Composition of the Volatile Oils of the Aerial Parts ofPedicularis sibthorpii and P. wilhelmsiana Growing in Iran

Laleh Khodaei 1, Abbas Delazar 1, Hossein Nazemiyeh 1,Solmaz Asnaashari 2, Lutfun Nahar 3 and Satyajit Dey Sarker 4*

1 School of Pharmacy and Drug Applied Research Center,Tabriz University of Medical Sciences, Tabriz, Iran

2 Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz, Iran3 Leicester School of Pharmacy, De Montfort University, The Gateway, Leicester, UK

4 Department of Pharmacy, School of Applied Sciences, University of Wolverhampton,MA Building, Wulfruna Street, Wolverhampton WV 1 1LY, England, UK

Abstract: The aerial parts of Pedicularis sibthorpii and P. wilhelmsiana were collected from the EastAzerbaijan province, Iran, and their volatile oils were analyzed by GC-FID and GC-MS. While 19 components,representing 89.8 % of the total oil, were identified from the volatile oil of P. sibthorpii, the identity of 36components, constituting 81.5 % of the total oil, was confirmed from that of P. wilhelmsiana. 1-Octen-3-ol(55.2 %), linalool (5.5 %), E-2-hexenal (4.4 %), Z-3-hexenol (4.4 %) and 3-octanol (2.7 %) were found to bethe major components of the volatile oil of P. sibthorpii. The volatile oil of P. wilhelmsiana mainly containeddocosane (29.2 %), hexacosane (4.9 %), carvacrol (4.6 %), 1-octen-3-ol (4.5 %) and heptacosane (4.3 %).

Key words: Pedicularis sibthorpii, Pedicularis wilhelmsiana, Scrophulariaceae, volatile oilcomposition, carvacrol, linalool.

IntroductionThe family Scrophulariaceae comprises ca. 400

genera and 4500 species 1. The genus PedicularisL., incorporating about 500 species, is one of thosegenera of this family. About 340 species of thisgenus are endemic to China.2 Several species ofthis genus, e.g., P. muscicola, P. oliveriana, P.kansuensis and P. rhinanthoides, are used inTibetan medicine system 2. Traditionally, manyPedicularis species have long been used in theTraditional Chinese Medicine (TCM) as a cardio-tonic, to improve blood circulation, and for thetreatment of exhaustion, collapse, senility and

digestive problems. It is effective in relievinguneasiness of body and mind 3,4. Some species ofthe Pedicularis are also used in the treatment ofmalignant sores 5. To the best of our knowledge,there is only one previous phytochemical studyreported on P. sibthorpii and P. wilhelmsiana,revealing the presence of phenylpropanoidglycosides 6, but the volatile oils of these plantshave never been analyzed before. As part of ouron-going studies on plant-derived volatile oils 7-

15, we now report on the GC-FID and GC-MSanalyses of the volatile oils of the aerial parts ofP. sibthorpii and P. wilhelmsiana.

*Corresponding author (Satyajit Dey Sarker)E-mail: < s.sarker@wlv.ac.uk > © 2012, Har Krishan Bhalla & Sons

Journal of Essential Oil Bearing PlantsISSN Print: 0972-060X Online: 0976-5026www.jeobp.com

Jeobp 15 (3) 2012 pp 352 - 356 352

Received 28 November 2011; accepted in revised form 25 December 2011

ExperimentalPlant materialThe aerial parts of Pedicularis sibthorpii Boiss.

and P. wilhelmsiana Fisch. ex M. Bieb. werecollected from the East Azerbaijan province ofIran in May 2009. Voucher specimens for thiscollection (Tbz-FPh-701 & 700, respectively)have been deposited in the Herbarium of theFaculty of Pharmacy, Tabriz, Iran.

Essential oil extractionDried and ground aerial parts of each species

(100 g) were separately subjected to hydro-distillation with distilled water (500 mL) in aClevenger-type apparatus for 5 h. At the end ofeach distillation the oils were recovered by n-hexane, dried anhydrous Na2SO4, measured, andstored in dark glass bottles at 4°C for furtheranalysis.

GC-MS analysisThe volatile oils were analyzed using a

Shimadzu GCMS-QP5050A gas chromatograph-mass spectrometer (GC-MS) fitted with a fusedsilica DB-1 capillary column (60 m x 0.25 mmi.d., 0.25 μm film thickness). Nitrogen was usedas carrier gas at a flow rate of 1.1 mL/min. Theoven temperature was kept at 50°C for 2 min, andprogrammed to rise to 230°C at a rate of 2°C/minand then kept constant for 8 min. The injectortemperature was 250°C and split ratio wasadjusted at 1:51. The mass spectral (MS) data wereobtained at the following conditions: ionizationpotential 70 eV; ion source temperature 200°C;quadrupole temperature 100oC; solvent delay 3min; EM voltage 3000 volts.

GC-FID analysisFor quantitation (area %), the GC analyses were

also performed on an Agilent 6890 seriesapparatus fitted with a FID detector. The FIDdetector temperature was 300°C. To obtain thesame elution order as with GC-MS, simultaneousauto-injection was performed on a duplicate ofthe same column applying the same operationalconditions. Relative percentage amounts of theseparated compounds were calculated from FIDchromatograms.

The constituents of the essential oils were

identified by their Kovats indices undertemperature-programmed conditions for n-alkanes(C9-C17) and the oil on a DB-1 column under thesame chromatographic conditions. Identificationof individual compounds was carried out bycomparison of their mass spectra with those ofthe internal reference mass spectra library, theNIST NBS54K Library or with authenticcompounds and confirmed by comparison of theirKovats indices with authentic compounds or withthose of reported in the literature.16-21 For quanti-fication purpose, relative area percentagesobtained by FID were used without the use ofcorrection factors.

Results and discussionHydrodistillation of the aerial parts of

Pedicularis sibthorpii and P. wilhelmsiana,collected from the East Azerbaijan province, Iran,afforded 0.04 % and 0.14 % (w/w) volatile oils,respectively. The volatile oils thus obtained wereanalyzed by GC-FID and GC-MS. Tables 1 and 2display the results of the qualitative andquantitative analyses of these oils listed in orderof elution.

A total of 19 components, representing 89.8 %of the total oil, were identified from the volatileoil of P. sibthorpii. 1-Octen-3-ol (55.2 %), linalool(5.5 %), E-2-hexenal (4.4 %), Z-3-hexenol (4.4%) and 3-octanol (2.7 %) were found to be themajor components of the volatile oil of this plant(Table 1). All identified compounds belong to thegroup of oxygenated hydrocarbons including afew monoterpenes.

The identity of 36 components, constituting81.5 % of the total oil, was confirmed from thevolatile oil of P. wilhelmsiana (Table 2). The majorcompounds, identified in the volatile oil of P.wilhelmsiana, were docosane (29.2 %),hexacosane (4.9 %), carvacrol (4.6 %), 1-octen-3-ol (4.5 %) and heptacosane (4.3 %). Whilemajority of these components belong tooxygenated hydrocarbons, there were at least 10non-oxygenated hydrocarbons among theidentified compounds. Monoterpenes, e.g.,linalool, geraniol and carvacrol, as well assesquiterpenes, e.g., β-caryophyllene, α- and β-selinene, spathulenol and guaiol, were present inthis oil.

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Table 1. GC-MS and GC-FID data of the componentsof the volatile oil of Pedicularis sibthorpii

No. Compound % Area KI Molecular Molecularformula weight

1 2-Hexenal (E) 4.37 815 C6H10O 982 3-(Z)-Hexenol 4.37 844 C6H12O 1003 n-Hexanol 1.37 846 C6H14O 1024 n-Heptanal 0.81 876 C7H14O 1145 1-Octen-3-one 0.55 948 C8H14O 1266 Acetonyl acetone 1.91 961 C8H14O2 1147 1-Octen-3-ol 55.19 968 C8H16O 1288 3-Octanol 2.73 979 C8H18O 1309 Benzenacetaldehyde 1.60 1003 C8H18O 120

10 3,5-Octadiene-2-one 2.45 1027 C8H12O 12411 Linalool oxide 0.55 1045 C10H18O2 17012 1-Nonanal 0.81 1081 C9H18O 14213 Linalool 5.46 1098 C10H18O 15414 Menthol 1.09 1166 C10H20O 15615 α-Terpineol 1.64 1289 C10H18O 15416 Damascenone 1.37 1357 C13H18O 19017 β-Ionone 0.55 1462 C13H20O 19218 Hexahydrofarensyl acetone 1.91 1829 C18H36O 26819 Phytol 1.09 2097 C20H40O 296

Total 89.82

It is interesting to note that, while sesquiterpeneswere identified in the volatile oil of P.wilhelmsiana, there was no sesquiterpene detectedin the volatile oil of P. sibthorpii. Similarly, therewas no non-oxygenated hydrocarbon identifiedfrom the volatile oil of P. sibthorpii. While 1-Octen-3-ol (55.2 %) was found to be the mostabundant component of the volatile oil of P.

sibthorpii, it was present in a small quantity (4.5%) in P. wilhelmsiana. Although both species arefrom the same genus Pedicularis, the chemicalprofiles of their volatile oils were significantlydifferent.

To the best of our knowledge, this is the firstever report on the analysis of volatile oils fromany species of the genus Pedicularis.

Table 2. GC-MS and GC-FID data of the componentsof the volatile oil of Pedicularis wilhelmsiana

No. Compound % Area KI Molecular Molecularformula weight

1 2-Hexenal (E) 0.89 815 C6H10O 982 3-(Z)-Hexenol 0.89 844 C6H12O 1003 n-Hexanol 0.89 846 C6H14O 1024 n-Heptanal 0.30 876 C7H14O 1145 2,3-Octanedione 0.30 961 C8H14O2 1426 1-Octen-3-ol 4.47 968 C8H16O 128

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table 2. (continued).

No. Compound % Area KI Molecular Molecularformula weight

7 Phenylacetaldehyde 0.60 1003 C8H8O 1208 3,5-Octadiene-2-one 0.75 1027 C8H12O 1249 Linalool oxide (cis) 0.30 1045 C10H18O2 170

10 1-Octanol 0.15 1061 C8H18O 13011 Nonanal 2.39 1081 C9H18O 14212 linalool 2.53 1098 C10H18O 15413 (2E,6Z)-Nonadienal 0.15 1144 C9H14O 13814 1-Nonanol 0.30 1155 C9H20O 14415 Geraniol 0.45 1238 C10H18O 15416 Carvacrol 4.61 1283 C10H14O 15017 α-Terpenes acetate 0.45 1332 C12H20O2 19618 Damascenone 1.34 1357 C13H18O 19019 β-Caryophyllene 0.60 1416 C15H24 20420 β-Selinene 2.83 1419 C15H24 20421 α-Selinene 0.60 1504 C15H24 20422 δ-Cadinene 0.45 1511 C15H24 20423 Spathulenol 1.34 1571 C15H24O 22024 Caryophyllene oxide 1.50 1578 C15H24O 22025 Cubenol 1.19 1610 C15H26O 22226 Guaiol 0.60 1632 C15H26O 22227 Torreyol 2.98 1639 C15H26O 22228 Hexadecanal 0.30 1819 C16H32O 24029 6,10,14-Trimethyl-2- 3.57 1823 C18H36O 268

pentdecanone30 Nonadecane 0.75 1900 C19H40 26831 n-Hexadecanoic acid 0.60 1957 C16H32O2 25632 Docosane 29.21 2200 C22H46 31033 Tetracosane 2.08 2400 C24H50 33834 Hexacosane 4.91 2600 C26H54 36635 Heptacosane 4.32 2700 C27H56 38036 Octacosane 1.93 2800 C28H58 394

Total 81.45

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