Indirect Enantioseparations: Recent Advances in Chiral Metabolomics for Biomedical Research

Abstract

Chiral metabolomics is starting to become a well-defined research field, powered by the recent advances in separation techniques. This review aimed to cover the most relevant advances in indirect enantioseparations of endogenous metabolites that were published over the last 10 years, including improvements and development of new chiral derivatizing agents, along with advances in separation methodologies. Moreover, special emphasis is put on exciting advances in separation techniques combined with mass spectrometry, such as chiral discrimination by ion-mobility mass spectrometry together with untargeted strategies for profiling of chiral metabolites in complex matrices. These advances signify a leap in chiral metabolomics technologies that will surely offer a solid base to better understand the specific roles of enantiomeric metabolites in systems biology.

Recent Advances in Separation and Analysis of Chiral Compounds

“…Chemical derivatization is an important strategy for MS discrimination of enantiomers. It is mostly used to analyze chiral compounds via LC-MS, GC-MS, and CE-MS by transforming enantiomers to diastereomers for easier separation by chromatography. , However, typical derivatization reagents are normally not capable of selectively labeling enantiomers or bringing weight difference between enantiomers, so direct enantiomer discrimination by MS is difficult to achieve . Therefore, specific derivatization reactions leading to different m / z values of parent ions or product ions for enantiomers are needed for chiral compounds by direct MS detection.…”

Stereoselective Amine-omics Using Heavy Atom Isotope Labeled l- and d-Marfey’s Reagents

“…A significant challenge in amine and amino acid analyses is their generally poor retention on reverse-phase media, necessitating chemical derivatization. Heavy atom isotope based derivatization reagents, such as 13 C 2 -dansyl chloride, have been instrumental in selectively identifying and quantifying amines and phenolic hydroxy compounds. , HRMS data collected from 12 C-dansyl chloride and 13 C 2 -dansyl chloride derivatized samples can be processed to selectively identify and quantify amines and phenolic hydroxy compounds, and this labeling approach has been applied in several analyses. , Chiral amine-omics approaches have recently received increased interest. − However, an amine-omics approach based on the widely used Marfey’s reagent appears lacking. This study explores a heavy atom isotope labeled Marfey’s reagent approach for amine metabolomics, capitalizing on the stereoselectivity offered by Marfey’s reagent.…”

Enantioanalysis of Cysteine Using an Enantioselective Stochastic Platform: A Key Factor on Early Diagnosis of Breast Cancer

“…The study of enantiomers of amino acids has been a subject of investigation in metabolomics research in recent years. [2][3][4][5][6] Cysteine (Cys) levels have been found to play a significant influence in the diagnostics of breast cancer. 7 Titanium dioxide (TiO 2 ) and diamond (D), are widely used as materials for the design of electrochemical sensors.…”