Changes on Grape Aroma Composition as a Consequence of Foliar Application of Methyl Jasmonate and Nano-Sized Particles Doped with Methyl Jasmonate

Citation: Marín-San Román, S.; Pérez-Álvarez, E.P.; Sáenz de Urturi, I.; Parra-Torrejón, B.; Ramírez- Rodríguez, G.B.; Delgado-López, J.M.; Garde-Cerdán, T. Changes on Grape Aroma Composition as a Consequence of Foliar Application of Methyl Jasmonate and Nano-Sized Particles Doped with Methyl Jasmonate. Appl. Sci. 2023,13, 2487. https://doi.org/10.3390/ app13042487 Academic Editor: Alessandro Genovese Received: 4 January 2023 Revised: 9 February 2023 Accepted: 9 February 2023 Published: 15 February 2023 Copyright: © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). applied sciences Article Changes on Grape Aroma Composition as a Consequence of Foliar Application of Methyl Jasmonate and Nano-Sized Particles Doped with Methyl Jasmonate Sandra Marín-San Román1, Eva Pilar Pérez-Álvarez 1,* , Itziar Sáenz de Urturi 1, Belén Parra-Torrejón2, Gloria B. Ramírez-Rodríguez 2, JoséManuel Delgado-López 2and Teresa Garde-Cerdán1,* 1Grupo VIENAP, Instituto de Ciencias de la Vid y del Vino, Consejo Superior de Investigaciones Científicas (CSIC), Universidad de La Rioja, Gobierno de La Rioja, Ctra. de Burgos, km. 6, 26007 Logroño, Spain 2 Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, Av. Fuente Nueva, s/n, 18071 Granada, Spain *Correspondence: [email protected] (E.P.P.-Á.); teresa.gar[email protected] (T.G.-C.) Abstract: In recent years, foliar application of elicitors to the vineyard has been increasingly used, in particular, elicitation with methyl jasmonate (MeJ). However, due to the high cost of this compound, it is necessary to find a form of application in which the amount to be used is considerably reduced. Therefore, the aim of this work was study for the first time the influence of foliar application of nanoparticles doped with MeJ (ACP-MeJ) and foliar application of methyl jasmonate (MeJ), using a dose of 1 mM versus 10 mM, respectively, on volatile composition of Tempranillo grapes during two consecutive vintages. Grape volatile composition was determined by SPME-GC-MS. The obtained results reveal that MeJ application increased the concentration of terpenoids, and total C6 compounds in 2019 and 2020, and C13 norisoprenoids in 2019. In addition, ACP-MeJ enhanced the amount of terpenoids, and benzenoids in 2020. These are encouraging results considering that the ACP-MeJ dose was 10 times lower than that of MeJ. Therefore, the foliar application of MeJ supported on nanoparticles could be a tool in order to improve grape volatile composition, favoring a more viable and sustainable viticulture. Keywords: nanoparticles; methyl jasmonate; volatile compounds; grape varietal aroma; elicitors 1. Introduction Aroma is one of the most important parameters to determine must and wine quality, also influences the grape flavor and contributes to the sensory character of the wine [ 1 – 4 ]. The grape volatile compounds belong to several groups: terpenoids, C13 norisoprenoides, benzenoid compounds, esters, C6 compounds, alcohols, thiols and methoxypyrazines [ 5 – 7 ]. The amount of these compounds depend on several factors such as grape variety, season, terroir, grape maturity, viticultural practices, etc. [ 1 , 8 – 10 ]. Foliar fertilization is a technique that is increasingly used as allows a quick and efficient assimilation of the products applied to the plant, reducing soil contamination and costs [10–12]. Foliar application of elicitors, molecules capable of activating the defensive systems of plants, can increase the synthesis of secondary metabolites [ 12 – 14 ]. Methyl jasmonate is a volatile organic compound derived from jasmonic acid [ 15 , 16 ]. This elicitor has been mainly implicated as a mediator of plant responses triggered by wounding and insect feeding and is involved in the pathogen resistance [15,17,18]. Foliar application of methyl jasmonate has been shown to increase the synthesis of secondary metabolites such as amino acids [ 19 ], phenolic compounds [ 14 , 18 , 20 ], and volatile compounds [ 5 , 18 – 21 ]. Despite this, methyl jasmonate is a compound with a very high cost and with low chemical stability. In the last decade, nanotechnology has opened new horizons in several disciplines, including and agriculture [ 22 ]. Nanotechnology is providing very interesting results in Appl. Sci. 2023,13, 2487. https://doi.org/10.3390/app13042487 https://www.mdpi.com/journal/applsci Appl. Sci. 2023,13, 2487 2 of 18 agriculture by improving the efficiency of agrochemicals [ 23 , 24 ]. Specifically in viticulture, there are few studies [ 25 ] in which nanocarriers have been applied to vineyards to improve the efficiency of fertilizers (i.e., urea) or elicitors (i.e., MeJ) [ 26 – 30 ]. In this line, biomimetic calcium phosphate nanoparticles (ACP-NPs) have been proposed as promising MeJ nanocarrier providing slow release kinetic and protection against thermal degradation [ 31 ]. ACP-NPs are non-toxic and biocompatible nanomaterials widely used in biomedicine for drug delivery, dental remineralization or bone tissue engineering [ 32 ]. But, the effect of the foliar application of this nanoelicitor on grape aromatic composition has not been studied so far, only in the wine volatile composition, i.e., fermentative aromas [ 33 ]. Hence, this work aims at evaluating the influence of foliar application of nanoparticles doped with MeJ (ACP-MeJ) and foliar application of methyl jasmonate (MeJ) in conventional form on volatile composition of Vitis vinifera L. cv. Tempranillo grapes during two vintages. 2. Materials and Methods 2.1. Vineyard Site, Grapevine Treatments and Samples This study was conducted, during the 2019 and 2020 vintages, on Vitis vinifera L. cv. Tempranillovines belonging to an experimental vineyard located at Finca La Grajera, Logroño, La Rioja (Spain). These vines were planted in 1997 using R-110 rootstock and treated according to local viticultural practices. They were trained in a VSP (vertical shoot positioned) trellis system, with a spacing between vines of 2.80 m between rows, and 1.25 m within the same row. For further information, climatic data were obtained from the Agroclimatic Information Service (SIAR), which were collected by an automatic weather station located near the area. During 2019, from the beginning of April to 1 September, the accumulated rainfall was 247.8 L/m 2 , and the average temperatures were: 27 ◦ C the maximum, 13.8 ◦ C the mean, and 3.7 ◦ C the minimum. For the year 2020, in the same period, the accumulated rainfall was 217.8 L/m 2 , and the average temperatures were: 26.3 ◦C the maximum, 13.8 ◦ C the mean, and 3.7 ◦ C the minimum. Foliar applications of free methyl jasmonate (MeJ) and amorphous calcium phosphate nanoparticles functionalized with MeJ (ACP-MeJ) were studied. To carry out the field experiments, free MeJ aqueous solution (10 mM) and ACP-MeJ aqueous suspension (1 mM MeJ) were prepared following previous [ 19 , 27 , 34 ]. Tween 80 were used in both cases as wetting agent (1 mL/L). ACP-MeJ nanoparticles were synthesized and fully characterized as described in detail elsewhere [ 31 ]. All treatments were applied first at veraison and second one week later. The concentration of treatment applied to the leaves of each plant was 200 mL/plant in each of the two applications. For the control only the plants were sprayed with the aqueous solution of Tween 80. Each of the treatments was carried out in triplicate, and each replicate consisted of 10 vines. All treatments were arranged in a complete randomized block design. The berries were harvested at their optimum point of technological maturity (weight of 100 berries constant, and 13% (v/v) of probable alcohol). Once harvested, they were destemmed and crushed until the must was obtained. The general parameters of all the musts were then measured, and aliquots of each must sample were frozen ( − 20 ◦ C) for subsequent analysis of the aromatic composition. 2.2. General Parameters Determination Enological parameters ( ◦ Brix, probable alcohol, pH, total acidity . . . ) were determined by official methods established by the OIV [ 35 ]. The remaining general parameters such as glucose + fructose fractions, glucose (and fructose indirectly, as subtraction of glucose + fructose − glucose), malic acid, total phenols and nitrogen, were determined by enzymatic methods, with the Miura One equipment (TDI, Barcelona, Spain). The results obtained for these parameters are shown as the mean ±standard deviation (n = 3). 2.3. Analysis of Grape Volatile Compounds by HS-SPME-GC-MS Determination of volatile compounds in the musts was carried out by head space solid-phase microextraction (HS-SPME) and their subsequent analysis by gas chromatog- Appl. Sci. 2023,13, 2487 3 of 18 raphy (GC) coupled to mass spectrometry (MS), according to the method described by Garde-Cerdán et al., 2018 [34] . The SPMEfiberusedwasdivinylbenzene/carboxen/polydime thylsiloxane (DVB/CAR/PDMS, 50/30 µ m) (Supelco, Bellenfonte, PA, USA). In 20 mL vials (Supelco), 9 mL of sample, 2.5 g NaCl and 10 µ L of internal standard (2-octanol) were added. After adding a stir bar, the vial was closed and placed in the GC-MS (Agilent, Palo Alto, CA, USA). Sample conditioning was done at 60 ◦ C, for 15 min and with stirring. After this step, the fiber was automatically inserted into the headspace in order to the extraction of the volatile compounds could take place, for 105 min, with agitation. After the extraction process was completed, the fiber was immediately introduced into the GC injection port at 250 ◦ C and held for 15 min for desorption of the compounds of interest. The capillary column used for analyte separation is SPB ™ -20 (30 m × 0.25 mm I.D. × 0.25 µ m film thickness) (Supelco). Helium was used as the carrier gas at a flow rate of 1.2 mL/min. The chromatographic conditions used were: initial temperature, 40 ◦ C for 5 min, a temperature gradient of 2 ◦ C/min, up to a final temperature of 220 ◦ C, to be maintained for 20 min (total time = 115 min). The ionization of the volatile compounds was performed at 70 eV. The detector worked at full scan (35—300 m/z). Identification was carried out using the NIST library and comparing with mass spectra and retention time of chromatographic standards, when available, as well as with data found in the literature. Semi-quantification was performed by relating the areas of each compound to the area and known concentration of the internal standard. Since the treatments were performed in triplicate, the results of grape volatile compounds are expressed as the mean concentration and standard deviation of the three replicates (n= 3). 2.4. Statistical Analyses Statistical analysis of the data was performed with the SPSS statistical package version 21.0 for Windows (SPSS, Chicago, IL, USA). Analysis of variance (ANOVA) (p< 0.05) was performed for general parameters and volatile compound data. To evaluate possible differences between treatments, the Duncan test was performed at the 95% probability level. A multivariate factor analysis was also performed (with treatment and season as factors) considering oenological parameters and grape aromatic compounds. Finally, a discriminant analysis was performed to classify the samples according to their volatile composition. 3. Results and Discussion 3.1. Effect of the Foliar MeJ and ACP-MeJ Treatments on the Must General Parameters Table 1shows the enological parameters in the grapes from control and vines treated with methyl jasmonate (MeJ) and with nanoparticles doped with MeJ (ACP-MeJ), in 2019 and 2020 seasons. In 2019, MeJ treatment significantly decreased ◦ Brix, probable grade, glucose + fructose (Glu + Fru), glucose (Glu), and fructose (Fru) content with respect to control grapes, while total acidity, total phenols, amino nitrogen, and yeast assimilable nitrogen (YAN) increased when vines were foliarly treated with MeJ. However, ACP- MeJ treatment showed no significant differences with respect to the control in any of the parameters studied except for total phenols, which concentration increased (Table 1). In 2020 season, MeJ and ACP-MeJ foliar application did not affect must enological parameters. This result are similar to those reported by Garde-Cerdán et al., 2018 [ 34 ] which found only small or no differences in these parameters after MeJ application. Although overall precipitation and average temperatures were similar in 2019 and 2020, August rainfall was 11.5 L/m 2 in 2019 and 32.9 L/m 2 in 2020. Since this month is where the berry ripening process is completed, this may be the reason why the weight of 100 berries is higher in 2020 than in 2019 (Table 1). Appl. Sci. 2023,13, 2487 4 of 18 Table 1. General parameters in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons . 2019 2020 Control MeJ ACP-MeJ Control MeJ ACP-MeJ Weight of 100 berries (g) 113.68 ±11.07 a 141.81 ±27.18 a 116.94 ±4.62 a 199.57 ±7.27 a 207.67 ±40.39 a 194.90 ±20.65 a ◦Brix 24.70 ±0.72 b 22.23 ±1.17 a 23.37 ±0.49 ab 22.30 ±0.92 a 22.17 ±2.31 a 22.37 ±0.38 a Probable alcohol (% v/v)14.63 ±0.49 b 12.92 ±0.80 a 13.71 ±0.35 ab 12.97 ±0.63 a 12.89 ±1.58 a 13.01 ±0.26 a pH 3.83 ±0.05 a 3.78 ±0.10 a 3.82 ±0.09 a 3.76 ±0.01 a 3.70 ±0.07 a 3.73 ±0.06 a Total acidity (g/L) * 4.61 ±0.11 a 5.20 ±0.36 b 5.13 ±0.26 ab 4.12 ±0.33 a 4.54 ±1.08 a 4.03 ±0.21 a Glu + Fru (g/L) 249.86 ±9.97 b 215.50 ±12.29 a 231.40 ±10.82 ab 216.42 ±10.70 a 218.62 ±26.56 a 223.84 ±2.98 a Glu (g/L) 120.18 ±5.13 b 102.88 ±6.89 a 110.89 ±4.94 ab 107.31 ±4.54 a 106.08 ±12.84 a 108.61 ±2.98 a Fru (g/L) 129.68 ±4.84 b 112.62 ±5.43 a 120.51 ±6.26 ab 109.11 ±6.53 a 112.54 ±13.76 a 114.72 ±0.98 a Malic acid (g/L) 2.24 ±0.24 a 2.54 ±0.32 a 2.51 ±0.56 a 1.21 ±0.08 a 1.54 ±0.22 a 1.39 ±0.18 a Total phenols (mg/L) 1185.33 ±72.31 a 1306.57 ±61.35 b 1351.40 ±27.32 b 541.60 ±64.02 a 603.07 ±73.82 a 582.70 ±66.02 a Ammonium nitrogen (mg N/L) 78.00 ±8.22 a 106.34 ±15.68 a 101.40 ±20.40 a 121.16 ±3.52 a 101.66 ±19.58 a 114.66 ±6.24 a Amino nitrogen (mg N/L) 118.51 ±14.33 a 202.11 ±50.59 b 175.71 ±24.66 ab 152.53 ±14.33 a 139.63 ±35.64 a 152.24 ±5.50 a YAN (mg N/L) 196.51 ±21.18 a 308.45 ±64.76 b 277.11 ±44.31 ab 273.69 ±17.69 a 241.29 ±55.05 a 266.90 ±11.62 a * As g/L of tartaric acid. YAN: yeast assimilable nitrogen. All parameters are listed with their standard deviation (n = 3). For each season and parameter, different letters indicate significant differences between the samples (p≤0.05). Appl. Sci. 2023,13, 2487 5 of 18 3.2. Influence of the Foliar MeJ and ACP-MeJ Treatments on Must Volatile Compounds Figures 1–3and Table 2show the results of must volatile primary aroma content in control and in samples from treated grapevines with methyl jasmonate (MeJ) and with nanoparticles doped with MeJ (ACP-MeJ), in 2019 and 2020 seasons. A total of 37 compounds were identified and semi-quantified, including terpenoids, C 13 norisoprenoids, benzenoid compounds, alcohols, carbonyl compounds, C6 compounds, and other compounds. Appl. Sci. 2023, 13, x FOR PEER REVIEW 6 of 20 3.2. Influence of the Foliar MeJ and ACP-MeJ Treatments on Must Volatile Compounds Figures 1–3 and Table 2 show the results of must volatile primary aroma content in control and in samples from treated grapevines with methyl jasmonate (MeJ) and with nanoparticles doped with MeJ (ACP-MeJ), in 2019 and 2020 seasons. A total of 37 compounds were identified and semi-quantified, including terpenoids, C13 norisoprenoids, benzenoid compounds, alcohols, carbonyl compounds, C6 compounds, and other compounds. Figure 1. Terpenoids concentration (µg/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n = 3). For each season and compound, different letters indicate significant differences between samples (p ≤ 0.05). 0,000 0,020 0,040 0,060 0,080 0,100 0,120 0,140 0,160 0,180 2019 2020 Concentration (mg/L) a) Limonene a b b ab b a 0,000 0,050 0,100 0,150 0,200 0,250 0,300 0,350 0,400 0,450 2019 2020 Concentration (mg/L) b) p-Cymene b a c a a b 0,000 0,050 0,100 0,150 0,200 0,250 2019 2020 Concentration (mg/L) c) Linalool b a c a b b 0,000 0,020 0,040 0,060 0,080 0,100 0,120 0,140 0,160 0,180 2019 2020 Concentration (mg/L) d) a-Terpineol b a c a c b 0,000 0,005 0,010 0,015 0,020 0,025 0,030 0,035 0,040 0,045 0,050 2019 2020 Concentration (mg/L) e) Geraniol b b a a ab b 0,000 0,020 0,040 0,060 0,080 0,100 0,120 0,140 0,160 0,180 0,200 2019 2020 Concentration (mg/L) f) Geranic acid b a a b a b 0,000 0,005 0,010 0,015 0,020 0,025 0,030 0,035 0,040 2019 2020 Concentration (mg/L) g) Geranyl acetone a b b a b b 0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,700 0,800 0,900 1,000 2019 2020 Concentration (mg/L) h) Total terpenoids Control MeJ ACP-MeJ a b c a c b ( ( ( ( ( ( ( ( Figure 1. Terpenoids concentration ( µ g/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n= 3). For each season and compound, different letters indicate significant differences between samples (p≤0.05). Appl. Sci. 2023,13, 2487 6 of 18 Appl. Sci. 2023, 13, x FOR PEER REVIEW 7 of 20 Figure 2. C13 norisoprenoids concentration (µg/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n = 3). For each season and compound, different letters indicate significant differences between samples (p ≤ 0.05). TDN: 1,1,6-trimethyl-1,2-dihydronaphthalene. 0,000 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000 2019 2020 Concentration (mg/L) a) (E)-b-Damascenone b a c a a a 0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,700 2019 2020 Concentration (mg/L) b) (Z)-b-Damascenone b c a a a a 0,000 0,050 0,100 0,150 0,200 0,250 0,300 2019 2020 Concentration (mg/L) c) b-Ionone a b b a a b 0,000 0,020 0,040 0,060 0,080 0,100 0,120 0,140 0,160 0,180 0,200 2019 2020 Concentration (mg/L) d) b-Cyclocitral a b b a a a 0,000 0,050 0,100 0,150 0,200 0,250 0,300 0,350 0,400 0,450 0,500 2019 2020 Concentration (mg/L) e) TDN a b c b a b 0,000 2,000 4,000 6,000 8,000 10,000 12,000 2019 2020 Concentration (mg/L) f) Total C13 norisoprenoids Control MeJ ACP-MeJ b a c a a a ( ( ( ( ( ( Figure 2. C 13 norisoprenoids concentration ( µ g/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n= 3). For each season and compound, different letters indicate significant differences between samples (p ≤ 0.05). TDN: 1,1,6-trimethyl-1,2-dihydronaphthalene. Figure 1shows the concentration of terpenoids found in the control samples and in the grapes from the treatments with MeJ and ACP-MeJ, in 2019 and 2020 seasons. In 2019, limonene (Figure 1a), geraniol (Figure 1e), and geranyl acetone (Figure 1g) decreased their concentration in ACP-MeJ grapes relative to control and MeJ grapes. This effect had already been observed in Vitis vinifera L. cv. Tempranillo variety after the application of MeJ [ 34 ]. The MeJ-based treatment showed no significant differences with the control for these compounds. For the same year, p-cymene (Figure 1b), linalool (Figure 1c), and α -terpineol ( Figure 1d ), which are very important terpenoids for grape and wine aroma [ 36 ], increased their content in MeJ grapes, and decreased it in ACP-MeJ samples with respect to control one. In the case of geranic acid (Figure 1f), both treatments significantly decreased the amount of this compound. Finally, in the same year, total terpenoids concentration (Figure 1h) increased in grapes from the foliar application of MeJ, and decreased in grapes treated with ACP-MeJ with respect to control grapes. In 2020, limonene and p-cymene (Figure 1a,b) increased their concentration in MeJ grapes relative to control grapes. This effect had already been observed in Vitis vinifera ‘Garnacha’ variety after the application of MeJ [ 12 ]. The MeJ-doped nanoparticles treatment showed no significant differences in those compounds with the control samples. In the Appl. Sci. 2023,13, 2487 7 of 18 Garde-Cerdán et al., 2018 [ 34 ] study, it is shown that the synthesis of p-cymene increases upon application of MeJ. Moreover, for the same year, linalool (Figure 1c), geranic acid (Figure 1f) and geranyl acetone (Figure 1g), significantly increased their concentration in MeJ-treated and ACP-MeJ-treated samples with respect to the control. In the case of α -terpineol (Figure 1d), both foliar treatments increased the content of this compound in the grapes, with ACP-MeJ increasing to a greater extent. Regarding geraniol (Figure 1e), only the ACP-MeJ treatment significantly increased the amount of this compound with respect to the control grapes, despite being a treatment with a concentration 10 times lower. In this season, the total concentration of terpenoids (Figure 1h) increased significantly with both treatments with respect to the control grapes, being more effective the application with MeJ. The increase in the amount of terpenoids after foliar application with MeJ has been previously demonstrated by other groups [ 5 , 12 , 37 ]. However, some studies have also found that the content of total terpenoids decreases when MeJ is applied [ 34 , 38 ]. In general, the treatments increased the amount of several terpenoids found in the grapes (Figure 1). This may be due to the foliar treatments were applied during veraison, moment when free terpenoids start to be produced [ 12 , 39 ]. These compounds are high volatile compounds, and have very low perception threshold, and therefore represent one of the most important group of aromatic compounds [ 12 , 40 ], and among these, linalool, α -terpineol, and geraniol, which are some of the most odoriferous monoterpenes [5]. Appl. Sci. 2023, 13, x FOR PEER REVIEW 8 of 20 Figure 3. Benzenoid compounds concentration (µg/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n = 3). For each season and compound, different letters indicate significant differences between samples (p ≤ 0.05). Figure 1 shows the concentration of terpenoids found in the control samples and in the grapes from the treatments with MeJ and ACP-MeJ, in 2019 and 2020 seasons. In 2019, limonene (Figure 1a), geraniol (Figure 1e), and geranyl acetone (Figure 1g) decreased their concentration in ACP-MeJ grapes relative to control and MeJ grapes. This effect had already been observed in Vitis vinifera L. cv. Tempranillo variety after the application of MeJ [34]. The MeJ-based treatment showed no significant differences with the control for these compounds. For the same year, p-cymene (Figure 1b), linalool (Figure 1c), and α-terpineol (Figure 1d), which are very important terpenoids for grape and wine aroma [36], increased their content in MeJ grapes, and decreased it in ACP-MeJ samples with respect to control one. In the case of geranic acid (Figure 1f), both treatments significantly decreased the amount of this compound. Finally, in the same year, total terpenoids concentration (Figure 1h) increased in grapes from the foliar application of MeJ, and decreased in grapes treated with ACP-MeJ with respect to control grapes. In 2020, limonene and p-cymene (Figure 1a,b) increased their concentration in MeJ grapes relative to control grapes. This effect had already been observed in Vitis vinifera ‘Garnacha’ variety after the application of MeJ [12]. The MeJ-doped nanoparticles treatment showed no significant differences in those compounds with the control samples. In 0,000 5,000 10,000 15,000 20,000 25,000 2019 2020 Concentration (mg/L) a) 2-Phenylethanol c b a a a b 0,000 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 2019 2020 Concentration (mg/L) b) 2-Phenylethanal b b a a a a 0,000 0,005 0,010 0,015 0,020 0,025 2019 2020 Concentration (mg/L) c) Eugenol a b c 0,000 0,200 0,400 0,600 0,800 1,000 1,200 1,400 1,600 1,800 2019 2020 Concentration (mg/L) d) Benzyl alcohol a b c a a b 0,000 5,000 10,000 15,000 20,000 25,000 2019 2020 Concentration (mg/L) e) Total benzenoids Control MeJ ACP-MeJ a b c b a a Figure 3. Benzenoid compounds concentration ( µ g/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. All parameters listed with their standard deviation (n= 3). For each season and compound, different letters indicate significant differences between samples (p≤0.05). Appl. Sci. 2023,13, 2487 8 of 18 Table 2. Alcohols, carbonyl compounds, C6 compounds and other compounds concentration ( µ g/L) in grapes from control, methyl jasmonate (MeJ) and nanoparticles doped with MeJ (ACP-MeJ) foliar treatments, in 2019 and 2020 seasons. 2019 2020 Control MeJ ACP-MeJ Control MeJ ACP-MeJ Alcohols n-Heptanol 0.062 ±0.010 c 0.046 ±0.008 b 0.028 ±0.005 a 0.047 ±0.002 a 0.044 ±0.009 a 0.045 ±0.009 a n-Octanol 0.191 ±0.014 b 0.174 ±0.017 b 0.107 ±0.013 a 0.326 ±0.018 b 0.234 ±0.042 a 0.238 ±0.048 a n-Nonanol 0.064 ±0.006 b 0.059 ±0.010 b 0.031 ±0.007 a 0.197 ±0.036 b 0.245 ±0.048 b 0.093 ±0.015 a 1-Octen-3-ol 0.595 ±0.043 b 0.296 ±0.063 a 0.243 ±0.031 a 0.174 ±0.036 b 0.074 ±0.006 a 0.147 ±0.030 b 2-Ethyl-1-hexanol 3.088 ±0.060 b 1.798 ±0.309 a 1.625 ±0.137 a 1.870 ±0.131 b 0.863 ±0.132 a 2.140 ±0.446 b Total 4.001 ±0.108 b 2.373 ±0.387 a 2.035 ±0.167 a 2.613 ±0.048 b 1.460 ±0.156 a 2.663 ±0.502 b Carbonyl compounds Heptanal 0.055 ±0.009 b 0.034 ±0.007 a 0.033 ±0.004 a 0.014 ±0.002 b 0.007 ±0.001 a 0.010 ±0.001 a (E)-2-Octenal 0.059 ±0.005 a 0.051 ±0.009 a 0.051 ±0.006 a 0.043 ±0.009 b 0.024 ±0.004 a 0.042 ±0.007 b Nonanal 0.204 ±0.039 b 0.115 ±0.028 a 0.083 ±0.011 a 0.381 ±0.074 b 0.143 ±0.025 a 0.236 ±0.040 a (E)-2-Nonenal 0.065 ±0.007 a 0.068 ±0.007 a 0.065 ±0.007 a 0.047 ±0.008 b 0.031 ±0.001 a 0.024 ±0.005 a Decanal 0.076 ±0.013 b 0.070 ±0.011 b 0.046 ±0.009 a 0.112 ±0.023 b 0.068 ±0.014 a 0.040 ±0.005 a (E,E)-2,4-Hexadienal 1.177 ±0.245 b 1.567 ±0.261 b 0.691 ±0.110 a 0.711 ±0.133 b 0.208 ±0.015 a 0.836 ±0.109 b (E,E)-2,4-Nonadienal 0.097 ±0.011 b 0.112 ±0.026 b 0.059 ±0.001 a 0.040 ±0.005 b 0.026 ±0.005 a 0.046 ±0.007 b γ-Decalactone 0.125 ±0.024 b 0.157 ±0.030 b 0.054 ±0.008 a 0.146 ±0.029 a 0.141 ±0.021 a 0.274 ±0.044 b 6-Methyl-3,5-heptadien-2-one 0.086 ±0.017 b 0.079 ±0.015 b 0.046 ±0.009 a 0.022 ±0.005 a 0.029 ±0.004 a 0.027 ±0.005 a Total 1.942 ±0.278 b 2.254 ±0.286 b 1.128 ±0.102 a 1.515 ±0.258 b 0.676 ±0.049 a 1.535 ±0.106 b C6 compounds n-Hexanol 5.904 ±1.031 b 7.018 ±1.447 b 3.479 ±0.575 a 22.311 ±3.544 a 42.324 ±4.178 b 19.316 ±4.032 a n-Hexanal 22.040 ±2.145 b 28.064 ±5.929 b 8.021 ±1.150 a 11.784 ±1.942 b 16.831 ±2.431 c 7.163 ±1.427 a (Z)-3-Hexen-1-ol +(E)-2-Hexen-1-ol 1.027 ±0.187 b 0.340 ±0.065 a 0.361 ±0.081 a 0.669 ±0.115 a 1.080 ±0.206 b 0.553 ±0.107 a (E)-2-Hexenal 5.474 ±1.044 b 10.305 ±2.251 c 1.346 ±0.166 a 9.629 ±0.776 a 19.002 ±3.906 b 8.177 ±0.496 a Total 34.445 ±3.815 b 45.727 ±8.718 c 13.206 ±1.925 a 44.393 ±4.949 a 79.237 ±5.398 b 35.209 ±5.113 a Other compounds Hexyl acetate n.d. n.d. n.d. 0.206 ±0.043 a 0.721 ±0.159 b 0.554 ±0.115 b Methyl jasmonate 0.064 ±0.006 a 0.077 ±0.009 a 0.121 ±0.016 b 1.738 ±0.381 b 0.222 ±0.038 a 0.114 ±0.022 a All parameters are listed with their standard deviation (n = 3). For each season and compound, different letters indicate significant differences between the samples (p ≤ 0.05). n.d.: not detected. Appl. Sci. 2023,13, 2487 9 of 18 Figure 2shows the concentration of C 13 norisoprenoids found in the control and in the grapes from the applications to vines of MeJ and ACP-MeJ, in 2019 and 2020 seasons . In 2019 , (E)- β -damascenone (Figure 2a), (Z)- β -damascenone (Figure 2b), and 1,1,6-trimetil-1,2- dihidronaftaleno (TDN) (Figure 2e), increased their concentration in MeJ grapes and decreased their concentration in ACP-MeJ samples with respect to control. The (E)- β -damascenone (Figure 2a) was the most abundant C 13 norisoprenoid in the samples, predominantly over the rest of the compounds of this group. This fact is expected because this compound is one of the most abundant norisoprenoid in the grapes [ 12 , 41 ]. TDN is one of the most polarising, and maybe the less studied C 13 norisoprenoid [ 39 ], its typical aroma descriptor is pretolor kerosene. In the case of β -ionone (Figure 2c), which provides violet notes [ 42 ], and β -cyclocitral (Figure 2d), both significantly decreased their amount in ACP-MeJ grapes relative to control and MeJ samples. Regarding the total C 13 norisoprenoids (Figure 2f) in 2019, MeJ treatment increased its content with respect to control grapes. This could be probably due to the fact that the MeJ increases the activity of the enzymes involved in the synthesis of these compounds [ 43 ], which derive from biodegradation of carotenoids [ 40 , 44 ], whereas ACP-MeJ treatment decreased it. Therefore, despite applying the same product, the dose was 10 times lower, and maybe it was too low to affect enzyme activity. In 2020, (E)- β -damascenone (Figure 2a), (Z)- β -damascenone (Figure 2b), and β - cyclocitral (Figure 2d), did not suffer variations in their content in MeJ and ACP-MeJ grapes with respect to control samples. In this season, β -ionone (Figure 2c) significantly increased its amount in MeJ grapes with respect to ACP-MeJ and control grapes. The increase of β -ionone with MeJ may be justified because β -ionone is a derivative of β -carotene [ 39 ], and MeJ accelerates its degradation [ 45 ]. TDN (Figure 2e) increased its concentration in grapes from both treatments (MeJ and ACP-MeJ) with respect to control grapes. As for total C 13 norisoprenoids (Figure 2f), in 2020 neither treatment had a significant effect on its amount with respect to control samples. Interestingly, C 13 norisoprenoids, derived from the breakdown of carotenoids via chemical, photochemical and oxidase-coupled degradation or enzymatic cleavage [ 5 ], generally unchanged with the MeJ treatments in 2020 . These results contrast with those obtained by Gutiérrez-Gamboa et al., 2019 [ 38 ], where the application with MeJ decreased the amount of C13 norisoprenoids. Terpeneoids and C 13 norisoprenoids are very important in the floral aroma of grapes. Respect to the C 13 norisoprenoids, β -damascenone and β -ionone are the most important, since they strongly contribute to the desirable flavor and odor in wines, due to their low perception thresholds [40,46]. Figure 3shows the concentration of benzenoids found in the control and in the grapes from the foliar treatments with MeJ and ACP-MeJ, in 2019 and 2020 seasons. In 2019, 2-phenylethanol (Figure 3a), eugenol (Figure 3c) and benzyl alcohol (Figure 3d) decreased their concentration in grapes from both treatments (MeJ and ACP-MeJ) with respect to control grapes, with significantly lower content in ACP-MeJ samples. In the study of Marín-San Román et al., 2020 [ 12 ], 2-phenylethanol also decreased when MeJ is applied to vines. 2-Phenylethanal (Figure 3b) significantly decreased its amount in grapes from ACP-MeJ treatment with respect to control and MeJ samples. Finally, in 2019, the content of total benzenoids (Figure 3e) decreased with both treatments respect to control samples, with significantly lower content in ACP-MeJ grapes. This trend was also observed in the work of Gutiérrez-Gamboa et al., 2019 [38]. Regarding to the 2020 season, the concentration of 2-phenylethanol (Figure 3a) and benzyl alcohol (Figure 3d) increased in ACP-MeJ grapes with respect to those from the other two samples. 2-Phenylethanol and benzyl alcohol, which in grapes derive from aromatic amino acids, were the principal benzenoid compounds [ 5 ]. The content of 2-phenylethanal in grapes (Figure 3b) showed no significant differences in MeJ treatments with respect to the control. Eugenol was not detected in grapes in this second season (Figure 3c). The concentration of total benzenoids (Figure 3e) significantly increased with the ACP-MeJ treatment with respect to the control and MeJ ones. Appl. Sci. 2023,13, 2487 16 of 18 Author Contributions: Conceptualization, T.G.-C., J.M.D.-L. and E.P.P.-Á.; methodology, T.G.-C., J.M.D.-L., E.P.P.-Á. and G.B.R.-R.; formal analysis, S.M.-S.R., I.S.d.U. and T.G.-C.; investigation, B.P.-T. , G.B.R.-R., S.M.-S.R. and I.S.d.U.; data curation, S.M.-S.R.; writing—original draft preparation, S.M.- S.R. and T.G.-C.; writing—review and editing, all authors; supervision, T.G.-C., J.M.D.-L. and E.P.P.-Á.; funding acquisition, T.G.-C. and J.M.D.-L. All authors have read and agreed to the published version of the manuscript. Funding: This work has been carried out thanks to funding from the Ministerio de Ciencia, Innovación y Universidades (FEDER/MCIU/AEI, Spain) through the Projects RTI2018-096549-B-I00 and RTI-2018-095794-A-C22. S.M.-S.R. thanks Gobierno de La Rioja for her predoctoral contract. J.M.D.-L. and E.P.P.-Á. acknowledge the Ministerio de Ciencia, Innovación y Universidades for their Ramón y Cajal and Juan de la Cierva-Incorporación contracts, respectively. G.B.R.-R. would like to thank to Junta de Andalucía for her postdoctoral contract (PAIDI 2020, DOC_01383). Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: Not applicable. Conflicts of Interest: The authors declare no conflict of interest. References 1. Perestrelo, R.; Barros, A.S.; Rocha, S.M.; Câmara, J.S. Optimisation of solid-phase microextraction combined with gas chromatography–mass spectrometry based methodology to establish the global volatile signature in pulp and skin of Vitis vinifera L. grape varieties. Talanta 2011,85, 1483–1493. [CrossRef] [PubMed] 2. Aleixandre-Tudo, J.L.; Weightman, C.; Nieuwoudt, H.; Du Toit, W. 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