Negative‐charge driven fragmentations for evidencing zwitterionic forms from doubly charged coppered peptides
Bibliographic record
Abstract
In aqueous solution, amino acids (AA) and peptides are known to exist as zwitterions over a large pH range. However, in the gas phase, i.e. in electrospray (ESI), the zwitterionic form becomes unfavorable owing to the absence of stabilizing effects from intermolecular solvation. Nevertheless, during mass spectrometry experiments, the presence of a metallic cation can reinforce the zwitterionic character of the molecule and thus influence its fragmentation under low energy collision-induced dissociation (CID) conditions. The [M + Cu(II)](2+) complexes of six pentapeptides (YGGFL, YGGFL(NH(2)), YGGFK, YGGFQ, KYGGF and QYGGF) were analyzed by collision to highlight the presence of zwitterions. The experiments were performed on a 3D-ion trap equipped with an orthogonal ESI source. For each peptides studied, negative-charge driven fragmentations on globally positively charged ions were observed. These fragmentation mechanisms, generally observed in the negative mode, suggest the competitive deprotonation of the C-terminal carboxylic acid or of the tyrosine side-chain residue for each peptide studied and thus a zwitterionic form to preserve the charge balance. Moreover, the specific loss of (CH(3)--C(6)H(4)--O)(*) characterizes YGGFK compared to YGGFQ and the specific loss of styrene characterizes KYGGF compared to QYGGF. These results allow the differentiation of the two couples of isobaric pentapeptides. An unusual loss of NH(4) (+), which occurred from the N-terminus, was also observed for YGGFL, YGGFL(NH(2)), YGGFK and YGGFQ. Finally, the reduction of Cu(II) to Cu(I), concomitant with the (CH(3)--C(6)H(4)--O)(*) release, was pointed out for YGGFK.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.007 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".