栀子鲜花花水和鲜花细胞液气相和液相的成分分析

徐晓俞,李爱萍,吴思逢,李程勋,郑开斌

Composition Analysis of Gas Phase and Liquid Phase of Fresh Floral Water Extract and Fresh Flowers Cell Sap from Gardenia jasminoides

XU XiaoYu,LI AiPing,WU SiFeng,LI ChengXun,ZHENG KaiBin

表2 栀子鲜花花水和细胞液的化学成分及其相对含量（高于0.1%）

Table 2 Chemical constituents and relative percentage of floral water extract and flowers cell sap from Gardenia jasminoides (above 0.1%)

编号 No. 保留 时间 Retention time (min) 加和离子 模式 Additive ion mode m/z Mass charge ratio 分子式 Molecular formula 成分名称 Compound name 相对含量 Relative content (%) 鲜花花水 FFWE 鲜花细胞液 FFCS 正离子模式 Positive ion mode 负离子模式 Negative ion mode 正离子模式 Positive ion mode 负离子模式 Negative ion mode 氨基酸类 Amino acids 1 2.44 M+K-2H 152.0111 C5H9NO2 L-脯氨酸 L-Proline - 0.59±0.02 - 3.05±0.06** 2 3.10 M-H 300.1221 C17H19NO4 3-(3,4-二羟苯基)-N-[2-(4-羟苯基)乙基]丙氨酸3-(3,4-Dihydroxyphenyl)-N-[2-(4-hydroxyphenyl)ethyl]propanimidic acid - - - 0.17±0.01** 单萜类 Monoterpeniods 3 3.50 M+H 153.1271 C10H16O 桧醇 Sabinol 0.48±0.01** - 0.23±0.01 - 4 6.16 M+H-H2O, M+H 135.1168 C10H16O (S)-(-)-紫苏醇 (S)-(-)-Perillyl alcohol 13.73±0.27** - 5.11±0.15 - 5 3.09 M-H 183.0657 C9H12O4 京尼平酸 Genipic acid - 1.76±0.05** - 0.18±0.01 6 4.61 M-H, M+Na-2H 315.1801 C16H28O6 薄荷醇-葡萄糖醛酸 Menthol-glucoronide - 0.83±0.02** - 0.18±0.01 倍半萜类 Sesquiterpenoids 7 3.60 M+ACN+Na 494.2162 C24H30O7 蜜环菌醛H Melleolide H - - 0.23±0.01** - 8 5.61 M+H-2H2O, M+Na, M+H-H2O 249.1470 C15H22O4 青蒿琥酯 Artemin 0.06±0.00 - 0.19±0.01** - 9 5.65 M+H-H2O, M+H 203.1790 C15H24O 氧化石竹烯 Caryophyllene epoxide 0.38±0.01 - 1.77±0.05** - 10 5.76 M+H 205.1947 C15H24 α-佛手柑油烯 alpha-Bergamotene - - 0.11±0.00** - 11 6.03 M+H 205.1948 C15H24 (+)-长叶环烯 Longicyclene - - 0.12±0.00** - 12 7.61 M+H 205.1949 C15H24 α-石竹烯 α-Humulene 0.06±0.00 - 0.39±0.01** - 二萜类 Diterpenoids 13 5.69 2M+H 661.2964 C19H22O5 赤霉素A62 Gibberellin A62 - - 0.10±0.00** - 14 7.53 M+Na-2H 421.1863 C20H32O8 辛卡西醇B Cincassiol B - 1.56±0.05** - 0.30±0.01 三萜类 Triterpenoids 15 6.37 M+H, M+Na, M+H-H2O 489.3558 C30H48O5 山茶皂苷元B Camelliagenin B 2.16±0.06** - 0.02±0.00 - 16 6.63 M+H-H2O, M+H 491.3712 C30H50O5 山茶皂苷元C Camelliagenin C 0.18±0.01** - - - 17 3.86 M+Cl 541.1830 C26H34O10 异柠檬苦素酸 Isolimonic acid - 0.20±0.01 - 0.64±0.02** 18 4.25 M+Na-2H 803.4226 C41H66O14 麦德龙苷D Madlongiside D - 4.35±0.09** - 0.23±0.01 19 5.22 M-H, M+Cl 503.3367 C30H48O6 羟基积雪草苷 Madecassic acid - 20.20±0.61** - 0.02±0.00 黄酮类 Flavonoids 20 4.72 M+H 823.3062 C39H50O19 朝藿定D Hexandraside D - - 0.11±0.00** - 香豆素类 Coumarins 21 4.38 M+H, M+ CH3OH+H 179.0699 C9H6O2 香豆素 Coumarin - - 0.74±0.02** - 22 0.66 M+H 141.1134 C6H12N4 六亚甲基四胺 Methenamine 0.33±0.01** - 0.11±0.00 - 23 1.90 M+H, 2M+H 217.0974 C12H12N2O2 L-1,2,3,4-四氢-β-咔啉-3-羧酸 L-1,2,3,4-Tetrahydro-beta-carboline-3- carboxylic acid 0.35±0.01 - 3.17±0.06** - 24 2.39 M+H 476.3055 C21H41N5O7 乙基紫苏霉素 Netilmicin 0.17±0.00 - 0.18±0.01** - 25 2.86 M+H-H2O, M+H 120.0446 C7H7NO2 氨茴酸 Anthranilic acid 1.15±0.03 - 2.02±0.06** - 26 4.38 M+H-H2O 172.0752 C11H11NO2 吲哚-3-丙酸 Indole-3-propionic acid - - 0.44±0.01** - 27 5.19 2M+ACN+H 706.3567 C14H24N2O7 大观霉素 Spectinomycin 0.29±0.01** - 18.16±0.36** - 28 7.50 M+H 270.3152 C18H39N 十八胺 Octadecylamine 0.14±0.00 - 0.15±0.00** - 29 9.68 M+H, M+Na, 2M+H, 2M+Na 338.3415 C22H43NO 芥酸酰胺 13Z-Docosenamide 43.66±1.31** - 19.41±0.58 - 30 1.92 M-H2O-H 171.0926 C11H14N2O 艾胺 Alline - - - 0.57±0.02** 31 2.78 M-H 164.0353 C8H7NO3 2-甲酰胺基苯甲酸 N-formylanthranilic acid - - - 0.26±0.01 32 2.99 M-H2O-H 146.0248 C8H7NO3 (R)-2-羟基-2H-1,4-苯并恶嗪-3(4H)-酮 (R)-2-Hydroxy-2H-1,4-benzoxazin-3 (4H)-one - - - 0.31±0.01 33 3.11 M-H 136.0405 C7H7NO2 葫芦巴碱 Trigonelline - - - 1.58±0.05** 34 3.72 M+FA-H 462.1899 C21H27N3O6 (E)-卡西定 (E)-Casimiroedine - - - 0.22±0.01** 35 3.93 M+Cl 296.0910 C11H19NO6 百脉根苷 Lotaustralin - - - 0.23±0.01** 36 3.97 M+FA-H 302.1028 C8H20NO6P 甘油磷酰胆碱 Glycerophosphocholine - 1.54±0.05** - - 37 4.16 M-H2O-H 322.1069 C19H19NO5 4-羟基降南天竹宁 4-Hydroxynornantenine - - - 0.58±0.02** 38 4.42 M-H2O-H 742.2463 C39H43N3O11S 曲贝替定 Trabectedin - - - 3.30±0.07** 39 4.43 M-H 357.3149 C17H19NO5 3-(3,4-二羟苯基)-N-[2-(5-羟苯基)乙基] 丙酮酸3-(3,4-Dihydroxyphenyl)-N-[2-(5- hydroxyphenyl)ethyl]propanimidic acid - 0.40±0.01 - 3.33±0.10** 40 4.46 3M-H 482.1357 C9H7NO2 喹啉-4,8-二醇 Quinoline-4,8-diol - - - 0.30±0.01** 41 5.26 M+Cl 700.2743 C33H47NO13 纳他霉素 Natamycin - - - 2.61±0.05** 42 5.97 M+FA-H 236.1049 C10H13N3O 4-羟基异喹胍 4-Hydroxydebrisoquine - 1.25±0.04** - - 甾体类 Steroids 43 5.61 M+H 305.2095 C19H28O3 16-氧雄甾烯二醇 16-Oxoandrostenediol 0.12±0.00** - - - 芳香类 Aromatics 44 4.24 M+H 133.1012 C10H12 对-孟-1,3,5,8-四烯 p-Mentha-1,3,5,8-tetraene 8.46±0.25 - 8.03±0.24 - 45 4.25 M+H 107.0858 C8H10 间二甲苯 m-Xylene 1.31±0.04** - 1.11±0.03 - 46 9.22 M+H, M+Na, M+K, 2M+Na 391.2835 C24H38O4 邻苯二甲酸二(2-乙基己)酯 Bis(2-ethylhexyl) phthalate 10.41±0.31** - 4.21±0.13 - 47 4.60 M-H 549.1998 C27H34O12 络石苷 Tracheloside - - - 0.43±0.01** 醇类 Alcohols 48 3.19 M+H-H2O, 2M+Na 361.1640 C20H26O7 氨茶醇 Carinol - - 0.19±0.01** - 49 3.75 M+H-H2O, M+H, M+Na 171.1491 C10H18O2 反式-对-孟-2-烯-1,4-二醇 trans-p-Menth-2-ene-1,4-diol 5.78±0.17** - 4.45±0.13 - 50 5.24 M+ACN+H 158.1538 C7H16O 正庚醇 1-Heptanol 0.22±0.01** - 0.15±0.00 - 51 5.30 M+ACN+Na 482.2169 C23H30O7 星形曲霉毒素 Asteltoxin - - 0.11±0.00** - 52 0.76 M-H 349.1855 C16H30O8 反式-对-孟-1,7,8-三醇 8-葡萄糖苷 trans-p-Menthane-1,7,8-triol 8-glucoside - 1.78±0.05** - - 53 3.40 M+FA-H 351.1796 C18H26O4 5'-羧基-γ-色原烷醇 5'-Carboxy-gamma-chromanol - 0.96±0.03** - - 54 3.95 M-H 375.1431 C20H24O7 加利烷醇 Carissanol - - - 0.53±0.02** 55 4.45 M-H 356.9991 C16H30O9 反式-对-孟-1,7,8-三醇 9-葡萄糖苷 trans-p-Menthane-1,7,8-triol 9-glucoside - 0.38±0.01 - 3.39±0.07** 56 4.48 M+FA-H 356.3675 C18H26O5 6'-羧基-γ-色原烷醇 6'-Carboxy-gamma-chromanol - 0.35±0.01 - 3.49±0.07** 57 7.55 M+Na-2H 303.1568 C16H26O4 乳聚醇 CLactapiperanol C - - - 0.41±0.01** 酚类 Phenols 58 2.73 M+H 153.0544 C8H8O3 香草醛 Vanillin 0.49±0.02** - 0.28±0.01 - M-H 151.0400 - 12.15±0.24** - 3.60±0.11 59 6.45 M+H-H2O, 2M+H 653.3095 C20H22O4 (+)-加利恩 (+)-Galeon - - 1.01±0.03** - 60 8.88 M+H 413.3017 C27H40O3 4-甲氧基-3-牛龙牛儿基牛龙牛儿酯-1,2-二羟基苯4-Methoxy-3-geranylgeranyl-1,2- dihydroxybenzene - - 0.31±0.01** - 61 4.27 M+K-3H 360.4726 C27H36O11 杨梅醇 6-葡萄糖苷 Myricanol 6-glucoside - 0.54±0.02 - 2.81±0.06** 酸类 Acids 62 6.13 M+H-2H2O 337.1317 C17H24O9 3,4,5-三羟基-6-[4-(3-羟丁基)-2-甲氧苯基]噁烷-2-羧酸3,4,5-Trihydroxy-6-[4-(3-hydroxybutyl)-2-methoxyphenoxy]oxane-2-carboxylic acid 0.16±0.00** - 0.13±0.00 - 63 7.15 M+Na 317.2084 C18H30O3 9顺,11反-共轭亚油酸 13-OxoODE 0.19±0.01** - - - 64 0.26 M-H 112.9861 C2HF3O2 三氟乙酸 Trifluoroacetic acid - 10.30±0.31** - 2.90±0.06 65 2.15 M-H2O-H 311.0781 C14H18O9 6-(5-乙基-2,3-二羟苯氧基)-3,4,5-三羟基噁烷-2-羧酸6-(5-Ethyl-2,3-dihydroxyphenoxy)-3,4,5-trihydroxyoxane-2-carboxylic acid - 1.32±0.04** - - 66 3.39 M-H2O-H 157.0506 C7H12O5 2-异丙基苹果酸 2-Isopropylmalic acid - - - 0.15±0.00** 67 4.14 M-H 173.1181 C9H18O3 (±)-3-羟基壬酸 (±)-3-Hydroxynonanoic acid - 0.32±0.01** - 0.27±0.00 68 4.28 M+Cl, M+K-3H 360.1568 C36H32O20S (5-{8-[5,7-二羟基-2-(4-羟苯基)-4-氧-3,4-二氢-2H-1-苯并吡喃-3-烷基]-5-羟基-4-氧-7-{[3,4,5-三羟基-6-(羟甲基)噁烷-2-烷基]氧}-3,4-二氢-2H-1-苯并吡喃-2-烷基}-3-羟苯基)氧化磺酸(5-{8-[5,7-Dihydroxy-2-(4-hydroxyphenyl)-4-oxo-3,4-dihydro-2H-1-benzopyran-3-yl]-5-hydroxy-4-oxo-7-{[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-3,4-dihydro-2H-1-benzopyran-2-yl}-3- hydroxyphenyl)oxidanesulfonic acid - 0.53±0.02 - 2.86±0.06** 69 4.38 M-H 358.2622 C9H18O4 (±)-4-羟基壬酸 (±)-4-Hydroxynonanoic acid - 0.44±0.01 - 3.18±0.06** 70 4.50 M-H3O-H 356.0518 C7H12O6 3-异丙基苹果酸 3-Isopropylmalic acid - 0.34±0.01 - 3.54±0.11** 71 4.79 M+Cl, M+K-2H 835.1021 C36H32O19S (5-{8-[5,7-二羟基-2-(4-羟基苯基)-4-氧-3,4-二氢-2H-1-苯并吡喃-3-烷基]-5-羟基-4-氧-7-{[3,4,5-三羟基-6-(羟甲基)噁烷-2-烷基]氧}-3,4-二氢-2H-1-苯并吡喃-2-烷基}-2-羟基苯基)氧化磺酸(5-{8-[5,7-Dihydroxy-2-(4-hydroxyphenyl) -4-oxo-3,4-dihydro-2H-1-benzopyran-3-yl]-5-hydroxy-4-oxo-7-{[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-3,4- dihydro-2H-1-benzopyran-2-yl}-2- hydroxyphenyl)oxidanesulfonic acid - - - 0.94±0.03** 72 6.94 M-H 319.2267 C20H32O3 11(S)-羟基二十碳-5Z,8Z,12E,14Z-四烯酸 11(S)-HETE - 1.65±0.05** - 0.63±0.02 73 7.48 M-H 277.1435 C16H22O4 2,5,7,8-四甲基-6-羟基苯并二氢吡喃基-2-丙酸 α-CEHC - 2.42±0.07** - 0.22±0.01 74 8.94 M-H 279.2322 C18H32O2 17-十八炔酸 17-Octadecynoic Acid - 13.46±0.27** - 0.80±0.02 75 9.14 M-H 305.2469 C20H34O2 5(Z),11(Z),14(Z)-二十碳三烯酸 5(Z),11(Z),14(Z)-Eicosatrienoic acid - 0.60±0.02** - - 76 9.32 M-H 307.2627 C20H36O2 5(Z),14(Z)-二十碳二烯酸 5(Z),14(Z)-Eicosadienoic Acid - 2.83±0.08** - - 77 9.47 M-H 333.2788 C22H38O2 顺13,16,19-二十二碳三烯酸 Docosatrienoic Acid - 1.19±0.04** - - 酮类 Ketones 78 2.76 M+CH3OH+H 361.1639 C19H20O5 1-(3,4-二羟苯基)-7-(4-羟苯基)庚烷- 3,5-二酮1-(3,4-Dihydroxyphenyl)-7-(4- hydroxyphenyl)heptane-3,5-dione - - 0.14±0.00** - 79 3.49 M+ACN+Na 448.1750 C22H24O6 12-去氢波森 12-Dehydroporson - - 0.16±0.00** - 80 4.23 M+H-H2O, M+H 93.0704 C7H10O 3-甲基-2-环己烯-1-酮 3-Methyl-2-cyclohexen-1-one 0.28±0.01** - 0.24±0.01 - 81 4.76 M+H-H2O, M+Na 313.1425 C19H22O5 6-(1-羟基-2-甲基丁基-3-烯-2-烷基)- 2-(2-羟丙基-2-烷基)-2H,3H,7H-呋喃[3,2-g]苯并吡喃-7-酮6-(1-Hydroxy-2-methylbut-3-en-2-yl)-2-(2-hydroxypropan-2-yl)-2H,3H,7H-furo [3,2-g]chromen-7-one 0.16±0.00** - - - 82 2.44 3M-H 545.1655 C9H10O4 1-(2,6-二羟基-4-甲氧基苯基)乙酮 2',6'-Dihydroxy-4'-methoxyacetophenone - 0.09±0.00 - 3.49±0.10** 83 4.35 M-H3O-H 358.8937 C11H12O4 4-(3,4-亚甲基二氧苯基)-3-丁酮 4-(3,4-Methylenedioxyphenyl)-3-butanone - 0.47±0.01 - 3.07±0.06** 84 4.78 M-H2O-H 173.0605 C11H12O3 胡椒基丙酮 4-(3,4-Methylenedioxyphenyl)-2-butanone - 1.48±0.05** - - 85 4.80 M-H, M+FA-H 329.1381 C19H22O5 3-羟基-2-(2-羟丙基-2-烷基)-6-(2-甲丁基-3-烯-2-烷基)-2H,3H,7H-呋喃[3,2-g]色原烷-7-酮3-Hydroxy-2-(2-hydroxypropan-2-yl)-6-(2-methylbut-3-en-2-yl)-2H,3H,7H-furo[3,2-g]chromen-7-one - 0.02±0.00 - 23.98±0.48** 酯类 Esters 86 4.75 M+Na, 2M+Na, M+H-H2O 327.1589 C20H24O5 异千叶蓍酯二烯 Isoachifolidiene 0.58±0.02 - 16.76±0.50** - 87 5.67 M+ACN+H 390.2268 C20H28O5 蜂斗菜内酯C Bakkenolide C 0.21±0.01 - 0.52±0.02** - 88 3.48 M-H 171.1027 C9H16O3 乙酰乙酸异戊酯 3-Methylbutyl 3-oxobutanoate - 9.00±0.18** - 7.83±0.16 89 4.01 M+FA-H 399.1330 C17H22O8 蒽酸甲酯 F 葡萄糖苷 Methyl helianthenoate F glucoside - - - 2.51±0.08** 90 4.52 M-H 355.7360 C9H16O4 3-甲丁基 4-氧丁酸酯 3-Methylbutyl 4-oxobutanoate - 0.33±0.01 - 3.60±0.07** 肽类 Peptides 91 5.00 M+H 640.2524 C27H37N5O13 苏氨酸-苯丙氨酸-葡萄糖-葡萄糖-天冬氨酸 Thr Phe Glu Glu Asp - - 0.42±0.01** - 92 5.27 M+H 446.2743 C23H35N5O4 赖氨酸-异亮氨酸-色氨酸 Lys Ile Trp 0.20±0.01** - - - 93 5.37 M+H 473.1920 C22H28N6O4S 色氨酸-蛋氨酸-组氨酸 Trp Met His - - 0.25±0.01** 94 6.49 M+H 474.3047 C20H39N7O6 谷氨酰胺-丙氨酸-赖氨酸-赖氨酸 Gln Ala Lys Lys 0.77±0.02** - - - 95 5.18 M-H2O-H 283.1539 C11H22N6O4 精氨酸-谷氨酰胺 Arginyl-Glutamine - 0.96±0.03** - 0.24±0.01 96 6.39 M-H 592.2326 C28H39N3O9S 4-羟基-17β-雌二醇-2-S-谷胱甘肽 4-Hydroxy-17beta-estradiol-2-S- glutathione - - - 0.51±0.02** 胺类 Amines 97 7.20 M+H-H2O 444.3312 C24H47NO7 葡萄糖鞘氨醇半乳糖苷 Glucosylsphingosine 0.24±0.01** - - - 其他类 Others 98 2.92 M+H-2H2O 343.1540 C20H26O7 15-羟基勒普妥卡品 15-Hydroxyleptocarpin 0.01±0.00 - 0.27±0.01** - M-H 377.1591 - 0.11±0.00 - 2.80±0.08** 99 2.49 2M+FA-H 505.2998 C12H22O4 塔罗霉素A Talaromycin A - 0.65±0.02** - -