Table 2B.
Volatile precursors detected in Tempranillo throughout maturation stages.
| Metabolites | λmax | RT | T1 | T2 | T3 | T4 | T5 | T6 | T7 | T8 | T9 | T10 |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| AMINO ACIDS | ||||||||||||
| Isoleucine | 0.0054 | 0.0045 | 0.0128 | 0.0016 | 0.0083 | 0.0033 | 0.0020 | 0.0228 | 0.0104 | 0.0032 | ||
| Leucine | 0.0167 | 0.0173 | 0.0519 | 0.0072 | 0.0443 | 0.0175 | 0.0102 | 0.1005 | 0.0596 | 0.0153 | ||
| Phenylalanine* | 0.0478 | 0.0578 | 0.1588 | 0.0255 | 0.1013 | 0.0457 | 0.0404 | 0.1215 | 0.1178 | 0.0368 | ||
| Valine | 0.0128 | 0.0097 | 0.0230 | 0.0039 | 0.0138 | 0.0066 | 0.0039 | 0.0364 | 0.0220 | 0.0059 | ||
| LIPIDS | ||||||||||||
| Linoleic Acid | 0.0098 | 0.0089 | 0.0086 | 0.0057 | 0.0056 | 0.0076 | 0.0076 | 0.0112 | 0.0064 | 0.0056 | ||
| Linolenic Acid | 0.0444 | 0.0850 | 0.0767 | 0.0286 | 0.0822 | 0.0232 | 0.0344 | 0.4349 | 0.0582 | 0.0372 | ||
| CAROTENOIDS | ||||||||||||
| Unknown carotenoid (1) | (375) 400, 421, 441 | 1.15 | 0.0786 | 0.0457 | 0.1030 | NF | NF | NF | NF | NF | NF | NF |
| Unknown carotenoid (2) | (375) 400, 421, 441 | 1.34 | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| Unknown carotenoid (3) | 398, 422, 444 | 1.52 | 0.0561 | 0.0595 | 0.0569 | 0.0244 | 0.0188 | 0.0131 | 0.0064 | NF | NF | NF |
| Unknown carotenoid (4) | 421, 444, 470 | 1.70 | 0.0175 | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| Unknown carotenoid (5) | (375) 400, 421, 441 | 1.83 | NF | NF | 0.0300 | 0.0284 | 0.0182 | 0.0165 | 0.0049 | NF | 0.1232 | NF |
| Neochrome-like structure | 400, 421, 445 | 2.00 | 0.1990 | NF | NF | NF | NF | NF | NF | 0.0189 | 0.1600 | NF |
| Neochrome a | 401, 419, 446 | 2.27 | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| Neoxanthin | 420, 440, 466 | 2.40 | NF | NF | NF | NF | NF | NF | 0.1006 | NF | 0.1230 | NF |
| Neochrome b | 402, 421, 447 | 2.63 | 0.0867 | 0.0686 | 0.0503 | NF | NF | NF | NF | NF | 0.0115 | 0.0709 |
| Luteoxanthin isomer | 402, 421, 447 | 2.84 | 0.3063 | 0.2396 | 0.0970 | 0.3509 | 0.0790 | NF | NF | NF | 0.0689 | NF |
| All-trans-violaxanthin | 416, 442, 463 | 2.87 | NF | NF | NF | NF | NF | 0.2267 | 0.2435 | NF | NF | NF |
| 9-cis-violaxanthin | 438, 462 | 2.91 | NF | 0.1184 | NF | NF | NF | 0.1511 | NF | NF | NF | NF |
| Luteoxanthin | 421, 444, 465 | 3.05 | NF | NF | 0.0299 | 0.0247 | 0.0137 | 0.0554 | 0.1522 | NF | 0.3048 | 1.2015 |
| Auroxanthin | 403, 425, 444 | 3.13 | 0.3277 | 0.1742 | 0.0646 | NF | NF | NF | NF | 0.0619 | 0.1520 | NF |
| Flavoxanthin | (375), 402, 423, 446 | 3.47 | 0.7499 | 0.2313 | 0.1284 | NF | NF | NF | NF | 0.1691 | 0.1482 | NF |
| All-trans-lutein | 445, 472 | 4.09 | 9.9916 | 7.6905 | 4.9760 | 4.4097 | 2.2627 | 2.9679 | 2.8582 | 1.9456 | 2.6001 | 2.7767 |
| Zeaxanthin | 450, 476 | 4.77 | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| 13Z or 13Z′ lutein | 442, 468 | 4.87 | 0.9707 | 0.2728 | 0.1881 | 0.4108 | 0.0538 | 0.2203 | NF | 0.1092 | 0.1751 | 1.0202 |
| 9Z or 9Z′ lutein | 438, 467 | 4.98 | 0.0866 | 0.1354 | 0.2069 | 0.0162 | NF | 0.1210 | NF | NF | NF | NF |
| Lutein-like structure | 424, 446, 473 | 5.14 | 0.0352 | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| 9Z or 9Z′ lutein-like structure | 440, 468 | 5.45 | 0.5244 | 0.6207 | 0.7687 | 0.6037 | 0.2918 | 0.1278 | 0.1456 | 0.2171 | 0.3323 | 0.5097 |
| Lutein-like structure | 424, 446, 473 | 5.50 | 0.3054 | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| 5,8-epoxy-β-carotene | 406, 426, 450 | 6.29 | 0.9041 | 0.5826 | 0.5256 | 0.3810 | 0.0945 | 0.2507 | 0.1520 | 0.1829 | 0.1075 | NF |
| All-trans-α-carotene | 444, 470 | 6.42 | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF |
| All-trans-β-carotene | 452, 477 | 7.01 | 4.9373 | 3.8749 | 0.6841 | 1.4960 | 0.8937 | 1.3463 | 1.5620 | 0.9064 | 0.9788 | 0.2520 |
| 9-cis-β-carotene | 423, 447, 473 | 7.13 | 1.7399 | 1.1741 | 0.6765 | 0.5374 | 0.2493 | 0.3821 | 0.3580 | 0.2368 | 0.3233 | NF |
| Unknown carotenoid (6) | 422, 446 | 7.75 | 0.0771 | 0.0364 | 0.0296 | NF | NF | NF | NF | NF | NF | NF |
| All-trans-δ-carotene | 453 | 8.02 | 0.0279 | 0.0426 | 0.0164 | NF | NF | NF | NF | NF | NF | NF |
| TOTAL | 21.4219 | 15.3672 | 8.6320 | 8.2832 | 3.9756 | 5.8788 | 5.5834 | 3.8481 | 5.6087 | 5.8310 | ||
| CHLOROPHYLLS | ||||||||||||
| Pyropheophorbide b | 436, 655 | 2.08 | NF | NF | NF | NF | NF | NF | NF | 0.0192 | NF | NF |
| Pyropheophorbide a | 410, 665 | 2.22 | NF | NF | NF | NF | NF | NF | NF | 0.0276 | 0.0912 | NF |
| Chlorophyll b | 469, 651 | 3.73 | NF | 2.6581 | NF | 2.7103 | 0.9423 | 3.1888 | 3.6151 | NF | 1.0158 | 2.2874 |
| Chlorophyll a | 432, 665 | 5.05 | NF | NF | NF | NF | NF | 0.0474 | 0.4265 | NF | NF | NF |
| Unknown chlorophyll derivative (1) | 401 | 5.64 | 1.0691 | 0.2496 | 0.3093 | NF | NF | NF | 0.0205 | NF | NF | NF |
| Unknown chlorophyll derivative (2) | 402 | 6.04 | 0.1963 | 0.0974 | 0.1222 | NF | NF | NF | 0.0186 | 0.0705 | 0.0444 | NF |
| Pheophytin a-like (1) | 410 | 6.12 | 0.1168 | 0.0516 | 0.1256 | NF | 0.0577 | NF | NF | 0.0256 | 0.0258 | 0.0198 |
| Pheophytin a-like (2) | 415, 445, 665 | 6.39 | 0.0698 | NF | 0.0585 | NF | 0.0390 | NF | NF | NF | NF | NF |
| Pheophytin b-like | 419, 436, 656 | 6.52 | 0.8094 | 0.4350 | 0.8440 | 0.2006 | 0.1131 | NF | NF | 0.2263 | 0.1325 | NF |
| Pheophytin b | 432, 654 | 6.89 | 14.1734 | 7.8599 | 11.3427 | 3.8593 | 3.0228 | 0.4781 | 0.4265 | 2.3711 | 3.3644 | 1.4385 |
| Pheophytin a | 408, 666 | 6.91 | 5.3704 | 3.2120 | 3.4230 | 2.0915 | 1.0261 | 1.0585 | 0.7032 | 0.6567 | 1.1197 | 0.5704 |
| TOTAL | 21.8052 | 14.5636 | 16.2253 | 8.8616 | 5.2010 | 4.7727 | 5.2103 | 3.3968 | 5.7939 | 4.3161 | ||
| OTHERS | ||||||||||||
| α-tocopherol | 290 | 2.74 | 45.1689 | 28.6563 | 12.3871 | 22.0931 | 13.4224 | 21.0568 | 19.4971 | 19.3449 | 25.3264 | 11.9777 |
| Ubiquinone | 296 | 5.89 | 27.9983 | 25.4948 | 18.1442 | 8.6920 | NF | 21.2234 | 13.5892 | 6.9020 | 19.9027 | NF |
| Unknown | 255 | 6.28 | 119.4096 | NF | 93.9746 | NF | NF | NF | NF | 54.0751 | NF | NF |
| TOTAL | 192.5768 | 54.1511 | 124.5060 | 30.7851 | 13.4224 | 42.2802 | 33.0863 | 80.3219 | 45.2291 | 11.9777 | ||
| PHENYLPROPANOIDES | ||||||||||||
| Benzoic acid | 0.0095 | 0.0053 | 0.0034 | 0.0006 | 0.0002 | 0.0002 | 0.0002 | 0.0001 | 0.0001 | 0.0001 | ||
| Caffeic acid | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| Cinnamic acid | 0.0001 | 0.0001 | 0.0005 | 0.0001 | 0.0003 | 0.0001 | 0.0001 | 0.0004 | 0.0004 | 0.0001 | ||
| Coniferyl acetate | 0.0008 | 0.0006 | 0.0006 | 0.0006 | 0.0006 | 0.0007 | 0.0007 | 0.0006 | 0.0006 | 0.0005 | ||
| Coniferyl alcohol | 0.0006 | 0.0003 | 0.0003 | 0.0001 | NF | 0.0004 | NF | NF | NF | NF | ||
| Coniferyl aldehyde | 0.0016 | 0.0007 | 0.0002 | 0.0003 | 0.0001 | 0.0004 | 0.0003 | 0.0001 | NF | NF | ||
| Coumaric acid | 0.0040 | 0.0030 | 0.0021 | 0.0017 | 0.0012 | 0.0013 | 0.0009 | 0.0014 | 0.0012 | 0.0010 | ||
| Ferulic acid | 0.0018 | 0.0009 | NF | 0.0003 | NF | NF | NF | NF | NF | NF | ||
| Hydroxyconiferyl alcohol | 0.0003 | 0.0002 | 0.0001 | 0.0001 | 0.0001 | 0.0001 | 0.0001 | 0.0001 | NF | NF | ||
| Sinapyl alcohol | 0.0007 | 0.0003 | NF | 0.0001 | NF | NF | 0.0002 | NF | NF | NF | ||
| TERPENES | ||||||||||||
| α-terpinol-[xylosyl-(1->6)-glucoside] | 0.0003 | 0.0002 | 0.0001 | 0.0002 | 0.0001 | 0.0002 | 0.0002 | 0.0001 | 0.0002 | 0.0002 | ||
| α-terpinol-beta-d-glucoside | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| L-Linalool 3-[xylosyl-(1->6)-glucoside] | 0.0003 | 0.0002 | 0.0001 | 0.0000 | 0.0000 | 0.0002 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | ||
| Limonene-arabinofuranose | 0.0000 | 0.0002 | 0.0001 | 0.0001 | 0.0001 | 0.0001 | 0.0003 | 0.0002 | 0.0001 | 0.0002 | ||
| Limonene-arabinofuranose-glucoside | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| Linalool-arabinofuranose | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| Linalyl-beta-d-glucoside | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-arabinofuranose1** | 0.0007 | 0.0004 | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-arabinofuranose2** | 0.0002 | 0.0002 | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-arabinofuranose-glucoside1** | 0.0004 | 0.0002 | 0.0001 | 0.0001 | 0.0000 | 0.0002 | 0.0000 | NF | NF | NF | ||
| E-/Z-linalool oxide-arabinofuranose-glucoside2** | 0.0002 | 0.0001 | 0.0001 | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-glucoside1** | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-glucoside2** | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-rhamnopyranose1** | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-rhamnopyranose2** | NF | NF | NF | NF | NF | NF | NF | NF | NF | NF | ||
| E-/Z-linalool oxide-Rhamnopyranoside-glucoside** | 0.0001 | 0.0000 | 0.0001 | 0.0000 | NF | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | ||
| E-/Z-linalool oxide-Rhamnopyranoside-glucoside2** | 0.0000 | NF | 0.0000 | 0.0000 | NF | 0.0000 | NF | NF | 0.0000 | 0.0000 | ||
Isoprenoids (carotenoids, chlorophylls, ubiquinone, and a-tocopherol) were identified and quantified by LC-DAD-APCI-MS and data are expressed as μg/mg DW; other metabolite precursors were detected and relatively quantified by LC-APCI-MS (lipids) and LC-ESI-MS (amino acids, phenylpropanoids, terpene glucosides) and data are expressed as fold on the internal standard level (APCI, a-tocopherol acetate; ESI, formononetin). For more details, see materials and methods.
*
Also involved in phenylpropanoid-derived volatiles.
**
Not possible discriminating the E- and Z- isomers.