Gas Phase Studies of Organic and Biological Species Using Mass Spectrometry

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ISBN 13 :
Total Pages : 100 pages
Book Rating : 4.:/5 (889 download)

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Book Synopsis Gas Phase Studies of Organic and Biological Species Using Mass Spectrometry by : Mu Chen

Download or read book Gas Phase Studies of Organic and Biological Species Using Mass Spectrometry written by Mu Chen and published by . This book was released on 2014 with total page 100 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Gas Phase Reactivity Studies of Organic Species Using Mass Spectrometry

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ISBN 13 :
Total Pages : 57 pages
Book Rating : 4.:/5 (83 download)

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Book Synopsis Gas Phase Reactivity Studies of Organic Species Using Mass Spectrometry by : Sisi Zhang

Download or read book Gas Phase Reactivity Studies of Organic Species Using Mass Spectrometry written by Sisi Zhang and published by . This book was released on 2012 with total page 57 pages. Available in PDF, EPUB and Kindle. Book excerpt: DNA damaged bases are one of the reasons for a variety diseases, such as carcinogenesis, aging and cell death. uracil is a nucleobase that arises from cytosine deamination. N-Deprotonated uracil functions as a leaving group during the deamination process. Theoretically, in the SN2 reaction, leaving group ability tracks with pKa of the conjugate acid in the solution phase, that is, lower pKa is associated with better leaving group ability. In the gas phase, leaving group ability is better with higher acidity of the conjugate acid. The studies we did previously showed that although 3-methyluracil is as acidic as hydrochloric acid in the gas phase, the leaving group ability of chloride is better than deprotonated 3-methyluracil. The reason we propose this is that the electron delocalization in the transition state of SN2 reaction cannot be fully recognized as in acidity. Therefore, we designed substituted aniline and amine with leaving groups with or without the ability of electron delocalization and found that substituted amine with leaving groups that did not have the ability of electron delocalization tracked better with acidity than the one with the ability of electron delocalization. The result is consistent with our proposal. We also tested the Hammond postulate with the calculation results. Another focus of interest is N-heterocyclic singlet carbenes (NHCs), which are ligands of a variety of organometallic catalysts. Presumably the ligands are more effective if they are more basic, that is, with higher proton affinity. The protonated carbenes are also an important class of ionic liquids, known as green solvents with several advantages over traditional organic solvents. Strassner et al designed a new type of ionic liquid imidazolium salt with tunable para-aryl substituent, and we measured the acidity of these tunable aryl-alkyl ionic liquids (TAAILs). The proton-bound dimers of dimethyl imidazole and PCy3 are found to exhibit interesting reactivity. In addition to producing just protonated carbenes and protonated phosphine with collision induced dissociation (CID), the proton-bound dimers generate another ion of interest with m/z 295. We designed and synthesized the di-CD3 imidazole, and proved that the dimethyl system undergoes phosphine methylation during CID process.

Modern Mass Spectrometry

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Publisher : Springer Science & Business Media
ISBN 13 : 3540000984
Total Pages : 318 pages
Book Rating : 4.5/5 (4 download)

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Book Synopsis Modern Mass Spectrometry by : Peter B. Armentrout

Download or read book Modern Mass Spectrometry written by Peter B. Armentrout and published by Springer Science & Business Media. This book was released on 2003-06-23 with total page 318 pages. Available in PDF, EPUB and Kindle. Book excerpt: I Reactivity: E. Uggerud: Physical Organic Chemistry of the Gas Phase. Reactivity Trends for Organic Cations.- S. Petrie, D.K. Bohme: Mass Spectrometric Approaches to Interstellar Chemistry.- F. Turecek: Transient Intermediates of Chemical Reactions by Neutralization-Reionization Mass Spectrometry.- II Metalorganic Chemistry: D. Schröder, H. Schwarz: Diastereoselective Effects in Gas-Phase Ion Chemistry.- D.A. Plattner: Metalorganic Chemistry in the Gas Phase: Insight into Catalysis.- III Mass Spectrometric Methodology: T. Wyttenbach, M.T. Bowers: Gas-Phase Conformations: The Ion Mobility/Ion Chromatography Method.- P.B. Armentrout: Threshold Collision-Induced Dissociations for the Determination of Accurate Gas-Phase Binding Energies and Reaction Barriers.- IV Medicinal Chemistry: S.A. Trauger, T. Junker, G. Siuzdak: Investigating Viral Proteins and Intact Viruses with Mass Spectrometry M. Brönstrup: High-Throughput Mass Spectrometry for Compound Characterization in Drug Discovery.

Gas Phase Studies of N-heterocyclic Organic Species Using Mass Spectrometry

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ISBN 13 :
Total Pages : 96 pages
Book Rating : 4.:/5 (889 download)

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Book Synopsis Gas Phase Studies of N-heterocyclic Organic Species Using Mass Spectrometry by : Kai Wang

Download or read book Gas Phase Studies of N-heterocyclic Organic Species Using Mass Spectrometry written by Kai Wang and published by . This book was released on 2014 with total page 96 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation focuses on the examination of thermochemical properties, including gas phase acidities, proton affinities and tautomerism of two types of N-heterocyclic organic species: damaged nucleobases and 1,2,3-triazoles via mass spectrometry methods (bracketing method on FTMS and Cooks kinetics method on LCQ) and theoretical studies (quantum mechanical calculations). Reactivities of N-heterocyclic carbenes as organocatalysts were also studied in the gas phase. 3-Methyladenine DNA glycosylase II (AlkA), which is found in Escherichia coli, is an enzyme that cleaves a wide range of damaged nucleobases from DNA. Herein we study the 3-methylated AlkA purine substrates, 3-methyladenine, non-substituted purine and and a potential AlkA substrate, 6-chloropurine. We found that the damaged nucleobases are more acidic than normal nucleobases. Resulting from this increasing of acidity, it is expected that damaged nucleobases are easier to be cleaved from the DNA chain since their conjugate bases should be better leaving groups. We also find that the gas phase acidities correlate with AlkA excision rate. Thus, the results lend support to the theory that AlkA differentiates among substrates by cleaving those nucleobases which are the most facile to remove. We also focus on studying the gas phase properties of 1,2,3-triazoles, which, compared with their applications, are largely unknown. The gas phase acidities and proton affinities of benzotriazole, 4-phenyl-1,2,3-triazole, substituted 4-phenyl-1,2,3-triazoles are discussed herein. Moreover, the tautomerism prevalence of 4-phenyl-1,2,3-triazole is acertained by ion-molecule reaction coordinate analysis and H/D exchange studies. In order to study the reaction mechanism of N-heterocyclic carbenes catalyzed reactions such as benzoin condensation, we synthesized a thiazolium catalyst with ethyl sulfonyl group on C4 position of five-membered thiazolium ring. Upon deprotonation, the thiazolium-based carbene is given a negative charge, which renders the visibility for both the carbene and reaction intermediates via mass spectrometry. We herein isolate and study the fragmentation pattern of both free carbene and reaction intermediates using ESI-MS/MS technique. As comparison, we also employ an imidazolium-based NHC to study the benzoin condensation via mass spectrometry and characterize the catalyst as well as the intermediates.

Gas Phase Acidity and Proton Affinity Studies of Organic Species Using Mass Spectrometry

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ISBN 13 :
Total Pages : 147 pages
Book Rating : 4.:/5 (773 download)

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Book Synopsis Gas Phase Acidity and Proton Affinity Studies of Organic Species Using Mass Spectrometry by : Min Liu

Download or read book Gas Phase Acidity and Proton Affinity Studies of Organic Species Using Mass Spectrometry written by Min Liu and published by . This book was released on 2011 with total page 147 pages. Available in PDF, EPUB and Kindle. Book excerpt: DNA bases can be chemically or photochemically damaged from a variety of endogenous and exogenous sources. Such damaged bases are linked to carcinogenesis, aging and cell death. One of our main focuses is to examine the intrinsic reactivity of normal and damaged nucleobases in order to find out how damaged bases are different from normal bases. Particularly in this thesis we are interested in the thermochemical properties (acidity and proton affinity) of damaged bases 1, N6-ethenoadenine (eA) and O6-methylguanine (OMG). eA is one of the damaged nucleobases which can be excised by alkyladenine DNA glycosylase (AAG) in humans. We find that the N9-H of eA is more acidic than adenine and guanine, which might indicate that AAG may cleave certain damaged nucleobases as anions and deprotonated damaged bases are better leaving groups than normal adenine and guanine. Also the active site may take advantage of a nonpolar environment to favor deprotonated eA as a better leaving group than adenine and guanine. In addition we find the N9-H of OMG is less acidic than adenine and guanine. This result is consistent with the fact that OMG is not one of the substrates of AAG. Besides the damaged bases, we also studied the thermochemical properties and tautomerism of normal pyrimidine bases cytosine and thymine, because the first step to understand how damaged bases differ from normal bases is to characterize the naturally occurring normal compounds. One of our focuses is gas phase acidity studies of organic silanols and some known hydrogen-bonding organocatalysts. This project is in collaboration with Professor Annaliese Franz at UC Davis, who develops a series of organic silanols used as a new class of hydrogen bonding catalysts for enantioselective carbon-carbon bond forming reactions. It is generally accepted that silanols are more acidic than their carbon analogs, but we have found the theoretical carbon diol analogs are actually more acidic than silicon diols depending on substitution and structure. Also polarizability versus induction, gas phase versus solution phase, catalysis and molecular recognition are discussed. We are also interested in the proton affinity and reactivity of N-heterocyclic carbenes (NHCs). Stable NHCs are widely used as novel ligands for transition-metal-catalyzed reactions such as the Grubbs ruthenium olefin metathesis catalysis, palladium-catalyzed cross-coupling reactions and nickel-catalyzed cycloadditions. The dialkylimidazolium salts (protonated carbenes) are also an important class of ionic liquids, which are used as "green" nonvolatile solvents in organic synthesis. It has been found that the second generation of Grubbs metathesis catalyst comprising NHC is more active than the first generation catalyst containing tricyclohexyl phosphine (PCy3) only. More basic carbenes presumably will be more effective ligands. Therefore we are interested in the proton affinity of carbenes versus PCy3. By using the Cooks kinetic method we find both di-methyl carbene and ethyl methyl carbene have similar proton affinities to PCy3. However bracketing experiments conducted on a modified LCQ show that di-methyl carbene and ethyl methyl carbene are more basic than PCy3. This inconsistence is probably due to a technical problem with the Cooks method or ethylene elimination for the ethyl methyl carbene and PCy3 system during the Cooks experiments. Proton-bound dimers of carbenes and PCy3 are also found to exhibit interesting reactivity involving ethylene elimination, phosphine alkylation and/or cyclohexene elimination.

Reactive Intermediates

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Publisher : John Wiley & Sons
ISBN 13 : 9783527628735
Total Pages : 341 pages
Book Rating : 4.6/5 (287 download)

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Book Synopsis Reactive Intermediates by : Leonardo S. Santos

Download or read book Reactive Intermediates written by Leonardo S. Santos and published by John Wiley & Sons. This book was released on 2009-11-04 with total page 341 pages. Available in PDF, EPUB and Kindle. Book excerpt: During the last two decades there has been considerable growth in the development of electrospray ionization mass spectrometry (ESI-MS) as a practical method in the study of reaction mechanisms. This method allows the interception and characterization of key intermediates, either as transient species or as protonated/deprotonated forms of neutral species by API-MS. The outstanding features and advantages of ESI-MS make it one of the most suitable tools for the fast screening of intermediates directly from solution, providing hitherto unavailable chemical information to organic chemists. This monograph provides an overview of the mechanisms involved in ESI-MS, the historical perspectives before looking further in-depth at specific reactions and intermediates. Written by researchers in the field, this book is an unique resource for the understanding of this cutting-edge technique.

Fundamentals of Gas Phase Ion Chemistry

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Publisher : Springer Science & Business Media
ISBN 13 : 9401135185
Total Pages : 439 pages
Book Rating : 4.4/5 (11 download)

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Book Synopsis Fundamentals of Gas Phase Ion Chemistry by : K.R. Jennings

Download or read book Fundamentals of Gas Phase Ion Chemistry written by K.R. Jennings and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 439 pages. Available in PDF, EPUB and Kindle. Book excerpt: This volume presents the proceedings of the 1990 Advanced Study Institute entitled "Fundamentals of Gas Phase Ion Chemistry" held at Mont Ste. Odile , Alsace, France, 25th June -6th July, 1990. The Institute brought together over 100 physicists, physical and organic chemists working on a wide variety of topics with gas-phase ion chemistry as the common theme. Many different viewpoints, making use of very different experimental and theoretical approaches, were brought to bear on the subject and provided a stimulating and up-to-date account of the subject. Although the Institute was built around the invited lectures, many specific points were addressed in workshops which consisted of informal discussion groups which were organised by participants during the Institute. This volume therefore contains not only chapters based on the lectures but summaries of many of the workshops which adds considerably to the diversity of information presented. This Advanced Study Institute was the fifth in a series of NATO-sponsored institutes devoted to various aspects of the physics and chemistry of gas phase ions. These meetings have been held every four years since the first, held in Biarritz in 1974, considered "Interactions between Ions and Molecules". The five volumes which comprise the proceedings of these meetings illustrate very clearly the many advances in theory and experiment which have taken place over the last 20 years.

Mass Spectrometry

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Publisher : Royal Society of Chemistry
ISBN 13 : 1847556671
Total Pages : 450 pages
Book Rating : 4.8/5 (475 download)

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Book Synopsis Mass Spectrometry by : M E Rose

Download or read book Mass Spectrometry written by M E Rose and published by Royal Society of Chemistry. This book was released on 2007-10-31 with total page 450 pages. Available in PDF, EPUB and Kindle. Book excerpt: Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

Gas Phase Studies of Organic Reaction Mechanisms

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ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (946 download)

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Book Synopsis Gas Phase Studies of Organic Reaction Mechanisms by : Keyanna M. Conner

Download or read book Gas Phase Studies of Organic Reaction Mechanisms written by Keyanna M. Conner and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The competition between substitution (SN2) and elimination (E2) in nucleophilic reactions of alkyl halides has had a profound influence on the development of physical organic chemistry and remains an important testing ground for identifying reactivity patterns in gas-phase organic chemistry. Here, the competition between substitution and elimination, as well as the regioselectivity of E2 reactions have been examined in the gas phase. By doing so, the intrinsic reactivity patterns can be probed in the absence of solvation effects. The SN2 and E2 reactions of a large set of alkyl bromides with varying substitution patterns at the [alpha]- and [beta]-carbons were studied in the gas phase using naphthoate and phenoxide-based dianion nucleophiles. The experiments were performed in a quadrupole ion trap mass spectrometer equipped with electrospray ionization. The experimental work was supported by calculations at the MP2/6-31+G(d, p)//MP2/6-31+G(d) level. The naphthoate is a weaker base and leads to more products from the SN2 pathway. In accord with generalizations from condensed-phase results, primary bromides generally prefer substitution pathways and secondary bromides prefer eliminations. In the gas phase, polarizability is more important, and the highest SN2 reactivity is observed when the [beta]-carbon is 2° - steric crowding from [beta]-substituents is not as significant for un-solvated nucleophiles. In addition, the data confirms that alkyl substituents at the [beta]-carbon have a greater accelerating effect on E2 reactions than those at the [alpha]-carbon. Finally, computed data based on lowest enthalpy pathways provide poor descriptions of the reactions of the larger alkyl bromides and are skewed toward crowded systems that offer stabilizing, nonbonded interactions at the expense of conformational freedom. An investigation of regiochemical preferences of E2 reactions was also explored by synthesizing and analyzing the product distributions of a set of deuterium-labeled compounds capable of Saytzeff and Hofmann elimination. Gas-phase reactions of these substrates with dianion nucleophiles indicate that as expected, there is a preference for the Saytzeff product, which is also preferred in solution. This is the first study of E2 regioselectivity in the gas phase for a simple alkyl system.

Mass Spectrometry

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Publisher : Royal Society of Chemistry
ISBN 13 : 0851863388
Total Pages : 506 pages
Book Rating : 4.8/5 (518 download)

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Book Synopsis Mass Spectrometry by : M. E. Rose

Download or read book Mass Spectrometry written by M. E. Rose and published by Royal Society of Chemistry. This book was released on 1987 with total page 506 pages. Available in PDF, EPUB and Kindle. Book excerpt: Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

Study of Organic Reactions in Solution and in the Gas-phase by Electrospray Mass Spectrometry

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Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (14 download)

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Book Synopsis Study of Organic Reactions in Solution and in the Gas-phase by Electrospray Mass Spectrometry by : Claudio Iacobucci

Download or read book Study of Organic Reactions in Solution and in the Gas-phase by Electrospray Mass Spectrometry written by Claudio Iacobucci and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Mass Spectrometry of Organic Ions

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Publisher : Elsevier
ISBN 13 : 032314277X
Total Pages : 745 pages
Book Rating : 4.3/5 (231 download)

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Book Synopsis Mass Spectrometry of Organic Ions by : F.W. McLafferty

Download or read book Mass Spectrometry of Organic Ions written by F.W. McLafferty and published by Elsevier. This book was released on 2012-12-02 with total page 745 pages. Available in PDF, EPUB and Kindle. Book excerpt: Mass Spectrometry of Organic Ions covers the underlying theories and major applications of mass spectrometry. This 13-chapter book starts with a survey of the mechanisms by which organic ions can decompose and rearrange, as well as the generalized concept in terms of physical-organic chemistry. The discussion then shifts to the advantages and potential of mass spectrometry in structure determination by the elucidation of the empirical formulas of organic ions. Considerable chapters are devoted to the detailed correlations and mechanisms of the mass spectra of long-chain esters, alkylbenzenes, a variety of natural products, aliphatic compounds, and terpenes. The remaining chapters demonstrate the illustrative power of mass spectrometry in structure of petroleum, which is composed of hydrocarbon mixture. This book will be of great benefit to organic and analytical chemists, scientists, and students.

The Assignment of Gas Phase Ion Structures and Fragmentation Mechanisms by Mass Spectrometry

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Publisher :
ISBN 13 :
Total Pages : 326 pages
Book Rating : 4.:/5 (872 download)

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Book Synopsis The Assignment of Gas Phase Ion Structures and Fragmentation Mechanisms by Mass Spectrometry by : Martin Sirois

Download or read book The Assignment of Gas Phase Ion Structures and Fragmentation Mechanisms by Mass Spectrometry written by Martin Sirois and published by . This book was released on 1992 with total page 326 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Advances In Atmospheric Chemistry - Volume 2: Organic Oxidation And Multiphase Chemistry

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Publisher : World Scientific
ISBN 13 : 9813271841
Total Pages : 616 pages
Book Rating : 4.8/5 (132 download)

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Book Synopsis Advances In Atmospheric Chemistry - Volume 2: Organic Oxidation And Multiphase Chemistry by : John R Barker

Download or read book Advances In Atmospheric Chemistry - Volume 2: Organic Oxidation And Multiphase Chemistry written by John R Barker and published by World Scientific. This book was released on 2019-01-07 with total page 616 pages. Available in PDF, EPUB and Kindle. Book excerpt: This series presents authoritative invited summaries of research on atmospheric chemistry in a changing world. These range from comprehensive reviews of major subject areas to focused accounts by individual research groups. The topics may include laboratory studies, field measurements, in situ monitoring and remote sensing, studies of composition, chemical modeling, theories of atmospheric chemistry and climate, feedback mechanisms, emissions and deposition, biogeochemical cycles, and the links between atmospheric chemistry and the climate system at large.Volume 2 comprises chapters describing research on multiphase chemistry affecting air quality in China, on multiphase chemistry of organic compounds leading to secondary organic aerosol formation, on biogeochemical cycles involving ammonia, on oxidation of aromatic compounds, on reactions of Criegee intermediates (important in oxidation of alkenes), and on laboratory and field measurements of isotopic fractionation in the atmosphere.

The Encyclopedia of Mass Spectrometry

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Publisher : Elsevier Science
ISBN 13 : 9780080438467
Total Pages : 0 pages
Book Rating : 4.4/5 (384 download)

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Book Synopsis The Encyclopedia of Mass Spectrometry by : Nico Nibbering

Download or read book The Encyclopedia of Mass Spectrometry written by Nico Nibbering and published by Elsevier Science. This book was released on 2004-12-13 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Volume 4: Organic and Organometallic Compounds presents a cross section of applications in organic and organometallic chemistry in two parts. Chapters 1 to 6 are devoted to the fundamentals whereas chapters 7 and 8 cover applications to organic and organometallic compounds, either available as pure compounds or present in complex mixtures. Chapter 1 describes the theory for organic mass spectrometry, building on and complementing material in Volume 1. The themes for Chapter 2 are the structures and properties of gas-phase ions of conventional, distonic, and non-covalent complexes. Chapter 3 covers methodology used in study of gas-phase ions. Chapters 4 and 5 turn to mechanisms of both unimolecular and bimolecular reactions of ions and include topics in stereochemistry and radical chemistry. Chapter 6 contains a number of articles on the formation and reactivity of metal ion complexes and organometallic cations and anions, drawing connections with molecular recognition, catalysis and organic synthesis. Chapter 7 deals with the structure determination of organic compounds, including chiral compounds and natural products. In chapter 8 are contributions that provide illustrative examples of the determination of organic compounds present at low levels in complex samples that originate from various natural and biological sources. Included is an article on the determination of explosives.

The Encyclopedia of Mass Spectrometry, Ten-Volume Set

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Publisher : Elsevier Science
ISBN 13 : 9780080438504
Total Pages : 7000 pages
Book Rating : 4.4/5 (385 download)

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Book Synopsis The Encyclopedia of Mass Spectrometry, Ten-Volume Set by :

Download or read book The Encyclopedia of Mass Spectrometry, Ten-Volume Set written by and published by Elsevier Science. This book was released on 2013-09-27 with total page 7000 pages. Available in PDF, EPUB and Kindle. Book excerpt: Overview: The Encyclopedia of Mass Spectrometry The need for an encyclopedia of mass spectrometry (MS) becomes apparent when considering the subject's evolution. By 1990, MS had evolved as a discipline and as a technique for solving problems in chemistry. Along with nuclear magnetic resonance and optical spectroscopy, it was a tool for compound identification. For complex mixtures as found in environmental chemistry, flavors, energy materials, and small-molecule metabolism, gas chromatography-mass spectrometry had become the premier analytical method. Despite these advances, MS played in 1990 only a small role in polar and large-molecule analysis. Field desorption, fast atom bombardment, and Cf-252 plasma desorption gently pushed it into peptide sequencing and molecular weight determination of larger polymers. Although these ionizations had limitations, when they were coupled with tandem mass spectrometers, the future became clearer. MS now awaited the development of new ionization methods that would extend its capabilities into many different research laboratories. The inventions of electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) in the late 1980s opened the door for that greater role. Even the discipline of MS could expand by embracing the chemical-physical studies of proteins and oligodeoxynucleotides in the gas phase. The broad applicability of MS to a multitude of chemical, physical, and biological problems makes it now the central tool in chemical analysis. No longer a specialist's tool, it has assumed broad applicability and availability. To permit a full and fruitful expansion in other disciplines, the Encyclopedia of Mass Spectrometry is designed to be a learning tool to newcomers who do not have the theoretical and practical background needed to take advantage of the possibilities of MS. Moreover, the field is now so broad that the specialist also needs a resource to allow exploration of its vast reaches. The encyclopedia meets that need and strives to be an entrance into the subject and to serve as its major reference work. Volume 1: Theory and Ion Chemistry Volume 1 begins with two theory chapters. The first discusses theoretical aspects of ion collisions, chemistry, and dynamics, and the second introduces ab initio calculations of ions. The latter has become a nearly indispensable tool in ion chemistry studies today. Instrumentation is essential in fundamental investigations. Chapter 3 introduces instrumentation, with an emphasis on unusual instrumentation, generally not commercially available. Ion traps, ion cyclotron resonance mass spectrometers, and time-of-flight instruments, which are important in both fundamental studies and in applications, are also covered. Chapter 4 discusses myriad means of performing spectroscopic experiments on ions. In the next chapter, various methods of measuring thermodynamic information about ions are introduced and evaluated. Collisional activation and dissociation processes, in various incarnations, are in Chapter 6. Mobility experiments are the focus of the next chapter, which covers fundamental aspects and applications of this rapidly growing technology. Various means and uses of changing charge states of ions is the topic of chapter 8. Chapters 9 and 10 introduce the ion chemistry of organic ions, positive and negative, respectively. The last three chapters (Chapter 11-13) are expositions of the ion chemistry of clusters and solvation phenomena, inorganic chemistry, and the rapidly expanding area of biochemistry. Volume 2: Biological Applications Part A The focus of Volume 2 is peptides and proteins. The organization emphasizes separation techniques, preparation protocols, and fundamentals of ionic gas-phase species of biological importance. This volume is divided into four sections: (1) experimental approaches and protocols, (2) sequence analysis, (3) other structural analyses, and (4) targeted applications. The first section encompass separation procedures (e.g., 2-D gel electrophoresis), sample preparation (e.g., desalting and enzyme digestion), and instrumentation issues (e.g., high resolving power, molecular-weight determination, protein chips, and quantification). H/D exchange, analysis of membrane proteins, and bioinformatics are included. The next section on sequencing covers high energy and low energy CAD, protein identification, fundamentals of peptide fragmentation, bottom-up and top-down strategies, chemical derivatization, and post-source decay with MALDI. A section on structure analysis includes primary structure determination and issues with studying quaternary structure, protein-protein and protein-ligand complexes, disulfide analysis, phosphopeptides and phosphoproteins, selenoproteins, nitrated proteins, metal ion binding, and oxidized proteins. Additional coverage of methods for studying the biophysics of proteins is provided in Volume 6. The last chapter, Targeted Applications, focuses on neuropeptides, clinical applications, enzyme kinetics, imaging, and single-cell analysis. Volume 3: Biological Applications Part B Over the past decades, enormous gains have been made towards the analysis of all the biomolecules in cells. Although early attention was focused on peptides and proteins, a wealth of information is arising about other major biomolecules including nucleic acids, lipids and carbohydrates. In no small way, modern ionization methods, especially electrospray and matrix-assisted laser desorption, have provided a quantum leap in the capabilities of the tools we can now deploy in answering biological questions involving structure and molecular weight of virtually every type of molecule in the cell. Volume 3 covers classes carbohydrates, nucleic acids, and lipids. In addition, special areas of application are also included, such as pharmaceuticals, natural products, isotope ratio methods for biomolecules analysis, and clinical applications. The articles are arranged under general headings for continuity and ease of access, although several of these are of interest across the various disciplines. The articles cover basics and sufficient additional detail to bring the reader up-to-date on a given subject. Some advanced topics are also covered, either in a special section of an article or in additional reading citations. Volume 4: Organic and Organometallic Compounds This volume presents a cross section of applications in organic and organometallic chemistry in two parts. Chapters 1 to 6 are devoted to the fundamentals whereas chapters 7 and 8 cover applications to organic and organometallic compounds, either available as pure compounds or present in complex mixtures. Chapter 1 describes the theory for organic mass spectrometry, building on and complementing material in Volume 1. The themes for Chapter 2 are the structures and properties of gas-phase ions of conventional, distonic, and non-covalent complexes. Chapter 3 covers methodology used in study of gas-phase ions. Chapters 4 and 5 turn to mechanisms of both unimolecular and bimolecular reactions of ions and include topics in stereochemistry and radical chemistry. Chapter 6 contains a number of articles on the formation and reactivity of metal ion complexes and organometallic cations and anions, drawing connections with molecular recognition, catalysis and organic synthesis. Chapter 7 deals with the structure determination of organic compounds, including chiral compounds and natural products. In chapter 8 are contributions that provide illustrative examples of the determination of organic compounds present at low levels in complex samples that originate from various natural and biological sources. Included is an article on the determination of explosives. Volume 5: Elemental and Isotope Ratio Mass Spectrometry This volume focuses on (1) the plethora of mostly atomic ionization techniques that have been coupled to MS for elemental analysis, the measurement of isotope ratios, and even the determination of inorganic compounds and (2) the precise measurement of isotope ratios of organic elements as small gas molecules by isotope ratio mass spectrometry (IRMS). Volume 6: Ionization Methods Volume 6 captures the story of molecular ionization and its phenomenal evolution that makes mass spectrometry the powerful method it is today. Chapters 1 and 2 cover fundamentals and various issues that are common to all ionization (e.g., accurate mass, isotope clusters, and derivatization). Chapters 3-9 acknowledge that some ionization methods are appropriate for gas-phase molecules and others for molecules that are in the solid or liquid states. Chapters 3-6 cover gas-phase molecules, dividing the subject into: (1) ionization of gas-phase molecules by particles (e.g., EI), (2) ionization by photons, (3) ionization by ion-molecule and molecule-molecule reactions (e.g., APCI and DART), and ionization in Strong electric fields (i.e., Electrohydrodynamic and Field Ionization/Desorption). "Ionization in a Strong Electric Field" illustrates the transition to ionization of molecules in the solid or liquid states, covered in Chapters 7-9: (1) spray methods for ionization (e.g., electrospray), (2) desorption ionization by particle bombardment (e.g., FAB), and (3) desorption by photons (e.g., MALDI). Electrospray and MALDI also lead to applications in biophysical chemistry, the theme of Chapter 10. Chapter 11 reconsiders ionization from the view of choosing an ionization method. The range of subjects is from ionization of organic and biomolecules to the study of microorganisms. Volume 7: Mass Analyzers The volume is under preparation Volume 8: Hyphenated Methods Starting with gas chromatography-mass spectrometry (GC-MS) and continuing through GCxGC-MS, LC-MSn, and LC-NMR-MS, hyphenated methods have revolutionized chemical analysis. This volume covers that revolution in two parts. The first (Chapters 1-4) describes principles, instrumentation, and technology, and the second (Chapters 5-10) organizes major application areas in GC-MS and LC-MS. After a general introduction (Chapter 1), attention is paid to principles and instrumentation of GC-MS (Chapter 2) and LC-MS (Chapter 3). Other hyphenated methods, including online combinations of capillary electromigration methods and supercritical fluid chromatography with mass spectrometry, are in Chapter 4. Applications are then covered in the remaining chapters. The application-oriented chapters are focused on the role of mainly LC-MS in the pharmaceutical field (Chapter 5) and biochemical and biotechnological applications (Chapter 10), and the application of both GC-MS and LC-MS in relation to environmental analysis (Chapter 6), food safety and food analysis (Chapter 7), characterization of natural products (Chapter 8), and clinical, toxicological, and forensic analysis (Chapter 9). Volume 9: History of Mass Spectrometry This volume is under preparation. Volume 10: Index * This multi-volume work is the first to provide unparalleled and comprehensive coverage of the full range of topics and techniques * Suitable for new graduate students who are interested but not yet versed in the subject of mass spectrometry * Techniques, methods and applications of mass spectrometry are described in considerable detail; including limitations, current problems, and areas in which the method does not succeed well

Applications of Mass Spectrometry in Biological, Environmental and Gas-phase Organic Ion Chemistry

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Book Synopsis Applications of Mass Spectrometry in Biological, Environmental and Gas-phase Organic Ion Chemistry by : David R. Hilker

Download or read book Applications of Mass Spectrometry in Biological, Environmental and Gas-phase Organic Ion Chemistry written by David R. Hilker and published by . This book was released on 1981 with total page 322 pages. Available in PDF, EPUB and Kindle. Book excerpt: