A chiral GC-MS method for analysis of secondary amino acids after heptafluorobutyl chloroformate & methylamine derivatization
Language English Country Austria Media print-electronic
Document type Journal Article
Grant support
No. 17-22276S
Grantová Agentura České Republiky
No. BYCZ118
EU Fund Interreg project
PubMed
33586043
DOI
10.1007/s00726-021-02949-1
PII: 10.1007/s00726-021-02949-1
Knihovny.cz E-resources
- Keywords
- Enantiomeric separation, GC–MS, Heptafluorobutyl chloroformate, Imino acids, Methyl amide derivatives, Secondary amino acids,
- MeSH
- Fluorocarbons chemistry MeSH
- Formates chemistry MeSH
- Imino Acids analysis chemistry MeSH
- Calibration MeSH
- Humans MeSH
- Methylamines chemistry MeSH
- Gas Chromatography-Mass Spectrometry methods standards MeSH
- Reproducibility of Results MeSH
- Stereoisomerism MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Fluorocarbons MeSH
- Formates MeSH
- heptafluorobutyl chloroformate MeSH Browser
- Imino Acids MeSH
- methylamine MeSH Browser
- Methylamines MeSH
L-amino acids (L-AAs) play different important roles in the physiology of all living organisms. Their chiral counterparts, D-amino acids (D-AAs) are increasingly being recognized as essential molecules in many biological systems. Secondary amino acids with cyclic structures, such as prolines, exhibit conformational rigidity and thus unique properties in the structural and protein folding. Despite their widespread occurrence, much less attention was paid to their chiral analysis, particularly when the minor, typically D-enantiomer, is present in low amounts in a complex biological matrix. In this paper, a cost-effective, chiral GC-MS method is described for capillary Chirasil-L-Val separation of nine cyclic secondary amino acid enantiomers with four-, five-, and six-membered rings, involving azetidine-2-carboxylic acid, pipecolic acid, nipecotic acid, proline, isomeric cis/trans 3-hydroxy, 4-hydroxyproline, and cis/trans-5-hydroxy-L-pipecolic acid in the excess of its enantiomeric antipode. The sample preparation involves in-situ derivatization with heptafluorobutyl chloroformate, simultaneous liquid-liquid micro-extraction into isooctane followed by amidation of the arising low-polar derivatives with methylamine, an evaporation step, re-dissolution, and final GC-MS analysis. The developed method was used for analyses of human biofluids, biologically active peptides containing chiral proline constituents, and collagen.
See more in PubMed
Abe I, Fujimoto N, Nishiyama T, Terada K, Nakahara T (1996) Rapid analysis of amino acid enantiomers by chiral-phase capillary gas chromatography. J Chromatogr A 722:221–227 DOI
Abe I, Kawazuma M, Fujimoto N, Nakahara T (1995) N-alkyloxycarbonyl isobutylamides as readily prepared diamide derivatives of amino-acids for separation of enantiomeric isomers by chiral phase capillary gas-chromatography. Chem Lett 329–330
Abe I, Nakahara T (1996) Enantiomer separation of amino acids as their N-alkyloxycarbonyl alkylamide derivatives by chiral phase capillary GC. Hrc-J High Resolut Chromatogr 19:511–514 DOI
Ali HSM, Alhaj OA, Al-Khalifa AS, Bruckner H (2014) Determination and stereochemistry of proteinogenic and non-proteinogenic amino acids in Saudi Arabian date fruits. Amino Acids 46:2241–2257 DOI
Armstrong DW, Gasper M, Lee SH, Zukowski J, Ercal N (1993) D-amino-acid levels in human physiological fluids. Chirality 5:375–378 DOI
Baek SH, Lee JG, Park SY, Piao XL, Kim HY, Bae ON, Park JH (2012) Gas chromatographic determination of azetidine-2-carboxylic acid in rhizomes of Polygonatum sibiricum and Polygonatum odoratum. J Food Compos Anal 25:137–141 DOI
Bach TMH, Takagi H (2013) Properties, metabolisms, and applications of L-proline analogues. Appl Microbiol Biotechnol 97:6623–6634 DOI
Bellon G, Berg R, Chastang F, Malgras A, Borel JP (1984) Separation and evaluation of the cis and trans isomers of hydroxyprolines - effect of hydrolysis on the epimerization. Anal Biochem 137:151–155 DOI
DarkinRattray SJ, Gurnett AM, Myers RW, Dulski PM, Crumley TM, Allocco JJ, Cannova C, Meinke PT, Colletti SL, Bednarek MA, Singh SB, Goetz MA, Dombrowski AW, Polishook JD, Schmatz DM (1996) Apicidin: a novel antiprotozoal agent that inhibits parasite histone deacetylase. Proc Natl Acad Sci USA 93:13143–13147 DOI
Du S, Wang Y, Weatherly CA, Holden K, Armstrong DW (2018) Variations of L- and D-amino acid levels in the brain of wild-type and mutant mice lacking D-amino acid oxidase activity. Anal Bioanal Chem 410:2971–2979 DOI
EMA (2012) Guideline on bioanalytical method validation. uropean Medicines Agency, 1–23
FDA (2018) Bioanalytical Method Validation Guidance for Industry. U.S. Department of Health and Human Services Food and Drug Administration 1–44
Friedman M, Levin CE (2012) Nutritional and medicinal aspects of D-amino acids. Amino Acids 42:1553–1582 DOI
Fujita T, Amuro Y, Hada T, Higashino K (1999a) Plasma levels of pipecolic acid, both L- and D-enantiomers, in patients with chronic liver diseases, especially hepatic encephalopathy. Clin Chim Acta 287:99–109 DOI
Fujita T, Hada T, Higashino K (1999b) Origin of D- and L-pipecolic acid in human physiological fluids: a study of the catabolic mechanism to pipecolic acid using the lysine loading test. Clin Chim Acta 287:145–156 DOI
Futamura Y, Kurokawa M, Obata R, Nishiyama S, Sugai T (2005) Efficient route to (S)-azetidine-2-carboxylic acid. Biosci Biotechnol Biochem 69:1892–1897 DOI
Huang Y, Zhang WY, Shi Q, Toyo’oka T, Min JZ (2018) Determination of d, l-amino acids in collagen from pig and cod skins by UPLC using pre-column fluorescent derivatization. Food Anal Methods 11:3130–3137 DOI
Hušek P, Šimek P, Hartvich P, Zahradníčkova H (2008) Fluoroalkyl chloroformates in treating amino acids for gas chromatographic analysis. J Chromatogr A 1186:391–400 DOI
Hušek P, Šimek P, Matucha P (2003) Smooth esterification of di- and tricarboxylic acids with methyl and ethyl chloroformates in gas chromatographic profiling of urinary acidic metabolites. Chromatographia 58:623–630
Hušek P, Švagera Z, Hanzlíková D, Řimnáčová L, Zahradníčková H, Opekarová I, Šimek P (2016) Profiling of urinary amino-carboxylic metabolites by in-situ heptafluorobutyl chloroformate mediated sample preparation and gas chromatography-mass spectrometry. J Chromatogr A 1443:211–232 DOI
Ilisz I, Gecse Z, Pataj Z, Fulop F, Toth G, Lindner W, Peter A (2014) Direct high-performance liquid chromatographic enantioseparation of secondary amino acids on Cinchona alkaloid-based chiral zwitterionic stationary phases. Unusual temperature behavior. J Chromatogr A 1363:169–177 DOI
Ishii C, Akita T, Mita M, Ide T, Hamase K (2018) Development of an online two-dimensional high-performance liquid chromatographic system in combination with tandem mass spectrometric detection for enantiomeric analysis of free amino acids in human physiological fluid. J Chromatogr A 1570:91–98 DOI
Kalíková K, Šlechtová T, Tesařová E (2016) Enantiomeric ratio of amino acids as a tool for determination of aging and disease diagnostics by chromatographic measurement. Separations 3
Kiriyama Y, Nochi H (2016) D-Amino Acids in the Nervous and Endocrine Systems. Scientifica
Kirschner DL, Green TK (2009) Separation and sensitive detection of D-amino acids in biological matrices. J Sep Sci 32:2305–2318 DOI
Koppenhoefer B, Bayer E (1984) Chiral recognition in the resolution of enantiomers by Glc. Chromatographia 19:123–130 DOI
Langrock T, Garcia-Villar N, Hoffmann R (2007) Analysis of hydroxyproline isomers and hydroxylysine by reversed-phase HPLC and mass spectrometry. J Chromatogr B 847:282–288 DOI
Lenci E, Trabocchi A (2019) Occurrence of the d-Proline chemotype in enzyme inhibitors. Symmetry-Basel 11
Lorenzo MP, Dudzik D, Varas E, Gibellini M, Skotnicki M, Zorawski M, Zarzycki W, Pellati F, Garcia A (2015) Optimization and validation of a chiral GC-MS method for the determination of free D-amino acids ratio in human urine: application to a Gestational Diabetes Mellitus study. J Pharm Biomed Anal 107:480–487 DOI
Lüpke M, Brückner H (1998) Gas chromatographic evaluation of amino acid epimerisation in the course of gelatin manufacturing and processing. Zeitschrift Fur Lebensmittel-Untersuchung Und-Forschung a-Food Res Technol 206:323–328 DOI
Min JZ, Hatanaka S, Yu H, Higashi T, Inagaki S, Toyo’oka T (2011) Determination of DL-amino acids, derivatized with R(-)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N, N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole, in nail of diabetic patients by UPLC-ESI-TOF-MS. J Chromatogr B 879:3220–3228 DOI
Miyata T, Okano Y, Nagatatanoue J, Ijimamiyamura S, Iwamura H, Takahama K, Hitoshi T (1987) Identification and quantification of 5-hydroxypipecolic acid and 4-hydroxyproline in mammalian brain and blood by selected ion monitoring. Anal Biochem 163:303–308 DOI
Nič J, J.J., Košata B, Jenkins A, McNaught A, 2009. IUPAC Compendium of Chemical technology. IUPAC
Rubenstein E, McLaughlin T, Winant RC, Sanchez A, Eckart M, Krasinska KM, Chien A (2009) Azetidine-2-carboxylic acid in the food chain. Phytochemistry 70:100–104 DOI
Řimnáčova L, Hušek P, Šimek P (2014) A new method for immediate derivatization of hydroxyl groups by fluoroalkyl chloroformates and its application for the determination of sterols and tocopherols in human serum and amniotic fluid by gas chromatography-mass spectrometry. J Chromatogr A 1339:154–167 DOI
Schmidt SK, Hofner G, Wanner KT (2017) Determination of enantiomeric excess of nipecotic acid as 1-(7-nitrobenzo c 1,2,5 oxadiazol-4-yl) derivatives. Chirality 29:48–56 DOI
Szoko E, Vincze I, Tabi T (2016) Chiral separations for D-amino acid analysis in biological samples. J Pharm Biomed Anal 130:100–109 DOI
Šimek P, Hušek P, Zahradníčková H (2008) Gas chromatographic-mass spectrometric analysis of biomarkers related to folate and cobalamin status in human serum after dimercaptopropanesulfonate reduction and heptafluorobutyl chloroformate derivatization. Anal Chem 80:5776–5782 DOI
Šimek, P., Hušek, P., Zahradníčková, H., 2012. Heptafluorobutyl chloroformate-based sample preparation protocol for chiral and nonchiral amino acid analysis by gas chromatography, in: Alterman, M.A., Hunziker, P. (Eds.), Amino Acid Analysis: Methods and Protocols, pp. 137–152
Šimek P, Hušek P, Zahradníčková H (2019) Heptafluorobutyl chloroformate-based sample preparation protocol for nonchiral and chiral amino acid analysis by gas chromatorgraphy-mass spectrometry. In: M.A. Alterman (Ed.) Amino acid analysis methods and protocols, 2nd Edn. Springer, Silver Spring, pp. 237–251
Vránová V, Zahradníčkova H, Janous D, Skene KR, Matharu AS, Rejsek K, Formanek P (2012) The significance of D-amino acids in soil, fate and utilization by microbes and plants: review and identification of knowledge gaps. Plant Soil 354:21–39 DOI
Wang HN, Hussain AA, Pyrek JS, Goodman J, Wedlund PJ (2004) Assay for nipecotic acid in small blood samples by gas chromatography-mass spectroscopy. J Pharm Biomed Anal 34:1063–1070 DOI
Weiss M, Manneberg M, Juranville JF, Lahm HW, Fountoulakis M (1998) Effect of the hydrolysis method on the determination of the amino acid composition of proteins. J Chromatogr A 795:263–275 DOI
Yan PS, Song Y, Sakuno E, Nakajima H, Nakagawa H, Yabe K (2004) Cyclo(L-leucyl-L-prolyl) produced by Achromobacter xylosoxidans inhibits aflatoxin production by Aspergillus parasiticus. Appl Environ Microbiol 70:7466–7473 DOI
Zahradníčková H, Hušek P, Šimek P (2009) GC separation of amino acid enantiomers via derivatization with heptafluorobutyl chloroformate and Chirasil-L-Val column. J Sep Sci 32:3919–3924 DOI
A Protocol for GC-MS Profiling of Chiral Secondary Amino Acids