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Determination of Phenolic Compounds in Artichoke, Garlic and Spinach by Ultra-High-Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

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Abstract

Phenolic compounds were determined in artichoke (Cynara scolymus), garlic (Allium sativium) and spinach (Spinacia oleracea) using a single method based on simple extraction and ultra-high-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS/MS). Several compounds belonging to different families, such as phenolic acids, isoflavones, flavones and flavonols, were determined. The analytical procedure was validated in all the matrices, obtaining recoveries ranging from 60 to 120 % with reproducibility values (expressed as relative standard deviations (RSDs)) lower than 26 %. Limits of quantification (LOQs) were always equal to or lower than 50 μg/kg, except to kaempferol and its glucosides in spinach (LOQs = 75 μg/kg). Artichoke showed higher concentration of phenolic compounds (837.2 mg/kg dry weight (DW)) than garlic (26.5 mg/kg DW) or spinach (64.5 mg/kg DW). Apigenin 7-O-glucoside (from 147.0 to 722.7 mg/kg DW) was found to be the major flavonoid in all samples of artichoke investigated, while chlorogenic acid, whose concentration ranged from 37.8 to 734.7 mg/kg DW, is the major phenolic acid in this matrix. Regarding garlic, caffeic acid (from 1.7 to 28.3 mg/kg DW) and quercetin (from 9.0 to 18.9 mg/kg DW) were the compounds detected at higher concentrations, although in general the total content was very low in relation to other matrices. In relation to spinach, ferulic acid was the major phenolic compound, and its concentration ranged from 18.0 to 41.4 mg/kg DW.

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References

  • Abu-Reidah IM, Arraez-Roman D, Segura-Carretero A, Fernandez-Gutierrez A (2013) Extensive characterisation of bioactive phenolic constituents from globe artichoke (Cynara scolymus L.) by HPLC-DAD-ESI-QTOF-MS. Food Chem 141:2269–2277

    Article  CAS  Google Scholar 

  • Akasaka H, Sasaki R, Yoshida K, Takayama I, Yamaguchi T, Yoshida H, Mizushina Y (2013) Monogalactosyl diacylglycerol, a replicative DNA polymerase inhibitor, from spinach enhances the anti-cell proliferation effect of gemcitabine in human pancreatic cancer cells. Biochim Biophys Acta 1830:2517–2525

    Article  CAS  Google Scholar 

  • Alarcón-Flores MI, Romero-González R, Garrido Frenich A, Martínez Vidal JL (2013) Rapid determination of phenolic compounds in vegetables and fruits by ultra high performance liquid chromatography coupled to tandem mass spectrometry. Food Chem 141:1120–1129

    Article  Google Scholar 

  • Anouar E, Košinová P, Kozlowski D, Mokrini R, Duroux JL, Trouillas P (2009) New aspects of the antioxidant properties of phenolic acids: a combined theoretical and experimental approach. Phys Chem Chem Phys 11:7659–7668

    Article  CAS  Google Scholar 

  • Beato VM, Orgaz F, Mansilla F, Montaño A (2011) Changes in phenolic compounds in garlic (Allium sativum L.) owing to the cultivar and location of growth. Plant Foods Hum Nutr 66:218–223

    Article  CAS  Google Scholar 

  • Bottino A, Degl’innocenti E, Guidi L, Graziani G, Fogliano V (2009) Bioactive compounds during storage of fresh-cut spinach: the role of endogenous ascorbic acid in the improvement of product quality. J Agric Food Chem 57:2925–2931

    Article  CAS  Google Scholar 

  • Bozin B, Mimica-Dukic N, Samojlik I, Goran A, Igic R (2008) Phenolics as antioxidants in garlic (Allium sativum L., Alliaceae). Food Chem 111:925–929

    Article  CAS  Google Scholar 

  • Bundy R, Walker AF, Middleton RW, Wallis C, Simpson HCR (2008) Artichoke leaf extract (Cynara scolymus) reduces plasma cholesterol in otherwise healthy hypercholesterolemic adults: a randomized, double blind placebo controlled trial. Phytomedicine 15:668–675

    Article  Google Scholar 

  • Bunea A, Andjelkovic M, Socaciu C, Bobis O, Neacsu M, Verhe R, Camp JV (2008) Total and individual carotenoids and phenolic acids content in fresh, refrigerated and processed spinach (Spinacia oleracea L.). Food Chem 108:649–656

    Article  CAS  Google Scholar 

  • Cao G, Russell RM, Lischner N, Prior RL (1998) Serum antioxidant capacity is increased by consumption of strawberries, spinach, red wine or vitamin C in elderly women. J Nut 128:2383–2390

    CAS  Google Scholar 

  • Cao J, Chen W, Zhang Y, Zhang Y, Zhao X (2010) Content of selected flavonoids in 100 edible vegetables and fruits. Food Sci Technol Res 16:395–402

    Article  CAS  Google Scholar 

  • Chung LY (2006) The antioxidant properties of garlic compounds: allyl cysteine, alliin, allicin, and allyl disulfide. J Med Food 9:205–213

    Article  CAS  Google Scholar 

  • Durak I, Kavutcu M, Aytac B, Avci A, Devrim E, Özbek H, Öztürk HS (2004) Effects of garlic extract consumption on blood lipid and oxidant/antioxidant parameters in humans with high blood cholesterol. J Nutr Bioch 15:373–377

    Article  CAS  Google Scholar 

  • Estruch R, Ros E, Salas-Salvadó J, Covas MI, Corella D, Arós F, Gómez-Gracia E, Ruiz-Gutiérrez V, Fiol M, Lapetra J, Lamuela-Raventos RM, Serra-Majem L, Pintó X, Basora J, Muñoz MA, Sorlí JV, Martínez JA, Martínez-González MA (2013) Primary prevention of cardiovascular disease with a Mediterranean diet. N Engl J Med 368:1279–1290

    Article  CAS  Google Scholar 

  • Fantini N, Colombo G, Giori A, Riva A, Morazzoni P, Bombardelli E, Carai MAM (2011) Evidence of glycemia-lowering effect by a Cynara scolymus L. Extract in normal and obese rats. Phytother Res 25:463–466

    CAS  Google Scholar 

  • FAO statistics 2013 http://faostat3.fao.org/home/index.html (last accessed December 2013)

  • Gebhardt R (1997) Antioxidative and protective properties of extracts from leaves of the artichoke against hydroperoxide-induced oxidative stress in cultured rat hepatocytes. Toxicol Appl Pharm 144:279–286

    Article  CAS  Google Scholar 

  • Gorinstein S, Leontowicz H, Leontowicz M, Namiesnik J, Najman K, Drzewiecki J, Cvikrová M, Martincová O, Katrich E, Trakhtenberg S (2008) Comparison of the main bioactive compounds and antioxidant activities in garlic and white and red onions after treatment protocols. J Agric Food Chem 56:4418–4426

    Article  CAS  Google Scholar 

  • Howard LR, Pandjaitan N, Morelock T, Gil MI (2002) Antioxidant capacity and phenolic content of spinach as affected by genetics and growing season. J Agric Food Chem 50:5891–5896

    Article  CAS  Google Scholar 

  • Khanama UKS, Obab S, Yanaseb E, Murakami Y (2012) Phenolic acids, flavonoids and total antioxidant capacity of selected leafy vegetables. J Funct Food 4:979–987

    Article  Google Scholar 

  • Kmellár B, Fodor P, Pareja L, Ferrer C, Martínez-Uroz MA, Valverde A, Fernández-Alba AR (2008) Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatography-tandem mass spectrometry. J Chromatogr A 1215:37–50

    Article  Google Scholar 

  • Konar N, Poyrazoğlu ES, Demir K, Artik N (2012) Effect of different sample preparation methods on isoflavone, lignan, coumestan and flavonoid contents of various vegetables determined by triple quadrupole LC–MS/MS. J Food Compos Anal 26:26–35

    Article  CAS  Google Scholar 

  • Kopeć A, Piątkowska E, Leszczyńska T, Sikora E (2013) Healthy properties of garlic. Curr Nutr Food Sci 9:59–64

    Google Scholar 

  • Lanzotti V (2006) The analysis of onion and garlic. J Chromatogr A 1112:3–22

    Article  CAS  Google Scholar 

  • Lattanzio V, Kroon PA, Linsalata V, Cardinali A (2009) Globe artichoke: a functional food and source of nutraceutical Ingredients. J Funct Food 1:131–144

    Article  CAS  Google Scholar 

  • Lomnitski L, Bergman M, Nyska A, Ben-Shaul V, Grossman S (2003) Composition, efficacy, and safety of spinach extracts. Nutr Cancer 46:222–231

    Article  CAS  Google Scholar 

  • Mann J, Aune D (2010) Can specific fruits and vegetables prevent diabetes? BMJ 341:514

    Article  Google Scholar 

  • Mattila P, Hellström J (2007) Phenolic acids in potatoes, vegetables, and some of their products. J Food Compos Anal 20:152–160

    Article  CAS  Google Scholar 

  • Miean KH, Mohamed S (2001) Flavonoid (myricetin, quercetin, kaempferol, luteolin, and apigenin) content of edible tropical plants. J Agric Food Chem 49:3106–3112

    Article  CAS  Google Scholar 

  • Mileo AM, Di Venere D, Linsalata V, Fraioli R, Miccadei S (2012) Artichoke polyphenols induce apoptosis and decrease the invasive potential of the human breast cancer cell line MDA-MB 231. J Cell Physiol 227:3301–3309

    Article  CAS  Google Scholar 

  • Negro D, Montesano V, Grieco S, Crupi P, Sarli G, De Lisi A, Sonnante G (2012) Polyphenol compounds in artichoke plant tissues and varieties. J Food Sci 77:244–252

    Article  Google Scholar 

  • Núnez O, Gallart-Ayalaa H, Martins CPB, Lucci P (2012) New trends in fast liquid chromatography for food and environmental analysis. J Chromatogr A 1228:298–323

    Article  Google Scholar 

  • Nuutila AM, Kammiovirta K, Oksman-Caldentey KM (2002) Comparison of methods for the hydrolysis of flavonoids and phenolic acids from onion and spinach for HPLC analysis. Food Chem 76:519–525

    Article  CAS  Google Scholar 

  • Obioha UE, Suru SM, Ola-Mundathir KF, Faremi TY (2009) Hepatoprotective potentials of onion and garlic extracts on cadmium-induced oxidative damage in rats. Biol Trace Elem Res 129:143–156

    Article  CAS  Google Scholar 

  • Padiya R, Khataua TN, Bagul PK, Kuncha M, Banerjee SK (2011) Garlic improves insulin sensitivity and associated metabolic syndrome in fructose fed rats. Nutr Metab 8:53–60

    Article  CAS  Google Scholar 

  • Pandino G, Lombardo S, Mauromicale G (2013) Globe artichoke leaves and floral stems as a source of bioactive compounds. Ind Crop Prod 44:44–49

    Article  CAS  Google Scholar 

  • Rezazadeh A, Ghasemnezhad A, Barani M, Telmadarrehei T (2012) Effect of salinity on phenolic composition and antioxidant activity of artichoke (Cynara scolymus L.) leaves. J Med Plants Res 6:245–252

    Article  CAS  Google Scholar 

  • Sánchez-Rabaneda F, Jáuregui O, Lamuela-Raventós RM, Bastida J, Viladomat F, Codina C (2003) Identification of phenolic compounds in artichoke waste by high performance liquid chromatography–tandem mass spectrometry. J Chromatogr A 1008:57–72

    Article  Google Scholar 

  • Santos J, Oliveira MBPP, Ibánez E, Herrero M (2014) Phenolic profile evolution of different ready-to-eat baby-leaf vegetables during storage. J Chromatogr A 1327:118–131

    Article  CAS  Google Scholar 

  • Shukla Y, Kalra N (2007) Cancer chemoprevention with garlic and its constituents. Cancer Lett 247:167–181

    Article  CAS  Google Scholar 

  • Silva CL, Haesenb N, Câmara JS (2012) A new and improved strategy combining a dispersive-solid phase extraction-based multiclass method with ultra high pressure liquid chromatography for analysis of low molecular weight polyphenols in vegetables. J Chromatogr A 1260:154–163

    Article  CAS  Google Scholar 

  • Sultana B, Anwar F (2008) Flavonols (kaempferol, quercetin, myricetin) contents of selected fruits, vegetables and medicinal plants. Food Chem 108:879–884

    Article  CAS  Google Scholar 

  • Taskeen A, Naeem I, Bakhtawar S, Mehmood T (2010) A comparative study of flavonoids in fruits and vegetables with their products using reverse phase high performance liquid chromatography (RP-HPLC). EJEAFChe 9:1372–1377

    CAS  Google Scholar 

  • Tiveron AP, Melo PS, Bergamaschi KB, Vieira TMFS, Regitano-d’Arce MAB, Alencar SM (2012) Antioxidant activity of Brazilian vegetables and its relation with phenolic composition. Int J Mol Sci 13:8943–8957

    Article  CAS  Google Scholar 

  • Vallverdú-Queralt A, Rinaldi de Alvarenga JF, Estruch R, Lamuela-Raventos RM (2013) Bioactive compounds present in the Mediterranean sofrito. Food Chem 141:3365–3372

    Article  Google Scholar 

  • Zapolska-Downar D, Zapolski-Downar A, Naruszewicz M, Siennicka A, Krasnodebska B, Koldziej B (2002) Protective properties of artichoke (Cynara scolymus) against oxidative stress induced in cultured endothelial cells and monocytes. Life Sci 71:2897–2908

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are grateful to Andalusian Regional Government (Regional Ministry of Innovation, Science and Enterprise) (Ref. P11-AGR-7034). MIAF acknowledges her grant (FPU, Ref: AP 2009-2074) from the Spanish Ministry of Education. RRG is also grateful to Almeria University for personal funding.

Conflict of Interest

María Isabel Alarcón Flores declares that she has no conflict of interest. María Isabel Alarcón Flores has received a research grant from the Spanish Ministry of Education. Roberto Romero González declares that he has no conflict of interest. Jose Luís Martínez Vidal declares that he has no conflict of interest. Antonia Garrido Frenich declares that she has no conflict of interest. This article does not contain any studies with human or animal subjects.

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Correspondence to Antonia Garrido Frenich.

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Alarcón-Flores, M.I., Romero-González, R., Martínez Vidal, J.L. et al. Determination of Phenolic Compounds in Artichoke, Garlic and Spinach by Ultra-High-Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry. Food Anal. Methods 7, 2095–2106 (2014). https://doi.org/10.1007/s12161-014-9852-4

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