The studies of fat-solube
compounds in Odontotermes formosanus shiraki
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2
化合物的结构式(下标数字为序号)
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。
REFERNCES
[1] Zhong Guo Yao Yong Dong Wu Zhi Xie Zuo Zu. Zhong Guo Yao Yong Dong Wu Zhi (2).
Tianjing: Science and Technologe Press, 1983, 97.
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