Ultraviolet photodissociation and collision-induced dissociation for qualitative/quantitative analysis of low molecular weight compounds by liquid chromatography-mass spectrometry.

Collision-induced dissociation (CID) is the most wildly used fragmentation technique for qualitative and quantitative determination of low molecular weight compounds (LMWC). Ultraviolet photodissociation (UVPD) has been mainly investigated for the analysis of peptides and lipids while only in a limited way for LMWC. A triple quadrupole linear ion trap instrument has been modified to allow ultraviolet photodissociation (UVPD) in the end of the q2 region enabling various workflows with and without data-dependent acquisition (DDA) combining CID and UVPD in the same LC-MS analysis. The performance of UVPD, with a 266-nm laser, is compared to CID for a mix of 90 molecules from different classes of LMWC including peptides, pesticides, pharmaceuticals, metabolites, and drugs of abuse. These two activation methods offer complementary fragments as well as common fragments with similar sensitivities for most analytes investigated. The versatility of UVPD and CID is also demonstrated for quantitative analysis in human plasma of bosentan and its desmethyl metabolite, used as model analytes. Different background signals are observed for both fragmentation methods as well as unique fragments which opens the possibility of developing a selective quantitative assay with improved sample throughput, in particular for analytes present in different matrices.

Analysis of perchlorate in foods and beverages by ion chromatography coupled with tandem mass spectrometry (IC-ESI-MS/MS).

A new IC-ESI-MS/MS method, with simple sample preparation procedure, has been developed for quantification and confirmation of perchlorate (ClO4-) anions in water, fresh and canned food, wine and beer samples at low part-per-trillion (ng l(-1)) levels. To the best of our knowledge, this is the first time an analytical method is used for determination of perchlorate in wine and beer samples. The IC-ESI-MS/MS instrumentation consisted of an ICS-2500 ion chromatography (IC) system coupled to either an API 2000 or an API 3200 mass spectrometer. The IC-ESI-MS/MS system was optimized to monitor two pairs of precursor and fragment ion transitions, i.e., multiple reaction monitoring (MRM). All samples had oxygen-18 isotope labeled perchlorate internal standard (ISTD) added prior to extraction. Chlorine isotope ratio (35Cl/37Cl) was used as a confirmation tool. The transition of 35Cl16O4- (m/z 98.9) into 35Cl16O3- (m/z 82.9) was monitored for quantifying the main analyte; the transition of 37Cl16O4- (m/z 100.9) into 37Cl16O3- (m/z 84.9) was monitored for examining a proper isotopic abundance ratio of 35Cl/37Cl; and the transition of 35Cl18O4- (m/z 107.0) into 35Cl18O3- (m/z 89.0) was monitored for quantifying the internal standard. The minimum detection limit (MDL) for this method in de-ionized water is 5 ng l(-1) (ppt) using the API 2000 mass spectrometer and 0.5 ng l(-1) using the API 3200 mass spectrometer. Over 350 food and beverage samples were analyzed mostly in triplicate. Except for four, all samples were found to contain measurable amounts of perchlorate. The levels found ranged from 5 ng l(-1) to 463.5+/-6.36 microg kg(-1) using MRM 98.9-->82.9 and 100 microl injection.