SAFE结合GC-MS/O分离分析29种淡香型天然香辛料香气活性成分

Characterization of the aroma-active compounds in 29 elegant spices by SAFE combined with GC-MS/O

摘要:

采用溶剂萃取结合溶剂辅助蒸发萃取和气相色谱-质谱/嗅闻联用，萃取、分离、富集29种淡香型天然香辛料的香气成分，并进行定性鉴定和定量测定。将29种淡香型香辛料中各类香气活性化合物的种类和含量构建相关系数矩阵网络，建立不同香辛料的网络可视化图。结果表明，29种淡香型香辛料中，共检测到11类244种香气活性成分，包括烯烃类52种、醇类50种、酯类33种、酮类29种、醛类23种、酚类18种、含硫类11种、酸类10种、醚类8种、烷烃类7种和含氮类3种。芳樟醇、丁香酚和香兰素分别在29、27、25种淡香型香辛料中检出。香荚兰、枯茗、芒果和月桂叶中醛类化合物的总质量分数最高，分别主要含有香兰素（11326.29 mg/kg）、4-异丙基苯甲醛（10231.54 mg/kg）、柠檬醛（4.62 mg/kg）和4-异丙基苯甲醛（3471.25446 mg/kg）；枫茅、月桂叶、豆蔻、甘牛至、草果、迷迭香、罗幌子和藏红花中醇类化合物的总质量分数较高，分别主要含有香叶醇（1946.31 mg/kg）、α-松油醇（14070.98 mg/kg）、桉叶油醇（502.06 mg/kg）、芳樟醇（269.32 mg/kg）、反式-橙花叔醇（163.16 mg/kg）、(-)-4-萜品醇（3090.96 mg/kg）、桉叶油醇（52.22 mg/kg）、(1α,2α,5α)-2-甲基-5-(1-甲基乙基)-双环[3.1.0]己-2-醇（88.74 mg/kg）；刺柏、圆叶当归、姜黄、甘草、迷迭香、调料九里香和菖蒲中的烯烃类化合物质量分数最大，分别主要含有茴香脑（6961.66 mg/kg）、大根香叶烯（1050.88 mg/kg）、α-姜黄烯（1305.00 mg/kg）、反-菖蒲烯（435.68 mg/kg）、β-瑟林烯（1541.80 mg/kg）、β-瑟林烯（124.20 mg/kg）和茴香脑（801.68 mg/kg）；蒙百里香、葫芦巴、罗幌子中主要的酚类化合物为丁香酚，含量分别为1174.51、1489.32、82.18 mg/kg；刺山柑、白欧芹中主要的酯类化合物为乙酸松油酯，含量分别为1239.92和249.88 mg/kg；芒果、香椿中的含硫类物质种类和含量最高，分别主要为3-甲硫基丙醛（2.21 mg/kg）和1-甲基乙基丙基二硫（4.29 mg/kg）；芝麻主要以含氮化合物2,6-二甲基吡嗪（23.02 mg/kg）和醚类化合物4-烯丙基苯甲醚（1072.18 mg/kg）为主；石榴和山奈的主要香气成分为茴香脑，含量分别为136.07、132.13 mg/kg；杨桃的主要香气成分为水杨酸甲酯（3.76 mg/kg）。网络关系分析将29种淡香型香辛料分为4大类，其中香椿的介中心度最高，表明其在淡香型香辛料网络中起着核心桥梁作用。

Abstract:

A total of 244 aroma-active compounds including 52 olefins, 50 alcohols, 33 esters, 29 ketones, 23 aldehydes, 18 phenolics, 11 Sulfur-containing compounds, 10 acids, 8 esters, 7 alkanes and 3 nitrogen-containing compounds were identified in 29 elegant spices by the solvent extraction and solvent-assisted flavor evaporation extraction combined with GC-MS/O analysis. Vanilla (vanillin (11326.29 mg/kg), cumin (4-isopropylbenzaldehyde, 10231.54 mg/kg), mango (citral 4.62 mg/kg) and laurel (4-isopropylbenzaldehyde, 3471.25446 mg/kg) had the highest proportion of aldehydes. Srilanka citronella (geraniol, 1946.31 mg/kg), laurel (α-terpineol (14070.98 mg/kg; α-terpineol, 14070.98 mg/kg), cambodian cardamom (1,8-cineole, 502.06 mg/kg), sweet marijoram (linalool, 269.32 mg/kg), tsao-ko (nerolidol, 163.16 mg/kg; geraniol, 106.72 mg/kg), rosemary ((-)-4-terpineol, 3090.96 mg/kg), tamarind (1,8-cineole, 52.22 mg/kg; α-terpineol, 39.24 mg/kg), and saffron ((1α,2α,5α)-2-2-methyl-5-(1-methylethyl)-bicyclic [3.1.0] hex-2-ol, 88.74 mg/kg) had the highest proportion of alcohols. Juniper (anethole, 6961.66 mg/kg), angelia (germacrene D, 1050.88 mg/kg), turmeric (α-curcumene, 1305.00 mg/kg), licorice (trans-Calamenene, 435.68 mg/kg), rosemary (β-selinene, 1541.80 mg/kg; 4,7-dimethoxy-5-(2-propanyl)-1,3-benzodioxole, 1401.16 mg/kg), curry (β-selinene, 124.20 mg/kg) and sweet flag (anethole, 801.68 mg/kg) hag the highest proportion of olefins. Eugenol was the main phenolics in wild thyme (1174.51 mg/kg), fenugreek (1489.32 mg/kg), and tamarind (82.18 mg/kg). Terpinyl acetate was the main ester in caper (1239.92 mg/kg) and white mustard (249.88 mg/kg). Mango and Chinese mahogany had the highest amount and contents of sulfur-containing compounds, among them methional (2.21 mg/kg) and isopropylpropyldisulphide (4.29 mg/kg) were their main sulfur-containing compounds, respectively. 2,6-Dimethylpyrazine (23.02 mg/kg) and 4-allyl anisole (1072.18 mg/kg) were the main nitrogen-containing and ether compounds in sesame, respectively. Quantitative matrix describing network structure analysis divided the 29 elegant spices into 4 categories, and Chinese mahogany had the highest centrality, indicating its key role as a core bridge in the elegant spices network.