Peperomia

COMPOSITION OF THE ESSENTIAL OIL OF TWO PEPEROMIAFROM PERU: P. Galioides AND P. Chalhuapuquiana PAOLA DÌ LEO LÌRA 1 , YONÌ FARFÁN 2 , CATALÌNA M. vAN BAREN 1 , ARNALDO L. BANDONÌ 1* , JORGE D. COUSSÌO 1 and ANA PASTOR DE ABRAM 2 1 Cátedra de Farmacognosia-IQUIMEFA (UBA-CONICET), Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires. Junín 956, 2º piso. (C 1113 AAD) - C.A. de Buenos Aires, Argentina. *[email protected]. TE: 54-11-4964-8247. FAX: 54-11-4508-3642 2 Departamento de Ciencias, Sección Química, Pontifcia Universidad Católica del Perú. Av. Universitaria s/n Lima 32, Perú. AbSTRACT The volatile oil composition obtained from fresh and dried aerial parts of Peperomia galioides H.B.K. and Peperomia chalhuapuquiana Trelease have been investigated by GC/FID/MS. Seventy two compounds were identifed on P. galioides. The main constituents were found to be β-caryophyllene (13.1-16.0%), α-humulene (13.2- 17.3%) and epi-α-bisabolol (15.1-21.3%). In contrast, the oils of Peperomia chal- huapuquiana were found to contain sabinene (20.5-31.0%), cryptone (8.5-8.7%) and caryophyllene oxide (8.8-10.2%), furthermore other thirty nine compounds were identifed. Key Word Index: Peperomia galioides, Peperomia chalhuapuquiana, essential oil, sabinene, β-caryophyllene, epi-α-bisabolol. RESUMEN Se analizó la composición del aceite esencial obtenido de las partes aéreas frescas y desecadas de Peperomia galioides H.B.K. y Peperomia chalhuapuquiana Trelease, utilizando un sistema GC/FID/MS. Setenta y dos compuestos fueron identifcados en P. galioides, siendo los principales: β-cariofleno (13.1-16.0%), α-humuleno (13.2- 17.3%) y epi-α-bisabolol (15.1-21.3%). En el caso de Peperomia chalhuapuquiana se encontraron como mayoritarios: sabineno (20.5-31.0%), criptona (8.5-8.7%) y óxido de cariofleno (8.8-10.2%), además de otros 39 compuestos. Introduction The genus Peperomia Ruiz and Pavón (Ruiz and Pavon, 1794) is one of the larg- est genera of Angiosperms together with another huge genus, Piper, comprising about 1500-1700 species. Most of them are compact, small perennial epiphytes growing on rotten woods. They are native to Central and South America (Wanke, et al., 2006). Though most Peperomia species are mainly used as ornamental, some of them are used in folk medicine to treat many diseases (Dias dos Santos, et al., 2001). Peperomia galioides H.B.K. (Pg), locally named “Sach´a congona”, “orq´o congona”, 8 Paola Di leo lira, et al. “congona” and “congona macho”, is an endangered succulent herb very used in Peruvian traditional medicine (Hammond, et al., 1998). It grows on the sides of trees and among spiny shrubs with very superf- cial roots. De Feo, in a survey of medicinal and magical plants used in the northern Pe- ruvian Andes, mentioned the popular uses of this species in different pharmaceutical formulations: decoction of the aerial parts is used as vulnerary meanwhile that of the leaves as antiinfammatory in earaches (auricular); leaves juice has decongestive properties for burns, and is also used as lenitive for hemorrhoids, and for frictions against hair-loss. The infusion from fresh leaves is effective in the treatment of scurvy (De Feo, 1992). According to information obtained from one of us from the com- munity of Lares (168 km from Cusco), the leaves juice is used as antispasmodic and analgesic in earaches (2-3 drops directly in the ear), and the hole plant in cataplasm is applied on cuts and external wounds to enhance healing. Other reported uses are in the treatment of gastric ulcers (Hammond, et al., 1998; Neto, et al., 2002), hepatic affections, cardiotonic and against bone’s fracture pain (Agapito Francia and Sung, 2003; Palacios Vaccaro, 1993). Signifcant wound-healing activity was detected by Vil- legas et al. (Villegas, et al., 1997; Villegas, et al., 2001 ) who tested a lyophilized extract from P. galioides in mice, and reported the isolation of (+)-epi-α-bisabolol as the compound responsible for this activity. Afterwards, the same group reported the ethanol extract of the whole plant to have antibacterial activity against Staphylococ- cus aureus and Staphylococcus epidermidis (Neto, et al., 2002), and by bioassay-guided fractionation found grifolin and grifolic acid, as the active compounds (Langfeld, et al., 2004). The essential oil, rich in sesqui- terpenes, also showed antibacterial activity as was recently communicated (Mahiou, et al., 1995). The petroleum ether extract from the whole plant, showed signifcant in vitro antiparasitic activity against Leishmania sp. and Trypanosoma cruzi due to the pres- ence of prenylated compounds (Mahiou, et al., 1996; Zoghbi, et al., 2005). Peperomia chalhuapuquiana Trelease (Pc), locally named “Sach´a chullco”, “china congona“ and “congona hembra”, is popularly used as infusion to alleviate stomach aches. It grows in the fences of farms among stones. No previous phytochemical study on this species has been reported. The composi- tion of the essential oil from other species of Peperomia has been published (Dias dos Santos, et al., 2001; Zoghbi, et al., 2005; da Silva, et al., 1999; Moreira, et al., 1999). Here we report the composition of the essential oils obtained from Peperomia chalhuapuquiana and Peperomia galioides from Peru. ExPERIMENTAL PART Aerial parts of Peperomia galioides and Peperomia chalhuapuquiana were collected in Lares at 3050 m.o.s.l., district of Lares, Calca province, Peru, in January 2005, and were identifed by Alfredo Tupayachi. Voucher specimens are deposited in the Herbarium of the University of San Antonio de Abad, Cusco. Part of the plant material collected of each species was air dried dur- ing one day in a shadowed place. The other part was immediately processed. Hydrodis- tillation was made in a Clevenger-type ap- paratus during 3 hs, and the oils obtained were identifed as (F) from fresh material and (S) from dried material, respectively. The oils were dried over anhydrous sodium sulfate and stored at 4°C in the dark. GC-FID-MS ANALySIS Quantitative and qualitative data were carried out on a Perkin Elmer GC Clarus 500 equipped with an unique split/split- less injector (split ratio: 1:100) connected, Composition of the essential oil of two Peperomia Rev. Latinoamer. Quím. 35/1 (2007) 9 through a fow divisor, to two capillary columns (fused silica, 60 m x 0,25 mm i.d., 0.25μm flm thickness) coated with: a) Polyethyleneglycol (MW aprox. 20.000) (DB-Wax, J&W Scientifc) and b) 5% phe- nyl-95% dimethylpolysiloxane (DB-5, J&W Scientifc). The polar column is connected to a FID detector, while the non polar col- umn is connected to a FID detector and also to MS quadrupole detector (70 eV) using a vent system (MSVent™). Carrier gas: He- lium (setted at constant fow, 1.87 ml/min). Oven temperature was programmed at an initial temperature of 90ºC, increasing at a rate of 3ºC/min to 225ºC and remaining for 15 min. Injector and FID detectors tem- peratures: 255ºC and 275ºC, respectively. Injected volume: 0.2 μL of a dilution 10% in ethanol. Temperature of the transfer line: 180ºC. Ion source temperature: 150ºC. Acquisition mass range: 40-300 m/z. Quantitative data were determined from GC-FID area values on the two columns and expressed as percentages obtained by peak-area percentage. The components of the oil were identifed by comparison of their retention indices relative to C 6 -C 20 alkanes on both columns, and their mass spectral data with those from electroni- cally libraries (NIST, 2002; Mc Lafferty and Stauffer, 2000; Adams, 2001; users) and with data published in the literature. For each compound the minor response from both columns were used. RESULTS AND DISCUSSION The yields of each essential oil based on dried weight were (%v/w): Pc-F: 0.2%, Pc- S: 1.0%, Pg-F: 0.3% and Pg-S: 0.4%. The fragrance of Pc is fruity meanwhile Pg has citric notes. No signifcant olfactive differ- ences were detected between oils coming from the respective fresh and dried mate- rial. According to our results, a careful dry- ing process does not affect its organoleptic qualities. The components identifed in the essential oils from P. chalhuapuquiana and P. galioides are shown in Table 1. Its chemi- cal profles are qualitatively very different. A total of 42 compounds were identifed in P. chalhuapuquiana representing the 85% of the total oil and is characterized mainly by the presence of monoterpenes (52.9-59.2%). This is the frst report about the chemical composition of this species. Meanwhile, a total of 72 constituents were identifed in P. galioides comprising nearly the 95% of the total oil, which is character- ized by the presence of a high content of sesquiterpenes (81.6-81.8%). Villegas (Vil- legas, et al., 2001) revealed the presence of epi-α-bisabolol and viridiforol in an hexane extract of this species. Both sesquiterpenes are present in the analyzed oil, being epi-α- bisabolol together with β-caryophyllene and α-humulene the major ones. The chemical composition of the essential oil we report here is very different from that of Belaunde et al. (2006), who informed β-pinene and limonene as the main components within the monoterpenes, and globulol and β- caryophyllene as the main sesquiterpenes present (Mahiou, et al., 1995). The presence of nonanal and decanal in this oil justifes the citric aroma profle. Though arylpro- panoids are common compounds in the essential oils produced by Piperaceae spe- cies (Dias dos Santos, et al., 2001), only a minor quantity of safrol (0.1%) was detected in those from P. galioides. ACkNOWLEDGMENTS Part of this work was supported by Proyect B019 (UBACYT) in Argentina. In Perú, the Pontifcia Universidad Católica del Perú, supported this research. Authors wish to express their thanks to Red CYTED 306rt278. 10 Paola Di leo lira, et al. Table 1. Chemical composition of the essential oils from fresh and dried aerial parts of P. galioides and P. chalhuapuquiana. IK Compound ( % v/w) PgS PgF PcS PcF 947 α-thujene 0.1 0.1 1.1 1.2 954 α-pinene 1.5 1.0 1.3 1.7 976 sabinene 0.8 0.6 20.5 31.0 976 6-methyl-5-hepten-2-one 0.1 0.1 - - 981 myrcene 1.4 1.7 3.9 3.4 983 β-pinene 1.4 1.2 1.9 3.4 998 p-mentha-1(7)-8-diene - - 0.8 0.4 1013 p-cymene 0.1 0.2 0.5 0.5 1016 limonene 2.6 2.8 3.9 2.4 1019 β-phellandrene 0.2 0.2 5.4 1.7 1021 1,8-cineole 1.4 1.0 0.1 0.2 1022 cis-β-ocimene 0.1 0.3 - - 1048 cis-linalool oxide (furanoid) 0.1 tr - - 1022 cis-sabinene hydrate - - 0.3 0.3 1061 terpinolene 0.3 0.4 0.1 Tr 1068 linalool 0.8 0.5 0.3 0.4 1072 nonanal 0.1 0.1 - - 1119 trans-pinocarveol 0.1 tr 0.1 0.3 1133 sabina ketone - - 0.1 0.5 1133 nonanol 0.2 tr - - 1154 terpinen-4-ol 0.1 tr 0.5 0.3 1165 cryptone - - 8.7 8.5 1168 α-terpineol 0.1 0.1 - - 1170 decanal 0.9 0.4 - - 1173 myrtenal 0.1 0.1 - - 1217 nerol 0.1 tr - - 1220 cumin aldehyde - - 1.2 1.1 1259 p-menth-1-en-7-al - - 0.2 0.2 1261 2-undecanone 0.1 0.2 - - 1267 tridecane - - 0.5 0.3 1268 safrole 0.1 0.1 - - 1270 p-cimen-7-ol - - 1.2 1.5 1301 myrtenyl acetate 0.2 0.2 - - 1307 4-hidroxy criptone - - 0.5 0.5 1323 3-oxo-para-menth-1-en-7-al - - 0.3 0.4 1329 α-cubebene 0.1 tr 0.3 0.3 1339 α-longipinene 0.2 0.2 - - 1357 isoledene 0.1 0.1 - - 1363 α-copaene 0.8 0.6 1.8 1.6 1369 7-epi-sesquithujene 0.2 0.1 - - 1374 β-bourbonene 0.3 0.2 3.8 3.2 1375 β-elemene 0.2 0.1 - - 1380 methyl eugenol 0.1 0.2 - - 1384 sesquithujene 0.2 0.1 - - 1390 dodecanal 0.1 0.1 - - 1399 isocaryophyllene 0.2 0.1 0.4 0.3 1409 α-santalene 0.9 0.7 - - 1417 β-caryophyllene 16.0 13.1 7.0 4.3 1421 cis-α-bergamotene 0.7 0.6 - - 1423 β-cedrene 0.1 0.1 0.6 0.4 1426 α-guaiene 0.1 0.1 - - Composition of the essential oil of two Peperomia Rev. 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