Delicate polydimethylsiloxane hollow fibre membrane interfaces for condensed phase membrane introduction mass spectrometry (CP‐MIMS)
Bibliographic record
Abstract
RATIONALE: On-line analytical techniques such as condensed phase membrane introduction mass spectrometry (CP-MIMS) permit direct and rapid analyte measurements in complex samples. Direct, rapid analytical methods are desirable because they eliminate potential contamination and/or dilution from sample workup steps, facilitate rapid sample screening and allow 'real-time' monitoring applications. METHODS: PDMS hollow fibre membrane (HFM) flow cell interfaces (215 µm, 35 µm, and 0.5 µm thick composite) were coupled with an electrospray ionization (ESI) triple quadrupole mass spectrometer. A simultaneous push/pull methanol acceptor phase delivery system and membrane mounting via epoxy potting ensured that the delicate membranes were not ruptured during construction or sample measurements. Both flow cell and direct insertion 'J-Probe' interfaces using the 0.5 µm thick composite PDMS HFM were utilized for direct naphthenic acid measurements. RESULTS: Delicate HFM CP-MIMS interfaces were used for the rapid screening and continuous, on-line monitoring of carboxylic acids and hydroxylated compounds directly in complex sample matrices under ambient conditions at pptr - ppb detection limits. Push/pull acceptor phase (methanol) delivery maintained ambient hydrostatic pressures within the HFMs, improving ESI stability and analytical sensitivity, especially with stopped acceptor flow operation. Signal response times less than 2 min were achieved for thin, composite PDMS HFMs at 30°C. The continuous monitoring of naphthenic acid degradation was demonstrated. CONCLUSIONS: Delicate PDMS HFM CP-MIMS interfaces were developed and used for the direct, on-line detection of low volatility, polar analytes in complex aqueous samples. Composite PDMS HFM interfaces yielded the best overall analytical performance improvements, and were used to demonstrate the direct measurement of naphthenic acids in complex aqueous samples.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".