Skip to main content

Rapid and sensitive analysis of 27 underivatized free amino acids, dipeptides, and tripeptides in fruits of Siraitia grosvenorii Swingle using HILIC-UHPLC-QTRAP®/MS2 combined with chemometrics methods

Amino Acids volume 47, pages 1589–1603 (2015)Cite this article

Abstract

In the present study, a new strategy based on chemical analysis and chemometrics methods was proposed for the comprehensive analysis and profiling of underivatized free amino acids (FAAs) and small peptides among various Luo-Han-Guo (LHG) samples. Firstly, the ultrasound-assisted extraction (UAE) parameters were optimized using Plackett–Burman (PB) screening and Box–Behnken designs (BBD), and the following optimal UAE conditions were obtained: ultrasound power of 280 W, extraction time of 43 min, and the solid–liquid ratio of 302 mL/g. Secondly, a rapid and sensitive analytical method was developed for simultaneous quantification of 24 FAAs and 3 active small peptides in LHG at trace levels using hydrophilic interaction ultra-performance liquid chromatography coupled with triple–quadrupole linear ion-trap tandem mass spectrometry (HILIC-UHPLC-QTRAP®/MS2). The analytical method was validated by matrix effects, linearity, LODs, LOQs, precision, repeatability, stability, and recovery. Thirdly, the proposed optimal UAE conditions and analytical methods were applied to measurement of LHG samples. It was shown that LHG was rich in essential amino acids, which were beneficial nutrient substances for human health. Finally, based on the contents of the 27 analytes, the chemometrics methods of unsupervised principal component analysis (PCA) and supervised counter propagation artificial neural network (CP-ANN) were applied to differentiate and classify the 40 batches of LHG samples from different cultivated forms, regions, and varieties. As a result, these samples were mainly clustered into three clusters, which illustrated the cultivating disparity among the samples. In summary, the presented strategy had potential for the investigation of edible plants and agricultural products containing FAAs and small peptides.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

43,34 €

Price includes VAT (Finland)
Tax calculation will be finalised during checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  • Akamatsu S, Mitsuhashi T (2013) Development of a simple analytical method using capillary electrophoresis-tandem mass spectrometry for product identification and simultaneous determination of free amino acids in dietary supplements containing royal jelly. J Food Compos Anal 30:47–51

    CAS  Article  Google Scholar 

  • Bakirdere S, Bramanti E, D’ulivo A, Ataman OY, Mester Z (2010) Speciation and determination of thiols in biological samples using high performance liquid chromatography-inductively coupled plasma-mass spectrometry and high performance liquid chromatography-Orbitrap MS. Anal Chim Acta 680:41–47

    CAS  PubMed  Article  Google Scholar 

  • Ballabio D, Vasighi M (2012) A MATLAB toolbox for self organizing maps and supervised neural network learning strategies. Chemometr Intell Lab Syst 118:24–32

    CAS  Article  Google Scholar 

  • Ballabio D, Vasighi M, Consonni V, Kompany-Zareh M (2011) Genetic algorithms for architecture optimisation of counter-propagation artificial neural networks. Chemometr Intell Lab Syst 105:56–64

    CAS  Article  Google Scholar 

  • Bernal J, Mendiola J, Ibáñez E, Cifuentes A (2011) Advanced analysis of nutraceuticals. J Pharm Biomed 55:758–774

    CAS  Article  Google Scholar 

  • Bro R, Smilde AK (2014) Principal component analysis. Anal Methods 6:2812–2831

    CAS  Article  Google Scholar 

  • Carrera C, Ruiz-Rodríguez A, Palma M, Barroso CG (2015) Ultrasound-assisted extraction of amino acids from grapes. Ultrason Sonochem 22:499–505

    CAS  PubMed  Article  Google Scholar 

  • Castro-Perez J, Plumb R, Liang L, Yang E (2005) A high-throughput liquid chromatography/tandem mass spectrometry method for screening glutathione conjugates using exact mass neutral loss acquisition. Rapid Commun Mass Spectrum 19:798–804

    CAS  Article  Google Scholar 

  • Chen X, Zhuang J, Liu J, Lei M, Ma L, Chen J, Shen X, Hu L (2011) Potential AMPK activators of cucurbitane triterpenoids from Siraitia grosvenorii Swingle. Bioorgan Med Chem 19:5776–5781

    CAS  Article  Google Scholar 

  • Dago À, González I, Ariño C, Manuel Díaz-Cruz J, Esteban M (2014) Chemometrics applied to the analysis of induced phytochelatins in Hordeum vulgare plants stressed with various toxic non-essential metals and metalloids. Talanta 118:201–209

    CAS  PubMed  Article  Google Scholar 

  • Deshmukh S, Kamde K, Jana A, Korde S, Bandyopadhyay R, Sankar R, Bhattacharyya N, Pandey R (2014) Calibration transfer between electronic nose systems for rapid in situ measurement of pulp and paper industry emissions. Anal Chim Acta 841:58–67

    CAS  PubMed  Article  Google Scholar 

  • Duan L, Guo L, Liu K, Liu E, Li P (2014) Characterization and classification of seven Citrus herbs by liquid chromatography-quadrupole time-of-flight mass spectrometry and genetic algorithm optimized support vector machines. J Chromatogr A 1339:118–127

    CAS  PubMed  Article  Google Scholar 

  • Fiechter G, Mayer HK (2011) UPLC analysis of free amino acids in wines: profiling of on-lees aged wines. J Chromatogr B 879:1361–1366

    CAS  Article  Google Scholar 

  • Friedman M (2004) Applications of the ninhydrin reaction for analysis of amino acids, peptides, and proteins to agricultural and biomedical sciences. J Agr Food Chem 52:385–406

    CAS  Article  Google Scholar 

  • Gillette MA, Carr SA (2013) Quantitative analysis of peptides and proteins in biomedicine by targeted mass spectrometry. Nat Methods 10:28–34

    CAS  PubMed Central  PubMed  Article  Google Scholar 

  • Gökmen V, Serpen A, Mogol BA (2012) Rapid determination of amino acids in foods by hydrophilic interaction liquid chromatography coupled to high-resolution mass spectrometry. Anal Bioanal Chem 403:2915–2922

    PubMed  Article  Google Scholar 

  • Guna M, Londry FA (2011) Tandem ion trap design with enhanced mass analysis capabilities for large populations of ions. Anal Chem 83:6363–6367

    CAS  PubMed  Article  Google Scholar 

  • Guo S, Duan J, Qian D, Tang Y, Qian Y, Wu D, Su S, Shang E (2013) Rapid determination of amino acids in fruits of Ziziphus jujuba by hydrophilic interaction ultra-high-performance liquid chromatography coupled with triple-quadrupole mass spectrometry. J Agr Food Chem 61:2709–2719

    CAS  Article  Google Scholar 

  • Hakimzadeh N, Parastar H, Fattahi M (2014) Combination of multivariate curve resolution and multivariate classification techniques for comprehensive high-performance liquid chromatography-diode array absorbance detection fingerprints analysis of Salvia reuterana extracts. J Chromatogr A 1326:63–72

    CAS  PubMed  Article  Google Scholar 

  • He C, Zhu X, Liu L, He W (2012) Analysis and comparison the nutrient compositions of fresh and dry tissue culture seedling Luohanguo. Guihaia 32:706–709

    CAS  Google Scholar 

  • Ilisz I, Berkecz R, Péter A (2008) Application of chiral derivatizing agents in the high-performance liquid chromatographic separation of amino acid enantiomers: a review. J Pharmaceut Biomed 47:1–15

    CAS  Article  Google Scholar 

  • Kıvrak İ, Kıvrak Ş, Harmandar M (2014) Free amino acid profiling in the giant puffball mushroom (Calvatia gigantea) using UPLC–MS/MS. Food Chem 158:88–92

    PubMed  Article  Google Scholar 

  • Kumar N, Bansal A, Sarma G, Rawal RK (2014) Chemometrics tools used in analytical chemistry: an overview. Talanta 123:186–199

    CAS  PubMed  Article  Google Scholar 

  • Kuśmierek K, Bald E (2008) Reduced and total glutathione and cysteine profiles of citrus fruit juices using liquid chromatography. Food Chem 106:340–344

    Article  Google Scholar 

  • Lahrichi SL, Affolter M, Zolezzi IS, Panchaud A (2013) Food peptidomics: large scale analysis of small bioactive peptides-a pilot study. J Proteomics 88:83–91

    CAS  PubMed  Article  Google Scholar 

  • Li C, Lin L, Sui F, Wang Z, Huo H, Dai L, Jiang T (2014) Chemistry and pharmacology of Siraitia grosvenorii: a review. Chin J Nat Med 12:89–102

    PubMed  Google Scholar 

  • Megías C, Cortés-Giraldo I, Girón-Calle J, Vioque J, Alaiz M (2015) Determination of L-canavanine and other free amino acids in Vicia disperma (Fabaceae) seeds by precolumn derivatization using diethyl ethoxymethylenemalonate and reversed-phase high-performance liquid chromatography. Talanta 131:95–98

    PubMed  Article  Google Scholar 

  • Meisel H, FitzGerald RJ (2003) Biofunctional peptides from milk proteins: mineral binding and cytomodulatory effects. Curr Pharm Des 9:1289–1295

    CAS  PubMed  Article  Google Scholar 

  • Mudiam MKR, Ratnasekhar C (2013) Ultra sound assisted one step rapid derivatization and dispersive liquid–liquid microextraction followed by gas chromatography-mass spectrometric determination of amino acids in complex matrices. J Chromatogr A 1291:10–18

    CAS  PubMed  Article  Google Scholar 

  • Ni Y, Zhuang H, Kokot S (2014) A high performance liquid chromatography and electrospray ionization mass spectrometry method for the analysis of the natural medicine, Forsythia Suspensa. Anal Lett 47:102–116

    CAS  Article  Google Scholar 

  • Pirman DA, Reich RF, Kiss A, Heeren RMA, Yost RA (2013) Quantitative MALDI tandem mass spectrometric imaging of cocaine from brain tissue with a deuterated internal standard. Anal Chem 85:1081–1089

    CAS  PubMed  Article  Google Scholar 

  • Rambla-Alegre M, Esteve-Romero J, Carda-Broch S (2012) Is it really necessary to validate an analytical method or not? That is the question. J Chromatogr A 1232:101–109

    CAS  PubMed  Article  Google Scholar 

  • Rezazadeh M, Yamini Y, Seidi S, Aghaei A (2015) Pulsed electromembrane extraction for analysis of derivatized amino acids: a powerful technique for determination of animal source of gelatin samples. Talanta 136:190–197

    CAS  PubMed  Article  Google Scholar 

  • Sarmadi BH, Ismail A (2010) Antioxidative peptides from food proteins: a review. Peptides 31:1949–1956

    CAS  PubMed  Article  Google Scholar 

  • Schultz CL, Moini M (2003) Analysis of underivatized amino acids and their D/L-enantiomers by sheathless capillary electrophoresis/electrospray ionization-mass spectrometry. Anal Chem 75:1508–1513

    CAS  PubMed  Article  Google Scholar 

  • Stokvis E, Rosing H, Beijnen JH (2005) Stable isotopically labeled internal standards in quantitative bioanalysis using liquid chromatography/mass spectrometry: necessity or not? Rapid Commun Mass Spectrum 19:401–407

    CAS  Article  Google Scholar 

  • Syu KY, Lin C, Huang H, Lin J (2008) Determination of theanine, GABA, and other amino acids in green, oolong, black, and Pu-erh teas with dabsylation and high-performance liquid chromatography. J Agric Food Chem 56:7637–7643

    CAS  PubMed  Article  Google Scholar 

  • Takasaki M, Konoshima T, Murata Y, Sugiura M, Nishino H, Tokuda H, Matsumoto K, Kasai R, Yamasaki K (2003) Anticarcinogenic activity of natural sweeteners, cucurbitane glycosides, from Momordica grosvenori. Cancer Lett 198:37–42

    CAS  PubMed  Article  Google Scholar 

  • Tian M, Zhang J, Mohamed AC, Han Y, Guo L, Yang L (2014) Efficient capillary electrophoresis separation and determination of free amino acids in beer samples. Electrophoresis 35:577–584

    CAS  PubMed  Article  Google Scholar 

  • Troise AD, Fiore A, Roviello G, Monti SM, Fogliano V (2015) Simultaneous quantification of amino acids and Amadori products in foods through ion-pairing liquid chromatography-high-resolution mass spectrometry. Amino Acids 47:111–124

    CAS  PubMed  Article  Google Scholar 

  • Tuberoso CIG, Congiu F, Serreli G, Mameli S (2015) Determination of dansylated amino acids and biogenic amines in Cannonau and Vermentino wines by HPLC-FLD. Food Chem 175:29–35

    CAS  PubMed  Article  Google Scholar 

  • Vanloot P, Bertrand D, Pinatel C, Artaud J, Dupuy N (2014) Artificial vision and chemometrics analyses of olive stones for varietal identification of five French cultivars. Comput Electron Agric 102:98–105

    Article  Google Scholar 

  • Wang H, Duan J, Guo S, Qian D, Shang E (2013) Development and validation of a hydrophilic interaction ultra-high-performance liquid chromatography with triple quadrupole MS/MS for the absolute and relative quantification of amino acids in Sophora alopecuroides L. J Sep Sci 36:2244–2252

    CAS  PubMed  Article  Google Scholar 

  • Wu G (2013) Functional amino acids in nutrition and health. Amino Acids 45:407–411

    CAS  PubMed  Article  Google Scholar 

  • Yan J, Cai Y, Wang Y, Lin X, Li H (2014) Simultaneous determination of amino acids in tea leaves by micellar electrokinetic chromatography with laser-induced fluorescence detection. Food Chem 143:82–89

    CAS  PubMed  Article  Google Scholar 

  • Zhang H, Yang H, Zhang M, Wang Y, Wang J, Yau L, Jiang Z, Hu P (2012) Identification of flavonol and triterpene glycosides in Luo-Han-Guo extract using ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry. J Food Compos Anal 25:142–148

    CAS  Article  Google Scholar 

  • Zhang K, Wong JW, Krynitsky AJ, Trucksess MW (2014) Determining mycotoxins in baby foods and animal feeds using stable isotope dilution and liquid chromatography tandem mass spectrometry. J Agr Food Chem 62:8935–8943

    CAS  Article  Google Scholar 

  • Zhou G, Pang H, Tang Y, Yao X, Mo X, Zhu S, Guo S, Qian D, Qian Y, Su S (2013) Hydrophilic interaction ultra-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry for highly rapid and sensitive analysis of underivatized amino acids in functional foods. Amino Acids 44:1293–1305

    CAS  PubMed  Article  Google Scholar 

  • Zhou G, Yao X, Tang Y, Qian D, Su S, Zhang L, Jin C, Qin Y, Duan J (2014) An optimized ultrasound-assisted extraction and simultaneous quantification of 26 characteristic components with four structure types in functional foods from ginkgo seeds. Food Chem 158:177–185

    CAS  PubMed  Article  Google Scholar 

  • Zhou G, Fu L, Li X (2015) Optimisation of ultrasound-assisted extraction conditions for maximal recovery of active monacolins and removal of toxic citrinin from red yeast rice by a full factorial design coupled with response surface methodology. Food Chem 170:186–192

    CAS  PubMed  Article  Google Scholar 

Download references

Acknowledgments

We are pleased to thank Dr. Bin Hao (School of Pharmacy, Shanghai Jiao Tong University) for the help in HILIC-UHPLC-QTRAP®/MS2 tests.

Conflict of interest

The authors have no conflicts of interest.

Author information

Affiliations

  1. School of Pharmacy, Shanghai Jiao Tong University, Shanghai, 200240, China

    Guisheng Zhou, Mengyue Wang, Yang Li, Ying Peng & Xiaobo Li

Authors
  1. Guisheng Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mengyue Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ying Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiaobo Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiaobo Li.

Additional information

Handling Editor: D. Tsikas.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 2650 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhou, G., Wang, M., Li, Y. et al. Rapid and sensitive analysis of 27 underivatized free amino acids, dipeptides, and tripeptides in fruits of Siraitia grosvenorii Swingle using HILIC-UHPLC-QTRAP®/MS2 combined with chemometrics methods. Amino Acids 47, 1589–1603 (2015). https://doi.org/10.1007/s00726-015-2002-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00726-015-2002-5

Keywords

  • Siraitiae Fructus
  • Free amino acids
  • Peptides
  • HILIC-UHPLC-QTRAP®/MS2
  • Chemometrics
  • Artificial neural network