3.1. Physico-Chemical Analysis
The quality indices of the apricot accessions including fruit firmness, total soluble solids (TSS), titratable acidity (TA), and pH identified the fruits used in this study as ripe and ready-to-eat apricots.
Figure 1 shows the photos of the 12 Vesuvian apricot accessions analyzed in this study; the fruit qualitative traits, reported in
Table 2, indicated significant differences in the qualitative parameters of different accessions.
The analysis of fruit weight showed that ‘VI’ was the accession with the greatest weight (88.33 g), while the accession with the lowest weight is the ‘BE’ (36.98 g) and ‘PE’ (42.37 g). Our results agree with Di Vaio et al. [
22], who analyzed three different Campania accessions (Ceccona, Vitillo and Pellecchiella), and “Vitillo” showed the greatest weight of 72.93 g. The same study reported fruit weight values of the “Pellecchiella” accession grown in the National Park of the Vesuvius area approximately 60% higher than the same accession analyzed in the present study (68.11 g vs. 42.37 g). The ANOVA test reported significant statistical differences between the weight of the various accessions which reported an average weight of approximately 55.96 g, this difference is due to the variability of the different genotypes analyzed, all grown under the same environmental conditions. Souty et al. [
33] proposed the size, color, firmness, resistance to proposed manipulation, taste, aroma, and texture as the fundamental quality attributes in apricot fruit. In our study, pulp firmness ranged from 0.84 kg/0.5 cm
2 (for the ‘PE’ and ‘PI’ accession) to 2.97 kg/0.5 cm
2 (‘PAN’ accession), with a general average in the “Vesuvian apricots” of approximately 1.48 kg/0.5 cm
2, these values confirm the suitability of apricot fruit for fresh consumption. Our results highlighted lower pulp firmness values than those reported in the bibliography; in fact, Caliskan et al. [
34] reported fruit firmness between 1.1 and 4.8 kg/cm
2 among early matured fourteen apricot cultivars grown in the Mediterranean region and harvested in May in Turkey. Gurrieri et al. [
1] reported that firmness, attractiveness, and taste are the principal parameters affecting apricot fruit quality.
The TSS results (°brix) reported higher values in the ‘SC’ accession (18.17 °brix) and lower values in ‘VI’ (13.33 °brix), thus recording greater TSS of approximately 36.30%. The TSS results recorded in our study are similar to those reported by Di Vaio et al. [
22] on ‘Vitillo’, which showed values of approximately 12.20 °brix and by Leccese et al. [
2], with a value of approximately 12.10 °brix on the same accession. Juice acidity varied greatly among accessions, showing a range of 22.17 g/L of malic acid, for ‘PAL’ accession, and 6.90 g/L of malic acid for ‘PAO’, with a general average of 12.84 gL
−1 of malic acid. Our acidity results are similar to those reported by Lo Bianco et al. [
9], who reported on 16 apricot cultivars in the northern coast of Sicily, with mean values of 11.3 gL
−1. Leccese et al. [
35], in a study carried out on 18 apricot genotypes of the Italian and international germplasm, reported a TSS range of between 12 and 16 °Brix and TA ranged from 0.60 to 2.28% malic acid. The soluble solid content and the titratable acid are the most important factors affecting the taste of apricot. Ali et al. [
36] showed that on apricot cultivars grown in Northern Areas of Pakistan had a total soluble solids range from 12.67 to 20.00 °Brix, while the variation in acid content in terms of malic acid on a fresh weight basis ranged between 4.5 and 8.6 of malic acid. Vesuvian apricots showed a higher quantity of soluble solids than other apricot cultivars; in fact, Melgarejo et al. [
37], in a study conducted on apricots grown in southeastern Spain, reported TSS values between 9.5 and 13 °brix.
The composition of sugars and organic acids, as well as the sugar–acid ratio, may influence the taste of apricots [
38]. The TSS/TA ratio, an index which is used to determine fruit quality, was 0.62 for ‘FR’ and 2.46 for ‘PU’. Compared to other fruit species, apricots are characterized by high sugar–acid ratio. Therefore, apricots are ideal for processing into juices, wine, and jams. Higher TSS/TA ratios correlate well with a higher eating quality [
39]. Vesuvian apricot accessions present a choice of apricots with flavors from sour to sweet and offer the possibility to choose according to consumer and processing preferences. The pH showed results between 3.67 and 4.20, thus reporting higher values than the cultivars analyzed by Lo Bianco et al. [
9], who reported a range from 2.2 to 3.6, with Ninfa (cv. early) and Orange Red (cv. intermediate) showing above-average values and Palummella, Goldrich, Alba and Bulida showing below-average values. It is reported that it is possible to define superior-quality apricots as fruits that have TSS values ≥ 13 and a pulp strength ≤ 1 kg\0.5 cm
2. Another parameter used to express the quality of apricot fruits is TSS-F (soluble solids content-pulp hardness), which must have a value ≥ 12 [
40]. All the accessions analyzed show high values of TSS-F, with higher values in ‘SC’ (17.15) and lower values in the accession ‘VI’ (11.35). Overall, our results confirm that the analyzed Vesuvian apricots present excellent-quality fruits.
Table 3 shows the L*, a* and b* peel color coordinates of the 12 Vesuvian apricots. All peel color results indicated statistically significant differences among genotypes per
p < 0.05 of L*, a* and b* values. Color is among the most important external factors of fruit quality, as the appearance of the fruit greatly influences consumers [
11]. The study of the variability of apricot color is important for quality control to determine appropriate maturity, processing, consumption and selection of the best cultivar intended to be marketed. Color has a significant impact on consumer perception of apricot quality, especially regarding fruit attractiveness [
41]. L* defines the lightness, and a* and b* define the red greenness and blue yellowness, respectively.
In ‘PE’, the peel color showed a more orange color, with a higher a* value (39.73) and lower L* value (52.23); conversely, ‘PAN’ showed a whiter skin color, with lower a* values (2.46) and higher L* values (61.18). Higher chroma values were reported in ‘VM’ and ‘PU’ with 65.17 and 63.23, respectively. It is reported that carotenoid content in apricot fruit has been shown to correlate well with skin and flesh color, with apricots with orange-colored flesh containing higher levels of carotenoids than white-colored flesh [
33].
3.2. Sugar and Acid Content
In
Table 4, the principal sugars content is shown.
The total sugar content ranged from 260.40 mg/g d.w in ‘VM’ to 744.59 mg/g d.w in ‘SC’, and the latter showed the highest TSS value (
Table 2). In all accessions analyzed, the sugar content showed the following order: sucrose > glucose > fructose, confirming the order reported in previous works [
26,
42,
43,
44]. Sucrose was the most concentrated sugar, ranging between 191.25 mg/g d.w in ‘VM’ and 553.26 mg/g d.w in ‘SC’, and the content of glucose ranged between 59.73 mg/g d.w in ‘VM’ and 243.04 mg/g d.w in ‘PAN’, while the fructose content ranged between 9.42 mg/g d.w in VM and 43.64 mg/g d.w in ‘PAL’. The content of both sucrose and glucose was higher compared to the range reported by Naryal et al. [
42], who showed a range between 67.9 mg/g and 366.5 mg/g, and 37.3 mg/g to 152.9 mg/g, for sucrose and glucose, respectively, while the fructose content was lower for BE, PAN, PI, PO, VI and MI with respect to the minimum range reported by Naryal et al. [
42], who showed a range from 27.6 mg/g to 155.3 mg/g, depending on the region. The results of sucrose and glucose concentration were similar to Fan et al. [
26], who showed sucrose and glucose concentrations that ranged between 292.00 mg/g and 995.00 mg/g, and 82 mg/g and 303 mg/g, respectively, while the fructose content was lower compared to Fan et al. [
27], who showed a concentration that ranged between 44 mg/g and 173 mg/g. On the other hand, Drogoudi et al. [
10] showed sucrose, glucose and fructose concentrations that ranged between 284.00 mg/g, a higher concentration compared to sucrose content of BE and VM, and 449.00 mg/g, a lower concentration compared to SC; they found a range of glucose concentration from 53 mg/g, higher compared to VM, to 151 mg/g, a lower concentration compared to FR, PAL, PAN, PAO, PE, PI, VI, BE and a higher concentration compared to PO and VM, and a range of fructose concentration from 11 mg/g to 46 mg/g with a similar trend compared to our results, except for VM that showed a lower concentration (9.42 mg/g d.w). The concentration of sugar depended on the analyzed cultivar. Vega-Galvez et al. [
45] showed a concentration of sucrose of 228.4 mg/g d.w, the same concentration of glucose 59.2 mg/g d.w, similar to the minimum concentration reported in our range (59.73 mg/d d.w in VM), and a fructose content (72.5 mg/g d.w in
Prunus armeniaca L. var. Tilton) higher compared our results. Finally, Akin et al. [
46] showed a lower concentration compared to our results; in fact, the total sugar content ranged from 68.61 mg/d.w to 93.88 mg/g d.w and this could be derived from different cultivars and different regions.
Regarding the sourness of fruits, it depends largely on the relative amounts of sugars and organic acids present [
47,
48,
49,
50] and they are influenced by genotype, geographical location of cultivation, and fruit stage of maturity [
27,
44,
46,
51].
Table 5 shows the organic acid content in Vesuvian apricots analyzed.
The total organic acid content ranged from 39.71 g/kg d.w in ‘PU’ to 96.79 mg/kg d.w in ‘PAL’; the latter showed the lowest pH value and the highest TA value (
Table 2). Among organic acid citric, malic, fumaric, malic, ascorbic, shikimic, succinic and tartaric acid were found. Citric acid was the most abundant organic acid in the analyzed cultivars, with a concentration from 18.98 g/kg d.w in ‘PU’ to 56.25 g/kg d.w, in ‘BE’. The other most concentrated organic acids were malic acid (from 7.88 g/kg d.w in ‘PE’ to 39.01 g/kg d.w in ‘PAL’), an important sensory contributor for the sourness of fruits [
26], and tartaric acid (from 1.75 g/kg d.w in ‘PO’ to 21.18 g/kg d.w in ‘PAL’). Further, in ‘PAL’ the citric acid concentration was similar to the concentration of malic acid (34.77 g/kg d.w for citric acid and 39.01 g/Kg d.w for malic acid), while the citric acid content was similar to tartaric acid (19.06 g/Kg d.w for citric acid and 19.45 g/kg d.w for tartaric acid) in ‘PAN’. It is reported that in many fruits, the increase in soluble sugar concentration during ripening complements the presence of malic and citric acids and imparts on the flesh a sweet taste [
52]. Thus, in the unripe flesh of many fruits, a higher content of certain organic acids and a low content of sugars impart on the flesh a sour flavor, making them less palatable to animals [
50]. The flavor plays an important factor in consumer choice and satisfaction, which results from a union of taste and aroma [
26]. Additionally, Alajil et al. [
50] and Karatas [
25] showed that citric and malic acids were the most concentrated organic acids in apricots. The tartaric acid concentration was higher compared to Kim et al. [
51], who showed a concentration range from 1.6 g/kg d.w to 3.0 g/kg d.w in Japanese apricots. On the contrary, Salur-Can et al. [
52] showed that malic acid was more concentrated than citric acid (18 g/kg d.w for malic acid and 2 g/kg d.w for citric acid), while the authors showed a higher concentration (32 g/kg d.w) of succinic acid compared our results (from 0.59 g/kg d.w in ‘BE’ to 3.42 g/kg d.w in ‘SC’). Additionally, Karabulut et al. [
53] showed a higher concentration of malic acid, which ranged from 13.12 g/kg d.w to 18.77 g/kg d.w, than that of citric acid, which ranged from 14.59 mg/kg d.w to 25.03 mg/kg d.w, depending on apricot size. Furthermore, Su et al. [
54] and Akin et al. [
46] showed a variable content of both citric and malic acids that depended on apricot cultivar and region. The ascorbic acid content ranged from 0.23 g/kg d.w in ‘VM’ to 0.86 g/kg d.w in ‘VI’, and from 0.26 g/kg d.w to 0.35 g/kg d.w in the range reported by Akin et al. [
46], who showed a concentration that ranged from 0.26 g/kg d.w to 0.97 g/kg d.w in different Turkic apricots. The ascorbic acid has an essential function in different cellular processes, such as cellular oxidation as well as to protect the cellular content against oxidative damage resulting from reactive oxygen species (ROS), which cause different types of chronic disease. Furthermore, ascorbic acid has antioxidant functions and antitumor and antiviral activities [
55]. Further, our results showed a low and similar content among accessions. Finally, fumaric and shikimic acids in all analyzed samples were present at a concentration lower than 1 g/kg d.w; also Hasib et al. [
56], Bae et al. [
57] and Schmitzer et al. [
45] showed that fumaric and shikimic acids were the least concentrated organic acids in apricots. Malic and/or citric acid are abundant in the flesh of most fruits [
48,
57,
58,
59,
60]. For example, their content can account for up to 40–50% of the dry weight of the unripe flesh of fruits such as apricot [
61]. In many fruits, quinic acid can be abundant and can account for 20–30% of the dry weight of the flesh of some citrus fruits early in development [
62]. In a smaller number of fruits, either oxalic or tartaric acid can be very abundant. The total amount of organic acids that are present in the fleshy parts of fruits of different species and their cultivars can vary greatly, and can also vary in terms of the relative abundance of the individual organic acids. In addition, these contents are dependent on both the tissue of the fruit and its stage of development, as well as on diverse environmental factors [
48,
59,
60].
The content of organic acids and sugars significantly influences the sensory consistency, taste, and aroma of fruits [
26,
45]. Furthermore, from a nutritional point of view, organic acids contribute to maintain the acid–base balance in the intestine and to increase the bioavailability of iron [
63]. Moreover, the organic acids can help to stabilize water-soluble vitamins B and C, as well as to stimulate appetite and digestion and absorption of minerals including potassium, copper, zinc, iron, and calcium. Additionally, due to their ability to chelate metals, the organic acids may act as antioxidants playing an important role in the protection of many diseases including cardiovascular diseases, cancer, and inflammation. Furthermore, the organic acids are involved in different biological processes. In fact, they reduce the growth of bacteria, which aids in the preservation of fruits [
46]. Finally, the organic acid contents and their derivatives in the flesh of fruits have important dietary influences, affecting fruit taste and, in some cases, its suitability for processing into different fruit products [
64,
65,
66].
3.3. Antioxidant Activity and Identification and Quantification of Vesuvian Apricot Bioactive
The current study aimed to provide useful data about the chemical composition and comprehensive evaluation of the antioxidant activity of extracts derived from 12 apricot Vesuvian accessions. As reported in the literature, a significant number of phenolic compounds were determined in the apricot extracts, although a significant variability was reported in terms of polyphenol content among the apricot accession samples [
7].
Table 6 shows the total polyphenol content (TPC) detected with the Folin–Ciocalteu and the antioxidant activity evaluated with three different assays: DPPH, ABTS and FRAP.
The antioxidant activity showed a high variability between the different accessions. ‘PO’ showed a higher polyphenol content than ‘PAO’ (+~184%), reporting values of 5.69 mg GAE/g d.w and 2.00 mg GAE/g d.w, respectively. ‘BE’, ‘PAL’ and ‘PO’ showed a higher polyphenol content than the general average of the Vesuvian apricot analyzed, equal to 3.26 mg GAE/g d.w. In all three antioxidant assays ‘PO’ reported statistically higher values than the other accessions. For DPPH it reported values of 7.58 mmol trolox/kg d.w approximately 60% higher than the general average recorded which was equal to 4.74 mmol trolox/kg d.w. Statistically lower values were instead recorded in the PAN accession with 1.83 mmol trolox/kg d.w. In the ABTS and FRAP assays, the ‘PO’ accession reported antioxidant activity values on average 81% higher compared to the general averagwhile ‘PAO’ was the accession that reported lower values, respectively, equal to 5.91 mol trolox/kg d.w and 5.10 83 mmol trolox/kg d.w. Among the cultivars analyzed, the variability of the antioxidant capacity obtained was consistent and this variability was in line with literature data. In fact, it is widely reported that the antioxidant activity varies according to factors such as apricot cultivar, geographical source, irrigation regimes and sample extraction protocols [
36].
Our results have also shown a highly significant positive relationship between the total phenolic content and antioxidant activity (R = 0.76, 0.92 and 0.89 for DPPH, FRAP and ABTS, respectively). Such high R value suggested that the radical scavenging activity and ferric reducing ability could be credibly predicted on the basis of total phenolic content and directly confirmed that the phenolic compounds in the 12 Vesuvian apricot accessions were responsible for their antioxidant capacity. The present high correlation between antioxidant activity and phenolics agreed with previous studies [
10].
The influence of different accession on the qualitative and quantitative profile of polyphenolic compounds of apricot fruits is included in
Table 7.
Polyphenols have attracted more attention in recent years because of their antioxidant capacity useful to prevent several chronic diseases [
67]. Apricot occupies a distinct position among stone fruits due to its multifaceted compositional contour and significant functional potentials. Apricots contain a wide variety of phytochemicals that function as antioxidant. Literature reports that apricots contain appreciable amounts of total phenolic compounds and flavonoids which make them more valuable as functional food. The most representative polyphenols are quinic acid, chlorogenic acid, caffeic acid, epicatechin, rutin. Quinic acid showed high significant values in the ‘PE’ accession with values of 57.88 mg/100 g, and lower values were shown in the ‘PI’ accession with 6.83 mg/100 g. Chlorogenic acid showed significant values in the ‘SC’ accession with values of 68.99 mg/100 g, and the lowest values have been reported in the ‘PAO’ accession with 23.60 mg/100 g. Caffeic acid showed significantly high values in accession ‘PAL’ (17.60 mg/100 g) and ‘PU’ (16.94 mg/100 g), and less values in accession ‘VI’ (7.06 mg/100 g) and ‘VM’ (6.99 mg/100 g). Epicatechin values were high in the ‘VM’ accession with values of 16.56 mg/100 g, compared to ‘PAN’, ‘PAO’, ‘VI’ with values of 1.19, 1.06, 1.53 mg/100 g, respectively. Rutin, instead, was the most significant polyphenolic compound among all present with an average value of 77.79 mg/100 g, and its values were highly significant in the ‘PAL’, ‘PO’, ‘VI’ accessions with high values of 140.58, 127.32, 132.71 mg/100 g, respectively, less significant instead in the ‘VM’ accession with 25.57 mg/100 g. ‘PO’ and ‘VI’ showed a total polyphenol content approximately 29% higher than the general average, reporting values of 249.15 mg/100 g and 250.22 mg/100 g, respectively. The ‘PAN’ accession, on the other hand, reported a lower quantity than the general average of approximately 65% with values of 106.94 mg/100 g. Radi et al. [
68], characterized and identified the main phenolic compounds in French apricot. Eight compounds were isolated and identified by comparing their characteristics with commercial standards, namely protocatechuic acid, (+)-catechin, chlorogenic acid, (-)-epicatechin, naringenin-7-glucoside, quercetin-3-glucoside, quercetin-3-rhamnoglucoside also namely rutin, and kaempferol-3-rutinoside. The obtained results show that chlorogenic and neochlorogenic acids, (+)-catechin, (-)-epicatechin and rutin are the major compounds among the polyphenols. Di Vaio et al. [
22], evaluated the primary quality characteristics, including total antioxidant activity and total polyphenol content, of the most popular autochthonous apricot cultivars in Campania: Ceccona, Vitillo and Pellecchiella. Pellecchiella exhibited the highest Trolox Equivalent antioxidant capacity, whereas Ceccona had the largest concentration of phenolic compounds. The highest concentration of total phenolic compounds was found in Ceccona, which had 389.93 µg/g FW, followed by Vitillo (184.36 µg/g FW) and Pellecchiella (131.35 µg/g FW). In accordance with our previous work, the results obtained showed that the cultivar “Vitillo” has a higher concentration of the two most represented compounds (chlorogenic acid and rutin) than the cultivar “Pellecchiella. Göttingerová et al. [
69], identified phenolic compounds, organic acids, vitamin C, flavonoids, antioxidant capacity, and carotenoids in the fruits of particular 15 Czech apricot cultivars in order to demonstrate the high nutritional value of apricot. Chlorogenic acid is among the primary phenolic acids found in the fruit of the Prunus genus in the concentration range of 0.69 to 21.94 mg/100 g FW. The most prevalent flavanols from the flavan-3-ol group are catechin and epicatechin, which is present in a variety of plant species. Catechin was the most prevalent of these substances, with values ranging from 0.55 to 10.75 mg/100 g FW. The total polyphenol content in the set of cultivars under investigation ranged from 57.33 to 571.93 mg GAE/100 g FW. The antioxidant activity measured by using the assay was in the average of 203.42 mg TE/100 g FW. Antioxidant properties of fruit depend on the cultivar and are related to climatic conditions. Cultivar, growing region, and ripening stage play an important role in apricot’s nutritional and quality qualities. The harvest of fruits represents a crucial step to obtain the optimal compositions of bioactive compounds to determine the ideal time to harvest. For this reason, is important the chemical characterization of cultivars [
70]. In addition, as previously reported [
22] the quali-quantitative variability in the polyphenols composition of apricot extracts may be also caused by the genetic characteristics of the examined accessions. Particularly, the amounts of polyphenols produced during ripening could depend on the influence of affect biosynthetic pathways. Determining unambiguous fruit quality criteria has always been extremely challenging due to the genetic heterogeneity of apricot varieties. This study emphasizes the requirement to evaluate the apricot fruit’s possible health advantages. Due to its pharmacologically significant bioactive components, it has been reported having beneficial in treating conditions such as chronic gastritis, oxidative intestinal damage, hepatic steatosis, coronary heart disease and atherosclerosis [
63]. To create a better understanding of foods’ roles and functions in various disease prevention processes, it is necessary to pose more attention to foods and each of their constituent components. In-depth research will aid in making use of this resource in several human diseases.