instrument and used to characterise the bulk properties of the plasma in the near-Earth magnetosphere over five years (2001–2005. Results are presented in the form of 2-D xy, xz and yz GSM cuts through the magnetosphere using data obtained from the Cluster Science Data System (CSDS and the Cluster Active Archive (CAA. Analysis reveals the distribution of ~0–40 keV ions in the inner magnetosphere is highly ordered and highly responsive to changes in solar wind velocity. Specifically, elevations in temperature are found to occur across the entire nightside plasma sheet region during times of fast solar wind. We demonstrate that the nightside plasma sheet ion temperature at a downtail distance of ~12 to 19 Earth radii increases by a factor of ~2 during periods of fast solar wind (500–1000 km s⁻¹ compared to periods of slow solar wind (100–400 km s⁻¹. The spatial extent of these increases are shown in the xy, xz and yz GSM planes. The results from the study have implications for modelling studies and simulations of solar-wind/magnetosphere coupling, which ultimately rely on in situ observations of the plasma sheet properties for input/boundary conditions.

High resolution spectrometry for relativistic heavy ions

Energy Technology Data Exchange (ETDEWEB)

Gabor, G; Schimmerling, W; Greiner, D; Bieser, F; Lindstrom, P [California Univ., Berkeley (USA). Lawrence Berkeley Lab.

1975-12-01

Several techniques are discussed for velocity and energy spectrometry of relativistic heavy ions with good resolution. A foil telescope with chevron channel plate detectors is described. A test of this telescope was performed using 2.1 GeV/A C/sup 6 +/ ions, and a time-of-flight resolution of 160 ps was measured. Qualitative information on the effect of foil thickness was also obtained.

Gold chloride clusters with Au(III) and Au(I) probed by FT-ICR mass spectrometry and MP2 theory.

Science.gov (United States)

Lemke, Kono H

2014-05-07

Microsolvated clusters of gold chloride are probed by electrospray ionization mass spectrometry (ESI-MS) and scalar relativistic electronic structure calculations. Electrospray ionization of aqueous AuCl3 leads to mononuclear clusters of types [AuCl2](+)(H2O)n (n = 0-4), [AuOHCl](+)(H2O)n (n = 0-1) and [AuCl2](+)(HCl)2(H2O)n (n = 0-4). In addition, strong ion signals due to dinuclear [Au2Cl5-xOHx](+)(H2O)n (x = 0-1) are present in ESI mass spectra of aqueous AuCl3, with the abundance of individual dinuclear species controlled by the concentration-dependent variation of the precursor complexes [AuCl2-xOHx](+)(H2O)n and AuCl3. Equilibrium structures, energies and thermodynamic properties of mono- and dinuclear gold clusters have been predicted using MP2 and CCSD(T) theory, and these data have been applied to examine the influence of microsolvation on cluster stability. Specifically, results from CCSD(T) calculations indicate that non-covalently bound ion-neutral complexes Au(+)(Cl2)(H2O)n, with formal Au(I), are the dominant forms of mononuclear gold with n = 0-2, while higher hydrates (n > 2) are covalently bound [AuCl2](+)(H2O)n complexes in which gold exists as Au(III). MP2 calculations show that the lowest energy structure of dinuclear gold is an ion-molecule cluster [Au2Cl(Cl2)2](+) consisting of a single-bridged digold-chloronium ion bound end-on to two dichlorine ligands, with two higher energy isomers, single-bridged [Au2Cl3(Cl2)](+) and double-bridged [Au2Cl5](+) clusters. Finally, AuAu interactions in the singly-bridged clusters [Au2Cl(Cl2)2](+)(H2O)n and [Au2Cl3(Cl2)](+)(H2O)n are examined employing a wide range of computational tools, including natural bond order (NBO) analysis and localized orbital locator (LOL) profiles.

Indium tin oxide surface smoothing by gas cluster ion beam

CERN Document Server

Song, J H; Choi, W K

2002-01-01

CO sub 2 cluster ions are irradiated at the acceleration voltage of 25 kV to remove hillocks on indium tin oxide (ITO) surfaces and thus to attain highly smooth surfaces. CO sub 2 monomer ions are also bombarded on the ITO surfaces at the same acceleration voltage to compare sputtering phenomena. From the atomic force microscope results, the irradiation of monomer ions makes the hillocks sharper and the surfaces rougher from 1.31 to 1.6 nm in roughness. On the other hand, the irradiation of CO sub 2 cluster ions reduces the height of hillocks and planarize the ITO surfaces as smooth as 0.92 nm in roughness. This discrepancy could be explained by large lateral sputtering yield of the cluster ions and re-deposition of sputtered particles by the impact of the cluster ions on surfaces.

Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams.

Science.gov (United States)

Shon, Hyun Kyong; Yoon, Sohee; Moon, Jeong Hee; Lee, Tae Geol

2016-06-09

The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration.

Cluster ion-surface interactions: from meV to MeV energies

Energy Technology Data Exchange (ETDEWEB)

Nordlund, Kai; Meinander, Kristoffer; Jaervi, Tommi T.; Peltola, Jarkko; Samela, Juha [Accelerator Laboratory, University of Helsinki (Finland)

2008-07-01

The nature of cluster ion-surface interactions changes dramatically with the kinetic energy of the incoming cluster species. In this talk I review some of our recent work on the nature of cluster-surface interactions spanning an energy range from a few MeV/cluster to about 1 MeV/cluster and cluster sizes in the range of 10 - 1000 atoms/cluster. In the energy range of a few MeV/cluster ion, the kinetic energy of the incoming ion is insignificant compared to the energy gained when the surface potential energy at the cluster-surface interface is released and partly translated into kinetic energy. Even in this energy regime I show that surprisingly drastic effects can occur. When the energy of the incoming cluster is raised to a few eV/atom, the kinetic energy of the incoming cluster starts to affect the deposition. It will cause the cluster to entirely reform on impact. When the energy is raised to the range of keV's/cluster, the clusters start to penetrate the sample, fairly similar to conventional ion implantation. However, in dense targets the cluster ions may stick close to each other long enough to cause a significant enhancement of the heat spike in the material. Finally, I show that at kinetic energies around 1 MeV/cluster the cluster enhancement of the heat spike may lead to dramatic surface effects.

Ion clusters, REB, and current sheath characteristics in focused discharges

International Nuclear Information System (INIS)

Bortolotti, A.; Brzosko, J.; DeChiara, P.; Kilic, H.; Mezzetti, F.; Nardi, V.; Powell, C.; Zeng, D.

1990-01-01

Small fluctuations in the current sheath characteristics (peak current density, FWHM of leading sheath, control parameters of sheath internal structure) are linked to wide fluctuations of ion and ion cluster emission from the pinch. Magnetic probe data are used for correlating variations of current sheath parameters with particle emission intensity, Z/M composition, particle energy spectrum. The emission of ion and ion clusters at 90 degrees from the axis of a plasma focus discharge is monitored simultaneously with the 0 degrees emission. The particle energy spectrum is analyzed with a Thomson (parabola) spectrometer (time resolution ∼ 1 nanosec). The cross-sectional structure of the REB at 180 degrees along the discharge axis is monitored via the deposition of collective-field accelerated ions on a target in the REB direction. Etched tracks of ion and ion clusters are in all cases recorded on CR-39 plates. Sharp peaks of the D + -ion spectrum at 90 degrees are found for E > 200 keV/unit charge in all focused discharges. These peaks are due to ion crossing of the azimuthal magnetic field of the pinch region, in a predominant ion cluster structure

Mercury-induced fragmentation of n-decane and n-undecane in positive mode ion mobility spectrometry.

Science.gov (United States)

Gunzer, F

2015-09-21

Ion mobility spectrometry is a well-known technique for trace gas analysis. Using soft ionization techniques, fragmentation of analytes is normally not observed, with the consequence that analyte spectra of single substances are quite simple, i.e. showing in general only one peak. If the concentration is high enough, an extra cluster peak involving two analyte molecules can often be observed. When investigating n-alkanes, different results regarding the number of peaks in the spectra have been obtained in the past using this spectrometric technique. Here we present results obtained when analyzing n-alkanes (n-hexane to n-undecane) with a pulsed electron source, which show no fragmentation or clustering at all. However, when investigating a mixture of mercury and an n-alkane, a situation quite typical in the oil and gas industry, a strong fragmentation and cluster formation involving these fragments has been observed exclusively for n-decane and n-undecane.

Influence of residual Ar+ in Ar cluster ion beam for DLC film formation

International Nuclear Information System (INIS)

Kitagawa, Teruyuki; Miyauchi, Kazuya; Toyoda, Noriaki; Kanda, Kazuhiro; Ikeda, Tokumi; Tsubakino, Harushige; Matsuo, Jiro; Matsui, Shinji; Yamada, Isao

2003-01-01

In order to study the influences of residual Ar monomer ion (Ar + ) on sp 2 content and hardness of diamond like carbon (DLC) films formed by Ar cluster ion beam assisted deposition, Ar cluster ion, Ar + and their mixed ions (Ar cluster ion and Ar + ) bombardments were performed during evaporation of C 60 . From near edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopy measurements, lower sp 2 content in the carbon films was obtained with Ar cluster ion bombardment than that with Ar + and mixed ion. Furthermore higher hardness and smooth surface were shown with Ar cluster ion bombardments. Therefore it was important to reduce Ar + in Ar cluster ion beams to obtain hard DLC films with flat surface

Automated correlation and classification of secondary ion mass spectrometry images using a k-means cluster method.

Science.gov (United States)

Konicek, Andrew R; Lefman, Jonathan; Szakal, Christopher

2012-08-07

We present a novel method for correlating and classifying ion-specific time-of-flight secondary ion mass spectrometry (ToF-SIMS) images within a multispectral dataset by grouping images with similar pixel intensity distributions. Binary centroid images are created by employing a k-means-based custom algorithm. Centroid images are compared to grayscale SIMS images using a newly developed correlation method that assigns the SIMS images to classes that have similar spatial (rather than spectral) patterns. Image features of both large and small spatial extent are identified without the need for image pre-processing, such as normalization or fixed-range mass-binning. A subsequent classification step tracks the class assignment of SIMS images over multiple iterations of increasing n classes per iteration, providing information about groups of images that have similar chemistry. Details are discussed while presenting data acquired with ToF-SIMS on a model sample of laser-printed inks. This approach can lead to the identification of distinct ion-specific chemistries for mass spectral imaging by ToF-SIMS, as well as matrix-assisted laser desorption ionization (MALDI), and desorption electrospray ionization (DESI).

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

Science.gov (United States)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

International Nuclear Information System (INIS)

Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

2008-01-01

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

Science.gov (United States)

Bischoff, J.L.; Wooden, J.; Murphy, F.; Williams, Ross W.

2005-01-01

We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ???60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few ??m deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems. Copyright ?? 2005 Elsevier Ltd.

Traveling-wave ion mobility mass spectrometry of protein complexes

DEFF Research Database (Denmark)

Salbo, Rune; Bush, Matthew F; Naver, Helle

2012-01-01

The collision cross-section (Ω) of a protein or protein complex ion can be measured using traveling-wave (T-wave) ion mobility (IM) mass spectrometry (MS) via calibration with compounds of known Ω. The T-wave Ω-values depend strongly on instrument parameters and calibrant selection. Optimization ...

Nonlinear damage effect in graphene synthesis by C-cluster ion implantation

International Nuclear Information System (INIS)

Zhang Rui; Zhang Zaodi; Wang Zesong; Wang Shixu; Wang Wei; Fu Dejun; Liu Jiarui

2012-01-01

We present few-layer graphene synthesis by negative carbon cluster ion implantation with C 1 , C 2 , and C 4 at energies below 20 keV. The small C-clusters were produced by a source of negative ion by cesium sputtering with medium beam current. We show that the nonlinear effect in cluster-induced damage is favorable for graphene precipitation compared with monomer carbon ions. The nonlinear damage effect in cluster ion implantation shows positive impact on disorder reduction, film uniformity, and the surface smoothness in graphene synthesis.

New experiments in organic, fast-atom-bomdardment, and secondary-ion mass spectrometry

International Nuclear Information System (INIS)

DiDonato, G.C.

1987-01-01

The goal of research presented in this dissertation is the creative use of new ionization and instrumental techniques in mass spectrometry. This goal manifests itself in three areas of mass spectrometry. In the first portion, modern, state-of-the-art instrumentation and new experiments were used to re-examine the mass spectra of transition-metal acetates and acetylacetonates. High resolution, chemical ionization, negative chemical ionization, and extended-mass-range mass spectrometry uncovered a wealth of new gas-phase ionic species. Energy-resolved mass spectrometry/mass spectrometry was applied to the characterization of molecular and fragment ion first-row transition-metal acetylacetonates, and comprises the second portion of the thesis. Studies in fast-atom-bombardment mass spectrometry are the subject of the third portion of the dissertation. Since fast-atom bombardment samples a liquid matrix, absolute and relative abundances of sputtered secondary ions are influenced by solution chemistry. The design and construction of an imaging secondary-ion mass spectrometer is the subject of the final portion of the thesis. This instrument provides for direct mass-spectrometric analysis of thin-layer and paper chromatograms and electrophoretograms

Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

Science.gov (United States)

Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka; Marković, Nikola; Anghelone, Marta; Stoytschew, Valentin; Jakšić, Milko

2017-09-01

Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples were not embedded in the resin as is usually done when imaging of paint samples using different techniques in the field of cultural heritage.

Method and apparatuses for ion cyclotron spectrometry

Science.gov (United States)

Dahl, David A [Idaho Falls, ID; Scott, Jill R [Idaho Falls, ID; McJunkin, Timothy R [Idaho Falls, ID

2012-03-06

An ion cyclotron spectrometer may include a vacuum chamber that extends at least along a z-axis and means for producing a magnetic field within the vacuum chamber so that a magnetic field vector is generally parallel to the z-axis. The ion cyclotron spectrometer may also include means for producing a trapping electric field within the vacuum chamber. The trapping electric field may comprise a field potential that, when taken in cross-section along the z-axis, includes at least one section that is concave down and at least one section that is concave up so that ions traversing the field potential experience a net magnetron effect on a cyclotron frequency of the ions that is substantially equal to zero. Other apparatuses and a method for performing ion cyclotron spectrometry are also disclosed herein.

Dependence of energy per molecule on sputtering yields with reactive gas cluster ions

International Nuclear Information System (INIS)

Toyoda, Noriaki; Yamada, Isao

2010-01-01

Gas cluster ions show dense energy deposition on a target surface, which result in the enhancement of chemical reactions. In reactive sputtering with gas cluster ions, the energy per atom or molecule plays an important role. In this study, the average cluster size (N, the number of atoms or molecules in a cluster ion) was controlled; thereby the dependences of the energy per molecule on the sputtering yields of carbon by CO 2 cluster ions and that of Si by SF 6 /Ar mixed gas cluster ions were investigated. Large CO 2 cluster ions with energy per molecule of 1 eV showed high reactive sputtering yield of an amorphous carbon film. However, these ions did not cause the formation of large craters on a graphite surface. It is possible to achieve very low damage etching by controlling the energy per molecule of reactive cluster ions. Further, in the case of SF 6 /Ar mixed cluster ions, it was found that reactive sputtering was enhanced when a small amount of SF 6 gas (∼10%) was mixed with Ar. The reactive sputtering yield of Si by one SF 6 molecule linearly increased with the energy per molecule.

Differentiating Fragmentation Pathways of Cholesterol by Two-Dimensional Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Science.gov (United States)

van Agthoven, Maria A; Barrow, Mark P; Chiron, Lionel; Coutouly, Marie-Aude; Kilgour, David; Wootton, Christopher A; Wei, Juan; Soulby, Andrew; Delsuc, Marc-André; Rolando, Christian; O'Connor, Peter B

2015-12-01

Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry is a data-independent analytical method that records the fragmentation patterns of all the compounds in a sample. This study shows the implementation of atmospheric pressure photoionization with two-dimensional (2D) Fourier transform ion cyclotron resonance mass spectrometry. In the resulting 2D mass spectrum, the fragmentation patterns of the radical and protonated species from cholesterol are differentiated. This study shows the use of fragment ion lines, precursor ion lines, and neutral loss lines in the 2D mass spectrum to determine fragmentation mechanisms of known compounds and to gain information on unknown ion species in the spectrum. In concert with high resolution mass spectrometry, 2D Fourier transform ion cyclotron resonance mass spectrometry can be a useful tool for the structural analysis of small molecules. Graphical Abstract ᅟ.

Comparison of secondary ion emission yields for poly-tyrosine between cluster and heavy ion impacts

International Nuclear Information System (INIS)

Hirata, K.; Saitoh, Y.; Chiba, A.; Yamada, K.; Takahashi, Y.; Narumi, K.

2010-01-01

Emission yields of secondary ions necessary for the identification of poly-tyrosine were compared for incident ion impacts of energetic cluster ions (0.8 MeV C 8 + , 2.4 MeV C 8 + , and 4.0 MeV C 8 + ) and swift heavy monoatomic molybdenum ions (4.0 MeV Mo + and 14 MeV Mo 4+ ) with similar mass to that of the cluster by time-of-flight secondary ion mass analysis combined with secondary ion electric current measurements. The comparison revealed that (1) secondary ion emission yields per C 8 + impact increase with increasing incident energy within the energy range examined, (2) the 4.0 MeV C 8 + impact provides higher emission yields than the impact of the monoatomic Mo ion with the same incident energy (4.0 MeV Mo + ), and (3) the 2.4 MeV C 8 + impact exhibits comparable emission yields to that for the Mo ion impact with higher incident energy (14 MeV Mo 4+ ). Energetic cluster ion impacts effectively produce the characteristic secondary ions for poly-tyrosine, which is advantageous for highly sensitive amino acid detection in proteins using time-of-flight secondary ion mass analysis.

Application of ion mobility-mass spectrometry to microRNA analysis.

Science.gov (United States)

Takebayashi, Kosuke; Hirose, Kenji; Izumi, Yoshihiro; Bamba, Takeshi; Fukusaki, Eiichiro

2013-03-01

Liquid chromatography/mass spectrometry is widely used for studying sequence determination and modification analysis of small RNAs. However, the efficiency of liquid chromatography-based separation of intact small RNA species is insufficient, since the physiochemical properties among small RNAs are very similar. In this study, we focused on ion mobility-mass spectrometry (IM-MS), which is a gas-phase separation technique coupled with mass spectrometry; we have evaluated the utility of IM-MS for microRNA (miRNA) analysis. A multiply charged deprotonated ion derived from an 18-24-nt-long miRNA was formed by electrospray ionization, and then the time, called the "drift time", taken by each ion to migrate through a buffer gas was measured. Each multivalent ion was temporally separated on the basis of the charge state and structural formation; 3 types of unique mass-mobility correlation patterns (i.e., chainlike-form, hairpin-form, and dimer-form) were present on the two-dimensional mobility-mass spectrum. Moreover, we found that the ion size (sequence length) and the secondary structures of the small RNAs strongly contributed to the IM-MS-based separation, although solvent conditions such as pH had no effect. Therefore, sequence isomers could also be discerned by the selection of each specific charged ion, i.e., the 6(-) charged ion reflected a majority among chainlike-, hairpin-, and other structures. We concluded that the IM-MS provides additional capability for separation; thus, this analytical method will be a powerful tool for comprehensive small RNA analysis. Copyright © 2012. Published by Elsevier B.V.

Irradiation effects of Ar cluster ion beams on Si substrates

International Nuclear Information System (INIS)

Ishii, Masahiro; Sugahara, Gaku; Takaoka, G.H.; Yamada, Isao

1993-01-01

Gas-cluster ion beams can be applied to new surface modification techniques such as surface cleaning, low damage sputtering and shallow junction formation. The effects of energetic Ar cluster impacts on solid surface were studied for cluster energies of 10-30keV. Irradiation effects were studied by RBS. For Si(111) substrates, irradiated with Ar ≥500 clusters to a dose of 1x10 15 ion/cm 2 at acceleration voltage 15kV, 2x10 14 atoms/cm 2 implanted Ar atoms were detected. In this case, the energy per cluster atom was smaller than 30eV; at this energy, no significant implantation occurs in the case of monomer ions. Ar cluster implantation into Si substrates occurred due to the high energy density irradiation. (author)

A study of defect cluster formation in vanadium by heavy ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Sekimura, Naoto; Shirao, Yasuyuki; Morishita, Kazunori [Tokyo Univ. (Japan)

1996-10-01

Formation of defect clusters in thin foils of vanadium was investigated by heavy ion irradiation. In the very thin region of the specimens less than 20 nm, vacancy clusters were formed under gold ion irradiation, while very few clusters were detected in the specimens irradiated with 200 and 400 keV self-ions up to 1 x 10{sup 16} ions/m{sup 2}. The density of vacancy clusters were found to be strongly dependent on ion energy. Only above the critical value of kinetic energy transfer density in vanadium, vacancy clusters are considered to be formed in the cascade damage from which interstitials can escape to the specimen surface in the very thin region. (author)

Cluster-assistant generation of multiply charged atomic ions in nanosecond laser ionization of seeded methyl iodide beam

International Nuclear Information System (INIS)

Luo Xiaolin; Niu Dongmei; Kong Xianglei; Wen Lihua; Liang Feng; Pei Kemei; Wang Bin; Li Haiyang

2005-01-01

The photoionization of methyl iodide beam seeded in argon and helium is studied by time-of-flight mass spectrometry using a 25 ns, 532 nm Nd-YAG laser with intensities in the range of 2 x 10 10 -2 x 10 11 W/cm 2 . Multiply charged ions of I q+ (q = 2-3) and C 2+ with tens of eV kinetic energies have been observed when laser interacts with the middle part of the pulsed molecular beam, whose peak profiles are independent on the laser polarization directions. Strong evidences show that these ions are coming from the Coulomb explosion of multiply charged CH 3 I clusters, and laser induced inverse bremsstrahlung absorption of caged electrons plays a key role in the formation of multiply charged ions

Ion mobility spectrometry-hydrogen deuterium exchange mass spectrometry of anions: part 1. Peptides to proteins.

Science.gov (United States)

Donohoe, Gregory C; Khakinejad, Mahdiar; Valentine, Stephen J

2015-04-01

Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

Microscope mode secondary ion mass spectrometry imaging with a Timepix detector.

NARCIS (Netherlands)

Kiss, A.; Jungmann, JH; Smith, D.F.; Heeren, R.M.A.

2013-01-01

In-vacuum active pixel detectors enable high sensitivity, highly parallel time- and space-resolved detection of ions from complex surfaces. For the first time, a Timepix detector assembly was combined with a secondary ion mass spectrometer for microscope mode secondary ion mass spectrometry (SIMS)

Diagrams of ion stability in radio-frequency mass spectrometry

International Nuclear Information System (INIS)

Sudakov, M.Yu.

1994-01-01

For solving radio-frequency mass spectrometry problems and dynamic ion containment are studied and systematized different ways for constructing the ion stability diagrams. A new universal set of parameters is proposed for diagram construction-angular variables, which are the phase raid of ion oscillational motion during positive and negative values of the supplying voltage. An effective analytical method is proposed for optimization of the parameters of the pulsed supplying voltage, in particular its repetition rate

Individual analysis of nonmetallic Inclusions in Steel by using the gallium focused ion beam secondary ion mass spectrometry

International Nuclear Information System (INIS)

Tomiyasu, Bunbunoshin; Inami, Akihiro; Abe, Masakazu; Nihei, Yoshimasa.

1995-01-01

Nonmetallic inclusions frequently exert a lot of unfavorable influences on the quality of steel. The size of nonmetallic inclusions in current steel products is less than a few μm in diameter. It is desirable to make clear the origin and generation process of such small particles of nonmetallic inclusion. In order to measure the shape, size, composition and inner elemental distribution, development of characterization methods for each inclusion particle is required. By employing a gallium focused ion beam (FIB) as a primary ion beam of secondary ion mass spectrometry (SIMS), the particle analysis with high spatial resolution is easily achieved. In this paper, we present the novel individual analysis of nonmetallic inclusions in steel by gallium FIB SIMS. We analyzed in two ways the nonmetallic inclusion particles segregated by electron beam melting. (1) By cross-sectioning of the particle using a gallium FIB, elemental maps of cross-section were obtained. The elements were distributed inhomogeneously on the cross-section. (2) We carried out the compositional analysis for several particles individually. Ten particles were analyzed by the shave-off analysis and the multivariate cluster analysis. Based on the composition of each particle, the inclusions were classified into six types. (author)

The combined measurement of uranium by alpha spectrometry and secondary ion mass spectrometry (SIMS)

International Nuclear Information System (INIS)

Harvan, D.

2009-01-01

The aim of thesis was to found the dependence between radiometric method - alpha spectrometry and surface sensitive method - Secondary Ion Mass Spectrometry (SIMS). Uranium or naturally occurring uranium isotopes were studied. Samples (high polished stainless steel discs) with uranium isotopes were prepared by electrodeposition. Samples were measured by alpha spectrometry after electrodeposition and treatment. It gives surface activities. Weights, as well as surface's weights of uranium isotopes were calculated from their activities, After alpha spectrometry samples were analyzed by TOF-SIMS IV instrument in International Laser Centre in Bratislava. By the SIMS analysis intensities of uranium-238 were obtained. The interpretation of SIMS intensities vs. surface activity, or surface's weights of uranium isotopes indicates the possibility to use SIMS in quantitative analysis of surface contamination by uranium isotopes, especially 238 U. (author)

Coulomb frustration of the multiphoton ionization of metallic clusters under intense EUV FEL evidenced by ion spectrometry

International Nuclear Information System (INIS)

Mazza, T; Devetta, M; Milani, P; Motomura, K; Liu, X-J; Fukuzawa, H; Yamada, A; Nagaya, K; Iwayama, H; Sugishima, A; Mizoguchi, Y; Saito, N; Coreno, M; Nagasono, M; Tono, K; Togashi, T; Kimura, H; Okunishi, M; Fennel, Th; Senba, Y

2015-01-01

Free electron laser light sources delivering high intensity pulses of short wavelength radiation are opening novel possibilities for the investigation of matter at the nanoscale and for the discovery and understanding of new physical processes occurring at the exotic transient states they make accessible. Strong ionization of atomic constituents of a nano-sized sample is a representative example of such processes and the understanding of ionization dynamics is crucial for a realistic description of the experiments. We report here on multiple ionization experiments on free clusters of titanium, a high cohesive energy metal. The time of flight ion spectra reveal a saturation of the cluster ionization at ∼10 16 photons per pulse per cm 2 . Our results also show a clear lack of any explosion process, opposite to what is observed for a rare-gas cluster under similar conditions. A simple and generalized multi-step ionization model including Coulomb frustration of the photoemission process effectively reproduces with a good agreement the main features of the experimental observation and points to an interpretation of the data involving a substantial energy deposition into the cluster through electronic system heating upon scattering events within photoemission. (paper)

XPS investigation of monatomic and cluster argon ion sputtering of tantalum pentoxide

Energy Technology Data Exchange (ETDEWEB)

Simpson, Robin, E-mail: r.simpson@surrey.ac.uk [The Surface Analysis Laboratory, Department of Mechanical Engineering Sciences, University of Surrey (United Kingdom); Thermo Scientific, East Grinstead (United Kingdom); White, Richard G. [Thermo Scientific, East Grinstead (United Kingdom); Watts, John F.; Baker, Mark A. [The Surface Analysis Laboratory, Department of Mechanical Engineering Sciences, University of Surrey (United Kingdom)

2017-05-31

Highlights: • Ion beam induced oxide reduction from monatomic and gas cluster ion beam exposure are compared. • Lower relative level of preferential sputtering is shown in gas cluster ion beam depth profiling. • A lack of “steady state” is observed in gas cluster ion beam depth profiles of tantalum pentoxide. • Possible mechanisms behind the observed results, including temperature effects are proposed. - Abstract: In recent years, gas cluster ion beams (GCIB) have become the cutting edge of ion beam technology to sputter etch organic materials in surface analysis. However, little is currently known on the ability of argon cluster ions (Ar{sub n}{sup +}) to etch metal oxides and other technologically important inorganic compounds and no depth profiles have previously been reported. In this work, XPS depth profiles through a certified (European standard BCR-261T) 30 nm thick Ta{sub 2}O{sub 5} layer grown on Ta foil using monatomic Ar{sup +} and Ar{sub 1000}{sup +} cluster ions have been performed at different incident energies. The preferential sputtering of oxygen induced using 6 keV Ar{sub 1000}{sup +} ions is lower relative to 3 keV and 500 eV Ar{sup +} ions. Ar{sup +} ions exhibit a steady state O/Ta ratio through the bulk oxide but Ar{sub 1000}{sup +} ions show a gradual decrease in the O/Ta ratio as a function of depth. The depth resolution and etch rate is substantially better for the monatomic beam compared to the cluster beam. Higher O concentrations are observed when the underlying Ta bulk metal is sputtered for the Ar{sub 1000}{sup +} profiles compared to the Ar{sup +} profiles.

Depth resolution of secondary ion mass spectrometry

International Nuclear Information System (INIS)

Pustovit, A.N.

2004-01-01

The effect of the solid body discreteness in the direction of the normal to the sample surface on the depth resolution of the secondary ion mass spectrometry method is analyzed. It is shown that for this case the dependence of the width at the semi-height of the delta profiles of the studied elements depth distribution on the energy and angle of incidence of the initial ions should have the form of the stepwise function. This is experimentally proved by the silicon-germanium delta-layers in the silicon samples [ru

Study of Flux Ratio of C60 to Ar Cluster Ion for Hard DLC Film deposition

International Nuclear Information System (INIS)

Miyauchi, K.; Toyoda, N.; Kanda, K.; Matsui, S.; Kitagawa, T.; Yamada, I.

2003-01-01

To study the influence of the flux ratio of C60 molecule to Ar cluster ion on (diamond like carbon) DLC film characteristics, DLC films deposited under various flux ratios were characterized with Raman spectrometry and Near Edge X-ray Absorption Fine Structure (NEXAFS). From results of these measurements, hard DLC films were deposited when the flux ratio of C60 to Ar cluster ion was between 0.7 and 4. Furthermore the DLC film with constant sp2 content was obtained in the range of the ratio from 0.7 to 4, which contents are lower values than that of conventional films such as RF plasma. DLC films deposited under the ratio from 1 to 4 had hardness from 40 to 45GPa. It was shown that DLC films with stable properties of low sp2 content and high hardness were formed even when the fluxes were varied from 1 to 4 during deposition. It was indicated that this process was useful in the view of industrial application

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Science.gov (United States)

Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

1999-01-01

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

Gas cluster ion beam equipments for industrial applications

International Nuclear Information System (INIS)

Matsuo, J.; Takaoka, G.H.; Yamada, I.

1995-01-01

30 keV and 200 keV gas cluster ion beam equipments have been developed for industrial applications. A gas cluster source with a non-cooled nozzle was used for both the equipments. Sufficient monomer ion suppression was achieved by using an ExB filter and chromatic lenses mass filter with low extraction voltage. These equipments are suitable to be used for low-damage surface treatment of metals, insulators and semiconductors without heavy metal contamination. (orig.)

Crater formation by single ions, cluster ions and ion "showers"

CERN Document Server

Djurabekova, Flyura; Timko, Helga; Nordlund, Kai; Calatroni, Sergio; Taborelli, Mauro; Wuensch, Walter

2011-01-01

The various craters formed by giant objects, macroscopic collisions and nanoscale impacts exhibit an intriguing resemblance in shapes. At the same time, the arc plasma built up in the presence of sufficiently high electric fields at close look causes very similar damage on the surfaces. Although the plasma–wall interaction is far from a single heavy ion impact over dense metal surfaces or the one of a cluster ion, the craters seen on metal surfaces after a plasma discharge make it possible to link this event to the known mechanisms of the crater formations. During the plasma discharge in a high electric field the surface is subject to high fluxes (~1025 cm-2s-1) of ions with roughly equal energies typically of the order of a few keV. To simulate such a process it is possible to use a cloud of ions of the same energy. In the present work we follow the effect of such a flux of ions impinging the surface in the ‘‘shower’’ manner, to find the transition between the different mechanisms of crater formati...

Radiogas chromatography mass spectrometry in the selected ion monitoring mode

International Nuclear Information System (INIS)

Doerfler, D.L.; Rosenblum, E.R.; Malloy, J.M.; Naworal, J.D.; McManus, I.R.; Campbell, I.M.

1980-01-01

The value of selected ion monitoring in analyzing biological radio isotope incorporation experiments by radiogas chromatography mass spectrometry is illustrated with reference to the biosynthesis of the mycotoxin mycophenolic acid in Penicillium brevicompactum and the mode of action of the anticholesterolemic drug 20,25-diazacholesterol. Both examples used 1-[ 14 C]acetate precursors. It is shown that the increased sensitivity and specificity of the selected ion monitoring mode detector permits straightforward detection and identification of the relatively small cellular pools associated with metabolic intermediates. The computer program RADSIM is described. Problems that still exist in using radiogas gas chromatography mass spectrometry technology to analyse isotope incorporation experiments are discussed. (author)

Probing thin over layers with variable energy/cluster ion beams

International Nuclear Information System (INIS)

Spool, A.; White, R.

2006-01-01

A series of carbon-coated magnetic recording disks proved ideal for exploring sampling depth and ion formation trends as a function of variations in energy and cluster size (Au x ) of the primary ion beam, and variations in over coat thickness and type. Ion yield from the underlying metal layer increased with increasing energy and decreasing cluster size of the primary ions. The yields varied nearly linearly with over layer thickness. In contrast, M x Cs y depth profiles were unaffected by changes in the primary ion. The samples were fortuitously dosed with dinonyl phthalate, allowing a study similar to prior GSIMS work [I.S. Gilmore, M.P. Seah, J.E. Johnstone, in: A. Benninghoven, P. Bertrand, H.-N. Migeon, H.W. Werner (Eds.), Proceedings of the 12th International Conference on SIMS, Elsevier, Brussels, 2000, p. 801]. Ions prominent in the EI mass spectrum, including even electron ions, were more consistently enhanced at lower energies and higher cluster sizes than the primary (M + H) + ion. The total secondary ion count was inversely proportional to the film thickness. Secondary electrons, largely originating in the buried metal layer, may be inducing organic ion formation [A.M. Spool, Surf. Interface Anal. 36 (2004) 264

Visualization of metallodrugs in single cells by secondary ion mass spectrometry imaging.

Science.gov (United States)

Wu, Kui; Jia, Feifei; Zheng, Wei; Luo, Qun; Zhao, Yao; Wang, Fuyi

2017-07-01

Secondary ion mass spectrometry, including nanoscale secondary ion mass spectrometry (NanoSIMS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), has emerged as a powerful tool for biological imaging, especially for single cell imaging. SIMS imaging can provide information on subcellular distribution of endogenous and exogenous chemicals, including metallodrugs, from membrane through to cytoplasm and nucleus without labeling, and with high spatial resolution and chemical specificity. In this mini-review, we summarize recent progress in the field of SIMS imaging, particularly in the characterization of the subcellular distribution of metallodrugs. We anticipate that the SIMS imaging method will be widely applied to visualize subcellular distributions of drugs and drug candidates in single cells, exerting significant influence on early drug evaluation and metabolism in medicinal and pharmaceutical chemistry. Recent progress of SIMS applications in characterizing the subcellular distributions of metallodrugs was summarized.

Coupling Front-End Separations, Ion Mobility Spectrometry, and Mass Spectrometry For Enhanced Multidimensional Biological and Environmental Analyses

Science.gov (United States)

Zheng, Xueyun; Wojcik, Roza; Zhang, Xing; Ibrahim, Yehia M.; Burnum-Johnson, Kristin E.; Orton, Daniel J.; Monroe, Matthew E.; Moore, Ronald J.; Smith, Richard D.; Baker, Erin S.

2017-01-01

Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. Though IMS alone is useful, its coupling with mass spectrometry (MS) and front-end separations is extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information available from biological and environmental sample analyses. In fact, multiple disease screening and environmental evaluations have illustrated that the IMS-based multidimensional separations extract information that cannot be acquired with each technique individually. This review highlights three-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography, supercritical fluid chromatography, liquid chromatography, solid-phase extractions, capillary electrophoresis, field asymmetric ion mobility spectrometry, and microfluidic devices. The origination, current state, various applications, and future capabilities of these multidimensional approaches are described in detail to provide insight into their uses and benefits. PMID:28301728

An introduction to the technique of combined ion mobility spectrometry-mass spectrometry for the analysis of complex biological samples

International Nuclear Information System (INIS)

McDowall, Mark A.; Bateman, Robert H.; Bajic, Steve; Giles, Kevin; Langridge, Jim; McKenna, Therese; Pringle, Steven D.; Wildgoose, Jason L.

2008-01-01

Full Text: Ultra Performance Liquid Chromatography (UPLC) offers several advantages compared with conventional High Performance Liquid Chromatography (HPLC) as an 'inlet system' for mass spectrometry. UPLC provides improved chromatographic resolution, increased sensitivity and reduced analysis time. This is achieved through the use of sub 2μm particles (stationary phase) combined with high-pressure solvent delivery (up to 15,000 psi). When coupled with orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (MS), UPLC presents a means to achieve high sample throughput with reduced spectral overlap, increased sensitivity, and exact mass measurement capabilities with high mass spectral resolution (Ca 20,000 FWHM). Dispersive ion mobility spectrometry (IMS) implemented within a traveling-wave ion guide provides an orthogonal separation strategy for ions in the gas phase that can resolve isobaric ions formed by either Electrospray of MALDI ionization typically in Ca 20 mille seconds. All three techniques have the potential to be combined on-line (e.g. UPLC-IMS-MS/MS) in real time to maximize peak capacity and resolving power for the analysis of complex biological mixtures including; intact proteins, modified peptides and endogenous/exogenous metabolites

Mass spectrometric production of heterogeneous metal clusters using Knudsen cell

Directory of Open Access Journals (Sweden)

Veljković Filip M.

2016-01-01

Full Text Available Knudsen effusion mass spectrometry or high-temperature method of mass spectrometry for decades gives new information about saturated vapor of hardly volatile compounds and it is an important method in the discovery of many new molecules, radicals, ions and clusters present in the gas phase. Since pioneering works until now, this method has been successfully applied to a large number of systems (ores, oxides, ceramics, glass materials, borides, carbides, sulfides, nitrates, metals, fullerenes, etc which led to the establishment of various research branches such as chemistry of clusters. This paper describes the basic principles of Knudsen cell use for both identification of chemical species created in the process of evaporation and determination of their ionization energies. Depending on detected ions intensities and the partial pressure of each gaseous component, as well as on changes in partial pressure with temperature, Knudsen cell mass spectrometry enables the determination of thermodynamic parameters of the tested system. A special attention is paid to its application in the field of small heterogeneous and homogeneous clusters of alkali metals. Furthermore, experimental results for thermodynamic parameters of some clusters, as well as capabilities of non-standard ways of using Knudsen cells in the process of synthesis of new clusters are presented herein. [Projekat Ministarstva nauke Republike Srbije, br. 172019

Gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance mass spectrometry

International Nuclear Information System (INIS)

Joergensen, S.I.

1985-01-01

The subject of this thesis is gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry (chapter 2 contains a short description of this method). Three chapters are mainly concerned with mechanistic aspects of gas phase ion/molecule reactions. An equally important aspect of the thesis is the stability and reactivity of α-thio carbanions, dipole stabilized carbanions and homoenolate anions, dealt with in the other four chapters. (Auth.)

Range of plasma ions in cold cluster gases near the critical point

Energy Technology Data Exchange (ETDEWEB)

Zhang, G. [Cyclotron Institute, Texas A& M University, 77843 College Station, TX (United States); Quevedo, H.J. [Center for High Energy Density Science, C1510, University of Texas at Austin, Austin, TX 78712 (United States); Bonasera, A., E-mail: abonasera@comp.tamu.edu [Cyclotron Institute, Texas A& M University, 77843 College Station, TX (United States); Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Donovan, M.; Dyer, G.; Gaul, E. [Center for High Energy Density Science, C1510, University of Texas at Austin, Austin, TX 78712 (United States); Guardo, G.L. [Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Gulino, M. [Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Libera Universita' Kore, 94100 Enna (Italy); La Cognata, M.; Lattuada, D. [Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Palmerini, S. [Department of Physics and Geology, University of Perugia, Via A. Pascoli, 06123 Perugia (Italy); Istituto Nazionale di Fisica Nucleare, Section of Perugia, Via A. Pascoli, 06123 Perugia (Italy); Pizzone, R.G.; Romano, S. [Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Smith, H. [Center for High Energy Density Science, C1510, University of Texas at Austin, Austin, TX 78712 (United States); Trippella, O. [Department of Physics and Geology, University of Perugia, Via A. Pascoli, 06123 Perugia (Italy); Istituto Nazionale di Fisica Nucleare, Section of Perugia, Via A. Pascoli, 06123 Perugia (Italy); Anzalone, A.; Spitaleri, C. [Laboratori Nazionali del Sud-INFN, via S. Sofia 64, 95123 Catania (Italy); Ditmire, T. [Center for High Energy Density Science, C1510, University of Texas at Austin, Austin, TX 78712 (United States)

2017-05-18

We measure the range of plasma ions in cold cluster gases by using the Petawatt laser at the University of Texas-Austin. The produced plasma propagated in all directions some hitting the cold cluster gas not illuminated by the laser. From the ratio of the measured ion distributions at different angles we can estimate the range of the ions in the cold cluster gas. It is much smaller than estimated using popular models, which take only into account the slowing down of charged particles in uniform matter. We discuss the ion range in systems prepared near a liquid–gas phase transition. - Highlights: • We present experimental results obtained at the UT Petawatt laser facility, Austin, TX. • The ion range is strongly modified for cluster gases as compared to its value in a homogeneous system. • Large fluctuations are found if the cluster gas is prepared near the liquid–gas phase transition region.

Range of plasma ions in cold cluster gases near the critical point

International Nuclear Information System (INIS)

Zhang, G.; Quevedo, H.J.; Bonasera, A.; Donovan, M.; Dyer, G.; Gaul, E.; Guardo, G.L.; Gulino, M.; La Cognata, M.; Lattuada, D.; Palmerini, S.; Pizzone, R.G.; Romano, S.; Smith, H.; Trippella, O.; Anzalone, A.; Spitaleri, C.; Ditmire, T.

2017-01-01

We measure the range of plasma ions in cold cluster gases by using the Petawatt laser at the University of Texas-Austin. The produced plasma propagated in all directions some hitting the cold cluster gas not illuminated by the laser. From the ratio of the measured ion distributions at different angles we can estimate the range of the ions in the cold cluster gas. It is much smaller than estimated using popular models, which take only into account the slowing down of charged particles in uniform matter. We discuss the ion range in systems prepared near a liquid–gas phase transition. - Highlights: • We present experimental results obtained at the UT Petawatt laser facility, Austin, TX. • The ion range is strongly modified for cluster gases as compared to its value in a homogeneous system. • Large fluctuations are found if the cluster gas is prepared near the liquid–gas phase transition region.

Native tandem and ion mobility mass spectrometry highlight structural and modular similarities in clustered-regularly-interspaced shot-palindromic-repeats (CRISPR)-associated protein complexes from Escherichia coli and Pseudomonas aeruginosa.

Science.gov (United States)

van Duijn, Esther; Barbu, Ioana M; Barendregt, Arjan; Jore, Matthijs M; Wiedenheft, Blake; Lundgren, Magnus; Westra, Edze R; Brouns, Stan J J; Doudna, Jennifer A; van der Oost, John; Heck, Albert J R

2012-11-01

The CRISPR/Cas (clustered regularly interspaced short palindromic repeats/CRISPR-associated genes) immune system of bacteria and archaea provides acquired resistance against viruses and plasmids, by a strategy analogous to RNA-interference. Key components of the defense system are ribonucleoprotein complexes, the composition of which appears highly variable in different CRISPR/Cas subtypes. Previous studies combined mass spectrometry, electron microscopy, and small angle x-ray scattering to demonstrate that the E. coli Cascade complex (405 kDa) and the P. aeruginosa Csy-complex (350 kDa) are similar in that they share a central spiral-shaped hexameric structure, flanked by associating proteins and one CRISPR RNA. Recently, a cryo-electron microscopy structure of Cascade revealed that the CRISPR RNA molecule resides in a groove of the hexameric backbone. For both complexes we here describe the use of native mass spectrometry in combination with ion mobility mass spectrometry to assign a stable core surrounded by more loosely associated modules. Via computational modeling subcomplex structures were proposed that relate to the experimental IMMS data. Despite the absence of obvious sequence homology between several subunits, detailed analysis of sub-complexes strongly suggests analogy between subunits of the two complexes. Probing the specific association of E. coli Cascade/crRNA to its complementary DNA target reveals a conformational change. All together these findings provide relevant new information about the potential assembly process of the two CRISPR-associated complexes.

Dependence of surface smoothing, sputtering and etching phenomena on cluster ion dosage

CERN Document Server

Song, J H; Choi, W K

2002-01-01

The dependence of surface smoothing and sputtering phenomena of Si (1 0 0) solid surfaces irradiated by CO sub 2 cluster ions on cluster-ion dosage was investigated using an atomic force microscope. The flux and total ion dosage of impinging cluster ions at the acceleration voltage of 50 kV were fixed at 10 sup 9 ions/cm sup 2 s and were scanned from 5x10 sup 1 sup 0 to 5x10 sup 1 sup 3 ions/cm sup 2 , respectively. The density of hillocks induced by cluster ion impact was gradually increased with the dosage up to 5x10 sup 1 sup 1 ions/cm sup 2 , which caused that the irradiated surface became rough from 0.4 to 1.24 nm in root-mean-square roughness (sigma sub r sub m sub s). At the boundary of the ion dosage of 10 sup 1 sup 2 ions/cm sup 2 , the density of the induced hillocks was decreased and sigma sub r sub m sub s was about 1.21 nm, not being deteriorated further. At the dosage of 5x10 sup 1 sup 3 ions/cm sup 2 , the induced hillocks completely disappeared and the surface became very flat as much as sigma...

Multifactorial Understanding of Ion Abundance in Tandem Mass Spectrometry Experiments.

Science.gov (United States)

Fazal, Zeeshan; Southey, Bruce R; Sweedler, Jonathan V; Rodriguez-Zas, Sandra L

2013-01-29

In a bottom-up shotgun approach, the proteins of a mixture are enzymatically digested, separated, and analyzed via tandem mass spectrometry. The mass spectra relating fragment ion intensities (abundance) to the mass-to-charge are used to deduce the amino acid sequence and identify the peptides and proteins. The variables that influence intensity were characterized using a multi-factorial mixed-effects model, a ten-fold cross-validation, and stepwise feature selection on 6,352,528 fragment ions from 61,543 peptide ions. Intensity was higher in fragment ions that did not have neutral mass loss relative to any mass loss or that had a +1 charge state. Peptide ions classified for proton mobility as non-mobile had lowest intensity of all mobility levels. Higher basic residue (arginine, lysine or histidine) counts in the peptide ion and low counts in the fragment ion were associated with lower fragment ion intensities. Higher counts of proline in peptide and fragment ions were associated with lower intensities. These results are consistent with the mobile proton theory. Opposite trends between peptide and fragment ion counts and intensity may be due to the different impact of factor under consideration at different stages of the MS/MS experiment or to the different distribution of observations across peptide and fragment ion levels. Presence of basic residues at all three positions next to the fragmentation site was associated with lower fragment ion intensity. The presence of proline proximal to the fragmentation site enhanced fragmentation and had the opposite trend when located distant from the site. A positive association between fragment ion intensity and presence of sulfur residues (cysteine and methionine) on the vicinity of the fragmentation site was identified. These results highlight the multi-factorial nature of fragment ion intensity and could improve the algorithms for peptide identification and the simulation in tandem mass spectrometry experiments.

Coupling Front-End Separations, Ion Mobility Spectrometry, and Mass Spectrometry For Enhanced Multidimensional Biological and Environmental Analyses

Energy Technology Data Exchange (ETDEWEB)

Zheng, Xueyun; Wojcik, Roza; Zhang, Xing; Ibrahim, Yehia M.; Burnum-Johnson, Kristin E.; Orton, Daniel J.; Monroe, Matthew E.; Moore, Ronald J.; Smith, Richard D.; Baker, Erin M.

2017-06-12

Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. IMS alone is useful, but its coupling with mass spectrometry (MS) and front-end separations has been extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information in biological and environmental sample analyses. Multiple studies in disease screening and environmental evaluations have even shown these IMS-based multidimensional separations extract information not possible with each technique individually. This review highlights 3-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography (GC), supercritical fluid chromatography (SFC), liquid chromatography (LC), solid phase extractions (SPE), capillary electrophoresis (CE), field asymmetric ion mobility spectrometry (FAIMS), and microfluidic devices. The origination, current state, various applications, and future capabilities for these multidimensional approaches are described to provide insight into the utility and potential of each technique.

Maximizing Ion Transmission in Differential Mobility Spectrometry

Science.gov (United States)

Schneider, Bradley B.; Londry, Frank; Nazarov, Erkinjon G.; Kang, Yang; Covey, Thomas R.

2017-10-01

We provide modeling and experimental data describing the dominant ion-loss mechanisms for differential mobility spectrometry (DMS). Ion motion is considered from the inlet region of the mobility analyzer to the DMS exit, and losses resulting from diffusion to electrode surfaces, insufficient effective gap, ion fragmentation, and fringing field effects are considered for a commercial DMS system with 1-mm gap height. It is shown that losses due to diffusion and radial oscillations can be minimized with careful consideration of residence time, electrode spacing, gas flow rate, and waveform frequency. Fragmentation effects can be minimized by limitation of the separation field. When these parameters were optimized, fringing field effects at the DMS inlet contributed the most to signal reduction. We also describe a new DMS cell configuration that improves the gas dynamics at the mobility cell inlet. The new cell provides a gas jet that decreases the residence time for ions within the fringing field region, resulting in at least twofold increase in ion signal as determined by experimental data and simulations. [Figure not available: see fulltext.

The smoke ion source: A device for the generation of cluster ions via inert gas condensation

International Nuclear Information System (INIS)

McHugh, K.M.; Sarkas, H.W.; Eaton, J.G.; Bowen, K.H.; Westgate, C.R.

1989-01-01

We report the development of an ion source for generating intense, continuous beams of both positive and negative cluster ions. This device is the result of the marriage of the inert gas condensation method with techniques for injecting electrons directly into expanding jets. In the preliminary studies described here, we have observed cluster ion size distributions ranging from n=1-400 for Pb n + and Pb n - and from n=12-5700 for Li n - . (orig.)

Cluster Ion Implantation in Graphite and Diamond

DEFF Research Database (Denmark)

Popok, Vladimir

2014-01-01

Cluster ion beam technique is a versatile tool which can be used for controllable formation of nanosize objects as well as modification and processing of surfaces and shallow layers on an atomic scale. The current paper present an overview and analysis of data obtained on a few sets of graphite...... and diamond samples implanted by keV-energy size-selected cobalt and argon clusters. One of the emphases is put on pinning of metal clusters on graphite with a possibility of following selective etching of graphene layers. The other topic of concern is related to the development of scaling law for cluster...... implantation. Implantation of cobalt and argon clusters into two different allotropic forms of carbon, namely, graphite and diamond is analysed and compared in order to approach universal theory of cluster stopping in matter....

Fullerene nanostructure design with cluster ion impacts

Czech Academy of Sciences Publication Activity Database

Lavrentiev, Vasyl; Vacík, Jiří; Naramoto, H.; Narumi, K.

2009-01-01

Roč. 483, - (2009), s. 479-483 ISSN 0925-8388 R&D Projects: GA AV ČR IAA200480702; GA AV ČR IAA400100701; GA AV ČR(CZ) KAN400480701 Institutional research plan: CEZ:AV0Z10480505 Keywords : fullerene films, clusters C60+ * cluster ion implantation * patterning Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 2.135, year: 2009

Hierarchical cluster analysis of technical replicates to identify interferents in untargeted mass spectrometry metabolomics.

Science.gov (United States)

Caesar, Lindsay K; Kvalheim, Olav M; Cech, Nadja B

2018-08-27

Mass spectral data sets often contain experimental artefacts, and data filtering prior to statistical analysis is crucial to extract reliable information. This is particularly true in untargeted metabolomics analyses, where the analyte(s) of interest are not known a priori. It is often assumed that chemical interferents (i.e. solvent contaminants such as plasticizers) are consistent across samples, and can be removed by background subtraction from blank injections. On the contrary, it is shown here that chemical contaminants may vary in abundance across each injection, potentially leading to their misidentification as relevant sample components. With this metabolomics study, we demonstrate the effectiveness of hierarchical cluster analysis (HCA) of replicate injections (technical replicates) as a methodology to identify chemical interferents and reduce their contaminating contribution to metabolomics models. Pools of metabolites with varying complexity were prepared from the botanical Angelica keiskei Koidzumi and spiked with known metabolites. Each set of pools was analyzed in triplicate and at multiple concentrations using ultraperformance liquid chromatography coupled to mass spectrometry (UPLC-MS). Before filtering, HCA failed to cluster replicates in the data sets. To identify contaminant peaks, we developed a filtering process that evaluated the relative peak area variance of each variable within triplicate injections. These interferent peaks were found across all samples, but did not show consistent peak area from injection to injection, even when evaluating the same chemical sample. This filtering process identified 128 ions that appear to originate from the UPLC-MS system. Data sets collected for a high number of pools with comparatively simple chemical composition were highly influenced by these chemical interferents, as were samples that were analyzed at a low concentration. When chemical interferent masses were removed, technical replicates clustered in

Ionization and fragmentation of water clusters by fast highly charged ions

International Nuclear Information System (INIS)

Adoui, L; Cassimi, A; Gervais, B; Grandin, J-P; Guillaume, L; Maisonny, R; Legendre, S; Tarisien, M; Lopez-Tarifa, P; Alcami, M; Martin, F; Politis, M-F; Penhoat, M-A Herve du; Vuilleumier, R; Gaigeot, M-P; Tavernelli, I

2009-01-01

We study the dissociative ionization of water clusters by impact of 12 MeV/u Ni 25+ ions. Cold target recoil ion momentum spectroscopy (COLTRIMS) is used to obtain information about stability, energetics and charge mobility of the ionized water clusters. An unusual stability of the H 9 O + 4 ion is observed, which could be the signature of the so-called Eigen structure in gas-phase water clusters. From the analysis of coincidences between charged fragments, we conclude that charge mobility is very high and is responsible for the formation of protonated water clusters, (H 2 O) n H + , that dominate the mass spectrum. These results are supported by Car-Parrinello molecular dynamics and time-dependent density functional theory simulations, which also reveal the mechanisms of such mobility.

Ion counting method and it's operational characteristics in gas chromatography-mass spectrometry

International Nuclear Information System (INIS)

Fujii, Toshihiro

1976-01-01

Ion counting method with continuous channel electron multiplier which affords the direct detection of very small ion currents and it's operational characteristics were studied in gas chromatography-mass spectrometry. Then this method was applied to the single ion detection technique of GC-MS. A detection limit was measured, using various standard samples of low level concentration. (auth.)

Practical aspects of trapped ion mass spectrometry, 4 theory and instrumentation

CERN Document Server

March, Raymond E

2010-01-01

The expansion of the use of ion trapping in different areas of mass spectrometry and different areas of application indicates the value of a single source of information drawing together diverse inputs. This book provides an account of the theory and instrumentation of mass spectrometric applications and an introduction to ion trapping devices.

Prediction, Detection, and Validation of Isotope Clusters in Mass Spectrometry Data

Directory of Open Access Journals (Sweden)

Hendrik Treutler

2016-10-01

Full Text Available Mass spectrometry is a key analytical platform for metabolomics. The precise quantification and identification of small molecules is a prerequisite for elucidating the metabolism and the detection, validation, and evaluation of isotope clusters in LC-MS data is important for this task. Here, we present an approach for the improved detection of isotope clusters using chemical prior knowledge and the validation of detected isotope clusters depending on the substance mass using database statistics. We find remarkable improvements regarding the number of detected isotope clusters and are able to predict the correct molecular formula in the top three ranks in 92 % of the cases. We make our methodology freely available as part of the Bioconductor packages xcms version 1.50.0 and CAMERA version 1.30.0.

Ion-pairing reversed-phased chromatography/mass spectrometry of heparin

DEFF Research Database (Denmark)

Henriksen, Jens; Roepstorff, Peter; Ringborg, Lene H.

2006-01-01

not well characterised. In order to further characterise such mixtures, two on-line ion-pairing reverse-phased chromatography electrospray ionisation (ESI) mass spectrometry methods have been developed. One of the systems allows the determination of more than 200 components in a medium molecular weight...

Tandem ion mobility spectrometry coupled to laser excitation

Energy Technology Data Exchange (ETDEWEB)

Simon, Anne-Laure; Choi, Chang Min; Clavier, Christian; Barbaire, Marc; Maurelli, Jacques; Dagany, Xavier; MacAleese, Luke; Dugourd, Philippe, E-mail: philippe.dugourd@univ-lyon1.fr [Institut Lumière Matière, Université de Lyon, Université Lyon 1-CNRS, 69622 Villeurbanne cedex (France); Chirot, Fabien [Institut des Sciences Analytiques, Université de Lyon, Université Lyon 1-CNRS, 69622 Villeurbanne cedex (France)

2015-09-15

This manuscript describes a new experimental setup that allows to perform tandem ion mobility spectrometry (IMS) measurements and which is coupled to a high resolution time-of-flight mass spectrometer. It consists of two 79 cm long drift tubes connected by a dual ion funnel assembly. The setup was built to permit laser irradiation of the ions in the transfer region between the two drift tubes. This geometry allows selecting ions according to their ion mobility in the first drift tube, to irradiate selected ions, and examine the ion mobility of the product ions in the second drift tube. Activation by collision is possible in the same region (between the two tubes) and between the second tube and the time-of-flight. IMS-IMS experiments on Ubiquitin are reported. We selected a given isomer of charge state +7 and explored its structural rearrangement following collisional activation between the two drift tubes. An example of IMS-laser-IMS experiment is reported on eosin Y, where laser irradiation was used to produce radical ions by electron photodetachment starting from doubly deprotonated species. This allowed measuring the collision cross section of the radical photo-product, which cannot be directly produced with an electrospray source.

The adsorption of helium atoms on small cationic gold clusters.

Science.gov (United States)

Goulart, Marcelo; Gatchell, Michael; Kranabetter, Lorenz; Kuhn, Martin; Martini, Paul; Gitzl, Norbert; Rainer, Manuel; Postler, Johannes; Scheier, Paul; Ellis, Andrew M

2018-04-04

Adducts formed between small gold cluster cations and helium atoms are reported for the first time. These binary ions, Aun+Hem, were produced by electron ionization of helium nanodroplets doped with neutral gold clusters and were detected using mass spectrometry. For a given value of n, the distribution of ions as a function of the number of added helium atoms, m, has been recorded. Peaks with anomalously high intensities, corresponding to so-called magic number ions, are identified and interpreted in terms of the geometric structures of the underlying Aun+ ions. These features can be accounted for by planar structures for Aun+ ions with n ≤ 7, with the addition of helium having no significant effect on the structures of the underlying gold cluster ions. According to ion mobility studies and some theoretical predictions, a 3-D structure is expected for Au8+. However, the findings for Au8+ in this work are more consistent with a planar structure.

Ion induced electron emission statistics under Agm- cluster bombardment of Ag

Science.gov (United States)

Breuers, A.; Penning, R.; Wucher, A.

2018-05-01

The electron emission from a polycrystalline silver surface under bombardment with Agm- cluster ions (m = 1, 2, 3) is investigated in terms of ion induced kinetic excitation. The electron yield γ is determined directly by a current measurement method on the one hand and implicitly by the analysis of the electron emission statistics on the other hand. Successful measurements of the electron emission spectra ensure a deeper understanding of the ion induced kinetic electron emission process, with particular emphasis on the effect of the projectile cluster size to the yield as well as to emission statistics. The results allow a quantitative comparison to computer simulations performed for silver atoms and clusters impinging onto a silver surface.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling

Science.gov (United States)

Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Donohoe, Gregory C.; Valentine, Stephen J.

2016-03-01

Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H]2- ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H]3- ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H]2- ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H]3- ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

Structural elucidation of AgAsS2 glass by the analysis of clusters formed during laser desorption ionisation applying quadrupole ion trap time-of-flight mass spectrometry.

Science.gov (United States)

Mawale, Ravi Madhukar; Alberti, Milan; Zhang, Bo; Fraenkl, Max; Wagner, Tomas; Havel, Josef

2016-03-15

The structure of AgA(s)S2 glass, which has a broad range of applications, is still not well understood and a systematic mass spectrometric analysis of AgA(s)S2 glass is currently not available. Elucidation of the structure should help in the development of this material. The AgA(s)S2 glass was prepared by the melt-quenched technique. Laser desorption ionisation (LDI) using quadrupole ion trap time-of-flight mass spectrometry (QIT-TOFMS) was used to follow the generation of Ag(m)As(n)S(x) clusters. The stoichiometry of the clusters generated was determined via collision-induced dissociation (CID) and modelling of isotopic patterns. The AgA(s)S2 glass was characterised by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The LDI of AgA(s)S2 glass leads to the formation of unary (Ag+/− and As(3+)) species, 38 binary (As(n)S(x), Ag(m)S(x)), and 98 ternary (Ag(m)As(n)S(x)) singly charged clusters. The formation of silver-rich nano-grains during AgA(s)S2 glass synthesis has been identified using TEM analysis and also verified by QIT-TOFMS. TOFMS was shown to be a useful technique to study the generation of Ag(m)As(n)S(x )clusters. SEM, TEM and EDX analysis proved that the structure of AgA(s)S2 glass is ‘grain-like’ where grains are either: (1) Silver-rich ‘islands’ (Ag(m,) m up to 39) connected by arsenic and/or sulfur or arsenic sulfide chains or (2) silver sulfide (Ag2S)m (m = 9-20) clusters also similarly inter-connected. This obtained structural information may be useful for the development of ultra-high-density phase-change storage and memory devices using this kind of glass as a base.

Ion Mobility Separations of Isomers based upon Long Path Length Structures for Lossless Ion Manipulations Combined with Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Deng, Liulin [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Ibrahim, Yehia M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Baker, Erin S. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Aly, Noor A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Hamid, Ahmed M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zhang, Xing [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zheng, Xueyun [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Garimella, Sandilya V. B. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Webb, Ian K. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Prost, Spencer A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Sandoval, Jeremy A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Norheim, Randolph V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Anderson, Gordon A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Tolmachev, Aleksey V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Smith, Richard D. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA

2016-07-01

Mass spectrometry (MS)-based multi-omic measurements, including proteomics, metabolomics, lipidomics, and glycomics, are increasingly transforming our ability to characterize and understand biological systems, but, presently have limitations due to the chemical diversity and range of abundances of biomolecules in complex samples. Advances addressing these challenges increasingly are based upon the ability to quickly separate, react and otherwise manipulate sample components for analysis by MS. Here we report on a new approach using Structures for Lossless Ion Manipulations (SLIM) to enable long serpentine path ion mobility spectrometry (IMS) separations followed by MS analyses. This approach provides previously unachieved mobility biomolecule isomer separations for biomolecular species, in conjunction with more effective ion utilization, and producing a basis for the improved characterization of very small samples.

Acceleration of cluster and molecular ions by TIARA 3 MV tandem accelerator

CERN Document Server

Saitoh, Y; Tajima, S

2000-01-01

We succeeded in accelerating molecular and cluster ions (B sub 2 sub - sub 4 , C sub 2 sub - sub 1 sub 0 , O sub 2 , Al sub 2 sub - sub 4 , Si sub 2 sub - sub 4 , Cu sub 2 sub - sub 3 , Au sub 2 sub - sub 3 , LiF, and AlO) to MeV energies with high-intensity beam currents by means of a 3 MV tandem accelerator in the TIARA facility. These cluster ions were generated by a cesium sputter-type negative ion source. We tested three types of carbon sputter cathodes in which graphite powder was compressed with different pressures. The pressure difference affected the generating ratio of clusters generated to single atom ions extracted from the source and it appeared that the high-density cathode was suitable. We also investigated the optimum gas pressure for charge exchange in the tandem high-voltage terminal. Clusters of larger size tend to require lower pressure than do smaller ones. In addition, we were able to obtain doubly charged AlO molecular ions. (authors)

An alkali ion source based on graphite intercalation compounds for ion mobility spectrometry

International Nuclear Information System (INIS)

Tabrizchi, Mahmoud; Hosseini, Zahra S

2008-01-01

A variety of alkali cation emitters were developed as the ion source for ion mobility spectrometry. The cation emitters were constructed based on alkali ion graphite intercalation compounds (GICs). The compounds were prepared by fusing alkali salts with ground graphite. In order to produce alkali ions, the compounds were loaded on a filament and heated to red. Reactant ions of the form alk + ions were observed for the alkali salts NaCl, KCl.LiCl, CsCl and SrCl. In addition to Na + ions, K + ions were observed at the beginning of thermionic emission from Na-GIC. This is due to the low ionization potential of potassium that exists in trace amounts in sodium salts. In addition to the potassium ion, Na + was observed in the case of LiCl salt. The Na + and K + peaks originating from impurities totally disappeared after about 40 min. However, the thermionic emission of the main ion of the corresponding salt lasted for several days. No negative ions were observed upon reversing the drift field. Selected organic compounds (methyl isobutyl ketone, dimethyl sulfoxide, acetone and tetrahydrofuran) were also ionized via alkali cation attachment reaction. Distinct ion mobility patterns were observed for different substances using one type of alkali reactant ion. However, the ion mobility pattern for a given substance changed when a different alkali reactant ion was used. Ammonia and amines were not ionized when this source was used

Angular distributions of particles sputtered from multicomponent targets with gas cluster ions

Energy Technology Data Exchange (ETDEWEB)

Ieshkin, A.E. [Faculty of Physics, Lomonosov Moscow State University, Leninskie Gory, Moscow 119991 (Russian Federation); Ermakov, Yu.A., E-mail: yuriermak@yandex.ru [Skobeltsyn Nuclear Physics Research Institute, Lomonosov Moscow State University, Leninskie Gory, Moscow 119991 (Russian Federation); Chernysh, V.S. [Faculty of Physics, Lomonosov Moscow State University, Leninskie Gory, Moscow 119991 (Russian Federation)

2015-07-01

The experimental angular distributions of atoms sputtered from polycrystalline W, Cd and Ni based alloys with 10 keV Ar cluster ions are presented. RBS was used to analyze a material deposited on a collector. It has been found that the mechanism of sputtering, connected with elastic properties of materials, has a significant influence on the angular distributions of sputtered components. The effect of non-stoichiometric sputtering at different emission angles has been found for the alloys under cluster ion bombardment. Substantial smoothing of the surface relief was observed for all targets irradiated with cluster ions.

Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China); Ho, Hingman; Han, Quanbin [School of Chinese Medicine, Hong Kong Baptist University, 7 Baptist University Road, Kowloon Tong, Hong Kong (China); Fan, Xiaohui [College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058 (China); Zuo, Zhong, E-mail: joanzuo@cuhk.edu.hk [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China)

2015-01-01

Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA.

Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

International Nuclear Information System (INIS)

Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan; Ho, Hingman; Han, Quanbin; Fan, Xiaohui; Zuo, Zhong

2015-01-01

Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA

Novel product ions of 2-aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi-stage tandem mass spectrometry.

Science.gov (United States)

Johnson, Byron S; Burinsky, David J; Burova, Svetlana A; Davis, Roman; Fitzgerald, Russ N; Matsuoka, Richard T

2012-05-15

The 2-aminoaniline scaffold is of significant value to the pharmaceutical industry and is embedded in a number of pharmacophores including 2-aminoanilides and benzimidazoles. A novel application of coordination ion spray mass spectrometry (CIS-MS) for interrogating the silver ion (Ag(+)) complexes of a homologous series of these compounds using multi-stage tandem mass spectrometry is described. Unlike the ubiquitous alkali metal ion complexes, Ag(+) complexes of 2-aminoanilides and benzimidazoles were found to yield [M - H](+) ions in significant abundance via gas-phase elimination of the metal hydride (AgH) resulting in unique product ion cascades. Sample introduction was by liquid chromatography with mass spectrometry analysis performed on a hybrid linear ion trap/orbitrap instrument capable of high-resolution measurements. Rigorous structural characterization by multi-stage tandem mass spectrometry using [M +  H](+), [M - H](-) and [M - H](+) precursor ions derived from ESI and CIS experiments was performed for the homologous series of 2-aminoanilide and benzimidazole compounds. A full tabular comparison of structural information resulting from these product ion cascades was produced. Multi-stage tandem mass spectrometry of [M - H](+) ions resulting from Ag(+) complexes of 2-aminoanilides and benzimidazoles in CIS-MS experiments produced unique product ion cascades that exhibited complementary structural information to that obtained from tandem mass spectrometry of [M  +  H](+) and [M - H](-) ions by electrospray ionization (ESI). These observations may be broadly applicable to other compounds that are observed to form Ag(+) complexes and eliminate AgH. Copyright © 2012 John Wiley & Sons, Ltd.

The formation of magnetic silicide Fe3Si clusters during ion implantation

Science.gov (United States)

Balakirev, N.; Zhikharev, V.; Gumarov, G.

2014-05-01

A simple two-dimensional model of the formation of magnetic silicide Fe3Si clusters during high-dose Fe ion implantation into silicon has been proposed and the cluster growth process has been computer simulated. The model takes into account the interaction between the cluster magnetization and magnetic moments of Fe atoms random walking in the implanted layer. If the clusters are formed in the presence of the external magnetic field parallel to the implanted layer, the model predicts the elongation of the growing cluster in the field direction. It has been proposed that the cluster elongation results in the uniaxial magnetic anisotropy in the plane of the implanted layer, which is observed in iron silicide films ion-beam synthesized in the external magnetic field.

The formation of magnetic silicide Fe3Si clusters during ion implantation

International Nuclear Information System (INIS)

Balakirev, N.; Zhikharev, V.; Gumarov, G.

2014-01-01

A simple two-dimensional model of the formation of magnetic silicide Fe 3 Si clusters during high-dose Fe ion implantation into silicon has been proposed and the cluster growth process has been computer simulated. The model takes into account the interaction between the cluster magnetization and magnetic moments of Fe atoms random walking in the implanted layer. If the clusters are formed in the presence of the external magnetic field parallel to the implanted layer, the model predicts the elongation of the growing cluster in the field direction. It has been proposed that the cluster elongation results in the uniaxial magnetic anisotropy in the plane of the implanted layer, which is observed in iron silicide films ion-beam synthesized in the external magnetic field

Modification on surface oxide layer structure and surface morphology of niobium by gas cluster ion beam treatments

International Nuclear Information System (INIS)

Wu, A.T.; Swenson, D.R.; Insepov, Z.

2010-01-01

Recently, it was demonstrated that significant reductions in field emission on Nb surfaces could be achieved by means of a new surface treatment technique called gas cluster ion beam (GCIB). Further study as shown in this paper revealed that GCIB treatments could modify surface irregularities and remove surface asperities leading to a smoother surface finish as demonstrated through measurements using a 3D profilometer, an atomic force microscope, and a scanning electron microscope. These experimental observations were supported by computer simulation via atomistic molecular dynamics and a phenomenological surface dynamics. Measurements employing a secondary ion mass spectrometry found that GCIB could also alter Nb surface oxide layer structure. Possible implications of the experimental results on the performance of Nb superconducting radio frequency cavities treated by GCIB will be discussed. First experimental results on Nb single cell superconducting radio frequency cavities treated by GCIB will be reported.

Formation and metastable decomposition of unprotonated ammonia cluster ions upon femtosecond ionization

International Nuclear Information System (INIS)

Buzza, S.A.; Wei, S.; Purnell, J.; Castleman, A.W. Jr.

1995-01-01

The formation and metastable dissociation mechanism of unprotonated ammonia cluster ions, (NH 3 ) + n , produced by multiphoton ionization (MPI) at 624 nm and a nominal pulse width of 350 fs, are investigated through a reflectron time-of-flight (TOF) mass spectrometric technique. Detection of the unprotonated ions after femtosecond and nanosecond multiphoton ionization under various intensity conditions is explained. The role of the energy of the ionizing photons, and the observation of these ions after femtosecond MPI is examined. The formation of the unprotonated series is found to be a function of intensity in the case of ionization on the nanosecond time scale, but not so for the femtosecond time domain. The results can be explained in terms of ionization mechanisms and ionizing pulse durations. The findings of the present study suggest that the unprotonated ions are trapped behind the barrier to intracluster proton transfer and/or concomitant NH 2 loss. The studies of metastable decomposition also reveal that the unprotonated ammonia cluster ions dissociate in the field-free region of the TOF by losing an NH 2 radical rather than via the evaporative loss of NH 3 as occurs for protonated clusters. Additionally, isotopic investigations of the unimolecular decay reveal a strong dependence on the conditions of cluster formation. The cluster formation condition dependence of the unimolecular decay is further investigated by altering formation temperatures and observing the consequences reflected by changes in the spontaneous metastable decay rate constant. This is a unique example of a cluster system whose metastable dissociation does not obey an evaporative ensemble model

11. international conference on ion sources

International Nuclear Information System (INIS)

Leitner, D.; Lyneis, C.; Cheng, D.; Galloway, M.L.; Leitner, M.; Todd, D.S.; Ciavola, G.; Gammino, S.; Celona, L.; Ando, L.; Torrisi, L.; Cavenago, M.; Galata, A.; Spaedtke, P.; Tinschert, K.; Lang, R.; Iannucci, R.; Leroy, R.; Barue, C.; Hitz, D.; Koivisto, H.; Suominen, P.; Tarvainen, O.; Beijers, H.; Brandenburg, S.; Vanrooyen, D.; Hillo, C.; Kuchler, D.; Homeyer, H.; Rohrich, J.; Schachter, L.; Dobrescu, S.; Nakagawa, T.; Higurashi, Y.; Kidera, M.; Aihara, T.; Kase, M.; Goto, A.; Yang, Y.; Zhao, H.W.; Zhang, Z.M.; Zhang, X.Z.; Guo, X.H.; He, W.E.; Sun, L.T.; Yuan, P.; Song, M.T.; Xie, Z.Q.; Cao, Y.; Zhan, W.L.; Wei, B.W.; Bricault, P.; Lau, C.; Essabaa, S.; Cheikh Mhamed, M.; Bajeat, O.; Ducourtieux, M.; Lefort, H.; Panteleev, V.N.; Barzakh, A.E.; Fedorov, D.V.; Ionan, A.M.; Mezilev, K.A.; Moroz, F.V.; Orlov, S.Y.; Volkov, Y.M.; Andrighetto, A.; Lhersonneau, G.; Rizzi, V.; Tecchio, L.B.; Dubois, M.; Gaubert, G.; Jardins, P.; Lecesne, N.; Leroy, R.; Pacquet, J.Y.; Saint Laurent, M.G.; Villari, A.C.O.; Bajeat, O.; Essabaa, S.; Lau, C.; Menna, M.; Franberg, H.; Ammann, M.; Gdggeler, H.W.; Koster, U.; Allen, F.; Biedermann, C.; Radtke, R.; Ames, F.; Baartman, R.; Bricault, P.; Jayamanna, K.; Lamy, T.; McDonald, M.; Olivo, M.; Schmorl, P.; Yuan, D.H.L.; Asaji, T.; Sasaki, H.; Kato, Y.; Atabaev, B.; Radjabov, S.S.; Akhmadjanova, M.K.; Yuzikaeva, F.R.; Baoqun, Cui; Liqiang, Li; Yingjun, Ma; Shengyun, Zhu; Cong, Jiang

2005-01-01

This document gathers the summaries of the presentations made at ICIS05 (international conference on ion sources). It can be organized into 3 main topics: 1) 'fundamentals and theory' that deals with plasma, beam extraction, transport and emittance, diagnostics and simulation; 2) 'various types of ion sources' that include ECRIS, EBIS, microwave, negative, radioactive, polarized and laser ion sources, and charge breeders; and 3) 'ion sources and applications' in fields like accelerator injection, fusion energy, space propulsion, mass spectrometry, and neutron and cluster and rare nuclide production

Methodology for nuclear magnetic resonance and ion cyclotron resonance mass spectrometry

International Nuclear Information System (INIS)

Sehgal, Akansha

2014-01-01

This thesis encompasses methodological developments in both nuclear magnetic resonance and Fourier transform ion cyclotron resonance mass spectrometry. The NMR section explores the effects of scalar relaxation on a coupled nucleus to measure fast exchange rates. In order to quantify these rates accurately, a precise knowledge of the chemical shifts of the labile protons and of the scalar couplings is normally required. We applied the method to histidine where no such information was available a priori, neither about the proton chemical shifts nor about the one-bond scalar coupling constants J( 1 H 15 N), since the protons were invisible due to fast exchange. We have measured the exchange rates of the protons of the imidazole ring and of amino protons in histidine by indirect detection via 15 N. Not only the exchange rate constants, but also the elusive chemical shifts of the protons and the coupling constants could be determined. For the mass spectrometry section, the ion isolation project was initiated to study the effect of phase change of radiofrequency pulses. Excitation of ions in the ICR cell is a linear process, so that the pulse voltage required for ejecting ions must be inversely proportional to the pulse duration. A continuous sweep pulse propels the ion to a higher radius, whereas a phase reversal causes the ion to come to the centre. This represents the principle of 'notch ejection', wherein the ion for which the phase is reversed is retained in the ICR cell, while the remaining ions are ejected. The manuscript also contains a theoretical chapter, wherein the ion trajectories are plotted by solving the Lorentzian equation for the three-pulse scheme used for two-dimensional ICR. Through our simulations we mapped the ion trajectories for different pulse durations and for different phase relations. (author)

Heavy ion recoil spectrometry of SixGe1-x thin films

International Nuclear Information System (INIS)

Walker, S.R.; Johnston, P.N.; Bubb, I.F.; Cohen, D.D.; Dytlewski, N.; Hult, M.; Whitlow, H.J.; Zaring, C.; Oestling, M.

1993-01-01

Mass and energy dispersive recoil spectrometry employing 77 MeV 127 I ions from ANTARES (FN Tandem) facility at Lucas Heights has been used to examine the isotopic composition of samples of Si x Ge 1-x grown at the Australian National University by Electron Beam Evaporation (EBE). The recoiling target nuclei were analysed by a Time Of Flight and Energy (TOF-E) detector telescope composed of two timing pickoff detectors and a surface barrier (energy) detector. From the time of flight and energy, the ion mass can be determined and individual depth distributions for each element can be obtained. Recoil spectrometry has shown the presence of oxygen in the Si x Ge 1-x layer and has enabled the separate determination of energy spectra for individual elements. 9 refs., 3 figs

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation.

Science.gov (United States)

Di Giovanni, James P; Barkley, Robert M; Jones, David N M; Hankin, Joseph A; Murphy, Robert C

2018-04-23

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H] - ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H] - and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H 2 O-CO 2 ] - and [M-H-H 2 O] - displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H 2 O] - ion from LTB 4 was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H 2 O] - product ions from LTB 4 was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques. Graphical Abstract ᅟ.

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation

Science.gov (United States)

Di Giovanni, James P.; Barkley, Robert M.; Jones, David N. M.; Hankin, Joseph A.; Murphy, Robert C.

2018-04-01

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H]- ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H]- and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H2O-CO2]- and [M-H-H2O]- displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H2O]- ion from LTB4 was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H2O]- product ions from LTB4 was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques. [Figure not available: see fulltext.

Application of secondary ions mass spectrometry (SIMS) in studies of internal contamination

International Nuclear Information System (INIS)

Amaral, Ademir; Galle, Pierre; Colas-Linhart, Nicole

2000-01-01

Secondary Ion Mass Spectrometry (SIMS) permits the detection of stable and radioactive nuclides. Based on the ablation of specimens by ion bombardment this mass spectrometry method allows a rapid assessment of trace elements in biological samples. Its resolving mass power provides an efficient analytical method and, in particular, it makes possible accurate isotopic ratio determination. In this work, the application of SIMS has been investigated in studies of internal contamination. In vivo studies were carried out using duodenal tissue sections from rats contaminated with cerium. Tests were performed to localize this element as a result of the contamination. In this report, analytical procedures and the potential of SIMS in biological research are presented and discussed. (author)

Cluster ions and van der Waals molecules

CERN Document Server

Smirnov, Boris M

1992-01-01

This review discusses current ideas in the physics and chemistry of cluster ions and Van der Waals molecules as well as presenting numerical data on their parameters and the processes involving them. It is also a detailed reference on basic data relating to many species.

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

Science.gov (United States)

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

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

Science.gov (United States)

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

2012-02-03

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

Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

Science.gov (United States)

Farnsworth, Paul B.; Spencer, Ross L.

2017-08-01

Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

Performance evaluation of oxygen adsorbents using negative corona discharge–ion mobility spectrometry

Energy Technology Data Exchange (ETDEWEB)

Azadkish, Kamal; Jafari, Mohammad T., E-mail: jafari@cc.iut.ac.ir; Ghaziaskar, Hassan S.

2017-02-08

Trace amounts of oxygen was determined using negative corona discharge as an ionization source for ion mobility spectrometry. A point-in-cylinder geometry with novel design was used to establish the corona discharge without interferences of negative ions such as NO{sub X}{sup −}. The desirable background spectrum shows only electrons peak, providing the instrument capable of trace analysis of oxygen in gaseous samples. The limit of detection and linear dynamic range with high coefficient of determination (r{sup 2} = 0.9997), were obtained for oxygen as 8.5 and 28–14204 ppm, respectively. The relative standard deviations of the method for intraday and interday were obtained 4 and 11%, respectively. The satisfactory results revealed the ability of the negative corona discharge ion mobility spectrometry for investigating the performance of synthesized oxygen adsorbents in nitrogen streams. Two oxygen scavengers of MnO and Cu powder were prepared and the optimum temperature of the reactor containing MnO and Cu powder were obtained as 180 and 230 °C, respectively. Due to higher lifetime of copper powder, it was selected as the oxygen scavenger and some parameters such as: the type of adsorbent support, the size of adsorbent particles, and the amount of copper were studied for preparation of more efficient oxygen adsorbent. - Highlights: • Analysis of oxygen using negative corona discharge-ion mobility spectrometry was investigated for the first time. • Novel designed point-in-cylinder geometry was used to establish the corona discharge without interferences of negative ions. • The method was utilized to evaluate the performance of some synthesized oxygen scavengers.

Transmitted ion energy loss distributions to detect cluster formation in silicon

International Nuclear Information System (INIS)

Selen, L.J.M.; Loon, A. van; IJzendoorn, L.J. van; Voigt, M.J.A. de

2002-01-01

The energy loss distribution of ions transmitted through a 5.7±0.2 μm thick Si crystal was measured and simulated with the Monte Carlo channeling simulation code FLUX. A general resemblance between the measured and simulated energy loss distributions was obtained after incorporation of an energy dependent energy loss in the simulation program. The energy loss calculations are used to investigate the feasibility to detect the presence of light element dopant clusters in a host crystal from the shape of the energy loss distribution, with transmission ion channeling. A curved crystal structure is used as a model for a region in the host crystal with clusters. The presence of the curvature does have a large influence on the transmitted energy distribution, which offers the possibility to determine the presence of dopant clusters in a host crystal with transmission ion channeling

Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method.

Science.gov (United States)

Leveque, Nathalie L; Acheampong, Akwasi; Heron, Sylvie; Tchapla, Alain

2012-04-13

The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG((AAB and/or ABA))](+) generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)](+) or the neutral TAG molecule (TAG((AAB and/or ABA))) leading to [ref, Li](+). The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R(iso)), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures. Copyright © 2012 Elsevier B.V. All rights reserved.

11. international conference on ion sources

Energy Technology Data Exchange (ETDEWEB)

Leitner, D.; Lyneis, C.; Cheng, D.; Galloway, M.L.; Leitner, M.; Todd, D.S.; Ciavola, G.; Gammino, S.; Celona, L.; Ando, L.; Torrisi, L.; Cavenago, M.; Galata, A.; Spaedtke, P.; Tinschert, K.; Lang, R.; Iannucci, R.; Leroy, R.; Barue, C.; Hitz, D.; Koivisto, H.; Suominen, P.; Tarvainen, O.; Beijers, H.; Brandenburg, S.; Vanrooyen, D.; Hillo, C.; Kuchler, D.; Homeyer, H.; Rohrich, J.; Schachter, L.; Dobrescu, S.; Nakagawa, T.; Higurashi, Y.; Kidera, M.; Aihara, T.; Kase, M.; Goto, A.; Yang, Y.; Zhao, H.W.; Zhang, Z.M.; Zhang, X.Z.; Guo, X.H.; He, W.E.; Sun, L.T.; Yuan, P.; Song, M.T.; Xie, Z.Q.; Cao, Y.; Zhan, W.L.; Wei, B.W.; Bricault, P.; Lau, C.; Essabaa, S.; Cheikh Mhamed, M.; Bajeat, O.; Ducourtieux, M.; Lefort, H.; Panteleev, V.N.; Barzakh, A.E.; Fedorov, D.V.; Ionan, A.M.; Mezilev, K.A.; Moroz, F.V.; Orlov, S.Y.; Volkov, Y.M.; Andrighetto, A.; Lhersonneau, G.; Rizzi, V.; Tecchio, L.B.; Dubois, M.; Gaubert, G.; Jardins, P.; Lecesne, N.; Leroy, R.; Pacquet, J.Y.; Saint Laurent, M.G.; Villari, A.C.O.; Bajeat, O.; Essabaa, S.; Lau, C.; Menna, M.; Franberg, H.; Ammann, M.; Gdggeler, H.W.; Koster, U.; Allen, F.; Biedermann, C.; Radtke, R.; Ames, F.; Baartman, R.; Bricault, P.; Jayamanna, K.; Lamy, T.; McDonald, M.; Olivo, M.; Schmorl, P.; Yuan, D.H.L.; Asaji, T.; Sasaki, H.; Kato, Y.; Atabaev, B.; Radjabov, S.S.; Akhmadjanova, M.K.; Yuzikaeva, F.R.; Baoqun, Cui; Liqiang, Li; Yingjun, Ma; Shengyun, Zhu; Cong, Jiang

2005-07-01

This document gathers the summaries of the presentations made at ICIS05 (international conference on ion sources). It can be organized into 3 main topics: 1) 'fundamentals and theory' that deals with plasma, beam extraction, transport and emittance, diagnostics and simulation; 2) 'various types of ion sources' that include ECRIS, EBIS, microwave, negative, radioactive, polarized and laser ion sources, and charge breeders; and 3) 'ion sources and applications' in fields like accelerator injection, fusion energy, space propulsion, mass spectrometry, and neutron and cluster and rare nuclide production.

Aerosol Vacuum-Assisted Plasma Ionization (Aero-VaPI) Coupled to Ion Mobility-Mass Spectrometry

Science.gov (United States)

Blair, Sandra L.; Ng, Nga L.; Zambrzycki, Stephen C.; Li, Anyin; Fernández, Facundo M.

2018-02-01

In this communication, we report on the real-time analysis of organic aerosol particles by Vacuum-assisted Plasma Ionization-Mass Spectrometry (Aero-VaPI-MS) using a home-built VaPI ion source coupled to a Synapt G2-S HDMS ion mobility-mass spectrometry (IM-MS) system. Standards of organic molecules of interest in prebiotic chemistry were used to generate aerosols. Monocaprin and decanoic acid aerosol particles were successfully detected in both the positive and negative ion modes, respectively. A complex aerosol mixture of different sizes of polymers of L-malic acid was also examined through ion mobility (IM) separations, resulting in the detection of polymers of up to eight monomeric units. This noncommercial plasma ion source is proposed as a low cost alternative to other plasma ionization platforms used for aerosol analysis, and a higher-performance alternative to more traditional aerosol mass spectrometers. VaPI provides robust online ionization of organics in aerosols without extensive ion activation, with the coupling to IM-MS providing higher peak capacity and excellent mass accuracy. [Figure not available: see fulltext.

Structure investigation of metal ions clustering in dehydrated gel using x-ray anomalous dispersion effect

CERN Document Server

Soejima, Y; Sugiyama, M; Annaka, M; Nakamura, A; Hiramatsu, N; Hara, K

2003-01-01

The structure of copper ion clusters in dehydrated N-isopropylacrylamide/sodium acrylate (NIPA/SA) gel has been studied by means of small angle X-ray scattering (SAXS) method. In order to distinguish the intensity scattered by Cu ions, the X-ray anomalous dispersion effect around the Cu K absorption edge has been coupled with SAXS. It is found that the dispersion effect dependent on the incident X-ray energy is remarkable only at the momentum transfer q = 0.031 A sup - sup 1 , where a SAXS peak is observed. The results indicate that copper ions form clusters in the dehydrated gel, and that the mean size of clusters is the same as that of SA clusters produced by microphase separation. It is therefore naturally presumed that copper ions are adsorbed into the SA molecules. On the basis of the presumption, a mechanism is proposed for microphase-separation and clustering of Cu ions.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706 (United States)

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ions having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.

A theoretical investigation of the collective acceleration of cluster ions with accelerated potential waves

International Nuclear Information System (INIS)

Suzuki, Hiroshi; Enjoji, Hiroshi; Kawaguchi, Motoichi; Noritake, Toshiya

1984-01-01

A theoretical treatment of the acceleration of cluster ions for additional heating of fusion plasma using the trapping effect in an accelerated potential wave is described. The conceptual design of the accelerator is the same as that by Enjoji, and the potential wave used is sinusoidal. For simplicity, collisions among cluster ions and the resulting breakups are neglected. The masses of the cluster ions are specified to range from 100 m sub(D) to 1000 m sub(D) (m sub(D): mass of a deuterium atom). Theoretical treatment is carried out only for the injection velocity which coincides with the phase velocity of the applied wave at the entrance of the accelerator. An equation describing the rate for successful acceleration of ions with a certain mass is deduced for the continuous injection of cluster ions. Computation for a typical mass distribution shows that more than 70% of the injected particles are effectively accelerated. (author)

Cluster-assisted multiple ionization of methyl iodide by a nanosecond laser: Influence of laser intensity on the kinetic energy and peak profile of multicharged ions

International Nuclear Information System (INIS)

Wen Lihua; Li Haiyang; Luo Xiaolin; Niu Dongmei; Xiao Xue; Wang Bin; Liang Feng; Hou Keyong; Shao Shiyong

2006-01-01

The dependences of kinetic energies and peak profiles of multicharged ions of I q+ (q = 2-3) and C 2+ on the laser intensity have been studied in detail by time-of-flight mass spectrometry, those multicharged ions are produced by irradiation of methyl iodide cluster beam with a nanosecond 532 nm Nd-YAG laser. Our experiments show that the kinetic energies released of multicharged ions increase linearly with the laser intensity in the range of 3 x 10 9 -2 x 10 11 W/cm 2 . The peaks of multicharged ions are split to forward ions and backward ions, and the ratio of the backward ions to forward ions decreases exponentially with laser intensity. The decreasing of backward ions is probably due to Coulomb scattering by the heavier I + ions when they turn around through the laser focus point. The linear dependence of kinetic energy of multicharged ions on laser intensity is interpreted by the ionization mechanism, in which the laser induced inverse bremsstrahlung heating of electron is the rate-limiting step

Comparing the effect of pressure and temperature on ion mobilities

International Nuclear Information System (INIS)

Tabrizchi, Mahmoud; Rouholahnejad, Fereshteh

2005-01-01

The effect of pressure on ion mobilities has been investigated and compared with that of temperature. In this connection, an ion mobility spectrometry (IMS) cell, which employs a corona discharge as the ionization source, has been designed and constructed to allow varying pressure inside the drift region. IMS spectra were recorded at various pressures ranging from 15 Torr up to atmospheric pressure. The results show that IMS peaks shift perfectly linear with pressure which is in excellent agreement with the ion mobility theory. However, experimental ion mobilities versus temperature show deviation from the theoretical trend. The deviation is attributed to formation of clusters. The different behaviour of pressure and temperature was explained on the basis of the different impact of pressure and temperature on hydration and clustering of ions. Pressure affects the clustering reactions linearly but temperature affects it exponentially

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

Science.gov (United States)

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Evaluation of secondary ion yield enhancement from polymer material by using TOF-SIMS equipped with a gold cluster ion source

Energy Technology Data Exchange (ETDEWEB)

Aimoto, K. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)]. E-mail: dm053502@cc.seikei.ac.jp; Aoyagi, S. [Department of Regional Development, Faculty of Life and Environmental Science, Shimane University, 1060 Nishikawatsu-cho, Matsue-shi, Shimane 690-8504 (Japan); Kato, N. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan); Iida, N. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Yamamoto, A. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Kudo, M. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)

2006-07-30

We investigated the enhancement of the secondary ion intensity in the TOF-SIMS spectra obtained by Au{sup +} and Au{sub 3} {sup +} bombardment in comparison with Ga{sup +} excitation using polymer samples with different molecular weight distributions. Since the polymer samples used in this experiment have a wide molecular weight distribution, the advantages of the gold cluster primary ion source over monoatomic ion could accurately be evaluated. It was observed that the degree of fragmentation decreased by the usage of cluster primary ion beam compared with monoatomic ion beam, which was observed as a shift of the intensity distribution in the spectra. It was also found out that the mass effect of Au{sup +} and Ga{sup +} as monoatomic primary ion, resulted in about 10-60 times of enhancement for both samples with different molecular distributions. On the other hand, the Au{sub 3} {sup +} bombardment caused intensity enhancement about 100-2600 compared with Ga{sup +} bombardment, depending on the mass range of the detected secondary ion species. The cluster primary ion effect of Au{sub 3} {sup +}, compared with Au{sup +}, therefore, was estimated to be about 10-45.

Electrostatic ion trap and Fourier transform measurements for high-resolution mass spectrometry

International Nuclear Information System (INIS)

Bhushan, K. G.; Gadkari, S. C.; Yakhmi, J. V.; Sahni, V. C.

2007-01-01

We report on the development of an electrostatic ion trap for high-resolution mass spectrometry. The trap works on purely electrostatic fields and hence trapping and storing of ions is not mass restrictive, unlike other techniques based on Penning, Paul, or radio frequency quadrupole ion traps. It allows simultaneous trapping and studying of multiple mass species over a large mass range. Mass spectra were recorded in ''dispersive'' and ''self-bunching'' modes of ions. Storage lifetimes of about 100 ms and mass resolving power of about 20 000 could be achieved from the fifth harmonic Fourier transform spectrum of Xe ions recorded in the self-bunching mode

Summary of Industry-Academia Collaboration Projects on Cluster Ion Beam Process Technology

International Nuclear Information System (INIS)

Yamada, Isao; Toyoda, Noriaki; Matsuo, Jiro

2008-01-01

Processes employing clusters of ions comprised of a few hundred to many thousand atoms are now being developed into a new field of ion beam technology. Cluster-surface collisions produce important non-linear effects which are being applied to shallow junction formation, to etching and smoothing of semiconductors, metals, and dielectrics, to assisted formation of thin films with nano-scale accuracy, and to other surface modification applications. In 2000, a four year R and D project for development of industrial technology began in Japan under funding from the New Energy and Industrial Technology Development Organization (NEDO). Subjects of the projects are in areas of equipment development, semiconductor surface processing, high accuracy surface processing and high-quality film formation. In 2002, another major cluster ion beam project which emphasized nano-technology applications has started under a contract from the Ministry of Economy and Technology for Industry (METI). This METI project involved development related to size-selected cluster ion beam equipment and processes, and development of GCIB processes for very high rate etching and for zero damage etching of magnetic materials and compound semiconductor materials. This paper describes summery of the results.

Chemometrics for ion mobility spectrometry data: recent advances and future prospects

NARCIS (Netherlands)

Szymanska, E.; Davies, Antony N.; Buydens, L.M.C.

2016-01-01

Historically, advances in the field of ion mobility spectrometry have been hindered by the variation in measured signals between instruments developed by different research laboratories or manufacturers. This has triggered the development and application of chemometric techniques able to reveal and

Structure and reactivity of molybdenum oxide cluster ions in the gas phase

International Nuclear Information System (INIS)

Goncharov, V.B.; Fialko, E.F.

2002-01-01

A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

Pre-equilibrium (exciton) model and the heavy-ion reactions with cluster emission

CERN Document Server

Betak, E

2015-01-01

We bring the possibility to include the cluster emission into the statistical pre-equilibrium (exciton) model enlarged for considering also the heavy ion collisions. At this moment, the calculations have been done without treatment of angular momentum variables, but all the approach can be straightforwardly applied to heavy-ion reactions with cluster emission including the angular momentum variables. The direct motivation of this paper is a possibility of producing the superdeformed nuclei, which are easier to be detected in heavy-ion reactions than in those induced by light projectiles (nucleons, deuterons, $\\alpha$-particles).

Visualization of DNA clustered damage induced by heavy ion exposure

International Nuclear Information System (INIS)

Tomita, M.; Yatagai, F.

2003-01-01

Full text: DNA double-strand breaks (DSBs) are the most lethal damage induced by ionizing radiations. Accelerated heavy-ions have been shown to induce DNA clustered damage, which is two or more DNA lesions induced within a few helical turns. Higher biological effectiveness of heavy-ions could be provided predominantly by induction of complex DNA clustered damage, which leads to non-repairable DSBs. DNA-dependent protein kinase (DNA-PK) is composed of catalytic subunit (DNA-PKcs) and DNA-binding heterodimer (Ku70 and Ku86). DNA-PK acts as a sensor of DSB during non-homologous end-joining (NHEJ), since DNA-PK is activated to bind to the ends of double-stranded DNA. On the other hand, NBS1 and histone H2AX are essential for DSB repair by homologous recombination (HR) in higher vertebrate cells. Here we report that phosphorylated H2AX at Ser139 (named γ-H2AX) and NBS1 form large undissolvable foci after exposure to accelerated Fe ions, while DNA-PKcs does not recognize DNA clustered damage. NBS1 and γ-H2AX colocalized with forming discrete foci after exposure to X-rays. At 0.5 h after Fe ion irradiation, NBS1 and γ-H2AX also formed discrete foci. However, at 3-8 h after Fe ion irradiation, highly localized large foci turned up, while small discrete foci disappeared. Large NBS1 and γ-H2AX foci were remained even 16 h after irradiation. DNA-PKcs recognized Ku-binding DSB and formed foci shortly after exposure to X-rays. DNA-PKcs foci were observed 0.5 h after 5 Gy of Fe ion irradiation and were almost completely disappeared up to 8 h. These results suggest that NBS1 and γ-H2AX can be utilized as molecular marker of DNA clustered damage, while DNA-PK selectively recognizes repairable DSBs by NHEJ

The quantitative analysis of silicon carbide surface smoothing by Ar and Xe cluster ions

Science.gov (United States)

Ieshkin, A. E.; Kireev, D. S.; Ermakov, Yu. A.; Trifonov, A. S.; Presnov, D. E.; Garshev, A. V.; Anufriev, Yu. V.; Prokhorova, I. G.; Krupenin, V. A.; Chernysh, V. S.

2018-04-01

The gas cluster ion beam technique was used for the silicon carbide crystal surface smoothing. The effect of processing by two inert cluster ions, argon and xenon, was quantitatively compared. While argon is a standard element for GCIB, results for xenon clusters were not reported yet. Scanning probe microscopy and high resolution transmission electron microscopy techniques were used for the analysis of the surface roughness and surface crystal layer quality. The gas cluster ion beam processing results in surface relief smoothing down to average roughness about 1 nm for both elements. It was shown that xenon as the working gas is more effective: sputtering rate for xenon clusters is 2.5 times higher than for argon at the same beam energy. High resolution transmission electron microscopy analysis of the surface defect layer gives values of 7 ± 2 nm and 8 ± 2 nm for treatment with argon and xenon clusters.

Cluster chemical ionization for improved confidence level in sample identification by gas chromatography/mass spectrometry.

Science.gov (United States)

Fialkov, Alexander B; Amirav, Aviv

2003-01-01

Upon the supersonic expansion of helium mixed with vapor from an organic solvent (e.g. methanol), various clusters of the solvent with the sample molecules can be formed. As a result of 70 eV electron ionization of these clusters, cluster chemical ionization (cluster CI) mass spectra are obtained. These spectra are characterized by the combination of EI mass spectra of vibrationally cold molecules in the supersonic molecular beam (cold EI) with CI-like appearance of abundant protonated molecules, together with satellite peaks corresponding to protonated or non-protonated clusters of sample compounds with 1-3 solvent molecules. Like CI, cluster CI preferably occurs for polar compounds with high proton affinity. However, in contrast to conventional CI, for non-polar compounds or those with reduced proton affinity the cluster CI mass spectrum converges to that of cold EI. The appearance of a protonated molecule and its solvent cluster peaks, plus the lack of protonation and cluster satellites for prominent EI fragments, enable the unambiguous identification of the molecular ion. In turn, the insertion of the proper molecular ion into the NIST library search of the cold EI mass spectra eliminates those candidates with incorrect molecular mass and thus significantly increases the confidence level in sample identification. Furthermore, molecular mass identification is of prime importance for the analysis of unknown compounds that are absent in the library. Examples are given with emphasis on the cluster CI analysis of carbamate pesticides, high explosives and unknown samples, to demonstrate the usefulness of Supersonic GC/MS (GC/MS with supersonic molecular beam) in the analysis of these thermally labile compounds. Cluster CI is shown to be a practical ionization method, due to its ease-of-use and fast instrumental conversion between EI and cluster CI, which involves the opening of only one valve located at the make-up gas path. The ease-of-use of cluster CI is analogous

The formation of magnetic silicide Fe{sub 3}Si clusters during ion implantation

Energy Technology Data Exchange (ETDEWEB)

Balakirev, N. [Kazan National Research Technological University, K.Marx st. 68, Kazan 420015 (Russian Federation); Zhikharev, V., E-mail: valzhik@mail.ru [Kazan National Research Technological University, K.Marx st. 68, Kazan 420015 (Russian Federation); Gumarov, G. [Zavoiskii Physico-Technical Institute of Russian Academy of Sciences, 10/7 Sibirskii trakt st., Kazan 420029 (Russian Federation)

2014-05-01

A simple two-dimensional model of the formation of magnetic silicide Fe{sub 3}Si clusters during high-dose Fe ion implantation into silicon has been proposed and the cluster growth process has been computer simulated. The model takes into account the interaction between the cluster magnetization and magnetic moments of Fe atoms random walking in the implanted layer. If the clusters are formed in the presence of the external magnetic field parallel to the implanted layer, the model predicts the elongation of the growing cluster in the field direction. It has been proposed that the cluster elongation results in the uniaxial magnetic anisotropy in the plane of the implanted layer, which is observed in iron silicide films ion-beam synthesized in the external magnetic field.

Model Titan atmospheric hydrocarbon analysis by Ion Mobility Spectrometry in dry helium

International Nuclear Information System (INIS)

Kojiro, D.R.; Stimac, R.M.; Wernlund, R.F.; Cohen, M.J.

1990-01-01

Ion Mobility Spectrometry (IMS) is one analytical technique being investigated for the in situ analysis of the atmosphere of Titan. Any hydrocarbon ions that may form react immediately, in microseconds, with the high concentration of water vapor normally present in conventional IMS. By reducing the water concentration to the parts-per-billion range, the lifetime of the hydrocarbon ions may be increased to the milliseconds required for measurement. At low water level concentrations, other species may become the reactant ion. This study focuses on IMS analysis of expected Titan atmospheric hydrocarbons under very dry, low water concentration conditions

Mass spectrometric study of the negative and positive secondary ions emitted from ethanol microdroplets by MeV-energy heavy ion impact

Science.gov (United States)

Kitajima, Kensei; Majima, Takuya; Nishio, Tatsuya; Oonishi, Yoshiki; Mizutani, Shiori; Kohno, Jun-ya; Saito, Manabu; Tsuchida, Hidetsugu

2018-06-01

We have investigated the negative and positive secondary ions emitted from ethanol droplets by 4.0-MeV C3+ impact to reveal the characteristic features of the reaction processes induced by fast heavy ions at the liquid ethanol surface. Analysis of the secondary ions was performed by time-of-flight mass spectrometry for microdroplet targets in a high vacuum environment. Fragment ions, deprotonated cluster ions, and trace amounts of the reaction product ions are observed in the negative secondary ions. The main fragment anions are C2HmO- (m = 1, 3, and 5) and C2H- generated by loss of hydrogen and oxygen atoms. The reaction product anions include deprotonated glycols, larger alcohols, and their dehydrated and dehydrogenated forms generated by secondary reactions between fragments and radicals. Furthermore, C3Hm- (m = 0-2) and C4Hm- (m = 0 and 1) are observed, which could be produced through a plasma state generated in the heavy ion track. Deprotonated ethanol cluster ions, [(EtOH)n - H]-, are observed up to about n = 25. [(EtOH)n - H]- have smaller kinetic energies than the protonated cluster ions (EtOH)nH+. This probably represents the effect of the positive Coulomb potential transiently formed in the ion track. We also discuss the size distributions and structures of the water- and CH2OH-radical-attached ethanol cluster ions.

Characterizing the lipid and metabolite changes associated with placental function and pregnancy complications using ion mobility spectrometry-mass spectrometry and mass spectrometry imaging

Energy Technology Data Exchange (ETDEWEB)

Burnum-Johnson, Kristin E.; Baker, Erin S.; Metz, Thomas O.

2017-12-01

Successful pregnancy is dependent upon discrete biological events, which include embryo implantation, decidualization, and placentation. Problems associated with each of these events can cause infertility or conditions such as preeclampsia. A greater understanding of the molecular changes associated with these complex processes is necessary to aid in identifying treatments for each condition. Previous nuclear magnetic resonance spectroscopy and mass spectrometry studies have been used to identify metabolites and lipids associated with pregnancy-related complications. However, due to limitations associated with conventional implementations of both techniques, novel technology developments are needed to more fully understand the initiation and development of pregnancy related problems at the molecular level. In this perspective, we describe current analytical techniques for metabolomic and lipidomic characterization of pregnancy complications and discuss the potential for new technologies such as ion mobility spectrometry-mass spectrometry and mass spectrometry imaging to contribute to a better understanding of the molecular changes that affect the placenta and pregnancy outcomes.

Investigation of the negative ions in Ar/O.sub.2./sub. plasma of magnetron sputtering discharge with Al:Zn target by ion mass spectrometry

Czech Academy of Sciences Publication Activity Database

Pokorný, Petr; Mišina, Martin; Bulíř, Jiří; Lančok, Ján; Fitl, Přemysl; Musil, Jindřich; Novotný, Michal

2011-01-01

Roč. 8, č. 5 (2011), s. 459-464 ISSN 1612-8850 R&D Projects: GA AV ČR IAA100100718; GA AV ČR KAN400100653; GA ČR GP202/09/P324 Institutional research plan: CEZ:AV0Z10100522 Keywords : energy-resolved ion mass spectrometry * formation of negative ions * magnetron sputtering * mass spectrometry * transparent conductive oxide Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.468, year: 2011

Ionization of water clusters by fast Highly Charged Ions: Stability, fragmentation, energetics and charge mobility

International Nuclear Information System (INIS)

Legendre, S; Maisonny, R; Capron, M; Bernigaud, V; Cassimi, A; Gervais, B; Grandin, J-P; Huber, B A; Manil, B; Rousseau, P; Tarisien, M; Adoui, L; Lopez-Tarifa, P; AlcamI, M; MartIn, F; Politis, M-F; Penhoat, M A Herve du; Vuilleumier, R; Gaigeot, M-P; Tavernelli, I

2009-01-01

We study dissociative ionization of water clusters by impact of fast Ni ions. Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) is used to obtain information about stability, energetics and charge mobility of the ionized clusters. An unusual stability of the (H 2 O) 4 H ''+ ion is observed, which could be the signature of the so called ''Eigen'' structure in gas phase water clusters. High charge mobility, responsible for the formation of protonated water clusters that dominate the mass spectrum, is evidenced. These results are supported by CPMD and TDDFT simulations, which also reveal the mechanisms of such mobility.

Prediction of peptide drift time in ion mobility mass spectrometry from sequence-based features

KAUST Repository

Wang, Bing; Zhang, Jun; Chen, Peng; Ji, Zhiwei; Deng, Shuping; Li, Chi

2013-01-01

Background: Ion mobility-mass spectrometry (IMMS), an analytical technique which combines the features of ion mobility spectrometry (IMS) and mass spectrometry (MS), can rapidly separates ions on a millisecond time-scale. IMMS becomes a powerful tool to analyzing complex mixtures, especially for the analysis of peptides in proteomics. The high-throughput nature of this technique provides a challenge for the identification of peptides in complex biological samples. As an important parameter, peptide drift time can be used for enhancing downstream data analysis in IMMS-based proteomics.Results: In this paper, a model is presented based on least square support vectors regression (LS-SVR) method to predict peptide ion drift time in IMMS from the sequence-based features of peptide. Four descriptors were extracted from peptide sequence to represent peptide ions by a 34-component vector. The parameters of LS-SVR were selected by a grid searching strategy, and a 10-fold cross-validation approach was employed for the model training and testing. Our proposed method was tested on three datasets with different charge states. The high prediction performance achieve demonstrate the effectiveness and efficiency of the prediction model.Conclusions: Our proposed LS-SVR model can predict peptide drift time from sequence information in relative high prediction accuracy by a test on a dataset of 595 peptides. This work can enhance the confidence of protein identification by combining with current protein searching techniques. 2013 Wang et al.; licensee BioMed Central Ltd.

Prediction of peptide drift time in ion mobility mass spectrometry from sequence-based features

KAUST Repository

Wang, Bing

2013-05-09

Background: Ion mobility-mass spectrometry (IMMS), an analytical technique which combines the features of ion mobility spectrometry (IMS) and mass spectrometry (MS), can rapidly separates ions on a millisecond time-scale. IMMS becomes a powerful tool to analyzing complex mixtures, especially for the analysis of peptides in proteomics. The high-throughput nature of this technique provides a challenge for the identification of peptides in complex biological samples. As an important parameter, peptide drift time can be used for enhancing downstream data analysis in IMMS-based proteomics.Results: In this paper, a model is presented based on least square support vectors regression (LS-SVR) method to predict peptide ion drift time in IMMS from the sequence-based features of peptide. Four descriptors were extracted from peptide sequence to represent peptide ions by a 34-component vector. The parameters of LS-SVR were selected by a grid searching strategy, and a 10-fold cross-validation approach was employed for the model training and testing. Our proposed method was tested on three datasets with different charge states. The high prediction performance achieve demonstrate the effectiveness and efficiency of the prediction model.Conclusions: Our proposed LS-SVR model can predict peptide drift time from sequence information in relative high prediction accuracy by a test on a dataset of 595 peptides. This work can enhance the confidence of protein identification by combining with current protein searching techniques. 2013 Wang et al.; licensee BioMed Central Ltd.

Ion mobility spectrometry for food quality and safety.

Science.gov (United States)

Vautz, W; Zimmermann, D; Hartmann, M; Baumbach, J I; Nolte, J; Jung, J

2006-11-01

Ion mobility spectrometry is known to be a fast and sensitive technique for the detection of trace substances, and it is increasingly in demand not only for protection against explosives and chemical warfare agents, but also for new applications in medical diagnosis or process control. Generally, a gas phase sample is ionized by help of ultraviolet light, ss-radiation or partial discharges. The ions move in a weak electrical field towards a detector. During their drift they collide with a drift gas flowing in the opposite direction and, therefore, are slowed down depending on their size, shape and charge. As a result, different ions reach the detector at different drift times, which are characteristic for the ions considered. The number of ions reaching the detector are a measure of the concentration of the analyte. The method enables the identification and quantification of analytes with high sensitivity (ng l(-1) range). The selectivity can even be increased - as necessary for the analyses of complex mixtures - using pre-separation techniques such as gas chromatography or multi-capillary columns. No pre-concentration of the sample is necessary. Those characteristics of the method are preserved even in air with up to a 100% relative humidity rate. The suitability of the method for application in the field of food quality and safety - including storage, process and quality control as well as the characterization of food stuffs - was investigated in recent years for a number of representative examples, which are summarized in the following, including new studies as well: (1) the detection of metabolites from bacteria for the identification and control of their growth; (2) process control in food production - beer fermentation being an example; (3) the detection of the metabolites of mould for process control during cheese production, for quality control of raw materials or for the control of storage conditions; (4) the quality control of packaging materials during

Plasma diagnostics of the SIMPA Ecr ion source by X-ray spectroscopy, Collisions of H-like Neon ions with Argon clusters

International Nuclear Information System (INIS)

Adrouche, N.

2006-09-01

The first part of this thesis is devoted to the SIMPA ECR ion source characterization, first, I explored the ion source's capacities on the point of view of extracted currents for three elements, argon, krypton and neon. By analyzing the Bremsstrahlung spectra, I determined the electronic temperature in the plasma and the electronic and ionic densities. In a second time, I recorded high resolution X-spectra of argon and krypton plasma's. By taking into account the principal mechanisms of production of a K hole in the ions inside the plasma, I determined the ionic densities of the high charge states of argon. Lastly, I highlighted a correlation between the ions charge states densities with the intensities of extracted currents. The second part of the thesis is devoted to Ne 9+- argon clusters collisions. First, I presented simple and effective theoretical models allowing to describe the phenomena occurring during a collision, from the point of view of the projectile. I carried out a simulation for a collision of an ion Ne 9+ with an argon cluster of a given size, which has enabled us to know the energy levels populated during the electronic capture and to follow the number of electrons in each projectile shell. Lastly, I presented the first results of a collision between a Ne 9+ beam and argon clusters. These results, have enabled me by using projectile X-ray spectroscopy during the ions-clusters collision, to evidence a strong clustering of targets atoms and to highlight an electronic multi-capture in the projectile ion excited states. (author)

Analysis of Ketones by Selected Ion Flow Tube Mass Spectrometry

Czech Academy of Sciences Publication Activity Database

Smith, D.; Wang, T.; Španěl, Patrik

2003-01-01

Roč. 17, - (2003), s. 2655-2660 ISSN 0951-4198 R&D Projects: GA ČR GA202/03/0827; GA ČR GA203/02/0737 Institutional research plan: CEZ:AV0Z4040901 Keywords : mass spectrometry * selected ion flow tube * ketones Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.789, year: 2003

Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

Energy Technology Data Exchange (ETDEWEB)

Tuccitto, N. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)], E-mail: n.tuccitto@unict.it; Torrisi, V.; Delfanti, I.; Licciardello, A. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)

2008-12-15

Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au{sub n}{sup -}) in comparison with the molecular ions (M{sup -}) and clusters (M{sub x}Au{sub y}{sup -}) by using Bi{sup +}, Bi{sub 3}{sup +}, Bi{sub 5}{sup +} beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

Boosting Sensitivity in Liquid Chromatography–Fourier Transform Ion Cyclotron Resonance–Tandem Mass Spectrometry for Product Ion Analysis of Monoterpene Indole Alkaloids

Directory of Open Access Journals (Sweden)

Ryo eNakabayashi

2015-12-01

Full Text Available In metabolomics, the analysis of product ions in tandem mass spectrometry (MS/MS is noteworthy to chemically assign structural information. However, the development of relevant analytical methods are less advanced. Here, we developed a method to boost sensitivity in liquid chromatography–Fourier transform ion cyclotron resonance–tandem mass spectrometry analysis (MS/MS boost analysis. To verify the MS/MS boost analysis, both quercetin and uniformly labeled 13C quercetin were analyzed, revealing that the origin of the product ions is not the instrument, but the analyzed compounds resulting in sensitive product ions. Next, we applied this method to the analysis of monoterpene indole alkaloids (MIAs. The comparative analyses of MIAs having indole basic skeleton (ajmalicine, catharanthine, hirsuteine, and hirsutine and oxindole skeleton (formosanine, isoformosanine, pteropodine, isopteropodine, rhynchophylline, isorhynchophylline, and mitraphylline identified 86 and 73 common monoisotopic ions, respectively. The comparative analyses of the three pairs of stereoisomers showed more than 170 common monoisotopic ions in each pair. This method was also applied to the targeted analysis of MIAs in Catharanthus roseus and Uncaria rhynchophylla to profile indole and oxindole compounds using the product ions. This analysis is suitable for chemically assigning features of the metabolite groups, which contributes to targeted metabolome analysis.

Boosting Sensitivity in Liquid Chromatography–Fourier Transform Ion Cyclotron Resonance–Tandem Mass Spectrometry for Product Ion Analysis of Monoterpene Indole Alkaloids

Science.gov (United States)

Nakabayashi, Ryo; Tsugawa, Hiroshi; Kitajima, Mariko; Takayama, Hiromitsu; Saito, Kazuki

2015-01-01

In metabolomics, the analysis of product ions in tandem mass spectrometry (MS/MS) is noteworthy to chemically assign structural information. However, the development of relevant analytical methods are less advanced. Here, we developed a method to boost sensitivity in liquid chromatography–Fourier transform ion cyclotron resonance–tandem mass spectrometry analysis (MS/MS boost analysis). To verify the MS/MS boost analysis, both quercetin and uniformly labeled 13C quercetin were analyzed, revealing that the origin of the product ions is not the instrument, but the analyzed compounds resulting in sensitive product ions. Next, we applied this method to the analysis of monoterpene indole alkaloids (MIAs). The comparative analyses of MIAs having indole basic skeleton (ajmalicine, catharanthine, hirsuteine, and hirsutine) and oxindole skeleton (formosanine, isoformosanine, pteropodine, isopteropodine, rhynchophylline, isorhynchophylline, and mitraphylline) identified 86 and 73 common monoisotopic ions, respectively. The comparative analyses of the three pairs of stereoisomers showed more than 170 common monoisotopic ions in each pair. This method was also applied to the targeted analysis of MIAs in Catharanthus roseus and Uncaria rhynchophylla to profile indole and oxindole compounds using the product ions. This analysis is suitable for chemically assigning features of the metabolite groups, which contributes to targeted metabolome analysis. PMID:26734034

Methods of gas purification and effect on the ion composition in an RF atmospheric pressure plasma jet investigated by mass spectrometry

International Nuclear Information System (INIS)

Grosse-Kreul, Simon; Huebner, Simon; Schneider, Simon; Keudell, Achim von; Benedikt, Jan

2016-01-01

The analysis of the ion chemistry of atmospheric pressure plasmas is essential to evaluate ionic reaction pathways during plasma-surface or plasma-analyte interactions. In this contribution, the ion chemistry of a radio-frequency atmospheric pressure plasma jet (μ-APPJ) operated in helium is investigated by mass spectrometry (MS). It is found, that the ion composition is extremely sensitive to impurities such as N 2 , O 2 and H 2 O. Without gas purification, protonated water cluster ions of the form H + (H 2 O) n are dominating downstream the positive ion mass spectrum. However, even after careful feed gas purification to the sub-ppm level using a molecular sieve trap and a liquid nitrogen trap as well as operation of the plasma in a controlled atmosphere, the positive ion mass spectrum is strongly influenced by residual trace gases. The observations support the idea that species with a low ionization energy serve as a major source of electrons in atmospheric pressure helium plasmas. Similarly, the neutral density of atomic nitrogen measured by MS in a He/N 2 mixture is varying up to a factor 3, demonstrating the significant influence of impurities on the neutral species chemistry as well. (orig.)

Methods of gas purification and effect on the ion composition in an RF atmospheric pressure plasma jet investigated by mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Grosse-Kreul, Simon; Huebner, Simon; Schneider, Simon; Keudell, Achim von; Benedikt, Jan [Ruhr-Universitaet Bochum, Institute for Experimental Physics II, Bochum (Germany)

2016-12-15

The analysis of the ion chemistry of atmospheric pressure plasmas is essential to evaluate ionic reaction pathways during plasma-surface or plasma-analyte interactions. In this contribution, the ion chemistry of a radio-frequency atmospheric pressure plasma jet (μ-APPJ) operated in helium is investigated by mass spectrometry (MS). It is found, that the ion composition is extremely sensitive to impurities such as N{sub 2}, O{sub 2} and H{sub 2}O. Without gas purification, protonated water cluster ions of the form H{sup +}(H{sub 2}O){sub n} are dominating downstream the positive ion mass spectrum. However, even after careful feed gas purification to the sub-ppm level using a molecular sieve trap and a liquid nitrogen trap as well as operation of the plasma in a controlled atmosphere, the positive ion mass spectrum is strongly influenced by residual trace gases. The observations support the idea that species with a low ionization energy serve as a major source of electrons in atmospheric pressure helium plasmas. Similarly, the neutral density of atomic nitrogen measured by MS in a He/N{sub 2} mixture is varying up to a factor 3, demonstrating the significant influence of impurities on the neutral species chemistry as well. (orig.)

Ion-streaming induced order transition in three-dimensional dust clusters

International Nuclear Information System (INIS)

Ludwig, Patrick; Kählert, Hanno; Bonitz, Michael

2012-01-01

Dust dynamics simulations utilizing a dynamical screening approach are performed to study the effect of ion-streaming on the self-organized structures in a three-dimensional spherically confined complex (dusty) plasma. Varying the Mach number M, the ratio of ion drift velocity to the sound velocity, the simulations reproduce the experimentally observed cluster configurations in the two limiting cases: at M = 0 strongly correlated crystalline structures consisting of nested spherical shells (Yukawa balls) and, for M ⩾ 1, flow-aligned dust chains, respectively. In addition, our simulations reveal a discontinuous transition between these two limits. It is found that already a moderate ion drift velocity (M ≈ 0.1 for the plasma conditions considered here) destabilizes the highly ordered Yukawa balls and initiates an abrupt melting transition. The critical value of M is found to be independent of the cluster size. (paper)

Investigation of the alpha cluster model and the density matrix expansion in ion-ion collision

International Nuclear Information System (INIS)

Rashdan, M.B.M.

1986-01-01

This thesis deals with the investigation of the alpha cluster model (ACM) of brink and studies of the accuracy of the density matrix expansion (DME) approximation in deriving the real part of the ion-ion optical potential. the ACM is applied to calculate the inelastic 0 1 + →2 1 + charge form factor for electron scattering by 12 C to investigate the validity of this model for 12 C nucleus. it is found that the experimental curve can be fitted over the entire range of the momentum transfer by a generator - coordinate state for the 2 1 + state that consist of a superposition of two triangular ACM states with two different cluster separations and the same oscillator parameter

Electron-induced chemistry in microhydrated sulfuric acid clusters

Science.gov (United States)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Time of flight spectrometry in heavy ions backscattering analysis

International Nuclear Information System (INIS)

Chevarier, A.; Chevarier, N.

1983-05-01

Time of flight spectrometry for backscattering analysis of MeV heavy ions is proposed. The capabilities and limitations of this method are investigated. Depth and mass resolution obtained in measurements of oxide films thickness as well as in GaAs layers analysis are presented. The importance of minimizing pile-up without significant loss of resolution by use of an adequate absorber set just in front of the rear detector is underlined

Rapid thermal and swift heavy ion induced annealing of Co ion implanted GaN films

International Nuclear Information System (INIS)

Baranwal, V.; Pandey, A. C.; Gerlach, J. W.; Rauschenbach, B.; Karl, H.; Kanjilal, D.; Avasthi, D. K.

2008-01-01

Thin epitaxial GaN films grown on 6H-SiC(0001) substrates were implanted with 180 keV Co ions at three different fluences. As-implanted samples were characterized with secondary ion mass spectrometry and Rutherford backscattering spectrometry to obtain the Co depth profiles and the maximum Co concentrations. As-implanted samples were annealed applying two different techniques: rapid thermal annealing and annealing by swift heavy ion irradiation. Rapid thermal annealing was done at two temperatures: 1150 deg. C for 20 s and 700 deg. C for 5 min. 200 MeV Ag ions at two fluences were used for annealing by irradiation. Crystalline structure of the pristine, as-implanted, and annealed samples was investigated using x-ray diffraction, and the results were compared. Improvement of the crystalline quality was observed for rapid thermal annealed samples at the higher annealing temperature as confirmed with rocking curve measurements. The results indicate the presence of Co clusters in these annealed samples. Swift heavy ion irradiation with the parameters chosen for this study did not lead to a significant annealing

Dynamics of Neutral Cluster Growth and Cluster Ion Fragmentation for Toluene/Water, Aniline/Argon, and 4-Fluorostyrene/Argon Clusters: Covariance Mapping of the Mass Spectral Data

National Research Council Canada - National Science Library

Foltin, M

1998-01-01

.... To explore sensitivity of the parent ion/fragment ion correlation coefficient to cluster fragmentation, correlation coefficients are measured as a function of ionization photon energy as thresholds...

Detection of negative ions in glow discharge mass spectrometry for analysis of solid specimens

DEFF Research Database (Denmark)

Canulescu, Stela; Molchan, Igor S.; Tauziede, C.

2010-01-01

A new method is presented for elemental and molecular analysis of halogen-containing samples by glow discharge time-of-flight mass spectrometry, consisting of detection of negative ions from a pulsed RF glow discharge in argon. Analyte signals are mainly extracted from the afterglow regime...... be used to study the distribution of a tantalum fluoride layer within the anodized tantala layer. Further, comparison is made with data obtained using glow-discharge optical emission spectroscopy, where elemental fluorine can only be detected using a neon plasma. The ionization mechanisms responsible...... for the formation of negative ions in glow discharge time-of-flight mass spectrometry are briefly discussed....

Properties of ammonium ion-water clusters: analyses of structure evolution, noncovalent interactions, and temperature and humidity effects.

Science.gov (United States)

Pei, Shi-Tu; Jiang, Shuai; Liu, Yi-Rong; Huang, Teng; Xu, Kang-Ming; Wen, Hui; Zhu, Yu-Peng; Huang, Wei

2015-03-26

Although ammonium ion-water clusters are abundant in the biosphere, some information regarding these clusters, such as their growth route, the influence of temperature and humidity, and the concentrations of various hydrated clusters, is lacking. In this study, theoretical calculations are performed on ammonium ion-water clusters. These theoretical calculations are focused on determining the following characteristics: (1) the pattern of cluster growth; (2) the percentages of clusters of the same size at different temperatures and humidities; (3) the distributions of different isomers for the same size clusters at different temperatures; (4) the relative strengths of the noncovalent interactions for clusters of different sizes. The results suggest that the dipole moment may be very significant for the ammonium ion-water system, and some new stable isomers were found. The nucleation of ammonium ions and water molecules is favorable at low temperatures; thus, the clusters observed at high altitudes might not be present at low altitudes. High humidity can contribute to the formation of large ammonium ion-water clusters, whereas the formation of small clusters may be favorable under low-humidity conditions. The potential energy surfaces (PES) of these different sized clusters are complicated and differ according to the distribution of isomers at different temperatures. Some similar structures are observed between NH4(+)(H2O)n and M(H2O)n (where M represents an alkali metal ion or water molecule); when n = 8, the clusters begin to form the closed-cage geometry. As the cluster size increases, these interactions become progressively weaker. The successive binding energy at the DF-MP2-F12/VDZ-F12 level is better than that at the PW91PW91/6-311++G(3df, 3pd) level and is consistent with the experimentally determined values.

From molecular clusters to nanoparticles: second-generation ion-mediated nucleation model

Directory of Open Access Journals (Sweden)

F. Yu

2006-01-01

Full Text Available Ions, which are generated in the atmosphere by galactic cosmic rays and other ionization sources, may play an important role in the formation of atmospheric aerosols. In the paper, a new second-generation ion-mediated nucleation (IMN model is presented. The new model explicitly treats the evaporation of neutral and charged clusters and it describes the evolution of the size spectra and composition of both charged and neutral clusters/particles ranging from small clusters of few molecules to large particles of several micrometers in diameter. Schemes used to calculate the evaporation coefficients for small neutral and charged clusters are consistent with the experimental data within the uncertainty range. The present IMN model, which is size-, composition-, and type-resolved, is a powerful tool for investigating the dominant mechanisms and key parameters controlling the formation and subsequent growth of nanoparticles in the atmosphere. This model can be used to analyze simultaneous measurements of the ion-mobility spectra and particle size distributions, which became available only recently. General features of the spectra for ions smaller than the critical size, size-dependent fractions of charged nanoparticles, and asymmetrical charging of freshly nucleated particles predicted by the new IMN model are consistent with recent measurements. Results obtained using the second generation IMN model, in which the most recent thermodynamic data for neutral and charged H2SO4-H2O clusters were used, suggest that ion-mediated nucleation of H2SO4-H2O can lead to a significant production of new particles in the lower atmosphere (including the boundary layer under favorable conditions. It has been shown that freshly nucleated particles of few nanometers in size can grow by the condensation of low volatile organic compounds to the size of cloud condensation nuclei. In such cases, the chemical composition of nucleated particles larger than ~10 nm is dominated

Matrix-assisted laser desorption/ionization mass spectrometry for the structural characterization of modified oligonucleotides

International Nuclear Information System (INIS)

Hurst, G.B.; Hettich, R.L.; Buchanan, M.V.; Stemmler, E.A.

1993-01-01

Matrix-assisted laser desorption ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry (FTMS) and MALDI time-of-flight mass spectrometry (TOFMS) are being used to characterize conditions for the efficient desorption and ionization of normal and modified nucleic acid components. Basic and acidic matrix materials have been evaluated on the components. Basic and acidic matrix materials have been evaluated on the FTMS and TOFMS. Using MALDI-FTMS at 355 nm, less fragmentation has been observed using 2,5-dihydroxybenzoic acid, while more extensive fragmentation is observed for basic matrices, such as 1,5-diaminonaphthalene and 9-aminophenanthrene. Elevation of the cell pressure by the addition of Ar or CO 2 provides collisional cooling of desorbed ions, resulting in an enhancement of [M--H] - and structurally significant high-mass fragment ions. Using MALDI-TOFMS at 337 nm, fragmentation is significantly reduced relative to that observed on the FTMS, perhaps as a consequence of the longer times required for FTMS detection. On the FTMS and TOFMS, cluster ions have been observed in the negative ion mode when metal ions are present in the 2,5-dihydroxybenzoic acid matrix. Metal ion additions and clusters with matrix salts have also been observed for dinucleotides. Applications of MALDI-FTMS and MALDI-TOF to the detection of hydroxylated PAH nucleoside adducts are presented

The use of secondary ion mass spectrometry for uranium analysis in bioassays

International Nuclear Information System (INIS)

Amaral, Ademir de Jesus

1997-01-01

Today many researches are performed to use mass spectrometry as complementary methods to the alpha spectrometry. In this study performance of the secondary ion mass spectrometry (SIMS) are evaluated for traces of uranium analysis in biological tissues and more particularly in urine. A special attention is done for the samples preparation, using thin polymers. the SIMS method feasibility is presented. The second part of the thesis deals with the use of a tracer to quantify the urinary uranium, the 233 U. The isotopic ratio are obtained with a detection limit of 10 -6 Bq in 238 U per urine litre. Other biological samples are studied to illustrate the adaptability of the SIMS method to internal dosimetry. (A.L.B.)

A convenient method for calculation of ionic diffusion coefficients for accurate selected ion flow tube mass spectrometry, SIFT-MS

Science.gov (United States)

Dryahina, K.; Spanel, P.

2005-07-01

A method to calculate diffusion coefficients of ions important for the selected ion flow tube mass spectrometry, SIFT-MS, is presented. The ions, on which this method is demonstrated, include the SIFT-MS precursors H3O+(H2O)0,1,2,3, NO.+(H2O)0,1,2 and O2+ and the product ions relevant to analysis of breath trace metabolites ammonia (NH3+(H2O)0,1,2, NH4+(H2O)0,1,2), acetaldehyde (C2H4OH+(H2O)0,1,2), acetone (CH3CO+, (CH3)2CO+, (CH3)2COH+(H2O)0,1, (CH3)2CO.NO+), ethanol (C2H5OHH+(H2O)0,1,2) and isoprene (C5H7+, C5H8+, C5H9+). Theoretical model of the (12, 4) potential for interaction between the ions and the helium atoms is used, with the repulsive part approximated by the mean hard-sphere cross section and the attractive part describing ion-induced dipole interactions. The reduced zero-field mobilities at 300 K are calculated using the Viehland and Mason theory [L.A. Viehland, S.L. Lin, E.A. Mason, At. Data Nucl. Data Tables, 60 (1995) 37-95], parameterised by a simple formula as a function of the mean hard-sphere cross section, and converted to diffusion coefficients using the Einstein relation. The method is tested on a set of experimental data for simple ions and cluster ions.

Laser ionization of molecular clusters

International Nuclear Information System (INIS)

Desai, S.; Feigerle, C.S.

1995-01-01

Multiphoton ionization coupled with mass spectrometry was used to investigate molecular cluster distributions. Three examples will be discussed in this presentation. First, in studies of neat nitric oxide clusters, (NO) m , an interesting odd-even intensity alternation was observed and will be discussed in terms of electron-pairing considerations. In a separate study, the binary clusters comprising nitric oxide and methane preferentially form a stoichiometric cluster made up of repeating units of (NO) 2 CH 4 . These presumably represent a particularly strongly bound open-quotes van der Waalsclose quotes subunit. Finally, in similar studies of neat carbon disulfide clusters, (CS 2 ) m , additional photon absorption after the two-photon ionization step stimulates a series of intracluster ion-molecular reactions leading to formation of S m + and (CS) m + polymers, as well as intermediate species such as S m + (CS 2 ). This molecular cluster analogue of open-quotes laser snowclose quotes will be described in detail

Numerical investigation of depth profiling capabilities of helium and neon ions in ion microscopy

Directory of Open Access Journals (Sweden)

Patrick Philipp

2016-11-01

Full Text Available The analysis of polymers by secondary ion mass spectrometry (SIMS has been a topic of interest for many years. In recent years, the primary ion species evolved from heavy monatomic ions to cluster and massive cluster primary ions in order to preserve a maximum of organic information. The progress in less-damaging sputtering goes along with a loss in lateral resolution for 2D and 3D imaging. By contrast the development of a mass spectrometer as an add-on tool for the helium ion microscope (HIM, which uses finely focussed He+ or Ne+ beams, allows for the analysis of secondary ions and small secondary cluster ions with unprecedented lateral resolution. Irradiation induced damage and depth profiling capabilities obtained with these light rare gas species have been far less investigated than ion species used classically in SIMS. In this paper we simulated the sputtering of multi-layered polymer samples using the BCA (binary collision approximation code SD_TRIM_SP to study preferential sputtering and atomic mixing in such samples up to a fluence of 1018 ions/cm2. Results show that helium primary ions are completely inappropriate for depth profiling applications with this kind of sample materials while results for neon are similar to argon. The latter is commonly used as primary ion species in SIMS. For the two heavier species, layers separated by 10 nm can be distinguished for impact energies of a few keV. These results are encouraging for 3D imaging applications where lateral and depth information are of importance.

Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

Science.gov (United States)

Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

2016-02-18

Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

Microwave plasma ion sources for selected ion flow tube mass spectrometry: Optimizing their performance and detection limits for trace gas analysis

Czech Academy of Sciences Publication Activity Database

Španěl, Patrik; Dryahina, Kseniya; Smith, D.

2007-01-01

Roč. 267, 1-3 (2007), s. 117-124 ISSN 1387-3806 R&D Projects: GA ČR GA202/06/0776 Institutional research plan: CEZ:AV0Z40400503 Keywords : microwave plasma ion source * selected ion flow tube mass spectrometry * SIFT-MS * breath analysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.411, year: 2007

Radiocarbon detection by ion charge exchange mass spectrometry

International Nuclear Information System (INIS)

Hotchkis, Michael; Wei, Tao

2007-01-01

A method for detection of radiocarbon at low levels is described and the results of tests are presented. We refer to this method as ion charge exchange mass spectrometry (ICE-MS). The ICE-MS instrument is a two stage mass spectrometer. In the first stage, molecular interferences which would otherwise affect radiocarbon detection at mass 14 are eliminated by producing high charge state ions directly in the ion source (charge state ≥2). 14 N interference is eliminated in the second stage by converting the beam to negative ions in a charge exchange cell. The beam is mass-analysed at each stage. We have built a test apparatus consisting of an electron cyclotron resonance ion source and a pair of analysing magnets with a charge exchange cell in between, followed by an electrostatic analyser to improve the signal to background ratio. With this apparatus we have measured charge exchange probabilities for (C n+ → C - ) from 4.5 to 40.5 keV (n = 1-3). We have studied the sources of background including assessment of limits for nitrogen interference by searching for negative ions from charge exchange of 14 N ions. Our system has been used to detect 14 C in enriched samples of CO 2 gas with 14 C/ 12 C isotopic ratio down to the 10 -9 level. Combined with a measured sample consumption rate of 4 ng/s, this corresponds to a capability to detect transient signals containing only a few μBq of 14 C activity, such as may be obtained from chromatographic separation. The method will require further development to match the sensitivity of AMS with a gas ion source; however, even in its present state its sensitivity is well suited to tracer studies in biomedical research and drug development

Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

KAUST Repository

Hourani, Nadim; Andersson, Jan T.; Mö ller, Isabelle; Amad, Maan H.; Witt, Matthí as; Sarathy, Mani

2013-01-01

oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same

Uncovering biologically significant lipid isomers with liquid chromatography, ion mobility spectrometry and mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Steve; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin Shammel

2016-01-01

Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Liquid chromatography and mass spectrometry (LC-MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are unresolvable using present LC-MS approaches. Here we show that combining structurally-based ion mobility spectrometry (IMS) with LC-MS measurements distinguishes lipid isomers and allows insight into biological and disease processes.

Comprehensive lipidomic analysis of human plasma using multidimensional liquid- and gas-phase separations: Two-dimensional liquid chromatography-mass spectrometry vs. liquid chromatography-trapped-ion-mobility-mass spectrometry.

Science.gov (United States)

Baglai, Anna; Gargano, Andrea F G; Jordens, Jan; Mengerink, Ynze; Honing, Maarten; van der Wal, Sjoerd; Schoenmakers, Peter J

2017-12-29

Recent advancements in separation science have resulted in the commercialization of multidimensional separation systems that provide higher peak capacities and, hence, enable a more-detailed characterization of complex mixtures. In particular, two powerful analytical tools are increasingly used by analytical scientists, namely online comprehensive two-dimensional liquid chromatography (LC×LC, having a second-dimension separation in the liquid phase) and liquid chromatography-ion mobility-spectrometry (LC-IMS, second dimension separation in the gas phase). The goal of the current study was a general assessment of the liquid-chromatography-trapped-ion-mobility-mass spectrometry (LC-TIMS-MS) and comprehensive two-dimensional liquid chromatography-mass spectrometry (LC×LC-MS) platforms for untargeted lipid mapping in human plasma. For the first time trapped-ion-mobility spectrometry (TIMS) was employed for the separation of the major lipid classes and ion-mobility-derived collision-cross-section values were determined for a number of lipid standards. The general effects of a number of influencing parameters have been inspected and possible directions for improvements are discussed. We aimed to provide a general indication and practical guidelines for the analyst to choose an efficient multidimensional separation platform according to the particular requirements of the application. Analysis time, orthogonality, peak capacity, and an indicative measure for the resolving power are discussed as main characteristics for multidimensional separation systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Irradiation characteristics of metal-cluster-complex ions containing diverse multi-elements with large mass differences

International Nuclear Information System (INIS)

Fujiwara, Yukio; Kondou, Kouji; Teranishi, Yoshikazu; Nonaka, Hidehiko; Saito, Naoaki; Fujimoto, Toshiyuki; Kurokawa, Akira; Ichimura, Shingo; Tomita, Mitsuhiro

2007-01-01

Tetrairidium dodecacarbonyl, Ir 4 (CO) 12 , is a metal cluster complex which has a molecular weight of 1104.9. Using a metal-cluster-complex ion source, the interaction between Ir 4 (CO) n + ions (n=0-12) and silicon substrates was studied at a beam energy ranging from 2keV to 10keV at normal incidence. By adjusting Wien-filter voltage, the influence of CO ligands was investigated. Experimental results showed that sputtering yield of silicon bombarded with Ir 4 (CO) n + ions at 10keV decreased with the number of CO ligands. In the case of 2keV, deposition tended to be suppressed by removing CO ligands from the impinging cluster ions. The influence of CO ligands was explained by considering changes in surface properties caused by the irradiation of Ir 4 (CO) n + ions. It was also found that the bombardment with Ir 4 (CO) 7 + ions at 2.5keV caused deposition on silicon target

Applicability of ion mobility spectrometry for detection of quarantine pests in wood

Science.gov (United States)

Ewing, K. J.; Sanghera, J.; Myers, S. W.; Ervin, A. M.; Carey, C.; Gleason, G.; Mosser, L.; Levy, L.; Hennessey, M. K.; Bulluck, R.

2016-05-01

Visual inspection is the most commonly used method for detecting quarantine pests in agricultural cargo items at ports. For example, solid wood packing material (SWPM) at ports may be a pathway for wood pests and is a frequent item of inspection at ports. The inspection process includes examination of the external surface of the item and often destructive sampling to detect internal pest targets. There are few tools available to inspectors to increase the efficiency of inspection and reduce the labor involved. Ion mobility spectrometry (IMS) has promise as an aid for inspection. Because pests emit volatile organic compounds (VOCs) such as hormone like substances, Ion Mobility Spectrometry (IMS) was investigated for possible utility for detecting pests during inspection. SWPM is a major pest pathway in trade, and fumigation of many kinds of wood, including SWPM, with methyl bromide (MeBr) following a published schedule1 is regularly conducted for phytosanitary reasons prior to shipment to the United States. However, the question remains as to how long the methyl bromide remains in the wood samples after fumigation such that it could act as an interferent to the detection of pest related VOC emissions. This work investigates the capability of ion mobility spectrometry to detect the presence of residual methyl bromide in fumigated maple and poplar wood samples at different times post fumigation up to 118 days after fumigation. Data show that MeBr can be detected in the less dense poplar wood up to 118 days after fumigation while MeBr can be detected in the denser maple wood 55 days after fumigation.

Chemical speciation analysis for bromine in tap water by ion chromatography/inductively coupled plasma-mass spectrometry and electrospray ionization-mass spectrometry

International Nuclear Information System (INIS)

Kurata, Keigo; Suzuki, Yoshinari; Furuta, Naoki

2010-01-01

Bromide compounds in tap water were measured by using a hyphenated technique of ion chromatography coupled with inductively coupled plasma - mass spectrometry (IC/ICP-MS) and electrospray ionization mass spectrometry (ESI-MS). We identified bromide ion (Br - ), bromate ion (BrO 3 - ), bromochloroacetic acid (BCAA), dibromoacetic acid (DBAA) and bromodichloroacetic acid (BDCAA) by standard addition methods with IC/ICP-MS. Moreover, we identified BCAA and BDCAA by ESI-MS after separation with IC. Br - , BrO 3 - , BCAA, DBAA and BDCAA in tap water collected from around Tokyo area were quantified by IC/ICP-MS. The maximum concentration of BrO 3 - (1.8 ng mL -1 ) was observed in tap water collected from Bunkyo-ku, although this concentration was lower than 10 ng mL -1 , which is the regulated concentration in Japan. DBAA, which is regulated by United States Environmental Protection Agency, was detected in tap water collected from all sites, except for Ome. However, since BrO 3 - and DBAA are toxic, it is necessary to continue monitoring bromide compounds in tap water. (author)

Polar cap ion beams during periods of northward IMF: Cluster statistical results

Directory of Open Access Journals (Sweden)

R. Maggiolo

2011-05-01

Full Text Available Above the polar caps and during prolonged periods of northward IMF, the Cluster satellites detect upward accelerated ion beams with energies up to a few keV. They are associated with converging electric field structures indicating that the acceleration is caused by a quasi-static field-aligned electric field that can extend to altitudes higher than 7 RE (Maggiolo et al., 2006; Teste et al., 2007. Using the AMDA science analysis service provided by the Centre de Données de la Physique des Plasmas, we have been able to extract about 200 events of accelerated upgoing ion beams above the polar caps from the Cluster database. Most of these observations are taken at altitudes lower than 7 RE and in the Northern Hemisphere. We investigate the statistical properties of these ion beams. We analyze their geometry, the properties of the plasma populations and of the electric field inside and around the beams, as well as their dependence on solar wind and IMF conditions. We show that ~40 % of the ion beams are collocated with a relatively hot and isotropic plasma population. The density and temperature of the isotropic population are highly variable but suggest that this plasma originates from the plasma sheet. The ion beam properties do not change significantly when the isotropic, hot background population is present. Furthermore, during one single polar cap crossing by Cluster it is possible to detect upgoing ion beams both with and without an accompanying isotropic component. The analysis of the variation of the IMF BZ component prior to the detection of the beams indicates that the delay between a northward/southward turning of IMF and the appearance/disappearance of the beams is respectively ~2 h and 20 min. The observed electrodynamic characteristics of high altitude polar cap ion beams suggest that they are closely connected to polar cap auroral arcs. We discuss the implications of these Cluster observations above the polar cap on the magnetospheric

Molecular dynamic simulation of interaction of low-energy Ar and Xe ions with copper clusters at graphite surface

International Nuclear Information System (INIS)

Kornich, G.V.; Lozovskaya, L.I.; Betts, G.; Zaporozhchenko, V.I.; Faupel, F.

2005-01-01

One conducted molecular and dynamic simulation of sputtering of isolated clusters consisting of 13, 27 and 195 Cu atoms from the (0001) graphite surface by 200 eV energy Ar and Xe ions. It is shown that the factors of reflection of Ar and Xe ions from copper clusters differ from one another insignificantly, though the energy of the reflected Xe ions is essentially lower than that of Ar ions. The values of the factor of cluster sputtering by Xe ions are higher in contrast to sputtering by Ar ions. One identified two mechanisms of cluster sputtering resulting in the maximum of sputtering intensity at the polar angles near the normal one, and in periodicity of maximums within the azimuth distributions of sputtering intensity with 60 deg period [ru

Upgrading the Lyon cluster ion accelerator by a radiofrequency quadrupole

International Nuclear Information System (INIS)

Moser, H.O.; Schempp, A.

1987-02-01

The design is presented of an RFQ with variable final energy suitable to post-accelerate cluster ions from the Lyon electrostatic cluster-ion accelerator in the mass ranges from 1 to 25 μ and 1 to 50 μ to kinetic energies of 1.32-2.5 MeV and 2.64-5.0 MeV for cw and pulsed operation, respectively. Furthermore, a beam line is described which matches the electrostatically preaccelerated beam to the RFQ by use of electrostatic quadrupole triplets. When used without RFQ this beam line serves to improve beam parameters on the target, such as the particle flux density or beam divergence. The estimated costs of this project are about DM 345 000.- or FF 1 200 000.- without VAT. (orig.) [de

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

Science.gov (United States)

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.

Mass spectrometry and tandem mass spectrometry of citrus limonoids.

Science.gov (United States)

Tian, Qingguo; Schwartz, Steven J

2003-10-15

Methods for atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) of citrus limonoid aglycones and electrospray ionization tandem mass spectrometry (ESI-MS/MS) of limonoid glucosides are reported. The fragmentation patterns of four citrus limonoid aglycones (limonin, nomilin, obacunone, and deacetylnomilin) and six limonoid glucosides, that is, limonin 17-beta-D-glucopyranoside (LG), nomilin 17-beta-D-glucopyranoside (NG), nomilinic acid 17-beta-D-glucopyranoside (NAG), deacetyl nomilinic acid 17-beta-D-glucopyranoside (DNAG), obacunone 17-beta-D-glucopyranoside (OG), and obacunoic acid 17-beta-D-glucopyranoside (OAG) were investigated using a quadruple mass spectrometer in low-energy collisionally activated dissociation (CAD). The four limonoid aglycones and four limonoid glucosides (LG, OG, NAG, and DNAG) were purified from citrus seeds; the other two limonoid glucosides (NG and OAG) were tentatively identified in the crude extract of grapefruit seeds by ESI mass spectrometry in both positive and negative ion analysis. Ammonium hydroxide or acetic acid was added to the mobile phase to facilitate ionization. During positive ion APCI analysis of limonoid aglycones, protonated molecular ion, [M + H]+, or adduct ion, [M + NH3 + H]-, was formed as base peaks when ammonium hydroxide was added to the mobile phase. Molecular anions or adduct ions with acetic acid ([M + HOAc - H] and [M + HOAc]-) or a deprotonated molecular ion were produced during negative ion APCI analysis of limonoid aglycones, depending on the mobile-phase modifier used. Positive ion ESI-MS of limonoid glucosides produced adduct ions of [M + H + NH3]+, [M + Na]+, and [M + K]+ when ammonium hydroxide was added to the mobile phase. After collisionally activated dissociation (CAD) of the limonoid aglycone molecular ions in negative ion APCI analysis, fragment ions indicated structural information of the precursor ions, showing the presence of methyl, carboxyl, and oxygenated ring

Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

Science.gov (United States)

Chen, Yen-Ming; Hsu, Shih-Ting; Tseng, Yu-Hsien; Yeh, Te-Fu; Hou, Sheng-Shu; Jan, Jeng-Shiung; Lee, Yuh-Lang; Teng, Hsisheng

2018-03-01

This study uses graphene oxide quantum dots (GOQDs) to enhance the Li + -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF 6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li + -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO 4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li + -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion clustering in aqueous salt solutions near the liquid/vapor interface

Directory of Open Access Journals (Sweden)

J.D. Smith

2016-03-01

Full Text Available Molecular dynamics simulations of aqueous NaCl, KCl, NaI, and KI solutions are used to study the effects of salts on the properties of the liquid/vapor interface. The simulations use the models which include both charge transfer and polarization effects. Pairing and the formation of larger ion clusters occurs both in the bulk and surface region, with a decreased tendency to form larger clusters near the interface. An analysis of the roughness of the surface reveals that the chloride salts, which have less tendency to be near the surface, have a roughness that is less than pure water, while the iodide salts, which have a greater surface affinity, have a larger roughness. This suggests that ions away from the surface and ions near the surface affect the interface in opposite ways.

The Study of Titanium and Zirconium Ions in Water by MPT-LTQ Mass Spectrometry in Negative Mode.

Science.gov (United States)

Yang, Junqing; Zheng, Mei; Liu, Qiuju; Yang, Meiling Zhu Chushan; Zhang, Yan; Zhu, Zhiqiang

2017-09-26

Microwave plasma torches (MPTs) can be used as simple and low power-consumption ambient ion sources. When MPT-mass spectrometry (MPT-MS) is applied in the detection of some metal elements, the metallic ions exhibit some novel features which are significantly different with those obtained by the traditional inductively coupled plasma (ICP)-mass spectrometry (ICP-MS) and may be helpful for metal element analysis. As the representative elements of group IVA, titanium and zirconium are both of importance and value in modern industry, and they have impacts on human health. Here, we first provide a study on the complex anions of titanium and zirconium in water by using the MPT as ion source and a linear ion trap mass spectrometer (LTQ-MS). These complex anions were produced in the plasma flame by an aqueous solution flowing through the central tube of the MPT, and were introduced into the inlet of the mass spectrometry working in negative ion mode to get the feature mass spectrometric signals. Moreover, the feature fragment patterns of these ions in multi-step collision- induced dissociation processes have been explained. Under the optimized conditions, the limit of detection (LOD) using the MS² (the second tandem mass spectrometry) procedure was estimated to be at the level of 10μg/L for titanium and 20 μg/L for zirconium with linear dynamics ranges that cover at least two orders of magnitude, i.e., between 0-500 μg/L and 20-200 μg/L, respectively. These experimental data demonstrated that the MPT-MS is a promising and useful tool in field analysis of titanium and zirconium ions in water, and can be applied in many fields, such as environmental control, hydrogeology, and water quality inspection. In addition, MPT-MS could also be used as a supplement of ICP-MS for the rapid and on-site analysis of metal ions.

Bayesian Integration and Characterization of Composition C-4 Plastic Explosives Based on Time-of-Flight Secondary Ion Mass Spectrometry and Laser Ablation-Inductively Coupled Plasma Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Mahoney, Christine M.; Kelly, Ryan T.; Alexander, M. L.; Newburn, Matthew K.; Bader, Sydney P.; Ewing, Robert G.; Fahey, Albert J.; Atkinson, David A.; Beagley, Nathaniel

2016-02-25

Key elements regarding the use of non-radioactive ionization sources will be presented as related to explosives detection by mass spectrometry and ion mobility spectrometry. Various non-radioactive ionization sources will be discussed along with associated ionization mechanisms pertaining to specific sample types.

Ion mobility spectrometry-mass spectrometry (IMS-MS) for on- and offline analysis of atmospheric gas and aerosol species

Science.gov (United States)

Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan; Junninen, Heikki; Massoli, Paola; Lambe, Andrew T.; Kimmel, Joel R.; Cubison, Michael J.; Graf, Stephan; Lin, Ying-Hsuan; Budisulistiorini, Sri H.; Zhang, Haofei; Surratt, Jason D.; Knochenmuss, Richard; Jayne, John T.; Worsnop, Douglas R.; Jimenez, Jose-Luis; Canagaratna, Manjula R.

2016-07-01

Measurement techniques that provide molecular-level information are needed to elucidate the multiphase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS-MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS-MS after ionization with a custom-built nitrate chemical ionization (CI) source. This CI-IMS-MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field campaign in the forested SE US. The ambient IMS-MS signals are consistent with laboratory IMS-MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-D IMS-MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS-MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisionally induced dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the

Investigations on carbon cluster formation in heavy ion irradiated polymers

International Nuclear Information System (INIS)

Tripathy, S.P.; Mishra, R.; Mawar, A.K.; Dwivedi, K.K.; Khathing, D.T.; Srivastava, A.; Avasthi, D.K.; Ghosh, S.; Fink, D.

2000-01-01

In polymers, the carbonaceous clusters are supposed to be responsible for the electrical conductivity. So, the irradiation of organic polymers namely polypropylene (8μ) and polyimide (50μ) by energetic heavy ions 28 Si and 58 Ni produce significant changes in the size of these clusters leading to the corresponding change in the band gap and other electrical properties as revealed by the UV-VIS spectroscopic examinations. (author)

Detection of high mass cluster ions sputtered from Bi surfaces

Energy Technology Data Exchange (ETDEWEB)

Shepard, A; Hewitt, R W; Slusser, G J; Baitinger, W E; Cooks, R G; Winograd, N [Purdue Univ., Lafayette, Ind. (USA). Dept. of Chemistry; Delgass, W N [Purdue Univ., Lafayette, Ind. (USA); Varon, A; Devant, G [Societe RIBER, 92 - Rueil-Malmaison (France)

1976-12-01

The technique of secondary ion mass spectrometry (SIMS) has been employed to detect Bi/sup 3 +/ ions and associated oxides Bi/sub 3/Osub(x)sup(+)(x=1 to 4) from a Bi foil. Using a 3 keV Ar/sup +/ ion primary beam of 5x10/sup -7/ A/cm/sup 2/, mass resolution to nearly 700 with the requisite sensitivity has been achieved. The Bi surface was also monitored by X-ray photoelectron spectroscopy (XPS or ESCA). The presence of a weak O 1s peak at 532.7 eV and a strong SIMS Bi/sup 3 +/ peak is interpreted to mean that the oxygen is weakly incorporated into the Bi lattice without disrupting metal-metal bonds.

Electron-induced chemistry in microhydrated sulfuric acid clusters

Directory of Open Access Journals (Sweden)

J. Lengyel

2017-11-01

Full Text Available We investigate the mixed sulfuric acid–water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT calculations. The microhydration of (H2SO4m(H2On clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4m(H2OnHSO4− and (H2OnH2SO4−. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4−  ⋅  ⋅  ⋅  H3O+ formation in the neutral H2SO4(H2On clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO42(H2On this process starts as early as n ≥ 2 water molecules. The (H2SO4m(H2OnHSO4− clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4−  ⋅  ⋅  ⋅  H3O+ ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2OnH2SO4− cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid–water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid–water aerosols are discussed.

Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

Energy Technology Data Exchange (ETDEWEB)

Kulagin, N.A., E-mail: nkulagin@bestnet.kharkov.u [Kharkiv National University for Radio Electronics, Avenue Shakespeare 6-48, 61045 Kharkiv (Ukraine)

2011-03-15

Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr{sup +4} ions in oxides, Cu{sup +2} in HTSC, Nd{sup +2} in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10{sup -9} m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: External influence and variation of technology induce changes in valence of nl ions in compounds. Wave function of cluster presented as anti-symmetrical set of ions wave functions. The main equation describes the self-consistent field depending on state of all electrons of cluster. Level scheme of Cr{sup 4+} ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. Plasma treatment effects in appearance of systems of unit crystallites with size of about 10{sup -6}-10{sup -9} m.

Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

International Nuclear Information System (INIS)

Kulagin, N.A.

2011-01-01

Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr +4 ions in oxides, Cu +2 in HTSC, Nd +2 in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10 -9 m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: → External influence and variation of technology induce changes in valence of nl ions in compounds. → Wave function of cluster presented as anti-symmetrical set of ions wave functions. → The main equation describes the self-consistent field depending on state of all electrons of cluster. → Level scheme of Cr 4+ ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. → Plasma treatment effects in appearance of systems of unit crystallites with size of about 10 -6 -10 -9 m.

A four dimensional separation method based on continuous heart-cutting gas chromatography with ion mobility and high resolution mass spectrometry.

Science.gov (United States)

Lipok, Christian; Hippler, Jörg; Schmitz, Oliver J

2018-02-09

A two-dimensional GC (2D-GC) method was developed and coupled to an ion mobility-high resolution mass spectrometer, which enables the separation of complex samples in four dimensions (2D-GC, ion mobilility spectrometry and mass spectrometry). This approach works as a continuous multiheart-cutting GC-system (GC+GC), using a long modulation time of 20s, which allows the complete transfer of most of the first dimension peaks to the second dimension column without fractionation, in comparison to comprehensive two-dimensional gas chromatography (GCxGC). Hence, each compound delivers only one peak in the second dimension, which simplifies the data handling even when ion mobility spectrometry as a third and mass spectrometry as a fourth dimension are introduced. The analysis of a plant extract from Calendula officinales shows the separation power of this four dimensional separation method. The introduction of ion mobility spectrometry provides an additional separation dimension and allows to determine collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 800 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. Copyright © 2017 Elsevier B.V. All rights reserved.

Source-identifying biomarker ions between environmental and clinical Burkholderia pseudomallei using whole-cell matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).

Science.gov (United States)

Niyompanich, Suthamat; Jaresitthikunchai, Janthima; Srisanga, Kitima; Roytrakul, Sittiruk; Tungpradabkul, Sumalee

2014-01-01

Burkholderia pseudomallei is the causative agent of melioidosis, which is an endemic disease in Northeast Thailand and Northern Australia. Environmental reservoirs, including wet soils and muddy water, serve as the major sources for contributing bacterial infection to both humans and animals. The whole-cell matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (whole-cell MALDI-TOF MS) has recently been applied as a rapid, accurate, and high-throughput tool for clinical diagnosis and microbiological research. In this present study, we employed a whole-cell MALDI-TOF MS approach for assessing its potency in clustering a total of 11 different B. pseudomallei isolates (consisting of 5 environmental and 6 clinical isolates) with respect to their origins and to further investigate the source-identifying biomarker ions belonging to each bacterial group. The cluster analysis demonstrated that six out of eleven isolates were grouped correctly to their sources. Our results revealed a total of ten source-identifying biomarker ions, which exhibited statistically significant differences in peak intensity between average environmental and clinical mass spectra using ClinProTools software. Six out of ten mass ions were assigned as environmental-identifying biomarker ions (EIBIs), including, m/z 4,056, 4,214, 5,814, 7,545, 7,895, and 8,112, whereas the remaining four mass ions were defined as clinical-identifying biomarker ions (CIBIs) consisting of m/z 3,658, 6,322, 7,035, and 7,984. Hence, our findings represented, for the first time, the source-specific biomarkers of environmental and clinical B. pseudomallei.

Analysis of Petrol and Diesel Vapor Using Selective Ion Flow Tube/Mass Spectrometry

Czech Academy of Sciences Publication Activity Database

Ping, CH.; Weijun, Z.; Yaman, CH.; Španěl, Patrik; Smith, D.

2003-01-01

Roč. 5, - (2003), s. 548-551 ISSN 0253-3820 Institutional research plan: CEZ:AV0Z4040901 Keywords : selected ion flow tube/mass spectrometry * fuel vapor Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.224, year: 2003

Electron-capture negative-ion mass spectrometry: a technique for environmental contaminant identification

International Nuclear Information System (INIS)

Stemmler, E.A.

1986-01-01

Electron capture negative ion mass spectrometry (ECNIMS) is a method used to generate negative ions in a mass spectrometer by electron-molecule reactions. This technique facilitates the sensitive and selective detection of many toxic contaminants in environmental samples. Applications of this technique have been hindered by the limited understanding of instrumental parameters, by the questionable reproducibility of negative ion mass spectra, and by the inability to interpret negative ion mass spectra. Instrumental parameters which were important to control include the ion source temperature, ion source pressure, sample concentration, and the focus lens potential. The ability to obtain reproducible spectra was demonstrated by measurement of the spectrum of decafluorotriphenylphosphine (DFTPP) over a period of one year. Negative ion fragmentation mechanisms were studied by measuring the spectra of structurally related classes of compounds and isotopically labelled compounds. These results were combined with data obtained by other researchers. Fragmentations characteristic of particular functional groups or molecular structures have been summarized. From this data set, guidelines for the interpretation of electron capture negative ion mass spectra have been developed

The mobilies of chiral molecular cluster ions in He gas

International Nuclear Information System (INIS)

Saito, Kazuyuki; Matoba, Shiro; Koizumi, Tetsuo; Kojima, Takao M; Tanuma, Hajime; Shiromaru, Haruo

2012-01-01

We measured the mobilities of Li + -(2-butanol) and Li + -(limonene) ions in He gas at room temperature using a drift tube mass spectrometer. The zero field mobilities of Li + -(2-Butanol) and Li + -(Limonene) were much lower than the polarization limit, indicating that the geometric collision cross-sections between the cluster ions and He atom were larger than the cross-sections predicted by the presence of a polarization force alone.

Molecular growth in clusters of polycyclic aromatic hydrocarbons induced by collisions with ions

International Nuclear Information System (INIS)

Delaunay, Rudy

2016-01-01

This thesis concerns the experimental study of the interaction between low energy ions (keV range) and neutral isolated molecules or clusters of polycyclic aromatic hydrocarbons (PAH) in the gas phase. The use of ionising radiations on these complex molecular systems of astrophysical interest allowed to highlight processes of statistical fragmentation, corresponding to the redistribution of the energy through the degrees of freedom of the target, and non-statistical fragmentation, linked to binary collisions of the ions on the nuclei of the target. A mechanism of intermolecular growth in clusters of PAH is observed. It is associated to the ultrafast (≤ ps) formation of fragments inside the clusters following binary collisions. The presence of a molecular environment around the fragments formed during the interaction may initiate a process of reactivity between the fragments and the molecules of the clusters. More precisely, the study focusses on the importance of the electronic stopping power SE and the nuclear stopping power SN of the projectile ion. It shows that the molecular growth is enhanced when SN is higher than SE. This can be explained by the fact that the deposit of energy is mainly due to the interaction with the nuclei of the target. The process of growth has been observed for all the molecules of PAH studied during this thesis and also for nitrogenated analogues of the molecule of anthracene. This demonstrates that molecular growth may be efficiently induced by collisions of low energy ions with clusters of PAH. (author) [fr

Visualization of hydrogen in steels by secondary ion mass spectrometry

International Nuclear Information System (INIS)

Takai, Kenichi

2000-01-01

Secondary ion mass spectrometry (SIMS) enables us to visualize hydrogen trapping sites in steels. Information about the hydrogen trapping sites in high-strength steels by SIMS is very important to discuss environmental embrittlement mechanism for developing steels with a high resistance to the environmental embrittlement. Secondary ion image analysis by SIMS has made possible to visualize the hydrogen and deuterium trapping sites in the steels. Hydrogen in tempered martensite steels containing Ca tends to accumulate on inclusions, at grain boundaries, and in segregation bands. Visualization of hydrogen desorption process by secondary ion image analysis confirms that the bonding between the inclusions and the hydrogen is strong. Cold-drawn pearlite steels trap hydrogen along cold-drawing direction. Pearlite phase absorbs the hydrogen more than ferrite phase does. This article introduces the principle of SIMS, its feature, analysis method, and results of hydrogen visualization in steels. (author)

Observations on small anionic clusters in an electrostatic ion beam trap

International Nuclear Information System (INIS)

Eritt, Markus

2008-01-01

The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C n - n=2-12), aluminium (Al n - n=2-7) and silver clusters (Ag n - n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon emission. The thermionic evaporative decay of anionic aluminium and

Particle modeling of transport of α-ray generated ion clusters in air

International Nuclear Information System (INIS)

Tong, Lizhu; Nanbu, Kenichi; Hirata, Yosuke; Izumi, Mikio; Miyamoto, Yasuaki; Yamaguchi, Hiromi

2006-01-01

A particle model is developed using the test-particle Monte Carlo method to study the transport properties of α-ray generated ion clusters in a flow of air. An efficient ion-molecule collision model is proposed to simulate the collisions between ion and air molecule. The simulations are performed for a steady state of ion transport in a circular pipe. In the steady state, generation of ions is balanced with such losses of ions as absorption of the measuring sensor or pipe wall and disappearance by positive-negative ion recombination. The calculated ion current to the measuring sensor agrees well with the previous measured data. (author)

On the origin of field-aligned beams at the quasi-perpendicular bow shock: multi-spacecraft observations by Cluster

Directory of Open Access Journals (Sweden)

H. Kucharek

2004-07-01

Full Text Available Two distinct populations of reflected and accelerated ions are known to originate from quasi-perpendicular shocks, gyrating ions and reflected ion beams. Recent observations under such bow shock conditions with Cluster have shown strong evidence that both particle distributions appear to emerge from the same reflection process. In this paper the basic production mechanism of field-aligned beams has been investigated by using CLUSTER multi-spacecraft measurements. We have analyzed several quasi-perpendicular shocks with the Cluster Ion Spectrometry experiment (CIS and followed the spatial and temporal evolution of the reflected and transmitted ion populations across the shock. These observations show that the field-aligned beams most likely result from effective scattering in pitch angle during reflection in the shock ramp. Investigating a low Mach number shock, leakage of a fraction of the thermalized ion distribution in the downstream region does not appear to be the source as the volume in phase space occupied by beam ions is empty downstream of the shock ramp.

Electron attachment rate constant measurement by photoemission electron attachment ion mobility spectrometry (PE-EA-IMS)

International Nuclear Information System (INIS)

Su, Desheng; Niu, Wenqi; Liu, Sheng; Shen, Chengyin; Huang, Chaoqun; Wang, Hongmei; Jiang, Haihe; Chu, Yannan

2012-01-01

Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS), with a source of photoelectrons induced by vacuum ultraviolet radiation on a metal surface, has been developed to study electron attachment reaction at atmospheric pressure using nitrogen as the buffer gas. Based on the negative ion mobility spectra, the rate constants for electron attachment to tetrachloromethane and chloroform were measured at ambient temperature as a function of the average electron energy in the range from 0.29 to 0.96 eV. The experimental results are in good agreement with the data reported in the literature. - Highlights: ► Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS) was developed to study electron attachment reaction. ► The rate constants of electron attachment to CCl 4 and CHCl 3 were determined. ► The present experimental results are in good agreement with the previously reported data.

Secondary ion emission from ultra-thin oxide layers bombarded by energetic (MeV) heavy ions: depth of origin and layer homogeneity

International Nuclear Information System (INIS)

Allali, H.; Nsouli, B.; Thomas, J.P.; Cabaud, B.; Fuchs, G.; Hoareau, A.; Treilleux, M.; Danel, J.S.

1993-09-01

The escape depth of the secondary ions resulting from electronic sputtering of fast heavy ions in inorganic thin films has been investigated. Chromium layers deposited onto SiO 2 substrate as well as SiO x layers deposited onto chromium substrate have been characterized by secondary ion emission mass spectrometry (SIMS) in combination with time-of-flight (TOF) mass analysis (also referred as HSF-SIMS). These crossed experiments lead to a value around 1 nm for SiO x layers and 0.5 nm for Cr layers. On the other hand, HSF-SIMS can be used to correlate the intensity of the secondary ion emission to the film coverage rate and (or) the morphology of particular films like those produced by Low Energy Cluster Beam Deposition (LECBD). Using Sb deposits, the non-linear relationship between ion emission and coverage is interpreted in terms of sputtering enhancement in the individual supported clusters. (author) 22 refs., 9 figs., 1 tab

Low-energy electron collisions with metal clusters: Electron capture and cluster fragmentation

International Nuclear Information System (INIS)

Kresin, V.V.; Scheidemann, A.; Knight, W.D.

1993-01-01

The authors have carried out the first measurement of absolute cross sections for the interaction between electrons and size-resolved free metal clusters. Integral inelastic scattering cross sections have been determined for electron-Na n cluster collisions in the energy range from 0.1 eV to 30 eV. At energies ≤1 eV, cross sections increase with decreasing impact energies, while at higher energies they remain essentially constant. The dominant processes are electron attachment in the low-energy range, and collision-induced fragmentation at higher energies. The magnitude of electron capture cross sections can be quantitatively explained by the effect of the strong polarization field induced in the cluster by the incident electron. The cross sections are very large, reaching values of hundreds of angstrom 2 ; this is due to the highly polarizable nature of metal clusters. The inelastic interaction range for fragmentation collisions is also found to considerably exceed the cluster radius, again reflecting the long-range character of electron-cluster interactions. The important role played by the polarization interaction represents a bridge between the study of collision processes and the extensive research on cluster response properties. Furthermore, insight into the mechanisms of electron scattering is important for understanding production and detection of cluster ions in mass spectrometry and related processes

Chemisorption on size-selected metal clusters: activation barriers and chemical reactions for deuterium and aluminum cluster ions

International Nuclear Information System (INIS)

Jarrold, M.F.; Bower, J.E.

1988-01-01

The authors describe a new approach to investigating chemisorption on size-selected metal clusters. This approach involves investigating the collision-energy dependence of chemisorption using low-energy ion beam techniques. The method provides a direct measure of the activation barrier for chemisorption and in some cases an estimate of the desorption energy as well. They describe the application of this technique to chemisorption of deuterium on size-selected aluminum clusters. The activation barriers increase with cluster size (from a little over 1 eV for Al 10 + to around 2 eV for Al 27 + ) and show significant odd-even oscillations. The activation barriers for the clusters with an odd number of atoms are larger than those for the even-numbered clusters. In addition to chemisorption of deuterium onto the clusters, chemical reactions were observed, often resulting in cluster fragmentation. The main products observed were Al/sub n-1/D + , Al/sub n-2/ + , and Al + for clusters with n + and Al/sub n-1/D + for the larger clusters

Identification of chemical components in Baidianling Capsule based on gas chromatography-mass spectrometry and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

Science.gov (United States)

Wu, Wenying; Chen, Yu; Wang, Binjie; Sun, Xiaoyang; Guo, Ping; Chen, Xiaohui

2017-08-01

Baidianling Capsule, which is made from 16 Chinese herbs, has been widely used for treating vitiligo clinically. In this study, the sensitive and rapid method has been developed for the analysis of chemical components in Baidianling Capsule by gas chromatography-mass spectrometry in combination with retention indices and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Firstly, a total of 110 potential volatile compounds obtained from different extraction procedures including alkanes, alkenes, alkynes, ketones, ethers, aldehydes, alcohols, phenols, organic acids, esters, furans, pyrrole, acid amides, heterocycles, and oxides were detected from Baidianling Capsule by gas chromatography-mass spectrometry, of which 75 were identified by mass spectrometry in combination with the retention index. Then, a total of 124 components were tentatively identified by high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Fifteen constituents from Baidianling Capsule were accurately identified by comparing the retention times with those of reference compounds, others were identified by comparing the retention times and mass spectrometry data, as well as retrieving the reference literature. This study provides a practical strategy for rapidly screening and identifying the multiple constituents of a complex traditional Chinese medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion implantation induced conducting nano-cluster formation in PPO

International Nuclear Information System (INIS)

Das, A.; Patnaik, A.; Ghosh, G.; Dhara, S.

1997-01-01

Conversion of polymers and non-polymeric organic molecules from insulating to semiconducting materials as an effect of energetic ion implantation is an established fact. Formation of nano-clusters enriched with carbonaceous materials are made responsible for the insulator-semiconductor transition. Conduction in these implanted materials is observed to follow variable range hopping (VRH) mechanism. Poly(2,6-dimethyl phenylene oxide) [PPO] compatible in various proportion with polystyrene is used as a high thermal resistant insulating polymer. PPO has been used for the first time in the ion implantation study

Fourier Transfrom Ion Cyclotron Resonance Mass Spectrometry at High Magnetic Field

Science.gov (United States)

Marshall, Alan G.

1998-03-01

At high magnetic field (9.4 tesla at NHMFL), Fourier transform ion cyclotron resonance mass spectrometry performance improves dramatically: mass resolving power, axialization efficiency, and scan speed (each proportional to B), maximum ion mass, dynamic range, ion trapping period, kinetic energy, and electron self-cooling rate for sympathetic cooling (each proportional to B^2), and ion coalescence tendency (proportional 1/B^2). These advantages may apply singly (e.g., unit mass resolution for proteins of >100,000 Da), or compound (e.g., 10-fold improvement in S/N ratio for 9.4 T vs. 6 T at the same resolving power). Examples range from direct determination of molecular formulas of diesel fuel components by accurate mass measurement (=B10.1 ppm) to protein structure and dynamics probed by H/D exchange. This work was supported by N.S.F. (CHE-93-22824; CHE-94-13008), N.I.H. (GM-31683), Florida State University, and the National High Magnetic Field Laboratory in Tallahassee, FL.

Extreme ultraviolet fluorescence spectroscopy of pure and core-shell rare gas clusters at FLASH

Energy Technology Data Exchange (ETDEWEB)

Schroedter, Lasse

2013-08-15

The interaction of rare gas clusters with short-wavelength radiation of free-electron lasers (FELs) has been studied extensively over the last decade by means of electron and ion time-of-flight spectroscopy. This thesis describes the design and construction of a fluorescence spectrometer for the extreme ultraviolet (XUV) spectral range and discusses the cluster experiments performed at FLASH, the Free-electron LAser in Hamburg. Fluorescence of xenon and of argon clusters was studied, both in dependence on the FEL pulse intensity and on the cluster size. The FEL wavelength was set to the giant 4d-resonance of xenon at 13.5 nm and the FEL pulse intensity reached peak values of 2.7.10{sup 15} W/cm{sup 2}. For xenon clusters, charge states of at least 11+ were identified. For argon, charge states up to 7+ were detected. The cluster-size dependent study revealed a decrease of the fluorescence yield per atom with increasing cluster size. This decrease is explained with the help of a geometric model. It assumes that virtually the entire fluorescence yield stems from shells of ions on the cluster surface, whereas ions in the cluster core predominantly recombine non-radiatively with electrons. However, the detailed analysis of fluorescence spectra from clusters consisting of a core of Xe atoms and a surrounding shell of argon atoms shows that, in fact, a small fraction of the fluorescence signal comes from Xe ions in the cluster core. Interestingly, these ions are as highly charged as the ions in the shells of a pure Xe cluster. This result goes beyond the current understanding of charge and energy transfer processes in these systems and points toward the observation of ultrafast charging dynamics in a time window where mass spectrometry is inherently blind. (orig.)

Extreme ultraviolet fluorescence spectroscopy of pure and core-shell rare gas clusters at FLASH

International Nuclear Information System (INIS)

Schroedter, Lasse

2013-08-01

The interaction of rare gas clusters with short-wavelength radiation of free-electron lasers (FELs) has been studied extensively over the last decade by means of electron and ion time-of-flight spectroscopy. This thesis describes the design and construction of a fluorescence spectrometer for the extreme ultraviolet (XUV) spectral range and discusses the cluster experiments performed at FLASH, the Free-electron LAser in Hamburg. Fluorescence of xenon and of argon clusters was studied, both in dependence on the FEL pulse intensity and on the cluster size. The FEL wavelength was set to the giant 4d-resonance of xenon at 13.5 nm and the FEL pulse intensity reached peak values of 2.7.10 15 W/cm 2 . For xenon clusters, charge states of at least 11+ were identified. For argon, charge states up to 7+ were detected. The cluster-size dependent study revealed a decrease of the fluorescence yield per atom with increasing cluster size. This decrease is explained with the help of a geometric model. It assumes that virtually the entire fluorescence yield stems from shells of ions on the cluster surface, whereas ions in the cluster core predominantly recombine non-radiatively with electrons. However, the detailed analysis of fluorescence spectra from clusters consisting of a core of Xe atoms and a surrounding shell of argon atoms shows that, in fact, a small fraction of the fluorescence signal comes from Xe ions in the cluster core. Interestingly, these ions are as highly charged as the ions in the shells of a pure Xe cluster. This result goes beyond the current understanding of charge and energy transfer processes in these systems and points toward the observation of ultrafast charging dynamics in a time window where mass spectrometry is inherently blind. (orig.)

Ion emission in solids bombarded with Au{sub n}{sup +} (n = 1 - 9) clusters accelerated within the 0.15 - 1.25 MeV energy range; Emission ionique des solides a l'impact d'agregats Au{sub n}{sup +} (n=1-9) acceleres entre 0,15 et 1,25 MeV

Energy Technology Data Exchange (ETDEWEB)

Wehbe, Nimer [Universite Claude Bernard Lyon-I, 43 boulevard du 11 Novembre 1918, 69622 Villeurbanne cedex (France)

2006-06-15

This experimental work is devoted to the study of the ion emission in solids at the impact of gold clusters of energies within 0.15 to 1.25 MeV range. The physics of ion-solid collisions and the theoretical models of sputtering of solids under ion bombardment are presented in the first chapter. The chapter no. 2 deals with the description of the experimental setup. The study of a gold target allowed to evidence the role of the size and energy of the clusters in determining the emission intensity and the mass distribution of the ions. The 4. chapter gives results from the study of cesium iodide in which the intense emission of CsI clusters could be investigated quantitatively due to multiplicity measurements. Finally, the chapter no. 5 was devoted to the study of a biologic molecule, the phenylalanine, and of a pesticide molecule, chlorosulfuron. This work evidenced the importance of clusters for surface analyses by mass spectrometry.

Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

Science.gov (United States)

Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

2017-04-01

Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

Science.gov (United States)

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

Mixed clusters from the coexpansion of C2F6 and n2 in a pulsed, supersonic expansion cluster ion source and beam deflection time-of-flight mass spectrometer: A first application

Science.gov (United States)

Thompson, Steven D.

The following topics are discussed: (1) cluster ion genesis; (2) cluster ion detection; (3) Ion source; (4) pulse valve; (5) e-gun; (6) Ion optics; (7) a first order model; and (8) a modified Bakker's model.

Gas-phase reaction rate constants for atmospheric pressure ionization in ion-mobility spectrometry

International Nuclear Information System (INIS)

Vandiver, V.J.

1987-01-01

Ion-mobility spectrometry (IMS) is an instrumental technique in which gaseous ions are formed from neutral molecules by proton and charge transfer from reactant ions through collisional ionization. An abbreviated rate theory has been proposed for atmospheric pressure ionization (API) in IMS, but supporting experimental measurements have not been reported. The objectives of this thesis were (1) assessment of existing API rate theory using positive and negative product ions in IMS, (2) measurement of API equilibria and kinetics for binary mixtures, and (3) investigating of cross-ionizations with multiple-product ions in API reactions. Although IMS measurements and predictions from rate theory were comparable, shapes and slopes of response curves for both proton transfer and electron capture were not described exactly by existing theory. In particular, terms that are needed for calculation of absolute rate constants were unsuitable in the existing theory. These included recombination coefficients,initial number of reactant ions, and opposing ion densities

Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

Energy Technology Data Exchange (ETDEWEB)

Poad, Berwyck L.; Zheng, Xueyun; Mitchell, Todd A.; Smith, Richard D.; Baker, Erin M.; Blanksby, Stephen J.

2017-12-21

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.

Molecular depth profiling of trehalose using a C{sub 60} cluster ion beam

Energy Technology Data Exchange (ETDEWEB)

Wucher, Andreas [Department of Physics, University of Duisburg-Essen, D-47048 Duisburg (Germany)], E-mail: andreas.wucher@uni-due.de; Cheng Juan; Winograd, Nicholas [Department of Chemistry, Pennsylvania State University, University Park, PA 16802 (United States)

2008-12-15

Molecular depth profiling of organic overlayers was performed using a mass selected fullerene ion beam in conjunction with time-of-flight (TOF-SIMS) mass spectrometry. The characteristics of depth profiles acquired on a 300-nm trehalose film on Si were studied as a function of the impact kinetic energy and charge state of the C{sub 60} projectile ions. We find that the achieved depth resolution depends only weakly upon energy.

The matrix effect in secondary ion mass spectrometry

Science.gov (United States)

Seah, M. P.; Shard, A. G.

2018-05-01

Matrix effects in the secondary ion mass spectrometry (SIMS) of selected elemental systems have been analyzed to investigate the applicability of a mathematical description of the matrix effect, called here the charge transfer (CT) model. This model was originally derived for proton exchange and organic positive secondary ions, to characterise the enhancement or suppression of intensities in organic binary systems. In the systems considered in this paper protons are specifically excluded, which enables an assessment of whether the model applies for electrons as well. The present importance is in organic systems but, here we analyse simpler inorganic systems. Matrix effects in elemental systems cannot involve proton transfer if there are no protons present but may be caused by electron transfer and so electron transfer may also be involved in the matrix effects for organic systems. There are general similarities in both the magnitudes of the ion intensities as well as the matrix effects for both positive and negative secondary ions in both systems and so the CT model may be more widely applicable. Published SIMS analyses of binary elemental mixtures are analyzed. The data of Kim et al., for the Pt/Co system, provide, with good precision, data for such a system. This gives evidence for the applicability of the CT model, where electron, rather than proton, transfer is the matrix enhancing and suppressing mechanism. The published data of Prudon et al., for the important Si/Ge system, provides further evidence for the effects for both positive and negative secondary ions and allows rudimentary rules to be developed for the enhancing and suppressing species.

Heavy ion recoil spectrometry of Si{sub x}Ge{sub 1-x} thin films

Energy Technology Data Exchange (ETDEWEB)

Walker, S.R.; Johnston, P.N.; Bubb, I.F. [Royal Melbourne Inst. of Tech., VIC (Australia); Cohen, D.D.; Dytlewski, N. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Hult, M.; Whitlow, H.J. [Lund Institute of Technology, Solvegatan (Sweden). Department of Nuclear Physics; Zaring, C.; Oestling, M. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Solid State Electronics

1993-12-31

Mass and energy dispersive recoil spectrometry employing 77 MeV {sup 127}I ions from ANTARES (FN Tandem) facility at Lucas Heights has been used to examine the isotopic composition of samples of Si{sub x}Ge{sub 1-x} grown at the Australian National University by Electron Beam Evaporation (EBE). The recoiling target nuclei were analysed by a Time Of Flight and Energy (TOF-E) detector telescope composed of two timing pickoff detectors and a surface barrier (energy) detector. From the time of flight and energy, the ion mass can be determined and individual depth distributions for each element can be obtained. Recoil spectrometry has shown the presence of oxygen in the Si{sub x}Ge{sub 1-x} layer and has enabled the separate determination of energy spectra for individual elements. 9 refs., 3 figs.

Heavy ion recoil spectrometry of Si{sub x}Ge{sub 1-x} thin films

Energy Technology Data Exchange (ETDEWEB)

Walker, S R; Johnston, P N; Bubb, I F [Royal Melbourne Inst. of Tech., VIC (Australia); Cohen, D D; Dytlewski, N [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Hult, M; Whitlow, H J [Lund Institute of Technology, Solvegatan (Sweden). Department of Nuclear Physics; Zaring, C; Oestling, M [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Solid State Electronics

1994-12-31

Mass and energy dispersive recoil spectrometry employing 77 MeV {sup 127}I ions from ANTARES (FN Tandem) facility at Lucas Heights has been used to examine the isotopic composition of samples of Si{sub x}Ge{sub 1-x} grown at the Australian National University by Electron Beam Evaporation (EBE). The recoiling target nuclei were analysed by a Time Of Flight and Energy (TOF-E) detector telescope composed of two timing pickoff detectors and a surface barrier (energy) detector. From the time of flight and energy, the ion mass can be determined and individual depth distributions for each element can be obtained. Recoil spectrometry has shown the presence of oxygen in the Si{sub x}Ge{sub 1-x} layer and has enabled the separate determination of energy spectra for individual elements. 9 refs., 3 figs.

Observations on small anionic clusters in an electrostatic ion beam trap

Energy Technology Data Exchange (ETDEWEB)

Eritt, Markus

2008-10-02

The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C{sub n}{sup -} n=2-12), aluminium (Al{sub n}{sup -} n=2-7) and silver clusters (Ag{sub n}{sup -} n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

Science.gov (United States)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

Science.gov (United States)

Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

2004-05-01

The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

Effect of low-oxygen-concentration layer on iron gettering capability of carbon-cluster ion-implanted Si wafer for CMOS image sensors

Science.gov (United States)

Onaka-Masada, Ayumi; Nakai, Toshiro; Okuyama, Ryosuke; Okuda, Hidehiko; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Kurita, Kazunari; Sueoka, Koji

2018-02-01

The effect of oxygen (O) concentration on the Fe gettering capability in a carbon-cluster (C3H5) ion-implanted region was investigated by comparing a Czochralski (CZ)-grown silicon substrate and an epitaxial growth layer. A high Fe gettering efficiency in a carbon-cluster ion-implanted epitaxial growth layer, which has a low oxygen region, was observed by deep-level transient spectroscopy (DLTS) and secondary ion mass spectroscopy (SIMS). It was demonstrated that the amount of gettered Fe in the epitaxial growth layer is approximately two times higher than that in the CZ-grown silicon substrate. Furthermore, by measuring the cathodeluminescence, the number of intrinsic point defects induced by carbon-cluster ion implantation was found to differ between the CZ-grown silicon substrate and the epitaxial growth layer. It is suggested that Fe gettering by carbon-cluster ion implantation comes through point defect clusters, and that O in the carbon-cluster ion-implanted region affects the formation of gettering sinks for Fe.

On the mechanism of water cluster-ion formation in carbon dioxide

International Nuclear Information System (INIS)

Warneck, P.; Rakshit, A.B.

1981-01-01

A drift chamber mass spectrometer has been used to study the formation of water cluster-ions in carbon dioxide containing traces of water vapour. The dominant reaction sequences were identified up to the fourth generation of daughter ions starting with CO 2 + . The subsequent reaction mechanism remains uncertain and several possibilities are discussed. The final ions are H 3 O + H 2 O and H 3 O + (H 2 O) 2 . The significance of the reaction schemes to the radiation chemistry of carbon dioxide is pointed out. (orig.)

On the features, successes and challenges of selected ion flow tube mass spectrometry

Czech Academy of Sciences Publication Activity Database

Španěl, Patrik; Smith, D.

2013-01-01

Roč. 19, č. 4 (2013), s. 225-246 ISSN 1469-0667 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : selected ion flow tube mass spectrometry * SIFT-MS * breath metabolies Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.165, year: 2013

Simultaneous quantitative analysis of metabolites using ion-pair liquid chromatography-electrospray ionization mass spectrometry

NARCIS (Netherlands)

Coulier, L.; Bas, R.; Jespersen, S.; Verheij, E.; Werf, M.J. van der; Hankemeier, T.

2006-01-01

We have developed an analytical method, consisting of ion-pair liquid chromatography coupled to electrospray ionization mass spectrometry (IP-LC-ESI-MS), for the simultaneous quantitative analysis of several key classes of polar metabolites, like nucleotides, coenzyme A esters, sugar nucleotides,

Si clusters/defective graphene composites as Li-ion batteries anode materials: A density functional study

International Nuclear Information System (INIS)

Li, Meng; Liu, Yue-Jie; Zhao, Jing-xiang; Wang, Xiao-guang

2015-01-01

Highlights: • We study the interaction between Si clusters with pristine and defective graphene. • We find that the binding strength of Si clusters on graphene can be enhanced to different degrees after introducing various defects. • It is found that both graphene and Si cluster in the Si/graphene composites can preserve their Li uptake ability. - Abstract: Recently, the Si/graphene hybrid composites have attracted considerable attention due to their potential application for Li-ion batteries. How to effectively anchor Si clusters to graphene substrates to ensure their stability is an important factor to determine their performance for Li-ion batteries. In the present work, we have performed comprehensive density functional theory (DFT) calculations to investigate the geometric structures, stability, and electronic properties of the deposited Si clusters on defective graphenes as well as their potential applications for Li-ion batteries. The results indicate that the interfacial bonding between these Si clusters with the pristine graphene is quietly weak with a small adsorption energy (<−0.21 eV). Due to the presence of vacancy site, the binding strength of Si clusters on defective graphene is much stronger than that of pristine one, accompanying with a certain amount of charge transfer from Si clusters to graphene substrates. Moreover, the ability of Si/graphene hybrids for Li uptake is studied by calculating the adsorption of Li atoms. We find that both graphenes and Si clusters in the Si/graphene composites preserve their Li uptake ability, indicating that graphenes not only server as buffer materials for accommodating the expansion of Si cluster, but also provide additional intercalation sites for Li

Energetics and dynamics of the neutralization of clustered ions in ammonia and water vapour

International Nuclear Information System (INIS)

Sennhauser, E.S.; Armstrong, D.A.

1978-01-01

The energetics and dynamics of neutralization reactions of clustered ions in ammonia and water vapour have been analysed. Neutralization rate coefficients were calculated for the ions in ammonia and for H + .(H 2 O)sub(n) combining with various clustered anions in water vapour up to densities of 4 x 10 19 molecule cm -3 at 390 K. In the case of ammonia, calculations were also performed at 298 K. For all systems, fractional contributions of the neutralization coefficients for specific cluster sizes to the overall coefficient αsub(eff) were evaluated. The computed value of αsub(eff) for NH 3 was in reasonable agreement with experimental data in the [NH 3 ] range 0.3 to 4 x 10 19 molecule cm -3 , and general trends stemming from the effects of increasing ion mass were pointed out. Calculations of energies of individual cluster sizes indicate possible neutralization reaction mechanisms. With some exception, proton transfer is the only possible path and no H atoms should be formed. This is in general agreement with literature results for water vapour at approximately 390 K and with [H 2 O] >= 2 x 10 x 10 19 molecule cm -3 . (author)

Vacancy defect and defect cluster energetics in ion-implanted ZnO

Science.gov (United States)

Dong, Yufeng; Tuomisto, F.; Svensson, B. G.; Kuznetsov, A. Yu.; Brillson, Leonard J.

2010-02-01

We have used depth-resolved cathodoluminescence, positron annihilation, and surface photovoltage spectroscopies to determine the energy levels of Zn vacancies and vacancy clusters in bulk ZnO crystals. Doppler broadening-measured transformation of Zn vacancies to vacancy clusters with annealing shifts defect energies significantly lower in the ZnO band gap. Zn and corresponding O vacancy-related depth distributions provide a consistent explanation of depth-dependent resistivity and carrier-concentration changes induced by ion implantation.

Gas cluster ion beam assisted NiPt germano-silicide formation on SiGe

Energy Technology Data Exchange (ETDEWEB)

Ozcan, Ahmet S., E-mail: asozcan@us.ibm.com [IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120 (United States); Lavoie, Christian; Jordan-Sweet, Jean [IBM T. J. Watson Research Center, 1101 Kitchawan Road, Yorktown Heights, New York 10598 (United States); Alptekin, Emre; Zhu, Frank [IBM Semiconductor Research and Development Center, 2070 Route 52, Hopewell Junction, New York 12533 (United States); Leith, Allen; Pfeifer, Brian D.; LaRose, J. D.; Russell, N. M. [TEL Epion Inc., 900 Middlesex Turnpike, Bldg. 6, Billerica, Massachusetts 01821 (United States)

2016-04-21

We report the formation of very uniform and smooth Ni(Pt)Si on epitaxially grown SiGe using Si gas cluster ion beam treatment after metal-rich silicide formation. The gas cluster ion implantation process was optimized to infuse Si into the metal-rich silicide layer and lowered the NiSi nucleation temperature significantly according to in situ X-ray diffraction measurements. This novel method which leads to more uniform films can also be used to control silicide depth in ultra-shallow junctions, especially for high Ge containing devices, where silicidation is problematic as it leads to much rougher interfaces.

High mass accuracy and high mass resolving power FT-ICR secondary ion mass spectrometry for biological tissue imaging

NARCIS (Netherlands)

Smith, D.F.; Kiss, A.; Leach, F.E.; Robinson, E.W.; Paša-Tolić, L.; Heeren, R.M.A.

2013-01-01

Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the sub-micrometer scale. Such experiments are typically

Compositional changes of human hair melanin resulting from bleach treatment investigated by nanoscale secondary ion mass spectrometry.

Science.gov (United States)

Kojima, Toru; Yamada, Hiromi; Isobe, Mitsuru; Yamamoto, Toshihiko; Takeuchi, Miyuki; Aoki, Dan; Matsushita, Yasuyuki; Fukushima, Kazuhiko

2014-11-01

It is important to understand the influence of bleach treatment on human hair because it is one of the most important chemical treatments in hair cosmetic processes. A comparison of the elemental composition of melanin between virgin hair and bleached hair would provide important information about the structural changes of melanin. To investigate the elemental composition of melanin granules in virgin black hair and bleached hair, these hair cross-sections are analyzed by using a nanoscale secondary ion mass spectrometry (NanoSIMS). The virgin black hair and bleached hair samples were embedded in resin and smooth hair cross-sections were obtained using an ultramicrotome. NanoSIMS measurements were performed using a Cs(+) primary ion beam to detect negative secondary ions. More intensive (16) O(-) ions were detected from the melanin granules of bleached hair than from those of virgin black hair in NanoSIMS (16) O(-) ion image. In addition, it was indicated that (16) O(-) ion intensity and (16) O(-) /(12) C(14) N(-) ion intensity ratio of melanin granules in bleached hair were higher than those in virgin black hair. Nanoscale secondary ion mass spectrometry analysis of the cross-sections of virgin black hair and bleached hair indicated that the oxygen content in melanin granules was increased by bleach treatment. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

ION INJECTION AT QUASI-PARALLEL SHOCKS SEEN BY THE CLUSTER SPACECRAFT

International Nuclear Information System (INIS)

Johlander, A.; Vaivads, A.; Khotyaintsev, Yu. V.; Retinò, A.; Dandouras, I.

2016-01-01

Collisionless shocks in space plasma are known to be capable of accelerating ions to very high energies through diffusive shock acceleration (DSA). This process requires an injection of suprathermal ions, but the mechanisms producing such a suprathermal ion seed population are still not fully understood. We study acceleration of solar wind ions resulting from reflection off short large-amplitude magnetic structures (SLAMSs) in the quasi-parallel bow shock of Earth using in situ data from the four Cluster spacecraft. Nearly specularly reflected solar wind ions are observed just upstream of a SLAMS. The reflected ions are undergoing shock drift acceleration (SDA) and obtain energies higher than the solar wind energy upstream of the SLAMS. Our test particle simulations show that solar wind ions with lower energy are more likely to be reflected off the SLAMS, while high-energy ions pass through the SLAMS, which is consistent with the observations. The process of SDA at SLAMSs can provide an effective way of accelerating solar wind ions to suprathermal energies. Therefore, this could be a mechanism of ion injection into DSA in astrophysical plasmas

Relaxation effects in ionic mobility and cluster formation: negative ions in SF6 at high pressures

International Nuclear Information System (INIS)

Juarez, A M; De Urquijo, J; Hinojosa, G; Hernandez-Avila, J L; Basurto, E

2010-01-01

The relaxation effects of the ionic mobility and the formation of negative-ion clusters in SF 6 are studied in this work. For this purpose, we have measured the mobility of negative ions in SF 6 over the pressure range 100-800 Torr at a fixed value of density-normalized electric field, E/N, of 20 Td (1 Townsend = 10 -17 V cm 2 ). The data obtained show a clear dependence of the negative-ion drift velocity on drift distance. It is observed that the drift velocity (mobility) reaches a steady-state value only for drift distances above 2 cm, over the studied pressure range. In addition to this, we have observed that the ionic mobility depends strongly on the gas pressure. An explanation of this dependence of the ionic mobility on gas pressure is given in terms of a negative-ion clustering formation process. It was found that the assumption of a linear dependence of the cluster ion mass on pressure provides a satisfactory explanation for the observed mobilities.

Ultrasensitive probing of the protein resistance of PEG surfaces by secondary ion mass spectrometry

DEFF Research Database (Denmark)

Kingshott, P.; McArthur, S.; Thissen, H.

2002-01-01

The highly sensitive surface analytical techniques X-ray photoelectron spectroscopy (XPS) and time-of-flight static secondary ion mass spectrometry (ToF-SIMS) were used to test the resistance of poly(ethylene glycol) (PEG) coatings towards adsorption of lysozyme (LYS) and fibronectin (FN). PEG co...

Computer simulation program for medium-energy ion scattering and Rutherford backscattering spectrometry

Science.gov (United States)

Nishimura, Tomoaki

2016-03-01

A computer simulation program for ion scattering and its graphical user interface (MEISwin) has been developed. Using this program, researchers have analyzed medium-energy ion scattering and Rutherford backscattering spectrometry at Ritsumeikan University since 1998, and at Rutgers University since 2007. The main features of the program are as follows: (1) stopping power can be chosen from five datasets spanning several decades (from 1977 to 2011), (2) straggling can be chosen from two datasets, (3) spectral shape can be selected as Gaussian or exponentially modified Gaussian, (4) scattering cross sections can be selected as Coulomb or screened, (5) simulations adopt the resonant elastic scattering cross section of 16O(4He, 4He)16O, (6) pileup simulation for RBS spectra is supported, (7) natural and specific isotope abundances are supported, and (8) the charge fraction can be chosen from three patterns (fixed, energy-dependent, and ion fraction with charge-exchange parameters for medium-energy ion scattering). This study demonstrates and discusses the simulations and their results.

Negative-Ion source for mass selective photodetachment photoelectron spectroscopy

International Nuclear Information System (INIS)

Kaesmaier, R.; Baemann, C.; Drechsler, G.; Boesl, U.

1995-01-01

We have designed and constructed a negative ion source for mass spectrometry and mass selective photodetachement photoelectron spectroscopy. The characteristics of the source are high anion densities and a large variety of accessible systems. Thus, mass spectra and photoelectron spectra of large unvolatile moelcules (biomolecules), of metal-organic compounds and of molecule water clusters, especially mentioned in this article, have been measured. Combining mass spectrometry, photoelectron spectroscopy (PES) and high resolution ZEKE (zero kinetic energy)-PES (1) should make the apparatus to an ideal diagnostic tool for structural assignment

Design and implementation of embedded ion mobility spectrometry instrument based on SOPC

Science.gov (United States)

Zhang, Genwei; Zhao, Jiang; Yang, Liu; Liu, Bo; Jiang, Yanwei; Yang, Jie

2015-02-01

On the hardware platform with single CYCLONE IV FPGA Chip based on SOPC technology, the control functions of IP cores of a Ion Mobility Spectrometry instrument was tested, including 32 bit Nios II soft-core processor, high-voltage module, ion gate switch, gas flow, temperature and pressure sensors, signal acquisition and communication protocol. Embedded operating system μCLinux was successfully transplanted to the hardware platform, used to schedule all the tasks, such as system initialization, parameter setting, signal processing, recognition algorithm and results display. The system was validated using the IMS diagram of Acetone reagent, and the instrument was proved to have a strong signal resolution.

Angle resolved mass spectrometry of positive ions transmitted through high aspect ratio channels in a radio frequency discharge

NARCIS (Netherlands)

Stoffels - Adamowicz, E.; Stoffels, W.W.; Tachibana, K.; Imai, S.

1997-01-01

The behavior of positive ions in high aspect ratio structures, relevant to the reactive ion etching of deep trenches, has been studied by means of energy resolved mass spectrometry. High aspect ratio trenches are simulated by capillary plates with various aspect ratios. Angle resolved measurements

Interaction of ion clusters with fusion plasmas: Scaling laws

International Nuclear Information System (INIS)

Arista, N.R.; Bringa, E.M.

1997-01-01

The interaction between large ion clusters or very intense ion beams with fusion plasma is studied using the dielectric function formalism with appropriate quantum corrections. The contributions from individual and collective modes to the energy loss are calculated. The general properties of the interference effects are characterized in terms of the relevant parameters, and simple scaling laws are obtained. In particular, the conditions for a maximum enhancement in the energy deposition are derived. The study provides a unified view and a general formulation of collective effects in the energy loss for low and high velocities of the beam particles. copyright 1997 The American Physical Society

Ion-neutral Clustering of Bile Acids in Electrospray Ionization Across UPLC Flow Regimes

Science.gov (United States)

Brophy, Patrick; Broeckling, Corey D.; Murphy, James; Prenni, Jessica E.

2018-02-01

Bile acid authentic standards were used as model compounds to quantitatively evaluate complex in-source phenomenon on a UPLC-ESI-TOF-MS operated in the negative mode. Three different diameter columns and a ceramic-based microfluidic separation device were utilized, allowing for detailed descriptions of bile acid behavior across a wide range of flow regimes and instantaneous concentrations. A custom processing algorithm based on correlation analysis was developed to group together all ion signals arising from a single compound; these grouped signals produce verified compound spectra for each bile acid at each on-column mass loading. Significant adduction was observed for all bile acids investigated under all flow regimes and across a wide range of bile acid concentrations. The distribution of bile acid containing clusters was found to depend on the specific bile acid species, solvent flow rate, and bile acid concentration. Relative abundancies of each cluster changed non-linearly with concentration. It was found that summing all MS level (low collisional energy) ions and ion-neutral adducts arising from a single compound improves linearity across the concentration range (0.125-5 ng on column) and increases the sensitivity of MS level quantification. The behavior of each cluster roughly follows simple equilibrium processes consistent with our understanding of electrospray ionization mechanisms and ion transport processes occurring in atmospheric pressure interfaces. [Figure not available: see fulltext.

Adsorption and Formation of Small Na Clusters on Pristine and Double-Vacancy Graphene for Anodes of Na-Ion Batteries.

Science.gov (United States)

Liang, Zhicong; Fan, Xiaofeng; Zheng, Weitao; Singh, David J

2017-05-24

Layered carbon is a likely anode material for Na-ion batteries (NIBs). Graphitic carbon has a low capacity of approximately 35 (mA h)/g due to the formation of NaC 64 . Using first-principles methods including van der Waals interactions, we analyze the adsorption of Na ions and clusters on graphene in the context of anodes. The interaction between Na ions and graphene is found to be weak. Small Na clusters are not stable on the surface of pristine graphene in the electrochemical environment of NIBs. However, we find that Na ions and clusters can be stored effectively on defected graphene that has double vacancies. In addition, the adsorption energy of small Na clusters near a double vacancy is found to decrease with increasing cluster size. With high concentrations of vacancies the capacity of Na on defective graphene is found to be as much as 10-30 times higher than that of graphitic carbon.

Electrochemical lithiation of silicon electrodes. Neutron reflectometry and secondary ion mass spectrometry investigations

Energy Technology Data Exchange (ETDEWEB)

Jerliu, Bujar; Doerrer, Lars; Hueger, Erwin [Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany). AG Mikrokinetik; Seidlhofer, Beatrix-Kamelia; Steitz, Roland [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Berlin (Germany); Borchardt, Guenter; Schmidt, Harald [Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany). AG Mikrokinetik; Clausthaler Zentrum fuer Materialtechnik (CZM), Clausthal-Zellerfeld (Germany)

2017-11-15

In-situ neutron reflectometry and ex-situ secondary ion mass spectrometry in combination with electrochemical methods were used to study the lithiation of amorphous silicon electrodes. For that purpose specially designed closed three-electrode electrochemical cells with thin silicon films as the working electrode and lithium as counter and reference electrodes were used. The neutron reflectometry results obtained in-situ during galvanostatic cycling show that the incorporation, redistribution and removal of Li in amorphous silicon during a lithiation cycle can be monitored. It was possible to measure the volume modification during lithiation, which is found to be rather independent of cycle number, current density and film thickness and in good agreement with first-principles calculations as given in literature. Indications for an inhomogeneous lithiation mechanism were found by secondary ion mass spectrometry measurements. Lithium tracer diffusion experiments indicate that the diffusivities inside the lithiated region (D > 10{sup -15} m{sup 2} s{sup -1}) are considerably higher than in pure amorphous silicon as known from literature. This suggests a kinetics based explanation for the occurrence of an inhomogeneous lithiation mechanism.

Major signal suppression from metal ion clusters in SFC/ESI-MS - Cause and effects.

Science.gov (United States)

Haglind, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Pettersson, Curt E

2018-05-01

The widening application area of SFC-MS with polar analytes and water-containing samples facilitates the use of quick and simple sample preparation techniques such as "dilute and shoot" and protein precipitation. This has also introduced new polar interfering components such as alkali metal ions naturally abundant in e.g. blood plasma and urine, which have shown to be retained using screening conditions in SFC/ESI-TOF-MS and causing areas of major ion suppression. Analytes co-eluting with these clusters will have a decreased signal intensity, which might have a major effect on both quantification and identification. When investigating the composition of the alkali metal clusters using accurate mass and isotopic pattern, it could be concluded that they were previously not described in the literature. Using NaCl and KCl standards and different chromatographic conditions, varying e.g. column and modifier, the clusters proved to be formed from the alkali metal ions in combination with the alcohol modifier and make-up solvent. Their compositions were [(XOCH 3 ) n  + X] + , [(XOH) n  + X] + , [(X 2 CO 3 ) n  + X] + and [(XOOCOCH 3 ) n  + X] + for X = Na + or K + in ESI+. In ESI-, the clusters depended more on modifier, with [(XCl) n  + Cl] - and [(XOCH 3 ) n  + OCH 3 ] - mainly formed in pure methanol and [(XOOCH) n  + OOCH] - when 20 mM NH 4 Fa was added. To prevent the formation of the clusters by avoiding methanol as modifier might be difficult, as this is a widely used modifier providing good solubility when analyzing polar compounds in SFC. A sample preparation with e.g. LLE would remove the alkali ions, however also introducing a time consuming and discriminating step into the method. Since the alkali metal ions were retained and affected by chromatographic adjustments as e.g. mobile phase modifications, a way to avoid them could therefore be chromatographic tuning, when analyzing samples containing them. Copyright © 2018 Elsevier

Interlaboratory study of the ion source memory effect in 36Cl accelerator mass spectrometry

International Nuclear Information System (INIS)

Pavetich, Stefan; Akhmadaliev, Shavkat; Arnold, Maurice; Aumaître, Georges; Bourlès, Didier; Buchriegler, Josef; Golser, Robin; Keddadouche, Karim; Martschini, Martin; Merchel, Silke; Rugel, Georg; Steier, Peter

2014-01-01

Highlights: • Long-term memory effect in negative ion sources investigated for chlorine isotopes. • Interlaboratory comparison of four up-to date negative ion sources. • Ion source improvement at DREAMS for minimization of long-term memory effect. • Long-term memory effect is the limitation for precise AMS data of volatile elements. • Findings to be considered for samples with highly variable ratios of 36 Cl/Cl and 129 I/I. - Abstract: Understanding and minimization of contaminations in the ion source due to cross-contamination and long-term memory effect is one of the key issues for accurate accelerator mass spectrometry (AMS) measurements of volatile elements. The focus of this work is on the investigation of the long-term memory effect for the volatile element chlorine, and the minimization of this effect in the ion source of the Dresden accelerator mass spectrometry facility (DREAMS). For this purpose, one of the two original HVE ion sources at the DREAMS facility was modified, allowing the use of larger sample holders having individual target apertures. Additionally, a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, an interlaboratory comparison had been initiated. The long-term memory effect of the four Cs sputter ion sources at DREAMS (two sources: original and modified), ASTER (Accélérateur pour les Sciences de la Terre, Environnement, Risques) and VERA (Vienna Environmental Research Accelerator) had been investigated by measuring samples of natural 35 Cl/ 37 Cl-ratio and samples highly-enriched in 35 Cl ( 35 Cl/ 37 Cl ∼ 999). Besides investigating and comparing the individual levels of long-term memory, recovery time constants could be calculated. The tests show that all four sources suffer from long-term memory, but the modified DREAMS ion source showed the lowest level of contamination. The recovery times of the four ion sources were widely spread between

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules - application to a mixed reagent ion system for hydroperoxides and organic acids

Science.gov (United States)

Heikes, Brian G.; Treadaway, Victoria; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

2018-04-01

An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3-(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2-(H2O2) at m/z 66. O3 and NO give rise to species and cluster ions, CO3-(H2O) and NO3-(H2O), respectively, which interfere in the measurement of CH3OOH using O2-(CH3OOH) at m/z 80. The CO3-(H2O

High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry.

Science.gov (United States)

Fan, Ruo-Jing; Zhang, Fang; Chen, Xiu-Ping; Qi, Wan-Shu; Guan, Qing; Sun, Tuan-Qi; Guo, Yin-Long

2017-04-08

The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%-12.3% for intra-day and 0.9%-7.8% for inter-day) and good accuracy (91%-109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

A Novel Microwave-Induced Plasma Ionization Source for Ion Mobility Spectrometry

Science.gov (United States)

Dai, Jianxiong; Zhao, Zhongjun; Liang, Gaoling; Duan, Yixiang

2017-03-01

This work demonstrates the application of a novel microwave induced plasma ionization (MIPI) source to ion mobility spectrometry (IMS). The MIPI source, called Surfatron, is composed of a copper cavity and a hollow quartz discharge tube. The ion mobility spectrum of synthetics air has a main peak with reduced mobility of 2.14 cm2V-1s-1 for positive ion mode and 2.29 cm2V-1s-1 for negative ion mode. The relative standard deviations (RSD) are 0.7% and 1.2% for positive and negative ion mode, respectively. The total ion current measured was more than 3.5 nA, which is much higher than that of the conventional 63Ni source. This indicates that a better signal-to-noise ratio (SNR) can be acquired from the MIPI source. The SNR was 110 in the analysis of 500 pptv methyl tert-butyl ether (MTBE), resulting in the limit of detection (SNR = 3) of 14 pptv. The linear range covers close to 2.5 orders of magnitude in the detection of triethylamine with a concentration range from 500 pptv to 80 ppbv. Finally, this new MIPI-IMS was used to detect some volatile organic compounds, which demonstrated that the MIPI-IMS has great potential in monitoring pollutants in air.

Development of a short pulsed corona discharge ionization source for ion mobility spectrometry

International Nuclear Information System (INIS)

An Yuan; Aliaga-Rossel, R.; Choi, Peter; Gilles, Jean-Paul

2005-01-01

The development of a pulsed corona discharge ionization source and its use in ion mobility spectrometry (IMS) is presented. In a point-plane electrode geometry, an electrical pulse up to 12 kV, 150 ns rise time and 500 ns pulse width was used to generate a corona discharge in air. A single positive high voltage pulse was able to generate about 1.6x10 10 ions at energy consumption of 22 μJ. Since the temporal distribution of ions is in a pulsed form, the possibility of removal the ion gate has been investigated. By purposely arranging the interface between discharge field and drift field, nearly 10 7 positive ions were drawn into the drift region with absence of the ion gate after every single discharge. The positive spectrum of acetone dimer (working at room temperature) was obtained with a resolving power of 20 by using this configuration. The advantages of this new scheme are the low power consumption compared with the dc method as well as the simplicity of the IMS cell structure

Reprint of: Negative carbon cluster ion beams: New evidence for the special nature of C60

Science.gov (United States)

Liu, Y.; O'brien, S. C.; Zhang, Q.; Heath, J. R.; Tittel, F. K.; Curl, R. F.; Kroto, H. W.; Smalley, R. E.

2013-12-01

Cold carbon cluster negative ions are formed by supersonic expansion of a plasma created at the nozzle of a supersonic cluster beam source by an excimer laser pulse. The observed distribution of mass peaks for the Cn- ions for n > 40 demonstrates that the evidence previously given for the special stability of neutral C60 and the existence of spheroidal carbon shells cannot be an artifact of the ionization conditions.

Structure and dynamics of ion clusters in linear octupole traps: Phase diagrams, chirality, and melting mechanisms

International Nuclear Information System (INIS)

Yurtsever, E.; Onal, E. D.; Calvo, F.

2011-01-01

The stable structures and melting dynamics of clusters of identical ions bound by linear octupole radiofrequency traps are theoretically investigated by global optimization methods and molecular dynamics simulations. By varying the cluster sizes in the range of 10-1000 ions and the extent of trap anisotropy by more than one order of magnitude, we find a broad variety of stable structures based on multiple rings at small sizes evolving into tubular geometries at large sizes. The binding energy of these clusters is well represented by two contributions arising from isotropic linear and octupolar traps. The structures generally exhibit strong size effects, and chiral arrangements spontaneously emerge in many crystals. Sufficiently large clusters form nested, coaxial tubes with different thermal stabilities. As in isotropic octupolar clusters, the inner tubes melt at temperatures that are lower than the overall melting point.

Analysis of trace elements by means of accelerator secondary ion mass spectrometry

International Nuclear Information System (INIS)

Ender, R.M.

1997-01-01

The analysis of material composition and trace element concentration is of increasing interest primarily in semiconductor technology but also in metallurgy, geology, biology and medicine. At present, Secondary Ion Mass Spectrometry (SIMS) is in many respects the best technique to provide 3-dimensional information on the distribution of trace elements with concentrations below 1 ppm. However, due to the presence of molecular ions the detectability of many trace elements it restricted because of molecular mass interferences. In addition, detectors used in SIMS have a background counting rate of 0.1-1 Hz, which further limits trace element analysis. In Accelerator Mass Spectrometry (AMS) long-lived radionuclides are detected free of molecular interferences and detector background at isotopic ratios as low as 10 -15 . Moreover, isobaric interferences can be reduced as well. In order to benefit from these advantages a combination of SIMS and AMS (Accelerator SIMS) has been proposed almost 20 years ago, but no facility has ever been fully developed. It has been the aim of this work to add a new sputtering chamber for AMS measurements of ultrapure semiconductor material to the existing PSI/ETH AMS facility. To fulfill the requirements of material analysis, an UHV chamber with special precautions against contamination has been built and adapted to the existing AMS setup. For sputtering, a commercial Cs gun with an ExB filter and a 1 o beam bend for neutral particle suppression is used to obtain a pure Cs ion beam. The gun is equipped with different apertures for varying the diameter of the beam spot. With the integrated scanning unit the 10 keV Cs beam can be rastered over approximately 1 mm 2 . This allows different applications such as bulk analysis, depth profiling and imaging. The secondary ion extraction is matched to the ion optical and geometrical requirements of the existing accelerator mass spectrometer. (author) figs., tabs., 67 refs

Ag clustering investigation in laser irradiated ion-exchanged glasses by optical and vibrational spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Trave, E., E-mail: enrico.trave@unive.it [Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venezia, Dorsoduro 2137, I-30123 Venezia (Italy); Cattaruzza, E.; Gonella, F.; Calvelli, P. [Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venezia, Dorsoduro 2137, I-30123 Venezia (Italy); Quaranta, A. [Department of Materials Engineering and Industrial Technologies, University of Trento, via Mesiano 77, I-38050 Povo (Italy); Rahman, A.; Mariotto, G. [Department of Computer Science, University of Verona, Strada le Grazie 15, 37134 Verona (Italy)

2012-09-15

Highlights: Black-Right-Pointing-Pointer We modify the properties of Ag{sup +} exchanged glasses by thermal and laser treatment. Black-Right-Pointing-Pointer The induced microstructural changes are analyzed by optical and Raman spectroscopy. Black-Right-Pointing-Pointer Ag-based species in the glass show a peculiar PL activity in the UV-Vis range. Black-Right-Pointing-Pointer Raman and OA analysis allow for determining the Ag cluster size evolution. Black-Right-Pointing-Pointer Laser processing leads to different cluster formation and fragmentation mechanisms. - Abstract: Ion exchange process is widely used to dope silicate glass layers with silver for several applications, ranging from light waveguide to nanostructured composite glass fabrication. The silver-doped structure and its physical properties depend on the preparation parameters as well as on subsequent treatments. In particular, laser irradiation of the ion exchanged glasses has been demonstrated to be an effective tool to control cluster size and size distribution. Nevertheless, a complete comprehension of the basic phenomena and a systematic characterization of these systems are still lacking. In this paper, an extended optical characterization is presented for soda-lime glass slides, doped with silver by Ag{sup +}-Na{sup +} ion exchange, thermally treated and irradiated with a Nd:YAG laser beam at different wavelengths, and for different energy density. The samples were characterized by various spectroscopic techniques, namely, optical absorption, photoluminescence and micro-Raman analysis. The availability of all these characterization techniques allowed pointing out a suitable scenario for the Ag clustering evolution as a function of the ion exchange, annealing and laser irradiation parameters.

Spatial distribution of ion energy related on electron density in a plasma channel generated in gas clusters by a femtosecond laser

International Nuclear Information System (INIS)

Nam, S. M.; Han, J. M.; Cha, Y. H.; Lee, Y. W.; Rhee, Y. J.; Cha, H. K.

2008-01-01

Neutron generation through Coulomb explosion of deuterium contained gas clusters is known as one of the very effective methods to produce fusion neutrons using a table top terawatt laser. The energy of ions produced through Coulomb explosions is very important factor to generate neutrons efficiently. Until the ion energy reaches around∼MeV level, the D D fusion reaction probability increases exponentially. The understanding of laser beam propagation and laser energy deposition in clusters is very important to improve neutron yields. As the laser beam propagates through clusters medium, laser energy is absorbed in clusters by ionization of molecules consisting clusters. When the backing pressure of gas increases, the average size of clusters increases and which results in higher energy absorption and earlier termination of laser propagation. We first installed a Michelson interferometer to view laser beam traces in a cluster plume and to measure spatial electron density profiles of a plasma channel which was produced by a laser beam. And then we measured the energy of ions distributed along the plasma channel with a translating slit to select ions from narrow parts of a plasma channel. In our experiments, methane gas was used to produce gas clusters at a room temperature and the energy distribution of proton ions for different gas backing pressure were measured by the time of flight method using dual micro channel plates. By comparing the distribution of ion energies and electron densities, we could understand the condition for effective laser energy delivery to clusters

Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Waltman, Melanie J. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States)

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 ionized 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.

Structural characterization of phospholipids by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.

Science.gov (United States)

Marto, J A; White, F M; Seldomridge, S; Marshall, A G

1995-11-01

Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode.

Experimental study of the dissociation of 100-600 KeV hydrogen cluster ions in an argon gas target

International Nuclear Information System (INIS)

Chevallier, M.; Clouvas, A.; Frischkorn, H.J.; Gaillard, M.J.; Poizat, J.C.; Remillieux, J.

1985-09-01

We have studied the break-up of accelerated hydrogen cluster ions passing through an argon gas target. The absolute dissociation cross section has been measured for a wide variety of H n + (odd masses only) cluster ions, with n between 5 and 23 and with projectile velocities ranging from 1.5 to 5 x 10 8 cm/s. We discuss the dissociation processes and the dependence of their cross-sections upon the cluster mass and velocity

Clustering and Filtering Tandem Mass Spectra Acquired in Data-Independent Mode

Science.gov (United States)

Pak, Huisong; Nikitin, Frederic; Gluck, Florent; Lisacek, Frederique; Scherl, Alexander; Muller, Markus

2013-12-01

Data-independent mass spectrometry activates all ion species isolated within a given mass-to-charge window ( m/z) regardless of their abundance. This acquisition strategy overcomes the traditional data-dependent ion selection boosting data reproducibility and sensitivity. However, several tandem mass (MS/MS) spectra of the same precursor ion are acquired during chromatographic elution resulting in large data redundancy. Also, the significant number of chimeric spectra and the absence of accurate precursor ion masses hamper peptide identification. Here, we describe an algorithm to preprocess data-independent MS/MS spectra by filtering out noise peaks and clustering the spectra according to both the chromatographic elution profiles and the spectral similarity. In addition, we developed an approach to estimate the m/z value of precursor ions from clustered MS/MS spectra in order to improve database search performance. Data acquired using a small 3 m/z units precursor mass window and multiple injections to cover a m/z range of 400-1400 was processed with our algorithm. It showed an improvement in the number of both peptide and protein identifications by 8 % while reducing the number of submitted spectra by 18 % and the number of peaks by 55 %. We conclude that our clustering method is a valid approach for data analysis of these data-independent fragmentation spectra. The software including the source code is available for the scientific community.

Computer simulation program for medium-energy ion scattering and Rutherford backscattering spectrometry

Energy Technology Data Exchange (ETDEWEB)

Nishimura, Tomoaki, E-mail: t-nishi@hosei.ac.jp

2016-03-15

A computer simulation program for ion scattering and its graphical user interface (MEISwin) has been developed. Using this program, researchers have analyzed medium-energy ion scattering and Rutherford backscattering spectrometry at Ritsumeikan University since 1998, and at Rutgers University since 2007. The main features of the program are as follows: (1) stopping power can be chosen from five datasets spanning several decades (from 1977 to 2011), (2) straggling can be chosen from two datasets, (3) spectral shape can be selected as Gaussian or exponentially modified Gaussian, (4) scattering cross sections can be selected as Coulomb or screened, (5) simulations adopt the resonant elastic scattering cross section of {sup 16}O({sup 4}He, {sup 4}He){sup 16}O, (6) pileup simulation for RBS spectra is supported, (7) natural and specific isotope abundances are supported, and (8) the charge fraction can be chosen from three patterns (fixed, energy-dependent, and ion fraction with charge-exchange parameters for medium-energy ion scattering). This study demonstrates and discusses the simulations and their results.

Cluster observations of trapped ions interacting with magnetosheath mirror modes

Directory of Open Access Journals (Sweden)

J. Soucek

2011-06-01

Full Text Available Mirror modes are among the most intense low frequency plasma wave phenomena observed in the magnetosheaths of magnetized planets. They appear as large amplitude non-propagating fluctuations in the magnetic field magnitude and plasma density. These structures are widely accepted to represent a non-linear stage of the mirror instability, dominant in plasmas with large ion beta and a significant ion temperature anisotropy T⊥/T∥>1. It has long been recognized that the mirror instability both in the linear and non-linear stage is a kinetic process and that the behavior of resonant particles at small parallel velocities is crucial for its development and saturation. While the dynamics of the instability and the effect of trapped particles have been studied extensively in theoretical models and numerical simulations, only spurious observations of the trapped ions were published to date. In this work we used data from the Cluster spacecraft to perform the first detailed experimental study of ion velocity distribution associated with mirror mode oscillations. We show a conclusive evidence for the predicted cooling of resonant ions at small parallel velocities and heating of trapped ions at intermediate pitch angles.

Analysis of wax esters by silver-ion high-performance liquid chromatography-tandem mass spectrometry

Czech Academy of Sciences Publication Activity Database

Vrkoslav, Vladimír; Urbanová, Klára; Háková, Martina; Cvačka, Josef

2013-01-01

Roč. 1302, Aug 9 (2013), s. 105-110 ISSN 0021-9673 R&D Projects: GA ČR GA203/09/0139 Institutional support: RVO:61388963 Keywords : jojoba * human hair * wax esters * mass spectrometry * silver-ion liquid chromatography * long-chain esters Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.258, year: 2013

Amine reactivity with charged sulfuric acid clusters

Directory of Open Access Journals (Sweden)

B. R. Bzdek

2011-08-01

Full Text Available The distribution of charged species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS. Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid neutralization is cluster size-dependent. With increasing cluster size (and, therefore, a decreasing role of charge, both positively- and negatively-charged cluster compositions converge toward ammonium bisulfate. The reactivity of negatively-charged sulfuric acid-ammonia clusters with dimethylamine and ammonia is also investigated by FTICR-MS. Two series of negatively-charged clusters are investigated: [(HSO₄(H₂SO_4x]⁻ and [(NH_4x(HSO_4x+1(H₂SO₄₃]⁻. Dimethylamine substitution for ammonia in [(NH_{4 x}(HSO_{4 x+1}(H₂SO₄₃]⁻ clusters is nearly collision-limited, and subsequent addition of dimethylamine to neutralize H₂SO₄ to bisulfate is within one order of magnitude of the substitution rate. Dimethylamine addition to [(HSO₄ (H₂SO_{4 x}]⁻ clusters is either not observed or very slow. The results of this study indicate that amine chemistry will be evident and important only in large ambient negative ions (>m/z 400, whereas amine chemistry may be evident in small ambient positive ions. Addition of ammonia to unneutralized clusters occurs at a rate that is ~2–3 orders of magnitude slower than incorporation of dimethylamine either by substitution or addition

Charge-sign-clustering observed in high-multiplicity, high-energy heavy-ion collisions

International Nuclear Information System (INIS)

Takahashi, Y.; Gregory, J.C.; Hayashi, T.

1989-01-01

Charge-sign distribution in 200 GeV/amu heavy-ion collisions is studied with the Magnetic-Interferometric-Emulsion-Chamber (MAGIC) for central collision events in 16 O + Pb and 32 S + Pb interactions. Charge-sign clustering is observed in most of the fully-analyzed events. A statistical 'run-test' is performed for each measured event, which shows significant deviation from a Gaussian distribution (0,1) expected for random-charge distribution. Candidates of charge clusters have 5 - 10 multiplicity of like-sign particles, and are often accompanied by opposite-sign clusters. Observed clustering of identical charges is more significant in the fragmentation region than in the central region. Two-particle Bose-Einstein interference and other effects are discussed for the run-test examination. (author)

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection.

Science.gov (United States)

Matz, Laura M; Hill, Herbert H; Beegle, Luther W; Kanik, Isik

2002-04-01

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Smoothing of ZnO films by gas cluster ion beam

International Nuclear Information System (INIS)

Chen, H.; Liu, S.W.; Wang, X.M.; Iliev, M.N.; Chen, C.L.; Yu, X.K.; Liu, J.R.; Ma, K.; Chu, W.K.

2005-01-01

Planarization of wide-band-gap semiconductor ZnO surface is crucial for thin-film device performance. In this study, the rough initial surfaces of ZnO films deposited by r.f. magnetron sputtering on Si substrates were smoothed by gas cluster ion beams. AFM measurements show that the average surface roughness (R a ) of the ZnO films could be reduced considerably from 16.1 nm to 0.9 nm. Raman spectroscopy was used to monitor the structure of both the as-grown and the smoothed ZnO films. Rutherford back-scattering in combination with channeling effect was used to study the damage production induced by the cluster bombardment

Examination of Organic Vapor Adsorption onto Alkali Metal and Halide Atomic Ions by using Ion Mobility Mass Spectrometry.

Science.gov (United States)

Maiβer, Anne; Hogan, Christopher J

2017-11-03

We utilize ion mobility mass spectrometry with an atmospheric pressure differential mobility analyzer coupled to a time-of-flight mass spectrometer (DMA-MS) to examine the formation of ion-vapor molecule complexes with seed ions of K + , Rb + , Cs + , Br - , and I - exposed to n-butanol and n-nonane vapor under subsaturated conditions. Ion-vapor molecule complex formation is indicated by a shift in the apparent mobility of each ion. Measurement results are compared to predicted mobility shifts based upon the Kelvin-Thomson equation, which is commonly used in predicting rates of ion-induced nucleation. We find that n-butanol at saturation ratios as low as 0.03 readily binds to all seed ions, leading to mobility shifts in excess of 35 %. Conversely, the binding of n-nonane is not detectable for any ion for saturation ratios in the 0-0.27 range. An inverse correlation between the ionic radius of the initial seed and the extent of n-butanol uptake is observed, such that at elevated n-butanol concentrations, the smallest ion (K + ) has the smallest apparent mobility and the largest (I - ) has the largest apparent mobility. Though the differences in behavior of the two vapor molecules types examined and the observed effect of ionic seed radius are not accounted for by the Kelvin-Thomson equation, its predictions are in good agreement with measured mobility shifts for Rb + , Cs + , and Br - in the presence of n-butanol (typically within 10 % of measurements). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Raman spectroscopy of few-layer graphene prepared by C2–C6 cluster ion implantation

International Nuclear Information System (INIS)

Wang, Z.S.; Zhang, R.; Zhang, Z.D.; Huang, Z.H.; Liu, C.S.; Fu, D.J.; Liu, J.R.

2013-01-01

Few-layer graphene has been prepared on 300 nm-thick Ni films by C 2 –C 6 cluster ion implantation at 20 keV/cluster. Raman spectroscopy reveals significant influence of the number of atoms in the cluster, the implantation dose, and thermal treatment on the structure of the graphene layers. In particular, the graphene samples exhibit a sharp G peak at 1584 cm −1 and 2D peaks at 2711–2717 cm −1 . The I G /I 2D ratios higher than 1.70 and I G /I D ratio as high as 1.95 confirm that graphene sheets with low density of defects have been synthesized with much improved quality by ion implantation with larger clusters of C 4 –C 6

Analysis of chemical warfare agents in food products by atmospheric pressure ionization-high field asymmetric waveform ion mobility spectrometry-mass spectrometry.

Science.gov (United States)

Kolakowski, Beata M; D'Agostino, Paul A; Chenier, Claude; Mester, Zoltán

2007-11-01

Flow injection high field asymmetric waveform ion mobility spectrometry (FAIMS)-mass spectrometry (MS) methodology was developed for the detection and identification of chemical warfare (CW) agents in spiked food products. The CW agents, soman (GD), sarin (GB), tabun (GA), cyclohexyl sarin (GF), and four hydrolysis products, ethylphosphonic acid (EPA), methylphosphonic acid (MPA), pinacolyl methylphosphonic acid (Pin MPA), and isopropyl methylphosphonic acid (IMPA) were separated and detected by positive ion and negative ion atmospheric pressure ionization-FAIMS-MS. Under optimized conditions, the compensation voltages were 7.2 V for GD, 8.0 V for GA, 7.2 V for GF, 7.6 V for GB, 18.2 V for EPA, 25.9 V for MPA, -1.9 V for PinMPA, and +6.8 V for IMPA. Sample preparation was kept to a minimum, resulting in analysis times of 3 min or less per sample. The developed methodology was evaluated by spiking bottled water, canola oil, cornmeal, and honey samples at low microgram per gram (or microg/mL) levels with the CW agents or CW agent hydrolysis products. The detection limits observed for the CW agents in the spiked food samples ranged from 3 to 15 ng/mL in bottled water, 1-33 ng/mL in canola oil, 1-34 ng/g in cornmeal, and 13-18 ng/g in honey. Detection limits were much higher for the CW agent hydrolysis products, with only MPA being detected in spiked honey samples.

Molecular dynamics simulations to examine structure, energetics, and evaporation/condensation dynamics in small charged clusters of water or methanol containing a single monatomic ion.

Science.gov (United States)

Daub, Christopher D; Cann, Natalie M

2012-11-01

We study small clusters of water or methanol containing a single Ca(2+), Na(+), or Cl(-) ion with classical molecular dynamics simulations, using models that incorporate polarizability via the Drude oscillator framework. Evaporation and condensation of solvent from these clusters is examined in two systems, (1) for isolated clusters initially prepared at different temperatures and (2) those with a surrounding inert (Ar) gas of varying temperature. We examine these clusters over a range of sizes, from almost bare ions up to 40 solvent molecules. We report data on the evaporation and condensation of solvent from the clusters and argue that the observed temperature dependence of evaporation in the smallest clusters demonstrates that the presence of heated gas alone cannot, in most cases, solely account for bare ion production in electrospray ionization (ESI), neglecting the key contribution of the electric field. We also present our findings on the structure and energetics of the clusters as a function of size. Our data agree well with the abundant literature on hydrated ion clusters and offer some novel insight into the structure of methanol and ion clusters, especially those with a Cl(-) anion, where we observe the presence of chain-like structures of methanol molecules. Finally, we provide some data on the reparameterizations necessary to simulate ions in methanol using the separately developed Drude oscillator models for methanol and for ions in water.

Vacancy supersaturations produced by high-energy ion implantation

International Nuclear Information System (INIS)

Venezia, V.C.; Eaglesham, D.J.; Jacobson, D.C.; Gossmann, H.J.

1998-01-01

A new technique for detecting the vacancy clusters produced by high-energy ion implantation into silicon is proposed and tested. This technique takes advantage of the fact that metal impurities, such as Au, are gettered near one-half of the projected range (1/2 R p ) of MeV implants. The vacancy clustered region produced by a 2 MeV Si + implant into silicon has been labeled with Au diffused in from the front surface. The trapped Au was detected by Rutherford backscattering spectrometry (RBS) to profile the vacancy clusters. Cross section transmission electron microscopy (XTEM) analysis shows that the Au in the region of vacancy clusters is in the form of precipitates. By annealing MeV implanted samples prior to introduction of the Au, changes in the defect concentration within the vacancy clustered region were monitored as a function of annealing conditions

Mass spectrometry. [in organic chemistry

Science.gov (United States)

Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

1978-01-01

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Interlaboratory study of the ion source memory effect in {sup 36}Cl accelerator mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Pavetich, Stefan, E-mail: s.pavetich@hzdr.de [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Akhmadaliev, Shavkat [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Arnold, Maurice; Aumaître, Georges; Bourlès, Didier [Aix-Marseille Université, CEREGE CNRS-IRD, F-13545 Aix-en-Provence (France); Buchriegler, Josef [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Golser, Robin [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Keddadouche, Karim [Aix-Marseille Université, CEREGE CNRS-IRD, F-13545 Aix-en-Provence (France); Martschini, Martin [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Merchel, Silke; Rugel, Georg [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Steier, Peter [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria)

2014-06-01

Highlights: • Long-term memory effect in negative ion sources investigated for chlorine isotopes. • Interlaboratory comparison of four up-to date negative ion sources. • Ion source improvement at DREAMS for minimization of long-term memory effect. • Long-term memory effect is the limitation for precise AMS data of volatile elements. • Findings to be considered for samples with highly variable ratios of {sup 36}Cl/Cl and {sup 129}I/I. - Abstract: Understanding and minimization of contaminations in the ion source due to cross-contamination and long-term memory effect is one of the key issues for accurate accelerator mass spectrometry (AMS) measurements of volatile elements. The focus of this work is on the investigation of the long-term memory effect for the volatile element chlorine, and the minimization of this effect in the ion source of the Dresden accelerator mass spectrometry facility (DREAMS). For this purpose, one of the two original HVE ion sources at the DREAMS facility was modified, allowing the use of larger sample holders having individual target apertures. Additionally, a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, an interlaboratory comparison had been initiated. The long-term memory effect of the four Cs sputter ion sources at DREAMS (two sources: original and modified), ASTER (Accélérateur pour les Sciences de la Terre, Environnement, Risques) and VERA (Vienna Environmental Research Accelerator) had been investigated by measuring samples of natural {sup 35}Cl/{sup 37}Cl-ratio and samples highly-enriched in {sup 35}Cl ({sup 35}Cl/{sup 37}Cl ∼ 999). Besides investigating and comparing the individual levels of long-term memory, recovery time constants could be calculated. The tests show that all four sources suffer from long-term memory, but the modified DREAMS ion source showed the lowest level of contamination. The recovery times of the four ion

Comparison of Cocaine Detections in Corona Discharge Ionization-Ion Mobility Spectrometry and in Atmospheric Pressure Chemical Ionization-Mass Spectrometry

International Nuclear Information System (INIS)

Choi, Sung Seen; Kim, Yun Ki; Kim, Ok Bae; An, Seung Geon; Shin, Myung Won; Maeng, Seug Jin; Choi, Gyu Seop

2010-01-01

In this study, we determined the detection limit and reproducibility of the new IMS equipped with corona discharge ionization source using cocaine. The sample was injected with liquid solution to compare the results of APCI-MS. Ion mobility spectrometry (IMS) was a technique originally applied for the detection of trace compounds. IMS has been widely used to detect chemical warfare agents, explosives, and illegal drugs since it combines both high sensitivity (detection limits down to the ng/L range to pg/L range, ppb range and ppt range) and relatively low technical expenditure with high-speed data acquisition. The time required to acquire a single spectrum is in the range of several tens ms. The working principle is based on the drift of ions at ambient pressure under the influence of an external electric field

Comparison of Cocaine Detections in Corona Discharge Ionization-Ion Mobility Spectrometry and in Atmospheric Pressure Chemical Ionization-Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Choi, Sung Seen; Kim, Yun Ki; Kim, Ok Bae [Sejong University, Seoul (Korea, Republic of); An, Seung Geon; Shin, Myung Won; Maeng, Seug Jin; Choi, Gyu Seop [Wooju Communication and Technology Co., Seoul (Korea, Republic of)

2010-08-15

In this study, we determined the detection limit and reproducibility of the new IMS equipped with corona discharge ionization source using cocaine. The sample was injected with liquid solution to compare the results of APCI-MS. Ion mobility spectrometry (IMS) was a technique originally applied for the detection of trace compounds. IMS has been widely used to detect chemical warfare agents, explosives, and illegal drugs since it combines both high sensitivity (detection limits down to the ng/L range to pg/L range, ppb range and ppt range) and relatively low technical expenditure with high-speed data acquisition. The time required to acquire a single spectrum is in the range of several tens ms. The working principle is based on the drift of ions at ambient pressure under the influence of an external electric field.

Separation and characterization of metallosupramolecular libraries by ion mobility mass spectrometry.

Science.gov (United States)

Li, Xiaopeng; Chan, Yi-Tsu; Casiano-Maldonado, Madalis; Yu, Jing; Carri, Gustavo A; Newkome, George R; Wesdemiotis, Chrys

2011-09-01

The self-assembly of Zn(II) ions and bis(terpyridine) (tpy) ligands carrying 120° or 180° angles between their metal binding sites was utilized to prepare metallosupramolecular libraries with the connectivity. These combinatorial libraries were separated and characterized by ion mobility mass spectrometry (IM MS) and tandem mass spectrometry (MS(2)). The 180°-angle building blocks generate exclusively linear complexes, which were used as standards to determine the architectures of the assemblies resulting from the 120°-angle ligands. The latter ligand geometry promotes the formation of macrocyclic hexamers, but other n-mers with smaller (n = 5) or larger ring sizes (n = 7-9) were identified as minor products, indicating that the angles in the bis(terpyridine) ligand and within the coordinative tpy-Zn(II)-tpy bonds are not as rigid, as previously believed. Macrocyclic and linear isomers were detected in penta- and heptameric assemblies; in the larger octa- and nonameric assemblies, ring-opened conformers with compact and folded geometries were observed in addition to linear extended and cyclic architectures. IM MS(2) experiments provided strong evidence that the macrocycles present in the libraries were already formed in solution, during the self-assembly process, not by dissociation of larger complexes in the gas phase. The IM MS/MS(2) methods provide a means to analyze, based on size and shape (architecture), supramolecular libraries that are not amenable to liquid chromatography, LC-MS, NMR, and/or X-ray techniques.

GibbsCluster: unsupervised clustering and alignment of peptide sequences

DEFF Research Database (Denmark)

Andreatta, Massimo; Alvarez, Bruno; Nielsen, Morten

2017-01-01

motif characterizing each cluster. Several parameters are available to customize cluster analysis, including adjustable penalties for small clusters and overlapping groups and a trash cluster to remove outliers. As an example application, we used the server to deconvolute multiple specificities in large......-scale peptidome data generated by mass spectrometry. The server is available at http://www.cbs.dtu.dk/services/GibbsCluster-2.0....

Ion-neutral potential models in atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS.

Science.gov (United States)

Steiner, Wes E; English, William A; Hill, Herbert H

2006-02-09

The ion mobilities and their respective masses of several classes of amines (primary, secondary, and tertiary) were measured by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS. The experimental data obtained were comparatively analyzed by the one-temperature kinetic theory of Chapman-Enskog. Several theoretical models were used to estimate the collision cross-sections; they include the rigid-sphere, polarization-limit, 12-6-4, and 12-4 potential models. These models were investigated to represent the interaction potentials contained within the collision integral that occurs between the polyatomic ions and the neutral drift gas molecules. The effectiveness of these collision cross-section models on predicting the mobility of these amine ions was explored. Moreover, the effects of drift gas selectivity on the reduced-mass term and in the collision cross-section term was examined. Use of a series of drift gases, namely, helium, neon, argon, nitrogen, and carbon dioxide, made it possible to distinguish between mass effects and polarizability effects. It was found that the modified 12-4 potential that compensates for the center of charge not being at the same location as the centers of mass showed improved agreement over the other collision cross-section models with respect to experimental data.

Identification of the chemical constituents of Chinese medicine Yi-Xin-Shu capsule by molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation.

Science.gov (United States)

Wang, Hong-ping; Chen, Chang; Liu, Yan; Yang, Hong-Jun; Wu, Hong-Wei; Xiao, Hong-Bin

2015-11-01

The incomplete identification of the chemical components of traditional Chinese medicinal formula has been one of the bottlenecks in the modernization of traditional Chinese medicine. Tandem mass spectrometry has been widely used for the identification of chemical substances. Current automatic tandem mass spectrometry acquisition, where precursor ions were selected according to their signal intensity, encounters a drawback in chemical substances identification when samples contain many overlapping signals. Compounds in minor or trace amounts could not be identified because most tandem mass spectrometry information was lost. Herein, a molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation method for complex Chinese medicine chemical constituent analysis was developed. The precursor ions were selected according to their two-dimensional characteristics of retention times and mass-to-charge ratio ranges from herbal compounds, so that all precursor ions from herbal compounds were included and more minor chemical constituents in Chinese medicine were identified. Compared to the conventional automatic tandem mass spectrometry setups, the approach is novel and can overcome the drawback for chemical substances identification. As an example, 276 compounds from the Chinese Medicine of Yi-Xin-Shu capsule were identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Photoionization ion mobility spectrometry (UV-IMS) for the isomeric volatile organic compounds].

Science.gov (United States)

Li, Hu; Niu, Wen-qi; Wang, Hong-mei; Huang, Chao-qun; Jiang, Hai-he; Chu, Yan-nan

2012-01-01

The construction and performance study is reported for a newly developed ultraviolet photoionization ion mobility spectrometry (UV-IMS). In the present paper, an UV-IMS technique was firstly developed to detect eleven isomeric volatile organic compounds including the differences in the structure of carbon chain, the style of function group and the position of function group. Their reduced mobility values were determined and increased in this order: linears alcohols homemade UV-IMS was around ppb-ppm.

Comparison of dielectric barrier discharge, atmospheric pressure radiofrequency-driven glow discharge and direct analysis in real time sources for ambient mass spectrometry of acetaminophen

Energy Technology Data Exchange (ETDEWEB)

Kratzer, Jan [Institute for National Measurement Standards, National Research Council of Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada); Institute of Analytical Chemistry of the ASCR, v.v.i., Veveri 97, CZ-602 00 Brno (Czech Republic); Mester, Zoltan [Institute for National Measurement Standards, National Research Council of Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada); Sturgeon, Ralph E., E-mail: Ralph.Sturgeon@nrc-cnrc.gc.ca [Institute for National Measurement Standards, National Research Council of Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada)

2011-08-15

Three plasma-based ambient pressure ion sources were investigated; laboratory constructed dielectric barrier and rf glow discharges, as well as a commercial corona discharge (DART source). All were used to desorb and ionize a model analyte, providing sampling techniques for ambient mass spectrometry (MS). Experimental parameters were optimized to achive highest signal for acetaminophen as the analyte. Insight into the mechanisms of analyte desorption and ionization was obtained by means of emission spectrometry and ion current measurements. Desorption and ionization mechanisms for this analyte appear to be identical for all three plasma sources. Emission spectra differ only in the intensities of various lines and bands. Desorption of solid analyte requires transfer of thermal energy from the plasma source to sample surface, in the absence of which complete loss of MS response occurs. For acetaminophen, helium was the best plasma gas, providing 100- to 1000-fold higher analyte response than with argon or nitrogen. The same trend was also evident with background ions (protonated water clusters). MS analyte signal intensity correlates with the ion density (expressed as ion current) in the plasma plume and with emission intensity from excited state species in the plasma. These observations support an ionization process which occurs via proton transfer from protonated water clusters to analyte molecules.

Atmospheric-pressure solution-cathode glow discharge: A versatile ion source for atomic and molecular mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Schwartz, Andrew J. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Williams, Kelsey L. [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Hieftje, Gary M. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Shelley, Jacob T., E-mail: shellj@rpi.edu [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY, 12180 (United States)

2017-01-15

An atmospheric-pressure solution-cathode glow discharge (SCGD) has been evaluated as an ion source for atomic, molecular, and ambient desorption/ionization mass spectrometry. The SCGD consists of a direct-current plasma, supported in the ambient air in the absence of gas flows, and sustained upon the surface of a flowing liquid cathode. Analytes introduced in the flowing liquid, as an ambient gas, or as a solid held near the plasma are vaporized and ionized by interactions within or near the discharge. Introduction of acidic solutions containing metal salts produced bare elemental ions as well as H{sub 2}O, OH{sup −} and NO{sub 3}{sup −} adducts. Detection limits for these elemental species ranged from 0.1 to 4 ppb, working curves spanned more than 4 orders of linear dynamic range, and precision varied between 5 and 16% relative standard deviation. Small organic molecules were also efficiently ionized from solution, and both the intact molecular ion and fragments were observed in the resulting SCGD mass spectra. Fragmentation of molecular species was found to be tunable; high discharge currents led to harder ionization, while low discharge currents produced stronger molecular-ion signals. Ambient gases and solids, desorbed by the plasma from a glass probe, were also readily ionized by the SCGD. Indeed, strong analyte signals were obtained from solid samples placed at least 2 cm from the plasma. These findings indicate that the SCGD might be useful also for ambient desorption/ionization mass spectrometry. Combined with earlier results that showed the SCGD is useful for ionization of labile biomolecules, the results here indicate that the SCGD is a highly versatile ion source capable of providing both elemental and molecular mass-spectral information. - Highlights: • Solution-cathode glow discharge used as an ionization source for mass spectrometry. • SCGD-MS can provide atomic as well as intact molecular mass spectra. • Atomic limits of detection range

A REVIEW ON MASS SPECTROMETRY DETECTORS

OpenAIRE

Khatri Neetu; Gupta Ankit; Taneja Ruchi; Bilandi Ajay; Beniwal Prashant

2012-01-01

Mass spectrometry is an analytical technique for "weighing" molecules. Obviously, this is not done with a conventional scale or balance. Instead, mass spectrometry is based upon the principle of the motion of a charged particle that is called an ion, in an electric or magnetic field. The mass to charge ratio (m/z) of the ion affects particles motion. Since the charge of an electron is known, the mass to charge ratio (m/z) is a measurement of mass of an ion. Mass spectrometry research focuses ...

Metal cluster cation reactions: Carbon monoxide association to Cu + n ions

Science.gov (United States)

Leuchtner, R. E.; Harms, A. C.; Castleman, A. W., Jr.

1990-06-01

Copper cluster cations (Cu+n,n=1-14) were produced in a laser vaporization/flow tube apparatus and equilibrated to room temperature. The association rate constants of carbon monoxide onto these ions were measured; low-pressure, termolecular behavior was observed for the smaller species while for clusters greater than Cu+7, the longer lifetimes due to the increased number of degrees of freedom leads to pressure independence (>0.3 Torr) of the effective bimolecular rates. Unimolecular decay theory (RRKM) is used to explain the overall trend and when intrinsic surface site reactivity is taken into account, excellent agreement with measured reactivity is obtained.

Investigation of energy thresholds of atomic and cluster sputtering of some elements under ion bombardment

CERN Document Server

Atabaev, B G; Lifanova, L F

2002-01-01

Threshold energies of sputtering of negative cluster ions from the Si(111) surface were measured at bombardment by Cs sup + , Rb sup + , and Na sup + ions with energy of 0.1-3.0 keV. These results are compared with the calculations of the similar thresholds by Bohdansky etc. formulas (3) for clusters Si sub n sup - and Cu sub n sup - with n=(1-5) and also for B, C, Al, Si, Fe, Cu atoms. Threshold energies of sputtering for the above elements were also estimated using the data from (5). Satisfactory agreement between the experimental and theoretical results was obtained. (author)

Model of large volumetric capacitance in graphene supercapacitors based on ion clustering

Science.gov (United States)

Skinner, Brian; Fogler, M. M.; Shklovskii, B. I.

2011-12-01

Electric double-layer supercapacitors (SCs) are promising devices for high-power energy storage based on the reversible absorption of ions into porous conducting electrodes. Graphene is a particularly good candidate for the electrode material in SCs due to its high conductivity and large surface area. In this paper, we consider SC electrodes made from a stack of graphene sheets with randomly inserted spacer molecules. We show that the large volumetric capacitances C≳100F/cm3 observed experimentally can be understood as a result of collective intercalation of ions into the graphene stack and the accompanying nonlinear screening by graphene electrons that renormalizes the charge of the ion clusters.

Changes in cluster magnetism and suppression of local superconductivity in amorphous FeCrB alloy irradiated by Ar"+ ions

International Nuclear Information System (INIS)

Okunev, V.D.; Samoilenko, Z.A.; Szymczak, H.; Szewczyk, A.; Szymczak, R.; Lewandowski, S.J.; Aleshkevych, P.; Malinowski, A.; Gierłowski, P.; Więckowski, J.; Wolny-Marszałek, M.; Jeżabek, M.; Varyukhin, V.N.; Antoshina, I.A.

2016-01-01

We show that cluster magnetism in ferromagnetic amorphous Fe_6_7Cr_1_8B_1_5 alloy is related to the presence of large, D=150–250 Å, α-(Fe Cr) clusters responsible for basic changes in cluster magnetism, small, D=30–100 Å, α-(Fe, Cr) and Fe_3B clusters and subcluster atomic α-(Fe, Cr, B) groupings, D=10–20 Å, in disordered intercluster medium. For initial sample and irradiated one (Φ=1.5×10"1"8 ions/cm"2) superconductivity exists in the cluster shells of metallic α-(Fe, Cr) phase where ferromagnetism of iron is counterbalanced by antiferromagnetism of chromium. At Φ=3×10"1"8 ions/cm"2, the internal stresses intensify and the process of iron and chromium phase separation, favorable for mesoscopic superconductivity, changes for inverse one promoting more homogeneous distribution of iron and chromium in the clusters as well as gigantic (twice as much) increase in density of the samples. As a result, in the cluster shells ferromagnetism is restored leading to the increase in magnetization of the sample and suppression of local superconductivity. For initial samples, the temperature dependence of resistivity ρ(T)~T"2 is determined by the electron scattering on quantum defects. In strongly inhomogeneous samples, after irradiation by fluence Φ=1.5×10"1"8 ions/cm"2, the transition to a dependence ρ(T)~T"1"/"2 is caused by the effects of weak localization. In more homogeneous samples, at Φ=3×10"1"8 ions/cm"2, a return to the dependence ρ(T)~T"2 is observed. - Highlights: • The samples at high dose of ion irradiation become more homogeneous. • Gigantic increase in density of the samples (twice as much) is observed. • Ferromagnetism in large Fe–Cr clusters is restored. • Ferromagnetism of Fe–Cr clusters suppresses local superconductivity in them. • The participation of quantum defects in scattering of electrons is returned.

Electron impact ionization of size selected hydrogen clusters (H2)N: ion fragment and neutral size distributions.

Science.gov (United States)

Kornilov, Oleg; Toennies, J Peter

2008-05-21

Clusters consisting of normal H2 molecules, produced in a free jet expansion, are size selected by diffraction from a transmission nanograting prior to electron impact ionization. For each neutral cluster (H2)(N) (N=2-40), the relative intensities of the ion fragments Hn+ are measured with a mass spectrometer. H3+ is found to be the most abundant fragment up to N=17. With a further increase in N, the abundances of H3+, H5+, H7+, and H9+ first increase and, after passing through a maximum, approach each other. At N=40, they are about the same and more than a factor of 2 and 3 larger than for H11+ and H13+, respectively. For a given neutral cluster size, the intensities of the ion fragments follow a Poisson distribution. The fragmentation probabilities are used to determine the neutral cluster size distribution produced in the expansion at a source temperature of 30.1 K and a source pressure of 1.50 bar. The distribution shows no clear evidence of a magic number N=13 as predicted by theory and found in experiments with pure para-H2 clusters. The ion fragment distributions are also used to extract information on the internal energy distribution of the H3+ ions produced in the reaction H2+ + H2-->H3+ +H, which is initiated upon ionization of the cluster. The internal energy is assumed to be rapidly equilibrated and to determine the number of molecules subsequently evaporated. The internal energy distribution found in this way is in good agreement with data obtained in an earlier independent merged beam scattering experiment.

Time‐of‐flight secondary ion mass spectrometry imaging of biological samples with delayed extraction for high mass and high spatial resolutions

Science.gov (United States)

Vanbellingen, Quentin P.; Elie, Nicolas; Eller, Michael J.; Della‐Negra, Serge; Touboul, David

2015-01-01

Rationale In Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS), pulsed and focused primary ion beams enable mass spectrometry imaging, a method which is particularly useful to map various small molecules such as lipids at the surface of biological samples. When using TOF‐SIMS instruments, the focusing modes of the primary ion beam delivered by liquid metal ion guns can provide either a mass resolution of several thousand or a sub‐µm lateral resolution, but the combination of both is generally not possible. Methods With a TOF‐SIMS setup, a delayed extraction applied to secondary ions has been studied extensively on rat cerebellum sections in order to compensate for the effect of long primary ion bunches. Results The use of a delayed extraction has been proven to be an efficient solution leading to unique features, i.e. a mass resolution up to 10000 at m/z 385.4 combined with a lateral resolution of about 400 nm. Simulations of ion trajectories confirm the experimental determination of optimal delayed extraction and allow understanding of the behavior of ions as a function of their mass‐to‐charge ratio. Conclusions Although the use of a delayed extraction has been well known for many years and is very popular in MALDI, it is much less used in TOF‐SIMS. Its full characterization now enables secondary ion images to be recorded in a single run with a submicron spatial resolution and with a mass resolution of several thousand. This improvement is very useful when analyzing lipids on tissue sections, or rare, precious, or very small size samples. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26395603

Ion implantation artifacts observed in depth profiling boron in silicon by secondary ion mass spectrometry

International Nuclear Information System (INIS)

Chi, P.; Simons, D.S.

1987-01-01

A comparison study of depth profiling by secondary ion mass spectrometry (SIMS) and neutron depth profiling (NDP) was recently conducted. The specimens were portions of 5 cm diameter single crystal silicon slices in which B-10 had been implanted at various fluences and energies. NDP measurements were made on a 13 mm diameter area at the center of the wafers. SIMS measurements were taken from a 60 μm diameter area approximately 16 mm from the center of the wafer. One observation that emerged from this work was an apparent discrepancy between the profiles of B-10 measured by DNP and SIMS. The peaks of the SIMS profiles were typically deeper than those of NDP by as much as 30 nm, which is 10% of the projected range for a 70 keV implant. Moreover, the profiles could not be made to coincide by either a constant shift or a proportional change of one depth scale with respect to the other. The lateral inhomogeneity of boron that these experiments have demonstrated arises from the variable contribution of ion channeling during implantation

FY 2000 report on the results of the research and development project for new industry creation type industrial science technologies. Cluster ion beam process technology; 2000 nendo shinki sangyo soshutsugata sangyo kagaku gijutsu kenkyu kaihatsu seido seika hokokusho. Cluster ion beam process technology

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

Described herein are the FY 2000 results of development of cluster ion beams. This technology generates the strong ion beams of atom and molecule clusters, and irradiate them onto the solid surfaces, to create new materials or treat materials. It allows the nano-level treatment. The program for high-current cluster ion beam generation/irradiation technology for industrial purposes attains the target high-current beam of 500{mu}m. It is necessary to establish the optimum cluster size, irradiated energy and ion species for the highly functional surface treatment, for which applicable technologies, e.g., those related to time of flight and molecular dynamics, are developed. Studies on high-current, large-area irradiation technologies are started. The program for material processing technologies involves evaluation of crystalline defects formed during the beam implantation by photoluminescence spectroscopy, and studies on semiconductor surface processing technologies. The surface smoothening technology is investigated to reduce crystalline defects and stress-induced strains for difficult-to-process materials, e.g., SiC and diamond, and the good results are produced. The program for development of superflat/superhard thin film formation technology involves irradiation of the Ar ion beams during the deposition of C{sub 60}(fullerene), to produce the superhard thin film. (NEDO)

Relationship of Ambient Atmosphere and Biological Aerosol Responses from a Fielded Pyrolysis-Gas Chromatography-Ion Mobility Spectrometry Bioanalytical Detector

National Research Council Canada - National Science Library

Snyder, A

2003-01-01

.... A pyrolysis-gas chromatography-ion mobility spectrometry stand-alone bioaerosol system was interfaced to an aerosol concentrator to collect ambient background aerosols and produce bioanalytical...

Multielement ultratrace analysis in tungsten using secondary ion mass spectrometry

International Nuclear Information System (INIS)

Wilhartitz, P.; Virag, A.; Friedbacher, G.; Grasserbauer, M.

1987-01-01

The ever increasing demands on properties of materials create a trend also towards ultrapure products. Characterization of these materials is only possible with modern, highly sophisticated analytical techniques such as activation analysis and mass spectrometry, particularly SSMS, SIMS and GDMS. Analytical strategies were developed for the determination of about 40 elements in a tungsten matrix with high-performance SIMS. Difficulties like the elimination of interferences had to be overcome. Extrapolated detection limits were established in the range of pg/g (alkali metals, halides) to ng/g (e.g. Ta, Th). Depth profiling and ion imaging gave additional information about the lateral and the depth distribution of the elements. (orig.)

Size effects in van der Waals clusters studied by spin and angle-resolved electron spectroscopy and multi-coincidence ion imaging

International Nuclear Information System (INIS)

Rolles, D; Pesic, Z D; Zhang, H; Bilodeau, R C; Bozek, J D; Berrah, N

2007-01-01

We have studied the valence and inner-shell photoionization of free rare-gas clusters by means of angle and spin resolved photoelectron spectroscopy and momentum resolving electron-multi-ion coincidence spectroscopy. The electron measurements probe the evolution of the photoelectron angular distribution and spin polarization parameters as a function of photon energy and cluster size, and reveal a strong cluster size dependence of the photoelectron angular distributions in certain photon energy regions. In contrast, the spin polarization parameter of the cluster photoelectrons is found to be very close to the atomic value for all covered photon energies and cluster sizes. The ion imaging measurements, which probe the fragmentation dynamics of multiply charged van der Waals clusters, also exhibit a pronounced cluster size dependence

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.

Science.gov (United States)

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.

Photodissociation of Cr(CO) within methanol clusters: Observation of an isotope effect

International Nuclear Information System (INIS)

Peifer, W.R.; Garvey, J.F.

1991-01-01

Mixed van der Waals clusters containing Cr(CO) 6 and methanol are generated in the free-jet expansion of a pulsed beam of seeded helium and subjected to 248-nm multiphoton ionization (MPI), and the product ions are analyzed by time-of-flight mass spectrometry. The authors find that the multiphoton dissociation and ionization dynamics of solvated Cr(CO) 6 are strikingly different from those of the naked molecule. Two principle sequences of heterocluster ions are identified in the mass spectrum: a minor sequence with the empirical formula, S n Cr(CO) x + (x = 5,6), where S is a methanol molecule, and a major sequence with the empirical formula, S n Cr(CO) x + (x = 0,1,2). Implications are discussed regarding the general utility of MPI as a probe of the electronic structure and reactivity within van der Waals clusters

Plasma Desorption Mass Spectrometry using TANDEM accelerator in National Industrial Research Inst. of Nagoya

Energy Technology Data Exchange (ETDEWEB)

Mizota, Takeshi; Nakao, Setsuo; Niwa, Hiroaki; Saito, Kazuo [Particle Beam Sceince Laboratory, Multi-Function Material Science Department, National Industrial Research Inst. of Nagoya, Nagoya (Japan)

2001-02-01

Plasma Desorption Mass Spectrometry (PDMS) analysis was studied using TANDEM accelerator. The heavy ions of MeV range emit the secondary ions of atoms, molecules, polymers and clusters from the irradiated samples without destruction. The analysis system of PDMS designed and set-up using a mass spectrometer of Time of Flight and the TANDEM accelerator. The system performance was tested for C-60 fullerene on the surface of the samples using 11.2 MeV {sup 28}Si beams produced by the TANDEM accelerator of 1.7MV. The result shows that the hydrogen and hydrocarbons can be analyzed in the range of 1amu unit. The resolution (M/{delta}M) of the Mass Spectrometry system is confirmed to be about 1000 from the separation of the 720 and 721amu peaks, which is attributed to the C-60 fullerene including {sup 13}C atoms. (H. Katsuta)

Secondary ion emission from cleaned surfaces bombarded by 100 MeV accelerator beams at the GSI Darmstadt

International Nuclear Information System (INIS)

Wien, K.; Becker, O.; Guthier, W.; Knippelberg, W.; Koczon, P.

1988-01-01

The 1.4 MeV/n beam facility for the UNILAC/GSI has been used to study secondary ion emission from surfaces cleaned under UHV conditions by ion etching or cleaving of crystals. The desorption phenomena observed by means of TOF mass spectrometry can be classified as follows: (1) Clean metal surfaces emit metal ions being ejected by atomic collisions cascades. Electronic excitation of surface states seems to support ionization. (2) The desorption of contaminants adsorbed at the metal surface is strongly correlated with the electronic energy loss of the projectiles - even, if the content of impurities is very low. (3) Ion formation at the epitaxial surface of fluoride crystals as CaF 2 , MgF 2 and NaF is initiated by the electronic excitation of the crystal. At high beam energies the mass spectrum is dominated by a series of cluster ions. These cluster ions disappear below a certain energy deposit threshold, whereas small atomic ions are observed over the whole energy range

High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry

International Nuclear Information System (INIS)

Fan, Ruo-Jing; Zhang, Fang; Chen, Xiu-Ping; Qi, Wan-Shu; Guan, Qing; Sun, Tuan-Qi; Guo, Yin-Long

2017-01-01

The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%–12.3% for intra-day and 0.9%–7.8% for inter-day) and good accuracy (91%–109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. - Highlights: • The separation power of DTIMS-MS enhanced peak capacity, spectral clarity, and specificity of benzil labeled GCs and UCs. • Short-column LC for on-line desalting increased the throughput with a measurement cycle of 5.0 min. • CCS and accurate mass as a pair of qualifiers were used for the profiling and identification of GCs and UCs. • An integral abundance arising from 3-D ion features (RT, DT, m/z) was used as a novel quantifier for quantitation. • The developed method was applied to screen and quantify the GCs and UCs in human thyroid tissues.

High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Fan, Ruo-Jing [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Zhang, Fang, E-mail: fzhang@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Chen, Xiu-Ping; Qi, Wan-Shu [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Guan, Qing [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center, Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Sun, Tuan-Qi, E-mail: tuanqisun@163.com [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center, Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Guo, Yin-Long, E-mail: ylguo@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China)

2017-04-08

The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%–12.3% for intra-day and 0.9%–7.8% for inter-day) and good accuracy (91%–109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. - Highlights: • The separation power of DTIMS-MS enhanced peak capacity, spectral clarity, and specificity of benzil labeled GCs and UCs. • Short-column LC for on-line desalting increased the throughput with a measurement cycle of 5.0 min. • CCS and accurate mass as a pair of qualifiers were used for the profiling and identification of GCs and UCs. • An integral abundance arising from 3-D ion features (RT, DT, m/z) was used as a novel quantifier for quantitation. • The developed method was applied to screen and quantify the GCs and UCs in human thyroid tissues.

Application of secondary ion mass spectrometry (SIMS) to biological sample analysis

International Nuclear Information System (INIS)

Tamura, Hifumi

1990-01-01

Some major issues and problems related with the analysis of biological samples are discussed, focusing on demonstrated and possible solutions and the application of secondary ion mass spectrometry (SIMS) to investigation of the composition of biological samples. The effective use of secondary electrons in combination with negative ions is most practical for the analysis of biological samples. Regardless of whether positive or negative ions are used, the electric potential at the surface of a sample stays around a constant value because of the absense of the accumulation of electric charges at the surface, leading to almost complete avoidance of the charging of the biological sample. A soft tissue sample can suffer damage to the tissue or migration of atoms in removing water from the sample. Some processes including fixation and freeze drying are available to prevent this. The application of SIMS to biological analysis is still in the basic research stage and further studies will be required to develop practical methods. Possible areas of its application include medicine, pathology, toxicology, pharmacology, plant physiology and other areas related with marine life and marine contamination. (N.K.)

Determining Double Bond Position in Lipids Using Online Ozonolysis Coupled to Liquid Chromatography and Ion Mobility-Mass Spectrometry.

Science.gov (United States)

Harris, Rachel A; May, Jody C; Stinson, Craig A; Xia, Yu; McLean, John A

2018-02-06

The increasing focus on lipid metabolism has revealed a need for analytical techniques capable of structurally characterizing lipids with a high degree of specificity. Lipids can exist as any one of a large number of double bond positional isomers, which are indistinguishable by single-stage mass spectrometry alone. Ozonolysis reactions coupled to mass spectrometry have previously been demonstrated as a means for localizing double bonds in unsaturated lipids. Here we describe an online, solution-phase reactor using ozone produced via a low-pressure mercury lamp, which generates aldehyde products diagnostic of cleavage at a particular double bond position. This flow-cell device is utilized in conjunction with structurally selective ion mobility-mass spectrometry. The lamp-mediated reaction was found to be effective for multiple lipid species in both positive and negative ionization modes, and the conversion efficiency from precursor to product ions was tunable across a wide range (20-95%) by varying the flow rate through the ozonolysis device. Ion mobility separation of the ozonolysis products generated additional structural information and revealed the presence of saturated species in a complex mixture. The method presented here is simple, robust, and readily coupled to existing instrument platforms with minimal modifications necessary. For these reasons, application to standard lipidomic workflows is possible and aids in more comprehensive structural characterization of a myriad of lipid species.

2012 Gordon Research Conference On Molecular And Ionic Clusters

International Nuclear Information System (INIS)

McCoy, Anne

2012-01-01

The Gordon Research Conference on 'Molecular and Ionic Clusters' focuses on clusters, which are the initial molecular species found in gases when condensation begins to occur. Condensation can take place solely from molecules interacting with each other, mostly at low temperatures, or when molecules condense around charged particles (electrons, protons, metal cations, molecular ions), producing ion molecule clusters. These clusters provide models for solvation, allow a pristine look at geometric as well as electronic structures of molecular complexes or matter in general, their interaction with radiation, their reactivity, their thermodynamic properties and, in particular, the related dynamics. This conference focuses on new ways to make clusters composed of different kinds of molecules, new experimental techniques to investigate the properties of the clusters and new theoretical methods with which to calculate the structures, dynamical motions and energetics of the clusters. Some of the main experimental methods employed include molecular beams, mass spectrometry, laser spectroscopy (from infrared to XUV; in the frequency as well as the time domain) and photoelectron spectroscopy. Techniques include laser absorption spectroscopy, laser induced fluorescence, resonance enhanced photoionization, mass-selected photodissociation, photofragment imaging, ZEKE photoelectron spectroscopy, etc. From the theoretical side, this conference highlights work on potential surfaces and measurable properties of the clusters. The close ties between experiment, theory and computation have been a hallmark of the Gordon Research Conference on Molecular and Ionic Clusters. In the 2012 meeting, we plan to have sessions that will focus on topics including: (1) The use of cluster studies to probe fundamental phenomena; (2) Finite size effects on structure and thermodynamics; (3) Intermolecular forces and cooperative effects; (4) Molecular clusters as models for solvation; and (5) Studies of

Accelerator mass spectrometry of 41Ca with a positive-ion source and the UNILAC accelerator

International Nuclear Information System (INIS)

Steinhof, A.; Henning, W.; Mueller, M.; Roeckl, E.; Schuell, D.; Korschinek, G.; Nolte, E.; Paul, M.

1987-06-01

We have made first tests investigating the performance characteristics of the UNILAC accelerator system at GSI, in order to explore the sensitivity achievable in accelerator mass spectrometry (AMS) of 41 Ca with high-current positive-ion sources. Positively charged Ca 3+ ions of up to about 100 micro-amperes electrical current were injected from a penning-sputter source and, after further stripping to Ca 9+ , accelerated to 14.3 MeV/nucleon. The combination of velocity-focussing accelerator and magnetic ion-beam transport system completely eliminated background from the other calcium isotopes. Full-stripping and detection of 41 Ca 20+ ions with a magnetic spectrograph provides separation from isobaric 41 K and, at present, a level of sensitivity of 41 Ca/Ca ≅ 2x10 -15 . Future improvements and implications for dating of Pleistoscene samples will be discussed. (orig.)

Analysis of iodinated quorum sensing peptides by LC–UV/ESI ion trap mass spectrometry

Directory of Open Access Journals (Sweden)

Yorick Janssens

2018-02-01

Full Text Available Five different quorum sensing peptides (QSP were iodinated using different iodination techniques. These iodinated peptides were analyzed using a C18 reversed phase HPLC system, applying a linear gradient of water and acetonitrile containing 0.1% (m/v formic acid as mobile phase. Electrospray ionization (ESI ion trap mass spectrometry was used for the identification of the modified peptides, while semi-quantification was performed using total ion current (TIC spectra. Non-iodinated peptides and mono- and di-iodinated peptides (NIP, MIP and DIP respectively were well separated and eluted in that order. Depending on the used iodination method, iodination yields varied from low (2% to high (57%.

Structural Elucidation of cis / trans Dicaffeoylquinic Acid Photoisomerization Using Ion Mobility Spectrometry-Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zheng, Xueyun; Renslow, Ryan S.; Makola, Mpho M.; Webb, Ian K.; Deng, Liulin; Thomas, Dennis G.; Govind, Niranjan; Ibrahim, Yehia M.; Kabanda, Mwadham M.; Dubery, Ian A.; Heyman, Heino M.; Smith, Richard D.; Madala, Ntakadzeni E.; Baker, Erin S.

2017-03-15

Due to the recently uncovered health benefits and anti-HIV activities of dicaffeoylquinic acids (diCQAs), understanding their structures and functions is of great interest for drug discovery efforts. DiCQAs are analytically challenging to identify and quantify since they commonly exist as a diverse mixture of positional and geometric (cis/trans) isomers. In this work, we utilized ion mobility spectrometry coupled with mass spectrometry to separate the various isomers before and after UV irradiation. The experimental collision cross sections were then compared with theoretical structures to differentiate and identify the diCQA isomers. Our analyses found that naturally the diCQAs existed predominantly as trans/trans isomers, but after 3 h of UV irradiation, cis/cis, cis/trans, trans/cis, and trans/trans isomers were all present in the mixture. This is the first report of successful differentiation of cis/trans diCQA isomers individually, which shows the great promise of IMS coupled with theoretical calculations for determining the structure and activity relationships of different isomers in drug discovery studies.

Chemical degradation of selected Zn-based corrosion products induced by C{sub 60} cluster, Ar cluster and Ar{sup +} ion sputtering in the focus of X-ray photoelectron spectroscopy (XPS)

Energy Technology Data Exchange (ETDEWEB)

Steinberger, R., E-mail: roland.steinberger@jku.at [Christian Doppler Laboratory for Microscopic and Spectroscopic Material Characterization, Center for Surface and Nanoanalytics, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz (Austria); Sicking, J., E-mail: jens.sicking@bayer.com [Bayer AG, Engineering & Technology, Applied Physics, Chempark Building E 41, 51368 Leverkusen (Germany); Weise, J., E-mail: juliane.weise@physik.tu-freiberg.de [Institut für Experimentelle Physik, TU Bergakademie Freiberg, Leipziger Straße 23, 09599 Freiberg (Germany); Duchoslav, J., E-mail: jiri.duchoslav@jku.at [Christian Doppler Laboratory for Microscopic and Spectroscopic Material Characterization, Center for Surface and Nanoanalytics, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz (Austria); Greunz, T., E-mail: theresia.greunz@jku.at [Christian Doppler Laboratory for Microscopic and Spectroscopic Material Characterization, Center for Surface and Nanoanalytics, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz (Austria); Meyer, D.C., E-mail: Dirk-Carl.Meyer@physik.tu-freiberg.de [Institut für Experimentelle Physik, TU Bergakademie Freiberg, Leipziger Straße 23, 09599 Freiberg (Germany); Stifter, D., E-mail: david.stifter@jku.at [Christian Doppler Laboratory for Microscopic and Spectroscopic Material Characterization, Center for Surface and Nanoanalytics, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz (Austria)

2017-05-01

Highlights: • XPS investigations for various sputter concepts on Zn-based corrosions products. • Direct comparison of induced chemical damage for ion and cluster sputtering. • Azimuthal rotation or heavy projectile bombardment was not found to be beneficial. • Ar cluster etching is rated as unsuitable for surface cleaning or depth profiling. • C{sub 60} and Ar{sup +} are applicable for sputtering when degradation is carefully considered. - Abstract: Monoatomic ion sputtering is a common concept for surface sensitive analysis methods to clean surfaces prior investigation or to obtain information from deeper regions. However, severe damage of the materials – linked to preferential sputtering, ion implantation, atomic mixing and in worst case chemical degradation – can affect the validity of the analysis. Hence, the impact of C{sub 60} cluster etching, furthermore, of Ar{sup +} ion bombardment with and without azimuthal sample rotation and also the application of heavy projectiles (Xe{sup +} ions) was investigated to find a concept, which is less destructive or with less critical influence on the chemical nature of the investigated materials. In this work the focus is set on hydrozincite and zinc oxide, two common corrosion products of Zn-based coatings. As a main point, all the obtained results from (i) Ar{sup +} ion, (ii) Ar cluster, and (iii) C{sub 60} cluster etching on the degradation kinetics of hydrozincite were compared with respect to the reached sputter depth. In addition, the sputter rate of all three methods was experimentally determined for ZnO. In total, fully non-destructive conditions could not be found, but valuable knowledge on the type and rate of degradation, which is essential to choose the most suited sputter concept.

In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

Science.gov (United States)

Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

2016-01-01

Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy. PMID:27350565

Determination of clebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

Science.gov (United States)

Robinson, P R; Jones, M D; Maddock, J

1988-11-18

A procedure for the analysis of clebopride in plasma using capillary gas chromatography-negative-ion chemical ionization mass spectrometry has been developed. Employing an ethoxy analogue as internal standard, the two compounds were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyryl imidazole produced volatile monoheptafluorobutyryl derivatives whose ammonia negative-ion mass spectra proved ideal for selected-ion monitoring. The recovery of clebopride from plasma at 0.536 nmol/l was found to be 85.5 +/- 0.9% (n = 3) whilst measurement down to 0.268 nmol/l was possible with a coefficient of variation of 7.9%. Plasma levels of the compound are reported in two volunteers following ingestion of 1 mg of clebopride as the malate salt.

Changes in cluster magnetism and suppression of local superconductivity in amorphous FeCrB alloy irradiated by Ar{sup +} ions

Energy Technology Data Exchange (ETDEWEB)

Okunev, V.D., E-mail: okunev@mail.fti.ac.donetsk.ua [Donetsk Physiko-Technical Institute, Ukrainian Academy of Sciences, av. Nauki 46, 03028 Kiev (Ukraine); Samoilenko, Z.A. [Donetsk Physiko-Technical Institute, Ukrainian Academy of Sciences, av. Nauki 46, 03028 Kiev (Ukraine); Szymczak, H.; Szewczyk, A.; Szymczak, R.; Lewandowski, S.J.; Aleshkevych, P.; Malinowski, A.; Gierłowski, P.; Więckowski, J. [Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Wolny-Marszałek, M.; Jeżabek, M. [Institute of Nuclear Physics, Polish Academy of Sciences, Krakow (Poland); Varyukhin, V.N. [Donetsk Physiko-Technical Institute, Ukrainian Academy of Sciences, av. Nauki 46, 03028 Kiev (Ukraine); Antoshina, I.A. [Obninsk State Technical University of Atomic Energy, 249020 Obninsk (Russian Federation)

2016-02-01

We show that cluster magnetism in ferromagnetic amorphous Fe{sub 67}Cr{sub 18}B{sub 15} alloy is related to the presence of large, D=150–250 Å, α-(Fe Cr) clusters responsible for basic changes in cluster magnetism, small, D=30–100 Å, α-(Fe, Cr) and Fe{sub 3}B clusters and subcluster atomic α-(Fe, Cr, B) groupings, D=10–20 Å, in disordered intercluster medium. For initial sample and irradiated one (Φ=1.5×10{sup 18} ions/cm{sup 2}) superconductivity exists in the cluster shells of metallic α-(Fe, Cr) phase where ferromagnetism of iron is counterbalanced by antiferromagnetism of chromium. At Φ=3×10{sup 18} ions/cm{sup 2}, the internal stresses intensify and the process of iron and chromium phase separation, favorable for mesoscopic superconductivity, changes for inverse one promoting more homogeneous distribution of iron and chromium in the clusters as well as gigantic (twice as much) increase in density of the samples. As a result, in the cluster shells ferromagnetism is restored leading to the increase in magnetization of the sample and suppression of local superconductivity. For initial samples, the temperature dependence of resistivity ρ(T)~T{sup 2} is determined by the electron scattering on quantum defects. In strongly inhomogeneous samples, after irradiation by fluence Φ=1.5×10{sup 18} ions/cm{sup 2}, the transition to a dependence ρ(T)~T{sup 1/2} is caused by the effects of weak localization. In more homogeneous samples, at Φ=3×10{sup 18} ions/cm{sup 2}, a return to the dependence ρ(T)~T{sup 2} is observed. - Highlights: • The samples at high dose of ion irradiation become more homogeneous. • Gigantic increase in density of the samples (twice as much) is observed. • Ferromagnetism in large Fe–Cr clusters is restored. • Ferromagnetism of Fe–Cr clusters suppresses local superconductivity in them. • The participation of quantum defects in scattering of electrons is returned.

Plasma diagnostics of the SIMPA Ecr ion source by X-ray spectroscopy, Collisions of H-like Neon ions with Argon clusters; Diagnostic du plasma de la source d'ions ECR SIMPA par spectroscopie X, Collision d'ions neon hydrogenoides avec des agregats d'argon

Energy Technology Data Exchange (ETDEWEB)

Adrouche, N

2006-09-15

The first part of this thesis is devoted to the SIMPA ECR ion source characterization, first, I explored the ion source's capacities on the point of view of extracted currents for three elements, argon, krypton and neon. By analyzing the Bremsstrahlung spectra, I determined the electronic temperature in the plasma and the electronic and ionic densities. In a second time, I recorded high resolution X-spectra of argon and krypton plasma's. By taking into account the principal mechanisms of production of a K hole in the ions inside the plasma, I determined the ionic densities of the high charge states of argon. Lastly, I highlighted a correlation between the ions charge states densities with the intensities of extracted currents. The second part of the thesis is devoted to Ne{sup 9+-} argon clusters collisions. First, I presented simple and effective theoretical models allowing to describe the phenomena occurring during a collision, from the point of view of the projectile. I carried out a simulation for a collision of an ion Ne{sup 9+} with an argon cluster of a given size, which has enabled us to know the energy levels populated during the electronic capture and to follow the number of electrons in each projectile shell. Lastly, I presented the first results of a collision between a Ne{sup 9+} beam and argon clusters. These results, have enabled me by using projectile X-ray spectroscopy during the ions-clusters collision, to evidence a strong clustering of targets atoms and to highlight an electronic multi-capture in the projectile ion excited states. (author)

Mass spectrometry analysis of etch products from CR-39 plastic irradiated by heavy ions

Science.gov (United States)

Kodaira, S.; Nanjo, D.; Kawashima, H.; Yasuda, N.; Konishi, T.; Kurano, M.; Kitamura, H.; Uchihori, Y.; Naka, S.; Ota, S.; Ideguchi, Y.; Hasebe, N.; Mori, Y.; Yamauchi, T.

2012-09-01

As a feasibility study, gas chromatography-mass spectrometry (GC-MS) and matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) have been applied to analyze etch products of CR-39 plastic (one of the most frequently used solid states nuclear track detector) for the understanding of track formation and etching mechanisms by heavy ion irradiation. The etch products of irradiated CR-39 dissolved in sodium hydroxide solution (NaOH) contain radiation-induced fragments. For the GC-MS analysis, we found peaks of diethylene glycol (DEG) and a small but a definitive peak of ethylene glycol (EG) in the etch products from CR-39 irradiated by 60 MeV N ion beams. The etch products of unirradiated CR-39 showed a clear peak of DEG, but no other significant peaks were found. DEG is known to be released from the CR-39 molecule as a fragment by alkaline hydrolysis reaction of the polymer. We postulate that EG was formed as a result of the breaking of the ether bond (C-O-C) of the DEG part of the CR-39 polymer by the irradiation. The mass distribution of polyallylalcohol was obtained from the etch products from irradiated and unirradiated CR-39 samples by MALDI-MS analysis. Polyallylalcohol, with the repeating mass interval of m/z = 58 Da (dalton) between m/z = 800 and 3500, was expected to be produced from CR-39 by alkaline hydrolysis. We used IAA as a matrix to assist the ionization of organic analyte in MALDI-MS analysis and found that peaks from IAA covered mass spectrum in the lower m/z region making difficult to identify CR-39 fragment peaks which were also be seen in the same region. The mass spectrometry analysis using GC-MS and MALDI-MS will be powerful tools to investigate the radiation-induced polymeric fragments and helping to understand the track formation mechanism in CR-39 by heavy ions.

Mass spectrometry with accelerators.

Science.gov (United States)

Litherland, A E; Zhao, X-L; Kieser, W E

2011-01-01

As one in a series of articles on Canadian contributions to mass spectrometry, this review begins with an outline of the history of accelerator mass spectrometry (AMS), noting roles played by researchers at three Canadian AMS laboratories. After a description of the unique features of AMS, three examples, (14)C, (10)Be, and (129)I are given to illustrate the methods. The capabilities of mass spectrometry have been extended by the addition of atomic isobar selection, molecular isobar attenuation, further ion acceleration, followed by ion detection and ion identification at essentially zero dark current or ion flux. This has been accomplished by exploiting the techniques and accelerators of atomic and nuclear physics. In 1939, the first principles of AMS were established using a cyclotron. In 1977 the selection of isobars in the ion source was established when it was shown that the (14)N(-) ion was very unstable, or extremely difficult to create, making a tandem electrostatic accelerator highly suitable for assisting the mass spectrometric measurement of the rare long-lived radioactive isotope (14)C in the environment. This observation, together with the large attenuation of the molecular isobars (13)CH(-) and (12)CH 2(-) during tandem acceleration and the observed very low background contamination from the ion source, was found to facilitate the mass spectrometry of (14)C to at least a level of (14)C/C ~ 6 × 10(-16), the equivalent of a radiocarbon age of 60,000 years. Tandem Accelerator Mass Spectrometry, or AMS, has now made possible the accurate radiocarbon dating of milligram-sized carbon samples by ion counting as well as dating and tracing with many other long-lived radioactive isotopes such as (10)Be, (26)Al, (36)Cl, and (129)I. The difficulty of obtaining large anion currents with low electron affinities and the difficulties of isobar separation, especially for the heavier mass ions, has prompted the use of molecular anions and the search for alternative

Electron-ion collision rates in atomic clusters irradiated by femtosecond laser pulses

International Nuclear Information System (INIS)

Moll, M; Hilse, P; Schlanges, M; Bornath, Th; Krainov, V P

2010-01-01

In atomic clusters irradiated by femtosecond laser pulses, plasmas with high density and high temperature are created. The heating is mainly caused by inverse bremsstrahlung, i.e. determined by electron-ion collisions. In the description of the scattering of electrons on noble gas ions in such plasmas, it is important to account for the inner structure of the ions and the screening by the surrounding plasma medium which can be accomplished by using suitable model potentials. In the wide parameter range met in experiments, the Born approximation is not applicable. Instead, the electron-ion collision frequency is calculated on the basis of classical momentum transport cross sections. Results are presented for xenon, krypton and argon ions in different charge states. A comparison of these results to those for the scattering on Coulomb particles with the same charge shows an enhancement of the collision frequency. The Born approximation, however, leads to an overestimation.

Multi-capillary column-ion mobility spectrometry: a potential screening system to differentiate virgin olive oils.

Science.gov (United States)

Garrido-Delgado, Rocío; Arce, Lourdes; Valcárcel, Miguel

2012-01-01

The potential of a headspace device coupled to multi-capillary column-ion mobility spectrometry has been studied as a screening system to differentiate virgin olive oils ("lampante," "virgin," and "extra virgin" olive oil). The last two types are virgin olive oil samples of very similar characteristics, which were very difficult to distinguish with the existing analytical method. The procedure involves the direct introduction of the virgin olive oil sample into a vial, headspace generation, and automatic injection of the volatiles into a gas chromatograph-ion mobility spectrometer. The data obtained after the analysis by duplicate of 98 samples of three different categories of virgin olive oils, were preprocessed and submitted to a detailed chemometric treatment to classify the virgin olive oil samples according to their sensory quality. The same virgin olive oil samples were also analyzed by an expert's panel to establish their category and use these data as reference values to check the potential of this new screening system. This comparison confirms the potential of the results presented here. The model was able to classify 97% of virgin olive oil samples in their corresponding group. Finally, the chemometric method was validated obtaining a percentage of prediction of 87%. These results provide promising perspectives for the use of ion mobility spectrometry to differentiate virgin olive oil samples according to their quality instead of using the classical analytical procedure.

Carbon nanotube growth from catalytic nano-clusters formed by hot-ion-implantation into the SiO{sub 2}/Si interface

Energy Technology Data Exchange (ETDEWEB)

Hoshino, Yasushi, E-mail: yhoshino@kanagawa-u.ac.jp [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan); Arima, Hiroki; Yokoyama, Ai; Saito, Yasunao; Nakata, Jyoji [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan)

2012-07-01

We have studied growth of chirality-controlled carbon nanotubes (CNTs) from hot-implantation-formed catalytic nano-clusters in a thermally grown SiO{sub 2}/Si substrate. This procedure has the advantage of high controllability of the diameter and the number of clusters by optimizing the conditions of the ion implantation. In the present study, Co{sup +} ions with ion dose of 8 Multiplication-Sign 10{sup 16} cm{sup -2} are implanted in the vicinity of the SiO{sub 2}/Si interface at 300 Degree-Sign C temperature. The implanted Co atoms located in the SiO{sub 2} layer has an amorphous-like structure with a cluster diameter of several nm. In contrast, implanted Co atoms in the Si substrate are found to take a cobalt silicide structure, confirmed by the high-resolution image of transmission electron microscope. CNTs are grown by microwave-plasma-enhanced chemical vapor deposition. We have confirmed a large amount of vertically-aligned multi-walled CNTs from the Co nano-clusters formed by the hot-ion-implantation near the SiO{sub 2}/Si interface.

Bi-Directional Ion Emission from Massive Gold Cluster Impacts on Nanometric Carbon Foils

OpenAIRE

DeBord, J. Daniel; Della-Negra, Serge; Fernandez-Lima, Francisco A.; Verkhoturov, Stanislav V.; Schweikert, Emile A.

2012-01-01

Carbon cluster emission from thin carbon foils (5–40 nm) impacted by individual Aun+q cluster projectiles (95–125 qkeV, n/q = 3–200) reveals features regarding the energy deposition, projectile range, and projectile fate in matter as a function of the projectile characteristics. For the first time, the secondary ion emission from thin foils has been monitored simultaneously in both forward and backward emission directions. The projectile range and depth of emission were examined as a function...

Electronic and geometric structures of Ge{sub n}{sup -} and Ge{sub n}{sup +} (n=5-10) clusters in comparison with corresponding Si{sub n} ions

Energy Technology Data Exchange (ETDEWEB)

Li Baoxing; Cao Peilin; Song Bin; Ye Zhezhen

2003-02-10

Using full-potential linear-muffin-tin-orbital molecular-dynamics (FP-LMTO-MD) method, we have studied the geometric and electronic structures of ionic Ge{sub 5-10} clusters. Our calculations show that the ground state structures of some Ge cluster ions are different from those of their corresponding neutral Ge clusters. Furthermore, the positive Ge ions have more severe structural distortion than the negative Ge ions due to Jahn-Teller distortion. In addition, there are differences between the ground state structures of Ge ions and Si ions, although most of the Ge ions have similar geometrical configurations to their corresponding Si ions.

Mass spectrometry of long-lived radionuclides

International Nuclear Information System (INIS)

Becker, Johanna Sabine.

2003-01-01

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated--therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of 129 Xe + for the determination of 129 I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass

IR photodissociation spectroscopy of (OCS){sub n}{sup +} and (OCS){sub n}{sup −} cluster ions: Similarity and dissimilarity in the structure of CO{sub 2}, OCS, and CS{sub 2} cluster ions

Energy Technology Data Exchange (ETDEWEB)

Inokuchi, Yoshiya, E-mail: y-inokuchi@hiroshima-u.ac.jp; Ebata, Takayuki [Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)

2015-06-07

Infrared photodissociation (IRPD) spectra of (OCS){sub n}{sup +} and (OCS){sub n}{sup −} (n = 2–6) cluster ions are measured in the 1000–2300 cm{sup −1} region; these clusters show strong CO stretching vibrations in this region. For (OCS){sub 2}{sup +} and (OCS){sub 2}{sup −}, we utilize the messenger technique by attaching an Ar atom to measure their IR spectra. The IRPD spectrum of (OCS){sub 2}{sup +}Ar shows two bands at 2095 and 2120 cm{sup −1}. On the basis of quantum chemical calculations, these bands are assigned to a C{sub 2} isomer of (OCS){sub 2}{sup +}, in which an intermolecular semi-covalent bond is formed between the sulfur ends of the two OCS components by the charge resonance interaction, and the positive charge is delocalized over the dimer. The (OCS){sub n}{sup +} (n = 3–6) cluster ions show a few bands assignable to “solvent” OCS molecules in the 2000–2080 cm{sup −1} region, in addition to the bands due to the (OCS){sub 2}{sup +} ion core at ∼2090 and ∼2120 cm{sup −1}, suggesting that the dimer ion core is kept in (OCS){sub 3–6}{sup +}. For the (OCS){sub n}{sup −} cluster anions, the IRPD spectra indicate the coexistence of a few isomers with an OCS{sup −} or (OCS){sub 2}{sup −} anion core over the cluster range of n = 2–6. The (OCS){sub 2}{sup −}Ar anion displays two strong bands at 1674 and 1994 cm{sup −1}. These bands can be assigned to a C{sub s} isomer with an OCS{sup −} anion core. For the n = 2–4 anions, this OCS{sup −} anion core form is dominant. In addition to the bands of the OCS{sup −} core isomer, we found another band at ∼1740 cm{sup −1}, which can be assigned to isomers having an (OCS){sub 2}{sup −} ion core; this dimer core has C{sub 2} symmetry and {sup 2}A electronic state. The IRPD spectra of the n = 3–6 anions show two IR bands at ∼1660 and ∼2020 cm{sup −1}. The intensity of the latter component relative to that of the former one becomes stronger and stronger with

Nuclear Forensics: Measurements of Uranium Oxides Using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

Science.gov (United States)

2010-03-01

Isotope Ratio Analysis of Actinides , Fission Products, and Geolocators by High- efficiency Multi-collector Thermal Ionization Mass Spectrometry...Information, 1999. Hou, Xiaolin, and Per Roos. “ Critical Comparison of radiometric and Mass Spectrometric Methods for the Determination of...NUCLEAR FORENSICS: MEASUREMENTS OF URANIUM OXIDES USING TIME-OF-FLIGHT SECONDARY ION MASS

Qualitative and quantitative characterization of plasma proteins when incorporating traveling wave ion mobility into a liquid chromatography-mass spectrometry workflow for biomarker discovery: use of product ion quantitation as an alternative data analysis tool for label free quantitation.

Science.gov (United States)

Daly, Charlotte E; Ng, Leong L; Hakimi, Amirmansoor; Willingale, Richard; Jones, Donald J L

2014-02-18

Discovery of protein biomarkers in clinical samples necessitates significant prefractionation prior to liquid chromatography-mass spectrometry (LC-MS) analysis. Integrating traveling wave ion mobility spectrometry (TWIMS) enables in-line gas phase separation which when coupled with nanoflow liquid chromatography and data independent acquisition tandem mass spectrometry, confers significant advantages to the discovery of protein biomarkers by improving separation and inherent sensitivity. Incorporation of TWIMS leads to a packet of concentrated ions which ultimately provides a significant improvement in sensitivity. As a consequence of ion packeting, when present at high concentrations, accurate quantitation of proteins can be affected due to detector saturation effects. Human plasma was analyzed in triplicate using liquid-chromatography data independent acquisition mass spectrometry (LC-DIA-MS) and using liquid-chromatography ion-mobility data independent acquisition mass spectrometry (LC-IM-DIA-MS). The inclusion of TWIMS was assessed for the effect on sample throughput, data integrity, confidence of protein and peptide identification, and dynamic range. The number of identified proteins is significantly increased by an average of 84% while both the precursor and product mass accuracies are maintained between the modalities. Sample dynamic range is also maintained while quantitation is achieved for all but the most abundant proteins by incorporating a novel data interpretation method that allows accurate quantitation to occur. This additional separation is all achieved within a workflow with no discernible deleterious effect on throughput. Consequently, TWIMS greatly enhances proteome coverage and can be reliably used for quantification when using an alternative product ion quantification strategy. Using TWIMS in biomarker discovery in human plasma is thus recommended.

Structural calculations and experimental detection of small Ga mS n clusters using time-of-flight mass spectrometry

Science.gov (United States)

BelBruno, J. J.; Sanville, E.; Burnin, A.; Muhangi, A. K.; Malyutin, A.