Modification of Porous Silicon Surfaces with Activated Ester Monolayers
Bibliographic record
Abstract
A series of activated esters of undecylenic acid with activated ester end groups (3-nitrophenyl, N-succinimidyl, S-ethyl, and 2,2,2-trifluoroethyl) have been synthesized and covalently linked to a porous silicon (PSi) surface via a thermal hydrosilylation reaction. Diffuse reflectance infrared Fourier transform (DRIFT) or transmission FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the monolayers and to follow the course of reactions with primary amines in aqueous solution. It was found that the reaction of the 3-nitrophenyl undecylenate with the PSi surface resulted in significant oxidation of the surface. A control reaction with nitrobenzene confirmed that the arylnitro group was responsible for the surface oxidation and grafting of the nitroaromatic on the surface via a Si-O-N linkage. The N-succinimidyl (NHS) and thioethyl activated ester-modified surfaces formed monolayers with no apparent oxidation of the PSi surface. However, we find that the hydrophobic end groups prevent wetting of the porous structure and further reaction is not possible. Reactions of these groups could be achieved by the addition of 25% (v/v) of ethanol to the aqueous solution of amine, electrochemical partial oxidation of the surface, or preparation of mixed monolayers consisting of mixtures of undecylenic acid and the activated undecylenate ester in a ratio of 5:1 or higher. Under these conditions the NHS group was displaced by ethanolamine or n-butylamine. As expected, exposure of primary amines to the activated S-ethyl thioester did not result in any reaction. However, amide bond formation was observed upon reaction of the methyl ester of cysteine illustrating specificity of this activating group toward cysteine-terminated proteins.
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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 | 0.000 | 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) | 0.001 | 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".