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Acta Amazonica

Print version ISSN 0044-5967

Acta Amaz. vol.40 no.1 Manaus Mar. 2010

http://dx.doi.org/10.1590/S0044-59672010000100029 

QUÍMICA

 

Chemical composition of the essential oils from two subspecies of Protium heptaphyllum

 

Composição química do óleo essencial de duas subespécies do Protium heptaphyllum

 

 

Delcio Dias Marquesi; Rogério Antônio SartoriII; Telma Leda Gomes LemosiII; Luciana Lucas MachadoIV; João Sammy Nery de SouzaV; Francisco José Queiroz MonteVI

IUniversidade Federal do Acre. E-mail: delciomarques@globo.com
IIUniversidade Federal do Acre. E-mail: rogerio_sartori@yahoo.com.br
IIIUniversidade Federal do Ceará. E-mail: tlemos@dqoi.ufc.br
IVUniversidade Federal do Ceará. E-mail: luclucamachado@gmail.com
VUniversidade Federal do Ceará. E-mail: sammynery@yahoo.com.br
VIUniversidade Federal do Ceará. E-mail: fmonte@dqoi.ufc.br

 

 


ABSTRACT

Qualitative and quantitative analyses of the volatile constituents from resin of Protium heptaphyllum (Aubl.) Marchand subsp. ulei (Swat) Daly (PHU), and Protium heptaphyllum (Aubl.) Marchand subsp. heptaphyllum (PHH), Burseraceae were performed using GC-MS and GC-FID. The resins were collected around the city of Cruzeiro do Sul, state of Acre, Brazil. Essential oils from the two subspecies were extracted by hydrodistillation with a yield of 8.6% (PHU) and 11.3% (PHH); the main components were terpinolene (42.31%) and p-cymene (39.93%) for subspecies ulei (PHU) and heptaphyllum (PHH), respectively.

KEYWORDS: Protium heptaphyllum, essential oils, Burseraceae, terpinolene, p-cymene.


RESUMO

As análises qualitativa e quantitativa dos óleos essenciais obtidos das resinas das espécies Protium heptaphyllum (Aubl.) Marchand subespécie ulei (Swat) Daly (PHU) e Protium heptaphyllum (Aubl.) Marchand subespécie heptaphyllum (PHH), Burseraceae, foram realizadas utilizando cromatografia em fase gasosa acoplado a um espectrômetro de massa (CG-EM) e cromatografia a gás com detector de chama (CG-DIC). As resinas foram coletadas no Município de Cruzeiro do Sul, Acre, Brasil. O óleo essencial das oleoresinas foi extraído por hidrodestilação fornecendo rendimento 8,6% para PHU e 11,3% para PHH. Os monoterpenos terpinoleno (42.31%) e p-cimeno (39.93%) foram os constituintes principais para PHU e PHH, respectivamente.

PALAVRAS-CHAVE: Protium heptaphyllum, óleo essencial, Burseraceae, terpinoleno, p-cimeno.


 

 

INTRODUCTION

Many species of vegetal kingdom are characterized by having a large production of essential oil with possibilities of economic exploration, as occurs with the species of Citrus and Eucalyptus. Brazilian exportation of essential oils, plant extracts and oleoresin is around US$ 50.8 million dollars per year, with orange oil having the largest share of this amount (Sousa, 2005). The species of Burseraceae are known to exude resins that are rich in essential oils (Siani et al., 2004), triterpenes and other constituents (Rudiger et al., 2007). Some species of this family produce a great amount of essential oil that has potential possibilities of application in the perfumery industry (Siani et al., 2004) and the diversification of the plant species provides large economic viability (Gottelib & Kaplan, 1990).

The Burseraceae family comprises 18 genera with 700 species divided in three tribes: Protieae (three genera), Canarieae (eigth genera) and Bursereae (seven genera). The Protium genus (Tribe Protieae) is the main family member with 150 species. All tribes are represented in the America, Africa and Indo-Asian tropics, with the highest diversity found in Southern Hemisphere (Weeks et al., 2005). These species are widely spread all over Brazil, mainly in the Amazon Region, where the genus Protium makes up 80% of the Burseraceae (Siani et al., 2004). Alto Juruá Region, in the state of Acre, Brazil, P. heptaphyllum (Aubl.) March. subsp. ueli (Swat) Daly (PHU) and P. heptaphyllum (Aubl.) March. subsp. heptaphyllum (PHH) are widely found, and they are known as an excellent source of oleoresin. Its popular use in medicine is very common, being used as anti-inflammatory, analgesic, expectorant and insect repellant. The resin is also used in the manufacture of varnishes, as impermeable agent of woody boats and as incense in religious rituals (Bandeira et al., 2001). This paper reports by first time the chemical composition of the oleoresin from PHU and PHH collected in state of Acre.

 

MATERIAL E MÉTODOS

Plant material and essential oils extration method

The resins of P. heptaphyllum (Aubl.) Marchand. Subsp. ulei (Swat) Daly (PHU) and P. heptaphyllum (Aubl.) Marchand subsp. heptaphyllum (PHH) were collected in March 2006 the city of Cruzeiro do Sul, western area of Acre state, North of Brazil in BR 364 highway, (07º 35' 45.5" S/72º 46' 36.4" W) and in BR 307 highway (07º 29' 23.4" S/72º 54' 19.8" W), respectively. All species were classified by Dr. Douglas C. Daly and voucher specimens (PHU No. 18.379 and PHH No. 18.381) were deposited in the Herbarium of the Zoobotanic Park of the Universidade Federal do Acre (UFAC), Brazil. The resins of PHU (136g) and PHH (101g) were manually triturated and submitted to hydrodistillation for 8 hs. The oils were obtained in a modified Clevenger-type apparatus. After separation from water, the oils were dried with Na2SO4, stored in sealed glass tubes and maintained under refrigeration. The yields (w/v) to PHU (8.6%) and PHH (11.3%) were calculated based on the weight of fresh resin and the volume of oil extracted.

Gas chromatography and gas chromatography-mass spectrometry

Gas chromatography(GC-FID): The quantitative analysis of the oil were performed in an apparatus gas chromatography (GC) model Trace GC Ultra, equipped with a flame ionization detector (FID) using a dimethylpolysiloxane OV-5 fused silica capillary column (30m x 0.25mm, id x 0.25 μm film thickness) using the following conditions: helium was used as the carrier gas at a flow rate of 1 mL/min and 40 psi inlet pressure; column inlet split ratio 1:48; temperature program: 40-180ºC at 4ºC/min, then heated at a rate of 20ºC/min to 280ºC and held isothermal for 7 min; injector temperature 250ºC; detector with temperature of 280ºC.

Gas chromatography-mass spectrometry (GC-MS): The oil samples were analyzed in a gas chromatography Shimadzu model KP 5050A coupled to a mass detector using a OV-5 capillary column (30 m x 0.25 mm, i.d. x 0.25 μm film thickness) in the following: carrier gas hydrogen flow rate 1 mL/min and with split mode at ratio 1:48, ion source temperature 280ºC, ionizations voltage 70 eV, electron impact detection. The thermal conditions of the column were from 40ºC to 180ºC at 4ºC/min and then 180ºC to 280ºC at 20ºC/min, and held isothermal for 7 min.

The essential oils were analyzed by GC-FID an GC-MS, and individual components was identified comparing the mass spectrum obtained with the Wiley library, simulation of the Kovat index (Alencar et al., 1990), as well as visual comparison with the standard of fragmentation of spectra of mass described in the literature (Adams, 2007) and the database provided with the mass spectra (SciFinder).

 

RESULTS AND DISCUSSION

The composition of the oil from resin of two species of Protium named PHU and PHH is summarized in Table 1. A total of 32 compounds in the two oil samples were identified and they are arranged in the order of elution sequence in column OV-5. The analysis of oil from the resin of PHU and PHH showed predominantly constituted of monoterpenes.

 

 

Sixteen constituents (95.74%) were identified in the sample PHU representing fifteen monoterpenes (94.98%). The major constituent was terpinolene (42.31%) followed by p-cymen-8-ol (13.62%), limonene (11.87%) and p-cymene (4.75%). In the oil PHH were identified twenty-one constituents (98.53%). The p-cymene (39.93%) was the main constituent followed by n-tetradecane (13.38%), dihydro-4-carene (11.69%) and α-phellandrene (7.41%). The presence of the 5 sesquiterpenes β-(E)-caryophyllene, α-humulene, γ-gurjunene, β-bisabolene, α-bisabolene and four hydrocarbons (n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane) in the oil from PHH was a difference between the two analyzed subspecies, besides the main constituent.

The phytochemistry investigation of the essential oil from resin from the P. heptaphyllum (Aubl.) Marchand collected in the state of Ceará - Brazil, has enabled identification of 86.4% of monoterpenes, being the terpinolene (28.5%) the main constituent, followed by α-pinene (10.5%) and α-phellandrene (16.7%) (Bandeira et al., 2001). Other specimens have been collected in Amazonas - Brazil (Zoghbi et al., 1995) and in Pernambuco - Brazil (Pontes et al., 2007) where they performed investigations of the essential oil from the fruits and leaves.

The comparison of the chemical profile of the essential oil from the resin of P. heptaphyllum (Bandeira et al.; 2001) with the oil extracted P. heptaphyllum subsp. ulei (PHU) has provided some likenesses. The two species of P. heptaphyllum and PHU, presented a lot of monoterpenes 86.4% and 91.93%, respectively, and both had the terpinolene as the main component. However, the essential oil from the resin of P. heptaphyllum subsp. heptaphyllum (PHH) shows relevant differences among the three investigated species of Protium. The (PHH) specie was the only that showed four linear hydrocarbons with yield of 20.47%, being n-tretadecano (13.38%) the second most concentrated component.

 

ACKNOWLEDGMENTS

The authors acknowledge the financial support provided by the Brazillian agencies: CNPq, CAPES, FUNCAP, PRONEX, FUNTAC; Laboratory LBPN and Universidade Federal do Acre.

 

LITERATURE CITED

Adams, R.P. 2007. Identification of essential oils components by gas chromatography mass spectroscopy. 4th, Allured Pubishing Corporation, Carol Stream, Illinois, USA, 804 pp.         [ Links ]

Alencar, J.W.; Craveiro, A.A.; Matos, F.J.A.; Machado, M.I.L. 1990. Kovat's indices simulation in essential oils analysis. Química Nova, 13: 282-284.         [ Links ]

Bandeira, P.N.; Pessoa, O.D.L.; Trevisan, M.T.S.; Lemos, T.L.G. 2002. Metabólitos secundários de Protium heptaphyllum March. Química Nova, 25: 1078-1080.         [ Links ]

Bandeira, P.N.; Machado, M.I.L.; Cavalcanti, F.S.; Lemos, T.L.G. 2001. Essential oil composition of leaves, fruits and resin of Protium heptaphyllum (Aubl.) March. Journal of Essential Oil Research, 13: 33-34.         [ Links ]

Gottelib, O.R.; Kaplan, M.A.C. 1990. Amazônia: tesouro químico a preservar. Ciência Hoje, 11: 17-20.         [ Links ]

Pontes, W.J.T.; Oliveira, J.C.G. de; Câmara, C.A.G. da; Lopes, A.C.H.R.; Gondim-Júnior, M.G.C.; Oliveira, J.V. de; Barros, R.; Schwartz, M.O.E. 2007. Chemical composition and acaricidal activity of the leaf and fruit essential oils of Protium heptaphyllum (Aubl.) Marchand (Burseraceae). Acta Amazonica, 37: 103-110.         [ Links ]

Rudiger, A.L.; Siani, A.C.; Veiga-Junior, V.F. 2007. The chemistry and pharmacology of the South America genus Protium Burm, f. (Burseraceae). Pharmacognosy Reviews, 1: 93-104.         [ Links ]

Siani A.C.; Garrido, I.S.; Monteiro, S.S.; Carvalho, E.S.; Ramos, M.F.S. 2004. Protium icicariba as a source of volatile essences. Biochemical Systematic and Ecology, 32: 477-489.         [ Links ]

Sousa E.M.R. 2005. Estudos de fragrância amadereiras da Amazônia. Campinas, Brazil, Dissertação de Mestrado, Instituto de Química, Universidade Estadual de Campinas, Campinas, São Paulo, 148 pp.         [ Links ]

Weeks, A.; Daly, D.C.; Simpson, B.B. 2005. The phylogenetic and biogeography of the frankincense and myrrh family (Burseraceae) based on nuclear and chloroplast sequence data. Molecular Phylogenetics and Evolution, 35: 85-101.         [ Links ]

Zoghbi, M.G.B.; Maia, J.G.S.; Luz, A.I.R. 1995. Volatile constituints from leaves and stems of Protium heptaphyllum (Aubl.) March. Journal of Essential Oil Research, 7: 541-543.         [ Links ]

 

 

Recebido em 12/05/2009
Aceite em 07/07/2009

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