Dataset Information

Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation.

ABSTRACT: Collision-induced dissociation (CID) remains the predominant mass spectrometry-based method for identifying phosphorylation sites in complex mixtures. Unfortunately, the gas-phase reactivity of phosphoester bonds results in MS/MS spectra dominated by phosphoric acid (H3PO4) neutral loss events, suppressing informative peptide backbone cleavages. To understand the major drivers of H3PO4 neutral loss, we performed robust nonparametric statistical analysis of local and distal sequence effects on the magnitude and variability of neutral loss, using a collection of over 35,000 unique phosphopeptide MS/MS spectra. In contrast to peptide amide dissociation pathways, which are strongly influenced by adjacent amino acid side chains, we find that neutral loss of H3PO4 is affected by both proximal and distal sites, most notably basic residues and the peptide N-terminal primary amine. Previous studies have suggested that protonated basic residues catalyze neutral loss through direct interactions with the phosphate. In contrast, we find that nearby basic groups decrease neutral loss regardless of mobility class, an effect only seen by stratifying spectra by charge-mobility. The most inhibitory bases are those immediately N-terminal to the phosphate, presumably because of steric hindrances in catalyzing neutral loss. Further evidence of steric effects is shown by the presence of proline, which can dramatically reduce the presence of neutral loss when between the phosphate and a possible charge donor. In mobile proton spectra, the N-terminus is the strongest predictor of high neutral loss, with proximity to the N-terminus essential for peptides to exhibit the highest levels of neutral loss.

SUBMITTER: Brown R

PROVIDER: S-EPMC4509682 | biostudies-literature | 2015 Jul

REPOSITORIES: biostudies-literature

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Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation.

Brown Robert R Stuart Scott A SA Houel Stephane S Ahn Natalie G NG Old William M WM

Journal of the American Society for Mass Spectrometry 20150408 7

Collision-induced dissociation (CID) remains the predominant mass spectrometry-based method for identifying phosphorylation sites in complex mixtures. Unfortunately, the gas-phase reactivity of phosphoester bonds results in MS/MS spectra dominated by phosphoric acid (H3PO4) neutral loss events, suppressing informative peptide backbone cleavages. To understand the major drivers of H3PO4 neutral loss, we performed robust nonparametric statistical analysis of local and distal sequence effects on th ...[more]

PMID: 25851653

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Project description:Ungulates, in particular the Central European roe deer Capreolus capreolus and the North American white-tailed deer Odocoileus virginianus, are economically and ecologically important. The two species are risk factors for deer-vehicle collisions and as browsers of palatable trees have implications for forest regeneration. However, no large-scale management systems for ungulates have been implemented, mainly because of the high efforts and costs associated with attempts to estimate population sizes of free-living ungulates living in a complex landscape. Attempts to directly estimate population sizes of deer are problematic owing to poor data quality and lack of spatial representation on larger scales. We used data on >74,000 deer-vehicle collisions observed in 2006 and 2009 in Bavaria, Germany, to model the local risk of deer-vehicle collisions and to investigate the relationship between deer-vehicle collisions and both environmental conditions and browsing intensities. An innovative modelling approach for the number of deer-vehicle collisions, which allows nonlinear environment-deer relationships and assessment of spatial heterogeneity, was the basis for estimating the local risk of collisions for specific road types on the scale of Bavarian municipalities. Based on this risk model, we propose a new "deer-vehicle collision index" for deer management. We show that the risk of deer-vehicle collisions is positively correlated to browsing intensity and to harvest numbers. Overall, our results demonstrate that the number of deer-vehicle collisions can be predicted with high precision on the scale of municipalities. In the densely populated and intensively used landscapes of Central Europe and North America, a model-based risk assessment for deer-vehicle collisions provides a cost-efficient instrument for deer management on the landscape scale. The measures derived from our model provide valuable information for planning road protection and defining hunting quota. Open-source software implementing the model can be used to transfer our modelling approach to wildlife-vehicle collisions elsewhere.

Dataset Information

Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation.

Publications

Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation.

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