Novel Data on the Polyphenol Composition of Italian Ancient Apple Cultivars

Figures & data

Table 1  Phenolic compounds detected and identified in the apple pulps

		Rt (min)	[M-H]^− (m/z)	Fragment ions (m/z)
	Phenolic acids
1	Gallic acid	5,2	169	125
2	Caffeic acid	22,5	179	109
3	Ferulic acid	29,3	193	149, 178
	Other phenolic compounds
1	Procyanidin B1	3,5	577	451, 425
2	(+)-Catechin	5,0	289	245, 205
3	Procyanidin B2	5,7	577	451, 425
4	(-)-Epicatechin	8,9	289	245, 205
5	Cyanidin-3-O-glucoside	10,01	447	285
6	Chlorogenic acid	10,45	353	191
7	(-)-Epicatechin gallate	13,5	441	331, 289
8	Quercetin-3-O-galactoside	28,2	463	301, 343, 179
9	Phloridzin	30,0	435
10	Quercetin-3-O-rhamnoside	31,4	447	179, 151
The polyphenols are listed according to the elution order obtained with HPLC-MS analysis, on the Luna C18, 150 × 2.0 mm, 5 μm column.

Table 2  Pulp polyphenol composition of Italian ancient and commercial apple cultivars studied over three sampling years

		Concentration (mg/kg DW)
	Phenolic compound	Dominici	Giachetta	Golden Delicious	Grigia di Torriana	Pom d'Aram	Ronzè	Ros Borsetta
2007
Hydroxybenzoic acids	Gallic acid	20.2±1.2^b	21.6±3.8^bc	nd	16.2±0.1^b	9.5±2.5	8.7±1.4	27.7±4.0^c
Hydroxycinnamic acids and their esters	Caffeic acid	nd	33.9±5.9^c	nd	nd	6.7±1.7^ab	5.9±1.6^ab	8.3±2.3^b
	Ferulic acid	nd	nd	5.6±0.8^b	11.0±1.4^c	nd	nd	1.1±0.0^a
	Chlorogenic acid	130.3±66.4^a	672.9±392.5^ab	489.6±219.5^ab	868.4±148.3^b	366.3±114.5^ab	366.6±7.5^ab	461.9±258.9^ab
Flavan-3-ols	Procyanidin Bl	nd	nd	nd	76.6±25.9^b	nd	nd	22.8±12.7^a
	Procyanidin B2	175.9±56.4^c	55.0±23.0^b	17.5±6.4^a	429.4±199.2^d	nd	36.5±14.2^b	67.7±16.2^b
	(+)-Catechin	57.5±3.0^c	28.9±5.5^bc	15.5±5.0^ab	57.4±25.8^c	13.6±0.8^ab	nd	nd
	(−)-Epicatechin	134.6±4.6^a	54.7±25.3^a	50.0±9.8^a	279.8±119.0^b	43.2±14.4^a	21.0±5.6^a	22.7±12.9^a
	(−)-Epicatechin gallate	nd	nd	nd	12.7±1.7^c	1.9±0.1^a	nd	10.3±0.8^b
Dihydrochalcones	Phloridzin	32.2±11.4^bc	45.4±7.2^c	nd	121.0±6.8^d	16.8±7.4^ab	6.0±0.6^a	22.8±17.9^abc
Quercetin glycosides^MS	Quercetin-3-galactoside	2.0±0.9^b	0.6±0.1^a	0.4±0.1^a	0.5±0.0^a	0.5±0.2^a	0.4±0.0^a	0.4±0.0^a
	Quercetin-3-rhamnoside	26.7±20.3^a	9.2±0.1^a	22.5±8.2^a	nd	nd	nd	nd
Cyanidin glycosides	Cyanidin-3-glucoside	2.9±0.4^b	1.7±0.0^a	nd	nd	nd	nd	nd
	TP	582.1±25.9^a	923.8±451.6^a	601.3±248.3^a	1873.1±525.l^b	458.4±113.0^a	445.2±23.1^a	645.5±311.8^a
	Phenolic compound	Dominici	Giachetta	Golden Delicious	Grigia di Torriana	Pom d'Aram	Ronzè	Ros Borsetta
2008
Hydroxybenzoic acids	Gallic acid	22.1±2.7^d	17.6±2.6^cd	nd	11.6±0.3^bc	12.2±3.9^bcd	7.0±4.3^ab	33.8±6.5^e
Hydroxycinnamic acids	Caffeic acid	nd	nd	nd	nd	3.9±1.3^a	nd	22.3±9.9^b
and their esters	Ferulic acid	nd	69.3±10.9^b	10.4±2.1^a	1.9±0.7^a	nd	nd	2.4±1.0^a
	Chlorogenic acid	2082.1±273.4^b	1521.7±447.2^b	405.0±72.2^a	1475.7±327.8^b	400.4±34.7^a	366.6±7.5^a	1486.4±475.6^b
Flavan-3-ol	Procyanidin Bl	272.5±1.4^c	62.0±10.0^a	nd	248.7±58.7^c	29.7±0.8^a	nd	180.2±16.0^b
	Procyanidin B2	934.1±118.4^b	196.5±43.1^a	82.1±9.3^a	1143.8±237.3^b	nd	nd	274.4±64.1^a
	(+)-Catechin	111.1±0.5^c	36.0±5.5^ab	31.7±1. 1^ab	194.7±44.8^d	nd	78.6±48.1^bc	112.3±17.7^c
	(−)-Epicatechin	503.5±116.8^b	122.0±6.3^a	159.2±20.0^a	898.1±199.7^c	20.1±10.2^a	144.5±99.8^a	234.9±32.6^ab
	(−)-Epicatechin gallate	19.4±1.1^b	30.4±1.5^c	nd	35.0±6.9^c	5.5±0.5^a	nd	7.9±4.6^a
Dihydrochalcones	Phloridzin	86.3±13.1^b	nd	11.2±0.1^a	160.3±20.9^c	10.5±3.1^a	1.4±0.1^a	57.4±27.0^b
Quercetin glycosides^MS	Quercetin-3-galactoside	1.0±0.0^b	0.4±0.0^a	0.6±0.1^a	1.0±0.1^b	0.4±0.1^a	0.5±0.2^a	0.5±0.2^a
	Quercetin-3-rhamnoside	7.5±3.1^a	33.3±8.2^b	42.6±4.6^b	5.1±4.0^a	nd	nd	nd
Cyanidin glycosides	Cyanidin-3-glucoside	3.5±0.2^a	nd	nd	1.9±0.1^b	nd	nd	nd
	TP	4043.1±52.7^c	2089.3±382.8^b	742.9±105.3^a	4177.8±891.7^c	482.7±50.3^a	601.0±158.5^a	2412.5±619.4^b
	Phenolic compound	Dominici	Giachetta	Golden Delicious	Grigia di Torriana	Pom d'Aram	Ronzè	Ros Borsetta
2009
Hydroxybenzoic acids	Gallic acid	nd	nd	nd	nd	nd	nd	nd
Hydroxycinnamic acids	Caffeic acid	nd	nd	nd	nd	nd	nd	nd
and their esters	Ferulic acid	nd	nd	nd	nd	nd	nd	nd
	Chlorogenic acid	338.8±23.3^a	1279.5±53.1^b	347.4±61.6^a	1258.1 ±115.9^b	1150.5±166.3^b	1213.6±183.9^b	1235.1±291.3^b
Flavan-3-ols	Procyanidin Bl	88.9±13.6^a	5.3±0.4^a	75.3±2.8^a	338.0±25.3^b	132.4±17.4^a	318.8±114.9^b	297.7±47.2^b
	Procyanidin B2	211.7±8.4^a	458.0±42.0^a	472.9±108.1^a	2087.5±187.1^b	857.6±40.0^a	826.4±87.7^a	1618.9±619.2^b
	(+)-Catechin	nd	32.5±5.8^ab	nd	134.8±15.7^c	34.7±4.5^ab	56.4±1.6^b	140.7±40.1^c
	(−)-Epicatechin	86.2±6.4^a	132.4±5.7^a	146.1±28.0^a	912.5±111.6^c	284.9±26.1^ab	249.4±39.8^a	531.1±213.5^b
	(−)-Epicatechin gallate	nd	9.3±4.0^a	6.1±0.6^a	nd	nd	nd	14.4±0.2^b
Dihydrochalcones	Phloridzin	254.4±46.9^b	49.0±7.9^a	54.6±6.9^a	263.2±84.2^b	108.8±12.5^a	25.4±0.4^a	75.3±30.7^a
Quercetin glycosides^MS	Quercetin-3-galactoside	0.6±0.1^a	0.6±0.0^a	0.3±0.0^a	0.4±0.0^a	0.4±0.1^a	1.0±0.3^b	0.5±0.0^a
	Quercetin-3-rhamnoside	8.0±0.9^a	16.7±2.6^b	6.8±2.9^a	nd	nd	6.6±3.6^a	nd
Cyanidin glycosides	Cyanidin-3-glucoside	1.7±0.2^b	2.9±0.7^bc	nd	1.6±0.1^ab	2.6±0.2^bc	3.8±1.0^c	9.0±1.0^d
	TP	990.2±68.3^a	1986.1±101.9^abc	1109.7±191.3^ab	4996.1±371.6^e	2571.9±267.1^bcd	2701.3±430.5^cd	3922.8±1241.2^de
MS: quantified by HPLC-MS analysis; nd: not detected; TP: total phenolics.
^a–eValues within a row by the same letters are not significantly different at p ≤ 0.05. Values are the means ± SD (n = 3).

Table 3  Effect of the sampling year, cultivar, and their interaction on total phenolics and the content of each phenolic compound

	Cultivar (A)	Year (B)	AB
TP	***	*	***
Gallic acid	***	***	***
Cyanidin-3-glucoside	***	***	***
Procyanidin B2	***	ns	***
(+)-Catechin	***	ns	***
Chlorogenic acid	***	***	***
Caffeicacid	***	***	***
Procyanidin Bl	***	ns	***
(−)-Epicatechin	***	ns	***
Ferulic acid	***	***	***
Quercetin-3-galactoside	***	ns	***
(−)-Epicatechin gallate	***	***	***
Phloridzin	***	***	***
Quercetin-3-rhamnoside	***	***	***
ns: not significant.
*^,***Significantly different at p = 0.05 and p = 0.001, respectively.