Side-chain loss reactions of collisionally activated protonated peptoids: A mechanistic insight

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10394766" target="_blank" >RIV/00216208:11310/19:10394766 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=Vci5ZQPo.d" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=Vci5ZQPo.d</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.ijms.2018.10.032" target="_blank" >10.1016/j.ijms.2018.10.032</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Side-chain loss reactions of collisionally activated protonated peptoids: A mechanistic insight

Popis výsledku v původním jazyce

Peptoids constitute an emergent class of synthetic biocompatible macromolecules that are best described as polymers of N-substituted glycines. Peptides and peptoids are regioisomers with the side chains appended in peptoids to the nitrogen atoms rather than to the alpha-carbon atoms as in peptides. Peptide sequencing now takes great advantage of collision-induced dissociation experiments, based on the elucidation of the decomposition pathways of protonated peptides. In contrast, data on peptoid ion decompositions are to date scarcely present in the literature. Upon CID, protonated peptoids were recently shown to mostly dissociate by cleavages at the backbone amide bonds yielding B- and Y-fragment ions. In addition, the loss of the side-chain group and/or the formation of the side-chain fragment ion are common reactions for peptoids containing protonated N-alpha-aromatic side chain. In the present paper, we submitted protonated tailor-made peptoids to (energy-resolved) collision-induced dissociation experiments to investigate the side-chain loss reaction mechanisms. We also used orthogonal methods, such as quantum chemistry, ion mobility spectrometry and infrared photodissociation spectroscopy to establish the structures of the fragment ions. We ended up with different mechanistic scenarios consistent with the nature of the fragment ions and the kinetic energy dependence of decomposition reactions. Our mechanistic proposals associate the proton mobile model, proton bound dimer intermediacy and concerted rearrangement reactions.

Název v anglickém jazyce

Side-chain loss reactions of collisionally activated protonated peptoids: A mechanistic insight

Popis výsledku anglicky

Peptoids constitute an emergent class of synthetic biocompatible macromolecules that are best described as polymers of N-substituted glycines. Peptides and peptoids are regioisomers with the side chains appended in peptoids to the nitrogen atoms rather than to the alpha-carbon atoms as in peptides. Peptide sequencing now takes great advantage of collision-induced dissociation experiments, based on the elucidation of the decomposition pathways of protonated peptides. In contrast, data on peptoid ion decompositions are to date scarcely present in the literature. Upon CID, protonated peptoids were recently shown to mostly dissociate by cleavages at the backbone amide bonds yielding B- and Y-fragment ions. In addition, the loss of the side-chain group and/or the formation of the side-chain fragment ion are common reactions for peptoids containing protonated N-alpha-aromatic side chain. In the present paper, we submitted protonated tailor-made peptoids to (energy-resolved) collision-induced dissociation experiments to investigate the side-chain loss reaction mechanisms. We also used orthogonal methods, such as quantum chemistry, ion mobility spectrometry and infrared photodissociation spectroscopy to establish the structures of the fragment ions. We ended up with different mechanistic scenarios consistent with the nature of the fragment ions and the kinetic energy dependence of decomposition reactions. Our mechanistic proposals associate the proton mobile model, proton bound dimer intermediacy and concerted rearrangement reactions.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

International Journal of Mass Spectrometry

ISSN

1387-3806

e-ISSN

—

Svazek periodika

435

Číslo periodika v rámci svazku

January

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

10

Strana od-do

217-226

Kód UT WoS článku

000453773300029

EID výsledku v databázi Scopus

2-s2.0-85056227033