Recognition and quantification of binary and ternary mixtures of isomeric peptides by the kinetic method: metal ion and ligand effects on the dissociation of metal-bound complexes

Wu, Lei; Lemr, Karel; Aggerholm, Tenna; Cooks, R. Graham

doi:10.1016/s1044-0305(02)00868-1

Cited by 45 publications

(37 citation statements)

References 43 publications

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“…This is, however, limited to low mass compounds. A number of techniques utilizing branching ratios of product ions were also developed [6,11,12]. Alternatively, MS/MS spectra obtained at "low" and at "high" collision energies may be used to make this structural analysis.…”

mentioning

confidence: 99%

Tandem Mass Spectrometric Analysis of a Mixture of Isobars Using the Survival Yield Technique

Memboeuf

Jullien

Lartia

et al. 2011

J. Am. Soc. Mass Spectrom.

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Collision induced dissociation tandem mass spectrometry experiments were performed to unequivocally separate compounds from an isobaric mixture of two products. The Survival Yield curve was obtained and is shown to consist in a linear combination of the curves corresponding to the two components separately. For such a mixture, a plateau appears on the diagram in lieu of the continuous decrease expected allowing for the structural study of the two components separately. The width of the plateau critically relates to the fragmentation parameters of the two molecular ions, which need to be sufficiently different structurally for the plateau to be observed. However, at constant fragmentation parameters, we have observed the width significantly increases at large m/z. This makes the separation more and more efficient as isobars have larger m/z and the technique complementary to those applicable at low m/z only. We have observed that the vertical position of the plateau relates linearly to the relative concentration of the two compounds that may be useful for quantification. Repeatability was estimated at 2% on a quadrupole ion trap. An advantage of using survival yield curves only, is that a priori knowledge of the respective fragmentation patterns of the two isobars becomes unnecessary. Consequently, similar performances are obtained if fragments are isobaric, which is also demonstrated in our study. The critical case of reverse peptides, at low m/z and similar fragmentation parameters, is also presented as a limitation of the method.

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confidence: 99%

Tandem Mass Spectrometric Analysis of a Mixture of Isobars Using the Survival Yield Technique

Memboeuf

Jullien

Lartia

et al. 2011

J. Am. Soc. Mass Spectrom.

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“…which requires the analytes to be measured under different conditions to obtain two sets of equations to solve this two unknown system [17]. In this study, the capability of the kinetic method to rapid isomeric distinction and quantitation of monosaccharides is explored, using D-glucose, Dgalactose, and D-fructose (Scheme 1) as examples.…”

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confidence: 99%

Distinction and quantitation of sugar isomers in ternary mixtures using the kinetic method

Fouquet

Charles

2010

J. Am. Soc. Mass Spectrom.

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Quantitative isomeric analysis of fructose, galactose, and glucose was achieved using electrospray ionization and trimeric ion dissociation with data analysis by the kinetic method. Several L-amino acids and divalent metal cations were tested to select the best systems for isomeric distinction and quantitation of each monosaccharide. High discrimination could be achieved for most tested systems, and serine/Cu 2ϩ and aspartic acid/Mn 2ϩ were selected for quantitative analysis due to their ability to strongly distinguish the three analytes and to allow long-term reproducible measuring conditions. Accurate quantitative results were obtained for all isomers using three-point corrected calibration curves, which account for the competition effects evidenced to occur between sugars for the formation of the trimeric complexes. As a result, the relative proportion of one isomer in the liquid and in the gas phase depends on the sugar mixture composition. However, for a given reference/metal system, the extent of competition effects was shown to be constant within a given pair of sugars. The correction factors could thus be established based on data obtained from binary mixtures and successfully used for ternary sample analysis. (J Am Soc Mass Spectrom 2010, 21, 60 -67)

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“…This method could form the basis for possible future quantitative analyses of mixtures of larger peptides, as generated, for example, in combinatorial synthesis of peptides and peptide mimics. 23 Tetrapeptide systems have also been examined; it has been determined through experiments that the steric properties of positional peptides; AGGG, GAGG, GGAG, and GGGA are easily manipulated through the use of a fixed ligand. The steric interactions are magnified and this results in a larger R iso value, viz., greater isomeric discrimination.…”

Section: Extension To Positional Isomersmentioning

confidence: 99%

Final Report

Cooks¹

2006

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SummaryDetails of progress are provided in the sections which follow but first, for convenience, a short summary is given:· We have succeeded in developing simulation methods that reliably predict performance of ion trap mass spectrometers including the relationship between geometry, electric fields, ion motion, and mass spectra · These procedures have been used to optimize cylindrical ion traps (CITs) including those used in the commercial Griffin Analytical Technologies instruments · We have generalized the simulation program (ITSIM) to allow calculation of ion motion and of mass spectra in 3D electric fields of any arbitrary shape · We have invented the rectilinear ion traps (RIT), a version of linear ion trap which traps an order of magnitude more ions than previous 3D (Paul) ion traps · We have simulated and built arrays of ion traps suited to multiplexed mass analysis and other purposes · Practical applications of our ion traps in miniature mass spectrometers include air monitoring applications (DHS supported) and explosives monitoring experiments (TSA supported) both based on the fundamental DOE-supported work · Applications and simulations of ion motion in the newly commercialized high resolution mass spectrometer (Orbitrap) employed for the understanding of ion motion and its control developed using the ITSIM program · Large inverse KIEs have been discovered in halogen cluster ions and are interesting for their magnitude and mechanistic implications (threshold angular momentum effects on rotational predissociation) · The kinetic method of thermochemical estimation has been extended to quantitative chiral analysis and the methodology has been transferred to the pharmaceutical industry through lectures, discussions and collaborations · The kinetic method has also been successfully applied to the quantatitave analysis of structural isomers, especially isomeric peptides · The serine octamer has been generated by sublimation; this magic-number cluster exists in two isomeric forms and has a strong preference for homochirality. The implications of these and related observations on sprayed serine for the origin of homochirality on earth confirm our work in this area ITSIM: Ion SimulationsNew Version of ITSIM 6.0 The ion trap simulation program ITSIM has been developed and used in this laboratory since 1990. The main goal in using this program is to improve data for use in enhancing ion trap performance and developing new types of ion trap mass spectrometers. A field computational/trajectory simulation approach is adopted to obtain a detailed understanding of ion motion in ion trap instruments. The key

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Recognition and quantification of binary and ternary mixtures of isomeric peptides by the kinetic method: metal ion and ligand effects on the dissociation of metal-bound complexes

Cited by 45 publications

References 43 publications

Tandem Mass Spectrometric Analysis of a Mixture of Isobars Using the Survival Yield Technique

Tandem Mass Spectrometric Analysis of a Mixture of Isobars Using the Survival Yield Technique

Distinction and quantitation of sugar isomers in ternary mixtures using the kinetic method

Final Report

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