园艺学报 ›› 2024, Vol. 51 ›› Issue (1): 145-161.doi: 10.16420/j.issn.0513-353x.2023-0019
徐旭华1, 黄文洁1, 陈旭峰1, 陈园园1, 吴绍文1, 李红建2, 晏石娟1,*()
收稿日期:
2023-01-09
修回日期:
2023-03-06
出版日期:
2024-01-25
发布日期:
2024-01-16
通讯作者:
基金资助:
XU Xuhua1, HUANG Wenjie1, CHEN Xufeng1, CHEN Yuanyuan1, WU Shaowen1, LI Hongjian2, YAN Shijuan1,*()
Received:
2023-01-09
Revised:
2023-03-06
Published:
2024-01-25
Online:
2024-01-16
摘要:
为了探究‘丹霞2号’红茶在鲜叶采摘、萎凋、揉捻、发酵和干燥等5个加工阶段次生代谢产物动态变化特征及其对茶品质形成的影响,利用液相色谱串联四极杆—静电场轨道阱—线性离子阱质谱系统(LC-Q-LIT-OT-MS)对不同阶段茶叶进行了代谢组学分析。在‘丹霞2号’茶叶中共鉴定到124种代谢物,包括22种儿茶素类、19种儿茶素聚合物类和32种黄酮及黄酮糖苷等。多维统计数据分析显示,在由鲜叶采摘到萎凋、萎凋到揉捻、揉捻到发酵、发酵到干燥的转变中分别涉及162、412、308、126种代谢物的显著变化。其中红茶滋味品质特征成分种类和含量在揉捻和发酵两个阶段变化最为显著。儿茶素类物质的含量随着加工过程整体呈现下降趋势;儿茶素聚合物在揉捻期含量显著升高,随后在发酵和干燥过程中逐渐降低。黄酮类及黄酮糖苷类物质的含量整体呈现增加趋势,在揉捻或发酵阶段升高最为明显。儿茶素类、儿茶素聚合物、黄酮及其糖苷类的含量与天冬氨酸、谷氨酰胺、苯丙氨酸及可溶性糖的含量呈现正相关。
徐旭华, 黄文洁, 陈旭峰, 陈园园, 吴绍文, 李红建, 晏石娟. ‘丹霞2号’红茶加工过程中品质特征成分的动态变化研究[J]. 园艺学报, 2024, 51(1): 145-161.
XU Xuhua, HUANG Wenjie, CHEN Xufeng, CHEN Yuanyuan, WU Shaowen, LI Hongjian, YAN Shijuan. Research on the Dynamic Change of Tea Quality-related Chemical Compositions During‘Danxia 2’Black Tea Processing[J]. Acta Horticulturae Sinica, 2024, 51(1): 145-161.
图1 LC-Q-LIT-OT-MS 在正离子(ESI+)、负离子(ESI-)扫描模式下分析‘丹霞2号’红茶代谢组的总离子流色谱图
Fig. 1 The total ion chromatograms of‘Danxia 2’black tea determined in the ESI+ and ESI- mode by LC-Q-LIT-OT-MS-based metabolomics
保留时间/ min Retention time | 代谢物 Metabolite | 实测质荷比/ (m/z) Accurate mass | 理论质荷比/(m/z) Theoretical mass | 分子式 Formula | 检测模式 Detection mode |
---|---|---|---|---|---|
儿茶素类 Catechins(22) | |||||
5.423 | 儿茶素 Catechin | 289.0717 | 289.0718 | C15H14O6 | ESI- |
6.050/6.050 | 表儿茶素 Epicatechin | 291.0857/289.0719 | 291.0863/289.0718 | C15H14O6 | ESI+/ESI- |
4.605 | 没食子儿茶素 Gallocatechin | 305.0666 | 305.0667 | C15H14O7 | ESI- |
12.645 | 儿茶素3-O-没食子酸酯 Catechin 3-O-gallate | 441.0828 | 441.0827 | C22H18O10 | ESI- |
5.265/5.265 | 表儿茶素3-O-没食子酸酯 Epicatechin 3-O-gallate | 443.0966/441.0826 | 443.0973/441.0827 | C22H18O10 | ESI+/ESI- |
2.688 | 表没食子儿茶素 Epigallocatechin | 305.0666 | 305.0667 | C15H14O7 | ESI- |
4.289 | 表没食子儿茶素没食子酸酯 Epigallocatechin gallate | 457.0776 | 457.0776 | C22H18O11 | ESI- |
7.640/7.640 | 没食子儿茶素3-O-没食子酸酯 Gallocatechin 3-O-gallate | 459.0914/457.078 | 459.0922/457.0776 | C22H18O11 | ESI+/ESI- |
4.933/4.933 | 表阿福豆素3-O-没食子酸酯 Epiafzelechin 3-O-gallate | 427.1017/425.0878 | 427.1024/425.0878 | C22H18O9 | ESI+/ESI- |
6.278 | 表没食子儿茶素3,5-双没食子酸酯Epigallocatechin 3,5-digallate | 609.0885 | 609.0886 | C29H22O15 | ESI- |
8.47/8.48 | 表儿茶素3-O-对羟基苯甲酸酯 Epicatechin 3-O-p-hydroxybenzoate | 411.1075/409.0931 | 411.1074/409.0929 | C22H18O8 | ESI+/ESI- |
9.380 | 表没食子儿茶素3-O-对香豆素 Epigallocatechin 3-O-p-coumarate | 451.1034 | 451.1035 | C24H20O9 | ESI- |
9.500 | 表儿茶素3-O-(3-O-甲基)没食子酸酯 Epicatechin 3-O-(3-O-methyl)gallate | 457.1129 | 457.1129 | C23H20O10 | ESI+ |
6.253/6.258 | 表阿福豆素 Epiafzelechin | 275.0896/273.0768 | 275.0914/273.0768 | C15H14O5 | ESI+/ESI- |
11.940 | 表没食子儿茶素3-O-肉桂酸酯 Epigallocatechin 3-O-cinnamate | 437.1223 | 437.1231 | C24H20O8 | ESI+ |
12.590/12.590 | 3-O-没食子酰-表儿茶素-(4β->8)-儿茶素3-O-galloyl-epicatechin-(4β->8)-catechin | 731.1594/729.1473 | 731.1607/729.1461 | C37H30O16 | ESI+/ESI- |
4.177 | 表儿茶素3-葡萄糖苷 Epicatechin 3-glucoside | 451.1245 | 451.1246 | C21H24O11 | ESI- |
12.84 | 没食子儿茶素-(4α->8)-表儿茶素Gallocatechin-(4α->8)-epicatechin | 593.1301 | 593.1300 | C30H26O13 | ESI- |
8.120/8.120 | 表没食子儿茶素3-O-(3-O-甲基)没食子酸酯Epigallocatechin 3-O- (3-O-methyl)gallate | 473.1069/471.093 | 473.1078/471.0933 | C23H20O11 | ESI+/ESI- |
5.520 | 8-C-抗坏血酸表没食子儿茶素3-O-没食子酸酯8-C-Ascorbyl epigallocatechin 3-O-gallate | 631.0949 | 631.0941 | C28H24O17 | ESI- |
11.430/11.430 | 表茶黄棓灵3-O-没食子酸酯 Epitheaflagallin 3-O-gallate | 553.0969/551.0829 | 553.0977/551.0831 | C27H20O13 | ESI+/ESI- |
8.410 | 表没食子儿茶素-(4β->8)-表儿茶-3-O-没食子酸酯 Epigallocatechin-(4β->8)-epicatechin-3-O-gallate ester | 747.1553 | 747.1556 | C37H30O17 | ESI+ |
儿茶素聚合物 Dimeric,oligomeric and polymeric of catechins(19) | |||||
6.390/6.390 | 聚酯型儿茶素B Theasinensin B | 763.1491/761.1359 | 763.1505/761.1359 | C37H30O18 | ESI+/ESI- |
4.765 | 聚酯型儿茶素A Theasinensin A | 913.1468 | 913.1468 | C44H34O22 | ESI- |
0.807 | 聚酯型儿茶素C Theasinensin C | 609.1249 | 609.1249 | C30H26O14 | ESI- |
6.420/6.420 | 聚酯型儿茶素F Theasinensin F | 899.1665/897.1519 | 899.1665/897.1519 | C44H34O21 | ESI+/ESI- |
7.290 | 新唢呐草素I Tellimagrandin I | 785.0859 | 785.0843 | C34H26O22 | ESI- |
7.450 | 茶氨酸-3-没食子酸酯 Theacitrin-3-gallate | 761.1326 | 761.1348 | C37H28O18 | ESI+ |
7.670 | 乌龙茶素3′-O-没食子酸酯 Oolongtheanin 3′-O-gallate | 883.1357 | 883.1363 | C43H32O21 | ESI- |
9.040 | 茶氨酸C Theacitrin C | 911.1321 | 911.1312 | C44H32O22 | ESI+ |
9.040 | 茶氨酸A Theacitrin A | 759.1204 | 759.1203 | C37H28O18 | ESI- |
9.610 | 茶黄素 Theaflavin | 565.1344 | 565.1341 | C29H24O12 | ESI+ |
11.260 | 茶黄素3-O-没食子酸酯 Theaflavin 3-O-gallate | 715.1309 | 715.1305 | C36H28O16 | ESI- |
10.340 | 茶黄酸 Theaflavic acid | 427.0674 | 427.0671 | C21H16O10 | ESI- |
9.463 | 茶黄素3,3′-双没食子酸酯 Theaflavin 3,3′-digallate | 867.1414 | 867.1414 | C43H32O20 | ESI- |
12.190 | 乌龙茶素 Oolongtheanin | 731.1253 | 731.0124 | C36H28O17 | ESI- |
12.450/12.450 | 脱氢茶黄素 Dehydrotheaflavin | 579.1127/577.0984 | 579.1133/577.0977 | C29H22O13 | ESI+/ESI- |
12.650/12.650 | 茶黄酸盐B Theaflavate B | 717.144/699.137 | 701.1501/699.1355 | C36H28O15 | ESI+/ESI- |
7.210 | 原花青素B2 Procyanidin B2 | 865.1985 | 865.1985 | C45H38O18 | ESI- |
8.970 | 原花青素B4 Procyanidin B4 | 577.1354 | 577.1351 | C30H26O12 | ESI- |
10.610/10.610 | 茶多醌 Theanaphthoquinone | 535.1229/533.1094 | 535.1234/533.1089 | C28H22O11 | ESI+/ESI- |
黄酮和黄酮糖苷Flavone and flavone glycosides(32) | |||||
9.860 | 芦丁 Rutin | 611.1597 | 611.1607 | C27H30O16 | ESI+ |
1.490 | 圣草酚 Eriodictyol | 288.0633 | 288.0628 | C15H11O6 | ESI+ |
9.980/9.980 | 茶黄棓灵 Theaflagallin | 401.0855/399.0719 | 401.0867/399.0722 | C20H16O9 | ESI+/ESI- |
4.170/4.170 | 白矢车菊素 Leucocyanidin | 307.0807/305.0668 | 307.0812/305.0667 | C15H14O7 | ESI+/ESI- |
11.640 | 槲皮素 Quercetin | 301.0353 | 301.0354 | C15H10O7 | ESI- |
5.270/5.270 | 槲皮-3-O-葡萄糖苷 Quercetin-3-O-glucoside | 465.1027/463.0881 | 465.1027/463.0881 | C21H20O12 | ESI+/ESI- |
8.752/8.572 | 槲皮-3-O-半乳糖苷 Quercetin-3-O-galactoside | 465.1026/463.08842 | 465.1028/463.0881 | C21H20O12 | ESI+/ESI- |
11.080/11.150 | 槲皮素3-O-鼠李糖苷 Quercetin 3-O-rhamnoside | 449.1072/447.0932 | 449.1078/447.0933 | C21H20O11 | ESI+/ESI- |
5.920 | 飞燕草素3-O-β-D-(6-O-(E)-对香豆素基)吡喃半乳糖苷 Delphinidin 3-O-β-D-(6-O-(E)-p-coumaryl)galactopyranoside | 610.1332 | 610.1328 | C30H27O14 | ESI- |
5.970 | 花青素3-O-(2-O-β-吡喃木糖基)-β-吡吡喃半乳糖苷 Cyanidin 3-O-(2-O-β-xylopyranosyl)-β- galactopyranoside | 580.1428 | 580.1433 | C26H29O15 | ESI- |
7.030 | 二氢山奈酚 Dihydrokaempferol | 289.0707 | 289.0707 | C15H12O6 | ESI+ |
7.640 | Assamicain A | 915.1629 | 915.1625 | C44H36O22 | ESI- |
7.890 | 二氢槲皮素 Dihydroquercetin | 303.0511 | 303.0510 | C15H12O7 | ESI- |
8.950/8.950 | 杨梅素 Myricetin | 319.0443/317.0302 | 319.0448/317.0303 | C15H10O8 | ESI+/ESI- |
9.090/9.090 | 杨梅素3-O-葡萄糖苷 Myricetin 3-O-glucoside | 481.0976/479.0831 | 481.0976/479.0831 | C21H20O13 | ESI+/ESI- |
9.190/9.190 | 杨梅素3-O-半乳糖苷 Myricetin 3-O-galactoside | 481.0967/479.0829 | 481.0977/479.0831 | C21H20O13 | ESI+/ESI- |
9.190/9.190 | 山奈酚 Kaempferol | 287.0543/285.0404 | 287.0550/285.0404 | C15H10O6 | ESI+/ESI- |
10.450 | 山奈酚-3-O-阿拉伯糖苷Kaempferol-3-O-arabinoside | 419.0747 | 419.0972 | C20H18O10 | ESI+ |
6.483 | 山奈酚-3-芸香苷 Kaempferol-3-rutinoside | 595.1651 | 595.1657 | C27H30O15 | ESI+ |
6.517 | 山奈酚-3-O-葡萄糖苷 Kaempferol-3-O-glucoside | 447.0934 | 447.0932 | C21H20O11 | ESI+ |
6.846 | 山奈酚-3-O-半乳糖苷Kaempferol-3-O-galactoside | 447.0934 | 447.0932 | C21H20O11 | ESI+ |
9.780 | 槲皮素3-木糖-(1->2)-鼠李糖基-(1->6)-葡萄糖苷 Quercetin 3-xylosyl-(1->2)-rhamnosyl- (1->6)-glucoside | 741.1884 | 741.1883 | C32H38O20 | ESI- |
9.880 | 槲皮素3-葡萄糖基-(1->3)-鼠李糖基-(1->6)-半乳糖苷 Quercetin 3-glucosyl-(1->3)-rhamnosyl- (1->6)-galactoside | 771.1989 | 771.1989 | C33H40O21 | ESI- |
10.780 | 山奈酚3-葡萄糖基-(1->3)-鼠李糖基-(1->6)-半乳糖苷 Kaempferol 3-glucosyl-(1->3)-rhamnosyl- (1->6)-galactoside | 755.2041 | 755.204 | C33H40O20 | ESI- |
11.080 | 山奈酚3-鼠李糖基-(1->3)-鼠李糖-(1->6)-葡萄糖苷 Kaempferol 3-rhamnosyl-(1->3)- rhamnosyl-(1->6)-glucoside | 739.2096 | 739.2091 | C33H40O19 | ESI- |
11.140 | 牡荆-2-O-葡萄糖苷 Vitexin-2-O-glucoside | 595.1649 | 595.1657 | C27H30O15 | ESI- |
11.450 | 茶花粉黄酮 Pollenitin | 315.0514 | 315.0510 | C16H12O7 | ESI- |
10.930 | 牡荆素 Vitexin | 433.1129 | 433.1129 | C21H20O10 | ESI+ |
13.740 | 芹菜素 Apigenin | 269.0457 | 269.0455 | C15H10O5 | ESI- |
8.741 | 芹菜素6-C-葡糖基-8-C-阿拉伯糖苷 Apigenin 6-C-glucosyl-8-C-arabinoside | 725.1934 | 725.1934 | C32H38O19 | ESI- |
7.293 | 槲皮素3-O-葡糖苷酸 Quercetin 3-O-glucuronide | 477.0674 | 477.0675 | C21H18O13 | ESI- |
5.078 | 槲皮素3-O-葡糖基-芸香糖苷 Quercetin 3-O-glucosyl-rutinoside | 771.1989 | 771.1989 | C33H40O21 | ESI- |
氨基酸Amino acids(19) | |||||
0.764/0.764 | 精氨酸 Arginine | 175.1189/173.1042 | 175.1190/173.1044 | C6H14N4O2 | ESI+/ESI- |
0.762 | 谷氨酸 Glutamic acid | 148.0604 | 148.0604 | C5H9NO4 | ESI+ |
0.761 | 谷氨酰胺 Glutamine | 145.0618 | 145.0619 | C5H10N2O3 | ESI- |
1.023 | 亮氨酸 Leucine | 132.1019 | 132.1019 | C6H13NO2 | ESI+ |
0.742 | 赖氨酸 Lysine | 147.1128 | 147.1128 | C6H14N2O2 | ESI+ |
1.631 | 哌啶酸 Pipecolic acid | 130.0862 | 130.0863 | C6H11NO2 | ESI+ |
1.049 | 脯氨酸 Proline | 116.0706 | 116.0706 | C5H9NO2 | ESI+ |
0.761/0.761 | 焦谷氨酸 Pyroglutamic acid | 130.0498/128.0353 | 130.0499/128.0353 | C5H7NO3 | ESI+/ESI- |
1.842 | 茶氨酸 Theanine | 175.1077 | 175.1077 | C7H14N2O3 | ESI+ |
5.691 | 色氨酸 Tryptophan | 203.0826 | 203.0826 | C11H12N2O2 | ESI- |
0.812/0.812 | 缬氨酸 Valine | 118.0862/116.0717 | 118.0862/116.0717 | C5H11NO2 | ESI+/ESI- |
1.060/1.060 | 丝氨酸 Serine | 106.0497/104.0353 | 106.0499/104.0353 | C3H7NO3 | ESI+/ESI- |
1.080 | 苏氨酸 Threonine | 120.0654 | 120.0655 | C4H9NO3 | ESI+ |
1.070 | 天冬酰胺 Asparagine | 133.0607 | 133.0608 | C4H8N2O3 | ESI+ |
1.070 | 天冬氨酸 Aspartic acid | 134.0447 | 134.0448 | C4H7NO4 | ESI+ |
1.220 | 蛋氨酸 Methionine | 150.0581 | 150.0583 | C5H11NO2S | ESI+ |
1.060 | 组氨酸 Histidine | 156.0766 | 156.0768 | C6H9N3O2 | ESI+ |
3.990 | 苯丙氨酸 Phenylalanine | 166.0861 | 166.0863 | C9H11NO2 | ESI+ |
1.420/1.420 | 酪氨酸 Tyrosine | 182.0809/180.0666 | 182.0812/180.0666 | C9H11NO3 | ESI+/ESI- |
有机酸Organic acids(7) | |||||
5.950 | 香豆酸 Coumaric acid | 163.0401 | 163.0401 | C9H8O3 | ESI- |
2.320 | 没食子酸 Gallic acid | 169.0142 | 169.0142 | C7H6O5 | ESI- |
5.960 | 咖啡酸 Caffeic acid | 179.0349 | 179.0350 | C9H8O4 | ESI- |
12.110 | 茉莉酸 Jasmonic acid | 209.1185 | 209.1183 | C12H18O3 | ESI- |
4.840 | 泛酸 Pantothenic acid | 218.1034 | 218.1034 | C9H17NO5 | ESI- |
1.130 | 抗坏血酸 Ascorbic acid | 175.0246 | 175.0248 | C6H8O6 | ESI- |
1.646 | 5-没食子酰奎宁酸 5-Galloylquinic acid | 345.0809 | 345.0816 | C14H16O10 | ESI+ |
糖类Sugars(8) | |||||
1.130 | 木酮糖 Xylulose | 149.0455 | 149.0455 | C5H10O5 | ESI- |
7.790 | 苄基β-D-吡喃葡萄糖苷 Benzyl β-D-glucopyranoside | 269.1031 | 269.1031 | C13H18O6 | ESI- |
1.110/1.110 | 麦芽糖 Maltose | 341.1089/343.1234 | 341.1089/343.1235 | C12H22O11 | ESI+/ESI- |
1.070 | 棉子糖 Raffinose | 503.1619 | 503.1618 | C18H32O16 | ESI- |
6.560 | 香豆酰β-D-吡喃葡萄糖苷 Coumaroyl β-D-glucopyranoside | 325.0929 | 325.0929 | C15H18O8 | ESI- |
6.690/7.030 | 阿魏酰-β-D-吡喃葡萄糖苷Feruloyl-β-D-glucopyranoside | 357.1173/355.1034 | 357.1180/355.1035 | C16H20O9 | ESI+/ESI- |
1.170 | 6-O-没食子酰葡萄糖 6-O-galloylglucose | 331.0671 | 331.0671 | C13H16O10 | ESI- |
9.740 | 苯乙基β-D-吡喃葡萄糖苷 Phenylethyl β-D-glucopyranoside | 285.1324 | 285.1332 | C14H20O6 | ESI+ |
酚酸Phenolic acids(5) | |||||
5.810 | 木麻黄素 Strictinin | 633.0733 | 633.0733 | C27H22O18 | ESI- |
7.410 | 4-对香豆酰奎宁酸 4-p-Coumaroylquinic acid | 337.0931 | 337.0929 | C16H18O8 | ESI- |
2.192 | 1-咖啡酰奎宁酸 1-Caffeoylquinic acid | 353.0878 | 353.0878 | C16H18O9 | ESI- |
0.768/0.768 | 奎尼酸 Quinic acid | 193.0706/191.0561 | 193.0707/191.0561 | C7H12O6 | ESI+/ESI- |
3.304 | 原儿茶酸 Protocatechuic acid | 153.0193 | 153.0193 | C7H6O4 | ESI- |
生物碱Alkaloids(3) | |||||
4.990/4.990 | 茶碱 Theophylline | 181.0717/179.0574 | 181.0720/179.0574 | C7H8N4O2 | ESI+/ESI- |
4.978/5.346 | 咖啡碱 Caffeine | 195.0876 | 195.0877 | C8H10N4O2 | ESI+ |
1.018 | 哌啶 Piperidine | 86.0964 | 86.0964 | C5H11N | ESI+ |
核苷和核苷酸Nucleosides and nucleotides(4) | |||||
0.848 | 腺苷酸 Adenosine monophosphate | 346.0558 | 346.0558 | C10H14N5O7P | ESI- |
1.595 | 鸟苷 Guanosine | 284.0989 | 284.0989 | C10H13N5O5 | ESI+ |
2.603 | 1-甲基黄嘌呤 1-Methylxanthine | 167.0563 | 167.0564 | C6H6N4O2 | ESI+ |
5.331 | 甲硫腺苷 Methylthioadenosine | 298.0968366 | 298.0968 | C11H15N5O3S | ESI+ |
激素Hormones(2) | |||||
9.100 | 茉莉酸甲酯 Methyl jasmonate | 225.1477 | 225.1485 | C13H20O3 | ESI+ |
15.380 | 赤霉素A53 Gibberellin A53 | 349.1979 | 349.2010 | C20H28O5 | ESI+ |
其他Others(3) | |||||
8.490 | 淫羊藿次苷B5 Icariside B5 | 389.2159 | 389.2170 | C19H32O8 | ESI+ |
0.769 | N-乳酰基乙醇胺 N-Lactoyl ethanolamine | 132.0666 | 132.0666 | C5H11NO3 | ESI- |
8.260 | 核黄素 Riboflavin | 377.1449 | 377.1456 | C17H20N4O6 | ESI+ |
表1 ‘丹霞2号’红茶中鉴定的124种代谢物
Table 1 124 metabolites identified in‘Danxia 2’black tea
保留时间/ min Retention time | 代谢物 Metabolite | 实测质荷比/ (m/z) Accurate mass | 理论质荷比/(m/z) Theoretical mass | 分子式 Formula | 检测模式 Detection mode |
---|---|---|---|---|---|
儿茶素类 Catechins(22) | |||||
5.423 | 儿茶素 Catechin | 289.0717 | 289.0718 | C15H14O6 | ESI- |
6.050/6.050 | 表儿茶素 Epicatechin | 291.0857/289.0719 | 291.0863/289.0718 | C15H14O6 | ESI+/ESI- |
4.605 | 没食子儿茶素 Gallocatechin | 305.0666 | 305.0667 | C15H14O7 | ESI- |
12.645 | 儿茶素3-O-没食子酸酯 Catechin 3-O-gallate | 441.0828 | 441.0827 | C22H18O10 | ESI- |
5.265/5.265 | 表儿茶素3-O-没食子酸酯 Epicatechin 3-O-gallate | 443.0966/441.0826 | 443.0973/441.0827 | C22H18O10 | ESI+/ESI- |
2.688 | 表没食子儿茶素 Epigallocatechin | 305.0666 | 305.0667 | C15H14O7 | ESI- |
4.289 | 表没食子儿茶素没食子酸酯 Epigallocatechin gallate | 457.0776 | 457.0776 | C22H18O11 | ESI- |
7.640/7.640 | 没食子儿茶素3-O-没食子酸酯 Gallocatechin 3-O-gallate | 459.0914/457.078 | 459.0922/457.0776 | C22H18O11 | ESI+/ESI- |
4.933/4.933 | 表阿福豆素3-O-没食子酸酯 Epiafzelechin 3-O-gallate | 427.1017/425.0878 | 427.1024/425.0878 | C22H18O9 | ESI+/ESI- |
6.278 | 表没食子儿茶素3,5-双没食子酸酯Epigallocatechin 3,5-digallate | 609.0885 | 609.0886 | C29H22O15 | ESI- |
8.47/8.48 | 表儿茶素3-O-对羟基苯甲酸酯 Epicatechin 3-O-p-hydroxybenzoate | 411.1075/409.0931 | 411.1074/409.0929 | C22H18O8 | ESI+/ESI- |
9.380 | 表没食子儿茶素3-O-对香豆素 Epigallocatechin 3-O-p-coumarate | 451.1034 | 451.1035 | C24H20O9 | ESI- |
9.500 | 表儿茶素3-O-(3-O-甲基)没食子酸酯 Epicatechin 3-O-(3-O-methyl)gallate | 457.1129 | 457.1129 | C23H20O10 | ESI+ |
6.253/6.258 | 表阿福豆素 Epiafzelechin | 275.0896/273.0768 | 275.0914/273.0768 | C15H14O5 | ESI+/ESI- |
11.940 | 表没食子儿茶素3-O-肉桂酸酯 Epigallocatechin 3-O-cinnamate | 437.1223 | 437.1231 | C24H20O8 | ESI+ |
12.590/12.590 | 3-O-没食子酰-表儿茶素-(4β->8)-儿茶素3-O-galloyl-epicatechin-(4β->8)-catechin | 731.1594/729.1473 | 731.1607/729.1461 | C37H30O16 | ESI+/ESI- |
4.177 | 表儿茶素3-葡萄糖苷 Epicatechin 3-glucoside | 451.1245 | 451.1246 | C21H24O11 | ESI- |
12.84 | 没食子儿茶素-(4α->8)-表儿茶素Gallocatechin-(4α->8)-epicatechin | 593.1301 | 593.1300 | C30H26O13 | ESI- |
8.120/8.120 | 表没食子儿茶素3-O-(3-O-甲基)没食子酸酯Epigallocatechin 3-O- (3-O-methyl)gallate | 473.1069/471.093 | 473.1078/471.0933 | C23H20O11 | ESI+/ESI- |
5.520 | 8-C-抗坏血酸表没食子儿茶素3-O-没食子酸酯8-C-Ascorbyl epigallocatechin 3-O-gallate | 631.0949 | 631.0941 | C28H24O17 | ESI- |
11.430/11.430 | 表茶黄棓灵3-O-没食子酸酯 Epitheaflagallin 3-O-gallate | 553.0969/551.0829 | 553.0977/551.0831 | C27H20O13 | ESI+/ESI- |
8.410 | 表没食子儿茶素-(4β->8)-表儿茶-3-O-没食子酸酯 Epigallocatechin-(4β->8)-epicatechin-3-O-gallate ester | 747.1553 | 747.1556 | C37H30O17 | ESI+ |
儿茶素聚合物 Dimeric,oligomeric and polymeric of catechins(19) | |||||
6.390/6.390 | 聚酯型儿茶素B Theasinensin B | 763.1491/761.1359 | 763.1505/761.1359 | C37H30O18 | ESI+/ESI- |
4.765 | 聚酯型儿茶素A Theasinensin A | 913.1468 | 913.1468 | C44H34O22 | ESI- |
0.807 | 聚酯型儿茶素C Theasinensin C | 609.1249 | 609.1249 | C30H26O14 | ESI- |
6.420/6.420 | 聚酯型儿茶素F Theasinensin F | 899.1665/897.1519 | 899.1665/897.1519 | C44H34O21 | ESI+/ESI- |
7.290 | 新唢呐草素I Tellimagrandin I | 785.0859 | 785.0843 | C34H26O22 | ESI- |
7.450 | 茶氨酸-3-没食子酸酯 Theacitrin-3-gallate | 761.1326 | 761.1348 | C37H28O18 | ESI+ |
7.670 | 乌龙茶素3′-O-没食子酸酯 Oolongtheanin 3′-O-gallate | 883.1357 | 883.1363 | C43H32O21 | ESI- |
9.040 | 茶氨酸C Theacitrin C | 911.1321 | 911.1312 | C44H32O22 | ESI+ |
9.040 | 茶氨酸A Theacitrin A | 759.1204 | 759.1203 | C37H28O18 | ESI- |
9.610 | 茶黄素 Theaflavin | 565.1344 | 565.1341 | C29H24O12 | ESI+ |
11.260 | 茶黄素3-O-没食子酸酯 Theaflavin 3-O-gallate | 715.1309 | 715.1305 | C36H28O16 | ESI- |
10.340 | 茶黄酸 Theaflavic acid | 427.0674 | 427.0671 | C21H16O10 | ESI- |
9.463 | 茶黄素3,3′-双没食子酸酯 Theaflavin 3,3′-digallate | 867.1414 | 867.1414 | C43H32O20 | ESI- |
12.190 | 乌龙茶素 Oolongtheanin | 731.1253 | 731.0124 | C36H28O17 | ESI- |
12.450/12.450 | 脱氢茶黄素 Dehydrotheaflavin | 579.1127/577.0984 | 579.1133/577.0977 | C29H22O13 | ESI+/ESI- |
12.650/12.650 | 茶黄酸盐B Theaflavate B | 717.144/699.137 | 701.1501/699.1355 | C36H28O15 | ESI+/ESI- |
7.210 | 原花青素B2 Procyanidin B2 | 865.1985 | 865.1985 | C45H38O18 | ESI- |
8.970 | 原花青素B4 Procyanidin B4 | 577.1354 | 577.1351 | C30H26O12 | ESI- |
10.610/10.610 | 茶多醌 Theanaphthoquinone | 535.1229/533.1094 | 535.1234/533.1089 | C28H22O11 | ESI+/ESI- |
黄酮和黄酮糖苷Flavone and flavone glycosides(32) | |||||
9.860 | 芦丁 Rutin | 611.1597 | 611.1607 | C27H30O16 | ESI+ |
1.490 | 圣草酚 Eriodictyol | 288.0633 | 288.0628 | C15H11O6 | ESI+ |
9.980/9.980 | 茶黄棓灵 Theaflagallin | 401.0855/399.0719 | 401.0867/399.0722 | C20H16O9 | ESI+/ESI- |
4.170/4.170 | 白矢车菊素 Leucocyanidin | 307.0807/305.0668 | 307.0812/305.0667 | C15H14O7 | ESI+/ESI- |
11.640 | 槲皮素 Quercetin | 301.0353 | 301.0354 | C15H10O7 | ESI- |
5.270/5.270 | 槲皮-3-O-葡萄糖苷 Quercetin-3-O-glucoside | 465.1027/463.0881 | 465.1027/463.0881 | C21H20O12 | ESI+/ESI- |
8.752/8.572 | 槲皮-3-O-半乳糖苷 Quercetin-3-O-galactoside | 465.1026/463.08842 | 465.1028/463.0881 | C21H20O12 | ESI+/ESI- |
11.080/11.150 | 槲皮素3-O-鼠李糖苷 Quercetin 3-O-rhamnoside | 449.1072/447.0932 | 449.1078/447.0933 | C21H20O11 | ESI+/ESI- |
5.920 | 飞燕草素3-O-β-D-(6-O-(E)-对香豆素基)吡喃半乳糖苷 Delphinidin 3-O-β-D-(6-O-(E)-p-coumaryl)galactopyranoside | 610.1332 | 610.1328 | C30H27O14 | ESI- |
5.970 | 花青素3-O-(2-O-β-吡喃木糖基)-β-吡吡喃半乳糖苷 Cyanidin 3-O-(2-O-β-xylopyranosyl)-β- galactopyranoside | 580.1428 | 580.1433 | C26H29O15 | ESI- |
7.030 | 二氢山奈酚 Dihydrokaempferol | 289.0707 | 289.0707 | C15H12O6 | ESI+ |
7.640 | Assamicain A | 915.1629 | 915.1625 | C44H36O22 | ESI- |
7.890 | 二氢槲皮素 Dihydroquercetin | 303.0511 | 303.0510 | C15H12O7 | ESI- |
8.950/8.950 | 杨梅素 Myricetin | 319.0443/317.0302 | 319.0448/317.0303 | C15H10O8 | ESI+/ESI- |
9.090/9.090 | 杨梅素3-O-葡萄糖苷 Myricetin 3-O-glucoside | 481.0976/479.0831 | 481.0976/479.0831 | C21H20O13 | ESI+/ESI- |
9.190/9.190 | 杨梅素3-O-半乳糖苷 Myricetin 3-O-galactoside | 481.0967/479.0829 | 481.0977/479.0831 | C21H20O13 | ESI+/ESI- |
9.190/9.190 | 山奈酚 Kaempferol | 287.0543/285.0404 | 287.0550/285.0404 | C15H10O6 | ESI+/ESI- |
10.450 | 山奈酚-3-O-阿拉伯糖苷Kaempferol-3-O-arabinoside | 419.0747 | 419.0972 | C20H18O10 | ESI+ |
6.483 | 山奈酚-3-芸香苷 Kaempferol-3-rutinoside | 595.1651 | 595.1657 | C27H30O15 | ESI+ |
6.517 | 山奈酚-3-O-葡萄糖苷 Kaempferol-3-O-glucoside | 447.0934 | 447.0932 | C21H20O11 | ESI+ |
6.846 | 山奈酚-3-O-半乳糖苷Kaempferol-3-O-galactoside | 447.0934 | 447.0932 | C21H20O11 | ESI+ |
9.780 | 槲皮素3-木糖-(1->2)-鼠李糖基-(1->6)-葡萄糖苷 Quercetin 3-xylosyl-(1->2)-rhamnosyl- (1->6)-glucoside | 741.1884 | 741.1883 | C32H38O20 | ESI- |
9.880 | 槲皮素3-葡萄糖基-(1->3)-鼠李糖基-(1->6)-半乳糖苷 Quercetin 3-glucosyl-(1->3)-rhamnosyl- (1->6)-galactoside | 771.1989 | 771.1989 | C33H40O21 | ESI- |
10.780 | 山奈酚3-葡萄糖基-(1->3)-鼠李糖基-(1->6)-半乳糖苷 Kaempferol 3-glucosyl-(1->3)-rhamnosyl- (1->6)-galactoside | 755.2041 | 755.204 | C33H40O20 | ESI- |
11.080 | 山奈酚3-鼠李糖基-(1->3)-鼠李糖-(1->6)-葡萄糖苷 Kaempferol 3-rhamnosyl-(1->3)- rhamnosyl-(1->6)-glucoside | 739.2096 | 739.2091 | C33H40O19 | ESI- |
11.140 | 牡荆-2-O-葡萄糖苷 Vitexin-2-O-glucoside | 595.1649 | 595.1657 | C27H30O15 | ESI- |
11.450 | 茶花粉黄酮 Pollenitin | 315.0514 | 315.0510 | C16H12O7 | ESI- |
10.930 | 牡荆素 Vitexin | 433.1129 | 433.1129 | C21H20O10 | ESI+ |
13.740 | 芹菜素 Apigenin | 269.0457 | 269.0455 | C15H10O5 | ESI- |
8.741 | 芹菜素6-C-葡糖基-8-C-阿拉伯糖苷 Apigenin 6-C-glucosyl-8-C-arabinoside | 725.1934 | 725.1934 | C32H38O19 | ESI- |
7.293 | 槲皮素3-O-葡糖苷酸 Quercetin 3-O-glucuronide | 477.0674 | 477.0675 | C21H18O13 | ESI- |
5.078 | 槲皮素3-O-葡糖基-芸香糖苷 Quercetin 3-O-glucosyl-rutinoside | 771.1989 | 771.1989 | C33H40O21 | ESI- |
氨基酸Amino acids(19) | |||||
0.764/0.764 | 精氨酸 Arginine | 175.1189/173.1042 | 175.1190/173.1044 | C6H14N4O2 | ESI+/ESI- |
0.762 | 谷氨酸 Glutamic acid | 148.0604 | 148.0604 | C5H9NO4 | ESI+ |
0.761 | 谷氨酰胺 Glutamine | 145.0618 | 145.0619 | C5H10N2O3 | ESI- |
1.023 | 亮氨酸 Leucine | 132.1019 | 132.1019 | C6H13NO2 | ESI+ |
0.742 | 赖氨酸 Lysine | 147.1128 | 147.1128 | C6H14N2O2 | ESI+ |
1.631 | 哌啶酸 Pipecolic acid | 130.0862 | 130.0863 | C6H11NO2 | ESI+ |
1.049 | 脯氨酸 Proline | 116.0706 | 116.0706 | C5H9NO2 | ESI+ |
0.761/0.761 | 焦谷氨酸 Pyroglutamic acid | 130.0498/128.0353 | 130.0499/128.0353 | C5H7NO3 | ESI+/ESI- |
1.842 | 茶氨酸 Theanine | 175.1077 | 175.1077 | C7H14N2O3 | ESI+ |
5.691 | 色氨酸 Tryptophan | 203.0826 | 203.0826 | C11H12N2O2 | ESI- |
0.812/0.812 | 缬氨酸 Valine | 118.0862/116.0717 | 118.0862/116.0717 | C5H11NO2 | ESI+/ESI- |
1.060/1.060 | 丝氨酸 Serine | 106.0497/104.0353 | 106.0499/104.0353 | C3H7NO3 | ESI+/ESI- |
1.080 | 苏氨酸 Threonine | 120.0654 | 120.0655 | C4H9NO3 | ESI+ |
1.070 | 天冬酰胺 Asparagine | 133.0607 | 133.0608 | C4H8N2O3 | ESI+ |
1.070 | 天冬氨酸 Aspartic acid | 134.0447 | 134.0448 | C4H7NO4 | ESI+ |
1.220 | 蛋氨酸 Methionine | 150.0581 | 150.0583 | C5H11NO2S | ESI+ |
1.060 | 组氨酸 Histidine | 156.0766 | 156.0768 | C6H9N3O2 | ESI+ |
3.990 | 苯丙氨酸 Phenylalanine | 166.0861 | 166.0863 | C9H11NO2 | ESI+ |
1.420/1.420 | 酪氨酸 Tyrosine | 182.0809/180.0666 | 182.0812/180.0666 | C9H11NO3 | ESI+/ESI- |
有机酸Organic acids(7) | |||||
5.950 | 香豆酸 Coumaric acid | 163.0401 | 163.0401 | C9H8O3 | ESI- |
2.320 | 没食子酸 Gallic acid | 169.0142 | 169.0142 | C7H6O5 | ESI- |
5.960 | 咖啡酸 Caffeic acid | 179.0349 | 179.0350 | C9H8O4 | ESI- |
12.110 | 茉莉酸 Jasmonic acid | 209.1185 | 209.1183 | C12H18O3 | ESI- |
4.840 | 泛酸 Pantothenic acid | 218.1034 | 218.1034 | C9H17NO5 | ESI- |
1.130 | 抗坏血酸 Ascorbic acid | 175.0246 | 175.0248 | C6H8O6 | ESI- |
1.646 | 5-没食子酰奎宁酸 5-Galloylquinic acid | 345.0809 | 345.0816 | C14H16O10 | ESI+ |
糖类Sugars(8) | |||||
1.130 | 木酮糖 Xylulose | 149.0455 | 149.0455 | C5H10O5 | ESI- |
7.790 | 苄基β-D-吡喃葡萄糖苷 Benzyl β-D-glucopyranoside | 269.1031 | 269.1031 | C13H18O6 | ESI- |
1.110/1.110 | 麦芽糖 Maltose | 341.1089/343.1234 | 341.1089/343.1235 | C12H22O11 | ESI+/ESI- |
1.070 | 棉子糖 Raffinose | 503.1619 | 503.1618 | C18H32O16 | ESI- |
6.560 | 香豆酰β-D-吡喃葡萄糖苷 Coumaroyl β-D-glucopyranoside | 325.0929 | 325.0929 | C15H18O8 | ESI- |
6.690/7.030 | 阿魏酰-β-D-吡喃葡萄糖苷Feruloyl-β-D-glucopyranoside | 357.1173/355.1034 | 357.1180/355.1035 | C16H20O9 | ESI+/ESI- |
1.170 | 6-O-没食子酰葡萄糖 6-O-galloylglucose | 331.0671 | 331.0671 | C13H16O10 | ESI- |
9.740 | 苯乙基β-D-吡喃葡萄糖苷 Phenylethyl β-D-glucopyranoside | 285.1324 | 285.1332 | C14H20O6 | ESI+ |
酚酸Phenolic acids(5) | |||||
5.810 | 木麻黄素 Strictinin | 633.0733 | 633.0733 | C27H22O18 | ESI- |
7.410 | 4-对香豆酰奎宁酸 4-p-Coumaroylquinic acid | 337.0931 | 337.0929 | C16H18O8 | ESI- |
2.192 | 1-咖啡酰奎宁酸 1-Caffeoylquinic acid | 353.0878 | 353.0878 | C16H18O9 | ESI- |
0.768/0.768 | 奎尼酸 Quinic acid | 193.0706/191.0561 | 193.0707/191.0561 | C7H12O6 | ESI+/ESI- |
3.304 | 原儿茶酸 Protocatechuic acid | 153.0193 | 153.0193 | C7H6O4 | ESI- |
生物碱Alkaloids(3) | |||||
4.990/4.990 | 茶碱 Theophylline | 181.0717/179.0574 | 181.0720/179.0574 | C7H8N4O2 | ESI+/ESI- |
4.978/5.346 | 咖啡碱 Caffeine | 195.0876 | 195.0877 | C8H10N4O2 | ESI+ |
1.018 | 哌啶 Piperidine | 86.0964 | 86.0964 | C5H11N | ESI+ |
核苷和核苷酸Nucleosides and nucleotides(4) | |||||
0.848 | 腺苷酸 Adenosine monophosphate | 346.0558 | 346.0558 | C10H14N5O7P | ESI- |
1.595 | 鸟苷 Guanosine | 284.0989 | 284.0989 | C10H13N5O5 | ESI+ |
2.603 | 1-甲基黄嘌呤 1-Methylxanthine | 167.0563 | 167.0564 | C6H6N4O2 | ESI+ |
5.331 | 甲硫腺苷 Methylthioadenosine | 298.0968366 | 298.0968 | C11H15N5O3S | ESI+ |
激素Hormones(2) | |||||
9.100 | 茉莉酸甲酯 Methyl jasmonate | 225.1477 | 225.1485 | C13H20O3 | ESI+ |
15.380 | 赤霉素A53 Gibberellin A53 | 349.1979 | 349.2010 | C20H28O5 | ESI+ |
其他Others(3) | |||||
8.490 | 淫羊藿次苷B5 Icariside B5 | 389.2159 | 389.2170 | C19H32O8 | ESI+ |
0.769 | N-乳酰基乙醇胺 N-Lactoyl ethanolamine | 132.0666 | 132.0666 | C5H11NO3 | ESI- |
8.260 | 核黄素 Riboflavin | 377.1449 | 377.1456 | C17H20N4O6 | ESI+ |
图2 ‘丹霞2号’红茶5个加工阶段的正(ESI+)、负(ESI-)离子模式OPLS-DA模型得分图 S1:鲜叶采摘;S2:萎凋;S3:揉捻;S4:发酵;S5:干燥。下同。
Fig. 2 The score plots of OPLS-DA model for‘Danxia 2’black tea from the five processing stages S1:Fresh leaves plucking;S2:Withering;S3:Rolling;S4:Fermentation;S5:Drying. The same below.
图3 ‘丹霞2号’相邻红茶加工阶段的差异代谢物分析 红色数字表示上调差异代谢物个数,绿色数字表示下调差异代谢物个数。
Fig. 3 Analysis of differential metabolites for‘Danxia 2’black tea in two adjacent processing stages Numbers marked with red color indicates the number of up-regulated differential metabolites,and those marked green indicates the number of down-regulated differential metabolites.
图6 ‘丹霞2号’红茶五个加工阶段的代谢产物的相关性分析 热图色块代表归一化后的代谢产物相对含量,蓝色代表代谢产物相对含量低,红色代表相对含量高。
Fig. 6 Correlation analysis of metabolites accumulated in‘Danxia 2’tea leaves during black tea processing The heatmap colour blocks represent the relativecontent of metabolite after normalization,blue color represents low level and red color represents high level of metabolite.
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