白兰地是一种以葡萄为原料、经发酵、蒸馏、橡木桶陈酿、调配而成的蒸馏酒,具有独特的香气和口感特征。特别是经过橡木桶的长期贮存,这个过程会持续几个月到几年,甚至数十年,从而给白兰地带来了更多的风味,包括香气以及不挥发物质带来的味觉味感特征。白兰地最早出现于法国干邑地区,并在全球范围内不断流行、发展。目前世界知名白兰地有法国的干邑白兰地及雅文邑白兰地、西班牙的赫雷斯白兰地以及中国的可雅白兰地等[1-2]。
风味是构成白兰地品质的核心要素,与其化学成分密切相关,解析白兰地中微量且种类众多的挥发性化合物和非挥发化合物已成为风味领域多年来的热点之一。目前已经开展了大量关于白兰地中的挥发性化合物的研究,如李元一等[3]通过全二维气相色谱-飞行时间质谱成功鉴定出512种挥发性化合物,并通过香气库筛选出157种潜在的香气活性物质。该团队随后进一步证实内酯类化合物在白兰地的风味中扮演着重要的角色[4]。相对于挥发性组分,对白兰地中的非挥发化合物的研究则相对较少。已发现一部分非挥发的氨基酸、糖类和酚类化合物等,如PETROSYAN[5]通过氨基酸检测仪在白兰地中检测出酪氨酸和苯丙氨酸等23种氨基酸,其总氨基酸的质量浓度为16.23～93.26 mg/L;MART
NEZ等[6]通过液相色谱-示差折光仪器鉴定了白兰地中存在葡萄糖、阿拉伯糖、D-半乳糖醛酸等5种单糖;CANAS等[7]借助液相色谱-二级管阵列检测器发现酚酸的含量随着陈酿时间的延长而增加;该团队随后又总结了白兰地中常见的低分子质量酚类,并介绍了它们在白兰地中感官特性和抗氧化性的作用[8]。国内研究者也对白兰地非挥发化合物展开了一些研究,如吴帅等[9]测定了30款白兰地样品中的酚类化合物,所有样品中均检出没食子酸和鞣花酸。尽管前人已经开展了部分探索,但这些研究大多局限于从几个或一类化合物的角度解释白兰地非挥发性化学组成,而对白兰地非挥发代谢物的整体组成尚未进行全面研究。
代谢组学是一种高通量、高灵敏度、高分辨率的分析方法,它能较全面地分析食品的化学组成,目前已广泛应用于酒精饮料领域。CAO等[10]基于代谢组学方法明确了葡萄酒的化学特征及葡萄品种差异。该方法还被用于探究酒龄和产地对威士忌化学成分的影响,并结合多元统计分析成功预测了威士忌的酒龄和产地[11]。在白兰地中,刘嘉飞等[12]应用代谢组学技术分析了真假干邑白兰地化学组成的差异,并进一步筛选出辨识真假干邑的标记物。
本项研究以3款典型干邑白兰地作为研究对象,采用广泛靶向代谢组学方法探究了干邑白兰地非挥发化合物组成特征,进而筛选并鉴定出不同来源干邑白兰地的差异代谢物。该研究不仅可以丰富白兰地风味化学的理论体系,同时也为生产上进一步调控白兰地风味提供重要的风味导向依据。
1 材料与方法
1.1 材料与试剂
选取市售3款XO等级的干邑白兰地为研究对象(表1),均由烟台张裕集团提供。每款3瓶,共9瓶。在进行化学分析之前,样品于20 ℃恒温避光存放。
表1 干邑白兰地样品信息
Table 1 Information on Cognac brandy samples
酒样编号样品产地级别酒精度/%volXNS轩尼诗白兰地法国干邑XO40MDL马爹利白兰地法国干邑XO40RTM人头马白兰地法国干邑XO40
所使用试剂均为质谱级别。甲醇和乙腈,CNW Technologies GmbH公司;甲酸,Sigma-Aldrich公司;水由Merck Millipore仪器超滤。
1.2 仪器与设备
Heraeus Fresco17离心机,美国Thermc公司;ExionLC AD超高效液相,美国Sxiex公司;4000 Q TRAP高灵敏度质谱,美国Sxiex公司;ACQUITY UPLC HSS T3 column色谱柱,美国Waters公司。
1.3 代谢组学分析
1.3.1 代谢物提取
将200 μL白兰地氮气吹干后,复溶于1 000 μL含有内标(2-氯苯丙氨酸, 1 mg/L)的80%(体积分数)甲醇水溶液。样品随后经过30 s涡旋、4 min均质、30 min冰水浴超声处理后,使用12 000 r/min转速于4 ℃下离心15 min,收集上清液并通过0.22 μm滤膜过滤。在进行LC-MS/MS分析之前,样品在-80 ℃ 保存。
1.3.2 LC-MS/MS分析
参照CHEN等[13]方法,使用配有ACQUITY UPLC HSS T3 C18 column (1.8 μm, 2.1 mm×100 mm)的LC-MS/MS系统测定代谢物。流动相A相为0.1%(体积分数)的甲酸水溶液,B相为乙腈。梯度洗脱程序,设置如下:0～0.5 min 2%B,0.5～10 min 50%B,10～11 min 95%B,11～13 min 95%B,13～13.1 min 2%B,13.1～15 min 2%B。流速:0.40 mL/min,自动进样器温度:4 ℃,柱温:40 ℃,进样量:2 μL。
使用带有离子源(ESI)接口的质谱仪进行分离组分的鉴定。ESI正负离子模式运行,以方便离子阱和三重四极杆扫描。离子源参数如下:离子喷雾电压:+5 500/-4 500 V,气帘:2.41 bar,温度:400 ℃, 离子源气体1:4.14 bar,离子源气体2:4.14 bar,解聚电位:±100 V。三重四极杆扫描作为多反应监测(multiple reaction monitoring, MRM)实验获得,对每个单独的MRM的解聚电位和碰撞能量进行了优化。原始数据过滤、排列和计算均由SCIEX Analyst Work Station软件(1.6.1 版)完成。其保留时间、母离子、子离子、碰撞能量、解聚电位用于定性,数据库源于自建数据库和公共数据库。峰面积用于定量,将数据采用“内标归一”表示其相对含量,其计算如(1)所示:
内标归一化
(1)
1.4 数据处理
主成分分析(principal components analysis,PCA)、层次聚类分析(hierarchical cluster analysis,HCA)和正交偏最小二乘判别分析(orthogonal partial least-squares discrimination analysis,OPLS-DA)均由SIMCA(14.1 版,MSK Data Analytics Solutions,瑞典于默奥)分析。使用IBM SPSS Statistics 22.0进行t检验。通过https://www.bioinformatics.com.cn在线网站绘制化合物类别个数占比图、火山图、热图。自建数据库为上海百趣生物技术有限公司提供,公共数据库指MassBank、KNApSAck、 HMDB、MoTo DB、METLIN。
2 结果与分析
2.1 白兰地非挥发代谢物鉴定
样品中通过UPLC-MS/MS总共鉴定出638种代谢物(附表1,https://doi.org/10.13995/j.cnki.11-1802/ts.037532)。代谢物根据其结构可分为十类(图1),包括酚类(257种,40.28%)、萜类(84种,13.17%)、生物碱类(53种,8.31%)、脂类(39种,6.11%)、氨基酸及其衍生物(36种,5.64%)、有机酸及其衍生物(32种,5.02%)、糖类及其衍生物(29种,4.55%)、核苷酸及其衍生物(21种,3.29%)、醌类(13种,2.04%)和其他类(74种,11.60%)。酚类化合物的数量和含量在白兰地的非挥发代谢物中具有绝对优势,尤其是酚酸及其衍生物、香豆素。萜类化合物的种类较多,以单萜、二萜、倍半萜等不同小类存在于白兰地中。其他类主要有杂环类、植物激素等代谢物。这些化学成分大致代表了白兰地的非挥发性成分,其中大多数化合物是首次在白兰地中发现,且一部分化合物具有味觉贡献、抗氧化作用以及抗肿瘤和抗疟疾等生理活性,如苦味物质4-甲基伞形酮和秦皮乙素[14]、具有抗氧化作用的没食子酸和鞣花酸[8]、具有抗肿瘤作用的杨梅酮等[15]。此外,在3个不同来源干邑白兰地中,除了少数几个特有化合物,其余化合物均在所有样品中检测出,即其非挥发化学差异更多集中在含量,而非种类上。
图1 干邑白兰地代谢物类别及个数占比
Fig.1 The categories and proportions of metabolites in Cognac brandy
附表1 干邑白兰地非挥发代谢物
Table S1 Non-volatile metabolites of cognac brandy
中文名称Compound name大类轩尼诗马爹利人头马脱落酸(+)-Abscisic acid其他4 176.43±1 443.495 364.69±1 172.454 421.43±1 564.85赤霉素A7Gibberellin A7萜类4 204.4±1 997.733 840.68±970.661 699.93±268.16(±)-茉莉酸(±)-Jasmonic acid脂质1 020.07±208.76722.38±428.76851±92.73水杨酸Salicylic acid酚类89 862.6±10 849.5391 850.89±26 806.192 899.63±22 082.29原儿茶酸Protocatechuic acid酚类1 314 452.25±314 773.091 135 065.91±213 204.75856 546.06±160 228.73茉莉酸甲酯Methyl jasmonate脂质20 949.07±4 499.4636 123.32±8 246.1339 602.15±9 969.29染料木素Genistein酚类7 189.05±1 984.946 946.93±1 206.976 737.5±5 169.22白杨素Chrysin酚类6 818.82±6 388.766 793.55±4 151.084 996.68±1 370.53吲哚-3-甲醛Indole-3-carboxaldehyde生物碱65 654.09±13 532.5676 702.24±10 964.8875 459.05±9 746.95金丝桃苷Hyperoside酚类4 447.54±2 784.271 303.4±375.183 716.96±1 834.58异槲皮苷Isoquercitrin酚类7 372.33±3 405.5417 966.1±9 420.938 676.71±4 211.27吲哚-3-乙酸Indole-3-acetic acid生物碱17 147.53±6 730.6412 005.65±7 076.8617 960.13±12 546.48DL-二氢玉米素DL-Dihydrozeatin其他29 027.21±7 313.8819 063.28±10 069.9515 811.55±8 751.26香叶木素Diosmetin酚类5 054.71±2 004.695 126.82±2 441.125 252.33±990.37L-酪氨酸L-Tyrosine氨基酸及衍生物6 122.65±1 425.142 151.84±1 015.232 909.09±1 784.1黄豆黄素Glycitein酚类11 463.03±12 044.179 915.11±3 919.2710 838.73±4 667.54染料木苷Genistin酚类5 452.66±689.786 522.98±1 990.184 539.18±3 592.88牡荆素Vitexin酚类14 877.75±20 643.6614 081.52±9 251.1826 351.61±22 112.28吲哚-丁酸3-Indolebutyric acid生物碱20 110.23±3 051.3516 862.67±3 069.1116 493.59±3 412.53异戊烯基腺嘌呤N6-(delta 2-Isopentenyl)-adenine核苷酸2 230.72±1 293.62 754.88±2 378.147 227.72±4 448.95反式玉米素trans-Zeatin其他2 189.13±820.484 068.25±1 404.333 420.23±629.22顺式玉米素cis-Zeatin其他3 673.21±1 977.523 485.3±1 793.983 595.94±680.79反式玉米素核苷trans-Zeatin-riboside其他1 964.05±691.613 380.86±2 648.591 514.22±487.88油菜素内酯Brassinolide其他3 585.88±2 174.843 571.53±260.4710 226.08±1 950.63异甘草素isoliquiritigenin酚类9 704.87±3 342.4810 701.46±7 668.186 678.01±1 725.63柚皮苷查尔酮Chalconaringenin酚类10 221.75±4 006.8210 267.12±7 015.295 223.54±347.11柚皮素Naringenin酚类7 568.19±599.5819 689.17±7 924.85 901.62±1 607.15根皮素Phloretin酚类7 146.09±4 321.545 098.35±1 265.152 600.61±1 177.6芫花素Genkwanin酚类2 432.51±2 623.992 146.82±1 540.591 578.3±379.7木犀草素Luteolin酚类3 085.19±1 311.623 064.42±1 046.481 747.72±468.97漆黄素Fisetin酚类7 650.61±4 144.114 772.28±1 086.923 163.8±266.22圣草酚Eriodictyol酚类3 719.65±1 979.783 721.93±2 424.454 896.68±2 630.17儿茶素Cianidanol酚类3 748.67±1 406.851 841.85±1 087.262 950.05±713.89花旗松素Taxifolin酚类39 303.56±4 766.8224 231.09±2 528.226 824.73±17 767.28表没食子儿茶素(-)-Epigallocatechin酚类10 160.58±6 171.519 221.36±62223 822.73±24 185(+)-没食子儿茶素Gallocatechin酚类51 005.59±65 182.1237 612.67±54 466.512 803.74±1 821.82芒柄花苷Ononin酚类1 829 622.2±1 007 351.161 207 812.37±323 937.271 568 179.92±241 075.83杨梅素Myricetin酚类5 377.16±1 849.415 661.41±3 507.68 623±2 952.81光甘草定Glabridin酚类2 812.88±2 110.251 045.57±334.782 172±813.29大豆苷Daidzin酚类3 117.48±3 551.322 946.74±1 382.793 038.27±2 128.48黄芩苷Baicalin酚类25 413.62±9 773.518 024.43±1 055.1321 311.98±4 354.74黄豆黄苷Glycitin酚类8 142.6±5 955.3313 280.68±7 337.3411 461.51±15 403.12紫云英苷Astragalin酚类4 827.08±2 179.93 290.83±854.833 359.7±2 566.75木犀草苷Cynaroside酚类5 415.25±2 895.442337.08±1802.143579.32±169.04异荭草素Homoorientin酚类22 126.31±9 255.4215 096.25±6 765.9715 402.75±12 245.09水飞蓟宾Silibinin酚类9 616.79±7 933.584 870.93±2 578.657 263.45±2 962.16夏佛塔苷Schaftoside酚类12070.69±5415.0912848.9±5611.0714 958.05±12 846.53葛根素Puerarin酚类271 826.52±110 916.71172 666.99±37 698.19223 686.54±94 733.89异鼠李素Isorhamnetin酚类2 868.27±1 613.052 313.38±522.1910±0L-脯氨酸L-Proline氨基酸及衍生物68 931.56±16 671.5677 068.3±11 468.6882 203.87±14 025.83L-丝氨酸L-Serine氨基酸及衍生物11 498.01±3 442.1210 758.32±5 321.0512 399±7 818.1L-精氨酸L-Arginine氨基酸及衍生物7 307.86±5 168.89 407.13±5 707.5612 069.69±10 304.73
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马L-天冬酰胺L-Asparagine氨基酸及衍生物11 760.84±9 991.321 831.17±14 307.8911 517.46±10 238.39L-鸟氨酸L-Ornithine氨基酸及衍生物2 169.97±1 581.99892.73±922.552 451.25±1 320.03L-天门冬氨酸L-Aspartic acid氨基酸及衍生物5 530.65±1 731.654 066.87±1 132.314 077.52±1 152.33L-瓜氨酸L-Citruline氨基酸及衍生物18 926.92±7 906.665 594.49±4 697.4313 380.47±14 709.08L-谷氨酸L-Glutamic acid氨基酸及衍生物13 377.66±5 869.9918 540.44±2 999.8316 775.59±6 054.64L-羟基脯氨酸4-Hydroxyproline氨基酸及衍生物13 321.05±7 153.478 595.9±5 042.0411 380.49±582.4L-蛋氨酸L-Methionine氨基酸及衍生物9 271.3±3 763.515 302.62±670.668 886.64±2 753.78L-丙氨酸L-Alanine氨基酸及衍生物11 228.55±2 332.647 493.26±5 762.2415 492.38±9 726.58L-赖氨酸L-Lysine氨基酸及衍生物8 119.96±4 160.916 734.01±5 605.024 451.17±5 570.86L-苯丙氨酸L-Phenylalanine氨基酸及衍生物5 452.15±4 346.269 799.34±5 609.0212 760.98±5 502.083-羟基-3-甲基谷氨酸3-Hydroxy-3-methylpentane-1,5-dioic acid氨基酸及衍生物3 234.27±1 606.651 851.7±980.421 081.94±148.1苹果酸Malic acid有机酸及其衍生物29 034.37±6 143.712 388.56±4 120.9318 293.71±8 495.26月桂酸Lauric acid脂质1 572.51±873.672 430.37±873.992 205.31±350.559(s)-氢过氧基-(9z,11e,15z)-十八三烯酸9(S)-HPOT脂质2 950.01±2 157.212 479.05±1 424.924 599.46±4 125.982-羟基戊二酸2-Hydroxyglutaric acid有机酸及其衍生物20 992.83±12 542.168 432.01±6 422.369 055.52±5 737.08异柠檬酸Isocitrate有机酸及其衍生物2 627.53±364.584 016.7±2 644.832 780.71±510.27恩贝灵Embelin其他578.3±250.09669.48±470.78408.12±189.35松属素Pinocembrin酚类6 461.72±5 480.125 143.18±2 680.836 872.67±4 579.335,7-二羟基-4'-甲氧基异黄酮Biochanin A酚类4 996.57±1 547.864 395.54±1 312.324 291.79±2 003.383,4-二甲氧基肉桂酸3,4-Dimethoxycinnamic acid酚类1 496.13±254.221 608.9±418.92847.72±72.72对羟基苯乙酸4-Hydroxyphenylacetic acid有机酸及其衍生物731.83±249.91 029.93±824.4957.98±37.21泽兰色原烯Eupatoriochromene其他6 322.4±4 998.966 020.24±2 273.48 093.65±1 046.95壬二酸Azelaic Acid脂质16 098.02±4 059.3216 219.3±5 677.8616 596.16±2 487.79棉子糖Raffinose糖类及其衍生物76 642.21±25 446.1760 502.13±32 393.81147 673.36±21 368.02D-山梨糖醇D-Sorbitol糖类及其衍生物197 733.51±64 915.25160 660.77±86 211.9125 368.98±32 812.87DL-4-羟基苯乳酸Hydroxyphenyllactic acid有机酸及其衍生物7 831.31±7 236.815 534.52±1 571.673 644.39±1 846.62肌醇myo-Inositol糖类及其衍生物97 304.64±31 947.7377 564.47±40 770.8373 534.48±29 871.23-呋喃羧酸Furan-3-carboxylic acid有机酸及其衍生物930±580.04774.76±147.841 195.25±241.27邻甲酚o-Cresol酚类8 425.51±3 251.9231 513.66±22 010.815 317.42±11 857.86D-葡萄糖-6-磷酸D-Glucose 6-phosphate糖类及其衍生物155 178.61±3 940.4179 175.16±88 923.2177 002.24±114 445.89D-果糖-6-磷酸D-Fructose 6-phosphate糖类及其衍生物1 488.37±898.551 370.58±740.571 797.2±978.36半乳糖-1-磷酸Galactose 1-phosphate糖类及其衍生物20 210±3 550.9518 137.04±6 417.298 776.78±3 691.02吴茱萸碱Evodiamine生物碱2 029.8±886.911 107.32±354.721 340.51±769.02和厚朴酚Hinokiol萜类687.21±577.411 348.09±936.481 393.75±1 452.423,4-二羟基杏仁酸3,4-Dihydroxymandelic acid酚类49 998.32±35 626.3936 610.92±16 650.0130 632.2±7 960.68亚麻酸Linolenic acid脂质3 293.46±308.444 321.16±2 764.362 747.54±2 637.614-吡哆酸4-Pyridoxic acid其他4 539.61±994.695 618.85±2 610.425 470.54±1 187.06D-麦芽糖D-Maltose糖类及其衍生物13 413 724.62±2 767 427.5322 482 850.56±8 491 341.022 968 131.1±826 396.422-酮丁酸2-Ketobutyric acid脂质44 212.18±8 914.8835 197.09±21 377.0323 973.03±15 944.39D-核糖D-Ribose糖类及其衍生物395 611.5±47 337.71304 826.13±171 977.34208 913.1±121 189.05D-阿拉伯糖D-Arabinose糖类及其衍生物395 611.5±47 337.71304 826.13±171 977.34208 913.1±121 189.05酒石酸Tartaric acid有机酸及其衍生物84 048.21±17 601.6475 085.19±49 496.6674 567.17±34 779.94戊二酸Glutaric acid有机酸及其衍生物4 176.94±644.573 462.48±1 043.533 927.09±1 062.242,3-二羟基苯甲酸2,3-Dihydroxybenzoic acid酚类3 270.7±1 020.754 158.08±1 304.413 142.69±1 698.36龙胆酸Gentisic acid酚类120 499.54±20 694.74110 238.4±23 959.2285 448.48±23 295.3苯基丙酮酸Phenylpyruvic acid有机酸及其衍生物8 241.46±2 975.254 943.28±869.556 364.77±2 318.27莽草酸Shikimic acid有机酸及其衍生物6 881.62±2 587.785 504.2±186.9210±0焦磷酸Pyrophosphate其他8 787.51±2 638.15 521.55±947.283 534.3±748.1葡糖酸内酯Gluconolactone糖类及其衍生物56 414.13±34 827.0533 967.62±12 374.5330 262.5±7 933.21秦皮乙素Esculetin酚类72 399.52±17 285.4647 066.16±16 473.1736 751.96±26 179.872',4',6'-三羟基苯乙酮2',4',6'-Trihydroxyacetophenone其他5 944.68±4 812.612 560.68±481.222 292.46±1 555.783,4-二羟基苯乙酸3,4-Dihydroxyphenylacetic acid有机酸及其衍生物3 223.71±2 149.942 468.16±253.693 791.07±1 855.35脱氧胞苷Deoxycytidine核苷酸1 824.08±711.031 953.74±579.14684.9±357.36
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马2'-脱氧肌苷2'-Deoxyinosine核苷酸10 278.3±9 624.5318 019.37±2 716.4113 740.37±5 373.13鞣花酸Ellagic acid酚类330 443.27±111 005.16285 247.92±57 854.1219 407.27±34 356.4葡萄糖酸Gluconic acid糖类及其衍生物684 559.39±190 072.67736 098.01±217 273.09556 190.65±255 155.782,4-二羟基-6-甲基苯甲酸乙酯Ethyl orsellinate酚类15 000.4±4 529.3530 021.61±12 746.924 065.7±12 547.09胞苷-5-单磷酸Cytidylic acid核苷酸76 782.41±6 313.1869 928.83±29 478.8741 805.86±14 520.69惕格酸Tiglic acid脂质36 977.84±10 686.537 839.51±21 974.3637 416.58±26 010.09D-葡萄糖醛酸D-glucoronic acid糖类及其衍生物307 482.77±34 433.85278 504.55±140 439.95447 877.94±159 329.27葫芦巴碱Trigonelline生物碱22 838.05±17 760.7119 866.93±5 675.1221 369.74±17 950.16对-氨基苯甲酸p-Aminobenzoate有机酸及其衍生物13 158.87±6 503.6714 116.07±11 260.1212 813.8±6 156.27甜菜碱醛Betaine aldehyde其他10 505.64±2 789.4216 139.8±13 777.2226 964.72±31 241.94天麻素Gastrodin酚类3 558.22±1 234.883 028.69±1 123.53 831.22±1 712.842-甲氧基-9-苯基-1H-萘嵌苯-1-酮2-O-Methylanigorufone其他6 047.45±6 793.456 789.1±2 768.982 870.32±2 364.4山奈酚Kaempferol酚类2 050.75±1 049.731 692.91±1 379.342 217.04±821.84矢车菊素Cyanidin酚类2 773.67±1 133.212 366.31±1 026.894 427±810.9巴西苏木素Brazilin酚类6 225.01±613.345 952.66±3 940.374 297.63±1 103.822',3,5,7-四羟基黄酮2',3,5,7-Tetrahydroxyflavone酚类5 903.49±1 660.554 948.08±2 111.146 298.34±3 199.073',4',5,7-四羟基异黄酮Orobol 酚类1 582.29±303.141 987.52±1 215.752 812.67±1 582.84去甲氧基茵陈色原酮Demethoxycapillarisin酚类2 517.96±701.263 610.95±1 927.22 676.91±1 767.72羟基大黄素Citreorosein其他2 845.22±1 451.222 100.33±1 297.363 029.84±1 493.512'-羟基染料木素2'-Hydroxygenistein酚类13 722.66±6 519.5716 403.11±5 110.888 447.84±1 729.21(-)-Sativan(-)-Sativan酚类2 266.29±1 138.723 163.95±1 855.852 770.76±1 709.4对羟苯基丙酸4-Hydroxyphenyl-2-propionic acid有机酸及其衍生物9 899.19±3 248.3611 287.41±6 991.496 250.21±1 519.58L-3-苯乳酸L-3-Phenyllactic acid有机酸及其衍生物13 185.02±1 664.159 846.51±1 304.4517 076.34±4 480.067-甲基黄嘌呤7-Methylxanthine核苷酸9 438.23±7 838.3210 384.8±6 6859 628.35±3 533.71氨基丙二酸Aminomalonic acid有机酸及其衍生物10 328.63±3 226.815 317.43±1 618.8210 280.62±2 148.53麦芽酚Maltol其他2 569 658.41±200 713.032 527 950.95±443 846.691 569 214.31±493 110.641,2,3-苯三酚Pyrogallol酚类288 401.86±83 793.61815 200.88±410 233.821 054 377.21±405 040.755-羟甲基糠醛5-Hydroxymethylfurfural其他10 657 500.59±1 609 920.189 614 713.02±1 099 857.3113 448 624.41±1 384 121.72D-2-氨基丁酸D-alpha-Aminobutyric acid氨基酸及衍生物600 154.57±188 264.05461 069.69±139 432.57507 532.18±84 376.1胆碱Choline其他52 608.2±24 178.4547 148.89±39 374.0437 985.96±18 908.98O-乙酰乙醇胺O-Acetylethanolamine其他162 407.32±23 361.22158 000.62±38 497.69185 467.12±49 797.47间羟基苯甲酸3-Hydroxybenzoic acid酚类20 833.47±15 644.813 194.37±548.7212 305.89±1 696.63原儿茶醛3,4-Dihydroxybenzaldehyde酚类113 144.87±50 261.56112 583.19±20 439.7112 603.96±38 347.363-乙基-1,2-苯二醇3-Ethyl-1,2-benzenediol酚类9 625.47±5 824.6511 244.29±6 586.4518 378.14±12 765.983-乙烯基环己基-3,5-二烯-1,2-醇Styrene-cis-2,3-dihydrodiol其他10 382.37±1 909.4211 015.46±1 299.5110 496.67±1 445.4芝麻酚Sesamol酚类3 507.17±2 236.444 727.12±2 604.236 135.45±1 630.75蛇床子素Osthol酚类11 152.72±7 627.398 697.4±5 171.326 339.13±2 463.59钓樟内酯Linderalactone萜类3 802.84±2 516.033 481.69±2 061.563 589.84±1 806.75苏式-1-C-丁香酚基丙三醇threo-1-C-Syringylglycerol酚类4 326.47±939.712 161.16±385.781 157.19±544.31氧化白藜芦醇Oxyresveratrol酚类1 945.42±1 453.715 744.63±2 828.542 155.38±1 175.03菱叶野决明碱Rhombifoline生物碱3 678.62±241.513 672.53±1 764.984 984.27±1 784.07山药素ⅢBatatasin III酚类3 706.22±2 983.674 638±3 785.336 230.54±2621.292-羟基肉桂酸2-Hydroxycinnamic acid酚类11 484.49±6 558.777 702.63±3 326.918 814.72±4 743.394-异丙基苯甲酸4-Isopropylbenzoic acid有机酸及其衍生物7 925.38±1 850.397 872.73±1 045.658 335.06±3 379.44肉桂酸Cinnamic acid酚类32 534.39±6 546.1714 744.17±1 575.0222 316.95±10 142.663-(2-羟基苯基)-2-丙烯醛3-(2-Hydroxyphenyl)-2-propenal酚类2 072.56±1 340.241 945.61±582.83 782.65±1581.51二氢香豆素3,4-Dihydrocoumarin酚类26 460.34±7 932.7824 328.68±14 557.7527 208.97±12 829.42花椒毒素Xanthotoxin酚类2 447.68±1 103.233 346.13±864.273 153.86±1 625.57异佛手柑内酯Isobergapten酚类1 485.99±1 013.92 695.28±1 108.542 194.18±1 643.17佛手苷内酯Bergapten酚类2 086.97±1 108.824 056.48±2 682.512 328.22±2 843.56-甲氧基当归素Sphondin酚类3 335.84±969.892 898.9±1 056.186 257.86±3 289.11鸟嘌呤Guanine核苷酸6 953±4 123.2216 531.91±6 867.557 656.64±3 025.84邻氨基苯甲酸甲酯Methyl anthranilate其他5 556.79±1 911.712 950.6±1 366.545 654.31±1 988.48
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马L-焦谷氨酸5-oxoproline氨基酸及衍生物11 991±4 697.6326 642.88±27 611.6922 633.45±26 887.08磷酸Phosphoric acid其他1 236 233.05±279 470.141 696 973.82±65 7051.611 314 156.2±93 850.64庚二酸Pimelic acid脂质29 311.45±20 438.546 788.82±45 758.2838 980.52±47 863.07异戊酸乙酯Ethyl isovalerate其他84 517.73±7 192.1780 337.26±32 865.848 243.7±20 523.213-辛醇3-Octyl alcohol脂质28 495.39±15 418.3721 380.75±2 162.2221 469.37±13 039.63腺嘌呤Adenine核苷酸19 410.72±22 923.328 570.72±2 437.3910 230.54±8 068.95N-乙酰苯胺N-Acetylarylamine其他16 686.92±7 661.027 705.71±1 280.948 551.6±2 137.16-羟基烟酸6-hydroxynicotinic acid其他5 278.93±2 994.014 038.49±1 100.135 513.06±2 526.23-羟基吡啶甲酸3-Hydroxypicolinic acid有机酸及其衍生物5 897.79±1 701.733 659.8±2 618.414 175.71±319.15N-乙酰-L-亮氨酸N-Acetyl-l-leucine氨基酸及衍生物2 574.89±740.363 798.5±1 340.454 732.82±2 035.89花椒毒酚Xanthotoxol酚类4 188.12±738.631 915.46±2 149.572 258.49±1 190.76香柑醇Bergaptol酚类3 209.97±318.632 158.89±269.052 634.88±769.25鸭嘴花碱酮Vasicinone生物碱5 472.25±1 163.662 927.12±608.93 911.98±2 842.81α-石竹烯Alpha-caryophyllene萜类51 712.72±17 585.4444 146±11 861.1539 428.43±8 168.92反式石竹烯Beta-caryophyllene萜类36 808.61±9 749.2748 500.9±23 072.3680 151.95±15 915.6N5-(L-1-羧乙基)-L-鸟氨酸N5-(L-1-Carboxyethyl)-L-ornithine氨基酸及衍生物3 975.05±2 017.914 718.21±1 006.1534 20.39±1 601.99鸭嘴花酚碱Vasicinol生物碱3 886.4±1 288.754 141.08±767.194 523.85±1 305.74N-甲基野靛碱N-Methylcytisine生物碱1 870.09±1 241.131 750.49±775.881 596.75±1 706.17松柏醛Coniferylaldehyde酚类1 795 804.87±731 414.83999 033.91±69 232.721 307 502.25±270 530.08甲基丁香酚Methyleugenol酚类4 785.67±2 648.976 840.4±2 054.329 558.12±2 364.618-氨基-7-氧代壬酸8-Amino-7-oxononanoic acid氨基酸及衍生物1 256.56±424.931 322.92±1 040.571 301.11±671.57N-乙酰-L-谷氨酸N-Acetyl-L-glutamic acid氨基酸及衍生物2 588.21±542.362 408.81±664.693 640.72±1 700.35L-高瓜氨酸L-Homocitrulline氨基酸及衍生物36 981.45±9 925.6730 289.86±12 522.5172 878.19±71 111.14犬尿喹啉酸Kynurenic acid生物碱6 872.74±755.259 733.31±5 229.658 385.64±6 386.657-乙氧基香豆素7-Ethoxycoumarin酚类5 380.99±4 095.872 827.09±639.093 997.36±311.36蒿本内酯Ligustilide其他4 673.48±1 488.64 120.07±1 521.264 908.02±1 875.582,5-二甲基-7-羟基色酮Altechromone A其他4 296.99±858.754 894.48±1 731.553 695.38±1 453.61乙酸龙脑酯Bornyl acetate萜类7 155.43±1 035.8810 221.18±1 971.7614 208.5±7 552.61茉莉酸Jasmonic acid有机酸及其衍生物4 321.58±954.687 597.52±1 291.558 667.75±4 126.393-(3,4-Dihydroxy-5-methoxy)-2-propenoic acid3-(3,4-Dihydroxy-5-methoxy)-2-propenoic acid酚类3 510.46±342.095 822.08±3 298.564 486.92±458.82骆驼蓬灵Harmaline生物碱2 245.71±1 762.381 594.42±826.623 107.72±2 257.73二氢赤松素Dihydropinosylvin酚类6 251.03±4 202.593 324.9±2 070.786 241.79±4 335.82黄酮Flavone酚类10 556.24±3 003.527 309.28±2 377.6812 146.42±1 702.18异秦皮啶Isofraxidin酚类82 329±30 532.1111 257.46±9 94291 619.49±19 599.244'-羟基查耳酮2-Benzal-4-hydroxyacetophenone酚类4 120.88±2 5776 684.75±3 246.294 179.56±3 612.17黄烷酮2,3-Dihydro-2-phenyl-4H-benzopyran-4-one酚类8 895.47±4 718.589 638.87±2 462.6812 075.15±7 344.61广藿香酮Pogostone其他9 896.9±1 956.65 189.47±4 048.098 896.74±4 347.12反式-3,4,5-三甲氧基肉桂醇3,4,5-Trimethoxycinnamyl alcohol酚类20381.87±7489.2222 933.34±11 975.7616 515.79±1 130.68N’-甲酰基犬尿氨酸N'-Formylkynurenine氨基酸及衍生物7 811.89±2 039.658 673.19±1 706.478 022.23±3 137.032-羟基-3-羧基苯亚甲基丙酮酸2-Hydroxy-3-carboxybenzalpyruvate有机酸及其衍生物7 156.35±296.529 721.92±12 852.964 729.82±782.16十五烷酸Pentadecanoic acid脂质4 078.14±2 291.973 470.29±330.045 586.26±3 176.43(-)-石杉碱甲(-)-Huperzine A萜类3 423.6±1 294.692 228.27±1 801.471 874.93±1 248.43LusianthridinLusianthridin其他3 269.06±704.663 778.08±2 751.153 024.63±808.55胞苷Cytidine核苷酸15 530.65±11 019.1516 229.89±12 311.7110 124.98±3 254.482-脱氧腺苷Deoxyadenosine核苷酸3 358.89±2 614.092 903.48±735.373 444.22±1 092.325'-脱氧腺苷5'-Deoxyadenosine核苷酸1 629.8±1 673.53828.08±445.093 153.94±2 944.03芹菜素Apigenin酚类19 663.6±5 841.0820 519.25±5 128.515 880.26±7 887.02别欧前胡素Alloimperatorin酚类17 439.37±2 021.2114 961.01±7 384.9915 080.93±5 214.98异欧前胡素Isoimperatorin酚类6 345.55±4 075.552 783.71±1 191.253 724.1±3 305.81天竺葵素Pelargonidin酚类4 608.83±3 569.213 367.63±1 432.583 900.41±1 096.02黄芩素Baicalein酚类9 010.61±6 698.135 698.92±2 481.48842.67±3512.173',4',7-三羟基异黄酮3',4',7-Trihydroxyisoflavone酚类6 853.81±3 106.517 957.03±2 615.899 827.29±87.03
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马4',6,7-三羟异黄酮6,7,4'-Trihydroxyisoflavone酚类2 469.1±606.226 670.04±2 659.234 280.38±1 531.82去甲汉黄芩素Norwogonin酚类5 521.83±2 370.16 807.74±4 011.66 672.16±6 573.21球松素Pinostrobin酚类2 317.38±1 035.686 019.28±3 703.361 942.92±913.99Naringenin chalconeNaringenin chalcone酚类9 817.72±2 604.7411 788.88±1 782.1410 165.53±3 441.639-甲氧基-alpha-拉帕醌9-Methoxy-alpha-lapachone其他6 400.98±7 347.734 362.24±3 040.013 229.57±393.35紫铆因Butein酚类15 531.55±6 431.5912 630.68±3 184.0418 451.97±4 505.96GlycinolGlycinol酚类3 803.94±958.143 277.69±1 849.193 009.86±1 461.783,4',7-三羟基黄烷酮Garbanzol酚类6 552.47±3 670.154 524.84±760.787 755.87±830.28降二氢辣椒碱Nordihydrocapsaicin酚类15 691.01±9 534.0623 472.54±12 230.711 515.01±1 238.68辛可宁Cinchonine生物碱61 153.5±18 733.3848 083.96±9 656.2649 734.54±9 235.519-KODE9-OxoODE脂质16 685.53±7 978.2410 815.51±6 100.8210±09(S)-HPODE(10E,12Z)-(9S)-9-Hydroperoxyoctadeca-10,12-dienoic acid脂质31 479.06±19 328.4130 100.24±16 323.3928 233.55±7 623.64辛可尼丁(-)-Cinchonidine生物碱125 492.56±26 137.5398 356.62±43 220.46100 947.82±6 922.676-姜酚6-Gingerol酚类48 399.36±15 381.1460 492.36±17 953.3944 880.03±6 338.625'-脱氧-5'-甲硫腺苷5'-S-Methyl-5'-thioadenosine核苷酸1 337.76±625.142 609.38±2 216.061 828.95±180.13尿嘧啶Uracil核苷酸5 459.22±1 209.035 500.37±596.565 862.51±2 626.15桑色素Morin酚类42 689.68±17 026.1124 011.18±5 026.4472 704.33±11 002.51槲皮素Quercetin酚类3 894.32±1 866.352 929.71±206.753 592.82±2 217.82飞燕草素Delphinidin酚类13 290.45±2 639.2212 319.24±6 195.4615 237.27±6 334.99羽扇豆醇Lupeol萜类7 023.33±1 952.386 986.12±5 567.4111 684.41±1 003.62蒲公英甾醇Taraxasterol萜类2 889.61±1 856.742 695.44±1 241.162 951.37±2 284.46紫菀酮Shionone萜类11 152.14±3 770.0312 010.48±11 686.4510 128.28±4 677.12MahanineMahanine生物碱2 119.57±852.25651.54±629.76473.22±97.83乙酸苄酯Benzyl acetate其他20 315.9±8 127.7915 562.39±6 077.9314 878.61±6 478.052-甲氧基-4-乙烯基苯酚2-Methoxy-4-vinylphenol酚类36 933.95±18 538.2149 338.31±17 597.8142 950.58±8 374.14左旋香芹酮(-)-Carvone萜类8 922.34±3 320.6210 179.24±1 855.117 849.25±6 772.99薄荷呋喃(R)-Menthofuran萜类17 328.1±13 656.1811 558.14±4 512.7213 195.55±5 829.42氢化肉桂酸Hydrocinnamic acid酚类9 576.54±2 893.497 845.68±1 278.776 026.58±2 156.224-羟基苯丙酮4'-Hydroxypropiophenone酚类15 849.66±1 802.438 763.96±2 896.5512 538.02±2 097.62对羟基肉桂醇p-Coumaryl alcohol酚类3 755.89±756.524 984.65±1 823.552 277.62±1 056.71硬脂酰胺Octadecanamide脂质161 896.14±22 972.1164 261.16±23 948.3185 562.31±27 833.45奇壬醇Kirenol萜类201 217.25±181 154.37245 892.1±77 911.75167 223.71±86 865.69桑辛素 OMoracin O酚类3 321.57±933.541 304.84±1 570.042 137.91±956.214',5,7-Trimethoxyflavone4',5,7-Trimethoxyflavone酚类3 385.89±1 962.214 860.68±3 041.693 285.12±990.59愈创木素Guaiacin酚类2 527.55±264.51 187.69±716.072 012.27±604.05安五脂素Anwulignan酚类6 389.34±3 217.335 445.87±1 210.915 406.23±1 125.24苜蓿素Tricin酚类10 767.62±5 162.6412 592.19±2 447.9911 855.57±6 512.8橙黄决明素Aurantio-obtusin其他9 588.64±4 942.356 633.46±2 916.412 013.03±1 500.61苦番红花素Picrocrocin萜类5 558.41±2 645.344 710.12±3 193.565 875.37±1 558.7对映-16β,17-二羟基-9(11)-贝壳杉烯-19-酸ent-16beta,17-dihydroxy-9(11)-kauren-19-oic acid萜类3 097.09±1 172.962 982.46±713.643 709.55±925.359,10-DHOME9,10-DHOME脂质8 315.41±5 957.4411 713.87±9 071.058 227.3±4 057.358(R)-HPETE8(R)-HPETE脂质24 334.14±15 809.6514 074.64±4 479.4514 888.01±5 118.52PsoralidinPsoralidin酚类17 618.36±8 656.7915 141.32±10 474.4716 951.34±9 707.9甲酰胺核苷酸AICA ribonucleotide核苷酸253 807.03±165 539.99405 861.22±129 341.29289 126.76±103 555.995,7,4'三羟基-6-异戊烯基异黄酮Wighteone酚类529 478.7±593 357.871 041 896±422 725.72593 681.61±314 270.14佛手柑素Bergamotine酚类23 792.23±14 630.4620 824.54±3 676.421 232.02±126.89丹参酮甲酯Methyl tanshinonate萜类13 606.21±11 348.0920 712.98±4 477.5212 850.63±8 725.42甲酸苄酯Benzyl formate其他56 334.09±9840.8534 051.07±351.8263 943.97±24 218.1对丙基苯酚4-Propylphenol酚类44 715.66±23 707.0634 051.07±351.8263 943.97±24 218.1苯甲酸甲酯Methyl benzoate其他5 466.85±3 634.773 246.01±625.616 035.72±2 8583-甲基水杨醛3-Methylsalicylaldehyde酚类7 516.62±2 838.089 362.33±2 559.1212 305.96±859.68
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马乙酸苯酯Phenyl acetate其他45 734.85±18 888.6667 114.03±21 751.0366 011.79±19 085.87大黄酚Chrysophanol其他8 271.06±2 687.624 451.14±1 828.295 463.86±1 881.56S-(苯基乙酰硫代羟肟酰基)-L-半胱氨酸S-(Phenylacetothiohydroximoyl)-L-cysteine氨基酸及衍生物19 134.96±3 784.9310 404.11±3 349.039 853.58±4 071.197,8-二羟基黄酮7,8-Dihydroxyflavone酚类1 692.96±877.495 002.51±3 317.122 610.27±1 016.85状芸香素Chalepensin酚类7 433.58±2 795.894 437.82±2 493.515 158.61±1 615.13芥酸Erucic acid脂质1 283 334.82±1 056 746.251 961 285.08±54 0731.71 372 487.58±674 000.35甜叶菊素ESterebin E萜类1 837.36±1 120.485 170.28±375.591 266.48±306.13(5Z,11Z,14Z)-8,9-二羟基-5,11,14-二十碳三烯酸8,9-DiHETrE脂质974 375.6±1 230 920.871 604 492.01±403 729.171 164 935.87±979 361.634',5,6,7-四甲氧基黄酮4',5,6,7-Tetramethoxyflavone酚类13 461.7±13 547.0715 049.9±11 019.1217 929.47±17 657.281-O-Caffeoylglucose1-O-Caffeoylglucose酚类6 935.49±4 157.372 507.3±1 449.86 211.41±2 562.16甘草异黄酮ALicoisoflavone A酚类1 1731.22±9 465.767 554.17±10 520.121 405.77±454.23迷迭香酸Rosmarinic acid酚类2 943.69±867.083 742.35±1 476.271 572.97±1 352.82豆甾-4-烯-3-酮Sitostenone脂质7 178.71±966.9810 255.65±3 598.786 035.73±2 147.44苯甲酸Benzoic acid有机酸及其衍生物283 292.37±81 264.85179 960.66±26 407.82236 030.4±37 514.44赤藓糖醇Erythritol糖类及其衍生物12 626.48±3 936.0718 705.37±4 866.9113 569.1±1 803.44烟酰胺Nicotinamide生物碱6 800.84±2 842.0127 429.53±30 986.397 805.39±1 380.53DL-1-苯乙醇1-Phenylethanol其他5 897.09±2 484.176 880.42±2 735.849 511.25±2 912.172,4-二甲基苯酚2,4-Dimethylphenol酚类12 425.05±3 317.419 464.67±11 56111 093.25±1 838.2413(s)-氢过氧基-(9z,11e,15z)-十八三烯酸13(S)-HPOT脂质16 153.09±3 945.6915 407.49±4 584.2415 099.75±2 777.12桑辛素 CMoracin C酚类98 098.43±25 837.5477 565.83±30 912.8781 563.81±12 466.52氯化缬草素Valechlorine萜类40 745.43±9 883.9516 133.24±9 982.4624 285.27±3 093.542-羟基丁酸2-Hydroxybutanoic acid有机酸及其衍生物11 965.25±7 776.214 598.34±8 065.5517 130.17±11 386.584-羟基丁酸4-Hydroxybutanoic acid有机酸及其衍生物7 772.36±1 406.39 134.36±6 639.5713 657.35±13 032.38麦芽三糖Maltotriose糖类及其衍生物22 523.91±3 163.9127 377.14±5 248.8137 809.88±3 455.49蔗果三糖1-Kestose糖类及其衍生物21 354.85±3 210.5617 714.7±11 790.2818 212.17±6 820.58乌头酸Aconitic acid有机酸及其衍生物16 735.01±7 667.229 890.03±3 250.9812 510.66±3 555.662-异丙基-3-氧代琥珀酸2-Isopropyl-3-oxosuccinate有机酸及其衍生物6 971.01±1 698.85 620.15±4 715.83 343.64±1 163.2胡桃酮Juglone其他11 155.95±4 922.89 344.07±2 441.6617 283.73±4 302.79L-茶氨酸L-Theanine氨基酸及衍生物7 768.22±3 658.66 492.16±1 706.936 385.36±2 952.58芦竹碱Gramine生物碱10 155.41±649.2913 797.88±8 042.0612 405.17±4 984.436(1H)-Azulenone, 2,3-dihydro-1,4-dimethyl6(1H)-Azulenone, 2,3-dihydro-1,4-dimethyl其他3 243.06±2 179.167 427.78±3 053.864 786.53±2 470.97三甲沙林Trioxsalen酚类4 246.17±377.5211 017.32±2 482.036 874.72±1 679.18愈伤酸Traumatic acid其他7 132.56±1 885.253 709.83±917.515 243.35±915.8优咕吨酮Euxanthone酚类3 144.96±2 083.042 247.48±1 174.821 239.59±625.792'-脱氧尿苷2'-Deoxyuridine核苷酸20 405.06±8 772.0327 105.31±4 568.4211 056.36±3 395.74美鼠李苷 ACascaroside A其他8 292.16±3 472.865 376.35±4 089.419 488.33±3 458.96葡萄糖基甘草苷Glucoliquiritin酚类8 292.16±3 472.865 376.35±4 089.417 147.02±4 262.93水黄皮素Karanjin酚类21 455.93±2 544.0216 149.2±5 811.1113 531.59±9 010.8外消旋12-氧代植物二烯酸12-OPDA脂质3 979.32±265.244 425.61±263.887 760.07±1 300.14乳糖醛酸Digalacturonic Acid糖类及其衍生物6 597.08±1 667.2412 258.93±7 518.487 702.43±2 632.68西瑞香素Daphnoretin酚类3 663.96±909.842 634.83±1 081.557 026.65±4 179.75洒维宁Savinin酚类1 802.16±588.353 979.05±3 732.282 794.84±1 342.57石竹素Caryophyllene oxide萜类81 525.15±23 024.6377 600.12±4 133.2886 513.81±27 879.563-羟基香豆素3-Hydroxycoumarin酚类17 185.47±3 095.5117 352.24±6 617.6624 736.19±9 747.13桂酸甲酯Methyl cinnamate酚类14 178.92±5 712.2314 528.82±5 099.6916 111.37±2 066.69大蒜素Allicin其他14 724.56±5 351.0710 317.74±5 280.1111 735.84±5 467.991-二十八烷醇1-Octacosanol脂质36 746.5±12 247.4964 334.62±25 711.4555 535.55±18 745.87α-香附酮alpha-Cyperone萜类21 241±3 951.3214 822.21±7 034.9116 458.91±7 138.91甜椒醇Capsidiol萜类11 690.35±6 561.689 921.69±2 211.89 619.05±1 352.32γ-L-谷氨酰-L-丙氨酸gamma-Glutamylalanine氨基酸及衍生物5 958.72±1 869.526 395.09±4 197.016 268.95±877.21
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马乙酸4-甲基伞形酯4-Methylumbelliferyl acetate酚类4 709.02±359.849 051.93±4 630.328 401.32±2 439.6缬草醛Baldrinal萜类7 272.69±5 315.553 864.14±2 352.387 664.59±5 275.91马兜铃对酮Aristolindiquinone其他23 425.99±9 553.6132 822.69±20 408.9726 246.45±10 554.46香附烯酮Cyperotundone萜类29 507.18±7 788.6716 056.66±2 204.1711 215.85±1 087.66乙酸橙花酯Nerylacetate萜类8 628.73±1 525.9310 401.38±2 712.248 716.74±2 014.61芦丁Rutin酚类4 140.49±3 054.126 307.52±2 001.13 672.53±1 015.77橙皮苷Hesperidin酚类3 038.51±529.541 329.63±1 137.262 746.26±615.6新橙皮苷Neohesperidin酚类2 347.85±1 179.131 329.63±1 137.262 346.81±1 015.05槲皮素-3-O-新橙皮苷Quercetin 3-O-neohesperidoside酚类2 976.68±3 817.561 486.59±1 447.462 431.58± 216.32蔗糖Sucrose糖类及其衍生物2 604 796.42±1 224 878.626 485 156.66±2 489 553.321 364 389.22±1 243 596.73prephenic acidPrephenate有机酸及其衍生物3 050.06±1 175.372 833.54±1 289.712 417.01±1 458.32松油基乙烯基单甲醚(E)-3-Hydroxy-5-methoxystilbene酚类10 862.7±6 611.696 784.94±7 198.5515 285.72±8 232.113-硝基-L-酪氨酸3-Nitro-L-tyrosine氨基酸及衍生物20 475.03±19 995.622 264.18±2 903.1114 005.22±16 703.69肉豆蔻油酸Myristoleic acid脂质15 402.19±3 866.2813 043.99±8 268.3410 487.48±1 979.07去氧拉巴醌Deoxylapachol其他16 155.49±5 198.5118 213.18±11 231.3229 796.89±10 517.78sn-甘油-3-磷酸胆碱Glycerophosphocholine糖类及其衍生物36 797.38±20 988.2251 975.56±13 186.2554 359.31±5 158.75葡萄糖-1-磷酸Glucose 1-phosphate糖类及其衍生物724 804.3±310 842.75611 869.17±305 132.29589 420.24±44 060.12甘露糖-6-磷酸Mannose 6-phosphate糖类及其衍生物34 437.02±17 589.4838 703.3±6 342.632 138.79±3 065.9桉叶油醇Cineole萜类60 674.56±45 116.7142 610.8±17 228.91125 382.49±91 421.24丁香醇Syringol酚类15 545.85±14 659.7414 455.65±11 430.9822 613.75±7 557.54(S)-(-)-紫苏醇(S)-(-)-Perillyl alcohol萜类183 834.44±39 759.94186 512.09±55 883.32225 630.84±84 657.094-异丙基甲苯p-Cymene萜类39 132.15±14 301.8728 852.78±4 324.2730 282.72±4 805.8扁桃酸Mandelic acid酚类86 799.49±26 317.783 709.28±22 845.2863 995.54±17 940.84-烯丙基苯酚Chavicol酚类26 671.96±19 309.5925 009.99±2 221.4127 524.53±10 334.85β-倒捻子素Beta-mangostin酚类5819.02±4332.948026.91±2774.217 683.99±3 763.49(+)-乐园树酮(+)-Glaucarubinone萜类3771.58±1414.554 812.15±3 915.843 850.1±2 718.97丹酚酸ASalvianolic acid A酚类3 433.28±1 346.171 752.03±829.433 306.6±1 106.69茴蒿素Alpha-Santonin萜类27 038.47±18 660.7711 413.73±5 573.3814 540.26±11 292.5乙酰色氨酸Acetyl tryptophan氨基酸及衍生物3 462.25±876.079 194.13±9 245.7810 555.65±9 242.9刺桐碱Hypaphorine生物碱4 771.28±2 395.148 564.31±3 615.0111 649.99±9 938.05日本前胡醇Decursinol其他4 723.96±807.823 459.14±1 840.244 924.13±1 637.86叶黄制菌素Xanthatin萜类2 470.64±314.191 833.8±695.812 852.9±1 787.76姜黄醇酮Curcolone萜类2 630.28±879.831 833.8±695.812 852.9±1 787.763-没食子酰基奎宁酸3-Galloylquinic acid酚类10 863.52±4 632.9113 561.52±2 978.5217 632.8±8 103.06母菊薁Chamazulene萜类6 010.73±839.923 672.8±1 548.756 201.61±738.95没食子酸甲酯Methyl gallate酚类32 207.54±3 953.6333 062.62±20 598.1633 740.91±7 031.64D-木酮糖D-Xylulose糖类及其衍生物58 017.77±16 391.0247 984.32±2 831.8233 412.11±8 065.14肉桂醛Cinnamaldehyde酚类4 834.46±378.515 713.06±4 374.24 478.18±1 992.56氧杂蒽酮I9-Hydroxycalabaxanthone酚类7 137.58±2 948.349 723.98±10 254.023 960.5±1 498.07赝靛黄素Pseudobaptigenin酚类10±04 126.2±2 662.683 223.16±1 817.45青蒿素Artemisinin萜类492 467.44±150 726.54482 695.04±92 315.65369 788.94±6 418.6丹参新酮Miltirone萜类3508 974.3±604 215.363 111 934.27±753344.653 029 849.27±495 552.28没食子酸辛酯Octyl Gallate酚类62 654.43±28 547.3262 273.12±39 489.8248 882.1±6 455.53AllysineAllysine(6-Oxo DL-Norleucine)氨基酸及衍生物36 988.74±18 813.2426 343.64±5 260.2220 294.47±9 528.69土木香内酯Alantolactone萜类16 409.3±2 682.6724 127.14±12 812.1830 142.7±25 879.52异土木香内酯Isoalantolactone萜类6 982.56±1 772.3910 505.39±3 425.5128 701.33±5 523.45英西卡林Encecalin其他7 334.85±3 336.719 033.21±3 223.6611 840.69±5 372.63木香烃内酯Costunolide萜类8 669.26±2 161.213 635.79±12 024.995 923.84±2 468.7二氢醉椒素Dihydrokavain其他8 347.11±1 885.787 700.06±4 495.697 406.99±3 423.78柳杉二醇11-鼠李糖苷Cryptomeridiol 11-rhamnoside萜类6 411.86±2 128.695 731.63±2 561.852 900.87±358.43麦芽四糖Maltotetraose糖类及其衍生物16 022.83±19 155.7819 934.66±3 147.712 198.71±5 631.95水苏糖Stachyose糖类及其衍生物16 745.49±18 272.1119 934.66±3 147.712 198.71±5 631.95(-)-表阿夫儿茶精(-)-Epiafzelechin酚类3 692.81±2 615.21 875.88±1 199.141 906.82±830.06
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马雏菊叶龙胆酮Bellidifolin酚类4 371.93±2 162.2510±010±0蒲公英甾酮Taraxasterone萜类3 334.4±1 128.43 046.84±556.442 291.25±1 299.77N-甲酰蛋氨酸N-formylmethionine氨基酸及衍生物5 328.15±2 888.14 267.79±1 484.023 599.78±1 418.39莱菔硫烷Sulforaphane其他7 530.3±3 129.355 805.34±1 317.177 628.42±4 337.49对甲苯酚p-Cresol酚类21 562.04±15 736.6123 236.03±11 382.3414 160.35±2 090.67苯乙酰甘氨酸Phenylacetylglycine氨基酸及衍生物10 891.2±7 601.66 816.52±2 963.076 527.5±1 042.96龙胆黄碱Gentioflavin生物碱13 440.3±6 875.875 293.88±1 360.648 400.95±3 075.89番荔枝碱(-)-Anonaine生物碱3 022.04±1 469.133 233.1±855.141 565.74±746.46咖啡因Caffeine生物碱1 527.56±971.733 667.56±3 282.973 793.58±1 640.69阿魏酸Ferulic acid酚类2 064.76±1 225.143 964.59±347.014 202.51±1 263.59(-)-白雀木醇L-Quebrachitol糖类及其衍生物8 601.98±1 075.5315 126.59±3 212.614 446.73±7 809.015-羟基松柏醛5-Hydroxyconiferaldehyde酚类8 601.98±1 075.5311 846.83±2 869.4714 446.73±7 809.01D-松醇D-Pinitol糖类及其衍生物6 872.77±2 038.036 288.06±4 143.749 116.59±1 363.523-羟基-4-甲氧基肉桂酸Isoferulic acid酚类15 859.58±7 155.3516 886.45±13 143.1710 186.03±5 366.6咖啡酸甲酯Methyl caffeate acid酚类24 111.32±11 868.2725 529.12±4 534.6829 763.04±3 806.19NeocnidilideNeocnidilide其他8 521.19±2 666.226 333.55±1 384.5811 282.56±5 452.37对羟基苯甲酸丁酯Butyl 4-Hydroxybenzoate酚类3 880.32±865.716 361.72±1 507.394 255.91±2 866.76石蒜碱Lycorine生物碱2 376.95±1 092.311 906.92±669.311 722.55±251.46麻醉椒碱Pipermethystine生物碱5 848.91±4 593.634 197.88±1 586.66 750.31±1 149.88芒果苷Mangiferin酚类2 757.34±2 157.944 607.08±889.081 252.34±603.15鱼藤素Deguelin酚类3 250.83±1 978.564 235.87±2 043.984 507.9±4 516.96小构树醇AKazinol A酚类33 893.49±32 399.9421 691.74±24 443.535 325.22±18 145.78可可碱Theobromine生物碱27 536.14±21 322.6518 759.08±11 956.2161 163.82±21 697.23茶碱Theophylline生物碱2 682.86±1 228.532 651.3±731.313 584.51±1 230.53异肌醇Inositol糖类及其衍生物2 239.21±341.471 838.98±222.221 238.96±478.33松柏醇Coniferyl alcohol酚类2 336.72±810.972 792.58±1 550.152 469.41±1 153.67咖啡酸Caffeic acid酚类7 522.12±1 493.926 614.77±3 842.549 589.32±2 493.944-羟基-3- 甲氧基扁桃酸Vanillylmandelic acid酚类22 245.65±3 964.7411 054.12±2 332.8221 969.42±2 781.05对羟基苯甲酸丙酯Propyl paraben酚类8 313.6±2 350.199 941.51±2 283.0916 769.46±7 475.58槲皮苷Quercitrin酚类7 015.21±3 392.0910 157.16±3 820.446 962±4 073.93甘草次酸(α型)18alpha-Glycyrrhetinic acid萜类3 264.27±1 059.31 796.82±1 026.442 379.5±1 326.62甘草次酸(β型)Glycyrrhetinic acid萜类8 142.19±1 648.673 672.09±917.272 959.29±894.4灵芝酸 JbGanoderic acid Jb萜类10 503.92±4 244.174 223.29±1 701.217 729.18±3 115.413-氧代坡模酸3-Oxopomolic acid萜类8124.78±6287.526 013.7±4 705.3514 352.94±2 616.5911-酮基-β-乳香酸11-Keto-beta-boswellic acid萜类5 022.36±646.144 733.11±3 242.55 020.91±1 035.81秦皮甲素Esculin酚类5 915.63±1 841.2611 282.25±4 763.3315 780.02±5 790.97去甲黄腐醇Desmethylxanthohumol酚类10 631.66±1 553.846 165.83±941.167 711.59±5 367.82三甲基芹菜素Trimethylapigenin酚类1 757.71±1 255.072 904.41±2 577.784 392.62±36.58桑橙素Maclurin酚类5 184.98±3 030.092 304.67±586.534 205±2 312.72AgrocybenineAgrocybenine生物碱5 563.45±3 738.656 894.22±6 341.878 822.85±2 669.01滨蒿內酯Scoparone酚类12 070.28±7 103.6414 508.62±1 381.4716 889.22±8 011.21α-鸢尾酮alpha-Irone萜类10 560.77±5 706.711 113.63±1 939.911 593.87±4 326.213-甲氧基-4,5-亚甲基二氧基肉桂醛3-Methoxy-4,5-methylenedioxycinnamaldehyde酚类12 807.87±5 117.2711 617.06±2 913.148 415.28±2 621.91一叶萩碱Securinine生物碱10 538.31±2 605.8513 042.96±1 488.9614 230.25±6 881.02麦珠子酸Alphitolic acid萜类4 324.56±3 302.6617 108.08±25 959.882 875.62±1 269.5Lucidumol ALucidumol A萜类3 701.21±2 579.112 091.43±18 051.073 718.61±634.333-羟基-苯乙酸3-Hydroxyphenylacetic acid酚类28 490.22±5 442.7121 364±7 20326 133.62±17 355.464-(乙氧基甲基)苯酚4-(Ethoxymethyl)phenol酚类316 529.11±94 554.11269 194.85±14 139.15294 649.24±37 838.63香兰素Vanillin酚类2 748 812.64±48 4921.282 541 210.7±447 269.34306 0521.83±428 723.613-(4-羟基苯基)-1-丙醇3-(4-Hydroxyphenyl)-1-propanol酚类11 261.38±3 008.048 878.24±3 009.066 616.06±3 360.75北美芹素(+)-Pteryxin酚类62 455.64±7 582.6754 454.17±6 484.9562 563.67±16 685.91反式-异扁柏脂素trans-Hinokiresinol酚类5 879.63±3 010.6911 134.73±637.594 607.06±1 333.63甜没药萜醇氧化物ABisabolol oxide A萜类23 834.3±13 651.9121 236.08±7 668.5131 548.05±5 215.19
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马肉桂酸苄酯Benzyl cinnamate酚类8 007.05±1 630.987 180.6±2 991.129 089.51±4 716.94无根藤辛Cassythicine生物碱3 558.59±2 559.813 167.49±1 044.782 092.88±527.41D-焦谷氨酸Pyrrolidonecarboxylic acid氨基酸及衍生物26 805.05±16 768.8418 109.56±4 056.8514 166.01±10 192.834-β-D-葡萄糖基-1,3,7-三羟基呫吨酮Lancerin酚类4 301.92±701.210±05 099.73±5 834.58忍冬苷Lonicerin酚类2 501.19±579.432 445.08±1 633.53 985.07±2 022.43枸橘苷Poncirin酚类3 305.5±2 030.642 162.25±928.662 616.06±2 219.41氯化天竺葵色素苷Pelargonidin-3,5-O-diglucoside chloride酚类2 350.71±949.632 518.32±1 000.088 078.69±4 378.23'-甲氧基芹菜苷Chrysoeriol 7-apiosylglucoside酚类2 212.52±833.364 071.94±2 073.293 720.28±4 326.11灵芝酸HGanoderic acid H萜类5 915.47±2 227.234 342.65±3 587.2416 705.08±8 576.23莴苣苦素Lactupicrin萜类2 380.87±1 383.251 150.53±831.1964.79±155.68异曼果斯廷1-Isomangostin酚类2 020.28±878.214 575.46±1 716.061 628.19±219.69DesoxypeganineDesoxypeganine生物碱1 390.94±478.213 393.13±520.25999.6±199.95四氢姜黄素Tetrahydrocurcumin酚类4 852.33±1 309.374 200.07±496.743 338.03±923.81牛蒡子苷元Arctigenin酚类6 006.26±1 624.774 838.13±1 921.3910 226.66±5 823.82丁香苷Syringin酚类2 876.1±870.634 120.52±1 892.452 653.96±562.96马钱苷Loganin萜类1 387.06±805.774 175.01±1 566.754 047.57±2 232.52姜黄素Curcumin酚类1 690.83±349.514 369.42±4 164.253 824.1±2 162.21帽柱木碱Mitraphylline生物碱14 147.73±5 274.469 371.21±4 683.058 095.88±4 857.61环姜黄素Cyclocurcumin酚类3 117.91±2 898.354 568.81±2 942.711 307.81±583.492-羟基呫吨酮2-Hydroxyxanthone酚类4 666.19±2 604.32 593.89±1 600.633 839.2±980.395-羧基香草酸5-Carboxyvanillic acid酚类3 752.47±2 812.632 248.36±787.013 760.45±1 714.43C-藜芦酰乙二醇C-Veratroylglycol酚类18 692.94±20 025.399 747.75±4 971.4210 779±5 699.9京尼平苷酸Geniposidic acid萜类1 378.22±1 192.66830.22±468.311 117.42±883.16异柿醌Isodiospyrin其他8 578.71±8 891.265 472.96±2 832.392 012.55±680.74DihydrozeatinDihydrozeatin其他1 251.69±512.62 220.58±1 691.991 204.58±189.76嘌呤碱Purine核苷酸2 880.73±1 299.992 503.03±1 705.312 410.01±1 507.031,2,4-三甲基苯1,2,4-Trimethylbenzene其他32 553.62±19 055.3428 989.79±8 334.3658 303.61±12 296.87异黄蝶呤Isoxanthopterin核苷酸8 197.32±3 598.047 220.17±1 271.983 376.52±262.14β-紫罗兰酮beta-Ionone萜类32 480.04±9 924.0224 650.88±6 778.9327 399.41±7 452.29香芹基乙酸Carvacryl acetate萜类19 041.79±878.918 446.68±10 523.1514 533.3±7 015.28天竺葵素-3-O-葡萄糖苷Pelargonidin-3-O-glucoside酚类1 078.77±1 067.832 294.46±50.061 829.96±440.98异牡荆黄素Isovitexin酚类14 877.75±20 643.663 262.47±754.5213 061.92±14 410.39阿福豆苷Afzelin酚类3 472.5±1 672.512 462.55±535.992 164.98±1 209.27菜油甾醇Campesterol脂质132 897.99±47 245.47131 089.34±18 509.41129 836.36±54 069.05DL-甘油酸Glyceric acid糖类及其衍生物147 863.39±27 049.2920 9771.26±99 833.3880 636.43±18 707.69槟榔次碱Arecaidine生物碱8 366.6±2 603.387 921.28±4 431.237 785.4±4 979.11柏木双黄酮Cupressuflavone酚类2 130.3±1 109.652 680.67±526.31 337.33±1 314.64紫草酸Lithospermic acid酚类7 050.43±5 143.091 787.05±437.725 061.73±2 044.45酸藤子醌Rapanone其他14 276.41±4 694.5314 537.5±6 102.8210 136.33±5 127.858-姜酚8-Gingerol酚类1 628.5±1 489.313 141.03±1 117.32 569.3±1 331.06日当药黄素Swertiajaponin酚类3 784.82±647.692 018.79±484.833 040.25±401.85芍药花青素-3-葡萄糖苷Peonidin-3-glucoside酚类4 387.76±3 663.693 273.01±2 107.372 856.54±2 239.94杨梅苷Myricitrin酚类8 460.55±5 247.288 642.99±3 301.44 770.17±2 551.39六羟黄酮Quercetagetin酚类80 857.38±66 691.5348 284.04±28 686.8848 040.12±44 946.88GossypetinGossypetin酚类4 711.96±1 520.36 215.66±4 600.474 794.17±2 319.02异甘草苷Isoliquiritin酚类1 334.13±875.781 084.74±340.142 038.61±376.343,4,5-三甲氧基苯甲酸乙酯Ethyl 3,4,5-trimethoxybenzoate其他8 366.35±6 745.262 174±564.314 097.75±2 534.83牡荆甙Agnuside萜类13 201.62±4 785.5315 729.12±3 817.3311 870.07±4 751.39豆甾醇Stigmasterol脂质34 686.58±19 44353 287.82±7 525.5739 902.8±18 171.69alpha-菠菜甾醇alpha-Spinasterol脂质21 668.58±29 673.785 752.79±2 109.7519 568.78±9 452.82缬草烯酸Valerenic acid萜类11 605.27±2 955.7829 193±25 246.2411 813.3±3 175.58蜂斗菜内酯ABakkenolide A萜类19 558.63±8 384.6221 386.48±15 479.7727 567.51±16 555.641'-乙酰氧基胡椒酚乙酸酯1'-Acetoxychavicol acetate其他25 582.4±6 898.8321 720.54±2 084.5529 321.55±4 793.78
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马AngustifolineAngustifoline生物碱2 646.58±390.574 421.74±2 214.542 750.38±2 083.67N-对香豆酰基腐胺N-p-Coumaroyl putrescine酚类3 753.09±2 366.925 202.38±4 209.484 893.26±2 842.7β-木香酸beta-Costic acid萜类6 048.41±3 367.44 693.65±2 740.066 874.44±1 078.51桑呋喃AMulberrofuran A其他1 703.99±458.312 558.95±1 532.862 892.38±1 450.31香草酸Vanillic acid酚类4 288.74±2 589.93 815.61±451.425 770.22±612.364-羟基扁桃酸p-Hydroxymandelic acid酚类15 587.62±5 083.0320 682.87±1 839.1831 625.51±5 927.38β-谷甾醇Beta-Sitosterol脂质11 014.61±7 426.919 788.87±1 703.529 272.58±4 897.46对羟基苯乙酰基甘氨酸p-Hydroxyphenylacetylglycine氨基酸及衍生物6 824.2±2 202.058 097.71±3 743.27 472.51±2 561.65cis-2-Methylaconitatecis-2-Methylaconitate有机酸及其衍生物4 756.5±2 441.997 331.95±6 176.596 322.39±438.29骆驼蓬碱Vasicine生物碱2 818.53±1 618.863 672.44±1 186.342 606.85±1 011.213-正丁烯基苯酞3-Butylidenephthalide其他10 542.12±2 865.648 930.66±4 114.188 928.27±2 333.922,6-二甲基-7-辛烯-2,3,6-三醇2,6-Dimethyl-7-octene-2,3,6-triol脂质791±696.02951.75±1 127.281 415.27±626.3Pseudouridine 5'-phosphatePseudouridine 5'-phosphate核苷酸82 545.87±11 516.5367 193.61±21 830.03287 762.65±89 538.8羟基(4-羟基-3-甲氧基苯基)乙醛3-Methoxy-4-hydroxyphenylglycolaldehyde酚类9 566.77±3 058.095 875.67±2 597.8610 722.37±7 538.16哈尔满碱Harman生物碱6060.84±3984.458003.15±1358.376979.18±1500.76二氢松柏醇Dihydroconiferyl alcohol酚类3 865.07±469.428 090.85±5 524.886 058.06±2 059.19LeucodopachromeLeucodopachrome生物碱19 718.2±9 060.0323 124.56±12 646.9918 936.59±4 281.98愈创木酚Guaiacol酚类285 534.24±176 860.36194 844.06±54 472.55199 717.93±89 835.01黃尿酸Xanthurenic acid生物碱3 187.62±1 051.36 231.51±2 242.554 174.46±1 419.43甲氧基吲哚乙酸Methoxyindoleacetic acid生物碱4 783.46±1 142.962 323.08±257.381 901.94±936.32去甲基雏菊叶龙胆酮Desmethylbellidifolin酚类2 243.74±869.371 045.34±774.252 152.23±1 880.13芒果苷元Norathyriol酚类2 237.38±940.81 045.34±774.252 152.23±1 880.13棕榈酸Palmitic acid脂质397 744.39±130 002.89380 738.18±160 262.34404 696.54±153 936.24甘草素Liquiritigenin酚类2 620.11±886.893 778.73±1 053.552 799.27±683.763,9-二羟基紫檀碱3,9-Dihydroxypterocarpan酚类4 674.33±1 114.074 968.68±2 010.026 361.32±1 534.86橄榄苦苷Oleuropein萜类4 968.07±4 158.73 217.91±429.652 418.5±1 469.78正己酸乙酯Ethyl caproate其他1 014 742.1±474 617.49961 380.46±371 731.34638 070.38±403 860.754-甲基-5-噻唑乙醇4-Methyl-5-thiazoleethanol其他10±09 674.27±2 230.6513 158.23±1 050.15水苏碱Proline betaine生物碱13 827.26±9 555.3812 326.49±1 082.149 718.98±2 329.26二氢麻醉椒苦素Dihydromethysticin其他47 386.86±20 864.0545 284.03±23 793.0643 972.08±5 394.01毛茶碱Antirhine生物碱6 273.24±4 194.595 240.43±1 031.24 924.27±969.738-甲基壬-6-烯酸8-Methylnonenoate脂质29 673.31±13 991.5840 661.74±12 727.9833 473.08±15 281.61氧化芳樟醇2-(2-Hydroxy-2-propyl)-5-methyl-5-vinyltetrahydrofuran萜类20 639.4±5 824.0436 889.9±21 183.9426 761.04±7 606.97乙酸糠酯Furfuryl acetate其他56 823.75±50 459.8639 941.08±27 196.0342 687.02±35 090.12硬脂酸Stearic Acid脂质24 940.15±7 550.5516 387.12±5 888.9324 788.03±6 765.918-乙酰氧基松脂醇8-Acetoxypinoresinol酚类1 983.61±581.622 191.56±1 774.831 349.65±741.32新木姜子素Neolitsine生物碱3 213.37±1 303.873 123.58±1 356.082 550.49±1 703.57D-甲基乌药碱N-Methylcoclaurine生物碱4 100.34±1 814.016 431.99±2 469.877 890.42±4 488.72Avenanthramide AAvenanthramide A酚类6 664.89±5 122.467 261.14±633.764 260.8±2 035.03N-对香豆酰真蛸胺N-p-Coumaroyloctopamine酚类4 543.26±2 273.268 610.1±4 565.148 835.36±1 251.51猕猴桃碱(S)-Actinidine萜类7 530.09±4 116.843 741.79±906.523 983.66±1 227.853-(Carboxymethylamino)propanoic acid3-(Carboxymethylamino)propanoic acid氨基酸及衍生物4 417.31±4 125.833 562.26±1 026.293 553.68±1 793.09哌啶Piperidine其他2 157.21±1 031.443 626.92±1 011.512 816.86±1 313.01alpha-己基肉桂醛alpha-Hexylcinnamaldehyde酚类6 407.68±5 015.155 685.92±463.443 326.09±420.942-羟基吡啶2-Hydroxypyridine其他3 430.6±1 410.553 999.85±1 839.374 340.97±1 479.33异戊胺3-Methyl-1-butylamine其他21 987.7±12 796.4819 763.88±9 349.3520 059.16±16 691.18奎宁酸Quinic acid有机酸及其衍生物3 477.16±609.934 776.58±2 942.616 851.47±342.617-(4-羟苯基)-1-苯基-4-庚烯-3-酮7-(4-Hydroxyphenyl)-1-phenyl-4-hepten-3-one其他193 930.37±80 771.13127 159.4±27 990.67148 893.6±36 229.82槲皮素3-O-葡萄糖酸苷Quercetin-3-O-glucuronide酚类1 635.79±597.997 116.47±4 561.653 636.51±612.28巴豆苷Crotonoside核苷酸17 203.62±6 997.0120 209.88±13 161.5612 342.4±11 132.75绣线菊碱ASpiramine A生物碱3 129.09±2 205.26723.33±237.61980.47±62.29
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马印乌头碱Indaconitine萜类12 548.64±1 655.75 675.51±1 324.996 982.33±2 287.67塔拉乌头胺Talatisamine生物碱11 996.64±5 676.7212 881.92±4 056.6512 931.53±2 278.15醋戊曲酯Acevaltrate萜类5 182.65±2 406.488 128.08±4 128.5718 943.07±8 248.182,3-脱氢水飞蓟宾A2,3-Dehydrosilybin A酚类3 347.1±369.834 184.55±4 015.772 881.64±1 920.69刺槐亭Dihydrorobinetin酚类8 861.42±3 650.754 931.64±2 863.312 617.13±497.98OleocanthalOleocanthal萜类13 136.99±4 401.9423 240.18±8 731.758 836±2 371.525-二十三烷基间苯二酚5-Tricosyl-1,3-benzenediol酚类4 695.55±3 002.223 154.08±975.94 437.6±672.05毛果芸香碱Pilocarpine生物碱7 711.17±6 755.26 055.39±1 685.266 619.07±3 945.51苯亚甲基苯乙酮Chalcone其他5 687.69±1 678.797 355.18±5 014.276 324.29±782.66蒽醌Anthraquinone其他16 795.37±9 608.128 778.24±4 42513 668.25±10 379.38芥子醛Sinapaldehyde酚类14 883.34±955.2310 971.61±3 071.2510 095.97±2 425.136-Methoxymellein6-Methoxymellein酚类8 924.64±1 426.716 794.22±1 149.1621 975.44±5 158.33樱草素Primin其他11 146.28±1 065.087 321.3±3 426.928 398.01±1 102.0922-脱氢赤桐甾醇22-Dehydroclerosterol脂质490 498.24±211 584.07258 305.92±31 177.46382 125.49±192 669.65异补骨脂素Angelicin酚类2 813.78±810.35 100.48±3 241.362 687.04±977.86甜菊苷Stevioside萜类3 205.2±1 004.3610±02 432.86±1 917.25甲氧醉椒素Yangonin其他12 485.69±5 275.1710 257.57±1 224.3419 130.33±5 532.73异龙胆黄素Isogentisin酚类2 042.34±969.511 944.3±1 248.111 432.9±892.05梓木内酯Catalpalactone其他3 523.1±2 035.577 359.39±1 304.348 557.67±6 067.61乙偶姻(R)-Acetoin其他15 605.64±13 164.7523 616.12±18 697.6422 275.98±19 017.49乌药醚内酯Linderane萜类2 121.11±875.682 628.73±2 322.742 152.23±1 880.13赝靛叶碱Baptifoline生物碱2 243.74±869.371 045.34±774.252 152.23±1 880.13缬草醚醛Homobaldrinal萜类5 180.37±2 226.074 068.38±820.073 840.5±2 353.92落新妇苷Astilbin酚类1 155.37±472.522 261.03±1 003.991 898.97±1 332.05杨梅酮Myricanone酚类2 123.62±291.782 049.35±723.54 982.14±2 243.27鬼臼毒素Podophyllotoxin酚类2 682.34±201.194 259.69±1 382.523 636.41±321.96去氧鬼臼脂素Deoxypodophyllotoxin酚类2 786.83±2 009.442 101.99±1 481.441 970.92±855.93新甘草酚Neoglycyrol酚类1 331.72±330.511 755.35±1 055.441 638.79±256.274'-去甲鬼臼毒素4'-Demethylpodophyllotoxin酚类5 247.76±3 048.514 975.27±835.43 840.92±1 815.6獐牙菜苷Sweroside萜类9 935.68±4 782.5414 880.11±12 338.7410 433.25±2 756.98表木栓醇Epifriedelanol萜类8 676.35±3 958.7912 575.61±4 732.8714 214.99±5 250.33过氧麦角甾醇Ergosterol peroxide脂质2 010.66±680.32 142±641.922 907.45±411.59姜黄醇Curcumol萜类39 471.3±22 847.7413 427.16±3 421.8234 987.77±15 392.5710-姜酚10-Gingerol酚类4 335.83±991.384 788.33±1 060.35 722.61±852.93甲基异石榴皮碱Methylisopelletierine生物碱8 498.97±4 770.628 680.28±2 832.677 473.28±2 967.65-十九烷基间苯二酚5-Nonadecylresorcinol酚类25 403.3±5 586.110 373.24±6 185.2211 784.65±456.53-羟基-2-甲基吡啶3-Hydroxy-2-methylpyridine其他7 347.64±2 120.96 105.49±1 722.445 060.64±4 010.4异迷迭香酸苷Salviaflaside酚类2 980.03±1 328.662 455.3±639.872 876.02±1 522.51维生素AVitamin A其他3 087.91±840.552 827.6±1 401.441 591.51±845.98黄檀素Dalbergin酚类2 601.18±986.78653.11±563.641 337±772.56肌苷Inosine核苷酸4 860.83±1 281.834 498.13±491.643 260.63±1 236.09N-(p-Hydroxyphenethyl)actinidineN-(p-Hydroxyphenethyl)actinidine其他6 517.45±1 448.177 339.11±1 236.45 298.16±1 701.42亚油酸甲酯Methyl linoleate脂质31 479.06±19 328.4130 100.24±16 323.3927 441.11±6 925.11灵芝醇AGanoderol A萜类12 559.95±3 247.055 880.33±1 338.196 406.18±1 572.38灵芝醛AGanoderal A萜类8 224.41±5 079.6310 091.68±7 426.410 664.69±8 409.72柠檬酸Limonexic acid有机酸及其衍生物4 197.81±340.766 067.59±4 398.474 491.17±3 093.78-羟基佛手苷内酯8-Hydroxybergapten酚类96 645.91±57 539.3784 793.71±42 839.149 056.48±45 794.01丁位十一内酯Undecanolactone其他11 804.83±10 080.8310 278.47±7 758.7310 512.27±1 206.3没食子酸Gallic Acid酚类91 508.4±14 23962 778.24±9 141.3191 100.67±25 747.43O-磷酸胆碱O-Phosphocholine其他5 642.65±4 189.985 617.98±2 405.792 398.71±1 007.47单葡萄糖醛酸甘草次酸Glycyrrhetic acid 3-O-mono-beta-D-glucu-ronide萜类10±0604.92±108.4810±05-十七烷基间苯二酚5-Heptadecylresorcinol酚类2 974.64±1 977.172 011.16±1 137.342 521.89±2 221.281-肉桂酰吡咯烷1-Cinnamoylpyrrolidine其他2 842.17±990.372 975.62±1 227.542 448.59±177.05
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马曲二糖Kojibiose糖类及其衍生物36 453 750.27±10 602 300.1827 616 697.56±3 251 398.9114 404 219.95±5 102 647.48D-α-生育酚alpha-Tocopherol其他5 293.71±2 650.332 375.59±577.884 373.16±1 232.31丁香酸Syringic acid酚类1 926.19±1 273.652 504.18±560.932 610.1±318.92乙酸香茅酯Citronellyl acetate萜类11 841.19±7 537.0710 409.35±2 109.0310 567.85±5 162.36没食子酸乙酯Ethyl gallate酚类3 382.07±2 042.284 334.72±1 511.682 451.77±833.45白三烯A4Leukotriene A4脂质3 323.42±2 613.998 707.42±8 532.821 782.25±308.6黄苷Xanthosine核苷酸32 045.37±7 777.9326 315.46±8 175.5522 739.45±7 091.15雄二烯二酮Boldione脂质2 440.74±819.743 888±1 478.82 958.11±1 553.63毛蕊异黄酮Calycosin酚类4 225.01±3 120.122 661.4±1 291.722 473.5±637.54柳杉酚Sugiol萜类1 574.07±1 525.481 789.4±864.391 476.67±1 206.26ω-羟基大黄素-8-甲醚Questinol其他3 781.59±2 202.866 293.95±1 484.162 765.88±546.9氧化苦参碱Oxymatrine生物碱2 855.93±2 683.952 383.24±615.521 361.34±1 068.951,7-二苯基-4-庚烯-3-酮1,7-Diphenyl-4-hepten-3-one其他2 886.27±1 111.445 605±664.385 237.41±727.59桂酸桂酯Cinnamyl cinnamate酚类6 252.72±1 202.446 166.29±1 192.288 823.66±1 663.8异亮氨酸Isoleucine氨基酸及衍生物3 784.54±985.924 897.13±499.195 056.36±6 014.17β-生育酚Beta-Tocopherol其他3 959.81±3 026.417 925.85±4 433.726 016.54±1 650.815-磷酸吡哆醛Pyridoxal 5'-phosphate其他1 001.27±341.47715.84±469.071 115.83±219.855,7-二羟基异黄酮5,7-Dihydroxyisoflavone酚类3 418.64±3 809.962 229.85±2 223.984 449.34±2 729.87羽扇豆鹼Lupanine生物碱2 517.94±857.27903.35±283.121 142.09±737.45泽兰内酯Eupatolide萜类2 356.56±1 234.512 178.07±930.423 091.46±506.11beta-羟基土木香内酯1beta-Hydroxyalantolactone萜类23 039.35±7 969.1925 765.94±4 418.9710 649.61±4 240.09苦参碱Matrine生物碱1 053.85±564.221 735.41±1 030.22991.46±442.842-吡啶甲酸2-Picolinic acid有机酸及其衍生物60 6097±404 807.32517 735±239 641.2419 544.72±174 376.22异烟酸Isonicotinic acid有机酸及其衍生物5 170.91±2 257.43 672.66±1 317.746 355.34±1 740.63甲基当药宁Swertiaperennin酚类3 733.37±3 268.755 077±1 435.015 871.49±1 281.12香橙素Aromadendrin酚类7 963.91±6 523.663 022.94±1 636.688 206.98±5 562.92二十碳五稀酸Eicosapentaenoic acid脂质53 277.31±28 483.6142 972.75±6 711.4724 809.16±6 686.18异贝壳杉烯酸Kaurenoic acid萜类4 232 107.86±1 415 037.123 516 774.12±309 218.623 483 378.22±1 386 220.64白当归脑Byakangelicol酚类6 788.07±4 605.733 828.39±2 743.578 593.82±5 070.33高淝任素Homoferreirin酚类1 477.55±5215 856±3 551.456 280.21±1 875.82CajanolCajanol酚类6 827.98±4 444.938 690.87±2 388.2216 471.8±5 767.135,6,3',4'-四羟基-7-甲氧基黄酮Pedalitin酚类7 008.76±2 474.966 759.94±6 114.6811 012.75±3 138.79景天胺(-)-Sedamine生物碱4 520.53±2 0294 484.17±441.213 931.3±358.09辛弗林Synephrine生物碱33 788.44±25 037.1219 379.91±5 901.6217 562.88±7 309.41Betulalbuside ABetulalbuside A其他5 685.29±1 055.014 037.26±1 813.495 699.84±2 233.82维生素CAscorbic acid其他9 646.09±4 397.348 583.42±9267 752.44±1 262.347-甲氧基香豆素Herniarin酚类6 428.52±2 393.3111 519.37±3 018.156 509.56±980.443-异丙基苹果酸3-Isopropylmalate有机酸及其衍生物17 294.99±7 992.8615 203.29±12 070.0316 096.6±10 318.02肉桂酸乙酯Ethyl cinnamate酚类6 320.05±3 647.729 854.24±2 175.025 108.56±2 109.134-甲基伞形酮4-Methylumbelliferone酚类6 622.05±4 325.495 204.4±2 378.853 587.09±1 888.49乙酸桂酯Cinnamyl acetat酚类9 554.17±6 045.219 644.92±5 734.179 308.58±1 546.33L-谷氨酰胺L-Glutamine氨基酸及衍生物8 119.96±4 160.916 734.01±5 605.024 147.67±5 045.73二烯丙基二硫醚Diallyl disulfide其他35 725.41±13 851.136 975.78±19 491.5825 247.78±11 241.912-甲酰胺基苯甲酸Formylanthranilic acid有机酸及其衍生物3 828.13±1 313.735 283.55±4 266.413 503.9±1 127.647-甲基鸟嘌呤7-Methylguanine核苷酸2 305.59±1 034.051 534.67±933.21 359.58±649.652-羟基-2H-1,4-苯并恶嗪-3 (4H) -one(R)-2-Hydroxy-2H-1,4-benzoxazin-3(4H)-one其他8 208.16±2 410.999 056.76±3 350.775 467.41±789.24-吡哆内酯4-Pyridoxolactone其他5 663.5±3 333.776 609.2±2 654.3610 579.55±6 292.77水杨酸乙酯Ethyl salicylate酚类20 315.15±8 901.8330 140.94±15 350.919 151.47±13 944.93钩藤碱;异钩藤碱Rhynchophylline;Isorhyncophylline生物碱6 364.22±4 750.062 120.9±896.263 718±2 321.39桂二萜醇Cinnzeylanol萜类4 131.07±2 362.366 677.54±2 0944 287.28±1 633.43牛心果碱Reticuline生物碱10±03 410.14±390.365 772.95±2 222.771-羟基-2-甲氧基蒽醌Alizarin 2-methyl ether其他1 813.8±1 372.1947.05±398.752 753.69±1 382.82松柏苷Coniferin酚类6 299.79±3 666.23 894.19±2 444.546 514.35±2 198.47
续表附表1
中文名称Compound name大类轩尼诗马爹利人头马Eurycomalactone;巨大戟二萜醇Eurycomalactone;Ingenol萜类6 233.06±3 808.529 145.59±5 814.616 442.31±3 574.39α-D-葡萄糖α-D-Glucose糖类及其衍生物1 129 428.04±382 842.261 238 816.08±136 201.72706 211.38±14 6341.17α-松油醇Alpha-Terpineol;Patulin萜类4 025.88±4 003.645 792.59±480.523 789.27±2 358.25异胡薄荷醇Isopulegol萜类1 918.57±414.32 633.07±1 098.331 518.64±594.29阿夫儿茶精(+)-Afzelechin酚类19 638.22±6 921.4917 307.02±9 636.9911 685.34±1 144.29异荭草苷Luteolin-6-C-glucoside酚类9 938.79±13 641.9311 342.11±16 491.167 958.99±10 125.14L(-)-茴香酮(-)-Fenchone萜类162 967.92±93 434.43224 147.92±148 370.01165 442.6±101 321.75喹啉Quinoline生物碱160 402.95±131 995.3898 541.63±27 572.67136 403.63±78 581.84三角叶皂苷;纤细薯蓣皂苷Deltonin;Gracillin脂质1 557.03±1 287.36656.44±428.672 726.06±1 205.1912-羟基松香酸12-Hydroxyabietic acid萜类4 055.46±1 485.881 399.75±1 487.554 223.62±1 030.63油酸;顺-6-十八碳烯酸Oleic acid;Vaccenic acid;Petroselinic acid脂质2 419 364.03±1 168 144.62 079 767.33±231 853.092 345 026.35±589 789.26
2.2 白兰地代谢物分析
为保证数据的同质性,首先对代谢物数据进行对数变换和帕累托缩放,随后进行无监督PCA和HCA,结果如图2所示。由图2-a可知,3个不同来源干邑白兰地具有较为明显差异,马爹利白兰地主要集中在第一象限,人头马白兰地集中在第二象限、轩尼斯白兰地则在第三象限,其中马爹利与人头马和轩尼诗相隔较远。无监督的HCA(图2-b)显示了与PCA类似的结果,表明轩尼诗白兰地在非挥发代谢物的组成及含量上与人头马白兰地更为接近。马爹利白兰地采用特朗塞森林的卢浮橡(Quercus patraea L.),而轩尼诗和人头马则采用了利穆赞森林的夏橡(Quercus robur L.),推测可能是由于陈酿使用的橡木桶不同,导致非挥发代谢物组成具有一定的特征及差异。
a-PCA;b-HCA
图2 干邑白兰地非挥发代谢物的PCA和HCA
Fig.2 The PCA and HCA of non-volatile metabolites in Cognac brandy
2.3 白兰地差异代谢物比较分析
2.3.1 差异代谢物火山图
为了探究不同来源干邑白兰地非挥发代谢物的差异,利用OPLS-DA模型(图3)进行两两比较。在所有模型中,OPLS-DA模型的R2和Q2均大于0.5,说明对样本的解释和预测能力良好。经200次置换验证,R2>Q2且Q2的起点为负数,该参数证明OPLS-DA模型是可靠的,可根据变量投影重要性(variable projection importance,VIP)筛选差异代谢物。
a-轩尼诗vs马爹利 (XNS vs MDL);b-轩尼诗vs人头马(XNS vs RTM);c-马爹利vs人头马 (MDL vs RTM)
图3 干邑白兰地两两对比的OPLS-DA模型及其200次置换验证
Fig.3 The OPLS-DA Model and its validation with 200 permutations of Cognac brandy in two-by-two comparison
以VIP≥1和P<0.05为标准,筛选出不同来源干邑白兰地两两之间的差异代谢物,并通过火山图展示代谢物的差异(图4)。结果显示,马爹利和人头马之间(MDL vs RTM)差异化合物的个数最多,有99种,包括20种上调代谢物,79种下调代谢物;其中亚油酸衍生物9-oxo-10(E),12(Z)-octadecadienoic acid在2个样品之间的差异倍数高达954倍。其次是轩尼诗和马爹利(XNS vs MDL),本组有78种差异化合物,包括60种上调代谢物和18种下调代谢物;轩尼诗中雏菊叶龙胆酮、4-β-D-葡萄糖基-1,3,7-三羟基呫吨酮以及甜菊苷的含量是马爹利中的300倍以上,而马爹利中4-甲基-5-噻唑乙醇和赝靛黄素含量则更高。轩尼诗和人头马(XNS vs RTM)之间差异代谢物的数目最少,有51种,包括23种上调化合物,28种下调化合物。差异化合物的组间分布如韦恩图所示(图4-d),3个比较组共计发现了170种差异代谢物(附表2,https://doi.org/10.13995/j.cnki.11-1802/ts.037532),其共有5种差异化合物(氯化缬草素、桑色素、棉子糖、4-甲基-5-噻唑乙醇和pseudouridine 5′-phosphate),MDL vs RTM、XNS vs MDL、XNS vs RTM各组特有61、43、14种差异代谢物。
a-轩尼诗vs马爹利 (XNS vs MDL)火山图;b-轩尼诗vs人头马(XNS vs RTM)火山图;c-马爹利vs人头马 (MDL vs RTM)火山图;d-韦恩图
图4 干邑白兰地差异物的火山图及韦恩图
Fig.4 The volcano plots and venn diagram of differential compounds in Cognac brandy
附表2 干邑白兰地差异代谢物
Table S2 Differential metabolites of cognac brandy
中文名称Compound name轩尼诗 vs 马爹利轩尼诗 vs 人头马轩尼诗 vs 人头马pVIPFDsigpVIPFDsigpVIPFDsig(±)-茉莉酸(±)-Jasmonic acid0.05 1.37 2.40 Up0.56 0.47 1.13 NotSig0.01 1.25 0.47 Down二氢玉米素DL-Dihydrozeatin0.00 1.41 2.51 Up0.06 1.18 1.73 NotSig0.31 0.75 0.69 NotSigL-酪氨酸L-Tyrosine0.01 1.81 4.66 Up0.07 1.36 2.04 NotSig0.11 1.21 0.44 NotSig顺式玉米素cis-Zeatin0.29 0.95 1.77 NotSig0.96 0.45 0.98 NotSig0.04 1.05 0.55 Down油菜素内酯Brassinolide0.64 0.44 1.26 NotSig0.01 1.74 0.33 Down0.00 1.66 0.26 Down儿茶素Cianidanol0.03 1.61 3.73 Up0.54 0.59 1.19 NotSig0.00 1.52 0.32 Down花旗松素Taxifolin0.01 1.13 1.82 Up0.54 0.76 1.30 NotSig0.56 0.59 0.71 NotSig(+)-没食子儿茶素Gallocatechin0.31 1.65 10.17 NotSig0.39 1.25 3.85 NotSig0.01 1.39 0.38 Down木犀草苷Cynaroside0.13 1.50 3.15 NotSig0.44 0.57 1.41 NotSig0.04 1.29 0.45 Down异鼠李素Isorhamnetin0.24 0.81 1.59 NotSig0.02 3.72 215.67 Up0.00 3.17 135.54 UpL-羟基脯氨酸4-Hydroxyproline0.16 1.06 1.88 NotSig0.90 0.66 1.04 NotSig0.03 1.09 0.55 DownL-蛋氨酸L-Methionine0.05 1.21 2.03 NotSig0.83 0.18 0.96 NotSig0.02 1.23 0.47 Down3-羟基-3-甲基谷氨酸3-Hydroxy-3-methylpentane-1,5-dioic acid0.10 1.11 1.90 NotSig0.04 1.53 2.68 Up0.06 0.78 1.41 NotSig苹果酸Malic acid0.02 1.77 4.12 Up0.17 1.02 1.53 NotSig0.06 1.40 0.37 NotSig2-羟基戊二酸2-Hydroxyglutaric acid0.05 1.84 5.23 Up0.20 1.35 2.06 NotSig0.19 0.99 0.39 NotSig3,4-二甲氧基肉桂酸3,4-Dimethoxycinnamic acid0.87 0.16 1.01 NotSig0.01 1.11 1.61 Up0.00 0.97 1.59 NotSig对羟基苯乙酸4-Hydroxyphenylacetic acid0.07 0.90 1.54 NotSig0.05 0.98 0.69 NotSig0.00 1.28 0.45 Down泽兰色原烯Eupatoriochromene0.56 0.33 1.45 NotSig0.51 0.96 0.73 NotSig0.02 1.14 0.50 Down棉子糖Raffinose0.04 1.21 2.17 Up0.02 1.39 0.47 Down0.00 1.76 0.22 DownD-山梨糖醇D-Sorbitol0.04 1.18 1.94 Up0.12 0.92 1.44 NotSig0.25 0.66 0.74 NotSig半乳糖-1-磷酸Galactose 1-phosphate0.05 0.99 1.67 NotSig0.05 1.35 2.15 Up0.32 0.67 1.29 NotSigD-麦芽糖D-Maltose0.46 0.44 0.88 NotSig0.01 1.93 4.25 Up0.00 1.79 4.82 Up2-酮丁酸2-Ketobutyric acid0.02 1.31 2.23 Up0.17 1.27 1.70 NotSig0.61 0.41 0.77 NotSigD-核糖D-Ribose0.02 1.30 2.15 Up0.15 1.13 1.73 NotSig0.66 0.21 0.80 NotSigD-阿拉伯糖D-Arabinose0.02 1.30 2.15 Up0.15 1.13 1.73 NotSig0.66 0.21 0.80 NotSig戊二酸Glutaric acid0.02 1.05 1.73 Up0.89 0.29 0.97 NotSig0.12 0.99 0.56 NotSig莽草酸Shikimic acid0.18 0.74 1.43 NotSig0.00 4.05 526.76 Up0.00 3.48 367.74 Up焦磷酸Pyrophosphate0.04 1.10 1.93 Up0.04 1.37 2.23 Up0.48 0.59 1.15 NotSig秦皮乙素Esculetin0.05 1.26 2.20 Up0.13 1.30 1.94 NotSig0.78 0.46 0.88 NotSig脱氧胞苷Deoxycytidine0.75 0.74 1.11 NotSig0.03 1.49 2.50 Up0.13 1.17 2.24 NotSigD-葡萄糖醛酸D-glucoronic acid0.03 1.08 1.71 Up0.07 0.99 0.65 NotSig0.02 1.38 0.38 Down矢车菊素Cyanidin0.31 0.59 1.39 NotSig0.10 1.17 0.56 NotSig0.02 1.32 0.41 Down巴西苏木素Brazilin0.00 1.21 1.96 Up0.22 0.71 1.31 NotSig0.21 0.84 0.67 NotSig2'-羟基染料木素2'-Hydroxygenistein0.67 0.82 0.86 NotSig0.35 0.68 1.54 NotSig0.04 1.07 1.79 Up对羟苯基丙酸4-Hydroxyphenyl-2-propionic acid0.20 0.71 0.74 NotSig0.11 0.86 1.46 NotSig0.02 1.13 1.98 Up氨基丙二酸Aminomalonic acid0.04 1.35 2.55 Up0.78 0.55 0.94 NotSig0.00 1.43 0.37 Down
续表附表2
中文名称Compound name轩尼诗 vs 马爹利轩尼诗 vs 人头马轩尼诗 vs 人头马pVIPFDsigpVIPFDsigpVIPFDsig麦芽酚Maltol0.10 0.61 1.22 NotSig0.03 1.05 1.55 Up0.09 0.68 1.26 NotSig1,2,3-苯三酚Pyrogallol0.01 1.58 0.31 Down0.03 1.83 0.25 Down0.45 0.63 0.79 NotSig5-羟甲基糠醛5-Hydroxymethylfurfural0.10 0.71 1.33 NotSig0.14 0.81 0.72 NotSig0.03 1.08 0.54 Down芝麻酚Sesamol0.54 0.62 1.25 NotSig0.09 1.24 0.50 NotSig0.03 1.30 0.40 Down苏式-1-C-丁香酚基丙三醇threo-1-C-Syringylglycerol0.01 1.25 2.08 Up0.00 1.81 3.54 Up0.08 0.96 1.70 NotSig菱叶野决明碱Rhombifoline0.06 0.99 1.55 NotSig0.11 0.89 0.69 NotSig0.03 1.27 0.45 Down山药素ⅢBatatasin III0.36 0.85 1.71 NotSig0.17 1.33 0.53 NotSig0.02 1.50 0.31 Down肉桂酸Cinnamic acid0.02 1.40 2.61 Up0.29 0.84 1.41 NotSig0.12 0.92 0.54 NotSig佛手苷内酯Bergapten0.05 1.17 0.52 Down0.75 0.60 0.73 NotSig0.62 1.13 1.42 NotSig鸟嘌呤Guanine0.03 1.25 0.48 Down0.58 0.50 0.83 NotSig0.03 1.05 1.74 Up邻氨基苯甲酸甲酯Methyl anthranilate0.11 1.16 2.08 NotSig0.87 0.64 0.95 NotSig0.02 1.23 0.46 Down异戊酸乙酯Ethyl isovalerate0.88 0.52 0.97 NotSig0.02 1.15 1.66 Up0.12 1.00 1.71 NotSigN-乙酰苯胺N-Acetylarylamine0.03 1.43 2.69 Up0.11 1.07 1.75 NotSig0.11 0.90 0.65 NotSig花椒毒酚Xanthotoxol0.00 2.08 5.90 Up0.17 1.09 1.64 NotSig0.14 1.68 0.28 NotSig香柑醇Bergaptol0.01 1.04 1.66 Up0.64 0.56 1.11 NotSig0.19 0.82 0.67 NotSig鸭嘴花碱酮Vasicinone0.03 1.31 2.34 Up0.40 0.99 1.40 NotSig0.30 0.88 0.60 NotSig反式石竹烯Beta-caryophyllene0.78 0.63 1.08 NotSig0.05 1.39 0.42 Down0.04 1.33 0.39 Down松柏醛Coniferylaldehyde0.05 1.17 1.96 Up0.31 0.57 1.25 NotSig0.03 0.91 0.63 NotSig甲基丁香酚Methyleugenol0.91 0.38 0.97 NotSig0.03 1.38 0.46 Down0.01 1.21 0.47 Down7-乙氧基香豆素7-Ethoxycoumarin0.27 1.09 2.57 NotSig0.68 0.51 1.27 NotSig0.00 1.20 0.49 Down3-(3,4-Dihydroxy-5-methoxy)-2-propenoic acid3-(3,4-Dihydroxy-5-methoxy)-2-propenoic acid0.00 1.09 0.58 Down0.03 0.90 0.72 NotSig0.04 0.65 1.24 NotSig黄酮Flavone0.09 1.04 1.83 NotSig0.38 0.55 0.82 NotSig0.00 1.28 0.45 Down广藿香酮Pogostone0.03 1.25 2.07 Up0.97 0.66 1.01 NotSig0.18 1.14 0.49 NotSig天竺葵素Pelargonidin0.31 0.95 2.21 NotSig0.80 0.35 1.15 NotSig0.02 1.12 0.52 Down紫铆因Butein0.32 0.90 1.40 NotSig0.19 0.79 0.77 NotSig0.04 1.11 0.55 DownGlycinolGlycinol0.01 1.21 1.99 Up0.75 0.83 1.11 NotSig0.23 0.96 0.56 NotSig3,4',7-三羟基黄烷酮Garbanzol0.36 0.76 1.47 NotSig0.36 1.00 0.74 NotSig0.04 1.16 0.51 Down9-KODE9-OxoODE0.49 0.80 1.33 NotSig0.01 4.31 1269.00 Up0.03 3.71 954.59 Up桑色素Morin0.02 1.30 2.26 Up0.05 1.26 0.52 Down0.01 1.71 0.23 Down羽扇豆醇Lupeol0.44 1.05 1.42 NotSig0.05 1.17 0.56 Down0.03 1.40 0.40 DownMahanineMahanine0.02 1.72 3.70 Up0.01 1.88 3.98 Up0.87 0.51 1.08 NotSig4-羟基苯丙酮4'-Hydroxypropiophenone0.04 1.28 2.04 Up0.20 0.62 1.18 NotSig0.08 1.06 0.58 NotSig桑辛素 OMoracin O0.00 2.21 9.53 Up0.34 0.92 1.39 NotSig0.04 1.92 0.15 Down愈创木素Guaiacin0.01 1.54 2.91 Up0.38 0.62 1.19 NotSig0.03 1.36 0.41 Down橙黄决明素Aurantio-obtusin0.40 0.56 1.31 NotSig0.25 0.87 0.70 NotSig0.04 1.10 0.54 Down甲酸苄酯Benzyl formate0.05 1.16 1.94 Up0.50 0.64 0.85 NotSig0.03 1.23 0.44 Down对丙基苯酚4-Propylphenol0.38 0.54 1.52 NotSig0.29 1.04 0.67 NotSig0.03 1.23 0.44 Down3-甲基水杨醛3-Methylsalicylaldehyde0.64 0.58 0.84 NotSig0.02 1.21 0.55 Down0.15 0.94 0.66 NotSig大黄酚Chrysophanol0.01 1.47 2.77 Up0.24 0.77 1.36 NotSig0.08 1.05 0.49 NotSigS-(苯基乙酰硫代羟肟酰基)-L-半胱氨酸S-(Phenylacetothiohydroximoyl)-L-cysteine0.01 1.11 1.77 Up0.08 1.20 1.70 NotSig0.92 0.73 0.96 NotSig甜叶菊素ESterebin E0.04 1.39 0.39 Down0.60 0.82 1.29 NotSig0.01 1.56 3.31 Up1-O-Caffeoylglucose1-O-Caffeoylglucose0.11 1.75 5.13 NotSig0.88 0.63 1.08 NotSig0.02 1.73 0.21 DownDL-1-苯乙醇1-Phenylethanol0.45 0.74 1.32 NotSig0.18 1.06 0.59 NotSig0.04 1.18 0.45 Down桑辛素 CMoracin C0.05 1.13 1.90 Up0.60 0.37 1.11 NotSig0.02 1.01 0.58 Down氯化缬草素Valechlorine0.01 1.70 3.66 Up0.03 1.02 1.54 Up0.01 1.34 0.42 Down麦芽三糖Maltotriose0.84 0.40 1.03 NotSig0.02 1.19 0.55 Down0.01 1.11 0.54 Down蔗果三糖1-Kestose0.03 1.30 2.23 Up0.87 0.43 1.05 NotSig0.15 1.16 0.47 NotSig2-异丙基-3-氧代琥珀酸2-Isopropyl-3-oxosuccinate0.65 0.44 1.11 NotSig0.08 1.28 1.98 NotSig0.01 1.07 1.79 Up胡桃酮Juglone0.47 0.67 1.33 NotSig0.20 1.04 0.61 NotSig0.03 1.20 0.46 Down2'-脱氧尿苷2'-Deoxyuridine0.32 0.68 0.81 NotSig0.13 1.02 1.67 NotSig0.01 1.17 2.05 Up美鼠李苷 ACascaroside A0.02 1.58 3.30 Up0.44 0.51 0.79 NotSig0.02 1.64 0.24 Down
续表附表2
中文名称Compound name轩尼诗 vs 马爹利轩尼诗 vs 人头马轩尼诗 vs 人头马pVIPFDsigpVIPFDsigpVIPFDsig葡萄糖基甘草苷Glucoliquiritin0.02 1.58 3.30 Up0.80 0.45 1.09 NotSig0.07 1.44 0.33 NotSig外消旋12-氧代植物二烯酸12-OPDA0.64 0.51 1.09 NotSig0.00 1.38 0.48 Down0.00 1.29 0.44 Down乙酸4-甲基伞形酯4-Methylumbelliferyl acetate0.01 1.26 0.47 Down0.01 1.27 0.53 Down0.48 0.43 1.13 NotSig香附烯酮Cyperotundone0.01 1.33 2.29 Up0.00 1.50 2.39 Up0.72 0.40 1.04 NotSig槲皮素-3-O-新橙皮苷Quercetin 3-O-neohesperidoside0.33 1.26 5.96 NotSig0.86 0.88 1.17 NotSig0.00 1.82 0.20 Down蔗糖Sucrose0.07 1.22 0.52 NotSig0.30 1.50 1.91 NotSig0.01 1.76 3.65 Up去氧拉巴醌Deoxylapachol0.79 0.45 0.93 NotSig0.05 1.29 0.52 Down0.03 1.07 0.55 Down葡萄糖-1-磷酸Glucose 1-phosphate0.12 1.03 1.90 NotSig0.68 0.63 1.12 NotSig0.01 1.04 0.59 Down丹酚酸ASalvianolic acid A0.06 1.10 1.96 NotSig0.86 0.38 0.96 NotSig0.02 1.16 0.49 Down母菊薁Chamazulene0.03 1.05 1.74 Up0.50 0.38 0.91 NotSig0.00 1.15 0.52 Down赝靛黄素Pseudobaptigenin0.03 3.59 0.00 Down0.06 3.81 0.00 NotSig0.60 0.97 1.32 NotSig异土木香内酯Isoalantolactone0.11 0.88 0.69 NotSig0.01 1.94 0.23 Down0.01 1.48 0.33 Down二氢醉椒素Dihydrokavain0.05 1.16 1.99 Up0.79 0.61 1.08 NotSig0.12 0.93 0.54 NotSig柳杉二醇11-鼠李糖苷Cryptomeridiol 11-rhamnoside0.74 0.12 1.08 NotSig0.05 1.26 2.04 NotSig0.00 1.14 1.89 Up雏菊叶龙胆酮Bellidifolin0.03 3.60 427.90 Up0.03 3.88 338.96 Up0.19 0.60 0.79 NotSig苯乙酰甘氨酸Phenylacetylglycine0.24 1.15 2.62 NotSig0.45 0.89 1.60 NotSig0.00 1.00 0.61 DownNeocnidilideNeocnidilide0.12 1.00 1.78 NotSig0.38 0.86 0.74 NotSig0.05 1.26 0.41 Down麻醉椒碱Pipermethystine0.36 0.88 1.68 NotSig0.48 1.00 0.74 NotSig0.03 1.24 0.44 Down可可碱Theobromine0.70 0.46 1.27 NotSig0.09 1.55 0.44 NotSig0.01 1.46 0.35 Down异肌醇Inositol0.07 0.91 1.45 NotSig0.02 1.10 1.69 Up0.58 0.36 1.17 NotSig咖啡酸Caffeic acid0.21 0.76 1.33 NotSig0.07 0.85 0.73 NotSig0.02 1.09 0.55 Down4-羟基-3- 甲氧基扁桃酸Vanillylmandelic acid0.02 1.42 2.65 Up0.78 0.36 0.95 NotSig0.00 1.44 0.36 Down甘草次酸(β型)Glycyrrhetinic acid0.03 1.49 2.83 Up0.03 1.52 2.53 Up0.73 0.61 0.89 NotSig灵芝酸 JbGanoderic acid Jb0.04 1.30 2.24 Up0.61 0.85 1.19 NotSig0.18 1.05 0.53 NotSig3-氧代坡模酸3-Oxopomolic acid0.16 1.37 2.87 NotSig0.06 1.33 0.50 NotSig0.00 1.89 0.17 Down秦皮甲素Esculin0.17 0.70 0.77 NotSig0.02 1.59 0.34 Down0.04 1.19 0.45 Down去甲黄腐醇Desmethylxanthohumol0.00 1.30 2.14 Up0.39 0.84 1.34 NotSig0.36 0.66 0.62 NotSig三甲基芹菜素Trimethylapigenin0.48 0.63 1.52 NotSig0.02 1.78 0.36 Down0.00 1.73 0.23 Down甜没药萜醇氧化物ABisabolol oxide A0.30 0.93 1.76 NotSig0.40 0.89 0.72 NotSig0.01 1.32 0.41 Down4-β-D-葡萄糖基-1,3,7-三羟基呫吨酮Lancerin0.00 3.64 421.27 Up0.76 0.74 0.77 NotSig0.22 3.38 0.00 NotSig灵芝酸HGanoderic acid H0.21 1.33 1.97 NotSig0.06 1.60 0.34 NotSig0.03 1.95 0.17 Down异曼果斯廷1-Isomangostin0.05 1.11 0.54 NotSig0.70 0.26 1.15 NotSig0.01 1.23 2.12 UpDesoxypeganineDesoxypeganine0.09 1.17 0.50 NotSig0.38 0.53 1.31 NotSig0.04 1.33 2.64 Up马钱苷Loganin0.02 1.35 0.42 Down0.14 1.61 0.29 NotSig0.46 0.73 0.69 NotSig帽柱木碱Mitraphylline0.04 1.32 2.48 Up0.23 0.93 1.64 NotSig0.37 0.53 0.66 NotSig1,2,4-三甲基苯1,2,4-Trimethylbenzene0.62 0.79 1.23 NotSig0.08 1.33 0.48 NotSig0.04 1.37 0.39 DownDL-甘油酸Glyceric acid0.60 0.53 0.89 NotSig0.05 1.12 1.74 NotSig0.03 1.13 1.95 Up日当药黄素Swertiajaponin0.04 1.28 2.08 Up0.42 0.48 1.15 NotSig0.06 1.12 0.55 NotSig异甘草苷Isoliquiritin0.73 0.68 1.14 NotSig0.08 1.17 0.58 NotSig0.01 1.16 0.51 Down香草酸Vanillic acid0.63 0.72 1.20 NotSig0.14 1.06 0.66 NotSig0.02 1.11 0.55 Down4-羟基扁桃酸p-Hydroxymandelic acid0.58 0.52 0.88 NotSig0.04 1.39 0.44 Down0.06 1.16 0.50 NotSigcis-2-Methylaconitatecis-2-Methylaconitate0.47 0.58 1.36 NotSig0.21 0.96 0.67 NotSig0.04 1.20 0.50 Down2,6-二甲基-7-辛烯-2,3,6-三醇2,6-Dimethyl-7-octene-2,3,6-triol0.27 1.10 3.38 NotSig0.28 1.33 0.54 NotSig0.02 1.89 0.16 DownPseudouridine 5'-phosphatePseudouridine 5'-phosphate0.00 1.09 1.73 Up0.01 1.82 0.26 Down0.01 1.94 0.15 Down二氢松柏醇Dihydroconiferyl alcohol0.01 1.25 0.48 Down0.17 1.01 0.57 NotSig0.55 0.67 1.18 NotSig黃尿酸Xanthurenic acid0.01 1.16 0.51 Down0.21 0.78 0.71 NotSig0.09 0.82 1.41 NotSig甲氧基吲哚乙酸Methoxyindoleacetic acid0.00 1.41 2.50 Up0.03 1.43 2.25 Up0.79 0.58 0.90 NotSig4-甲基-5-噻唑乙醇4-Methyl-5-thiazoleethanol0.01 3.68 0.00 Down0.00 4.32 0.00 Down0.00 1.28 0.43 Down氧化芳樟醇2-(2-Hydroxy-2-propyl)-5-methyl-5-vinyltetrahydrofuran0.03 1.04 0.59 Down0.07 0.83 0.71 NotSig0.28 0.60 1.20 NotSigN-对香豆酰真蛸胺N-p-Coumaroyloctopamine0.71 0.79 0.85 NotSig0.04 1.31 0.49 Down0.05 1.07 0.58 NotSig奎宁酸Quinic acid0.06 0.76 1.36 NotSig0.01 1.40 0.46 Down0.00 1.48 0.34 Down槲皮素3-O-葡萄糖酸苷Quercetin-3-O-glucuronide0.02 1.88 0.19 Down0.01 1.53 0.41 Down0.08 1.19 2.18 NotSig
续表附表2
中文名称Compound name轩尼诗 vs 马爹利轩尼诗 vs 人头马轩尼诗 vs 人头马pVIPFDsigpVIPFDsigpVIPFDsig绣线菊碱ASpiramine A0.13 1.77 6.17 NotSig0.21 1.40 2.93 NotSig0.01 1.21 0.47 Down印乌头碱Indaconitine0.02 1.43 2.55 Up0.08 1.06 1.69 NotSig0.25 0.76 0.66 NotSig刺槐亭Dihydrorobinetin0.08 1.00 1.75 NotSig0.02 1.66 2.99 Up0.02 1.02 1.71 Up5-二十三烷基间苯二酚5-Tricosyl-1,3-benzenediol0.28 1.03 2.03 NotSig0.98 0.29 0.99 NotSig0.04 1.19 0.49 Down6-Methoxymellein6-Methoxymellein0.07 0.98 1.59 NotSig0.00 1.59 0.38 Down0.00 1.71 0.24 Down甜菊苷Stevioside0.00 3.54 311.30 Up0.77 0.84 1.17 NotSig0.12 3.22 0.00 NotSig落新妇苷Astilbin0.00 1.23 0.50 Down0.36 0.58 0.56 NotSig0.78 0.65 1.12 NotSig杨梅酮Myricanone0.51 0.83 1.25 NotSig0.03 1.49 0.41 Down0.03 1.51 0.33 Down过氧麦角甾醇Ergosterol peroxide0.74 0.74 1.11 NotSig0.05 1.08 0.62 Down0.07 1.07 0.56 NotSig姜黄醇Curcumol0.08 1.47 3.55 NotSig0.92 0.54 1.04 NotSig0.04 1.48 0.29 Down5-十九烷基间苯二酚5-Nonadecylresorcinol0.04 1.22 2.08 Up0.03 1.29 1.98 Up0.82 0.50 0.95 NotSig维生素AVitamin A0.91 0.50 1.03 NotSig0.11 1.20 1.90 NotSig0.04 1.10 1.85 Up黄檀素Dalbergin0.03 1.61 3.03 Up0.22 1.27 1.66 NotSig0.34 1.12 0.55 NotSig灵芝醇AGanoderol A0.00 1.50 2.81 Up0.04 1.19 1.73 Up0.15 0.93 0.62 NotSig单葡萄糖醛酸甘草次酸Glycyrrhetic acid 3-O-mono-beta-D-glucuronide0.02 2.85 0.02 Down0.47 0.31 0.92 NotSig0.02 2.73 40.16 Up曲二糖Kojibiose0.16 0.79 1.41 NotSig0.01 1.45 2.36 Up0.09 0.93 1.68 NotSigD-α-生育酚alpha-Tocopherol0.12 1.43 3.06 NotSig0.77 0.68 1.13 NotSig0.04 1.37 0.37 Down白三烯A4Leukotriene A40.05 1.45 0.36 NotSig0.44 0.76 1.73 NotSig0.01 1.76 4.78 Up1,7-二苯基-4-庚烯-3-酮1,7-Diphenyl-4-hepten-3-one0.04 1.13 0.55 Down0.01 1.34 0.50 Down0.55 0.40 0.91 NotSig桂酸桂酯Cinnamyl cinnamate0.76 0.64 1.08 NotSig0.02 1.02 0.65 Down0.07 0.97 0.61 NotSig羽扇豆鹼Lupanine0.02 1.43 2.78 Up0.10 1.30 2.03 NotSig0.51 0.66 0.73 NotSig泽兰内酯Eupatolide0.25 0.66 1.69 NotSig0.24 0.95 0.70 NotSig0.00 1.34 0.42 Down1beta-羟基土木香内酯1beta-Hydroxyalantolactone0.81 0.31 1.07 NotSig0.12 1.30 2.05 NotSig0.02 1.10 1.92 Up高淝任素Homoferreirin0.02 1.61 0.29 Down0.03 1.98 0.21 Down0.36 0.68 0.72 NotSig5,6,3',4'-四羟基-7-甲氧基黄酮Pedalitin0.07 1.45 2.81 NotSig0.20 1.00 0.59 NotSig0.02 1.73 0.21 DownBetulalbuside ABetulalbuside A0.00 1.31 2.25 Up0.75 0.38 0.93 NotSig0.03 1.29 0.41 Down牛心果碱Reticuline0.01 3.44 0.00 Down0.02 4.04 0.00 Down0.11 1.20 0.43 NotSig1-羟基-2-甲氧基蒽醌Alizarin 2-methyl ether0.29 0.77 2.25 NotSig0.32 1.17 0.62 NotSig0.03 1.62 0.27 Down松柏苷Coniferin0.20 0.97 1.83 NotSig0.70 0.48 0.88 NotSig0.03 1.21 0.48 Down三角叶皂苷;纤细薯蓣皂苷Deltonin;Gracillin0.26 0.99 3.02 NotSig0.24 1.42 0.54 NotSig0.01 1.87 0.18 Down12-羟基松香酸12-Hydroxyabietic acid0.11 1.48 2.15 NotSig0.48 0.52 0.88 NotSig0.04 1.46 0.41 Down
2.3.2 差异物聚类分析
将上述170个差异化合物绘制热图(图5),其中酚类差异物最多(66种),其次为其他类(27种)、萜类(23种)、糖类及其衍生物(14种)。这些差异物的含量变化一方面可能由于所用橡木桶的品种不同而造成,同时,也会受到陈酿时间、调配等因素影响。接下来将重点讨论差异明显且对风味影响较大的酚类、萜类及糖类化合物。
图5 干邑白兰地差异物的热图
Fig.5 The heatmap of differential compounds in Cognac brandy
酚类对白兰地的物理、化学特性和感官特征起着决定性的作用。差异化合物个数最多的前3个小类分别是类黄酮(26种)、酚酸及其衍生物(18种)以及香豆素(9种)。尽管类黄酮中差异化合物数量较多,但它们在白兰地中绝对含量普遍较低[8]。相比之下,白兰地最主要的酚类化合物是酚酸及其衍生物,其来自于鞣花单宁及木质素的降解[16]。18种酚酸及其衍生物在不同来源干邑白兰地中有差异,除了5种差异物,其余化合物的含量如肉桂酸、咖啡酸、香草酸、松柏醛、肉桂酸等在马爹利中更低,这结果与前人其他研究一致,即在使用卢浮橡进行陈酿的白兰地中,酚酸及酚醛的含量也更低[17]。其次是香豆素类,它广泛存在于白兰地中,已报道简单香豆素能通过感知相互作用增强苦味作用[14]。本研究中有9种差异香豆素,包括了一些简单香豆素,如秦皮乙素、秦皮甲素,也有一些首次在白兰地中鉴定出的呋喃结构的香豆素,如佛手苷内酯、花椒毒酚。其中秦皮乙素的含量受到陈酿时间的影响,而商业白兰地经多种年份原酒勾调后可能导致不同来源白兰地中秦皮乙素的含量有区别[14]。木脂素是值得关注的一个亚类,由苯丙素衍生物(即C6-C3单体)聚合而成,有生理作用、健康功效以及味觉贡献[18-19]。样品中共鉴定到11种木脂素,其中愈创木素和芝麻酚是差异木脂素。
糖类也是白兰地中重要组成部分,其有2个主要来源,一是半纤维素受到烘烤或长时间陈酿降解为小分子糖类,二是人为添加焦糖到白兰地中进行调色。据报道,经40年陈酿的白兰地糖含量高达2 g/L[16]。本研究共发现6种低聚糖以及8种单糖及其衍生物是差异化合物。其中蔗糖和麦芽糖是商业白兰地中的最主要糖类,在轩尼诗和马爹利中很突出,可能与其调配工艺相关;而葡萄糖-1-磷酸、D-核糖、阿拉伯糖等5种单糖及其衍生物的含量在轩尼诗和人头马中更高。萜烯化合物促进白兰地感官特征的形成,不仅与香气特征紧密相关[20],还对苦味和甜味产生影响[21-22]。萜类化合物中有23种化合物具有差异,如甜菊苷和单葡萄糖醛酸甘草次酸,其中在马爹利白兰地中有15种差异化合物的含量均低于其他二者,尤其在二萜和三萜化合物中这种趋势更加明显。萜类化合物的含量变化可能与橡木桶的种类有关,已有研究表明在卢浮橡和夏橡之间萜类化合物组成和含量有一定的不同[21-22]。
2.3.3 KEGG分析代谢通路
基于KEGG数据库对170种差异代谢物进行通路分析(图6-a)。有133种差异物被注释到65条代谢通路,除了4条途径来自遗传信息或环境信息,其余途径均属于新陈代谢,表明大部分差异物与橡木的代谢有关。随后进行富集分析(图6-b),其中富集程度最高的前5条通路分别为:植物激素信号转导,与茉莉酸、二氢玉米素、油菜素内酯3种代谢成分有关;半乳糖代谢,主要包括半乳糖-1-磷酸等6种糖类化合物;黄酮类化合物的生物合成,主要包括儿茶素等8种黄酮化合物;苯丙烷类生物合成,主要包括松柏醛、松柏苷等6种代谢物;缬氨酸、亮氨酸和异亮氨酸的生物合成途径,包括2-酮丁酸和2-异丙基-3-氧代琥珀酸2种成分。
a-通路分析;b-富集分析
图6 干邑白兰地差异物KEGG通路分析及富集分析
Fig.6 The KEGG pathway analysis and enrichment analysis of differential compounds in Cognac brandy
3 结论
采用UPLC-MS/MS全面解析了非挥发化合物的组成,共鉴定了十类638种非挥发化合物,其中酚类化合物最多。PCA和HCA结果表明,不同来源白兰地具有明显的非挥发化合物组成特征。依据OPLS-DA和t-检验确定了170种差异化合物,其中酚类差异物最多(66种),其次为其他类(27种)、萜类(23种)、糖类及其衍生物(14种)。KEGG分析结果表明,差异化合物与橡木的代谢过程相关,其主要富集于植物激素信号转导、半乳糖代谢、黄酮类化合物的生物合成、苯丙烷类生物合成。本研究较为全面地分析了干邑非挥发代谢物的组成特征,有助于进一步剖析白兰地化学特征,完善白兰地风味化学的理论体系。
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