Probing Macromolecular Conformation in Restricted Geometry by PEF: Application to Hydrophobically Modified PAMAM Dendrimers Isolated Inside Surfactant Micelles
Bibliographic record
Abstract
The conformation of a series of zero-generation polyamidoamine dendrimers end-labeled with four 1-pyrene-butyroyl, -hexanoyl, -octanoyl, -decanoyl, and -dodecanoyl derivatives, referred to as the PyCX-PAMAM-G0 samples with X = 4, 6, 8, 10, and 12, respectively, was characterized in N, N -dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and aqueous solutions of 50 mM sodium dodecyl sulfate (SDS) or 50 mM dodecyltrimethylammonium bromide (DTAB). The conformation of the PyCX-PAMAM-G0 samples was determined from the global model-free analysis (MFA) of the fluorescence decays, which yielded the average rate constant (⟨ k ⟩) for pyrene excimer formation (PEF) between an excited and a ground-state pyrenyl labels, with ⟨ k ⟩ being proportional to the local concentration ([Py] loc ) of the pyrenyl labels within the macromolecular volume; ⟨ k ⟩-vs-[Py] loc plots yielded straight lines passing through the origin in DMF and DMSO, demonstrating that the internal segments of the dendrimers obeyed Gaussian statistics in these two solvents. In aqueous surfactant solutions, the hydrophobic pyrenyl labels induced the interactions of the PyCX-PAMAM-G0 dendrimers with the SDS and DTAB micelles. Plots of ⟨ k ⟩ as a function of [Py] loc yielded straight lines passing through the origin for the PyCX-PAMAM-G0 samples with X equal to 4, 6, and 8, indicating that the internal segments of these three dendrimers obeyed Gaussian statistics within the surfactant micelles. However, ⟨ k ⟩ departed from the straight lines for the PyCX-PAMAM-G0 samples with X = 10 and 12 associated with the SDS and DTAB micelles. This behavior indicated that [Py] loc was much larger than expected for the dendrimers prepared with longer alkanoyl linkers. This behavior was attributed to strong hydrophobic interactions between the longer linkers and the dodecyl tails of the surfactants in the hydrophobic core of the micelles, which induced a conformational change for the dendrimers inside the micelles, that could be probed at the molecular level by PEF.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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 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".