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Title: Speciation of chromium and manganese using pneumatically assisted electrospray mass spectrometry

Abstract

It is not an exaggeration to say that much of chemistry involves ions in solution. A technique which allows for ions to be transferred from solution into the gas phase and subsequently analyzed by mass spectrometric detection would be of importance. If structural information, representative of the solution chemistry could be gained from these gas-phase ions, this would also be important. Electrospray mass spectrometry (ES-MS) is such a technique.

Authors:
 [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
519128
Report Number(s):
IS-T-1799
ON: DE97002921; TRN: 97:004934
DOE Contract Number:
W-7405-ENG-82
Resource Type:
Thesis/Dissertation
Resource Relation:
Other Information: TH: Thesis (Ph.D.); PBD: [1997]
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CHROMIUM; MASS SPECTRA; AQUEOUS SOLUTIONS; CHEMICAL COMPOSITION; MANGANESE; MASS SPECTROMETERS; IONIZATION; ELECTRIC FIELDS

Citation Formats

Gwizdala, III, Albin B. Speciation of chromium and manganese using pneumatically assisted electrospray mass spectrometry. United States: N. p., 1996. Web. doi:10.2172/519128.
Gwizdala, III, Albin B. Speciation of chromium and manganese using pneumatically assisted electrospray mass spectrometry. United States. doi:10.2172/519128.
Gwizdala, III, Albin B. Thu . "Speciation of chromium and manganese using pneumatically assisted electrospray mass spectrometry". United States. doi:10.2172/519128. https://www.osti.gov/servlets/purl/519128.
@article{osti_519128,
title = {Speciation of chromium and manganese using pneumatically assisted electrospray mass spectrometry},
author = {Gwizdala, III, Albin B.},
abstractNote = {It is not an exaggeration to say that much of chemistry involves ions in solution. A technique which allows for ions to be transferred from solution into the gas phase and subsequently analyzed by mass spectrometric detection would be of importance. If structural information, representative of the solution chemistry could be gained from these gas-phase ions, this would also be important. Electrospray mass spectrometry (ES-MS) is such a technique.},
doi = {10.2172/519128},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Oct 17 00:00:00 EDT 1996},
month = {Thu Oct 17 00:00:00 EDT 1996}
}

Thesis/Dissertation:
Other availability
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  • The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide varietymore » of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.« less
  • Conjugated dienes were oxidized by hydrogen peroxide with methylrhenium trioxide (MTO) as catalyst. Methylrhenium bis-peroxide was the major reactive catalyst present. Hydroxyalkenes and trisubstituted silane were also tested. Mechanisms for each of these reactions are presented.
  • Suppression of mass spectral peaks due to matrix problem is a major hurdle to overcome during identification work. So far, preliminary studies have been done in investigating solutions containing various percentages of nitric and hydrochloric acid. Since other anions would also be present in real samples, also needed to be examined is how the extent of suppression of metal complexes by Cl - compares with suppression by other anions such as PO 4 3- or SO 4 2-. If suppression of other anions is as severe as that of the chloride ion, then it would be virtually impossible to analyzemore » unknown samples containing large amount of such anions by direct infusion electrospray mass spectrometry. It seems like a separation step is needed to separate these matrix anions from the metal complexes prior to putting the solution through the electrospray. However, separation of inorganic complexes can be difficult and has not been studied thoroughly as LC separation of bioorganic compounds. Both zinc and copper chloro complexes have been observed to be more tolerant to higher amount of chloride ion present in a solution compared to the group I and II metal chloro complexes. Other transition metals including the lanthanide complexes need to be examined more intensively to see how they fare against other transition metal complexes. So far, only preliminary work has been done in identifying inorganic species in solutions using both ICP-MS and ES-MS. The solution contained a number of metals but only one major anion, NO 3 -. Therefore, complex solutions containing a number of anions and metals can be examined to see if identification is still feasible. This identification work can be continued on into investigating real samples.« less
  • This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigatemore » toxic metal binding to the [Gln 11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will become routine tomorrow.« less
  • Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able tomore » analyze samples at the single cell level.« less