Seasonal essential oil variation of Aniba canelilla

Biochemical Systematics and Ecology 31 (2003) 69–75 www.elsevier.com/locate/biochemsyseco

Seasonal essential oil variation of Aniba canelilla F.S.N. Taveira a, W.N. de Lima b, E.H.A. Andrade c, J.G.S. Maia c,∗ a

c

Departamento de Quı´mica, Universidade Federal do Maranha˜o, 65080-040 Sa˜o Luis, MA, Brazil b Departamentos de Quı´mica, Universidade Federal do Para´, 66075-900 Bele´m, PA, Brazil Departamento de Botaˆnica, Museu Paraense Emı´lio Goeldi, CP 399, 66040-170, Bele´m, PA, Brazil Received 16 November 2001; accepted 27 March 2002

Abstract The essential oils of leaves, stem bark and trunk wood of Aniba canelilla, collected in the rainy and dry season from different soil types, were obtained by hydrodistillation and analysed by GC/MS. It has been observed that methyleugenol is also an important volatile constituent in the essential oil of A. canelilla, as well as 1-nitro-2-phenylethane. The percentage content of these two compounds was depending on the season time. In the rainy period the 1-nitro2-phenylethane reach values near 95%, while methyleugenol remain below 18%. By contrast, in the dry period 1-nitro-2-phenylethane decrease to 39%, while methyleugenol reach 45%. The leaf oils produced from specimens collected at different soil types in the dry season presented the lower percentage contents to 1-nitro-2-phenylethane and methyleugenol. In contrast, the mono- and sesquiterpenes compounds present in the same oils showed the higher percentage contents.  2002 Elsevier Science Ltd. All rights reserved. Keywords: A. canelilla; Lauraceae; Essential oil composition; 1-Nitro-2-phenylethane; Methyleugenol; Linalool; α-Copaene; β-Caryophyllene; (E)-nerolidol; Seasonal variation

∗

Corresponding author. Tel./Fax: +55-91-274-4025. E-mail address: [email protected] (J.G.S. Maia).

0305-1978/02/$ - see front matter  2002 Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 5 - 1 9 7 8 ( 0 2 ) 0 0 0 8 8 - 1

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1. Introduction Aniba canelilla (H.B.K.) Mez [syn. A. elliptica A. C. Sm., Cryptocarya canelilla Kunth], known as ‘casca-preciosa’ (precious bark), is an important and historical species in the Amazon region for the reason that it was confused with cinnamontrees during the voyage of Pizzaro and Orellana from the Andes to the Amazon estuary about 1540, and during the Humbolt and Bonpland’s 1800 expedition to find the ‘famous cinnamon’ of the Orinoco River. The odoriferous principle of bark and trunk wood of A. canelilla, responsible for the cinnamon odour, is 1-nitro-2-phenylethane (Gottlieb and Magalha˜es, 1960). 1-nitro-2-phenylethane is also reported in the essential oil of Ocotea pretiosa (Gottlieb and Magalha˜es, 1959). Methyleugenol and eugenol were also detected in the first chemical analysis of the essential oil of A. canelilla (Gottlieb and Magalha˜es, 1960). Data from benzyltetrahydroisoquinoline and tetrahydroprotoberberine alkaloids, fungistatic properties and LD50 of the essential oil of stem bark of A. canelilla have been published (Oger et al., 1993, 1994). Now, we are reporting the chemical analysis of the essential oils of some collections of A. canelilla made in the rainy and dry season of different types of soil at Southeast of Para´ State, Brazil. The work was part of a project to identify biogeochemical markers of mineral soils in the Amazon, based on essential oil analysis (Taveira, 1991). A. canelilla was selected because it is wide-spread in the Caraja´s Mineral Province and its major volatile constituents were previously identified.

2. Material and methods 2.1. Material and extraction of volatile constituents The leaves, stem bark and trunk wood of A. canelilla were collected in the areas of “Azul” (manganese mine), “Salobo” (copper mine) and “Zoobotanic Park” (urban area), during the rainy (March/April) and dry (October/November) season. These areas belong to Companhia Vale do Rio Doce (CVRD), in the Caraja´s Saw, Southeast of Para´ State, Brazil, where an important mineral project is located. A further sample of stem bark was collected (October/2000, dry season) in the area of Cauaxi River, Municipality of Paragominas, situated in the same region. Voucher specimens (Nos. 130.714, 131.451, 131.479, 133.926, 133.927) have been kept at the herbarium of Museu Paraense Emı´lio Goeldi, in the city of Bele´m, Para´ state, Brazil. The plant parts were air-dried (250 g, each) for 5–7 days, mill powdered and water-distilled for 4 h using a Clevenger-type apparatus. The distilled oils were dried over anhydrous sodium sulphate and the percentage content were calculated on basis of the dry weight of plant material. The plant collection site and the oil yields are listed in Table 1.

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Table 1 Collection data and oil yield of the samples of A. canelilla Reg. no.

Plant part

Season

Samples collection site

Vegetation type Oil yield

193F

Leaves

Rainy

Azul area— manganese mine

Primary highland forest

193C 193M 174F 174C 174M 194F

Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves

194C 194M 168F 168C 168M 203F

Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves

203C 203M 182F 182C 182M PPCE131

Stem bark Trunk wood Leaves Stem bark Trunk wood Stem bark

Dry

Rainy

Salobo area— copper mine

Dry

Rainy

Zoobotanic park—urban area

Secondary highland forest

Cauaxi river area

0.9 0.6 0.5 0.8 0.5 0.8

0.7 0.5 0.8 0.8 0.6 Reforested area 0.7

Dry

dry

0.5

Primary highland forest

0.8 0.7 0.8 0.9 0.7 1.0

2.2. Analysis of the volatile constituents Analyses of the volatile compounds were performed on two GC/MS instruments: a (1) HP 5988 and a (2) Finnigan Mat INCOS XL, with the following conditions: (1) WCOT SE-54 (25m × 0.32mm; 0.25 µm film thickness) and (2) WCOT DB5MS (30m × 0.25mm; 0.25 µm film thickness) fused silica capillary columns; temperature programmed (1) 50–180 °C (4 °C/min) and 180–250 °C (20 °C/min) and (2) 60–240 °C (3 °C/min); injector temperature, 220 °C; carrier gas, helium, adjusted to a linear velocity of 32 cm/s (measured at 100 °C); split flow was adjusted to give a 20:1 ratio; injection type, splitless (1 µl, of a 1:1000 hexane solution); EIMS, electron energy, 70 eV; ion source temperature and connection parts, 180 °C. Individual components were identified by comparison of both mass spectrum and their GC retention data with those of authentic compounds previously analysed and stored in the data system (Craveiro, 1980). Other identification were made by comparison of mass spectra with those in the data system libraries and cited in the literature (Adams, 1995). The retention indices were calculated for all volatile constituents using a n-alkanes homologous series.

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3. Results and discussion The GC/MS results revealed that methyleugenol is an important volatile constituent in the essential oil of A. canelilla, as well as 1-nitro-2-phenylethane. The percentage content of these two compounds varied with the season. These data are shown in Table 2. In the rainy period the 1-nitro-2-phenylethane values reach near by 95%, while methyleugenol remain below 18%. However, in the dry period 1-nitro-2-phenylethane decrease to less than 40%, while methyleugenol reaches 45%. The greatest value of 1-nitro-2-phenylethane (95.3%) and the least value of methyleugenol (0.2%) were observed in the leaves, during the rainy season. The minimum quantity of 1nitro-2-phenylethane (39.0%) and the highest quantity of methyleugenol (45.8%) were observed in the leaves for the former and in the trunk wood for the latter, during the dry season. Apparently, the essential oils obtained from specimens collected in different soil types presented a quantitative differentiation between themselves and in comparison with that produced from the specimen collected in the Zoobotanic Park, that is located in an area of non-mineralized soil. All samples showed similar profiles, except that the percentage content of 1-nitro-2-phenylethane in the essential oils of stem bark and trunk wood, collected during the dry season, increase from the manganese mineralized soil (48.6%; 47.5%), to the copper mineralized soil (56.2%; 53.3%) and to the non-mineralized soil (68.1%; 73.3%). By contrast, the values of methyleugenol increase from the sample oils of Zoobotanic Park (24.6%; 22.2%), to the sample oils of copper mineralized soil (39.5%; 38.0%) and finally to the manganese mineralized soil (45.3%; 45.8%). The leaf oils produced from specimens collected at different soil types in the dry season gave lower contents of 1-nitro-2-phenylethane and methyleugenol (182F: 42.1 and 0.6%; 168F: 39.3 and 0.5%; 174F: 39.0 and 0.5%, respectively). However, the mono- and sesquiterpenes compounds showed the higher percentage contents. For the copper mine leaf oil (168F) the rates were 10.0% of monoterpenes and 43.2% of sesquiterpenes; for the manganese mine leaf oil (174F) were 11.8 and 40.7%; and for the urban area leaf oil (182F) were 13.5 and 38.0%. The main monoterpene component identified in the dry-season leaf oils was linalool (changing from 6.7 to 12.7%), whereas the main sesquiterpenes were β-caryophyllene (8.5–22.3%), αcopaene (3.9–15.6%) and (E)-nerolidol (2.5–8.2%). The presence of small quantities of benzaldehyde, benzene acetaldehyde, benzonitrile and benzene acetonitrile identified mainly in the essential oils of leaves of A. canelilla is unusual and noteworthy, and they could be the end-products of phenylalanine degradation. If this is so then phenylalanine is probably the origin of 1-nitro2-phenylethane and methyleugenol, and both compounds seems to be biologically interchangeable depending on the impact of extrinsic factors. The chemical composition of the stem bark oil of A. canelilla collected in the Cauaxi River area, in the last dry season, is shown in Table 3. The percentage contents found, 1-nitro-2-phenylethane (52.4%) and methyleugenol (38.6%), were comparable with those observed for the stem barks samples collected in the Caraja´ s Saw. These results are based on single samples at each collection site and do not take

On SE-54 column.

Leaves Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves Stem bark Trunk wood Leaves Stem bark Trunk wood

193F 193C 193M 174F 174C 174M 194F 194C 194M 168F 168C 168M 203F 203C 203M 182F 182C 182M

a

Plant part

Reg.no.

Dry

Rainy

Dry

Rainy

Dry

Rainy

Season

Zoobotanic park

Cu mine

Mn mine

Collection site

70.6 94.3 70.0 39.0 48.6 47.5 94.5 87.1 80.4 39.3 56.2 53.3 95.3 78.2 69.2 42.1 68.1 73.3

1-Nitro-2phenylethanea 3.4 1.0 17.7 0.5 45.3 45.8 0.2 8.7 10.7 0.5 39.5 38.0 0.2 14.7 15.3 0.6 24.6 22.2

Methyleugenola

Table 2 Percentage content of 1-nitro-2-phenylethane and methyleugenol in the essential oils of A. canelilla—season depending

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Table 3 Constituents from essential oil of stem bark of A. canelilla Constituents

Retention indexa

Oil percentage

α-Pinene β-Pinene ⌬3-Carene Limonene β-Phellandrene Benzene acetaldehyde Benzonitrile α-Terpineol Safrole 1-nitro-2-phenylethane α-Cubebene Eugenol α-Copaene β-Elemene Methyleugenol α-Humulene β-Selinene α-Selinene δ-Cadinene trans-Calamenene Cadina-1,4-diene 1-epi-Cubenol Cubenol Selin-11-en-4-α-ol

938 978 1009 1029 1030 1043 1142 1188 1284 1304 1350 1355 1375 1392 1400 1453 1483 1492 1522 1530 1533 1626 1643 1653

0.3 0.2 0.2 0.1 0.1 0.3 0.1 tr 0.4 52.4 0.2 1.7 0.2 0.1 38.6 0.2 0.4 0.4 0.3 0.1 tr 0.1 0.1 2.5

a

On DB-5MS column.

into account within site variation. However, the chemical composition of the analysed essential oils appear to show quantitative variation due to the influence of local environmental conditions of soil and seasonal period of colletions. These findings have economic and ecological significance for species utility in cosmetic uses and biogeochemical studies.

Acknowledgements The authors are grateful to Pilot Program to Protect the Brazilian Rain Forest (PPG-7/European Community) for financial support.

References Adams, R.P., 1995. Identification of Essential Oil Components by Gas Chromatography/Mass Spectroscopy. Allied Publishing Corporation, Illinois. Craveiro, A.A., 1980. Identificac¸ a˜ o por computador de constituintes de o´ leos essenciais usando cromatog-

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rafia de fragmentos ioˆ nicos. Thesis presented to Organic and Inorganic Chemistry Department, Federal University of Ceara´ , Fortaleza. Gottlieb, O.R., Magalha˜ es, M.T., 1959. Occurrence of 1-nitro-2-phenylethane in Ocotea pretiosa and Aniba canelilla. J. Org. Chem. 24, 2070. Gottlieb, O.R., Magalha˜ es, M.T., 1960. Essential oil of the bark and wood of Aniba canelilla. Perf. Essent. Oil Rec. 51, 69–70. Oger, J.-M., Fardeau, A., Richomme, P., Fournet, A., Guinaudeau, H., 1993. Nouveaus alcaloı¨des isoquinole´ iques isole´ s d’une Lauraceae bolivienne: Aniba canelilla H.B.K. Can. J. Chem. 71, 1128–1135. Oger, J.-M., Richomme, P., Guinaudeau, H., Bouchara, J.P., Fournet, A., 1994. Aniba canelilla (H.B.K.) Mez essential oil: analysis of chemical constituents, fungistatic properties. J. Essent. Oil Res. 6, 493–497. Taveira, F.S.N., 1991. Plantas aroma´ ticas da Serra de Caraja´ s como prova´ veis marcadores biogeoquı´micos de solos mineralizados. Thesis presented to Programa de Po´ s-Graduac¸ a˜ o em Quı´mica de Produtos Naturais, Chemistry Department, Federal University of Para´ , Bele´ m.