Enantiomeric separation of <scp>d</scp>‐ and <scp>l</scp>‐serine using high‐performance liquid chromatography with electrochemical detection following pre‐column diastereomer derivatization

Yamashita, Kazuhide; Fukushima, Takeshi; Sasaki, Tsukasa; Arai, Kotaro; Toyo’oka, Toshimasa

doi:10.1002/bmc.1196

Cited by 4 publications

(1 citation statement)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The peak of (R)sulforaphane−(R)-leucine was detected at the retention time of (S)-sulforaphane−(S)-leucine, suggesting that this result can be used for peak confirmation of (S)-sulforaphane in broccoli samples. 46,47 Racemic iberin and (S)-sulforaphene (Figure 1A), which are sulforaphane-related compounds, were derivatized with (S)-leucine, and the iberin derivative was successfully resolved. Because racemic or (R)-sulforaphene was not commercially available, the resolvability of the sulforaphene derivative was not confirmed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

HPLC Separation of Sulforaphane Enantiomers in Broccoli and Its Sprouts by Transformation into Diastereoisomers Using Derivatization with (S)-Leucine

Okada

Yamamoto

Aizawa

et al. 2016

J. Agric. Food Chem.

View full text Add to dashboard Cite

Racemic sulforaphane, which was derivatized with (S)-leucine (l-leucine), was resolved by reversed phase HPLC with UV detection. The optimum mobile phase conditions were found to be 10 mM citric acid (pH 2.8) containing 22% methanol at 35 °C using detection at 254 nm. Sulforaphane enantiomers in florets and stems of five brands of broccoli and leaves and stems of three brands of broccoli sprouts were analyzed by the proposed HPLC method. Both sulforaphane enantiomers were detected in all of the samples. The S/R ratios of sulforaphane in broccoli samples were 1.5-2.6/97.4-98.5% for florets and 5.0-12.1/87.9-95.0% for stems. The S/R ratios in broccoli sprout samples were higher than those in broccoli samples and were found to be 8.3-19.7/80.3-91.7% for leaves and 37.0-41.8/58.2-63.0% for stems. (S)-Sulforaphane detected in the broccoli and its sprout samples was positively identified by separately using an HPLC with a chiral column (Chiralpak AD-RH) and mass spectrometry.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

HPLC Separation of Sulforaphane Enantiomers in Broccoli and Its Sprouts by Transformation into Diastereoisomers Using Derivatization with (S)-Leucine

Okada

Yamamoto

Aizawa

et al. 2016

J. Agric. Food Chem.

View full text Add to dashboard Cite

show abstract

Application of TLC, HPLC and GC methods to the study of amino acid and peptide enantiomers: a review

Dołowy

Pyka

2013

Biomedical Chromatography

View full text Add to dashboard Cite

Amino acids are very important organic compounds in nature. The biological activity of amino acids depends mainly on their stereoisomeric configuration (d- or l-). Thus, the stereochemical analysis of amino acids and peptides is an important aspect of their characterization. Owing to the increasing role of amino acid configuration in biomedical and pharmaceutical studies, numerous analytical methods have been described in the literature. Among a wide range of analytical techniques available for the steroselective separation of different amino acids, which were obtained from plants or biological samples, chromatographic methods such as thin-layer chromatography, high-performance chromatography and also gas chromatography are very useful. This review presents such systems developed for direct stereoisomeric separation and quantitative determination of amino acid and peptide enantiomers with emphasis on selected literature published during two last decades. Almost all aspects, including sample preparation prior chromatographic analysis, stationary phase, solvent system and detection system, are discussed. New possibilities in chiral amino acid analysis have been opened up by the application of mass spectrometry and infrared detection in thin-layer chromatography and mass spectrometry-selected ion monitoring detection system in gas chromatography. A modern trend in high-performance chromatography is two-dimensional chromatography. These innovations have led to decreased development time and increased amino acid resolution and detectability.

show abstract

Determination of d-serine in human serum by LC-MS/MS using a triazole-bonded column after pre-column derivatization with (S)-4-(3-isothiocyanatopyrrolidin-1-yl)-7- (N, N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole

et al. 2015

View full text Add to dashboard Cite

An LC-MS/MS-based method for determining D-serine (Ser), an endogenous co-agonist of the N-methyl-D-aspartate receptor, in human serum, was developed and validated using a triazole-bonded silica-packed column after pre-column fluorescence derivatization with a chiral labeling reagent, (S)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole. Enantiomeric separation of the D- and L-Ser derivatives occurred in the triazole-bonded column (R s: 1.85) with CH3CN/100 mM HCO2NH4 in H2O (95.5:4.5) as the mobile phase with isocratic elution. The ln(capacity factor of D-Ser) in the van't Hoff plot gradually decreased with the inverse of temperature, suggesting enhanced hydrophilic interactions with the triazole-bonded stationary phase with increasing column temperature, owing to decrease in the partition coefficient to the mobile phase. Multiple reaction monitoring (m/z 457.10 > 409.00) by triple quadrupole mass spectrometry was used for quantifying D-Ser in human serum. The presence of D-Ser in the serum was confirmed by treatment with commercial D-amino acid oxidase. A linear calibration curve was constructed in the D-Ser concentration range of 0.5-5.0 μM (r (2) = 0.999, n = 3) using D-homoserine as the internal standard. The precision and recovery values were adequate for quantification. The detection limit for D-Ser was 1.1 fmol/injection (signal-to-noise ratio = 3), owing to the high CH3CN content in the mobile phase. The proposed LC-MS/MS method showed few fluctuations in the retention times of D- and L-Ser, and R s was stable until the 40th injection of serum without column washing, and thus can be useful for D-Ser determination in human serum in clinical research.

show abstract

Enantiomeric separation of d‐ and l‐serine using high‐performance liquid chromatography with electrochemical detection following pre‐column diastereomer derivatization

Cited by 4 publications

References 14 publications

HPLC Separation of Sulforaphane Enantiomers in Broccoli and Its Sprouts by Transformation into Diastereoisomers Using Derivatization with (S)-Leucine

HPLC Separation of Sulforaphane Enantiomers in Broccoli and Its Sprouts by Transformation into Diastereoisomers Using Derivatization with (S)-Leucine

Application of TLC, HPLC and GC methods to the study of amino acid and peptide enantiomers: a review

Determination of d-serine in human serum by LC-MS/MS using a triazole-bonded column after pre-column derivatization with (S)-4-(3-isothiocyanatopyrrolidin-1-yl)-7- (N, N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole

Contact Info

Product

Resources

About