石头花属Gypsophila L. 为石竹目石竹科植物，约150种，分布于亚洲、欧洲及南美洲。我国有18种1变种^[1]。石头花属植物可供药用，也可供观赏。其具有清热凉血、活血化瘀、消肿止痛、化腐生肌等功效，可治虚劳骨蒸、阴虚久疾、小儿疳热等^[2,3]。现代研究表明，该属主要药用种类有长蕊石头花（又名霞草、丝石竹）、大叶石头花、头状石头花等，其中药用成分主要为皂苷类。其皂苷类成分也被证实在抗肿瘤、免疫调节等方面有显著的活性。本文着重阐述石头花属的植物资源、主要化学成分、药理作用3个方面的研究进展。 1 中国石头花属植物的分类

我国石头花属植物大多分布于西北、华北和东北地区，新疆是其分布和分化集中地，种数往东递减。河北石头花、华山石头花、刺序石头花和细叶石头花为我国特有种^[4]。目前研究发现长蕊石头花、草原石头花、大叶石头花等可供药用。按多年生或一年生、茎直立或斜升、植株高矮、苞片干膜质或叶状、花萼有无白色间隔及宽狭、花序形状、密集或疏散、有无刺、花梗粗细等将中国石头花属种分为5组^[4]。其种类及植物资源分布见表 1^[4,5]。

表 1(Table 1)

表 1 中国石头花属种类及植物资源分布 Table 1 Species in Gypsophila L. and their resource distribution in China 组名 种名 种数 产地 伞房花序组Sect. Corym- bosae Barkoudah 高石头花G. altissima L. 11种、 1变种 新疆（霍城、伊宁、察布查尔、昭苏、新源） 膜苞石头花G. cephalotes (Schrenk) F. N. Williams 新疆阿尔泰山、天山地区、塔什库尔干 长蕊石头花G. oldhamiana Miq. 辽宁、河北、山西、陕西、山东、江苏、河南 河北石头花G. tschiliensis J. Krause 河北小五台山、涞源县白石山、北京百花山 华山石头花G. huashanensis Y. W. Tsui. & D. Q. Lu 陕西华山、秦岭地区 草原石头花（原变种）G. davurica Turcz. ex Fenzl var. davurica 东北、内蒙古、河北（围场） 狭叶草原石头花（变种）G. davurica var. angustifolia Fenzl in Ledeb. 内蒙古东部 大叶石头花G. pacifica Kom. 东北 紫萼石头花G. patrinii Ser. 宁夏、甘肃、青海、新疆 头状石头花G. capituliflora Rupr. 蒙古、宁夏、甘肃、新疆 细叶石头花G. licentiana Hand. -Mazz. 河北、山西、内蒙古、陕西（北部）、宁夏、甘肃、青海、新疆 刺序石头花G. spinosa D. Q. Lu 新疆阿尔泰山、额尔齐斯河地区（吉木乃、布尔津、阿勒泰、北屯） 圆锥花序组Sect. Rokeje- ka (Forssk.) A. Br. 圆锥石头花G. paniculata L. 2种 新疆阿尔泰山、塔什库尔干 钝叶石头花G. perfoliata L. 新疆北部 异色组Sect. Heterochroa (Bge.) Fenzl 卷耳状石头花G. cerastioides D. Don 3种 西藏喜马拉雅山、横断山区（吉隆、亚东、错那、察隅、察瓦龙） 荒漠石头花G. desertorum (Bge.) Fenzl 内蒙古 绢毛石头花G. sericea (Ser.) Krylov 新疆阿尔泰山区（清河、福海） 缕丝花组Sect. Dichoglottis (Fisch. et Mey.) Fenzl 缕丝花G. elegans M. Bieb. 1种 北京、上海、杭州、庐山、呼和浩特、兰州、重庆、新疆等 长胚根组Sect. Macrorrhi- zaea Boiss. 细小石头花G. muralis L. 1种 黑龙江兴凯湖东岸

表 1 中国石头花属种类及植物资源分布 Table 1 Species in Gypsophila L. and their resource distribution in China

黄酮类化合物是许多中药中的有效成分，具有保肝、降血压、抗菌、抗心律失常等作用。此外，其还具有抗自由基、抑制肿瘤细胞和抗致癌促进因子作用，可以防止机体的脂质过氧化反应^[6]。目前从石头花属植物中共发现10个黄酮类化合物，具有黄酮（I）和双苯吡酮（II）2种母核（图 1），化合物名称及取代基见表 2。

图 1 石头花属植物的黄酮类成分母核 Fig. 1 Parent nuclei of flavonoids from plants in Gypsophila L.

表 2(Table 2)

表 2 石头花属植物的黄酮类成分 Table 2 Flavonoids from plants in Gypsophila L. 编号 化合物名称 母核 取代基 植物来源 参考文献 1 isoscoparin R1=R2=H,R3=CH3O b 7 2 isovitexin I R1=R2=R3=H a、e 8-9 3 2″-O-rhamnopyransoyl-isovitexin I R1=R3=H,R2=Rha e 9 4 isoorientin I R1=R2=H,R3=OH e 9 5 2″-O-rhamnopyransoyl-7- methoxylisoorientin I R1=CH3O,R2=Rha,R3=OH e 9 6 2″-O-rhamnopyransoyl-isoorientin I R1=H,R2=Rha,R3=OH e 9 7 apigenin 6-C-[α-L-arabinosyl-(1″→2″)-β-D-gluco- pyranosyl]-7-O-β-D-glucopyranoside I R1=Glc,R2=Ara,R3=H a 10 8 isoorientin-2″-O-α-L-arabinopyranosyl I R1=H,R2=Ara,R3=OH c 11 9 luteolin 7-O-α-L-arabinopyranosyl-6-C-β-glucopyranoside I R1=Ara,R2=H,R3=OH d 12 10 mangiferin II R1=H,R2=Glc e 9 a-G. oldhamiana b-G. capituliflora c-G. elegans d-G. repens e-G. pacifica

表 2 石头花属植物的黄酮类成分 Table 2 Flavonoids from plants in Gypsophila L.

目前，该属植物中的环肽类化合物结构式、名称和植物来源见图 2和表 3。

图 2 石头花属植物的环肽类成分结构 Fig. 2 Chemical structures of cyclic peptides from plants in Gypsophila L.

表 3(Table 3)

表 3 石头花属植物的环肽类化合物 Table 3 Cyclic peptides from plants in Gypsophila L. 编号 化合物名称 分子式 植物来源 参考文献 11 cyclo-(Gly1-Phe2-Asp3-Phe4-Ile5-Leu6-Pro7) C41H53N< sub>7O8 a 13 12 cyclo-(Pro1-Tyr2-Ser3-Phe4-Phe5-Val6-Ile7-Gln8) C51H67N9O11 a 14 13 cyclo-(Pro1-Phe2-Pro3-Pro4-Ser5-Thr6-Gly7-Leu8-Pro9-Ile10) C50H74N10O12 a 14 14 cyclo-(Pro1-Gly2-Ile3-Phe4-Thr5-Ile6-Ile7-Thr8) C42H66N8O10 a 14 15 cyclo-(Pro1-Gly2-Leu3-Ser4-Thr5-Ile6-Leu7-Thr8) C36H62N8O11 a 14 16 cyclo-(Pro1-Gly2-Leu3-Val4-Pro5-Ile6-Gly7) C31H51N7O7 a 14 17 cyclo-(Pro1-Gly2-Phe3-Asp4-Phe5-Ile6-Leu7) C41H55N7O9 a 14 18 cyclo-(Leu1-Pro2-Leu3-Trp4-Pro5-Gly6) C35H49N7O6 f 15 19 cyclo-(Leu1-Pro2-Tyr3-Phe4-Pro5-Gly6) C36H46N6O7 f 15 20 cyclo-(Ala1-Pro2-Tyr3-Leu4-Leu5-Pro6-Pro7-Ala8) C42H62N8O9 f 15 21 cyclo-(Leu1-Trp2-Pro3-Gly4-Gly5-Ser6-Ser7) C32H44N8O9 f 15 f-G. arabica

表 3 石头花属植物的环肽类化合物 Table 3 Cyclic peptides from plants in Gypsophila L.

目前，从该属中分离得到了2种母核的甾醇类化合物（图 3）。化合物名称、取代基和植物来源见表 4。

图 3 石头花属植物的甾醇类成分母核 Fig. 3 Parent nuclei of sterols from plants in Gypsophila L.

表 4(Table 4)

表 4 石头花属植物的甾醇类成分 Table 4 Sterols from plants in Gypsophila L. 编号 化合物名称 母核 取代基 植物来源 参考文献 22 β-D-glucoside-α-spinasterol III R1=Glc a 16-18 23 α-spinasterol III R1=H a 17-18 24 β-sitosterol IV R1=H a、b 7-8,16-18 25 daucosterol IV R1=Glc a、b 7-8,16-18

表 4 石头花属植物的甾醇类成分 Table 4 Sterols from plants in Gypsophila L.

采用顶空固体微萃取法、索氏提取法及水蒸气蒸馏法从长蕊石头花中提取挥发性成分，并用GC-MS联用技术确定了131种成分，主要为苯及苯的同系物、醇醚类、烷烃类、烯类、酯类、茚类、芴类及杂环类。主要化合物有3-methyl-butanal（26）、squalene（27）、1,2-benzenedicarboxylic acid diisooctyl ester（28）、naphazoline（29）、2- methyl-naphthalene（30）、4-methyl-1-pentanol（31）、anethole（32）、benzeneacetaldehyde（33）、methyl hexadecanoate（34）、naphazoline（35）、2,3- dihydro-4-methyl-1H-indene（36）、phenmetrazine（37）等^{[19,20,21,22]}。 2.5 三萜及其皂苷类

三萜及其皂苷类成分不仅是该属植物的主要化学成分，也是具有生物活性的有效成分。该属植物中的三萜类成分几乎都是五环三萜。石头花属中主要的三萜皂苷类化合物见图 4和表 5。

图 4 石头花属植物的三萜类成分母核及部分结构 Fig. 4 Parent nuclei and some structures of triterpenoids from plants in Gypsophila L.

表 5(Table 5)

表 5 石头花属植物的三萜类成分 Table 5 Triterpenoids from plants in Gypsophila L. 编号 化合物名称 母核 植物来源 参考文献 38 quillaic acid α-L-arabinopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→3)-β-D- xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester V a 23 39 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl quillaic acid methyl ester V a 24 40 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosy1-(1→3)]-β-D-glucuronop- yranosyl quillaic acid 28-{O-β-D-fucopyranosyl-(1→4)-[β-D-glucopyranosyl- (1→3)]-α-L-rhamnopyranosyl} ester V a 24 41 quillaic acid 3-O-β-D-galactopyranosyl-(1→2)-[β-D-galactopyranosyl-(1→3)]-β- D-glucuronopyranoside V a 25 42 quillaic acid V a 26-28 43 3-O-{β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl}quillaic acid 28-[α-L-arabinopyranosyl-(1→2)-α-L-arabinopyranosyl-(1→3)- β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl] ester V a 29-30 44 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl quillaic acid 28-O-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl- (1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester V g 31 45 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-β-D-glucopyranosyl-(1→3)-[β-D-glucopyranosyl-(1→4)]-α-L- rhamnopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→4)]-β-D-fucopyranosyl ester V e 32 46 3-O-β-D-galactopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→3)]-β-D-glucopyrano- syl quillaic acid 28-O-a-L-arabinopyranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-[β- D-glucopyranosyl-(1→3)]-α-L-rhamno pyranosyl-(1→2)-[α-L-rhamnopyranosyl- (1→4)]-β-D-fucopyranosyl ester V e 32 47 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-β-D-xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→3)-β-D- xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-[3,4-di-O-acetyl-β-D- quinovopyranosyl-(1→4)]-β-D-fucopyranoside V k 33 48 3-O-β- D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-β-D-xylopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]-α-L- rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-β-D-fucopyranosyl ester V l 34 49 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→3)-β-D- xylopyranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester V l 35 50 3-O-α-L-arabinopyranosyl-(1→2)-[β-D-galactopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl quillaic acid 28-O-α-L-arabinopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→3)- β-D-xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→2)-3-O-acetyl-4-O-cis-p- methoxycinnamoyl-β-D-fucopyranoside V n 36 51 3-O-α-L-arabinopyranosyl-(1→2)-[β-D-galactopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-β-D-xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→3)-β-D- xylopyranosyl-(1→2)-3-O-acetyl-4-O-trans-p-methoxycinnamoyl-β-D-fucopyranoside V n 36 52 3-{{O-β-D-xylopyranosyl-(1→4)-β-D-galactopyranosyl-(1→2)-O-[α-L-arabinopyrano- syl-(1→3)]-β-D-glucopyranuronosyl}oxy}quillaic acid 28-{O-β-D-xylopyranosyl- (1→3)-O-β-D-xylopyranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-O-β-D- quinovopyranosyl-(1→4)]-β-D-fucopyranosyl} ester V n 37 53 3-{{O-α-L-arabinopyranosyl-(1→3)-O-[β-D-galactopyranosyl-(1→2)]-β-D-glucopy- ranuronosyl}oxy}quillaic acid 28-{O-β-D-galactopyranosyl-(1→3)-O-β-D- xylopyranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl} ester V n 37 54 3-{{O-β-D-galactopyranosyl-(1→2)-O-[β-D-xylopyranosyl-(1→3)]-β-D-glucopy- ranosyl}oxy}quillaic acid methyl ester V n 37 55 3-{{O-β-D-glucopyranosyl-(1→2)-O-[β-D-xylopyranosyl-(1→3)]-β-D-glucopy- ranuronosyl}oxy}quillaic acid V n 37 56 3-{{O-β-D-galactopyranosyl-(1→4)-O-[β-D-glucopyranosyl-(1→2)]-β-D-glucopy- ranuronosyl}oxy}quillaic acid V n 37 57 3-{O-β-D-galactopyranosyl-(1→2)-O-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl} quillaic acid 28-{O-β-D-xylopyranosyl-(1→3)-O-β-D-xylopyranosyl- (1→4)-O-α-L-rhamnopyranosyl-(1→2)-O-[3,4-di-O-acetyl-β-D-quinovopyrano- syl-(1→4)]-β-D-fucopyranosyl} ester V n 38 58 rubicunoside C V n 38 59/60 3-O-[β-D-galactopyranosyl-(1→2)][β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl quillaic acid 28-O-[α-L-rhamnopyranosyl-(1→2)]-4-O-acetyl-3-O-(E/Z)-para- methoxycinnamoyl-β-D-fucopyranosyl ester V n 38 61 quillaic acid 3-O-β-D-xylopyranosyl-(1→3)-β-D-glucuronopyranoside V o 39 62 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl quillaic acid 28-O-(6-O-acetyl)-β-D-glucopyranosyl-(1→3)-[β-D-xylopy- ranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranoside V o 39 63 3-O-β-D-galactopyranosyl-(1→2)-6-O-methyl-β-D-glucuronopyranosyl quillaic acid V 39 64 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin methyl ester VI a 24 65 gypsogenin 28-O-α-D-galactopyranosyl-(1→6)-β-D-glucopyranosyl-(1→6)-[β-D- glucopyranosyl-(1→3)]-β-D-glucopyranosyl ester VI a 25 66 3-O-β-D-galactopyranosyl-(1→2)-β-D-glucuronopyranosyl gypsogenin 28-O-β-D- xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranoside VI a 25 67 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin 28-O-α-L-arabinopyranosyl-(1→3)-β-D-xylopyranosyl- (1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranoside VI a 25 68 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl gypsogenin 28-O-(6-O-acetyl)-β-D-glucopyraanosyl-(1→3)-[β-D-xylopy- ranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranoside VI a 25 69 3α-hydroxyepigypsogenin VI a 18,28 70 gypsogenin VI a 18,27-28 71 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-methyl-β-D-glucurono- pyranosyl gypsogenin 28-O-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl- (1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranoside VI a 30 72 3-O-β-D-xylopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucuronopy- ranosyl gypsogenin VI a 40 73 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucurono- pyranosyl)-28-O-(3-O-sulphate-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl- (1→4)]-α-L-rhamnopyranosyl-(1→2)-4-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 74 3-O-(β-D-xylopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(3-O-sulphate-β-D-glucopyranosyl -(1→3)-[β-D-xylopyranosyl- (1→4)]-α-L-rhamnopyranosyl-(1→2)-4-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 75 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopyranoyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(3-O-sulphate-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→ 4)]-α-L-rhamnopyranosyl-(1→2)-3-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 76 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopy ranoyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]-α-L- rhamnopyranosyl-(1→2)-4-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 77 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopyranoyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(6-O-acetyl-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]- α-L-rhamnopyranosyl-(1→2)-4-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 78 3-O-(β-D-xylopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(6-O-acetyl-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]- α-L-rhamnopyranosyl-(1→2)-4-O-acetyl-β-D-fucopyranosyl)-gypsogenin VI h 41 79 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopyranoyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]-α-L- rhamnopyranosyl-(1→2)-β-D-fucopyranosyl)-gypsogenin VI h 41 80 3-O-(α-L-arabinopyranosyl-(1→3)-[β-D-galactopyranosl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(6-O-acetyl-β-D-glucopyranosyl-(1→3)-[α-L-arabinopyranosyl- (1→3)-β-D-xylopyranosyl-(1→4)]-α-L< /i>-rhamnopyranosyl-(1→2)-4-O-acetyl- β-D-fucopyranosyl)-gypsogenin VI h 41 81 3-O-(β-D-xylopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(6-O-acetyl-β-D-glucopyranosyl-(1→3)-[α-L-arabinopyranosyl-(1→ 3)-β-D-xylopyranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-4-O-acetyl-β-D- fucopyranosyl)-gypsogenin VI h 41 82/83 3-O-(α-L-ara binopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→2)]-β-D-glucuronopy- ranosyl)-28-O-(β-D-glucopyranosyl-(1→3)-[α-L-arabinopyranosyl-(1→3)-β-D- xylopyranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-4-O-cis/trans-methoxy- cinnamoyl-β-D-fucopyranosyl)-gypsogenin VI h 41 84 3-O-β-arabinopyranosyl-(1→3)-[β-galactopyranosyl-(1→2)]-β-glucuronopyranosyl gypsogenin VI h 26 85 3-O-β-xylopyranosyl-(1→3)-[β-galactopyranosyl-(1→2)]-β-glucuronopyranosyl gypsogenin VI h 26 86 3β-hydroxyolean-12-en-23-oxo-28-oic acid 28-O-[β-D-glucopyranosyl-(1→2)-β- D-galactopyranosyl-(1→3)]-[β-D-glucopyranosyl-(1→6)]-β-D-galactopyranoside VI i 42 87 gypsogenin 28-O-β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→6)]-β-D- glucopyranoside VI j 43 88 3β-sulfate ester of gypsogenin 28-O-β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl- (1→6)]-β-D-glucopyranoside VI j 44 89 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyrano- syl gypsogenin 28-O-α-L-arabinopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→3)-β- D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester VI e 32 90 3-O-β-D-galactopyranosyl-(1→3)-β-D-glucuronopyranosyl gypsogenin 28-O-β-D- xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)- β-D-fucopyranosyl ester VI e 32 91 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)- [3,4-di-O-acetyl-β-D-quinovopyranosyl-(1→4)]-β-D-fucopyranoside VI k 33 92 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin α-L-arabinopyransyl-(1→3)-β-D-xylopyranosyl-(1→4)-α-L- rhamnopyranosyl-(1→2)-[3,4-di-O-acetyl-β-D-quinovopyranosyl-(1→4)]-β-D- fucopyranoside VI k 33 93 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin 28-β-D-xylopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]- α-L-rhamnopyranosyl-(1→2)-4-O-trans/cis-p-methoxycinnamoyl-β-D-fucopyranosyl VI k 33 94 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-6-O-methyl-β-D- glucuronopyranosyl gypsogenin 28-β-D-xylopyranosyl-(1→4)-[β-D-glucopyrano- syl-(1→3)]-α-L-rhamnopyranosyl-(1→2)-4-O-trans/cis-p-methoxycinnamoyl-β-D- fucopyranoside VI k 33 95/96 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-6-O-methyl-β-D- glucuronopyranosyl gypsogenin 28-β-D-xylopyranosyl-(1→4)-[β-D-glucopyrano- syl-(1→3)]-α-L-rhamnopyranosyl-(1→2)-3-O -trans/cis-p-methoxycinnamoyl-β-D- fucopyranosyl VI k 33 97 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyr- anosyl gypsogenin 28-O-β-D-xylopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]- α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-β-D-fucopyranosyl ester VI l 34 98 3-O-β-D-xylopyranosyl-(1→3)-[β-D-galactopyranosyl-(1→3)-β-D-g alactopyrano- syl-(1→2)]-β-D-glucuronopyranosyl gypsogenin 28-β-D-glucopyranosyl-(1→3)- [β-D-xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→4)]-α-Lrhamnopyranosyl-(1→2)- β-D-fucopyranosyl ester VI l 35 99 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopy- ranosyl gypsogenin 28-O-β-D-xylopyranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-α- L-rhamnopyranosyl-(1→2)-[(4-O-acetyl)-β-D-quinovopyranosyl-(1→4)]-β-D- fucopyranosyl ester VI m 34 100 gypsogenic acid 28-O-β-D-glucopyranosyl-(1→3)-{6-O-[3-hydroxy-3-methylglutaryl]- β-D-glucopyranosyl-(1→6)}-β-D-galactopyranosyl ester VI m 34 101 3-{{O-α-L-arabinopyranosyl-(1→2)-O-[β-D-xylopyranosyl-(1→3)]-β-D-glucopy- ranuronosyl}oxy}-gypsogenin 28-{O-β-D-xylopyranosyl-(1→3)-O-β-D-xylopy- ranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-4-O-[(E)-4-methoxycinnamoyl]- β-D-fucopyranosyl} ester VI n 37 102 3-β-O-(β-D-galactopyranosyl)-(1→3)-β-D-glucopyranosyl gypsogenin 28-O-{β-D- glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)- [β-D-fucopyranosyl-(1→3)]-α-L-arabinopyranosyl ester} VI n 38 103 junceosides C VI n 38 104 agrostemmoside A VI n 38 105 gypsogenin 28-O-[β-D-glucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→3)]-[β-D- glucopyranosyl-(1→6)]-β-D-galactopyranoside VI n 38 106 (3β)-3-O-{β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopy- ranuronosyl}gypsogenin 28-{α-L-arabinopyranosyl-(1→3)-β-D-xylopyranosyl- (1→4)-α-L-rhamnopyranosyl-(1→2)-(3-O,4-O-diacetyl-β-D-fucopyranosyl)}ester V I d 45 107 gypsogenic acid VII a 18,26-28 108 3β-hydroxyolean-12-en-23,28-dioic acid 28-O-[β-D-glucopyranosyl-(1→3)-β-D- glucopyranosyl-(1→2)][β-D-galactopyranosyl(1→6)]β-D-glucopyranoside VII i 42 109 3β-hydroxyolean-12-en-23,28-dioic acid 28-O-[β-D-glucopyranosyl-(1→2)-β-D- galactopyranosyl-(1→3)][β-D-glucopyranosyl(1→6)]β-D-galactopyranoside VII i 42 110 gypsogenic acid 28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl-(1→6)-[β- D-glucopyranosyl-(1→3)]-β-D-glucopyranosyl ester VII e 32 111 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-α-D-galactopyranosyl-(1→6)-β-D- glucopyranosyl-(1→6)-[β-D-glucopyranosyl-(1→3)]-β-D-glucopyranosyl ester VII e 32 112 (3β)-3-O-(β-D-xylopyranosyl)-gypsogenic acid 28-{β-D-glucopyranosyl-(1→6)- β-D-galactopyranosyl}ester VII d 45 113 (3β)-3-O-(β-D-xylopyranosyl)-gypsogenic acid 28-{β-D-xylopyranosyl-(1→2)-[β- D-glucopyranosyl-(1→6)]-β-D-galactopyranosyl}ester VII d 45 114 (3β)-3-O-(β-D-xylopyranosyl)-gypsogenic acid 28-{β-D-glucopyranosyl-(1→3)-[β- D-glucopyranosyl-(1→6)]-β-D-galactopyranosl}ester VII d 45 115 (3β)-3-O-{β-D-glucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→2)-[β-D-glucopy- ranosyl-(1→4)]-β-D-galactopyranosyl}gypsogenic acid VII d 45 116 (3β)-3-O-{β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopy- ranuronosyl}gypsogenic acid 28-{α-L-arabinopyranosyl-(1→4)-α-L-arabinopy- ranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-[β-D- quinovopyranosyl-(1→4)]-β-D-fucopyranosyl}ester VII d 45 117 vaccaric acid,β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]-α-L-rhamno- pyranosyl-(1→2)-β-D-fucopyranosyl ester VIII a 23 118 segetalic acid 28-O-α-L-arabinopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→3)-β- D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester IX a 25 119 collinsogenin X a 18,27-28,40 120 hederagenin XI a 18,27-28 121 23-sulfate ester of hederagenin 28-O-β-D-glucopyranosyl-(1→2)-[β-D-glucopyrano- syl (1→6)]-β-D-glucopyranoside XII j 44 122 3β-O-sulfate gypsogenin 28-O-β-D-glucopyranosyl ester XIII e 46 123 3β-O-sulfate gypsogenin XIII e 46 124 3-O-sulfoechinocystic acid 28-β-glucopyranosyl ester XIV h 47 125 3β-O-sulfate quillaic acid XIV e 46 126 3β-Osulfate oleanolic acid XV e 46 127 oleanolic acid XV a 18,27-28,40 128 3-O-sulfooleanolic acid 28-β-glucopyranosyl ester XV h 47 129 echinocystic acid XVI a 18,27-28 130 3-O-sulfoqu illaic acid 28-β-glucopyranosyl ester XVI h 47 131 hederagenin-3-O-sulfate XVII a 18,28 132 3-keto,16α-hydroxy,24-noroleanolic acid 28-O-α-L-arabiopyranosyl-(1→4)-α-L- arabinopyranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl- (1→2)-β-D-fucopyranosyl ester XVIII a 25 133 hederagonic acid XIX a 18,28 134 (3β,4α,20α)-3,29-dihydroxy-16,23-dioxo-28-norolean-17-en-3-yl-O-β-D-galacto- pyranosyl-(1→2)-O-[β-D-galactopyranosyl-(1→4)]-β-D-glucopyranuronosidic acid XX n 37 135 23-O-β-D-glucopyranosyl gypsogenic acid 28-O-β-D-glucopyranosyl-(1→3)-[β-D- glucopyranosyl-(1→6)]-β-D-glucopyranoside 30 136 (3β)-3-O-(sulfo)lup-20(29)-en-23,28-dioic acid 12 137 (3β)-3-O-(sulfo) lup-20(29)-en-23,28-dioic acid 28-O-β-D-glucopyranosyl ester 12 g-G. pilulifera h-G. trichotoma i-G.capillaris j-G. bermejoi k-G. perfoliata l-G. arrostii m-G. bicolor n-G. paniculata o-G. altissima

表 5 石头花属植物的三萜类成分 Table 5 Triterpenoids from plants in Gypsophila L.

石头花属中还含有其他化合物，如tetracosyl caffeate^[7]（138）、alternariol^[7]（139）、alternariol monomethylether^[7]（140）、syringaldehyde^[8]（141）、 arbutin^[8]（142）、octadecyl caffeate^[16,17,18]（143）、ferulic acid^[17,18]（144）、p-hydroxycinnamic acid^[48]（145）、dihydroferulic acid^[48]（146）、syringic acid^[48]（147）、vanillic acid^[48]（148）等。上述部分化合物的结构式见图 5。

图 5 石头花属植物的其他成分结构式 Fig. 5 Chemical structures of other compounds from plants in Gypsophila L.

采用MTT法及8种人源肿瘤细胞株（KB、PC-3M、A549、KeTr3、A2780、SMMC-7721、HT29、SGC7901）对霞草（长蕊石头花）中霞草皂苷（43）进行细胞毒活性评价，发现其具有一定的体外抑瘤作用，IC₅₀小于50 μg/mL^{[18,37,49,50,51]}。研究还表明，ip 7.5、10.0 mg/kg霞草皂苷（43）对小鼠S₁₈₀肉瘤和H₂₂肝癌具有明显的抑制作用，抑瘤率分别为32.8%、51.1%和42.3%、45.8%，与对照组比较均具有统计学意义，虽然抑瘤率不及阳性对照组，但不良反应较轻^[49]。

Arslan等^[31]发现石头花属植物G. pilulifera Boiss. & Heldr. 中化合物44对A549细胞具有明显的选择抑制活性（IC₅₀＞16 μmol/L）。 3.2 抗肥胖作用

韩立坤等^[52]通过探讨丝石竹水层的总皂苷部位对高脂肪饮食诱发小鼠肥胖的影响，发现其对胰脂肪酶活性呈浓度依赖性抑制，对血浆三酰甘油升高有抑制作用；对高脂肪饮食负荷而导致的体质量及脂肪量增加有抑制作用，证实其具有抗肥胖作用。Zheng等^[30]通过测定油酸（甘油三油酸酯中的油酸）的释放率测定脂肪酶活性，发现长蕊石头花中的皂苷成分43、71、135具有胰脂肪酶抑制作用，当这3种化合物的质量浓度均为1 mg/mL时，对脂肪酶活性抑制率分别为58.2%、99.2%和50.3%，具有明显的抗肥胖作用。 3.3 抗糖尿病作用

石头花属中的长蕊石头花、圆锥石头花中的部分皂苷具有抗糖尿病作用；有很强的α-葡萄糖苷酶抑制活性^[25,36,37]。α-葡萄糖苷酶抑制剂可以阻碍膳食碳水化合物的吸收，抑制餐后高血糖症。Luo等^[25]发现长蕊石头花中的化合物65、118、132具有比阿卡波糖更强的α-葡萄糖苷酶抑制活性。 3.4 保肝作用

从G. trichotoma Wender. 中分得的apigenin-O/ C-diglucoside具有抑制CCl_{4sub>诱导的肝脏氧化损伤的保护作用^[53]。从缕丝花中分得的isoorientin-2″-O-α- L-arabinopyranosyl（8）具有抗肝纤维化甚至肝硬化的作用^[11]。 3.5 免疫抑制作用}

Luo等^[25]研究表明，从霞草根中分离得到的化合物38在10～100 μg/mL时能有效增加粒细胞的吞噬作用（40%～75%），在100 ng/mL～1 pg/mL时，表现出对T细胞活化的免疫抑制作用。 3.6 抗氧化作用

黄海兰等^[54]发现霞草提取物具有较强的抗氧化活性。利用DPPH法、Marklund、邻二氮菲-Fe²⁺氧化法及磷钼络合物法测定各提取物抗氧化活性，同时与合成抗氧化剂BHT进行对照。结果表明，在实验所测浓度下，醋酸乙酯萃取物清除DPPH自由基能力比同浓度的BHT强，其还原能力与BHT非常接近。石油醚萃取物具有很强的清除羟自由基和过氧自由基能力，且均高于同浓度的BHT。张凤梅等^[55]发现满天星中的黄酮类化合物isoorientin-2″- O-α-L-arabinopyranosyl（8）具有较高的抗氧化活性（IC₅₀＝9.8 μmol/L）。 3.7 其他

霞草挥发油中的化学成分如squalene（27）具有抗肿瘤、抗疲劳、抗感染、免疫调节和抗氧化功效，广泛应用于医药、食品、化妆品工业等领域^[21]；naphazoline（29）为拟肾上腺素药，有收缩血管作用，用于过敏性及炎症性鼻充血、急慢性鼻炎、眼充血等，对细菌性过敏性结膜炎亦有效，并能减轻眼睑痉挛；anethole（32）对因化疗或放疗导致的白细胞减少症及其他原因引起的白细胞减少症有一定疗效；phenmetrazine（37）为拟交感神经药，与苯丙胺类似，作用于下丘脑饱感中枢，并影响糖代谢致食欲减退，体质量下降，可用于治疗肥胖症^[20]。 4 结语

石头花属植物中含有非常丰富的化合物，具有多种药理作用。目前，从石头花属植物中分离得到的化学成分主要是三萜及其皂苷类。有研究报道，其中总黄酮的量很高，是很多栽培蔬菜的几倍甚至上百倍。黄酮类物质具有保肝、降压、抗菌等多种药理作用^[56]。目前，对该属植物的研究虽然已取得了一些进展，但仍存在一些不足，主要体现在对该属植物的化学成分方面的研究不够全面，以及药理活性研究不够深入，如化合物的生物合成途径、单体化合物的活性筛选以及提高相对分子质量大、极性大的皂苷类化合物药理活性及生物利用度等方面的研究都有待进一步加强。因此，还需要利用现代药学的研究手段，结合细胞生物学、分子生物学等各相关学科知识，对石头花属中黄酮类、三萜类及其他有效成分进行合理的开发利用，扩展该属植物的应用范围，提高应用价值。