Xue Dejun
(Science & Technology Collegy of Jiangxi College of TCM, Nanchang 330006)
Abstract Pharmacological investigation showed that exhibited exprehensive activity on antiinflammation, antiaging, antirheumatism and so on. Sixty nine compounds of fat-solube composition in Odontotermes formosanus were isolated and identified by gas chromatography/mas spectrometry (GC-MS). Most of the chemical constituents from the animal were first reported.
Keywords Odontotermes formosanus, fat-solube compounds, gas chromalography/mas spectrometry
黑翅土白蚁脂溶性化学成分研究
薛德钧
（江西中医学院科技学院，南昌 330006）
2003年3月 日收到;国家自然科学基金资助项目(No.20062003)
摘要 黑翅土白蚁具有抗炎、抗衰老、提高机体免疫功能等广泛的生理活性。本文报道利用GC-MS法对江西产的黑翅土白蚁的脂溶性成分进行了提取、分离和鉴定。经与计算机NIST-MS数据库检索，确认了其中所含的69个化学物质。这些成分绝大多数均属首次从白蚁中分离得到。
关键词 黑翅土白蚁；脂溶性成分；气相色谱-质谱法
1.引言
白蚁是一种古老的昆虫，世界上共有3000余种，国内约有460余种。白蚁主食木材和含纤维的物质，常在桥梁、堤坝、树林和房舍中筑巢，对人类危害极大。白蚁的药用价值历代医书均有记载，其主要功效是滋补强壮作用。临床用于老年体虚、久病气血两亏等。现代医学研究表明，白蚁具有广泛的生理活性，主要在抗炎镇痛、补肾壮阳、抗氧化、抗疲劳、抗衰老、提高机体免疫功能等方面较为显著[1]。我们对江西产的黑翅土白蚁(Odontotermes formosanus shiraki)的乙醚提取物通过毛细管GC-MS法分离鉴定了其中所含的69种化学成分。
2.实验部分
2.1 仪器与材料
FINNIGAN Trace GC 2000 series, trace MS 2000 series(美国Thermofinnigan公司产)；黑翅土白蚁产自江西南昌下罗，由江西农业大学吴德龙副教授鉴定为Odontotermes formosanus shiraki。
2.2 脂溶性成分的制备
新鲜白蚁匀浆后用乙醚超声萃取三次，每次10min，合并萃取液浓缩至适量，备用。
2.3 实验条件
石英毛细柱（中性）HP-5MS，30m×0.25mm，膜厚0.25um，载气为氦气，汽化室温度250oC，柱流量1ml/min，程序升温从40oC开始以5oC/min升至350oC。电离源为EI，电子轰击能量70ev，离子源温度250oC，进样量1.0ml，分流比50:1，扫描范围30-500u.
3.实验结果
实验结果见表1,结构式见表2。
表1 黑翅土白蚁的脂溶性化学成分
| 序号 | 保留时间 | 化合物名称 | 分子式 | 正配率 |
| 1 | 3.33 | 1,1-diethoxyethane (1,1-二乙氧基乙烷) | C6H14O2 | 95 |
| 2 | 4.07 | 4-methylhyptane (4-甲基庚烯) | C8H18 | 95 |
| 3 | 4.48 | Ethyl-methylketonoxim (2-丁酮 ) | C4H9NO | 90 |
| 4 | 7.18 | 2,4-Dimethyl-1-heptene (2,4-二甲基-1-庚烯) | C9H18 | 93 |
| 5 | 11.99 | Normal-Docosane (正22烷) | C22H46 | 94 |
| 6 | 12.19 | 3,3-dimethyloctane (3,3-二甲基辛烷) | C10H22 | 94 |
| 7 | 13.55 | Decane (正癸烷) | C10H24 | 89 |
| 8 | 14.14 | 3,7-dimethyl-1-Octene(3,7-二甲基辛烯) | C10H20 | 92 |
| 9 | 14.41 | 4-Methylbenzaldehyde(4-甲基苯甲醛) | C8H80 | 91 |
| 10 | 14.45 | 4,7-dimethylundecane (4,7-二甲基十一烷) | C13H28 | 74 |
| 11 | 14.60 | 2,3,6,7-Tetramethyloctane (2,3,6,7-四甲基辛烷) | C12H26 | 71 |
| 12 | 14.77 | n-dodecane (十二烷) | C12H26 | 92 |
| 13 | 15.18 | 4-methylundecane (4-甲基十一烷) | C12H26 | 92 |
| 14 | 15.37 | 1,2,4,5-tetramethylbenzene (1,2,4,5-四甲基苯) | C10H14 | 95 |
| 15 | 16.20 | 1,2,3,4-tetramethylbenzene (1,2,3,4-四甲基苯) | C10H14 | 93 |
| 16 | 16.56 | 1,4-dimethoxybenzene (1,4-二氧甲基苯) | C8H10O2 | 92 |
| 17 | 17.20 | Naphthalene (萘) | C10H8 | 91 |
| 18 | 17.31 | 1-Dodecene (1-十二烯) | C12H24 | 89 |
| 19 | 18.59 | 4,6-dimethuldodecane (4,6-二甲基十二烷) | C14H30 | 88 |
| 20 | 19.52 | 2,6,11-trimethyldodeca (2,6,11-三甲基十二烷) | C15H32 | 88 |
| 21 | 19.89 | n-Heptadencane (正十七烷) | C17H36 | 92 |
| 22 | 20.09 | 3,7-dimethyldecane(3,7-二甲基癸烷) | C12H26 | 93 |
| 23 | 20.18 | Benzocycloheptatriene (苯并环庚-1,3-二烯) | C11H10 | 91 |
| 24 | 20.42 | 4,6,8-Trimethyl-1-nonene (4,6,8-三甲基-1-壬烯) | C12H24 | 93 |
| 25 | 20.58 | 4,8-dimethyltridecane (4,8-二甲基十三烷) | C15H32 | 89 |
| 26 | 21.30 | Methylalpha-Chlorophenylacetate (a-氯代苯乙酸甲酯) |
C9H9ClO2 | 93 |
| 27 | 25.24 | Eicosane (正二十烷) | C20H42 | 92 |
| 28 | 25.51 | Pentadecane (十五烷) | C15H32 | 90 |
| 29 | 26.15 | 2,4-bis(1,1-dimethylethyl)phenol (2,4-二叔丁基苯酚) |
C14H22O | 89 |
| 30 | 28.26 | diethylphthalate (邻苯二甲酸二乙酯) | C12H14O4 | 93 |
| 31 | 30.29 | 1-(3,4-dimethylphenyl)ethanone (3,4-二甲基苯乙酮) |
C10H12O | 91 |
| 32 | 30.87 | 3-Butylidene-1(3H)-isobenzofuranone | C12H12O2 | 94 |
| 33 | 32.29 | a-propylbenzenemethanol (a-苯基丁醇) | C10H14O | 91 |
| 34 | 32.52 | 1,2,3,5,6-Hexahydro-inden-4-on | C9H12O | 92 |
| 35 | 32.64 | 2-methyl-1-hexadecanol (2-甲基-1-十六醇) | C17H36O | 91 |
| 36 | 33.15 | Pentacosane (二十五烷) | C25H52 | 92 |
| 37 | 34.61 | 4-Trifluoroacetoxyhexadecane (三氟乙酸-4-十六醇酯) |
C18H33F3O2 | 78 |
| 38 | 34.85 | nonacosane (二十九烷) | C29H60 | 91 |
| 39 | 35.05 | 2-chloro-5-propionylbenzeneacetic (2-氯-5-丙烯氧基苯乙酸甲酯) |
C12H13ClO3 | 87 |
| 40 | 36.16 | 2-[9(z)-octadecenyloxy]ethanol {乙二醇-2-[9(z)-十八烯醇]-醚} |
C20H40O2 | 94 |
| 41 | 36.85 | Phthalic acid,butyl octylester (苯二甲酸丁辛酯) | C20H30O4 | 89 |
| 42 | 38.36 | Dibutyl phthalate (苯二甲酸二丁酯) | C16H22O4 | 90 |
| 43 | 38.44 | Heptacosane (二十七烷) | C27H56 | 92 |
| 44 | 40.34 | n-docosane (二十九烷) | C29H60 | 95 |
| 45 | 41.17 | Hexadecanoic acid,ethylester (十六碳酸乙酯) | C18H36O2 | 93 |
| 46 | 45.26 | 2R-cis-2-(1-emthylethyl)-3,4- oxazolidinedicarboxylic acid (2R-cis-2-(1-甲基乙基)-3,4噁唑烷二酸-3-单乙酯) |
C9H15NO5 | 95 |
| 47 | 46.34 | (E)-Ethyl-9-Octadecenoate (9-十八碳烯酸乙酯) | C20H38O2 | 99 |
| 48 | 47.18 | Octadecanoic acid,ethyl ester (十八碳酸乙酯) | C20H40O2 | 98 |
| 49 | 48.13 | N-phenyl-1-naphthalenamine (N-苯基-1-萘胺) | C16H13N | 92 |
| 50 | 50.21 | Tricosane (二十三烷) | C23H48 | 91 |
| 51 | 51.36 | 4,8,12,16-Tetramethylheptadecan-4-olide (4,8,12,16-四甲基十七碳烷-4-交酯) |
C21H40O2 | 92 |
| 52 | 52.96 | Pentatriacontane (正三十五烷) | C35H72 | 92 |
| 53 | 57.91 | Tetradecanamide (十四碳酸酰胺) | C14H29NO | 94 |
| 54 | 58.30 | (22R)-6a,11b,21-Trihydroxy-16a,17a- propyl- methlenedioxypregna-1,4-diene-3,20-dione [(22R)-6a,11b,21-三羟基-16a,17a-丙基亚甲基二氧孕甾-1,4-二烯-3,20-二酮] |
C25H34O7 | 96 |
| 55 | 59.78 | 4-(1-oxo-3-phenyl-2-propenyl)morpholine [4-(1-氧代-3-苯基-2-丙烯基)吗啉] |
C13H15NO2 | 95 |
| 56 | 60.75 | 9-n-Dodecyltetradecahydroanthracene (9-n-十二烷基十四氢蒽) |
C26H48 | 92 |
| 57 | 61.66 | 4-Octadecylmorpholine (4-十八烷基吗啉) | C22H45NO | 88 |
| 58 | 61.94 | 1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15- Hexadecamethyl-octasiloxane (1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-十六甲基八硅氧烷) |
C16H50O7Si8 | 83 |
| 59 | 62.24 | Dibutylphthalate (邻苯二甲酸二丁酯) | C16H22O4 | 96 |
| 60 | 62.79 | Ethylpentadecanoate (十五碳酸乙酯) | C17H34O2 | 98 |
| 61 | 64.23 | 3b-Cholesta-4,6-dien-3-ol (3b-胆甾-4,6-二烯-3-醇) |
C27H44O | 98 |
| 62 | 64.81 | 1-[2-(octadecyloxy)ethoxy]-9-Octadecene {1-[2-(氧代十八烷基)乙氧基]-9-十八烯烃} |
C38H76O2 | 92 |
| 63 | 65.23 | Hexadecamethylheptasiloxane (十六甲基七硅氧烷) | C16H48O6Si7 | 83 |
| 64 | 66.63 | Eicosane (二十烷) | C20H42 | 73 |
| 65 | 68.37 | Heptacosane (二十七烷) | C27H56 | 71 |
| 66 | 73.58 | 2-methylnonadecane (2-甲基十九烷) | C20H42 | 94 |
| 67 | 82.53 | 1-Heptatriacotanol (1-三十七烷醇) | C37H76O | 95 |
| 68 | 82.90 | Squalene (角鲨烯) | C30H50 | 95 |
| 69 | 71.37 | Diisooctylphthalate (邻苯二甲酸二异辛酯) | C24H38O4 | 91 |
表3 化合物的特征MS数据表
|
序号 |
m/z |
| 1 |
119,103,73,45(100%) |
| 2 |
114,85,70,55,43(100%) |
| 3 |
87,68,58,42(100%) |
| 4 |
126,83,70,55,43(100%) |
| 5 |
310,211,85,71,57,43(100%) |
| 6 |
142,113,85,71,57,43(100%) |
| 7 |
142,85,71,57,43(100%) |
| 8 |
140,125,97,83,43(100%) |
| 9 |
119,91(100%) |
| 10 |
184,85,71,57,43(100%) |
| 11 |
170,148,107,85,71,57,43(100%) |
| 12 |
170,127,98,85,71,57,43(100%) |
| 13 |
170,126,85,71,57,43(100%) |
| 14 |
134,119(100%) |
| 15 |
134,119(100%),41 |
| 16 |
138,123(100%) |
| 17 |
128(100%),102,74,51 |
| 18 |
168,140,111,97,83,69,55,41(100%) |
| 19 |
198,183,155,113,85,71,57(100%) |
| 20 |
212,197,169,141,113,85,57,43(100%) |
| 21 |
240,211,183,155,127,99,85,71,57,43(100%) |
| 22 |
170,155,127,99,85,71,57,43(100%) |
| 23 |
142(100%),128,115,89,63 |
| 24 |
168,153,111,85,71,57,43(100%) |
| 25 |
212,197,169,141,98,85,71,57,43(100%) |
| 26 |
184,149,125(100%) |
| 27 |
282,211,183,155,127,99,85,71,57,43(100%) |
| 28 |
212,183,155,127,99,85,71,57,43(100%) |
| 29 |
206,191(100%) |
| 30 |
222,177,149(100%) |
| 31 |
148,133(100%) |
| 32 |
188,159(100%) |
| 33 |
150,107(100%) |
| 34 |
136,108(100%) |
| 35 |
256,238,210,182,139,111,97,83,69,57,43(100%) |
| 36 |
352,239,211,183,155,127,99,85,71,57,43(100%) |
| 37 |
338,301,267,238,224,196,125,97,83,69,55,43(100%) |
| 38 |
408,365,267,155,99,85,71,57,43(100%) |
| 39 |
240,211(100%),181,89 |
| 40 |
312,250,109,96,82,69,55(100%) |
| 41 |
334,279,223,192,149(100%) |
| 42 |
278,274,223,149(100%) |
| 43 |
380,323,295,267,211,183,570,43(100%) |
| 44 |
310,267,211,183,155,127,85,71,51,43(100%) |
| 45 |
284,239,199,157,115,101,88(100%) |
| 46 |
216,188,174(100%),158 |
| 47 |
310,264,101,88,69,55(100%),41 |
| 48 |
312,269,241,213,185,157,115,101,88(100%) |
| 49 |
219(100%),191,165,140,115,77 |
| 50 |
324,295,239,155,99,85,71,51,43(100%) |
| 51 |
324,254,221,184,151,114,99(100%),83,69 |
| 52 |
492,441,418,388,295,257,43(100%) |
| 53 |
227,184,156,128,86,72,59(100%) |
| 54 |
446,403,387(100%),369,297,121,55 |
| 55 |
217,202,172,131(100%) |
| 56 |
360,303,264,236,205,191(100%) |
| 57 |
338,294,184,156,126,100(100%) |
| 58 |
578,563,503,429,401,341,281,207,147,73(100%) |
| 59 |
278,223,167,149(100%) |
| 60 |
270,227,185,157,115,101,88(100%) |
| 61 |
384,366,247,43(100%) |
| 62 |
564,475,313,250,111,57(100%) |
| 63 |
532,517,355,255,281,221,207,147,73(100%) |
| 64 |
282,211,183,99,85,71,57(100%) |
| 65 |
380,211,155,127,99,85,71,57(100%) |
| 66 |
282,267,239,211,183,99,57(100%) |
| 67 |
536,494,442,415,364,285,190,147,57,43(100%) |
| 68 |
410,367,341,2999,137,81,69(100%) |
| 69 |
390,279,167,149(100%),104,57,43 |
4.讨论
从白蚁机体中分离和鉴定了其中所含的69种脂溶性化学成分。结果表明白蚁机体成分复杂，除含有各种烃类化合物外，还含有甾体激素类、肟类、角鲨烯、含氮、氯、氟有机物、有机硅氧类、杂环化合物等。自然界中除海洋药物含有卤素外，陆生动植物种属中很少含有氟类化合物。为此，我们正对其所含化学成分进行药效学研究。
本文所报道的数据结果，仅是利用GC-MS法所得，未经其它辅助手段验证。