Structure and Reactivity of Mixed ω-Carboxyalkyl/Alkyl Monolayers on Silicon: ATR-FTIR Spectroscopy and Contact Angle Titration
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Bibliographic record
Abstract
The structure, reactivity, and acid-base properties of mixed monolayers prepared by photochemical reaction of hydrogen-terminated silicon with mixtures of ethyl undecylenate and n-alkenes were studied by ATR-FTIR spectroscopy and contact-angle measurements. The surface composition of the mixed monolayers and its correlation with the hydrolysis reactivity of terminal ethoxycarbonyl (ester) groups were investigated by systematically varying the mole fraction of ethyl undecylenate and the chain length of the unsubstituted alkenes in the binary deposition solution. It has been shown that the mole fraction of ester groups on the surface deviates only slightly from the mole fraction of ethyl undecylenate in the solution. The efficiency of ester hydrolysis under acidic conditions is significantly influenced by the monolayer structure, i.e., the surface density of ester groups and length of the unsubstituted alkyl chains. In addition, we find that mixed omega-alkanoic acid/alkyl monolayers on silicon (prepared via hydrolysis) exhibit well-defined contact angle titration curves from which the surface acid dissociation constants were determined. The results were compared with the acid-base properties reported in the literature for carboxylic acid-terminated alkylsiloxane monolayers on hydroxylated silicon and for omega-mercaptoalkanoic acid/alkanethiolate monolayers on gold. The weak pKa dependence (deltapKa approximately 1) on the surface density of carboxylic acid groups and on the length of unsubstituted alkyl chains is attributed to variations of the microenvironment of the acid moieties. These experimental findings provide fundamental knowledge at the molecular level for the preparation of bioreactive surfaces of controlled reactivity on crystalline semiconductor substrates.
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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