Digital Simulation and Experimental Validation of Redox Mediation at an Electroactive Monolayer-Coated Electrode
Bibliographic record
Abstract
A commercial digital simulation tool was used to simulate cyclic voltammetry (CV) data for redox mediation electrode reactions involving immobilized redox mediators. The system studied consists of a ferrocene-based redox mediator in an alkanethiolate-based self-assembled monolayer (SAM) on gold, with ferrocyanide in solution acting as electron donor to react with electrogenerated ferrocenium in the monolayer. Simulation parameters include rate constants for ferrocene oxidation/reduction in the monolayer, the mediation cross reaction between ferrocenium in the monolayer and ferrocyanide in solution, and the direct (unmediated) ferrocyanide oxidation/reduction reaction by long-range electron transfer across the monolayer. An excellent agreement between simulation and experiment was obtained using simulation parameters derived from independent experiments. The simulation method enables analysis of an entire voltammogram which can offer advantages over analytical approaches that consider only a portion of the data (e.g., a “foot-of-the-wave” analysis). The availability of a validated simulation tool allows questions about the anticipated reactivity of immobilized redox mediators to be addressed definitively via simulation, rather than by speculation on the effects one might expect to observe on a CV waveshape for a particular parameter change.
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 machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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 source (direct Gemma or distilled Codex), 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".