DOCSLIB.ORG

Use of Electrospray Ionization Mass Spectrometry (ESI-MS) for the Study of Metal (III) Extraction by Dialkyl Phosphoric Acid

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Use of Electrospray Ionization Mass Spectrometry (ESI-MS) for the Study of Metal (III) Extraction by Dialkyl Phosphoric Acid P2-31 Use of Electrospray Ionization Mass Spectrometry (ESI-MS) for the study of metal (III) extraction by dialkyl phosphoric acid E. Leclerc1, L. Berthon1, X. Heres1, B. Gannaz1, C. Berthon2, J.M. Adnet1 1CEA Valrhô, DEN/DRCP/SCPS/LCSE, B.P. 171, 30207 Bagnols sur Cèze, France 2CEA Valrhô, DEN/DRCP/SCPS/LCAM, B.P. 171, 30207 Bagnols sur Cèze, France Abstract –In the framework of nuclear waste reprocessing, separation processes of minor actinide from fission product are developed by CEA. In order to understand the mechanism involved in the extraction process, the complexes ligand - metallic cations formed in organic phase has been characterized. This paper deals with the extraction of lanthanides (III) and actinides (III) cations by dialkyl phosphoric acid (the bis- 1,3-dimethylbutylphosphoric acid). The associative properties of the extractant were studied, the complexes (metal-ligand) present in organic phase were identified and the interactions ligand-metal were characterized. The electrospray ionization -mass spectrometry (ESI-MS) was used to investigate organic solutions, and the results are compared with those obtained by other techniques like NMR, IRTF and distribution ratio studies. INTRODUCTION HBDMBP concentration was measured by To improve the management of radioactive acido-basic titration. Water concentration was wastes generated by spent nuclear fuel titrated by Karl Fisher analysis. reprocessing, CEA has undertaken the Aqueous phase: development of a liquid-liquid extraction process - pH 3 solution: glycolic acid 0.6 mol/L which has the objective, in particular, to separate adjusted to pH 3 with NaOH. the minor actinides [Am(III) and Cm(III)] from - europium solution: dissolution of europium high-level liquid waste [1] Dialkylphosphoric (III) nitrate in pH 3 solution. acid, like di(2-ethylhexyl)phosphoric acid The organic and aqueous solutions were shaked (HDEHP), proved to be a very efficient together at 25°C during 15 minutes and then extracting agent in the separation of trivalent centrifuged during 5 minutes and separated. lanthanides and actinides [2, 3]. Several - ESI-MS: A Brucker Esquire LC mass dialkylphosphoric acid have been tested to spectrometer was used. separate lanthanides from actinides using a Organic phase were contacted with the combination of buffer and complexant in appropriate aqueous phase (Vaq = 4 Vorg). aqueous phase. This present work deals with the Without metal, the organic phase was diluted extraction of the trivalent lanthanides and 1/10000e in acetonitrile/water (1:1 v/v). actinides by the bis-1,3-dimethylbutylphosphoric Eu-HBDMBP complex characterization: the acid (HBDMBP) diluted in dodecane. organic phase was diluted 1/10e in ethanol and The associative properties of the extractant were 1/100e in water/acetonitrile (1:1 v/v). studied, the complex (Metal-ligand) present in - NMR: A Unity Inova 400 MHz spectrometer organic phase were identified and the interaction was used. ligand - metal were characterized. - Distribution ratio studies: The ESI-MS technique was chosen to analyze Organic phases are contacted with the organic solutions. Indeed, the ‘gentle’ nature of appropriate aqueous phases (Vaq = Vorg) spiked the ESI [4] process allowed obtaining with 241Am(III) and 152Eu(III) at 25°C. An information about associative properties of the aliquots of each phases was then taken for organic molecule and providing structure, gamma counting (E = 59.64 keV for 241Am and stoichiometry of ligand-metal complexes in E = 121.8 keV for 152Eu). solution [5, 6]. The results are compared with - IRTF: a Brucker Equinox 55 those obtained by other techniques like NMR, spectrophotometer was used. IRTF and distribution ratio studies. AGGREGATION OF HBDMBP EXPERIMENTAL Dialkylphosphoric acids are considered to exist - Extraction conditions: as dimeric species in a non polar solvent [7, 8]. Organic phase: HBDMBP was diluted in The aggregation of the extractant in the organic dodecane. phase is expressed as: ATALANTE 2004 Nîmes (France) June 21-25, 2004 1 P2-31 n HL (HL)n Therefore, the plot of log(C( 1- )) vs. log(C( - n)) gives a straight line with slope n and the and characterized by the aggregation constant ordinate log(Kn/(( 1- n)^(n-1))). The slope of the Kn. The aggregation of HBDMBP in dodecane at plot log(C( 1- )) against log(C( - n)) is equal to 25°C is studied after contact with a pH=3 2 and the ordinate is -0.0205. -1 aqueous phase. Then n=2 and the constant K2 = 3.0±0.2 L.mol . The Fig. 2 presents the speciation diagram Electrospray Ionization - Mass Spectrometry (monomer, dimer of HBDMBP) and water The Fig. 1 shows the positive mass spectrum of concentration in organic phase vs. HBDMBP HBDMBP. The ions at m/z 289, 533, 821 and concentration: one H2O molecule seems interact + + 1087 correspond respectively to LNa , L2H , with one dimer molecule. + + L3Na and L4Na with L corresponds to + 1,2 HBDMBP molecule. The dimeric form (L2H ) is the main species. dimer 1 H2O Intens. 6 L x10 / l 0,8 o 1.0 m 533.2 + n i L2H n o i 0,6 t monomer a r t n 0.8 e c n o 0,4 C 0.6 0,2 y t i s n 0 e 0 0,5 1 1,5 2 2,5 3 3,5 t 0.4 HBDMBP Concentration (mol/L) n I 555.2 Fig. 2. Speciation diagram for HBDMBP diluted 0.2 + in dodecane at 25 °C after contact with a pH=3 + L3Na 99.0 LNa 820.9 + 289.2 aqueous phase. 267.0 351.3 L Na 4 1087.3 0.0 200 400 600 800 1000 m/z +MS m/z CHARACTERIZATION OF THE METAL- Fig. 1. ESI mass spectrum in the positive HBDMBP COMPLEXES ionization mode of HBDMBP 10-2 mol.L-1 This part deals with the extraction of metal diluted at 1/10000 in water/acetonitrile (1:1 v/v), nitrate by HBDMBP in pH=3 aqueous phase. cone voltage 30 V. Electrospray Ionization - Mass Spectrometry The positive ionization mode mass spectrum of NMR NMR can be used for aggregation studies [8, 9]. the organic phase is reported Fig. 3. Three ions at The chemical shift of 31P was measured as a m/z = 1215.5, 1481.6 and 1747.7 are particularly interesting and correspond respectively to function of the HBDMBP concentration. A shift + + + from -1.7 ppm for diluted solution to -4.5ppm for [EuL2(L-H)2] , [EuL3(L-H)2] and [EuL4(L-H)2] species (with L = HBDMBP). The most concentrated solution was observed. This gap is + enough to have a good precision for the abundant species is [EuL2(L-H)2] . An increase of the skimmer voltage leads to a disappearance determination of the dimerization constant. + + of the [EuL3(L-H)2] and [EuL4(L-H)2] (Fig. 4). The mass action law model is considered and This shows that the complex with four leads to the following equation: HBDMBP is the most stable species and the two others are probably species generated during the ≈ ’ ∆ Kn ionization step. log(C(δ1 −δ )) = n log(C(δ − δ n ))+ log∆ (n−1) « (δ1 − δ n ) In order to have more information about the With structure and the stability of the complexes, the - C: extractant concentration (mol.L-1), fragmentation of each of them has been studied - : experimental chemical shift, (Fig. 5 and 6). + - 1: chemical shift for the monomeric form (null The fragmentation of [EuL2(L-H)2] (Fig. 5) concentration), leads to three more important species at m/z = - n: chemical shift for the micellar form (infinite 1131.5 (loss of C6H12), m/z = 1047.4 concentration), (elimination of two C6H12 groups) and m/z = - n: aggregation number, 949.5 (loss of a HBDMBP molecule). The - Kn is the aggregation constant. weaker intensity of the peak issuing from the ATALANTE 2004 Nîmes (France) June 21-25, 2004 2 P2-31 loss of HBDMBP compared of the intensity of molecule of HBDMBP (two in the case of + the peak issuing from the loss of C6H12 show that [EuL4(L-H)2] ) (Fig. 6) and lead to an ion at m/z the interaction Eu-HBDMBP is very strong = 1215.6 (1213.5 for 151Eu) which corresponds to + because it is easier to break an oxygen-carbon [EuL2(L-H)2] . bond than a metal-ligand bond. Intens. Intens. + + I n te n s. [EuL (L-H) ] 14814181.6,6 [EuL (L-H) ] 14791479.,66 x 1 0 5 3 2 3 2 6000 + T=triester 200 533. L2H L=HBDMBP Spectre MS+2 [EuL3(L-H)2] 1 .0 99.1 + de2 [EuL (L-H) ] MS spe3ctrum2 2 + 5000 Spectre MS + [EuL (L-H) ] [EuL (L-H) ] 4 2 4 2 + 1745.7 + de [E2uL4(L-H)2] 1745,7 0 .8 [EuL (L-H) ] 2 2 150 MS spectrum + 1212155.6 ,6 TH y 4000 t 351.3 i 0 .6 s y t + n L5K i + e L4Na 1369 t s n 3000 100 1087 I + n 0 .4 [EuL2(L-H)2] + + e LNa [EuL2(L-H)2] t 289.2 + 1213,5 617.3 TLH 1215 n + + I 0 .2 L3Na [EuL4(L-H)2] + 2000 -L [EuL3(L-H)2] 821.1 1747 -L -L 1481 50 0 .0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0 m /z 1000 + M S m/z 1393.4 0 0 1200 1250 1300 1350 1400 1450 1500 m/z 1200 1300 1400 1500 1600 1700 1800 m/z Fig. 3. Positive ESI mass spectrum of the organic m/z m/z 2 + phase after dilution 1/10 in ethanol and 1/100 in Fig.
Load more

Recommended publications
  • (ESI) Electrospray Ionization
    Electrospray Ionization (ESI) • sample solution • voltage drop • solvent evaporates is injected between source, away as droplets directly into analyzer generates migrate across gap instrument ionized droplets “sheath gas” Electrospray Ionization (ESI) Injected solution usually includes ionizing agent H+ (from acid), Na+, K+ Large droplets from injected stream Resulting ions can be spontaneously eject singly or multiply smaller droplets (due to charged electrostatic repulsion) Electrospray Ionization (ESI) Multiply charged ions frequently observed. ESI M [M•H]+ + [M•2H]2+ + [M•3H]3+ + ... or [M•Na]+ + [M•2Na]2+ + [M•3Na]3+ + ... multiply lysozyme: charged big > 10 kDa protein (protonated) ions From this series of peaks, how do we determine mass of protein? Charge Ladders in Electrospray Ionization We know two things: 1. Any peak corresponds to [M•nH]n+; ion mass m =M+= M + n, charge z = n. 2. Peak to that peak’s left has one more proton attached, one more charge; ion mass m = M + n + 1, charge z = n + 1. Charge Ladders in Electrospray Ionization Set of simultaneous equations: (observed m/z #1) • z = M + z(H+) (observed m/z #2) • (z + 1) = M + z(H+) + 1 2 1 Charge Ladders in Electrospray Ionization Now performed by computer algorithm Set of simultaneous equations: that searches for ladders, outputs likely mass candidates. 1486 • z = M + z 1372.5 • (z + 1) = M + z + 1 Solution: z = 12 M = 17827.2 [M•13H]13+ 2 [M•12H]1 12+ actual MW lysozyme: 17825.2 If sample contains a mixture of counterions, can get messy. ESI-MS 22-mer single-stranded DNA (difficult to desalt) Atmospheric Pressure Chemical Ionization (APCI) •+ •+ Analogous to CI, but uses discharge to generate N2 /O2 , which then iiionizes evapora tdltllThthiited solvent molecules.
    [Show full text]
  • Contents • Introduction to Proteomics and Mass Spectrometry
    Contents • Introduction to Proteomics and Mass spectrometry - What we need to know in our quest to explain life - Fundamental things you need to know about mass spectrometry • Interfaces and ion sources - Electrospray ionization (ESI) - conventional and nanospray - Heated nebulizer atmospheric pressure chemical ionization - Matrix assisted laser desorption • Types of MS analyzers - Magnetic sector - Quadrupole - Time-of-flight - Hybrid - Ion trap In the next step in our quest to explain what is life The human genome project has largely been completed and many other genomes are surrendering to the gene sequencers. However, all this knowledge does not give us the information that is needed to explain how living cells work. To do that, we need to study proteins. In 2002, mass spectrometry has developed to the point where it has the capacity to obtain the "exact" molecular weight of many macromolecules. At the present time, this includes proteins up to 150,000 Da. Proteins of higher molecular weights (up to 500,000 Da) can also be studied by mass spectrometry, but with less accuracy. The paradigm for sequencing of peptides and identification of proteins has changed – because of the availability of the human genome database, peptides can be identified merely by their masses or by partial sequence information, often in minutes, not hours. This new capacity is shifting the emphasis of biomedical research back to the functional aspects of cell biochemistry, the expression of particular sets of genes and their gene products, the proteins of the cell. These are the new goals of the biological scientist: o to know which proteins are expressed in each cell, preferably one cell at a time o to know how these proteins are modified, information that cannot necessarily be deduced from the nucleotide sequence of individual genes.
    [Show full text]
  • An Organic Chemist's Guide to Electrospray Mass Spectrometric
    molecules Review An Organic Chemist’s Guide to Electrospray Mass Spectrometric Structure Elucidation Arnold Steckel 1 and Gitta Schlosser 2,* 1 Hevesy György PhD School of Chemistry, ELTE Eötvös Loránd University, Pázmány Péter sétány 1/A, 1117 Budapest, Hungary; [email protected] 2 Department of Analytical Chemistry, ELTE Eötvös Loránd University, Pázmány Péter sétány 1/A, 1117 Budapest, Hungary * Correspondence: [email protected] Received: 16 January 2019; Accepted: 8 February 2019; Published: 10 February 2019 Abstract: Tandem mass spectrometry is an important tool for structure elucidation of natural and synthetic organic products. Fragmentation of odd electron ions (OE+) generated by electron ionization (EI) was extensively studied in the last few decades, however there are only a few systematic reviews available concerning the fragmentation of even-electron ions (EE+/EE−) produced by the currently most common ionization techniques, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). This review summarizes the most important features of tandem mass spectra generated by collision-induced dissociation fragmentation and presents didactic examples for the unexperienced users. Keywords: tandem mass spectrometry; MS/MS fragmentation; collision-induced dissociation; CID; ESI; structure elucidation 1. Introduction Electron ionization (EI), a hard ionization technique, is the method of choice for analyses of small (<1000 Da), nonpolar, volatile compounds. As its name implies, the technique involves ionization by electrons with ~70 eV energy. This energy is high enough to yield very reproducible mass spectra with a large number of fragments. However, these spectra frequently lack the radical type molecular ions (M+) due to the high internal energy transferred to the precursors [1].
    [Show full text]
  • Orbitrap Fusion Tribrid Mass Spectrometer
    MASS SPECTROMETRY Product Specifications Thermo Scientific Orbitrap Fusion Tribrid Mass Spectrometer Unmatched analytical performance, revolutionary MS architecture The Thermo Scientific™ Orbitrap Fusion™ mass spectrometer combines the best of quadrupole, Orbitrap, and linear ion trap mass analysis in a revolutionary Thermo Scientific™ Tribrid™ architecture that delivers unprecedented depth of analysis. It enables life scientists working with even the most challenging samples—samples of low abundance, high complexity, or difficult-to-analyze chemical structure—to identify more compounds faster, quantify them more accurately, and elucidate molecular composition more thoroughly. • Tribrid architecture combines quadrupole, followed by ETD or EThCD for glycopeptide linear ion trap, and Orbitrap mass analyzers characterization or HCD followed by CID • Multiple fragmentation techniques—CID, for small-molecule structural analysis. HCD, and optional ETD and EThCD—are available at any stage of MSn, with The ultrahigh resolution of the Orbitrap mass subsequent mass analysis in either the ion analyzer increases certainty of analytical trap or Orbitrap mass analyzer results, enabling molecular-weight • Parallelization of MS and MSn acquisition determination for intact proteins and confident to maximize the amount of high-quality resolution of isobaric species. The unsurpassed data acquired scan rate and resolution of the system are • Next-generation ion sources and ion especially useful when dealing with complex optics increase system ease of operation and robustness and low-abundance samples in proteomics, • Innovative instrument control software metabolomics, glycomics, lipidomics, and makes setup easier, methods more similar applications. powerful, and operation more intuitive The intuitive user interface of the tune editor The Orbitrap Fusion Tribrid MS can perform and method editor makes instrument calibration a wide variety of analyses, from in-depth and method development easier.
    [Show full text]
  • Electrification Ionization: Fundamentals and Applications
    Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 11-12-2019 Electrification Ionization: undamentalsF and Applications Bijay Kumar Banstola Louisiana State University and Agricultural and Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Analytical Chemistry Commons Recommended Citation Banstola, Bijay Kumar, "Electrification Ionization: undamentalsF and Applications" (2019). LSU Doctoral Dissertations. 5103. https://digitalcommons.lsu.edu/gradschool_dissertations/5103 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. ELECTRIFICATION IONIZATION: FUNDAMENTALS AND APPLICATIONS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Bijay Kumar Banstola B. Sc., Northwestern State University of Louisiana, 2011 December 2019 This dissertation is dedicated to my parents: Tikaram and Shova Banstola my wife: Laxmi Kandel ii ACKNOWLEDGEMENTS I thank my advisor Professor Kermit K. Murray, for his continuous support and guidance throughout my Ph.D. program. Without his unwavering guidance and continuous help and encouragement, I could not have completed this program. I am also thankful to my committee members, Professor Isiah M. Warner, Professor Kenneth Lopata, and Professor Shengli Chen. I thank Dr. Fabrizio Donnarumma for his assistance and valuable insights to overcome the hurdles throughout my program. I appreciate Miss Connie David and Dr.
    [Show full text]
  • Electrospray Ionization and Samples Complexity in Meta-Metabolomics
    Electrospray Ionization and samples complexity in Meta-metabolomics: a biomarker or a suppressed ion? Hikmat Ghosson, Chandrashekhar Patil, Amani Ben Jrad, Delphine Raviglione, Marie-Virginie Salvia, Cédric Bertrand To cite this version: Hikmat Ghosson, Chandrashekhar Patil, Amani Ben Jrad, Delphine Raviglione, Marie-Virginie Salvia, et al.. Electrospray Ionization and samples complexity in Meta-metabolomics: a biomarker or a suppressed ion?. European RFMF Metabomeeting 2020, Jan 2020, Toulouse, France. European RFMF Metabomeeting 2020 Book Of Abstract, pp.248, 2020, Poster abstracts. hal-02456148 HAL Id: hal-02456148 https://hal.archives-ouvertes.fr/hal-02456148 Submitted on 27 Jan 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution - NonCommercial - NoDerivatives| 4.0 International License Project co-financed by the European Regional Development Fund (ERDF) Electrospray Ionization and samples complexity in Meta-metabolomics: a biomarker or a suppressed ion? Hikmat Ghosson1,2,*, Chandrashekhar Patil1, Amani Ben Jrad1,2, Delphine Raviglione1,2, Marie-Virginie Salvia1,2,3, Cédric Bertrand1,2,3,4 *: [email protected] 1: PSL Université Paris: EPHE-UPVD-CNRS, USR 3278 CRIOBE, Université de Perpignan, 52 Avenue Paul Alduy, 66860 Perpignan Cedex, France 2: UFR Sciences Exactes et Expérimentales, Université de Perpignan Via Domitia, 52 Avenue Paul Alduy, 66860 Perpignan Cedex, France 3: Laboratoire d’Excellence « CORAIL », Université de Perpignan, 52 Avenue Paul Alduy, 66860 Perpignan Cedex, France 4: S.A.S.
    [Show full text]
  • Spatially Resolved Metabolomics to Discover Tumor- Associated Metabolic Alterations
    Spatially resolved metabolomics to discover tumor- associated metabolic alterations Chenglong Suna, Tiegang Lia, Xiaowei Songa, Luojiao Huanga, Qingce Zanga, Jing Xua, Nan Bib, Guanggen Jiaoc, Yanzeng Haoc, Yanhua Chena, Ruiping Zhanga, Zhigang Luoa, Xin Lia, Luhua Wangb, Zhonghua Wangd, Yongmei Songe, Jiuming Hea,1, and Zeper Abliza,d,1 aState Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, 100050 Beijing, China; bDepartment of Radiation Oncology, Cancer Institute, Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, 100021 Beijing, China; cDepartment of Pathology and Thoracic Surgery, Linzhou Esophageal Cancer Hospital, 456500 Linzhou, China; dCenter for Imaging and Systems Biology, Minzu University of China, 100081 Beijing, China; and eState Key Laboratory of Molecular Oncology, Cancer Institute, Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, 100021 Beijing, China Edited by Matthew G. Vander Heiden, Koch Institute at Massachusetts Institute of Technology, and accepted by Editorial Board Member Rakesh K. Jain November 27, 2018 (received for review May 24, 2018) Characterization of tumor metabolism with spatial information tissue samples is lost over the course of elaborate sample pre- contributes to our understanding of complex cancer metabolic treatment (7). Matrix-assisted laser desorption ionization mass reprogramming, facilitating the discovery of potential metabolic spectrometry imaging (MALDI-MSI) is an effective tool to vi- vulnerabilities that might be targeted for tumor therapy. However, sualize the spatial location of proteins and metabolites with high given the metabolic variability and flexibility of tumors, it is still spatial resolution, but high-vacuum environments and matrix challenging to characterize global metabolic alterations in heteroge- assistance are usually needed for ionization (8–11).
    [Show full text]
  • Desorption Electrospray Ionization (DESI) Mass Spectrometry: a Brief Introduction and Overview
    Justin M. Wiseman, Brian C. Laughlin Prosolia, Inc., Indianapolis, IN USA, *[email protected] Desorption Electrospray Ionization (DESI) Mass Spectrometry: A brief introduction and overview A recent advancement in mass spectrometry is the ability to examine samples situated outside the vacuum system in the ambient environment with minimal sample preparation. This article presents an introduction to desorption electrospray ionization (DESI) mass spectrometry and an overview of recent literature and emerging methods. In DESI, electrically charged droplets are directed at the sample of interest; ions are generated of the sample constituents and are collected and mass analyzed in a standard commercial mass spectrometer. This method promises rapid, high-throughput analysis combined with the sensitivity and specificity of the mass spectrometer. Applications related to counterfeit tablet identification, metabolomics, and two-dimensional chemical imaging of biological tissues are briefly discussed. Mass spectrometry (MS) has significant advantages in speed, characteristics make DESI a suitable technique for rapid, in sensitivity and specificity over other methods of chemical situ analysis of samples in a variety of circumstances. For analysis, and its broad applicability has proven valuable in example, DESI has been applied to the rapid analysis of many different scientific fields; however, MS is limited in part chemical warfare agents and explosives present on common by the requirements for samples to be prepared prior to surfaces (i.e. paper, plastic, fabric, metal etc.) (7, 8). Limits of analysis. In most cases, the sample must be placed in vacuum detection in these studies reached levels of picograms to for analysis (e.g matrix-assisted laser desorption/ionization - femtograms for RDX (trinitrohexahydro-1,3,5-triazine), TNT MALDI) or dissolved or extracted in a solvent and sprayed in (1,3,5-trinotrotoluene), and DMMP atmosphere (e.g.
    [Show full text]
  • Desorption Electrospray Ionization Mass Spectrometry Imaging: Instrumentation, Optimization and Capabilities
    Brigham Young University BYU ScholarsArchive Theses and Dissertations 2014-03-13 Desorption Electrospray Ionization Mass Spectrometry Imaging: Instrumentation, Optimization and Capabilities Manan Dhunna Brigham Young University - Provo Follow this and additional works at: https://scholarsarchive.byu.edu/etd Part of the Biochemistry Commons, and the Chemistry Commons BYU ScholarsArchive Citation Dhunna, Manan, "Desorption Electrospray Ionization Mass Spectrometry Imaging: Instrumentation, Optimization and Capabilities" (2014). Theses and Dissertations. 3969. https://scholarsarchive.byu.edu/etd/3969 This Thesis is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Desorption Electrospray Ionization Mass Spectrometry Imaging: Instrumentation, Optimization and Capabilities TITLE PAGE Manan Dhunna A thesis submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Master of Science Paul Farnsworth, Chair Matthew Linford Steven Graves Department of Chemistry and Biochemistry Brigham Young University March 2014 Copyright © 2014 Manan Dhunna All Rights Reserved ABSTRACT Desorption Electrospray Ionization Mass Spectrometry Imaging: Instrumentation, Optimization and Capabilities Manan Dhunna Department of Chemistry and Biochemistry, BYU Master of Science Desorption Electrospray Ionization Mass spectrometry Imaging (DESI-MSI) is an area of great interest and a promising tool in the field of chemical imaging. It is a powerful, label-free technique, which can determine, map and visualize different molecular compounds on a sample surface. The amount of information acquired in a single DESI-MSI experiment is enormous compared to other techniques, as it can simultaneously detect different compounds with their spatial distribution on the surface.
    [Show full text]
  • Electrospray Ionization Mass Spectroscopy Shows Speciation of Phytate to Be Ph Dependent
    WFL Publisher ' Science and Technology 0t1t01 hiOildTtOOd. 10Meri-Rastilantie3 B. Fl-00980 Joiii,itil of Food Agriculture & Environment 101.6(2) 402-407. 2008 net Helsinki. Finland c-mail irmibamiom Id-toad Electrospray ionization mass spectroscopy shows speciation of phytate to be pH dependent Lynne Heighton , Walter F. Schmidt 2 Clifford P. Rice 2 and Ronald L. Siefert Che,ni.stri and Biochemistry Department, Univecsitv of Mamyland, College Park, MD 20742, USA.Environmental Management andBvproduct Utilization Laborator USDA/ARS/ANRIBarc-West, 10300 Baltimore Avenue, Beltsville, MD 20705, USA. University of Maryland, Chesapeake Biological Laboratory, One Williams St., Solo/lions, MD 20688, USA. Current address: Chemistry Department (Mail Stop 9B), United States NavalAcademv, 572 MHollowav Rd., Annapolis, MD 21402-5026, USA. e-ntail: schmnidtot@ba. ars. usda.goi heighton(à.unmd. edit Received 5 Jumicirr 2008, accepted 28 Marc!, 2008. Abstract Phosphorus (P) fate and transport is an emergent problem impacting environmental resources. Long time land application of P enriched manure has been implicated in the saturation of available P binding sites in many terrestrial, wetland and sediment systems. Transport of soluble or particle associated P by overland flow and possibly by subsurface leaching has increased eutrophication in waterways. So-inositol hcxkis phosphate or more commonly phytic acid (PA) is an organic phosphate molecule with twelve acidic protons. The acid dissociation constants (pKa) are 1.9(3), 2.4(2), 3.2(1), 5.2(l), 6.3(l), 8.0(1), 9.2( 1) and 9.5(2). The charged species fractions were calculated as a function of pH using the acid dissociation constants.
    [Show full text]
  • On-Line Time-Of-Flight Mass Spectrometric Analysis of Peptides Separated by Capillary Electrophoresis
    Anal. Chem. 1994,66, 3696-3701 On-Line Time-of-Flight Mass Spectrometric Analysis of Peptides Separated by Capillary Electrophoresis Llllng Fang, Rong Zhang, Evan R. Wllllams,t and Rlchard N. Zare' Department of Chemistry, Stanford University, Stanford, California 94305 Time-of-flight mass spectrometry (TOFMS) is coupled on- course of a CE peak. One way to implement this strategy is line with capillary electrophoresis (CE) to analyze mixtures to use time-of-flight mass spectrometry (TOFMS), which has of biomolecules using an electrospray ionization (ESI) inter- the advantages of high speed, simplicity, and high sensitivity. face. The eluent is electrosprayed directly from the CE capillary In this study, we use a linear TOFMS with a MS resolution using a thin gold wire to maintain its potential. The ions are of 100; however, the use of a reflectron design9 would offer extracted at right angles to the initial direction of the ion beam, mass resolution of more than 2000. ESI was first combined and a complete mass spectrum is recorded every 100 ~s.This with TOFMS by Dodonov, Chernushevich, and Laiko,lo who CE/ESI-TOFMS apparatus achieves a separation efficiency used an orthogonal ion extraction geometry. Subsequently, of 50 000 theoretical plates with a concentration detection several approaches for combining these techniques have been limit of (1-2) X molar, which corresponds to a mass reported."-16 detection limit of approximately 40-80 fmol per component. The major challenge to using ESI-MS as an on-line detector for CE separations is the provision of electrical contact at the Mass spectrometric detection of analytes separated by capillary outlet.
    [Show full text]
  • Atmospheric Pressure Chemical Ionization (APCI): Less Polar
    LC-MS Based Metabolomics AnalysingAnalysing thethe METABOLOMEMETABOLOME 1.1. MetaboliteMetabolite ExtractionExtraction 2.2. MetaboliteMetabolite detectiondetection (with(with oror withoutwithout separation)separation) 3.3. DataData analysisanalysis MetaboliteMetabolite DetectionDetection GC-MS: Naturally volatile or made volatile (any organic- flavors, sugars, lipids, acids) NMR – any compound containing hydrogen HP Liquid - Chromatography + detector Comon detectors- - UV-detector (phenolics) - MASS SPECTROMETER (MS) as detector (LC-MS) MetaboliteMetabolite DetectionDetection MASS SPECTROMETER (MS) as detector (LC-MS): Compounds that are not well characterized by other methods: Non volatile High molecular weight Too sensitive to heat to be analyzed by GC Your Result Sample LC/MS Sample Sample Efficient Separation Preparation Introduction Gradient (column) Data (computer) LC- MS Ions Ions Ionization UV Detection Separation MS Interface Spectra Today ComponentsComponents inin LCLC--MSMS Ion Ion Formation Sorting PeptiPeptiddee && ProteinProtein SeqSequuenciencinngg Compound ID APcI Analyzer Software LC Structure Elucidation ESI & Detector Quantitation Interface: Chemical Triple Quadrupole Atmospheric Results Separation Quadrupole -Time Of Flight Pressure Quadrupole - Ion-Trap Ionization FT-MS MassMass SpectrometerSpectrometer 1. Breaks up constituents into molecular ions and other fragments 2. The ions then pass through an electric and/or magnetic field that separates them according to their mass-to-charge ratio (m/z) 3. Measures masses MassMass SpectrometerSpectrometer 4. Universal detection method * compared to UV/VIS (PDA), fluorescence etc. * more specific than NMR 5. More sensitive for most compounds 6. Structural information on metabolite * fragmentation pattern * accurate mass 7. For both LC and GC TechnologyTechnology ofof LCLC--MSMS andand LCLC--MSMS--MSMS –– InterfacesInterfaces-- IonizationIonization (elimination(elimination ofof solventsolvent andand generationgeneration ofof gasgas--phasephase ions)ions) –– e.g.e.g.
    [Show full text]