为探究陈皮挥发油中抗氧化性的关键组分,采用水蒸气蒸馏法提取新会茶枝柑和福建芦柑陈皮挥发油,利用GC-MS法分析陈皮挥发油组成,以1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)、2,2′-联氮-双-3-乙基苯并噻唑啉-6-磺酸[2, 2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid),ABTS]自由基清除能力和还原能力评价陈皮挥发油及其单体的抗氧化性。2种陈皮挥发油中共鉴定出23种成分,均以D-柠檬烯含量最高,γ-萜品烯含量次之,其中新会陈皮挥发油具有相对较低的D-柠檬烯/γ-萜品烯值和倍半萜烯含量,同时邻甲氨基苯甲酸甲酯和香芹酚仅在新会陈皮挥发油中检出。抗氧化性测定结果显示,新会茶枝柑陈皮挥发油相比福建芦柑陈皮挥发油具有基本相同的自由基清除能力和较强的还原能力;单体中香芹酚的抗氧化性最高,弱低于阳性对照VC,单萜烯(萜品油烯、γ-萜品烯和α-松油烯)抗氧化性其次,D-柠檬烯与醛醇类含氧化合物的抗氧化性较低,邻甲氨基苯甲酸甲酯无显著的DPPH自由基清除活性,但具有较强的ABTS自由清除活性和还原能力。结合陈皮挥发油组成和抗氧化性测试表明香芹酚、单萜烯(萜品油烯、γ-萜品烯和α-松油烯)和邻甲氨基苯甲酸甲酯对陈皮挥发油的抗氧化性贡献较大。
To explore the potential antioxidants contribution to the antioxidant activity of Citri retriculatae pericarpium volatile oil, the volatile oil was extracted from Xinhui “Chachi” and Fujian “Ponkan” by steam distillation and then was analyzed by GC-MS. In addition, DPPH/ABTS radical scavenging activity and ferric reducing/antioxidant activity were used to evaluate the antioxidant activity of volatile oil and the compounds in volatile oil. The results showed that a total of 23 compounds were identified in Citri retriculatae pericarpium volatile oil from both Xinhui and Fujian, with D-limonene of the highest content and γ-terpinene of the second-highest content. Citri retriculatae pericarpium volatile oil from Xinhui had a lower ratio of D-limonene/γ-terpinene and sesquiterpene. Additionally, methyl o-methylaminobenzoate and carveol could be detected only in Citri retriculatae pericarpium volatile oil from Xinhui. Furthermore, the antioxidant activity test showed that, compared with Citri retriculatae pericarpium volatile oil from Fujian, Citri retriculatae pericarpium volatile oil from Xinhui possesses the same radical scavenging activity and stronger reducing power. Among all tested compounds, carveol possesses the highest antioxidant activity which slightly smaller than Vc, followed by monoterpene (γ-terpinene, terpinolene, α-terpinene). D-limonene, aldehydes and alcohols have a lower antioxidant activity among all tested compounds. However, methyl ortho-methylaminobenzoate had no significant DPPH radical scavenging activity even though it had relatively strong ABTS scavenging activity and reducing ability. Through the composition analysis and antioxidant activity test, carveol, monoterpene (γ-terpinene, terpinolene, α-terpinene) and methyl ortho-methylaminobenzoate could be considered to be the main contributors to the antioxidant activity of volatile oil from Citri retriculatae pericarpium.
[1] 国家药典委员会.中国人民共和国药典[M].北京:中国医药科技出版社,2015.
Commission.Pharmacopoeia of People's Republic of China[M].Beijing:China Medical Science Press,2015.
[2] QIN K,ZHENG L,CAI H,et al.Characterization of chemical composition of Citri retriculatae pericarpium volatile oil by comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry[J]. Evidence-Based Complementary and Alternative Medicine,2013,6:237 541.
[3] 崔佳韵,梁建芬.不同年份新会陈皮挥发油的抗氧化活性评价[J]. 食品科技,2019,44(1):98-102.
CUI J N,LIANG J F.Antioxidant capacities of essential oils in Xinhui pericarpium Citri reticulatae at different storage period[J]. Food Science and Technology,2019,44(1):98-102.
[4] HE Q,XIAO K.The effects of tangerine peel (Citri reticulatae pericarpium) essential oils as glazing layer on freshness preservation of bream (Megalobrama amblycephala) during superchilling storage[J].Food Control,2016,69:339-345.
[5] HE Q,YANG Z,GONG B.,et al.Quality evaluation focusing on tissue fractal dimension and chemical changes for frozen tilapia with treatment by tangerine peel extract[J].Scientific Reports,2017,7:42 202.
[6] YU X Y,ZHAO M Y,LIU F,et al.Antioxidants in volatile mail lard reaction products:Identification and interaction[J].LWT-Food Science and Technology,2013,53(1):22-28.
[7] HATAMNIA A A,ABBASPOUR N,DARVISHZADEH R.Antioxidant activity and phenolic profile of different parts of bene (Pistacia atlantica subsp.kurdica) fruits[J].Food Chemistry,2014,145:306-311.
[8] LUO M,LUO H,HU P,et al.Evaluation of chemical components in Citri reticulatae pericarpium of different cultivars collected from different regions by GC-MS and HPLC[J].Food Science & Nutrition,2018,6(2):400-416.
[9] 杨元丰,皮达,刘鑫,等.《中国药典》中四个品种来源的陈皮挥发油GC-MS分析比较[J].井冈山大学学报(自然科学版),2018,39(6):77-81.
YANG Y F,PI D,LIU X,et al.Comparison of GC-MS analysis of tangerine peel volatile oils from four varieties in “Pharmacopoeia of People's Republic of China”[J].Journal of Jinggangshan University(Natural Science),2018,39(6):77-81.
[10] 潘靖文.GC-MS分析不同采收期广陈皮中挥发油成分的变化[J].中国医药指南,2011,9(21):258-259.
PAN J W.Chemical variability of essential oils in the peel of tangerine peel in different harvesting periods by GC-MS[J].Guide of China Medicine,2011,9(21):258-259.
[11] 邹士玉,吴成顺,刘飞,等.不同产地陈皮油中3种多甲氧基黄酮含量及香气成分分析[J].广东农业科学,2015,42(22):79-85.
ZOU S Y,WU C S,LIU F,et al.Contents of three kinds of multi-methoxy flavonoids and aroma components in tangerine peel oils from different origins[J].Guangdong Agricultural Science,2015,42(22):79-85.
[12] 欧小群,王瑾,李鹏,等.广陈皮及其近缘品种挥发油成分的比较[J]. 中成药,2015,37(2):364-370.
ZHOU X,HUANG Q H,MO Y Y,et al.Analysis on the volatile oil of Xinhui Citri retriculatae pericarpium in different years by GC-MS[J].Journal of Chinese Medicinal Materials,2009,32(1):24-26.
[13] 周欣,黄庆华,莫云燕,等.GC/MS对不同年份新会陈皮挥发油的分析[J].中药材,2009,32(1):24-26.
ZHOU X,HUANG Q H,LIAO SM,et al.Analysis on volatile of Citri retriculatae pericarpium from different areas by GC-MS[J].Pharmacy Today,2009,19(4):43-45.
[14] 王智磊,伍清芳,刘素娟,等.GC-MS结合AMDIS及Kováts保留指数研究不同虫蛀程度陈皮挥发性成分变化规律[J].中华中医药杂志,2018,33(8):3 327-3 331.
WANG Z L,WU Q F,LIU S J,et al.Variation of volatile components in Citri reticulatae pericarpium after attack of insects by GC-MS combined with AMDIS and Kováts retention index[J].China Journal of Traditional Chinese Medicine and Pharmacy,2018,33(8):3 327-3 331.
[15] 王坚,陈鸿平,刘友平,等.不同贮藏年限新会陈皮挥发油成分动态变化规律研究[J].时珍国医国药,2013,24(12):2 831-2 834.
WANG J,CHEN H P,LIU Y P,et al.Chemical variability of essential oils in Xinhui Citri reticulatae pericarpium stored in different years[J].Lishizhen Medicine and Materia Medica Research,2013,24(12):2 831-2 834.
[16] 周欣,黄庆华,廖素媚,等.不同产地陈皮挥发油的对比分析[J].今日药学,2009,19(4):43-45.
ZHOU X,HUANG QH,LIAO SM,et al.Analysis on volatile of Citri retriculatae pericarpium from different areas by GC-MS[J].Pharmacy Today,2009,19(4):43-45.
[17] 练习中,陈梅斯,吴丽嫦.高效液相色谱-串联质谱法测定新会陈皮中2-甲氨基-苯甲酸甲酯和β-月桂烯[J].食品科技,2018,43(11):326-329.
LIAN X Z,CHEN M S,WU L C.Determination of dimethyl anthranilate and β-myrcene in Xinhui Citri retriculatae pericarpium by UPLC-MS-MS[J].Food Science and Technology,2018,43(11):326-329.
[18] 郑敏燕,古元梓,杜安,等.SPME/GC/MS对比分析不同年份陈皮挥发性成分[J].广东化工,2011,38(3):127-128,137.
ZHENG M Y,GU Y Z,DU A,et al.Comparative analysis of volatile components from Citri retriculatae pericarpium of different storage times by SPME/GC/MS[J].Guangdong Chemical Industry,2011,38(3):127-128,137.
[19] 甘芝霖,倪元颖.γ-萜品烯的体内外抗氧化性研究[J].食品工业科技,2019,40(6):100-105;113.
GAN Z L,NI Y Y.Antioxidant capacity of γ-terpinene in vitro and vivo[J].Science and Technology of Food Industry,2019,40(6):100-105;113.
[20] 黄娜娜.柑橘精油抗氧化特性及对皮肤细胞氧化损伤的保护作用研究[D].武汉:华中农业大学,2016.
HUANG N N.Antioxidant propertity of Citrus essential oil and research on the protective effect on skin fibroblast oxidative damage[D].Wuhan:Huazhong Agricultural University,2016.
