State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany,. The Chinese Academy of Sciences, Kunming 650204, ...
Acta Botanica Sinica 植 物 学 报
2004, 46 (5): 625－630
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Cyclopeptides from Three Arctic Caryophyllaceae Plants, Chemotaxonomy and Distribution Significance of Caryophyllaceae Cyclopeptides JIA Ai-Qun1 , TAN Ning-Hua1 , YANG Yong-Ping2 , WU Su-Gong2 , WANG Li-Qin 1 , ZHOU Jun1 * (1. State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, The Chinese Academy of Sciences, Kunming 650204, China; 2. Laboratory of Plant Biodiversity and Biogeography, Kunming Institute of Botany, The Chinese Academy of Sciences, Kunming 650204, China)
Abst r act : Five new cyclopeptides named arcticumin A (1 ), arcticumin B (2 ), arcticumin C (3 ), regelin A (4 ) and crassipin B (5 ) were isolated from three arctic Caryophyllaceae species (＜100 g), Cerastium arcticum Lange, C. regelii Ostenf. and Stellaria crassipes Hult., with structures elucidated primarily by FAB+ -MS and amino acids analysis. Based on the comparison of Caryophyllaceae cyclopeptides from both the Qinghai-Xizang (Tibet) Plateau and Arctic region, it is proposed that cyclopeptides are characteristic components of Caryophyllaceae and Arctic region is one part of the distribution center of Caryophyllaceae. Ke y wo rds: Stellaria crassipes ; Cerastium arcticum ; Cerastium regelii ; Caryophyllaceae; cyclopeptides; Arctic region; chemotaxonomy; distribution The Caryophyllaceae is an important plant family, containing 60 genera and over 2 000 species in t he world . In most taxonomic literatures, Caryophyllaceae is usually divided int o t hree su bfamilies, namely Pa ron ych oi dea e, Al sin oi dea e, an d Ca ryo ph yll oid ea e (Lu et a l., 2003). Biogeograp hically, Caryophyllaceae is almost d istributed all over the world, some species of which are found in Arctic region or Antarctic (Lu et al., 1996) though most species are distributed in the north temperate region, especially the Mediterranean and East Asia. Meanwhile, some species of the family, such as Pseu dostell aria heterophylla, Dia nth us chi nensis, Psa mmosil ene t un i co id es, Vacca ri a segetalis, have been traditionally used as herb medicine in China (Tang et al., 1996). By now, chemical studies o f more than 150 species of Caryophyllaceae have been conducted. The components investigated include cyclopeptides, saponins, ecdysteroids, flavon oids, alkalo ids, diterp enoids, amino acids, et c. Tan (Zhou et al., 2004) thou ght that cyclopeptides , saponins, ecdysteroids and flavonoids are present widely as characteristic components of Caryo phyllaceae, and five-ringed triterpenoid saponins and cyclopeptides have distinct distribution significance of Caryophyllaceae based on the statistical research of these two types of compounds, i.e. fiverin g ed t rit erp e n o id s ap o n in s ar e p r es en t ed in Pa ro n ych o i d ea e an d C a ryo p h yl l o i d ea e, rar e in
Al sino idea e; to b e more int eres tin g, cyclopep tid es are present in all three Caryophy llaceae su bfamilies, rich in Alsinoideae. Hence, cy clopeptides may be co nsidered as characteristic components, which are more important than ot her ch aracterist ic compo nent s su ch as five-rin ged triterpenoid saponins in this family. Cyclopeptides are cyclic compounds formed mainly with the peptide bonds of protein or non protein amino acids. Bas ed on the skeletal s truct ure, it was proposed on the systematic classification that cyclop eptides could be divided into two classes and six subclasses. The classification is shown as Fig.1 (Tan et al., 1997). Stellaria crassipes, Cerastium arcticum and C. regelii are three species distributed in Arctic region, and they belong to Alsineae tribe of Alsino ideae. The chemical studies of Stellaria and Cerastium are focused on cyclopeptides and flavonoids (Dubois et al., 1982a; 1982b; 1984; Zhao et al., 1995; 1997; Morita et al., 1996; 1997a; 1997b). Chemical inv estigations on t hese t hree species hav e not been reported till now. In this paper, we mainly present the chemical study of cy clo pep t id es fro m t h ree t race s amp les o f arct ic Cary ophyllaceae species Stell aria crassipes, Cerasti um arcticum and C. regelii. The chemotaxonomy and distribution significance of Caryophyllacea cyclopeptides are also discussed.
Received 24 Nov. 2003 Accepted 24 Feb. 2004 Supported by the National Natural Science Foundation of Ch ina (30370118) a nd the Provincia l Natural Scienc e Fund of Yunnan of China (2001B055M). * Author for correspondence. Tel: +86 (0)871 5223264; Fax: +86 (0)871 5223261; E-mail: .
JIA Ai-Qun et al.: Cyclopeptides from Three Arctic Caryophyllaceae Plants, Chemotaxonomy and Distribution Significance of Caryophyllaceae Cyclopeptides
0.000 522%), arct icumin B (2) (0.38 mg , 0.000 389%), arcticumin C (3) (0.46 mg, 0.000 471%), regelin A (4) (0.16 mg, 0.000 433%), respectively. 2.4 Data of cyclopeptides 1－ 5 Arcticumi n A (1) C36 H55 N7 O7 . Amin o acid analysis: Phe (1 eq.), Ile (3eq.), Gly (2 eq.) and Pro (1 eq.). Pos. FAB+MS m/z: 697 [M]+, 550, 436, 324, 267, 154, 97. Arcticumin B (2) C33 H53 N9 O16 . Amino acid analysis of the hydrolysate: Asp (1eq.), Thr (1 eq.), Ser (2 eq.), Glu (1 eq .), Gly (2 eq.) an d Val (2 eq.). Pos. FA B+-MS m/ z: 831 [M]+, 774, 730, 659, 631, 544, 445, 416, 388, 273, 186. Arcticumin C (3) C37 H51 N9 O14 . Amino acid analysis of the hydrolysate:Asp (1 eq.), Thr (1eq.), Ser (2 eq.), Gly (2 eq.), Ph e (1 eq.) and Pro (2 eq.). Pos. FAB+-M S m/z: 845 [M]+, 730, 661, 633, 486, 417, 389, 288, 231, 172, 144. Regelin A (4) C45 H68 N10 O13 . Amin o acid analy sis of the hydrolys ate: Ser (1 eq.), Glu (1eq.), Gly (3 eq.), Val (1 eq.), Leu (2 eq.), Phe (1 eq.) and Pro (1 eq.). Pos. FAB+-MS m/z: 956 [M]+, 809, 723, 695, 598, 513, 485, 398, 369, 341, 228, 99. Crassipin B (5) C33 H43 N7 O8 . Amino acid analysis of the hyd rolysate: Gly (3 eq.), A la (1eq.), Leu (1 eq.), Tyr (1 eq.) and Phe (1 eq.). Pos. FAB+-MS m/z: 665 [M]+, 594, 552, 523, 495, 348, 262, 234, 184. Acknowledgements: The authors are grateful to the members of the analytical group in the State Key Laboratory of Phytoch emistry and Plant Resources in West China, The Chinese Academy of Sciences for spectral measurements, to Prof. WU Zheng-Yi for his helpful advice. References: Dubois M A, Zoll A, Bouillant M L, Delaveau P. 1982a. Di-Cglycosylflavones du Cerastium arvense ssp. arvense nouvelles pourles Caryophyllaceae. Planta Med, 46: 56－57. Dubois M A, Zoll A, Bouillant M L, Chopin J . 1982b. New Cglycosylflavones from Cerastium arvense. Phytochemis try, 21: 1141－1143.
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