Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Overtone mobility spectrometry: part 3. On the origin of peaks.

ABSTRACT: The origin of non-integer overtone peaks in overtone mobility spectrometry (OMS) spectra is investigated by ion trajectory simulations. Simulations indicate that these OMS features arise from higher-order overtone series. An empirically-derived formula is presented as a means of describing the positions of peaks. The new equation makes it possible to determine collision cross sections from any OMS peak. Additionally, it is extended as a means of predicting the resolving power for any peak in an OMS distribution.

SUBMITTER: Valentine SJ

PROVIDER: S-EPMC3253535 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Overtone mobility spectrometry: part 3. On the origin of peaks.

Valentine Stephen J SJ Kurulugama Ruwan T RT Clemmer David E DE

Journal of the American Society for Mass Spectrometry 20110304 5

The origin of non-integer overtone peaks in overtone mobility spectrometry (OMS) spectra is investigated by ion trajectory simulations. Simulations indicate that these OMS features arise from higher-order overtone series. An empirically-derived formula is presented as a means of describing the positions of peaks. The new equation makes it possible to determine collision cross sections from any OMS peak. Additionally, it is extended as a means of predicting the resolving power for any peak in an ...[more]

PMID: 21472515

Similar Datasets

Overtone mobility spectrometry: part 1. Experimental observations.

Project description:A new method that allows a linear drift tube to be operated as a continuous ion mobility filter is described. Unlike conventional ion mobility instruments that use an electrostatic gate to introduce a packet of ions into a drift region, the present approach uses multiple segmented drift regions with modulated drift fields to produce conditions that allow only ions with appropriate mobilities to pass through the instrument. In this way, the instrument acts as a mobility filter for continuous ion sources. By changing the frequency of the applied drift fields it is possible to tune this instrument to transmit ions having different mobilities. A scan over a wide range of drift field frequencies for a single ion species shows a peak corresponding to the expected resonance time of the ions in one drift region segment and a series of peaks at higher frequencies that are overtones of the resonant frequency. The measured resolving power increases for higher overtones, making it possible to resolve structures that were unresolved in the region of the fundamental frequency. We demonstrate the approach by examining oligosaccharide isomers, raffinose and melezitose as well as a mixture of peptides obtained from enzymatic digestion of myoglobin.

| S-EPMC2709233 | biostudies-literature

Overtone mobility spectrometry: part 5. Simulations and analytical expressions describing overtone limits.

Project description:Mathematical expressions for the analytical duty cycle associated with different overtones in overtone mobility spectrometry are derived from the widths of the transmitted packets of ions under different instrumental operating conditions. Support for these derivations is provided through ion trajectory simulations. The outcome of the theory and simulations indicates that under all operating conditions there exists a limit or maximum observable overtone that will result in ion transmission. Implications of these findings on experimental design are discussed.

| S-EPMC4521626 | biostudies-literature

Overtone mobility spectrometry: part 2. Theoretical considerations of resolving power.

Project description:The transport of ions through multiple drift regions is modeled to develop an equation that is useful for an understanding of the resolving power of an overtone mobility spectrometry (OMS) technique. It is found that resolving power is influenced by a number of experimental variables, including those that define ion mobility spectrometry (IMS) resolving power: drift field (E), drift region length (L), and buffer gas temperature (T). However, unlike IMS, the resolving power of OMS is also influenced by the number of drift regions (n), harmonic frequency value (m), and the phase number (Phi) of the applied drift field. The OMS resolving power dependence upon the new OMS variables (n, m, and Phi) scales differently than the square root dependence of the E, L, and T variables in IMS. The results provide insight about optimal instrumental design and operation.

| S-EPMC2735887 | biostudies-literature

Gridless overtone mobility spectrometry.

Project description:A novel overtone mobility spectrometry (OMS) instrument utilizing a gridless elimination mechanism and cooperative radio frequency confinement is described. The gridless elimination region uses a set of mobility-discriminating radial electric fields that are designed so that the frequency of field application results in selective transmission and elimination of ions. To neutralize ions with mobilities that do not match the field application frequency, active elimination regions radially defocus ions toward the lens walls. Concomitantly, a lens-dependent radio frequency waveform is applied to the transmission regions of the drift tube resulting in radial confinement for mobility-matched ions. Compared with prior techniques, which use many grids for ion elimination, the new gridless configuration substantially reduces indiscriminate ion losses. A description of the apparatus and elimination process, including detailed simulations showing how ions are transmitted and eliminated is presented. A prototype 28 cm long OMS instrument is shown to have a resolving power of 20 and is capable of attomole detection limits of a model peptide (angiotensin I) spiked into a complex mixture (in this case peptides generated from digestion of ?-casein with trypsin).

| S-EPMC3994891 | biostudies-literature

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling.

Project description:Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H](2-) ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H](3-) ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H](2-) ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H](3-) ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

| S-EPMC4814291 | biostudies-literature

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 3. Estimating Surface Area Exposure by Deuterium Uptake.

Project description:Gas-phase hydrogen deuterium exchange (HDX), collision cross section (CCS) measurement, and molecular dynamics simulation (MDS) techniques were utilized to develop and compare three methods for estimating the relative surface area exposure of separate peptide chains within bovine insulin ions. Electrosprayed [M - 3H](3-) and [M - 5H](5-) insulin ions produced a single conformer type with respective collision cross sections of 528 ± 5 Å(2) and 808 ± 2 Å(2). [M - 4H](4-) ions were comprised of more compact (Ω = 676 ± 3 Å(2)) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å(2)) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M - 4H](4-) and [M - 5H](5-) ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis.

| S-EPMC4872623 | biostudies-literature

Mechanical overtone frequency combs.

Project description:Mechanical frequency combs are poised to bring the applications and utility of optical frequency combs into the mechanical domain. So far, their main challenge has been strict requirements on drive frequencies and power, which complicate operation. We demonstrate a straightforward mechanism to create a frequency comb consisting of mechanical overtones (integer multiples) of a single eigenfrequency, by monolithically integrating a suspended dielectric membrane with a counter-propagating optical trap. The periodic optical field modulates the dielectrophoretic force on the membrane at the overtones of a membrane's motion. These overtones share a fixed frequency and phase relation, and constitute a mechanical frequency comb. The periodic optical field also creates an optothermal parametric drive that requires no additional power or external frequency reference. This combination of effects results in an easy-to-use mechanical frequency comb platform that requires no precise alignment, no additional feedback or control electronics, and only uses a single, mW continuous wave laser beam. This highlights the overtone frequency comb as the straightforward future for applications in sensing, metrology and quantum acoustics.

| S-EPMC10020424 | biostudies-literature

Origin of new broad Raman D and G peaks in annealed graphene.

Project description:Since graphene, a single sheet of graphite, has all of its carbon atoms on the surface, its property is very sensitive to materials contacting the surface. Herein, we report novel Raman peaks observed in annealed graphene and elucidate their chemical origins by Raman spectroscopy and atomic force microscopy (AFM). Graphene annealed in oxygen-free atmosphere revealed very broad additional Raman peaks overlapping the D, G and 2D peaks of graphene itself. Based on the topographic confirmation by AFM, the new Raman peaks were attributed to amorphous carbon formed on the surface of graphene by carbonization of environmental hydrocarbons. While the carbonaceous layers were formed for a wide range of annealing temperature and time, they could be effectively removed by prolonged annealing in vacuum. This study underlines that spectral features of graphene and presumably other 2-dimensional materials are highly vulnerable to interference by foreign materials of molecular thickness.

| S-EPMC3776959 | biostudies-literature

Joint Bounding of Peaks Across Samples Improves Differential Analysis in Mass Spectrometry-Based Metabolomics.

Project description:As mass spectrometry-based metabolomics becomes more widely used in biomedical research, it is important to revisit existing data analysis paradigms. Existing data preprocessing efforts have largely focused on methods which start by extracting features separately from each sample, followed by a subsequent attempt to group features across samples to facilitate comparisons. We show that this preprocessing approach leads to unnecessary variability in peak quantifications that adversely impacts downstream analysis. We present a new method, bakedpi, for the preprocessing of both centroid and profile mode metabolomics data that relies on an intensity-weighted bivariate kernel density estimation on a pooling of all samples to detect peaks. This new method reduces this unnecessary quantification variability and increases power in downstream differential analysis.

| S-EPMC5362739 | biostudies-literature

Evaluating lipid mediator structural complexity using ion mobility spectrometry combined with mass spectrometry.

Project description:AIM:Lipid mediators (LMs) are broadly defined as a class of bioactive lipophilic molecules that regulate cell-to-cell communication events with many having a strong correlation with various human diseases and conditions. LMs are usually analyzed with LC-MS, but their numerous isomers greatly complicate the measurements with essentially identical fragmentation spectra and LC separations are not always sufficient for distinguishing the features. Results/methodology: In this work, we characterized LMs using ion mobility spectrometry (IMS) coupled with MS (IMS-MS). The collision cross-sections and m/z values from the IMS and MS analyses displayed distinct trend lines. Specifically, the structural trend lines for sodiated LMs originating from docosahexaenoic acid had the smallest collision cross-section values in relation to m/z, while those from linoleic acid had the largest. LC-IMS-MS analyses were also performed on LMs in flu infected mouse tissue samples. These multidimensional studies were able to assess known LMs while also detecting new species. CONCLUSION:Adding IMS separations to conventional LC-MS analyses show great utility for enabling better identification and characterization of LMs in complex biological samples.

| S-EPMC6040087 | biostudies-other

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data