A facile and fully automated on-fiber derivatization protocol for direct analysis of short-chain aliphatic amines using a matrix compatible solid-phase microextraction coating

Abstract

Solid-phase microextraction (SPME) analysis of short-chain aliphatic amines (C3-C6) in aqueous solutions was investigated using pentafluorobenzaldehyde (PFBAY) as on-fiber derivatization reagent. A standard gas generating vial agent was used for on-fiber loading of the derivatization agent so as to avoid the need for its regeneration at each derivatization cycle. Several parameters such as loading time, reaction temperature, and reaction/extraction time were optimized for headspace and direct sampling in aqueous solutions. Three different coating chemistries were tested and their performances compared in order to achieve the best compromise between sensitivity and analysis throughput. The newly developed PDMS/DVB/PDMS coating showed superior performance in terms of extraction efficiency while the capability to prevent on-fiber degradation of the derivatizing products. The optimized method was used for quantitation of short-chain aliphatic amines in aqueous samples and provided detection limits in the low ppb range for all the amines tested with accuracy values between 79 and 120%. The method was applied towards the analysis of environmental water samples and the accuracy of the results was evaluated by different calibration approaches.

Advances in Solid Phase Microextraction and Perspective on Future Directions

“…Similarly, a vial based on a crushed PDMS sorbent with a 13 component mixture was used for the specific application of mass spectral tuning of field portable GC-MS instrumentation . Likewise, a pentafluorobenzaldehyde (PFBAY) generating vial was used to facilitate the on-fiber derivatization of short-chain aliphatic amines from surface water samples . In addition to the abovementioned specific applications, these standard generators are most commonly used as a simple quality control device to ensure stable response, as they can be easily placed in a heated block on a GC autosampler or transported on-site in a battery-operated block heater to perform quality control injections on portable GC-MS instrumentation before and after samplings …”

Hunting Molecules in Complex Matrices with SPME Arrows: A Review

“…In addition, Helin et al did not report any issues when using SPME Arrow for HS amines in water with an SPME Arrow [17]. Finally, Gionfriddo et al demonstrated short-chain aliphatic amines are best analyzed with the use of derivatization [28].…”

Problems Caused by Moisture in Gas Chromatographic Analysis of Headspace SPME Samples of Short-Chain Amines

“…Additionally, with derivatization, the volatility can be decreased and retention in GC increased. As an example, Gionfriddo et al successfully utilized onfiber derivatization using pentafluorobenzaldehyde (PFBAY) as reagent for determination of short-chain aliphatic amines in aqueous samples by SPME-GC/MS [19].…”