Redox‐Triggered Reversible Switching between Dynamic and Quasi‐static α‐Helical Peptides
Bibliographic record
Abstract
Abstract We report the reversible transformation between a singly stapled dynamic α‐helical peptide and a doubly stapled quasi‐static one through redox‐triggered dithiol/disulfide conversions of a stapling moiety. This process allows the rate of interconversion between the right‐handed ( P ) and left‐handed ( M ) α‐helices to be altered by a factor of approximately 10 3 before and after the transformation. An as‐obtained doubly stapled α‐helical peptide, which is composed of an achiral peptide having an l ‐valine carboxylic acid residue at the C‐terminus, a disulfide‐based reversible staple, and a biphenyl‐based fixed staple, adopts an ( M )‐rich form as a kinetically trapped state. The ( M )‐rich helix was subsequently transformed into the thermodynamically stable ( P )‐rich form in 1,1,2,2‐tetrachloroethane with the half‐life time ( t 1/2 ) of approximately 44 days at 25 °C. Reduction of the doubly stapled peptide with tri‐ n ‐butylphosphine in tetrahydrofuran/water (10/1, v/v) produced the corresponding singly stapled dynamic α‐helical peptide bearing two thiol groups at the side chains, which underwent solvent‐induced reversible helicity inversion. The resulting dithiol of the singly stapled peptide could be reoxidized to form the original doubly stapled form using 4,4’‐dithiodipyridine. Furthermore, the P / M interconversion of a doubly stapled peptide with two flexible hydrocarbon‐based staples is considerably more rapid than that with more rigid staples.
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 | 0.002 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".