Precolumn derivatization reagents for high‐speed analysis of amines and amino acids in biological fluid using liquid chromatography/electrospray ionization tandem mass spectrometry

A rapid analytical method for amines and amino acids was developed, involving derivatization with the novel reagent 3‐aminopyridyl‐N‐hydroxysuccinimidyl carbamate (APDS), followed by reversed‐phase high‐performance liquid chromatography and electrospray ionization tandem mass spectrometry (HPLC/ESI‐MS/MS). More than 100 different analytes with amino groups, including amino acids in biological fluids such as mammalian plasma, could be measured within 10 min. The analytes were easily derivatized with APDS under the mild conditions. Selective reaction monitoring of ESI‐MS/MS in positive mode was carried out to include the transitions of all of the protonated molecular ions of analytes derivatized with APDS to the common fragment at m/z 121, which was derived from the amino pyridyl moiety of the reagent. We evaluated the retention time precision, the quantification limits, the linearity, the intra‐ and inter‐day precisions and the accuracy of 22 typical amino acids found in biological fluids, by analyzing a standard amino acid mixture and rat plasma. The intra‐day relative standard deviations (RSDs) of the retention times of the 22 amino acids and their internal standards were within 0.9% and the inter‐day RSDs were less than 1.1%, except for asparagines, with an RSD of 1.9%. The intra‐day and inter‐day RSDs of amino acid analyses in rat plasma were within 8.0% and 4.5%, respectively. The method, which facilitates the amino acid analysis of more than 100 samples in a day, represents an alternative to traditional amino acid analysis techniques, such as chromatography using postcolumn derivatization by ninhydrin. Copyright © 2009 John Wiley & Sons, Ltd.     

2‐benzothiazolyl phenacyl sulfoxide,a new precursor for 2‐oxo‐2‐phenylethanethial

Previously, a facile formation of a thioaldehyde by the thermolysis of a heteroaryl phenacyl sulfoxide was confirmed by the detection of a cycloadduct with 2,3‐dimethyl‐1,3‐butadiene. The usefulness of benzothiazolyl phenacyl sulfoxide as a precursor for 2‐oxo‐2‐phenylethanethial was studied under the same conditions in the presence of various dienes and anthracene. In all cases, the Diels‐Alder cycloadducts were formed in moderate to good yields, and the addition of triethylamine as external base was revealed to be effective for carrying out the thermolysis under milder reaction conditions and for the improvement of yields. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 363–367, 1999