Two-Dimensional (2D) Pulsed Electron Paramagnetic Resonance Study of VO<sup>2+</sup>−Triphosphate Interactions: Evidence for Tridentate Triphosphate Coordination, and Relevance To Bone Uptake and Insulin Enhancement by Vanadium Pharmaceuticals
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Bibliographic record
Abstract
Two- and four-pulse electron spin echo envelope modulation (ESEEM) and four-pulse two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopies have been used to determine the solution structure of a 3:1 triphosphate:vanadyl solution at pH 5.0. Limited quantitative data were extracted from the two pulse spectra; however, HYSCORE proved to be more useful in the detection and interpretation of the (31)P and (1)H couplings. Three sets of cross-peaks were observed for each nucleus. For the (31)P couplings, three sets of cross-peaks were observed in the HYSCORE spectrum, and contour line shape analysis yielded coupling constants of approximately 15, 9, and 1 MHz. HYSCORE cross-peaks in the proton region were partially overlapping; however, interpretation of the proton coupling was simplified through the use of one-dimensional four-pulse ESEEM and subsequent analysis of the sum combination peaks. Comparison of the derived isotropic and anisotropic coupling constants with results from earlier ESEEM and electron nuclear double resonance (ENDOR) studies was consistent with the presence of at least one, and most likely two, water molecules coordinated in the equatorial plane of the vanadyl cation. The vanadyl-triphosphate system was shown to be an accurate model of the in vivo vanadyl-phosphate coupling constants determined in an earlier study (Dikanov, S. A.; Liboiron, B. D.; Thompson, K. H.; Vera, E.; Yuen, V. G.; McNeill, J. H.; Orvig, C. J. Am. Chem. Soc. 1999, 121, 11004.) Comparison of these values to those found in previous spectroscopic studies of vanadyl-triphosphate interactions, along with a detailed structural interpretation, are presented. This work represents the first detection of tridentate polyphosphate coordination to the vanadyl ion, and the first observation of an axial phosphate interaction not previously reported in earlier ENDOR and pulsed electron paramagnetic resonance studies.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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