A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for direct and on-line measurements of pharmaceuticals and contaminants in small, complex samples

作者：Duncan Kyle D; Willis Megan D; Krogh Erik T; Gill Christopher G^*

来源：Rapid Communications in Mass Spectrometry, 2013, 27(11): 1213-1221.

DOI：10.1002/rcm.6560

RATIONALE High-throughput, automated analytical measurements are desirable in many analytical scenarios, as are rapid sample pre-screening techniques to identify 'positive' samples for subsequent measurements using more time-consuming conventional methodologies (e.g., liquid chromatography/mass spectrometry (LC/MS)). A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for the direct and continuous, on-line measurement of pharmaceuticals and environmental contaminants in small, complex samples is presented. METHODS A miniature polydimethylsiloxane hollow fibre membrane (PDMS-HFM) probe is coupled with an electrospray ionization (ESI) triple quadrupole mass spectrometer. Analytes are transported from the probe to the ESI source by a methanol acceptor phase. The probe can be autosampler mounted and directly inserted in small samples (400 L) allowing continuous and simultaneous pptrppb level detection of target analytes (chlorophenols, triclosan, gemfibrozil, nonylphenol) in complex samples (artificial urine, beer, natural water, waste water, plant tissue). RESULTS The probe has been characterized and optimized for acceptor phase flow rate, sample mixing and probe washing. Signal response times, detection limits and calibration data are given for selected ion monitoring (SIM) and tandem mass spectrometry (MS/MS) measurements of target analytes at trace levels. Comparisons with flow cell type CP-MIMS systems are given. Analyte depletion effects are evaluated for small samples (400 L). On-line measurements in small volumes of complex samples, temporally resolved reaction monitoring and in situ/in vivo demonstrations are presented. CONCLUSIONS The miniature CP-MIMS probe developed was successfully used for the direct, on-line detection of target analytes in small volumes (40mL to 400 L) of complex samples at pptr to low ppb levels. The probe can be readily automated as well as deployed for in situ/in vivo monitoring, including reaction monitoring, small sample measurements and direct insertion in living plant tissue.

• 出版日期2013-6-15