通过对顶空固相微萃取(headspace-solid phase microextraction,HS-SPME)、同时蒸馏萃取(simultaneous distillation-extraction,SDE)和液液萃取(liquid-liquid extraction, LLE)3种提取方式的选择、优化,建立了液液萃取结合气相色谱-质谱对山药酒中萜烯类化合物的分析方法。经方法学评估,各萜类化合物线性良好(R2≥0.993 6),定量限为1.86~89.88 μg/L,相对标准偏差小于1.7%,加标回收率为92.68%~103.21%。采用该方法对市售3类山药酒进行分析,准确定量了10种萜烯类化合物,包括5种单萜类化合物、3种倍半萜类化合物以及二萜类化合物和三萜类化合物各1种;各类山药酒中萜烯类化合物组成相近,含量存在差异,与原料产地和加工工艺具有一定的相关性,含量较丰富的长叶松烯、(-)-龙脑、香茅醇和角鲨烯等赋予了山药酒独特的风味及保健功效,为深入研究山药酒的活性成分提供数据支撑。
By selecting and optimizing three extraction methods: headspace-solid phase microextraction (HS-SPME), simultaneous distillation-extraction (SDE), and liquid-liquid extraction (LLE), LLE coupled with GC-MS was developed and applied to determine terpenoids in yam wine. The established methodology displayed a good linear relationship (R2≥0.993 6) of each terpenoid. The quantification limit of the method was in a range of 1.86-89.88 μg/L, the RSD value was less than 1.7%, and the recovery rate was in a range of 92.68%-103.21%. A total of ten terpenoids were accurately quantified by this method in three types of commercial yam wine, including five monoterpenoids, three sesquiterpenes, one diterpenoids, and one triterpenoids. The composition of terpenoids in each yam wine was similar, but their contents were different, which had certain correlations with the origin of raw materials and the processing technology. The major components were longifolene, (-)-borneol, citronellol, and squalene, which provide yam wine unique flavor and health functions. This study provides data support for further studying the active ingredients of yam wine.
[1] 林英男. 复合酶法制备发酵型山药酒及其澄清工艺的研究[D]. 济南:齐鲁工业大学, 2014.
[2] 师彦平. 单萜和倍半萜化学[M]. 北京:化学工业出版社, 2008.
[3] 范文来,胡光源,徐岩. 顶空固相微萃取-气相色谱-质谱法测定药香型白酒中萜烯类化合物[J]. 食品科学, 2012, 33(14): 110-116.
[4] 胡光源,范文来,徐岩,等. 董酒中萜烯类物质的研究[J]. 酿酒科技, 2011(7): 29-33.
[5] PANIGHEL A, FLAMINI R. Solid phase extraction and solid phase microextraction in grape and wine volatile compounds analysis[J]. Sample Preparation, 2015, 2(1):55-65.
[6] SONG M, XIA Y, TOMASINO E. Investigation of a quantitative method for the analysis of chiral monoterpenes in white wine by HS-SPME-MDGC-MS of different wine matrices[J]. Molecules, 2015, 20(4): 7 359-7 378.
[7] 宋静,陈平,王玉莹,等. 苹果酒、醋中香气物质分析[J]. 中国酿造, 2013, 32(6):145-150.
[8] CAMARA J S, ALVES M A, MARQUES J C. Development of headspace solid-phase microextraction-gas chromatography–mass spectrometry methodology for analysis of terpenoids in Madeira wines[J]. Analytica Chimica Acta, 2005, 555(2):191-200.
[9] 董智哲,谷风林,徐飞,等. 固相微萃取和同时蒸馏萃取法分析海南香草兰挥发性成分[J]. 食品科学, 2014, 35(2):158-163.
[10] 姜文广,范文来,徐岩,等. 溶剂辅助蒸馏-气相色谱-串联质谱法分析酿酒葡萄中的游离态萜烯类化合物[J]. 色谱, 2007, 25(6): 881-886.
[11] FAN W L, QIAN M C. Identification of aroma compounds in Chinese ‘Yanghe Daqu’ liquor by normal phase chromatography fractionation followed by gas chromatography[sol ]olfactometry[J]. Flavour & Fragrance Journal, 2010, 21(2):333-342.
[12] 王志娟,张生万,赵景龙,等. 竹叶青酒易挥发成分顶空固相微萃取-气相色谱-质谱分析[J]. 食品科学, 2014, 35(8):253-258.
[13] 吴娟,谢晋,张群林,等.中药引经理论的现代研究进展和思路[J].中国中药杂志,2016,41(13):2 428-2 434.
[14] 曾一翚,梁景河,黄子强,等. 长叶烯的化学及其应用[J]. 贵州林业科技, 1984(4):12-32.
[15] 姜冬梅,朱源,余江南,等. 芳樟醇药理作用及制剂研究进展[J]. 中国中药杂志, 2015, 40(18):3 530-3 533.
[16] BATISTA P A, WEMER M F, OLIVVEIRA E C, et al. Evidence for the involvement of ionotropic glutamatergic receptors on the antinociceptive effect of (-)-linalool in mice.[J]. Neuroscience Letters, 2008, 440(3):299-303.
[17] 张丽丽,马晓琳,王冬,等. 高产橙花叔醇的酵母细胞工厂创建[J]. 中国中药杂志, 2017, 42(15):2 962-2 968.
[18] 雷茜茜. 角鲨烯的抗氧化活性及其脂质体制备研究[D]. 海口:海南大学, 2013.
[19] DEY P, RAY S, CHAUDHURI T K. Immunomodulatory activities and phytochemical characterisation of the methanolic extract of Dioscorea alata, aerial tuber[J]. Journal of Functional Foods, 2016, 23:315-328.
[20] CHAN W K, TAN L T H, CHAN K G, et al. Nerolidol: a sesquiterpene alcohol with multi-faceted pharmacological and biological activities[J]. Molecules, 2016, 21(5): 52.