Tautomeric Equilibria in Phenolic A-Ring Derivatives of Prodigiosin Natural Products
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Bibliographic record
Abstract
The prodigiosin natural products contain a common 4-methoxy-pyrromethene chromophore that is attached to a pyrrole A-ring that has its lone-pair nitrogen electrons in conjugation with the pyrromethene entity. This feature is known to play a key role in the biological activities (anticancer, antimicrobial, and immunosuppressive) of the prodigiosins. In an attempt to alter or improve upon the therapeutic potential of the prodigiosins, we have synthesized two new isomeric analogues that contain phenolic A-ring systems (a para (p)-phenol; an ortho (o)-phenol with respect to the pyrromethene) with lone-pair oxygen electrons in conjugation with the pyrromethene chromophore of the natural product. Herein, we report on the optical properties of the phenolic prodigiosin analogues that have been measured using absorbance and steady-state emission spectroscopy. For both analogues absorption measurements in aprotic solvents show that the neutral (L) ligands exist as the enol tautomers with lambda(max) ~ 460 nm, as noted for the parent prodigiosin natural product. However, in polar protic solvents the phenolic derivatives undergo ground-state prototropic tautomerization to generate keto tautomers with lambda(max) ~ 530 nm. This unique feature for a prodigiosin analogue involves proton transfer from the phenolic OH to the pyrromethene N1 proton acceptor atom. Tautomeric equilibrium constants (KT) of 1.4 in 1:4 MeCN/H2O (v/v) have been determined from examination of the absorption spectra. Titration of the o-phenolic derivative with Zn(II) in methanol yielded a 40-fold increase in fluorescence intensity (lambda(max) 542 nm) and generated a new 1:1 complex with Zn(II) with a log K of 5.29, suggesting the potential utility of this analogue to act as a fluorescence probe in a biological matrix to monitor Zn(II) concentrations. Our results demonstrate that phenolic A-ring derivatives of prodigiosins possess some unique properties that may act to enhance the biological properties of the prodigiosin natural products.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it