Using Chemical Derivatization to Determine the Human Urinary Acidic Catecholamine Metabolites Quantitatively by Liquid Chromatography/Electrospray Ionization‐Tandem Mass Spectrometry

Abstract

Based on a 4,6-dimethoxy-2-(methylsulfonyl)pyrimidine (DMMSP) labeling reagent, a sensitive method to determine acidic catecholamine metabolites homovanillic acid (HVA), vanillymandelic acid (VMA), 3,4-dihydroxymandelic acid (DOMA) and 3,4-dihydroxyphenylacetic acid (DOPAC) has been developed using simple chemical derivatization with liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). Acidic catecholamine metabolites were converted to stable 4,6-dimethoxypyrimidinyl (DMP) derivatives by one-step derivatization. Because of bulky DMP group(s) introduced into the structures of these metabolites, subsequent analysis by LC/ESI-MS/MS in positive ionization with multiple reaction monitoring (MRM) allowed specific detection of DMP derivatives of these metabolites with a wide linear relationship range. The limits of detection were in the range of 1-5 ng/mL. The mean recoveries determined were 100.2%-104.4%. Both relative standard deviation and error for intra-and inter-day measurements were less than 10% for acidic catecholamine metabolites. This strategy enabled accurate and specific determination of acidic catecholamine metabolites in human urine.

Single‐Molecule Sensing of Acidic Catecholamine Metabolites Using a Programmable Nanopore

“…Taking the minimum concentration of the analyte required to detect at least 5 events within 10 min of measurement as the standard, the limits of detection of all three acidic metabolites were shown in Table S4. Since the concentration of acidic catecholamine metabolites in physiological samples (human urine or plasma) is much lower than this limit of detection, [4b,d] the sensing strategy in its current configuration is not expected to be used for direct sensing of physiological samples without any sample enrichment prior to the measurement. However, engineering strategies including reduction of the volume of the measurement chamber, establishing an array of nanopores or inclusion of multiple PBA reactive sites may solve this challenge [13]…”

Fast Determination of Phenanthrene in Soil by Gas Chromatography‐Mass Spectrometry Using Chemometric Resolution and Standard Addition Method

“…Hyphenated chromatographic techniques, such as high-performance liquid chromatography with diode array detector (HPLC-DAD), [1,2] gas chromatographymass spectrometry (GC-MS) [3][4][5] and liquid chromatography-mass spectrometry (LC-MS) [6,7] have played a key role in environmental monitoring. For enhancing the analytical capacity, two-or multi-dimensional chromatographic techniques were developed for analyzing real complex samples.…”

Thin-layer chromatography-an image-processing method for the determination of acidic catecholamine metabolites

“…Currently, the most widely used methods are based on GC or HPLC coupled with MS, fluorescence, or electrochemical detection . Although these methods can give the most reliable results, they require sophisticated equipment and some limitations as the conversion into volatile compounds, coeluting interference, or time consuming sample pretreatment procedures (such as SPE or precolumn derivatization) may occur when biological samples are analyzed . Although there some are studies concerning the analysis of catecholamine derivatives by thin‐layer chromatography (TLC) , they are focused on separation efficiency and none of these works have developed a sensitive and rapid TLC quantitative evaluation study.…”