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Determination and stereochemistry of proteinogenic and non-proteinogenic amino acids in Saudi Arabian date fruits

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Abstract

Whereas an abundance of literature is available on the occurrence of common proteinogenic amino acids (AAs) in edible fruits of the date palm (Phoenix dactylifera L.), recent reports on non-proteinogenic (non-coded) AAs and amino components are scarce. With emphasis on these components we have analyzed total hydrolysates of twelve cultivars of date fruits using automated ion-exchange chromatography, HPLC employing a fluorescent aminoquinolyl label, and GC–MS of total hydrolysates using the chiral stationary phases Chirasil®-L-Val and Lipodex® E. Besides common proteinogenic AAs, relatively large amounts of the following non-proteinogenic amino acids were detected: (2S,5R)-5-hydroxypipecolic acid (1.4–4.0 g/kg dry matter, DM), 1-aminocyclopropane-1-carboxylic acid (1.3–2.6 g/kg DM), γ-amino-n-butyric acid (0.5–1.2 g/kg DM), (2S,4R)-4-hydroxyproline (130–230 mg/kg DM), l-pipecolic acid (40–140 mg/kg DM), and 2-aminoethanol (40–160 mg/kg DM) as well as low or trace amounts (<70 mg/kg DM) of l-ornithine, 5-hydroxylysine, β-alanine, and in some samples (<20 mg/kg DM) of (S)-β-aminoisobutyric acid and (<10 mg/kg DM) l-allo-isoleucine. In one date fruit, traces of α-aminoadipic acid could be determined. Enantiomeric analysis of 6 M DCl/D2O hydrolysates of AAs using chiral capillary gas chromatography–mass spectrometry revealed the presence of very low amounts of d-Ala, d-Asp, d-Glu, d-Ser and d-Phe (1.2–0.4 %, relative to the corresponding l-enantiomers), besides traces (0.2–1 %) of other d-AAs. The possible relevance of non-proteinogenic amino acids in date fruits is briefly addressed.

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Abbreviations

GC–MS:

Gas chromatography mass spectrometry

M:

Molecular mass (weight)

HPLC or LC:

High performance liquid chromatography

SIM:

Selected ion monitoring

AQC:

6-Aminoquinoyl-carbamyl-N-hydroxysuccinimidyl carbamate

AMQ:

6-Aminoquinoline

iTRAQ™:

Isobaric tag for relative and absolute quantitation

MSTFA:

N-methyl-N-trimethylsilyl-trifluoroacetamide

DCl/D2O:

Deuterium chloride in deuterium oxide

TFAA:

Trifluoroacetic acid anhydride

TFA:

Trifluoroacetyl

Me:

Methyl

Et:

Ethyl

Chirasil®-L-Val:

Dimethylpolysiloxane functionalized with l-Val-tert.butylamide

Lipodex® E:

(3-Butyl-2,6-pentyl)-γ-cyclodextrine

α-aminoadipic acid:

α-Aaa or a-AAA

β-Ala or b-Ala:

β-Alanine

Aba or a-AB:

α-Amino-n-butyric acid

β-Aba or β-Aib:

β-Aminoisobutyric acid

Acc:

1-Aminocyclopropane-1-carboxylic acid

Cit:

Citrulline

Cys:

Cystine

Eta:

Ethanolamine

GABA:

γ-Amino-n-butyric acid

Hyl or Hy-Lys:

5-Hydroxylysine

Hyp:

(2S,4R)-4-hydroxyproline (trans-4-hydroxy-l-proline)

Nle:

Norleucine (internal standard)

Orn:

Ornithine

Pip:

Pipecolic acid

Pip(OH):

(2S,5R)-5-hydroxypipecolic acid (trans-5-hydroxypipecolic acid)

Carn:

Carnosine

Csystat:

Cystathionine

1-M-His:

1-Methylhistidine

3-M-His:

3-Methylhistidine

P-Ser:

O-Phosporyl-l-serine

P-Eta:

Phosphoethanolamine

Sar:

Sarcosine

Tau:

Taurine

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Acknowledgments

This project was supported by NSTIP strategic technologies program number 11-AGR 1600-2 of the Kingdom of Saudi Arabia. HB acknowledges his position as a Visiting Professor and Scientific Consultant at KSU. Special thanks are addressed to Katja Dettmer, University of Regensburg, and Małgorzata Jaworska, National Medicines Institute, Warsaw, Jürgen Gerhardt, C.A.T. Tübingen, and Frank Gutjahr, Chromatographie Balingen, for valuable discussions and assistance in parts of the work, in particular disproving or confirming the presence of tentatively assigned amino compounds in selected date samples.

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The authors declare that they have no conflict of interest.

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Ali, H.S.M., Alhaj, O.A., Al-Khalifa, A.S. et al. Determination and stereochemistry of proteinogenic and non-proteinogenic amino acids in Saudi Arabian date fruits. Amino Acids 46, 2241–2257 (2014). https://doi.org/10.1007/s00726-014-1770-7

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