Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers
Peptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both char...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/22/6964 |
| _version_ | 1797509193688678400 |
|---|---|
| author | Monika Kijewska Dorota Gąszczyk Remigiusz Bąchor Piotr Stefanowicz Zbigniew Szewczuk |
| author_facet | Monika Kijewska Dorota Gąszczyk Remigiusz Bąchor Piotr Stefanowicz Zbigniew Szewczuk |
| author_sort | Monika Kijewska |
| collection | DOAJ |
| description | Peptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both charge remote (ChR) and charge-directed (ChD) fragmentation. A series of model peptide conjugates derivatized with <i>N</i>,<i>N</i>,<i>N</i>-triethyloammonium (TEA), 1-azoniabicyclo[2.2.2]octane (ABCO), 2,4,6-triphenylopyridinium (TPP) and tris(2,4,6-trimetoxyphenylo)phosphonium (TMPP) groups were analyzed by their fragmentation pathways both in collision-induced dissociation (CID) and electron-capture dissociation (ECD) mode. The effect of the fixed-charge tag type and peptide sequence on the fragmentation pathways was investigated. We found that the aspartic acid effect plays a crucial role in the CID fragmentation of TPP and TEA peptide conjugates whereas it was not resolved for the peptides derivatized with the phosphonium group. ECD spectra are mostly dominated by c<sub>n</sub> ions. ECD fragmentation of TMPP-modified peptides results in the formation of intense fragments derived from this fixed-charge tag, which may serve as reporter ion. |
| first_indexed | 2024-03-10T05:14:24Z |
| format | Article |
| id | doaj.art-fb09efd484c948ca890ac8e3f83dd244 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T05:14:24Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-fb09efd484c948ca890ac8e3f83dd2442023-11-23T00:36:27ZengMDPI AGMolecules1420-30492021-11-012622696410.3390/molecules26226964Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization EnhancersMonika Kijewska0Dorota Gąszczyk1Remigiusz Bąchor2Piotr Stefanowicz3Zbigniew Szewczuk4Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, PolandFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, PolandFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, PolandFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, PolandFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, PolandPeptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both charge remote (ChR) and charge-directed (ChD) fragmentation. A series of model peptide conjugates derivatized with <i>N</i>,<i>N</i>,<i>N</i>-triethyloammonium (TEA), 1-azoniabicyclo[2.2.2]octane (ABCO), 2,4,6-triphenylopyridinium (TPP) and tris(2,4,6-trimetoxyphenylo)phosphonium (TMPP) groups were analyzed by their fragmentation pathways both in collision-induced dissociation (CID) and electron-capture dissociation (ECD) mode. The effect of the fixed-charge tag type and peptide sequence on the fragmentation pathways was investigated. We found that the aspartic acid effect plays a crucial role in the CID fragmentation of TPP and TEA peptide conjugates whereas it was not resolved for the peptides derivatized with the phosphonium group. ECD spectra are mostly dominated by c<sub>n</sub> ions. ECD fragmentation of TMPP-modified peptides results in the formation of intense fragments derived from this fixed-charge tag, which may serve as reporter ion.https://www.mdpi.com/1420-3049/26/22/6964derivatizationfixed charge tagquaternary ammonium saltmass spectrometryelectron-capture dissociationcollision induced dissociation |
| spellingShingle | Monika Kijewska Dorota Gąszczyk Remigiusz Bąchor Piotr Stefanowicz Zbigniew Szewczuk Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers Molecules derivatization fixed charge tag quaternary ammonium salt mass spectrometry electron-capture dissociation collision induced dissociation |
| title | Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers |
| title_full | Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers |
| title_fullStr | Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers |
| title_full_unstemmed | Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers |
| title_short | Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers |
| title_sort | analysis of fragmentation pathways of peptide modified with quaternary ammonium and phosphonium group as ionization enhancers |
| topic | derivatization fixed charge tag quaternary ammonium salt mass spectrometry electron-capture dissociation collision induced dissociation |
| url | https://www.mdpi.com/1420-3049/26/22/6964 |
| work_keys_str_mv | AT monikakijewska analysisoffragmentationpathwaysofpeptidemodifiedwithquaternaryammoniumandphosphoniumgroupasionizationenhancers AT dorotagaszczyk analysisoffragmentationpathwaysofpeptidemodifiedwithquaternaryammoniumandphosphoniumgroupasionizationenhancers AT remigiuszbachor analysisoffragmentationpathwaysofpeptidemodifiedwithquaternaryammoniumandphosphoniumgroupasionizationenhancers AT piotrstefanowicz analysisoffragmentationpathwaysofpeptidemodifiedwithquaternaryammoniumandphosphoniumgroupasionizationenhancers AT zbigniewszewczuk analysisoffragmentationpathwaysofpeptidemodifiedwithquaternaryammoniumandphosphoniumgroupasionizationenhancers |