气相色谱-质谱联用法测定广玉兰果壳和种子中挥发性化学成分(已发表).doc

气相色谱-质谱联用法测定广玉兰果壳和种子中挥发性化学成分范小春1，2，梁光义1，2*，曹佩雪2，王道平2 1 贵阳中医学院，贵阳 550002； 2贵州省、中国科学院天然产物化学重点实验室， 贵阳 550002摘要：目的: 分析广玉兰果壳和种子的挥发性成分，并比较其异同与含量差异。方法：采用水蒸气蒸馏法分别提取果壳和种子中的挥发性成分，用气相色谱-质谱对其挥发性成分进行鉴定。结果：从广玉兰果壳中分离出111种组分，共鉴定了79种化合物，占挥发油总量的56.54%；从种子中分离出88种组分，共鉴定了58种化合物，占挥发油总量的46.02%；其中果壳和种子的共有成分21种（果壳占总挥发油含量的28.46%，种子占33.77%）。结论：为进一步研究开发广玉兰的果壳与种子提供依据。关键词：广玉兰；挥发性成分；气质联用（GC-MS）Analysis of Volatile Chemical Constituents in Hull and Seeds of Magnolia grandiflora by GC-MS SpectrometryFAN Xiao-chun1, 2, LIANG Guang-yi1, 2*, CAO Pei-xue,WANG Dao-ping（1. Guiyang College of Traditional Chinese Medicine，Guiyang 550002， China 2. The key laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guizhou Guiyang 550002）ABSTRACT：OBJECTIVE: To analyse and compare the volatile components which were extracted from hull and seed of Magnolia grandiflora . METHODS: The volatile components were extracted from hull and seeds of Magnolia grandiflora by steam distillation and the chemical components of them were identified by GC-MS .RESULTS : One hundred and eleven compounds were extracted from the hull, seventy-eight compounds were identified, accounting for 56.54%of the total volatile oil, and eighty-nine compounds were extracted from seed , fifty-eight compounds were identified, accounting for 46.02 % of the total volatile oil. Twenty-one compounds were common in both of hull and seeds. CONCLUSION:The results of the studies can be referenced when the hull and seeds of Magnolia grandiflora need to be further studied.Key words：Magnolia grandiflora；Volatile Chemical Constituents；GC-MS基金项目：国家中医药管理局重点学科，黔科合计工字 20094008号作者简介：范小春，女，硕士研究生，研究方向：主要从事天然药物化学研究。Tel：（0851）3807713 E-mail: 409271850*通讯作者：梁光义，男，硕士学位，教授，博士生导师，研究方向：主要从事天然药物化学研究。 Tel:E-mail: guangyi_ 广玉兰（Magnolia grandiflora）为木兰科木兰属植物，又称大花玉兰、洋玉兰、玉兰，主产地为我国长江流域以南地带。广玉兰叶、花、种子、果壳均可入药，其叶及花中含有挥发油、木兰花碱等多种化学成分，果实中含有脂肪酸，花、叶可提取香料，种子可榨油，其叶乙酸乙酯提取物中还含有黄酮类和酚类化合物，叶和果实中含有五种倍半萜内酯1-2。其幼果水提取物含生物碱、皂苷及黄酮苷，乙醇提取物含黄酮和强心苷3-4。文献研究未发现有对广玉兰果壳和种子中挥发性成分进行对比性研究。本文采用水蒸气蒸馏法提取广玉兰果壳和种子中的挥发性成分，并用气相色谱-质谱联用鉴定其成分，进行对比分析果壳和种子中的所含挥发性成分差异，为进一步研究开发广玉兰的果壳与种子提供依据。1 实验部分11 仪器与材料 广玉兰果实购于贵阳市万东桥药材市场（产地：贵州），由贵阳中医学院何顺志教授鉴定为木兰科木兰属植物广玉兰. Magnolia grandiflora ，正己烷（分析纯，天津市致远化学试剂有限公司），气相色谱-质谱联用仪（HP6890/5975C，美国安捷伦公司），电热套（山东鄄城华鲁仪器公司）。12 挥发油的提取广玉兰成熟果实的果壳与种子剥离，分别粉碎，各称取150g，用适量蒸馏水浸泡5h，用挥发油提取器按常规提取7h直至挥发油量不再增加。得果壳挥发油0.15mL，收率为0.1（mL/g）；种子挥发油0.15mL，收率为0.1（mL/g），所得挥发油均为黄色透明油状物，具有特殊香味。13 GC-MS实验条件1.31 色谱条件色谱柱：Zebron ZB-5MSI 5% Phenyl-95%DiMethylpolysiloxane （300.25mm0.25m）弹性石英毛细管柱，柱温45（保留2min），以5min升温至300，保持2min；汽化室温度250；载气为高纯He（99.999%）；柱前压7.62psi，载气流量1.0mL/min；进样量1L，分流比201，溶剂延迟时间：5min。132质谱条件离子源为EI源；离子源温度230；四极杆温度150；电离能量70eV；发射电流34.6A；倍增器电压1052；接口温度280；扫描质量范围20450amu。2结果与分析所提取的果壳和种子挥发油按上述条件进行测试，得到的总离子流色谱图见图1和图2。所得质谱信息经计算机用NIST05和NTST275数据库检索与标准图谱对照分析，确认了其中部分化学成分。广玉兰果壳和种子的挥发油成分的分析结果见表1。7图1 广玉兰果壳的挥发性成分总离子流图图2 广玉兰种子的挥发油总离子流图表 广玉兰果壳与种子中挥发油化学成分分析结果序号化合物分子式相对含量(%)果壳 种子1p-Cymene p-伞花烃 C10H140.0500.1122Chavicol 佳味醇C9H10O0.0340.0873-Cubebene -库比烯C15H240.0972.7094-Bergamotene -香柑油烯C15H240.1000.1295-Caryophyllen -石竹烯C15H242.6304.3856Germacrene-D 大栊牛儿烯DC15H241.6451.56873,7-Guaiadiene 3,7-愈创木二烯C15H240.1330.1718-Amorphene, (-) -紫穗槐烯C15H243.4916.2109-Selinene -芹子烯C15H243.8460.38310-Cadinene -桅子C15H246.41513.65511(+)-Aromadendrene 香木兰烯C15H240.943-12(+)-Spathulenol 叶桉油烯醇C15H24O7.2180.14913-Longipinene -长叶蒎烯C15H241.0930.24614-Ylangene -衣兰烯C15H240.2970.92115gamma. gurjunene -古芸烯C15H240.46216-Copaene -荜澄茄烯C15H240.54717-Elemene -榄香烯C15H24-18trans-Bergamotene 反佛手柑油烯C15H240.76819-Humulene -律草烯C15H240.72720-Muurolene -衣兰油烯C15H240.98321-Bisabolene -甜没药烯C15H240.86422-Cadinene -桅子C15H24-23Selina-3,7(11)-diene 芹子烷-3,711 齐墩果二烯C15H240.09524Valencene 凡伦橘烯C15H240.55825-Bisabolene -甜没药烯C15H241.16026-Bulnesene -布藜烯C15H240.54427-Cedrene -柏木烯C15H241.54528Tridecane 十三烷C13H280.10129Copaene 可巴烯C15H242.10930Cadina-1(10),4-diene 杜松烯C15H240.15331Bicyclosesquiphellandrene 二环倍半水芹烯C15H240.07732-cadinene -桅子C15H240.60833-Cubebene 荜澄茄油烯C14H300.38234n-Tetradecane 正十四烷C14H300.08835-Calacorene -白菖考烯C15H200.18236n-Heptacosane正二十七烷C27H560.02237Dehydroaromadendrene 脱氢香橙烯C15H22-38n-Dodecane 十二烷C12H260.02839Tridecane (CAS) 正十三烷C13H280.16140Eicosane 二十烷C20H420.0290.268411,4-Dimethylbenzene 1,4-二甲苯C8H100.010-42-pipene -蒎烯C10H160.090-43Camphene 莰烯C10H160.069-44-Plnene -蒎烯C10H160.332-45Limonene 苧稀C10H160.07046Terpinolen 异松油烯C10H160.14947-terpipene -松油烯C10H160.08048Octadecan 十八烷基异氰酸酯C18H380.07949Calacorene 二去氢菖蒲烯C13H161.23750Tetracosane 二十四烷C24H500.97451Heptadecane, 9-octyl- 9-辛基十七烷C25H520.89252Octacosane 二十八烷C28H580.47153Hentriacontane 正三十一烷C31H640.79754Ledene 喇叭烯C15H24O0.18255Caryophyllene Oxiie 石竹素C15H24O5.93456isospathulenol 异大花桉油醇C15H24O1.08057Valerenol 缬草萜烯醇C15H24O0.53158(+)-Costol -木香醇C15H24O0.07759Nerolidol 橙花叔醇C15H26O-60Viridiflorol 绿花白千层醇C15H26O5.41761Pulespenone 胡薄荷烯酮C10H14O0.523622-Methylacetophenone 2-甲基苯乙酮C9H10O0.406633,7-dimethyl-1,5,7-octatrien-3-ol 3,7-二甲基-1,5,7-辛三烯-3-醇C10H16O0.53864d-Pinocarvone右旋松香芹酮C10H14O0.05365alpha.-Thujenal C10H14O0.182661,8-Cineole 1,8-桉叶油素C10H18O0.04467Borneol-L 右旋龙脑C10H18O0.21068terpinene-4-ol 4-萜烯醇C10H18O0.03169CIS-Myrtanol 桃金娘烷醇C10H18O0.14470Levo-bornyl acetate 左旋乙酸冰片酯C10H18O0.42771Ethanone, 1-(4-methyl-3-cyclohexen-1-yl)-,(.+-.)- 1-乙酰基环已烯C9H14O0.02472Pinocarveol, trans-(-)- 反松香芹醇C10H16O 0.07573Camphor 樟脑C10H16O 0.06574Heptanal 庚醛C7H14O0.017-753-Methyl-1-butanol 3-甲基-1-丁醇C5H12 O0.012-762-Methyl-1-butanol 2-甲基-1-丁醇C5H12 O0.017-77-Fenchyl Alocohl -小茴香醇C10H18O0.0810.03078Isobutyl 2-methylbutyrate 2-甲基丁酸异丁酯C9H18O20.1510.28279Methyl palmitate 棕榈酸甲酯C17H34O20.0691.37280Palmitic acid 棕榈酸C16H32O20.0330.78881Ethyl palmitate 软脂酸乙酯C18H36O20.0290.11682Methyl elaidate 反油酸甲酯C19H36O20.0760.18883n-Butyl isovalerate 异戊酸丁酯C9H18O20.100846-Methoxy-1-acetonaphthone1-乙酰-6-甲氧基萘C13H12O20.193852-Methoxy-4-methylphenol 2-甲氧基-4-甲基苯酚C8H10O21.09086Propyl Phthala 邻苯二甲酸二丙酯C14H18O40.036872,5-Dimethylamphetamine 2,5-二甲基苯丙胺C11H17N0.013889,17-Octadecadienal, (Z)-(CAS) (Z)- 9,17-十八碳二烯醛C18H32O0.01989 5-Allyl-5-isobutylbarbituric acid 5-烯丙基-5-异丁基巴比妥酸C11H16N2O30.05790Amyl methyl carbinol 甲基戊基甲醇C10H16 O0.20691Isobuiyl Isovalerate 异戊酸异丁酯C9H18O20.28392Amyl isobutyrate 异丁酸戊酯C9H18O20.05493Amyl butyrate 丁酸戊酯C9H18O20.04994N-Bbuiyl 2-Methyl N-Buiyrate 2-甲基丁酸丁酯C9H18O20.06995Butyl Valerate 戊酸丁酯C9H18O20.020963-Methyl-4-octanone 3-甲基-4-辛基酮C9H18O0.080975-Nonanone 二丁基酮C9H18O0.03798-Phellandrene -水芹烯C10H160.08399Cajeputol 桉树脑C10H18O0.190100 5-Methylhexan-1-al 5-甲基乙醛C7H14O0.047101Caprylic alcohol 正辛醇C8H18O0.081102Isoamyl-2-methyl Butyrate 2-甲基丁酸异戊酯C10H20O20.5581032-Methylbutyl 2-methylbutyrate 2-甲基-丁酸-2-甲基丁酯C10H20O20.443104Amyl isovalerate 异戊酸正戊酯,C10H20O2105Esiragole 龙蒿脑C10H12O0.126106Propyl valerate 戊酸丙酯C8H16O20.0411072,4-Decadienal 2,4-癸二烯醛C10H16O0.144108Nepetalactone 假荆芥内酯C10H14O20.037109Eugenol 丁香酚C10H12O20.034110Globulol 蓝桉醇C15H26O0.597111-Cadinol-荜茄醇C15H26O0.472112ethyl 9-hexadecenoate 9 - 十六碳烯酸乙酯C18H34O20.082113Ethyl oleate 油酸乙酯C20H38O20.102114Magnolol厚朴酚C18H18O20.318在上述实验条件下，从广玉兰果壳中分离出111种组分，鉴定了79种化合物；从种子中分离出88种组分，鉴定了58种化合物，其中果壳和种子的共有成分21种。从表中可以看出，已鉴定广玉兰的果壳和种子共有挥发油成分21种（果壳占总挥发油含量的28.46%，种子占33.77%），其中10种为萜烯类，主要成分有-石竹烯（果壳含2.63%，种子含4.39%）、-紫穗槐烯（果壳含3.49%，种子含6.20%）等；6种为酯类，主要成分有软脂酸乙酯（果壳含0.03%，种子含0.15%）、反油酸甲酯（果壳含0.08%，种子含0.19%）、2-甲基丁酸异丁酯（果壳含0.15%，种子含0.28%）等；其他的主要为醇类，主要成分有叶桉油烯醇（果壳含7.22%，种子含0.15%）、-小茴香醇（果壳含0.08%，种子含0.03%）等；此外，还含有-桅子（果壳含6.42%，种子含13.66%）。虽然果壳和种子所含共有成分种类较多，但一些主要成分并不一致，含量差别较大，如-芹子烯（果壳含3.85%，种子含0.38%）、-库比烯（果壳含0.10%，种子含2.71%）