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Author: Bryan C. Katzenmeyer Publisher: ISBN: Category : Chemistry Languages : en Pages : 301
Book Description
This dissertation focuses on utilizing mass spectrometry (MS) and tandem mass spectrometry (MS/MS), combined with the coupling of liquid chromatography (LC) and/or ion mobility (IM) spectrometry, to characterize polymeric materials. Chapter II will introduce history and basic principles of mass spectrometry and liquid chromatography including background on instrumentation and theory. Chapter III will discuss the materials and instrumentation used in the various projects. Chapters IV-VII are research project chapters as described below. Lastly, Chapter VIII concludes this dissertation with a summary. Following the last chapter are appendices with supplemental data and copyright permissions for this dissertation. Chapter IV details the characterization of two nonionic surfactants consisting of a methoxylated glucose core (glucam) that was either chain-extended with ethylene oxide and then esterified with stearic acid to generate poly(ethylene oxide) glucam stearate(s) or only esterified with stearic acid which made glucam stearate(s). The use of LC-MS, LC-MS/MS, IM-MS, and MS/MS made it possible to separate and determine the compositions for each component in the mixtures resulting from the synthesis of these amphiphilic polymers. Components of (PEO)n-glucam stearate(s) were readily separated by their hydrophobicity and degrees of esterification by LC-MS and IM-MS. Each method offers complementary information, with LC-MS excelling in the separation and characterization of highly hydrophobic amphiphilles and IM-MS provides a quicker analysis of minor trace components. Electron transfer dissociation (ETD) was also applied as a novel MS/MS application to poly(ethylene oxide) glucam stearate(s). However, when compared to traditional MS/MS activation techniques (collisionally activated dissociation (CAD)), ETD unveiled no significant structural information when compared to CAD activation of the same oligomer. Specifically, ETD caused no unique cleavages across the sugar core as seen in oligosaccharide systems. In Chapter V, several homopolymers of poly(dimethylsiloxane) (PDMS) with different polymer end groups were studied by MS/MS. Detailed CAD mass spectra of PDMS homopolymers containing [alpha, omega] -bis(hydroxyl)-, [alpha, omega] -bis(3-aminopropyl)-, and [alpha, omega] -bis(ethoxy)- end groups are reported herein. MS/MS spectra indicate that chargeremote intramolecular rearrangements, H-atom abstraction, and intramolecular nucelophilic substitutions give rise to the fragments seen from the PDMS polymers studied. PDMS end groups are found to significantly influence the fragmentation pathways of energetically excited precursor ions from these type of polymers. Chapter VI of this dissertation discusses the MS and MS/MS characterization of several poly(phosphazene)s. Higher order cyclic poly(dichlorophosphazene)s and poly(bis(phenoxy)phosphazene) were analyzed. The MS/MS fragmentation pattern of poly(bis(phenoxy)phosphazene) indicated that this polymer had a tadpole architecture. Based on both the positive and negative ion MS/MS data, lateral chain fragmentation dominates in all cases and losses of bis(phenoxy)phosphazene are observed from oligomers having a tale larger than the trimer. Only in negative mode can the cyclic trimer ring open via charge-induced dissociation and expel one unit of bis(phenoxy)phosphazene. These data provide strong additional evidence that these polymers form a tadpole architecture. Lastly, in Chapter VII three polyesters were studied. Two homopolymers, poly(lactide) (PLA) and poly(glycolide) (PGA), and one copolymer, poly(lactide-coglycolide) (PLGA). Oligomers of PLA undergo a series of 1,5-hydrogen rearrangement (1,5-rH) reactions. Whereas oligomers of PGA fragment via intramolecular transesterifications. The PLGA copolymer was found to contain cyclic and linear (with HO- and -H end groups) copolymers. Fragmentation proceeded via 1,5-rH reactions that opened the cyclic copolymer and intramolecular transesterifications. In the case of linear copolymers containing at least two glycolide units, the MS/MS spectra provide direct information on the block length of each monomer.
Author: Bryan C. Katzenmeyer Publisher: ISBN: Category : Chemistry Languages : en Pages : 301
Book Description
This dissertation focuses on utilizing mass spectrometry (MS) and tandem mass spectrometry (MS/MS), combined with the coupling of liquid chromatography (LC) and/or ion mobility (IM) spectrometry, to characterize polymeric materials. Chapter II will introduce history and basic principles of mass spectrometry and liquid chromatography including background on instrumentation and theory. Chapter III will discuss the materials and instrumentation used in the various projects. Chapters IV-VII are research project chapters as described below. Lastly, Chapter VIII concludes this dissertation with a summary. Following the last chapter are appendices with supplemental data and copyright permissions for this dissertation. Chapter IV details the characterization of two nonionic surfactants consisting of a methoxylated glucose core (glucam) that was either chain-extended with ethylene oxide and then esterified with stearic acid to generate poly(ethylene oxide) glucam stearate(s) or only esterified with stearic acid which made glucam stearate(s). The use of LC-MS, LC-MS/MS, IM-MS, and MS/MS made it possible to separate and determine the compositions for each component in the mixtures resulting from the synthesis of these amphiphilic polymers. Components of (PEO)n-glucam stearate(s) were readily separated by their hydrophobicity and degrees of esterification by LC-MS and IM-MS. Each method offers complementary information, with LC-MS excelling in the separation and characterization of highly hydrophobic amphiphilles and IM-MS provides a quicker analysis of minor trace components. Electron transfer dissociation (ETD) was also applied as a novel MS/MS application to poly(ethylene oxide) glucam stearate(s). However, when compared to traditional MS/MS activation techniques (collisionally activated dissociation (CAD)), ETD unveiled no significant structural information when compared to CAD activation of the same oligomer. Specifically, ETD caused no unique cleavages across the sugar core as seen in oligosaccharide systems. In Chapter V, several homopolymers of poly(dimethylsiloxane) (PDMS) with different polymer end groups were studied by MS/MS. Detailed CAD mass spectra of PDMS homopolymers containing [alpha, omega] -bis(hydroxyl)-, [alpha, omega] -bis(3-aminopropyl)-, and [alpha, omega] -bis(ethoxy)- end groups are reported herein. MS/MS spectra indicate that chargeremote intramolecular rearrangements, H-atom abstraction, and intramolecular nucelophilic substitutions give rise to the fragments seen from the PDMS polymers studied. PDMS end groups are found to significantly influence the fragmentation pathways of energetically excited precursor ions from these type of polymers. Chapter VI of this dissertation discusses the MS and MS/MS characterization of several poly(phosphazene)s. Higher order cyclic poly(dichlorophosphazene)s and poly(bis(phenoxy)phosphazene) were analyzed. The MS/MS fragmentation pattern of poly(bis(phenoxy)phosphazene) indicated that this polymer had a tadpole architecture. Based on both the positive and negative ion MS/MS data, lateral chain fragmentation dominates in all cases and losses of bis(phenoxy)phosphazene are observed from oligomers having a tale larger than the trimer. Only in negative mode can the cyclic trimer ring open via charge-induced dissociation and expel one unit of bis(phenoxy)phosphazene. These data provide strong additional evidence that these polymers form a tadpole architecture. Lastly, in Chapter VII three polyesters were studied. Two homopolymers, poly(lactide) (PLA) and poly(glycolide) (PGA), and one copolymer, poly(lactide-coglycolide) (PLGA). Oligomers of PLA undergo a series of 1,5-hydrogen rearrangement (1,5-rH) reactions. Whereas oligomers of PGA fragment via intramolecular transesterifications. The PLGA copolymer was found to contain cyclic and linear (with HO- and -H end groups) copolymers. Fragmentation proceeded via 1,5-rH reactions that opened the cyclic copolymer and intramolecular transesterifications. In the case of linear copolymers containing at least two glycolide units, the MS/MS spectra provide direct information on the block length of each monomer.
Author: Nadrah Alawani Publisher: ISBN: Category : Chemistry Languages : en Pages : 238
Book Description
This dissertation focuses on coupling mass spectrometry (MS) and tandem mass spectrometry (MS/MS) to thermal degradation, liquid chromatography (LC) and/or ion mobility (IM) spectrometry for the characterization of complex mixtures. In chapter II, an introduction of the history and the principles of mass spectrometry (MS) and liquid chromatography (LC) are discussed. Chapter III illustrates the materials and instrumentation used to complete this dissertation. Polyethers have been characterized utilizing tandem mass spectrometry (MS/MS), as presented in Chapter IV and Chapter VI. Diblock copolymers of polyethylene oxide and polycaprolactone, PEO-b-PCL, have been characterized by matrix-assisted laser desorption/ionization quadrupole/time-of-flight mass spectrometry (MALDI-Q/ToF) and LC-MS/MS (Chapter V). Thermoplastic elastomers have been characterized by thermal degradation using an atmospheric solids analysis probe (ASAP) and ion mobility mass spectrometry (IM-MS), as discussed in Chapter VII. Interfacing separation techniques with mass spectrometry permitted the detection of species present with low concentration in complex materials and improved the sensitivity of MS. In chapter IV, the fragmentation mechanisms in MS/MS experiments of cyclic and linear poly(ethylene oxide) macroinitiators are discussed. This study aimed at determining the influence of end groups on the fragmentation pathways. In the study reported in Chapter V, ultra high performance liquid chromatography (UHPLC) was interfaced with MS and MS/MS to achieve the separation and in-depth characterization and separation of amphiphilic diblock copolymers (PEO-b-PCL) in which the architecture of the PEO block is linear or cyclic. Applying UPLC-MS and UPLC-MS/MS provides fast accurate information about the number and type of the blocks in the copolymers. Chapter VI reports MS/MS and IM-MS analyses which were performed to elucidate the influence of molecular size and collision energy on the fragmentation pathways of polyethers subjected to collisionally activated dissociation (CAD). Survival yields and collision cross-sections were derived for several oligomers of polybutylene oxide (PBO) and polytetrahydrofuran (PTHF) polymers by MS/MS and IM-MS, in order to understand their fragmentation energetics and fully characterize their structures. In Chapter VII, application of atmospheric solids analysis probe (ASAP) and ion mobility (IM) separation were coupled with mass spectrometry (MS) and tandem mass spectrometry (MS/MS) to characterize commercially available thermoplastic elastomers. These compounds are mainly composed of thermoplastic copolymers, but also contain additional chemicals to enhance their properties or to protect them from degradation. Using ASAP-IM-MS enables fast analysis, involving mild degradation at atmospheric pressure (ASAP) and subsequent characterization of the desorbates and pyrolyzates by ion mobility mass spectrometry (IM-MS) and tandem mass spectrometry (MS/MS). Such multidimensional dispersion considerably simplifies the resulting spectra, permitting the conclusive separation and characterization of the multicomponent materials examined. Chapter VIII summarizes the findings of this dissertation and is followed by appendices with supplemental data and the copyright permissions obtained for this dissertation.
Author: Nilüfer Solak Publisher: ISBN: Category : Chemistry, Analytic Languages : en Pages : 221
Book Description
"This dissertation focuses on coupling liquid chromatography (LC) and/or ion mobility (IM) spectrometry to mass spectrometry (MS) and their application to characterization of complex mixtures. Fatty acid ethyl esters (FAEEs) in meconium, polyethylene oxide (PEO) copolymers, the nonionic surfactant Polysorbate 85, and poly(butylene adipate) were characterized by LC-MS[superscript n] and/or IMMS[superscript n]. Coupling of a separation technique to mass spectrometry improves the sensitivity of MS, thus permitting the detection of species present in low concentration. FAEEs are metabolites of ethanol. They are formed by nonoxidative metabolization of ethanol. FAEEs accumulate in various tissues. Ethanol can easily penetrate the placenta and results in the formation and deposition of FAEEs in fetal tissues including meconium. Therefore, FAEEs may be used as biomarkers for heavy alcohol consumption during pregnancy. In the first chapter of this dissertation (chapter 4), FAEEs were extracted from meconium and analyzed by LC-MS to determne the amount of ethyl linoleate, ethyl oleate, and ethyl palmitate. Among the fifty samples run, two were from mothers who had admitted alcohol consumption during pregnancy and those samples were found to contain high amounts of ethyl linoleate and ethyl palmitate. In the follow chapter of this dissertation (chapter 5), tandem mass spectrometry analyses were performed on PEO oligomers to elucidate their fragmentation pathways. These mechanisms derived the structural elucidation of the PEO copolymers analyzed by LC-MS[superscript n] in subsequent studies, as itemized below. In chapter 6, different chain lengths of a PEO-poly(propylene oxide) (PPO) triblock and a PEO-PPO random copolymer was separated and identified by LC-MS[superscript n]. Separation of the oligomers were based on their propylene oxide (PO) content. Oligomers with higher PO content had longer retention times. A putative PEO-poly(dimethylsiloxane) block copolymer was also investigated; in this case, unexpected minor byproducts/starting materials which could not be observed by MS were detected and identified using the LC-MS[superscript n] technique. Chapter 7 focuses on the LC-MS[superscript n] characterization of a commercial surfactant, Polysorbate 85. It is composed of many species with different degrees of esterification. Some of those species have identical nominal masses which complicates their characterization by MS. Therefore, a separation technique is needed prior to MS analysis. Reverse phase LC separated the oligomers based on their hydrophilicity/hydrophobicity. In addition, LC-MS2 experiments unveiled the esterification degree of the oligomers. A novel technique, IMMS, was also employed for characterization of the constituents of Polysorbate 85. IMMS disperses ions according to their collision cross sections and charge states. Oligomers with a different number of ester moieties could be separated and identified. Finally, Chapter 8 reports how IMMS was used to disperse and characterize linear and cyclic poly(butylene adipate) oligomers. The separation of the oligomers was based on their charge states. IMMS improved the sensitivity of MS and permitted the detection of +3 and +4 charged ions which were undetectable in the single-stage mass spectrum."--Abstract.
Author: Harald Pasch Publisher: Springer Science & Business Media ISBN: 3642360807 Category : Technology & Engineering Languages : en Pages : 291
Book Description
This book presents the principle ideas of combining different analytical techniques in multi-dimensional analysis schemes. It reviews the basic principles and instrumentation of multi-dimensional chromatography and the hyphenation of liquid chromatography with selective spectroscopic detectors and presents experimental protocols for the analysis of complex polymers. It is the consequent continuation of "HPLC of Polymers" from 1999 by the same authors. Like its 'predecessor', this book discusses the theoretical background, equipment, experimental procedures and applications for each separation technique, but in contrast treats multi-dimensional and coupled techniques. "Multidimensional HPLC of Polymers" intends to review the state of the art in polymer chromatography and to summarize the developments in the field during the last 15 years. With its tutorial and laboratory manual style it is written for beginners as well as for experienced chromatographers, and will enable its readers (polymer chemists, physicists and material scientists, as well as students of polymer and analytical sciences) to optimize the experimental conditions for their specific separation problems.
Author: Dwight R. Stoll Publisher: CRC Press ISBN: 1000817334 Category : Science Languages : en Pages : 401
Book Description
Two-dimensional liquid chromatography (2D-LC) is finding increasingly wide application principally due to the analysis of mixtures of moderate to high complexity. Many industries are developing increasingly complex products that are challenging the separation capabilities of state-of-the-art 1D-LC and need new analytical methodologies with substantially more resolving power, and 2D-LC meets that need. This text, organized by two leaders in the field, establishes a sound fundamental basis for the principles of the technique, followed by a discussion of important practical considerations. The book begins with an introduction to multi-dimensional separations and a discussion of the history and development of the technique over the past 40 years, followed by several chapters that provide a theoretical basis for development of 2D-LC methods, including foundational concepts regarding separation complementarity, under-sampling, and dynamics of liquid chromatography separations. Instrumentation for 2D-LC is discussed extensively, including practical aspects such as interface selection and setup. Building on this foundation, two separate chapters are focused on method development for non-comprehensive and comprehensive separations, followed by a chapter dedicated to data analysis. Finally, applications of 2D-LC in several fields ranging from pharmaceutical analysis to polymer science are summarized. The book is an important resource for both students and practitioners who are already using 2D-LC or are interested in getting started in the field. Key Features: Demonstrates the conditions under which a 2D-LC method should be considered as an alternative to a 1D-LC method Establishes a sound fundamental basis of the principles of the technique, followed by guidelines for method optimization Provides a single source for technical knowledge advances and practical guidance described in recent literature Assists with the initial decision to develop a 2D-LC method Guides the reader in developing a high-quality method that meets the needs of their application
Author: Danijela Smiljanic Publisher: ISBN: Category : Chemistry Languages : en Pages : 154
Book Description
This dissertation focuses on coupling separation techniques such as ion mobility (IM) and liquid chromatography (LC) to mass spectrometry and their application to characterization of complex mixtures. Non-covalent complexes between poly(ethylene imine) (PEI) and single stranded oligodeoxynucleotides (ODNs), as well as components from black raspberries, were characterized utilizing ion mobility mass spectrometry (IM-MS) and liquid chromatography mass spectrometry (LC-MS), respectively. Interfacing these separation methods to mass spectrometry allows for detection and identification of isobaric species and species present in low concentration. Non-covalent complexes between low molecular weight poly(ethylene imine) (PEI 400 and 800) and single-stranded oligodeoxynucleotides (ODNs) were investigated for five ODNs, including d(TTTTT), d(CCCCC), d(AAAAA), d(GGGGG) and d(GCGAT). In chapter 4 the compositions, as well as solution and gas-phase stabilities of the complexes (termed polyplexes) were examined by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS2). Independent of the mixing ratio of the reactants, the polyplex with 1:1 polymer-to-nucleotide stoichiometry, PN, is the dominant product. The gas-phase stabilities, assessed by MS2 and collisionally activated dissociation, follow the same order, providing evidence that the polyplex structures in aqueous solution and the more hydrophobic environment of the gas phase are very similar. Non-covalent complexes with different composition but the same molecular mass were corroborated by ion mobility mass spectrometry (IM-MS). In chapter 5 of this dissertation an investigation of the expanded non-covalent system, ternary complexes, of poly(ethylene imine), single-stranded oligodeoxynucleotides and glutamic acid entities, is discussed. The solution stabilities and gas-phase stabilities of the ternary complexes (termed terplexes) were examined by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS2). In addition, higher order ternary structures with multiple units of polymer and/or nucleotide present within the terplex were identified utilizing IM-MS. Finally, chapter 6 provides information on characterization of non-anthocyanin components from black raspberry fractions by interfacing liquid chromatography (LC) to mass spectrometry. The black raspberry extracts were provided from the lab of Dr. Joseph C. Scheerens at Ohio Agricultural Research and Development Center, Wooster, Ohio. Combination of LC-MS, ESI-MS and MS2 provided structural information for the corresponding components.
Author: W. Radke Publisher: Elsevier Inc. Chapters ISBN: 0128071109 Category : Science Languages : en Pages : 55
Book Description
In the last decade, the use of interaction chromatography and hyphenated techniques has become increasingly important for the characterization of polymeric materials. Interaction chromatography allows separation by other structural features than molar mass, while hyphenation with mass spectroscopy or spectroscopic techniques provides detailed characterization of the separated chromatographic fractions. This chapter gives an overview of the principles and applications of interaction chromatography and the information that can be determined by hyphenation of polymer chromatography with mass spectrometry and spectroscopic techniques.
Author: Alexandre A. Shvartsburg Publisher: CRC Press ISBN: 9781420051070 Category : Science Languages : en Pages : 322
Book Description
Over the last decade, scientific and engineering interests have been shifting from conventional ion mobility spectrometry (IMS) to field asymmetric waveform ion mobility spectrometry (FAIMS). Differential Ion Mobility Spectrometry: Nonlinear Ion Transport and Fundamentals of FAIMS explores this new analytical technology that separates and characterizes ions by the difference between their mobility in gases at high and low electric fields. It also covers the novel topics of higher-order differential IMS and IMS with alignment of dipole direction. The book relates the fundamentals of FAIMS and other nonlinear IMS methods to the physics of gas-phase ion transport. It begins with the basics of ion diffusion and mobility in gases, covering the main attributes of conventional IMS that are relevant to all IMS approaches. Building on this foundation, the author reviews diverse high-field transport phenomena that underlie differential IMS. He discusses the conceptual implementation and first-principles optimization of FAIMS as a filtering technique, emphasizing the dependence of FAIMS performance metrics on instrumental parameters and properties of ion species. He also explores ion reactions in FAIMS caused by field heating and the effects of inhomogeneous electric field in curved FAIMS gaps. Written by an accomplished scientist in the field, this state-of-the-art book supplies the foundation to understand the new technology of nonlinear IMS methods.
Author: Steven A. Cohen Publisher: John Wiley & Sons ISBN: 0470276258 Category : Science Languages : en Pages : 490
Book Description
Multidimensional Liquid Chromatography (MDLC) is a very powerful separation technique for analyzing exceptionally complex samples in one step. This authoritative reference presents a number of recent contributions that help define the current art and science of MDLC. Topics covered include instrumentation, theory, methods development, and applications of MDLC in the life sciences and in industrial chemistry. With the information to help you perform very difficult separations of complex samples, this reference includes chapters contributed by leading experts or teams of experts.
Author: Harald Pasch Publisher: Springer Science & Business Media ISBN: 3642582656 Category : Technology & Engineering Languages : en Pages : 234
Book Description
Polymers are mainly characterized by molar mass, chemical composition, functionality and architecture. The determination of the complex structure of polymers by chromatographic and spectroscopic methods is one of the major concerns of polymer analysis and characterization. This lab manual describes the experimental approach to the chromatographic analysis of polymers. Different chromatographic methods, their theoretical background, equipment, experimental procedures and applications are discussed. The book will enable polymer chemists, physicists and material scientists as well as students of macromolecular and analytical science to optimize chromatographic conditions for a specific separation problem. Special emphasis is given to the description of applications for homo- and copolymers and polymer blends.
Author: Bryan C. Katzenmeyer
Author: Bryan C. Katzenmeyer
Author: Nadrah Alawani
Author: Nilüfer Solak
Author: Harald Pasch
Author: Dwight R. Stoll
Author: Danijela Smiljanic
Author: W. Radke
Author: Alexandre A. Shvartsburg
Author: Steven A. Cohen
Author: Harald Pasch