Vine-Shoot Tannins: Effect of Post-pruning Storage and Toasting

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Bioactive Constituents, Metabolites, and Functions

VINE-SHOOT TANNINS: EFFECT OF POSTPRUNING STORAGE AND TOASTING TREATMENT Cristina Cebrían-Tarancon, Rosario Sanchez-Gomez, Sergio Gómez-Alonso, Isidro HermosinGutierrez, Adela Mena-Morales, Esteban García-Romero, M. Rosario Salinas, and Amaya Zalacain J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b01540 • Publication Date (Web): 17 May 2018 Downloaded from http://pubs.acs.org on May 17, 2018

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Journal of Agricultural and Food Chemistry

VINE-SHOOT TANNINS: EFFECT OF POST-PRUNING STORAGE AND TOASTING TREATMENT Cebrián-Tarancón, Cristina1; Sánchez-Gómez, Rosario1; Gómez-Alonso, Sergio2; Hermosín┼

Gutierrez, Isidro2 ; Mena-Morales, Adela3; García-Romero, Esteban3; Salinas, M. Rosario1; Zalacain, Amaya1*

1

Universidad de Castilla-La Mancha, E.T.S.I. Agrónomos y Montes, Cátedra de Química Agrícola, Avda. de España s/n, 02071 Albacete, Spain.

2

Universidad de Castilla-La Mancha, Instituto Regional de Investigación Científica Aplicada, Avda. Camilo José Cela s/n, 13071 Ciudad Real, Spain 3

Instituto de la Vid y el Vino de Castilla-La Mancha, Carretera de Albacete s/n, 13700 Tomelloso, Spain ┼ In Memoriam

*Corresponding Author, (Tel: +34 967 599210, Fax: +34 967 599238, e-mail: [email protected])

1

ACS Paragon Plus Environment


1

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ABSTRACT

2

For first time vine-shoot tannin composition was carried out by means of HPLC–DAD-

3

ESI-MS/MS. Two vine-shoot cultivars (Airén and Cencibel) with different post-pruning

4

storage time and submitted to a toasting process, were assayed. There was no trace of

5

gallotannins nor ellagitannins, but a high proanthocyanidins content and a mean degree of

6

polymerization (mDP) close to 3 was characterized. The higher concentration of

7

proanthocyanidins corresponded to Airén after 6 months post-pruning storage and at 3 months

8

for Cencibel. Procyanidins were the most abundant fraction (70-95%), which decreased with

9

storage, and especially significant was the contribution of B1, B2 and B4 dimers.

10

Prodelphinidins were also found (8-24%), increasing their % with storage time. Toasting

11

produced a considerable reduction on proanthocyanidins content and a loss of a monomer

12

mDP unit, suggesting that if used as oenological tannins, then they may be more bitter and

13

less astringent when compared with the non-toasted vine-shoot samples.

14 15

KEYWORDS: Post-pruning Storage, Proanthocyanidins, Tannin, Toasted, Vine-shoots

16 17 18

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19

1. INTRODUCTION

20

The quantity and quality of grape production depends on a correct balance between vine

21

vegetative and fruit growth which is controlled by vineyard pruning. Vine-shoots (or grape

22

canes) are the residues generated counting approximately in the world for 1.98·107 tons each

23

year, therefore this biomass need to be exploited somehow.

24

Vine-shoots chemical characterization has been extensively studied lately, in terms of their

25

low molecular weight phenolic compounds1-5, volatile,6,

26

composition.8,

27

according to their post-pruning storage time, not only in terms of the stilbene family

28

previously studied,2-4 but in relation with other minor compounds such as low molecular

29

weight phenolic compounds, procyanidin dimers (B1 and B2) and volatiles.10 Several authors

30

have shown that during vine-shoots post-harvest storage the gene expression of phenylalanine

31

ammonia-lyase (PAL), cinnamate 4-hydroxylase (C4H) and 4-coumarate-CoA ligase (4CL)

32

are active under certain storage conditions, and particularly the stilbene synthase (STS)

33

inducing the generation of stilbenoids).

34

modified if they are submitted to a toasting process,11-13 especially to enhance flavour

35

compounds, revealing some similarities with the oak wood used as reference. Thus, vine-

36

shoots may be also proposed as enological additive in the near future in the same way as oak

37

chips are commonly used. However, in any case no studies have been carried out the

38

complete tannin fraction characterization of vine-shoots, in terms of hydrolyzable and

39

condensed ones.

9

7

mineral,6,

8

and protein

Recently, it has been shown that such chemical characterization varied

3, 5

Vine-shoots chemical composition can be also

40

Tannins are classified into hydrolyzable as ellagitannins or gallotannins, and as condensed

41

tannins, such as proanthocyanidins. 14 Ellagitannins used in enology are oak or chestnut which

42

include high levels of castalagin, roburin E, vescalagin and grandinin, and low molecular

43

weight phenolic compounds, such as ellagic and gallic acids.16 Gallotannin, known as tannic 3



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44

acid 17, and chestnut extracts are also commercially available. Similar polyphenolic profile to

45

oak is chestnut although its low molecular weight phenolic compounds and tannic contents

46

are higher, highlighting the presence of gallotannins and the high levels of gallic acid.18

47

Different condensed tannin (proanthocyanidins) composition is found in different parts of

48

grape cluster, skins, seeds and stems. While in grape seed mainly procyanidins are quantified,

49

grape skins include procyanidins and prodelphinidins.

50

about stems proanthocyanidins, but previous results indicate the predominance of

51

procyanidins dimers B1, B4 and B2 3-O-gallate22. Recently, vine-shoots characterization10, 23

52

pointed out the presence of some procyanidins dimers such as B1 and/or B2 together with a

53

tentatively identified prodelphinidin dimer.23

54

20, 21

There are fewer studies known

In this sense, it would be very interesting to study the potential of vine-shoots as

55

oenological tannins.

Therefore, the aim of this work is to determine the condensed

56

(proanthocyanidins) and hydrolyzable tannins (gallotannins and ellagitannins) in vine-shoots

57

by HPLC–DAD-ESI-MS/MS. Special emphasis will be taken on the differences between

58

post-pruning storage time samples and their toasting process.

59 60

2. MATERIALS AND METHODS

61

2.1. Vine-shoot samples

62

Airén (VIVC: 157) and Cencibel (VIVC: 12350) vine-shoots were pruned in two vineyards

63

of D.O. Mancha (Castilla-La Mancha, Spain) after 90 days of their grape harvest. Planting

64

density was 2000 vines/ha and the surface of each vineyard was 3 ha. Fifty vines of each

65

vineyard were selected and 0.5 kg were pruned of each vine, making a total of 25 kg of vine-

66

shoots collected for each variety and vineyard. Samples were stored intact at dark and room

67

temperature (18 ± 3 ºC) till their grounding to a particle size (less than 10 mm) according to

4


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68

Cebrián et al.10 at different post-pruning times: one (1 mo), three (3 mo) and six (6 mo)

69

months.

70

In order to obtain the toasted samples, a 180 °C treatment was applied during 45 min on

71

part of dried vine-shoots from 6 mo sampling time in an air circulation oven (Heraeus T6,

72

Hanau Deutschland).13 Final humidity was measured for each vine-shoots variety (non-

73

toasted and toasted) and sampling times, resulting 24.22%, 14.26%, 7.98% and 2.22% for

74

Airén; and 23.63%, 14.12%, 7.86% and 2.49 for Cencibel vine-shoots at 1, 3 and 6 months

75

(non-toasted and toasted), respectively.

76 77

2.2. Vine-shoot extraction procedure

78

Samples from the two cultivars, Airén (AVS) and Cencibel (CVS), at 1, 3 and 6 months

79

after their pruning, and the last one, also toasted (CVST) according to Cebrián-Tarancón et

80

al.13 were extracted in duplicate, with an ethanol/water solution (12.5/87.5; v/v) and corrected

81

to pH 3.62 with tartaric acid and a microwave NEOS device (Milestone, Italy), according to

82

Cebrián et al.10

83

2.3. Extracts analysis

84

2.3.1. Isolation, identification and quantitation of vine-shoot hydrolyzable tannins by

85

HPLC–DAD-ESI-MS/MS

86

First of all, the total content of gallotannins and ellagitannins was estimated after acidic

87

hydrolysis of 300 µl of vine-shoot extracts. The samples (before and after the acid-catalyzed

88

hydrolysis reaction) were analyzed by HPLC–DAD-ESI-MS/MS following a previously

89

reported method 24. The compounds identification was carried out by means of spectroscopic

90

data (UV–vis and MS/MS) obtained from authentic standards or previously reported

91

findings.25,

92

obtained for gallic and ellagic acids.

26

The quantitation was performed at 280 nm using the calibration curves

5



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2.3.2. Isolation, identification and quantification of vine-shoot proanthocyanidins by HPLC-

94

ESI-MS/MS.

95

Eight vine-shoot extracts (0.25 mL) were submitted to an HPLC-ESI-MS/MS analysis of flavan-

96

3-ol monomers and their structural information was obtained following the method of acid-

97

catalyzed depolymerization induced by pyrogallol.27,28 For the identification and

98

quantitation of diverse flavan-3-ols, commercial standards of the monomers (+)-catechin,

99

(−)-epicatechin, (−)-epigallocatechin, (−)-gallocatechin, and (−)-epicatechin 3-O-gallate, and

100

B1, B2 dimers were purchased in Extrasynthèse (Genay, France). B4 was kindly supplied by

101

Professor Victor Freitas (Universidad do Porto, Portugal). The total content of polymeric

102

proanthocyanidins was quantitated as equivalents of (+)-catechin and their structural features

103

were characterized as: t he mean degree of polymerization (mDP), which was calculated by

104

adding terminal and extension units (in moles) and dividing by the terminal units; the

105

percentage of prodelphinidins, which was calculated as the quotient between total (+)-

106

gallocatechin, (−)-epigallocatechin, (-)-epigallocatechin-3-O-gallate of terminal and extension

107

units, related to the total units content, expressed as a percentage; the percentage of

108

procyanidins, as 100-% prodelphinidins; and the percentage of galloylation, which was

109

calculated as the addition of (+)-catechin-3-O-gallate, (-)-epicatechin-3-O-gallate, (-)-

110

epigallocatechin-3-O-gallate of terminal and extension units dividing by the total units

111

content, expressed as a percentage.

112

2.4. Statistical analysis

113

The statistical elaboration of the data was performed using SPSS Version 22.0 statistical

114

package for Windows (SPSS, Chicago, USA). Tannin composition data were processed using

115

the variance analysis (ANOVA). Differences between means were compared by Tukey test at

116

a 99.95% probability level. All analyses were made in triplicate and the results were given as

117

mean values with their corresponding standard deviations.

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118

To study the relation that exists between toasted Airén and Cencibel vine-shoots after 6

119

months of post-pruning storage time and their non-toasted respective ones, Pearson

120

correlation coefficient has been used (significance of the correlation coefficient for p ≤ 0.05).

121 122

RESULTS AND DISCUSION

123

The importance of the post-pruning storage time on vine-shoot minor metabolites

124

(phenolic and volatile compounds) has a direct impact on their concentration,10 especially in

125

low molecular weight phenolic compounds, which also constitute the structural units of

126

condensed tannins.

127

Related to the hydrolyzable tannin fraction (gallotannins and ellagitannins), the estimation

128

assay based on the release of gallic and/or ellagic acids after acidic hydrolysis did not yield

129

any of the two cited constituent acids. Moreover, the specific chromatographic analysis of

130

ellagitannins did not allow the identification of any of the oak-like ellagitannins, such as

131

castalagin, vescalagin, roburins A to E or grandinin. These results strongly suggest that vine-

132

shoots do not contain nor gallotannins or ellagitannins, which was not surprising, as the other

133

part of grape cluster such as seeds, stems and skins have failed to exhibit the presence of

134

hydrolyzable tannins.29-31

135

Meanwhile, proanthocyaninds (condensed tannins) and their constituting units were

136

positively identified and quantified (Tables 1, 2 and 3). Table 1 shows the main parameters

137

to describe the structure characteristics of the proanthocyanidin fraction: the mean

138

polymerization degree (mDP), the total content of proantocyanidins and the percentage of

139

procyanidins and prodelphinidins, together with the percentage of galloylation. The

140

concentration of total proanthocyanidins were different among the vine-shoot varieties and

141

the post-pruning storage time. Airén vine-shoots showed a higher content of total

142

proanthocyanidins at 6 months post-pruning, whereas in Cencibel it was found at 3 months, 7



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143

but the content in both cases was similar. Such increment may be justified by the gene

144

expression

145

leucoanthocyanidin reductase (LAR) and anthocyanidin reductase (ANR) among others

146

that produce the flavan-3-ol monomers for the formation of proanthocyanidins

147

polymers.

148

harvest storage

149

other enzymes involved within proanthocyanidins synthesis.

of

32, 33

different enzymes such

as phenylalanine

ammonia-lyase

(PAL),

It has been already observed that PAL is induced during vine-shoots post3, 5

, although a more exhaustive genetic study should be carried out with

150

Regarding to mDP, which were in average higher than 2, no significant differences

151

(p>0.05) were found according to neither post-pruning time nor to the both vine-shoot

152

cultivars. The percentage of galloylation was not significantly different over the post-pruning

153

time (Table 1), but it was among cultivars, showing the samples from Airén the highest

154

values, similar to those of grape seeds and higher than in grape skins.20, 31 It has been reported

155

that a higher galloylation percentage lead to a greater perception of “coarseness”.34 Also,

156

since the mDP of both cultivars were similar, then it can be suggested that if Airén vine-

157

shoots were used as enological tannins, they may contributed with a “coarser” note than

158

Cencibel ones.

159

Besides, the polymer molecular size (mDP) and especially the monomeric composition of

160

proanthocyanidins have a considerable influence not only on the perception of astringency,

161

but on bitterness. So, shorter polymers are more bitter and less astringent than large molecular

162

weight derivates.31 Therefore, if they are used as enological tannins, then their organoleptic

163

contribution would be expect to be less astringent and more bitter than grape seeds or skins,

164

which show mDP values between 5-15 and 20-50, respectively, for different cultivars.20, 31

165

Vine-shoot proanthocyanidins fractionation shows a major percentage of procyanidins,

166

.decreasing with post-pruning storage; the percentage of prodelphinidins ranging between 6-

167

24%, which unlike procyanidins, increases with storage (Table 1). Similar composition of 8


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procyanidins and prodelphinidins was also found in grape skins20 and stems,35 but not in

169

seeds, that only have procyanidins.20, 31

170

The fraction of procyanidins dimers (B1, B2 and B4) represented approximately the 65-

171

81% of the total procyanidin fraction in Airén vine-shoots and between 47-69% for Cencibel

172

vine-shoots. Such content may be complete with other procyanidins trimers or tetramers as

173

observed in other grape products.22, 36 Among all procyanidins dimers, B1, (-)-epicatechin-

174

(4β→8) - (+)-catechin, was the most abundant one (Table 2). The total dimers content

175

increases with the post-pruning time, being at 6 months the higher values in Airén and at 3

176

months in Cencibel cultivar.

177

The % of prodelphinidins, express as the units of (+)-gallocatechin, (-)-epigallocatechin

178

and (-)-epigallocatechin-3-O-gallate, makes the difference among all vine-shoot samples

179

(Table 1). Vines-shoot samples contain a noticeable percentage of prodelphinidins (8-20%),

180

lower than those quantified in different grape skins varieties 20-60%.20 Vine-shoot

181

prodelphinidins percentage was significantly higher at 3 and 6 months of post-pruning time in

182

both. The comparison among varieties showed significant differences at the first sampling

183

time. Moreover, the importance of prodelphinidins in relation to the perception of astringency

184

was studied in previous works with other grape products: the presence of epigallocatechin

185

units in the proanthocyanidins decrease the “coarseness” perception through the increase of

186

the degree of B-ring trihydroxylation.37,38 Then, the expected organoleptic contribution of

187

vine-shoot proanthocyanidins probably lead to a smoother and less “coarse” tannin during

188

the post-pruning storage time.

189

Although the mDP remains constant during post-pruning storage, there were changes in

190

terms of their individual units, terminal and extension ones.

The total content of the

191

extension units was slightly more than double than the terminal units (Table 3), fact related

192

to the obtained mDP values (Table 1). The content of all units was significantly higher in 9



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Airén than in Cencibel vine-shoots. In case of extension units, (-)-epicatechin was the most

194

abundant monomer, followed by (+)-catechin, at 6 months of post-pruning time in Airén and

195

at 3 months post-pruning in case of Cencibel. The abundance of both monomers, is

196

attributed to the high content of procyanidins dimers present in the samples (B1, B2 and B4).

197

The third most abundant extension unit was catechin-3-O-gallate, which had the highest

198

content in Airén cultivar at 6 months and in Cencibel at 3 months post-pruning storage time.

199

(+)-Catechin-3-O-gallate and (-)-epigallocatechin-3-O-gallate, as extension units, increased

200

their concentration with post-pruning storage, above all, between first and second sampling

201

times. Prodelphinidins unit as (-)-epigallocatechin increased significantly with storage time,

202

being higher in Airén at 6 months than in Cencibel cultivar. (+)-Gallocatechin, as extension

203

unit, was not quantified in the vine-shoot samples, although it has been detected in other

204

grape wastes such as seeds.21

205

With regard to the terminal units (Table 3), (+)-catechin was the most abundant one

206

followed by (-)-epicatechin, as they are the constituents of procyanidins dimers, the major

207

vine-shoot proanthocyanidin fraction. (+)-Catechin did not present significant differences

208

between post-pruning sampling times in Airén, whereas the highest (+)-catechin

209

concentration was found at 3 months in Cencibel. Similar trend was found for (-)-epicatechin

210

in both varieties. Gallate terminal units, as (-)-epicatechin-3-O-gallate, was the most abundant

211

one, increased its content with post-pruning time for Airén cultivar, although the highest

212

concentration in Cencibel was quantified after 3 months of post-pruning storage. (-)-

213

Epigallocatechin-3-O-gallate was the second gallate in abundance. (+)-Gallocatechin content

214

was higher at 3 and 6 months, but only statistically significant in Airén. (-)-Epigallocatechin

215

was the extension unit most affected by post-pruning storage, increasing up to 10 times in

216

Cencibel cultivar at 3 months, while the increment in Airén was about 6 times more at 6

217

months.

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Vine-shoots toasting, as well as for other woods, modifies the chemical composition of

219

some minor metabolites of great interest in the oenological industry,11-13 but its effect on the

220

tannin fraction remained unstudied. Table 4 shows the proanthocyanidin composition of

221

toasted vine-shoots of Airén and Cencibel cultivars after 6 months of post-pruning storage.

222

As it was expected, toasting decreased the proanthocyanidin content quantified in a 65% in

223

Airén (AVS-6 mo) and 45% in Cencibel (CVS-6 mo), effect that it was also observed on

224

different oak woods or chestnut.

225

unit lost shown by the mDP parameter, leading samples with 2.29 for AVST-6 mo and 2.04

226

for CVST-6 mo units, which were significantly different from those shown by their

227

respective non-toasted: 2.67 and 2.51 in Airén and Cencibel, respectively. Regarding to %

228

procyanidins, % prodelphinidins and % of galloylation, no significant differences were

229

observed in relation to non-toasted samples (Table 4). The total concentration of

230

procyanidins dimers (B1, B2 and B4) showed a significant decrease in relation with the non-

231

toasted samples (Table 4), being B4 the most different one. In both samples, the total

232

extension monomeric units concentration was significantly different from their respective

233

non-toasted samples (Table 4), represented by the main monomer (-)-epicatechin, which was

234

approximately the 62% of the mentioned fraction for both cultivars. (+)-Catechin-3-O-

235

gallate followed by (-)-epigallocatechin-3-O-gallate were the most abundant gallates, as

236

referred for their respective non-toasted samples.

16, 18

Such decrement could be attributed to the monomer

237

The most abundant terminal monomeric unit was (+)-catechin, followed by (-)-

238

epicatechin and (+)-gallocatechin (Table 4). (+)-Catechin-3-O-gallate, that was not found in

239

non-toasted samples, has been quantified in toasted samples, with a significant concentration

240

in both cultivars.

241

Then, proanthocyanidins content decreased in toasted vine-shoots when compared with

242

their respective non-toasted samples, showing a lower molecular size. Taking into account

11



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243

that vine-shoot chips may be used in winemaking,13 these results may suggest that their

244

expected sensory contribution may be more bitter and less astringent in comparison with non-

245

toasted samples, as such structural differences are known to contribute to wine sensory

246

perception . 34, 44

247

As conclusion, for first time the tannin characterization of vine-shoots has been performed

248

in terms of hydrolyzable and condensed tannins fractions. This study was carried out in two

249

vine-shoot cultivars with a post-pruning time up to 6 months, as well as samples submitted to

250

a toasting process. Only proanthocyanidins were detected, being significantly higher in Airén

251

than in Cencibel cultivars. The mean degree of polymerization was close to 3 for all samples

252

and no significant differences were found according to the post-pruning times studied. The

253

main proanthocyanidins fraction corresponded to procyanidins, especially in their dimers

254

form, which decreased with storage time. It is noticeable the high amount of prodelphinidins

255

in relation with other grape derivates, increasing with storage. The percentage of galloylation

256

was not significantly different over post-pruning time, but higher in Airén cultivar.

257

Vine-shoots toasting produced a significant loss on the total proanthocyanidins content

258

with a reduction of one monomer unit for mDP parameter, but their compositional fraction

259

percentage was kept. Then, the different uses of such vine-shoots (toasted and non-toasted)

260

in winemaking by their contribution in wine sensory properties should be verify in future

261

studies.

262

Supporting Information

263

Table S1. ANOVA Statistical Parameters (F and P) For The Structural Characteristics And

264

Composition Of Vine-Shoot Flavan-3-ols Polymers, From Airén And Cencibel Cultivars

265

Along Post-Pruning Storage Time.

12


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266

Table S2. ANOVA Statistical Parameters (F And P) For Vine-Shoot Procyanidins Dimers

267

Content (mg/Kg Dry Weight) From Airén And Cencibel Cultivars Along Post-Pruning

268

Storage Time.

269

Table S3. ANOVA Statistical Parameters (F and P) For Flavan-3-Ol Monomers Content

270

(mg/Kg Dry Weight) From In Airén And Cencibel Vine-Shoot Proanthocyanidins

271

Structures, As Terminal And Extension Units, According To Post-Pruning Storage Time.

272 273

Funding

274

Many thanks for the financial support given by the Ministry of Economy and

275

Competitiveness-FEDER of the Spanish Government to the Project AGL2015-65133-C2-1-R.

276 277

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Page 20 of 26

TABLES Table 1. Structural Characteristics And Composition Of Vine-Shoot Flavan-3-Ols Polymers, From Airén And Cencibel Cultivars Along PostPruning Storage Time. * AVS-1 mod

AVS-3 moe

AVS-6 mof

CVS-1 mog

CVS-3 moh

CVS-6 moi

Proanthocyanidins (g/kg)

0.76 ± 0.13 a, α

1.04 ± 0.10 ab, α

1.22 ± 0.08 b, β

0.80 ± 0.07 A, α

1.30 ± 0.06 B, β

0.94 ± 0.03 A, α

Mean Degree Polymerisation (mDP)

2.78 ± 0.23 a, α

2.36 ± 0.04 a, α

2.67 ± 0.01 a, α

2.44 ± 0.01 A, α

2.28 ± 0.09 A, α

2.51 ± 0.19 A, α

% Galloylation

10.60 ± 0.08 a, β

10.44 ± 0.51 a, β

9.74 ± 0.12 a, β

8.90 ± 0.02 A, α

9.14 ± 0.42 A, α

8.48 ± 0.13 A, α

% Procyanidins

92.16 ± 0.63 c, α

81.45 ± 0.44 b, α

77.71 ± 1.49 a, α

94.17 ± 0.69 C, β

83.14 ± 2.33 B, α

76.26 ± 0.04 A, α

% Prodelphinidins

7.84 ± 0.63 a, β

18.55 ± 0.44 b, α

22.69 ± 1.49 c, α

5.83 ± 0.69 A, α

16.86 ± 2.33 B, α

23.74 ± 0.04 C, α

d

AVS-1 mo: Airén vine-shoots at 1 month; e AVS-3 mo: Airén vine-shoots at 3 months; f AVS-6 mo: Airén vine-shoots at 6 months; g CVS-1 mo: Cencibel vine-shoots at 1 month;

h

CVS-3 mo: Cencibel vine-shoots at 3 months; i CVS-6 mo: Cencibel vin e-shoots at 6 months. *For each compound, different small letters indicate significant differences among Airén vine-shoots along post-pruning time, capital letters indicate significant differences among Cencibel vine-shoots along post-pruning time and different Greek letters indicate, for each post-pruning time, differences among vine-shoots varieties according to the Tukey test (p ≤ 0.05). The mean values (n = 4) are shown with their standard deviation. n.d. not detected

20


Page 21 of 26


Table 2. Evolution Of Vine-Shoot Procyanidins Dimers Content (Mg/Kg Dry Weight) From Airén And Cencibel Cultivars Along Post-Pruning Storage Time. * AVS-1 mod

AVS-3 moe

AVS-6 mof

CVS-1 mog

CVS-3 moh

CVS-6 moi

Dimer B1

402.86 ± 5.23 a, β

371.56 ± 23.48 a, α

613.78 ± 28.69 b, β

244.49 ± 25.81 a, α

489.58 ± 1.58 b, β

481.78 ± 49.24 b, α

Dimer B2

168.23 ± 2.11 a, α

195.60 ± 16.82 a, α

277.37 ± 16.11 b, α

165.60 ± 13.37 a, α

319.80 ± 1.44 b, β

270.62 ± 39.25 b, α

Dimer B4

96.28 ± 0.63 a, β

108.22 ± 8.87 a, α

187.79 ± 5.17 b, β

67.29 ± 3.59 a, α

151.81 ± 3.41 b, β

134.76 ± 14.82 b, α

Total (mg/kg)

667.37 ± 7.97 a, β

675.38 ± 49.18 a, α

1078.95 ± 49.97 b, β

477.38 ± 42.77 a, α

961.19 ± 6.42 b, β

887.16 ± 103.32 b, α

Compounds

d

AVS-1 mo: Airén vine-shoots at 1 month; e AVS-3 mo: Airén vine-shoots at 3 months; f AVS-6 mo: Airén vine-shoots at 6 months; g CVS-1 mo: Cencibel

vine-shoots at 1 month;

h

CVS-3 mo: Cencibel vine-shoots at 3 months; i CVS-6 mo: Cencibel vin e-shoots at 6 months.

*For each compound, different small letters indicate significant differences among Airén vine-shoots along post-pruning time, capital letters indicate significant differences among Cencibel vine-shoots along post-pruning time and different Greek letters indicate, for each post-pruning time, differences among vine-shoots varieties according to the Tukey test (p ≤ 0.05). The mean values (n = 4) are shown with their standard deviation. n.d. not detected.

21



Page 22 of 26

Table 3. Flavan-3-ol Monomers Content (mg/kg Dry Weight) From In Airén And Cencibel Vine-Shoot Proanthocyanidins Structures, As Terminal And Extension Units, According To Post-Pruning Storage Time.* AVS-1 mod

AVS-3 moe

AVS-6 mof

CVS-1 mog

CVS-3 moh

CVS-6 moi

67.62 ± 3.67 a, β

45.28 ± 7.76 a, α

125.17 ± 9.35 b, β

46.49 ± 3.64 A, α

92.17 ± 2.62 C, β

64.15 ± 2.73 B, α

329.78 ± 47.52 a, α

369.69 ± 35.35 a, α

427.31 ± 19.11 a, β

353.18 ± 31.44 A, α

470.00 ± 18.64 B, α

344.92 ± 18.82 A, α

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

(-)-Epigallocatechin

12.06 ± 1.12 a, β

40.90 ± 3.00 b, α

76.84 ± 14.39 c, α

6.76 ± 3.17 A, α

54.40 ± 0.92 B, β

60.45 ± 3.27 B, α

(+)-Catechin-3-O-gallate

60.02 ± 7.52 a, β

75.76 ± 3.90 ab, α

93.91 ± 4.74 b, β

46.56 ± 4.86 A,

86.97 ± 4.76 B, α

60.75 ± 2.10 A, α

(-)-Epicatechin-3-O-gallate

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

(-)-Gallocatechin-3-O-gallate

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

10.34 ± 1.44 a, α

28.42 ± 0.00 b, α

34.33 ± 5.37 b, α

6.62 ± 2.78 A, α

33.81 ± 2.65 B, β

31.69 ± 0.68 B, α

475.28 ± 65.45 a, α

590.05 ± 50.02 ab, α

757.57 ± 52.97 b, β

459.61 ± 45.89 A, α

710.60 ± 10.08 B, β

561.96 ± 10.03 A, α

157.64 ± 50.08 a, α

200.25 ± 35.27 a, α

208.12 ± 9.22 a, β

177.81 ± 12.83 a, α

259.98 ± 13.13 b, β

174.43 ± 23.97 a, α

(-)-Epicatechin

46.63 ± 8.77 a, α

74.84 ± 0.56 b, α

61.15 ± 5.83 ab, α

73.14 ± 5.49 a, β

107.67 ± 2.79 b, β

62.31 ± 3.96 a, α

(+)-Gallocatechin

19.95 ± 1.067 a, α

62.59 ± 3.81 b, α

85.71 ± 7.76 c, β

17.10 ± 4.02 a, α

72.26 ± 6.08 b, α

60.87 ± 4.39 b, α

5.53 ± 0.34 a, β

22.13 ± 4.95 b, α

28.03 ± 4.12 b, α

3.64 ± 0.87 a, α

29.64 ± 2.25 c, α

22.70 ± 1.52 b, α

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

44.15 ± 7.88 a, α

69.29 ± 2.46 b, α

64.83 ± 0.33 b, β

56.06 ± 4.62 b, α

73.93 ± 3.02 c, α

41.12 ± 2.71 a, α

Extension Units (+)-Catechin (-)-Epicatechin

(+)-Gallocatechin

(-)-Epigallocatechin-3-O-gallate Total (mg/Kg) Terminal Units

(+)-Catechin


(+)-Catechin-3-O-gallate (-)-Epicatechin-3-O-gallate

22


Page 23 of 26


n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

n.d. j

8.84 ± 1.91 a, α

16.47 ± 0.68 b, α

15.92 ± 2.12 b, α

7.77 ± 1.96 a, α

23.94 ± 4.38 b, β

14.55 ± 0.43 ab, α

282.74 ± 70.65 a, α

445.57 ± 47.74 a, α

463.76 ± 29.38 a, β

335.51 ± 29.80 a, α

567.43 ± 31.64 b, β

375.97 ± 36.98 a, α

(-)-Gallocatechin-3-O-gallate (-)-Epigallocatechin-3-O-gallate Total (mg/Kg) d

AVS-1 mo: Airén vine-shoots at 1 month; e AVS-3 mo: Airén vine-shoots at 3 months; f AVS-6 mo: Airén vine-shoots at 6 months; g CVS-1 mo: Cencibel vine-shoots at 1 month;

h

CVS-3 mo: Cencibel vine-shoots at 3 months; i CVS-6 mo: Cencibel vin e-shoots at 6 months. j n.d. not detected.

*For each compound, different small letters indicate significant differences among Airén vine-shoots along post-pruning time, capital letters indicate significant differences among Cencibel vineshoots along post-pruning time and different Greek letters indicate, for each post-pruning time, differences among vine-shoots varieties according to the Tukey test (p ≤ 0.05). The mean values (n = 4) are shown with their standard deviation.

23



Page 24 of 26

Table 4. Proanthocyanidins And Their Monomer Composition Structures Expressed As Terminal And Extension Units, Of Toasted Airén And Cencibel Vine-Shoots After 6 Months Of Post-Pruning Storage Time.

AVS-6 moa

AVST-6 mob

Fe

Pf

CVS-6 moc

CVST-6 mod

Fe

Pf

Proanthocyanidins (g/Kg)

1.22 ± 0.08

0.40 ± 0.05

143.046

0.007

0.94 ± 0.03

0.47 ± 0.02

386.155

0.003

Mean Degree Polymerisation (mDP)

2.67 ± 0.01

2.29 ± 0.10

29.435

0.032

2.51 ± 0.19

2.04 ± 0.06

10.973

0.080

% Galloylation

9.74 ± 0.12

8.88 ± 0.40

8.312

0.102

8.48 ± 0.13

8.51 ± 0.78

0.002

0.967

% Procyanidins

77.71 ± 1.49

77.42 ±2.31

0.003

0.959

76.26 ± 0.04

75.07 ± 1.47

1.298

0.373

% Prodelphinidin

22.69 ± 1.49

22.58 ± 2.31

0.003

0.959

23.74 ± 0.04

24.93 ± 1.47

1.298

0.373

Dimer B1 (mg/Kg)

613.78 ± 28.69

105.74±3.71

616.603

0.002

481.78 ± 49.24

134.75 ± 1.69

99.204

0.010

Dimer B2 (mg/Kg)

277.37 ± 16.11

40.65 ± 1.11

429.894

0.002

270.62 ± 39.25

61.01± 0.01

57.033

0.017

Dimer B4 (mg/Kg)

187.79 ± 5.17

34.14 ± 0.24

1764.686

0.001

134.76 ± 14.82

34.00 ± 1.56

91.410

0.011

(+)-Catechin

125.17 ± 9.35

35.79 ± 4.16

152.631

0.006

64.15 ± 2.73

33.90 ± 1.46

190.653

0.005

(-)-Epicatechin

427.31 ± 19.11

135.61 ± 14.11

301.462

0.003

344.92 ± 18.82

147.38 ± 15.71

129.920

0.008

n.d. j

n.d. j

-

-

n.d. j

n.d. j

-

-


76.84 ± 14.39

20.70 ± 1.26

30.188

0.032

60.45 ± 3.27

24.99 ± 1.97

172.501

0.006

(+)-Catechin-3-O-gallate

93.91 ± 4.74

18.75 ± 0.85

486.532

0.002

60.75 ± 2.10

17.35 ± 3.83

197.693

0.005

(-)-Epicatechin-3-O-gallate

n.d. j

n.d. j

-

-

n.d. j

n.d. j

-

-

(-)-Gallocatechin-3-O-gallate

n.d. j

n.d. j

-

-

n.d. j

n.d. j

-

-

34.33 ± 5.37

7.54 ± 0.57

49.295

0.020

31.69 ± 0.68

9.06 ± 0.58

1283.177

0.001

Extension units

(+)-Gallocatechin

(-)-Epigallocatechin-3-O-gallate

24


Page 25 of 26


757.57 ± 52.97

218.41 ± 20.95

179.206

0.020

561.96 ± 10.03

232.67 ± 15.52

635.000

0.002

(+)-Catechin

208.12 ± 9.22

79.12 ± 17.70

83.536

0,012

174.43 ± 23.97

104.60 ± 6.45

15.834

0.058

(-)-Epicatechin

61.15 ± 5.83

27.19 ± 5.97

33.155

0.029

62.31 ± 3.96

37.22 ± 6.59

21.276

0.044

(+)-Gallocatechin

85.71 ± 7.76

28.45 ± 0.48

108.429

0.009

60.87 ± 4.39

33.47 ± 2.19

62.432

0.016


28.03 ± 4.12

10.70 ± 1.99

28.699

0.033

22.70 ± 1.52

16.62 ± 0.06

31.809

0.030

n.d. j

12.73 ± 2.63

162.023

46.947

n.d. j

20.93 ± 2.42

149.279

0.007

64.83 ± 0.33

16.86 ± 2.27

877.065

0.001

41.12 ± 2.71

18.48 ± 2.68

70.644

0.014

n.d. j

n.d. j

-

-

n.d. j

n.d. j

-

-

15.92 ± 2.12

6.41 ± 0.49

38.219

0.025

14.55 ± 0.43

8.61 ± 1.37

34.482

0.028

463.76 ± 29.38

181.46 ± 30.57

88.673

0.011

375.97 ± 36.98

239.92 ± 4.37

26.702

0.035

Total (mg/Kg) Terminal units

(+)-Catechin-3-O-gallate (-)-Epicatechin-3-O-gallate (-)-Gallocatechin-3-O-gallate (-)-Epigallocatechin-3-O-gallate Total (mg/Kg) a

AVS-6 mo: Airén vine-shoots at 6 months; b AVST-6 mo: Airén toasted vine-shoots at 6 months; c CVS-6 mo: Cencibel vine-shoots at 6 months; d CVST-6 mo: Cencibel toasted vine-shoots at 6

months. e F values showed the Pearson correlation coefficient; f p value showed the significance of the correlation coefficient (p ≤ 0.05). j n.d. not detected. The mean values (n = 4) are shown with their standard deviation.

25



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Table of Contents (TOC) Graphic

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Vine-Shoot Tannins: Effect of Post-pruning Storage and Toasting

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