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Chromatographic profiles of tryptophan and kynurenine enantiomers derivatized with ( S )‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐( N , N ‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole using LC–MS/MS on a triazole‐bonded column
Author(s) -
Iizuka Hideaki,
Harashima Takahiro,
Takahashi Shuhei,
Kuwabara Ryosuke,
Naito Yoko,
Sakamoto Tatsuya,
Onozato Mayu,
Ichiba Hideaki,
Fukushima Takeshi
Publication year - 2017
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22726
Subject(s) - chemistry , chromatography , ammonium formate , enantiomer , tryptophan , resolution (logic) , tandem mass spectrometry , reagent , kynurenine , high performance liquid chromatography , hydrophilic interaction chromatography , mass spectrometry , amino acid , stereochemistry , organic chemistry , biochemistry , artificial intelligence , computer science
Abstract d ‐ and l ‐Tryptophan (Trp) and d ‐ and l ‐kynurenine (KYN) were derivatized with a chiral reagent, ( S )‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐(N,N‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole (DBD‐PyNCS), and were separated enantiomerically by high‐performance liquid chromatography (HPLC) equipped with a triazole‐bonded column (Cosmosil HILIC) using tandem mass spectrometric (MS/MS) detection. Effects of column temperature, salt (HCO 2 NH 4 ) concentration, and pH of the mobile phase in the enantiomeric separation, followed by MS detection of ( S )‐DBD‐PyNCS‐ d , l ‐Trp and ‐ d , l ‐KYN, were investigated. The mobile phase consisting of CH 3 CN/10 mM ammonium formate in H 2 O (pH 5.0) (90/10) with a column temperature of 50–60 °C gave satisfactory resolution ( R s) and mass‐spectrometric detection. The enantiomeric separation of d , l ‐Trp and d , l ‐KYN produced R s values of 2.22 and 2.13, and separation factors (α) of 1.08 and 1.08, for the Trp and KYN enantiomers, respectively. The proposed LC–MS/MS method provided excellent detection sensitivity of both enantiomers of Trp and KYN (5.1–19 nM).