Qualitative and quantitative analyses of polyphenols extracted from 21 Malus domestica cultivars using ultra high performance liquid chromatography with diode array detection coupled to heated electrospray ionization mass spectrometric detection was performed for separation of 27 phenolic compounds on a reversed phase UHPLC column with an optimized gradient consisting of 1% formic acid in water and 1% formic acid in methanol within 20 minutes. According to retention times, UV maxima and mass spectra of the peaks in the chromatograms obtained from extracts of apple peel, flesh and leaves, the polyphenolic compounds were identified and quantified. Based on fragmentation patterns, 6 phenolic acids, 5 flavan-3-ols, 5 dihydrochalcones, 8 flavonols and 3 flavone derivatives were characterized in the studied samples. The method was then employed for analysis of the polyphenolic pattern of 21 apple cultivars, both commercial and autochthonous for the Macedonian region, as well as for monitoring the influence of long term storage on the polyphenolic content and composition of apple fruits and for comparison of polyphenolic profiles of apple cultivars during two years of harvesting. The obtained results revealed minor differences in the quality and major variation in the content of phenolic compounds in the flesh, peel and leaves in the studied apple cultivars that is attributed mainly to cultivar differences and meteorological factors.
ScalbertA, ManachC, MorandC, RémésyC, JiménezL. (2005) Dietary polyphenols and the prevention of diseases. Critical Reviews in Food Science and Nutrition, 45, 287–306.
2.
ScalbertA, JohnsonIT, SaltmarshM. (2005) Polyphenols: antioxidants and beyond., American Journal of Clinical Nutrition, 81, 215S–217S.
3.
VitaJA. (2005) Polyphenols and cardiovascular disease: effects on endothelial and platelet function. American Journal of Clinical Nutrition, 81, 292S–297S.
4.
NapolitanoA, CasconeA, GrazianiG, FerracaneR, ScalfiL, Di VaioC, RitieniR, FoglianoV. (2004) Influence of variety and storage on the polyphenol composition of apple flesh. Journal of Agricultural and Food Chemistry, 52, 6526–6531.
5.
EscarpaA, GonzalezMC. (1998) High-performance liquid chromatography with diode-array detection for the determination of phenolic compounds in peel and pulp from different apple varieties. Journal of Chromatography A, 823, 331–337.
6.
KhanizadehS, TsaoR, RekikaD, YangR, CharlesMT, VasanthaRupasinghe HP. (2008) Polyphenol composition and total antioxidant capacity of selected apple genotypes for processing. Journal of Food Composition and Analysis, 21, 396–401.
7.
TsaoR, YangR, YoungJC, ZhuH. (2003) Polyphenolic profiles in eight apple cultivars using high-performance liquid chromatography (HPLC). Journal of Agricultural and Food Chemistry, 51, 6347–6353.
8.
VrhovsekU, RigoA, TononD, MattiviF. (2004) Quantitation of polyphenols in different apple varieties. Journal of Agricultural and Food Chemistry, 52, 6532–6538.
9.
JakobekL, BarronAR. (2016) Ancient apple varieties from Croatia as a source of bioactive polyphenolic compounds. Journal of Food Composition and Analysis, 45, 9–15.
10.
StrackeBA, RuferCE, WeibelFP, BubA, WatzlB. (2009) Three-year comparison of the polyphenol contents and antioxidant capacities in organically and conventionally produced apples (Malus domestica Bork. cultivar ‘Golden Delicious'). Journal of Agricultural and Food Chemistry, 57, 4598–4605.
11.
LachmanJ, ŠulcM, SusJ, PavlíkováO. (2006) Polyphenol content and antiradical activity in different apple varieties. Horticultural Science (Prague), 33, 95–102.
12.
KislichenkoVS, NovoselEN. (2007) Flavonoids from leaves of Pyrus communis, Malus sylvestris, and Malus domestica. Chemistry of Natural Compounds, 43, 584–585.
13.
PetkovsekMM, SlatnarA, StamparF, VebericR. (2011) Phenolic compounds in apple leaves after infection with apple scab. Biologia Plantarum, 55, 725–730.
14.
CeymannM, ArrigoniE, SchärerH, BozziNising A, HurrellRF. (2012) Identification of apples rich in health-promoting flavan-3-ols and phenolic acids by measuring the polyphenol profile. Journal of Food Composition and Analysis, 26, 128–135.
15.
ŠavikinK, ŽivkovićJ, ZdunićG, GođevacD, ĐorđevićB, DojěinovićB, ĐorđevićN. (2014) Phenolic and mineral profiles of four Balkan indigenous apple cultivars monitored at two different maturity stages. Journal of Food Composition and Analysis, 35, 101–111.
16.
Alonso-SalcesRM, KortaE, BarrancoA, BerruetaLA, GalloB, VicenteF. (2001) Determination of polyphenolic profiles of Basque cider apple varieties using accelerated solvent extraction. Journal of Agricultural and Food Chemistry, 49, 3761–3767.
17.
BartoloméB, HernándezT, BengoecheaML, QuesadaC, Gómez-CordovésC, EstrellaI. (1996) Determination of some structural features of procyanidins and related compounds by photodiode-array detection. Journal of Chromatography A, 723, 19–26.
18.
RakG, FodorP, AbrankóL. (2010) Three-step HPLC–ESI-MS/MS procedure for screening and identifying non-target flavonoid derivatives. International Journal of Mass Spectrometry, 290, 32–38.
19.
StobieckiM. (2000) Application of mass spectrometry for identification and structural studies of flavonoid glycosides. Phytochemistry, 54, 237–256.
20.
MarchRE, LewarsEG, StadeyCJ, MiaoX-S, ZhaoX, MetcalfeCD. (2006) A comparison of flavonoid glycosides by electrospray tandem mass spectrometry. International Journal of Mass Spectrometry, 248, 61–85.
21.
ZhaoY, LiX, ZengX, HuangS, HouS, LaiX. (2014) Characterization of phenolic constituents in Lithocarpus polystachyus. Analytical Methods, 6, 1359–1363.
22.
LuY, FooLY. (1997) Identification and quantification of major polyphenols in apple pomace. Food Chemistry, 59, 187–194.
23.
MangasJJ, RodríguezR, SuárezB, PicinelliA, DapenaE. (1999) Study of the phenolic profile of cider apple cultivars at maturity by multivariate techniques. Journal of Agricultural and Food Chemistry, 47, 4046–4052.
24.
Analytical Procedures and Methods Validation for Drugs and Biologics Guidance for Industry, U.S. Department of Health and Human Services, Food and Drug Administration, Center for Drug Evaluation and Research (CDER), Center for Biologics Evaluation and Research, Pharmaceutical Quality, 2015, 1–15.
25.
DarbyshireR, WebbL, GoodwinI, BarlowEWR. (2014) Challenges in predicting climate change impacts on pome fruit phenology. International Journal of Biometeorology, 58, 1119–1133.
26.
NicholasKA, MatthewsMA, LobellDB, WillitsNH, FieldCN. (2011) Effect of vineyard-scale climate variability on Pinot noir phenolic composition. Agricultural and Forest Meteorology, 151, 1556–1567.
27.
HagenSF, BorgeGIA, BengtssonGB, BilgerW, BergeA, HaffnerK, SolhaugKA. (2007) Phenolic contents and other health and sensory related properties of apple fruit (Malus domestica Borkh, cv. Aroma): Effect of postharvest UV-B irradiation. Postharvest Biology and Technology, 45, 1–10.
28.
PetkovskaA, GjamovskiV, StefovaM. (2016) Comparison of different extraction solvents for assay of the polyphenol content in the peel and pulp of apple cultivars from Macedonia. Macedonian Journal of Chemistry and Chemical Engineering, 35, 29–38.
29.
GoldingJB, McGlassonWB, WyllieSG, LeachDN. (2001) Fate of apple peel phenolics during cool storage. Journal of Agricultural and Food Chemistry, 49, 2283–2289.
30.
van der SluisAA, DekkerM, de JagerA, JongenWMF. (2001) Activity and concentration of polyphenolic antioxidants in apple: effect of cultivar, harvest year, and storage conditions. Journal of Agricultural and Food Chemistry, 49, 3606–3613.
