Boron Isotope Tag-Assisted Ultrahigh-Performance Liquid Chromatography Coupled with High-Resolution Mass Spectrometry for Discovery and Annotation of cis-Diol-Containing Metabolites

Abstract

cis-Diol-containing metabolites are widely distributed in living organisms, and they participate in the regulation of various important biological activities. The profiling of cis-diolcontaining metabolites could help us in fully understanding their functions. In this work, based on the characteristic isotope pattern of boron, we employed a boronic acid reagent as the isotope tag to establish a sensitive and selective liquid chromatography−highresolution mass spectrometry method for the screening and annotation of cis-diol-containing metabolites in biological samples. Boronic acid reagent 2-methyl-4-phenylaminomethylphenylboronic acid was used to label the cis-diol-containing metabolites in biological samples to improve the selectivity and MS sensitivity of cis-diol-containing metabolites. Based on the characteristic 0.996 Da mass difference of precursor ions and the peak intensity ratio of 1:4 originating from 10 B and 11 B natural isotopes, the potential cis-diol-containing metabolites were rapidly screened from biological samples. Potential cis-diol-containing metabolites were annotated by database searching and analysis of fragmentation patterns obtained by multistage MS (MS n ) via collision-induced dissociation. Importantly, the cis-diol position could be readily resolved by the MS 3 spectrum. With this method, a total of 45 cisdiol-containing metabolites were discovered in rice, including monoglycerides, polyhydroxy fatty acids, fatty alcohols, and so forth. Furthermore, the established method showed superiority in avoiding false-positive results in profiling cis-diol-containing metabolites.

Machine learning-empowered cis-diol metabolic fingerprinting enables precise diagnosis of primary liver cancer

“…Liquid chromatography (LC) and capillary electrophoresis (CE) are leveraged by most traditional MS-based methods for separation. 25–27 However, these separation techniques are also associated with apparent drawbacks. LC requires a long analysis time ( i.e.…”

Biosensors with Boronic Acid-Based Materials as the Recognition Elements and Signal Labels

“…Boronate-affinity materials were primarily employed to immobilize and isolate cis -diol-containing compounds ten years ago in combination with traditional detection techniques [ 7 , 8 , 9 , 10 ]. For instance, boronic acid-modified columns and beads have been used to enrich glycoproteins for mass spectroscopy-based glycoproteome analysis [ 11 , 12 , 13 , 14 ]. Meanwhile, boronic acid derivatives with fluorescent or electrochemical properties are used to detect small cis -diol-containing species through the boronate-affinity-induced signal change [ 15 ].…”

Rapid and Economical Chemoselective Metabolomics Using Boronate Ester Formation on a Monolithic Substrate

“…The above two features can significantly reduce the strategy time from days to minutes. Based on the natural isotopic abundance of boron (B), we can recognize and identify labeled metabolites with MS with no need for isotopic reagents [13] and with greatly improved method economy.…”