Preliminary investigation of the simultaneous detection of sugars, ascorbic acid, citric acid, and sodium benzoate in non-alcoholic beverages by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the simultaneous detection of sugars, ascorbic acid, citric acid, sodium and/or potassium benzoate in non-alcoholic beverages, with meso-tetrakis(pentafluorophenyl)porphyrin (MW 974) as a matrix. Using potassium hydroxide as dopant, fructose/glucose was detected as the potassiated molecule at m/z 219, whereas potassiated sucrose, [Sucrose. K](+), was detected at m/z 381. Using sodium hydroxide as dopant, the fructose and sucrose ions were detected at m/z 203 and 365, respectively. Citric acid generated multiple ions at m/z 269, 307, and 345, which were assigned to [Citricbond;H+2K](+), [Citricbond;2H+3K](+), and [Citricbond;3H+4K](+), respectively. However, a stored methanolic solution of citric acid produced additional ions at m/z 283, 297, and 321, which were attributed to [Citricbond;2H+CH(3)+2K](+), [Citricbond;3H+2CH(3)+2K](+), and [Citricbond;3H+CH(3)+3K](+), respectively, due to esterification that took place during storage. The limits of detection in water were: ascorbic acid, 0.30 wt%; citric acid, 0.5 wt%; and sodium benzoate, 0.001 wt%. In the beverage formulations, the limits of detection were: ascorbic acid 0.3 wt%, citric acid 0.3 wt%, and sodium benzoate 0.02 wt%. Spiking a water or beverage solution that contained ascorbic and/or citric acid with less than 0.6 wt% of tartaric acid lowered the detection limits of ascorbic and citric acids to 0.2 wt%. This study demonstrates the potential for using MALDI-TOFMS in the quality control analyses of non-alcoholic beverages, particularly with regard to the detection of low molecular weight organic acids in commercial beverage formulations.

Comparative quantitative fatty acid analysis of triacylglycerols using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gas chromatography.

Quantitative analyses of fatty acids from five triacylglycerol products, coconut oil, palm kernel oil, palm oil, lard and cocoa butter, were carried out using two analytical methods: matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and gas chromatography (GC), in an effort to validate the application of MALDI-TOFMS in quantitative fatty acid analysis. For the GC analysis, transmethylated products were used, whereas, for the MALDI-TOF analysis, saponified products were used. Under MALDI-TOF conditions, the acids were detected as sodiated sodium carboxylates [RCOONa + Na](+) consistent with the mode of ionization that was previously reported. Thus, the MALDI-TOF mass spectrum of saponified coconut oil showed the presence of sodiated sodium salts of caprylic acid (7.5 +/- 0.67, m/z 189), capric acid (6.9 +/- 0.83, m/z 217), lauric acid (47.8 +/- 0.67, m/z 245), myristic acid (20.4 +/- 0.51, m/z 273), palmitic acid (9.8 +/- 0.47, m/z 301), linoleic acid (0.9 +/- 0.07, m/z 325), oleic acid (4.8 +/- 0.42, m/z 327) and stearic acid (2.0 +/- 0.13, m/z 329). Saponified palm kernel oil had a fatty acid profile that included caprylic acid (3.5 +/- 0.59), capric acid (4.7 +/- 0.82), lauric acid (58.6 +/- 2.3), myristic acid (20.9 +/- 1.5), palmitic acid (7.2 +/- 1.1), oleic acid (3.8 +/- 0.62) and stearic acid (1.2 +/- 0.15). Saponified palm oil gave myristic acid (0.83 +/- 0.18), palmitic acid (55.8 +/- 1.7), linoleic acid (4.2 +/- 0.51), oleic acid (34.5 +/- 1.5), stearic acid (3.8 +/- 0.26) and arachidic acid (0.80 +/- 0.22). Saponified lard showed the presence of myristic acid (1.5 +/- 0.24), palmitic acid (28.9 +/- 1.3), linoleic acid (13.7 +/- 0.67), oleic acid (38.7 +/- 1.4), stearic acid (12.8 +/- 0.64) and arachidic acid (2.4 +/- 0.35). Finally, for saponified cocoa butter, the fatty acid distribution was: palmitic acid (32.3 +/- 1.0), linoleic acid (2.6 +/- 0.35), oleic acid (34.9 +/- 1.7) and stearic acid (30.3 +/- 1.6). Quantitative gas chromatographic analysis of the corresponding methyl esters from these triacylglycerol products yielded data that were mostly in agreement with the MALDI-TOFMS data. The MALDI-TOF experiment, however, proved to be superior to the GC experiment, particularly with regard to baseline resolution of unsaturated acids. Furthermore, the ability of MALDI-TOFMS to detect low concentrations of fatty acids rendered it more sensitive than the GC methodology.