COMPOSITION OF THE ESSENTIAL OIL OF TWO PEPEROMIA FROM PERU: P. Galioides AND P. Chalhuapuquiana

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1 COMPOSITION OF THE ESSENTIAL OIL OF TWO PEPEROMIA FROM PERU: P. Galioides AND P. Chalhuapuquiana Paola Di Leo Lira 1, Yoni Farfán 2, Catalina M. van Baren 1, Arnaldo L. Bandoni 1*, Jorge D. Coussio 1 and Ana Pastor De Abram 2 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 identified on P. galioides. The main constituents were found to be β-caryophyllene ( %), α-humulene ( %) and epi-α-bisabolol ( %). In contrast, the oils of Peperomia chalhuapuquiana were found to contain sabinene ( %), cryptone ( %) and caryophyllene oxide ( %), furthermore other thirty nine compounds were identified. 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 identificados en P. galioides, siendo los principales: β-cariofileno ( %), α-humuleno ( %) y epi-α-bisabolol ( %). En el caso de Peperomia chalhuapuquiana se encontraron como mayoritarios: sabineno ( %), criptona ( %) y óxido de cariofileno ( %), además de otros 39 compuestos. Introduction The genus Peperomia Ruiz and Pavón (Ruiz and Pavon, 1794) is one of the largest genera of Angiosperms together with another huge genus, Piper, comprising about 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, 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. *abandoni@ffyb.uba.ar. TE: FAX: Departamento de Ciencias, Sección Química, Pontificia Universidad Católica del Perú. Av. Universitaria s/n Lima 32, Perú.

2 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 superficial roots. De Feo, in a survey of medicinal and magical plants used in the northern Peruvian 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 antiinflammatory 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 community 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). Significant wound-healing activity was detected by Villegas 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 Staphylococcus aureus and Staphylococcus epidermidis (Neto, et al., 2002), and by bioassay-guided fractionation found grifolin and grifolic acid, as the active compounds (Langfield, et al., 2004). The essential oil, rich in sesquiterpenes, also showed antibacterial activity as was recently communicated (Mahiou, et al., 1995). The petroleum ether extract from the whole plant, showed significant in vitro antiparasitic activity against Leishmania sp. and Trypanosoma cruzi due to the presence 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 composition 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 identified 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 during one day in a shadowed place. The other part was immediately processed. Hydrodistillation was made in a Clevenger-type apparatus during 3 hs, and the oils obtained were identified 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/splitless injector (split ratio: 1:100) connected,

3 Composition of the essential oil of two Peperomia Rev. Latinoamer. Quím. 35/1 (2007) 9 through a flow divisor, to two capillary columns (fused silica, 60 m x 0,25 mm i.d., 0.25μm film thickness) coated with: a) Polyethyleneglycol (MW aprox ) (DB-Wax, J&W Scientific) and b) 5% phenyl-95% dimethylpolysiloxane (DB-5, J&W Scientific). The polar column is connected to a FID detector, while the non polar column is connected to a FID detector and also to MS quadrupole detector (70 ev) using a vent system (MSVent ). Carrier gas: Helium (setted at constant flow, 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 temperatures: 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: 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 identified by comparison of their retention indices relative to C 6 -C 20 alkanes on both columns, and their mass spectral data with those from electronically 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. essential oils from P. chalhuapuquiana and P. galioides are shown in Table 1. Its chemical profiles are qualitatively very different. A total of 42 compounds were identified in P. chalhuapuquiana representing the 85% of the total oil and is characterized mainly by the presence of monoterpenes ( %). This is the first report about the chemical composition of this species. Meanwhile, a total of 72 constituents were identified in P. galioides comprising nearly the 95% of the total oil, which is characterized by the presence of a high content of sesquiterpenes ( %). Villegas (Villegas, et al., 2001) revealed the presence of epi-α-bisabolol and viridiflorol in an hexane extract of this species. Both sesquiterpenes are present in the analyzed oil, being epi-αbisabolol 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 justifies the citric aroma profile. Though arylpropanoids are common compounds in the essential oils produced by Piperaceae species (Dias dos Santos, et al., 2001), only a minor quantity of safrol (0.1%) was detected in those from P. galioides. 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 significant olfactive differences were detected between oils coming from the respective fresh and dried material. According to our results, a careful drying process does not affect its organoleptic qualities. The components identified in the Acknowledgments Part of this work was supported by Proyect B019 (UBACYT) in Argentina. In Perú, the Pontificia Universidad Católica del Perú, supported this research. Authors wish to express their thanks to Red CYTED 306rt278.

4 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 α-pinene sabinene methyl-5-hepten-2-one myrcene β-pinene p-mentha-1(7)-8-diene p-cymene limonene β-phellandrene ,8-cineole cis-β-ocimene cis-linalool oxide (furanoid) 0.1 tr cis-sabinene hydrate terpinolene Tr 1068 linalool nonanal trans-pinocarveol 0.1 tr sabina ketone nonanol 0.2 tr terpinen-4-ol 0.1 tr cryptone α-terpineol decanal myrtenal nerol 0.1 tr cumin aldehyde p-menth-1-en-7-al undecanone tridecane safrole p-cimen-7-ol myrtenyl acetate hidroxy criptone oxo-para-menth-1-en-7-al α-cubebene 0.1 tr α-longipinene isoledene α-copaene epi-sesquithujene β-bourbonene β-elemene methyl eugenol sesquithujene dodecanal isocaryophyllene α-santalene β-caryophyllene cis-α-bergamotene β-cedrene α-guaiene

5 Composition of the essential oil of two Peperomia Rev. Latinoamer. Quím. 35/1 (2007) 11 Table 1. Continua IK Compound ( % v/w) PgS PgF PcS PcF 1432 neryl acetone aromadendrene cis-β-farnesene epi-β-santalene sesquisabinene β-santalene α-humulene allo aromadendrene α-acoradiene γ-muurolene dodecanol ar-curcumene germacrene D pentadecane viridiflorene epi-cubebol bicyclogermacrene β-bisabolene β-curcumene γ-cadinene δ-cadinene β-sesquiphellandrene 0.1 tr trans-calamenene 0.3 tr tr tr 1544 selina 3,7 (11) diene trans-nerolidol germacrene B spathulenol caryophyllene oxide globulol viridiflorol tetradecanal humulene epoxide II tau cadinol bisabolol oxide II epi α-bisabolol Total * experimental IK Order of elution on DB-5 column References Adams, R.P. Identification of Essential Oil Components by Gas Chromatography and Quadrupole Mass Spectrometry. Allured Publ. Corp., Carol Stream IL, Agapito Francia, T.R. and Sung, I. Fitomedicina.1100 Plantas Medicinales, Editorial Isabel Lima-Perú, Belaunde, A., De Martino, L., Mancini E. and De Feo, V. Composizione Chimica e Attivita Antibatterica dell olio Essenziale di Peperomia galioides HBK. Proceedings of the XVº Congresso Italo-latinoamericano di Etnomedicina, Perugia, settembre da Silva, M.H.L., Zoghbi, M.G.B., Andrade, E.H.A. and Maia, J.G.S. The essential oils of Pe-

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