Assessment of the sesquiterpenic profile of Ferula gummosa oleo-gum-resin (galbanum) from Iran. Contributes to its valuation as a potential source of sesquiterpenic compounds

Industrial Crops and Products 44 (2013) 185–191

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Short communication

Assessment of the sesquiterpenic profile of Ferula gummosa oleo-gum-resin (galbanum) from Iran. Contributes to its valuation as a potential source of sesquiterpenic compounds Hossein T. Jalali a , Sílvia Petronilho b , Juan J. Villaverde c , Manuel A. Coimbra b , M. Rosário M. Domingues b , Zahra J. Ebrahimian d , Armando J.D. Silvestre c , Sílvia M. Rocha b,∗ a

Department of Pulp & Paper Technology, Shahid Beheshti University, Tehran 19839-63113, Iran QOPNA Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal c CICECO Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal d Department of Food Technology, Islamic Azad University, Amol Branch, Amol 46351-43358, Iran b

a r t i c l e

i n f o

Article history: Received 26 June 2012 Accepted 15 October 2012 Keywords: Ferula gummosa Boiss Oleo-gum-resin Essential oil Sesquiterpenic compounds Two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–ToFMS)

a b s t r a c t The sesquiterpenic composition of the essential oil of Iranian oleo-gum-resin Ferula gummosa Boiss was studied by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–ToFMS). A total of 106 sesquiterpenic compounds, including 61 hydrocarbons, 29 alcohols, 2 aldehydes, 10 oxides, 2 ketones, 1 furan, and 1 epoxide, were tentatively identified. From these, 68 are reported for the first time in F. gummosa species. Moreover, the most abundant sesquiterpenic compounds detected were the alcohols bulnesol, ␣-eudesmol, and ␣-bisabolol. This work allowed to achieve a deep characterization of the sesquiterpenic composition of F. gummosa oil, a crucial step in the bioprospection of this biomass plant material as a source of sesquiterpenic compounds. Furthermore, this approach can promote the market confidence allowing a more efficient quality control and preventing adulterations. © 2012 Elsevier B.V. All rights reserved.

1. Introduction Ferula is a genus of perennial herbs belonging to the Apiaceae family. This genus comprises about 170 species distributed from central Asia, with Iran and Afghanistan among the major areas of occurrence, westward throughout the Mediterranean region to northern Africa and central Asia (Sahebkar and Iranshahi, 2011). Thirty species of Ferula have been represented in Iranian flora, of which some are endemic (e.g. Ferula gummosa, Ferula persica, and Ferula tabasensis) (Asili et al., 2009). Heretofore, more than 70 species of this genus have been phytochemically investigated and based on the findings, Ferula spp. have been turned out to be a source of bioactive compounds such as the sesquiterpenes (Sahebkar and Iranshahi) and their derivatives (Iranshahy and Iranshahi, 2011). F. gummosa Boiss can live about 6–8 years (Mortazaienezhad and Sadeghian, 2006) reaching 0.8–3 m height when growing naturally in Iran. This resinous and odorous plant propagates naturally at a temperature below 5 ◦ C in the north and west Iranian mountainous regions 1800–3000 m above sea level, with average precipitation of 250–500 mm/year (Mortazaienezhad

∗ Corresponding author. Tel.: +351 234401508; fax: +351 234370084. E-mail address: [email protected] (S.M. Rocha). 0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2012.10.031

and Sadeghian, 2006). The F. gummosa stem contains typically several elliptical ducts dispersed in a phloem filled with oleogum-resin that can be exuded naturally or manually during the vegetative period of the plant (Mortazaienezhad and Sadeghian, 2006). The F. gummosa root is glandular and rich in oleo-gumresin too (Mortazaienezhad and Sadeghian, 2006). These exudates are commonly referred to as galbanum (Nadjafi et al., 2006). F. gummosa plants older than three years (and never the flowering plants) are harvested during June–September, with an average galbanum production of around 10 g per plant (Mortazaienezhad and Sadeghian, 2006). If adequately harvested without damaging the plant, this activity can preserve the plant and maximize the oleoresin production (Mortazaienezhad and Sadeghian, 2006). The galbanum from F. gummosa is known for its bioactive properties namely the anti-microbial, anti-inflammatory, anticonvulsant, carminative, expectorant, anti-catarrh, anti-rheumatic, anti-nociceptive, anti-hysteric, laxative, aphrodisiac, antiseptic, analgesic, and anti-diabetic, among numerous other medicinal applications (Sayyah et al., 2001; Mandegary et al., 2004; Kouyakhi et al., 2008). Galbanum is also used in the manufacture of textiles and cosmetics, and also of various glues (Mortazaienezhad and Sadeghian, 2006). The chemical composition of the essential oils of various Ferula species growing in Iran has been investigated by several authors

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(Sadraei et al., 2001; Ghannadi and Amree, 2002; Ghasemi et al., 2005; Mortazaienezhad and Sadeghian, 2006; Abedi et al., 2008; Kouyakhi et al., 2008; Jalali et al., 2012). Mortazaienezhad and Sadeghian (2006) reported only the identification of the major components of galbanum, from which monoterpenes accounted for ∼82% of the oil composition. Several studies on volatile composition of F. gummosa oleoresin essential oil from Iran (Abedi et al., 2008; Ghannadi and Amree, 2002; Ghasemi et al., 2005; Kouyakhi et al., 2008) have demonstrated that this fraction is mainly composed by monoterpene hydrocarbons (ca. 73–88%), among which the ␤-pinene, ␣-pinene, ␦-3-carene, and sabinene are the predominant ones. More recently, Jalali et al. (2012) reported a detailed study of the monoterpenic composition of F. gummosa oleo-gumresin from Iran, identifying 130 monoterpenic compounds in this oil, from which 25 were reported for the first time in this species. In that study, the monoterpenic fraction accounted for ∼15% of the oil composition, which was markedly different from previous reports (Ghasemi et al., 2005; Mortazaienezhad and Sadeghian, 2006; Abedi et al., 2008; Kouyakhi et al., 2008). The sesquiterpenic fraction was composed mainly by germacrene D (0–4.5%), germacrene B (0–7.17%) and calarene (0–6.7%) (Ghasemi et al., 2005; Kouyakhi et al., 2008; Sayyah et al., 2001). Due to the wide range of health application properties referred above, galbanum is one of the most important rangeland products exported by Iran (Nadjafi et al., 2006). Therefore, it is of paramount importance to carry out a detailed characterization of this natural resource. This knowledge will allow a more efficient control of its quality for existent applications and to prevent adulterations. It also opens new opportunities for its exploitation with increased added value. One-dimensional gas chromatography (1D GC) is widely applied in the analysis of plant related products, providing rewarding analytical results. However, comprehensive two-dimensional gas chromatography (GC × GC) has emerged as a powerful separation technique for the characterization of complex samples. Briefly, GC × GC employs two orthogonal mechanisms to separate the constituents of the sample within a single analysis based on the application of two GC columns coated with different stationary phases (Górecki et al., 2006). Thus, commonly a non-polar/polar phase combination, connected in series through a modulator interface, achieves this goal. The chromatographic resolution is greatly enhanced when compared to the 1D GC. Besides chromatographic separation, also sensitivity and limits of detection are improved due to the focusing of the peak in the modulator and the separation of analytes from chemical background (Marriott et al., 2004). On the other hand, the use of the time-of-flight mass spectrometry (ToF-MS) detector provides sufficient data density to address the requirements of GC × GC separations (Górecki et al., 2006). Recently, GC × GC–ToFMS has been successfully applied for a detailed characterization of the monoterpenic composition of F. gummosa oleo-gum-resin (Jalali et al., 2012). However, a deep characterization of the sesquiterpenic fraction was not carried out. Thus, based on our previous report (Jalali et al., 2012), which clearly pointed out the predominance of the sesquiterpenic fraction in the studied F. gummosa oleo-gum-resin sample, in the present work, an exhaustive characterization of the sesquiterpenic fraction was performed using GC × GC–ToFMS.

2. Materials and methods 2.1. Raw material F. gummosa galbanum was collected at an altitude of ca. 2550 m above sea level in Firuzkooh north of Iran (35◦ 45 34.43 N, 52◦ 45 25.44 E) during September 2009. A voucher specimen has

been deposited in the Herbarium of the Research Institute of Forests and Rangelands (TARI), Tehran, Iran. According to previous studies carried out in our laboratory (Jalali et al., 2011, 2012), after removal of the soil around the bottom of herb stem, a scratch was performed on the surface near the root and exudates were collected in stainless steel foils. The oleo-gum-resin was collected during 8 days from about 50 randomly selected healthy plants of 4–6 years old. The exudates were combined and kept inside of double layer tied enclosed plastic containers in a refrigerator at 4 ◦ C. Approximately 10.0 g of the exudate (galbanum) were submitted to steam distillation during 3 h. The sample recovered in water was extracted with diethyl ether, dried over anhydrous sodium sulphate and the solvent was carefully removed using a rotary evaporator, yielding 1.0 g of crude oil (10% yield), that was stored at 4–6 ◦ C until analysis. 2.2. GC × GC–ToFMS analysis The analysis of F. gummosa oil was carried out based on a previously reported work (Jalali et al., 2012) using a LECO Pegasus 4D (LECO, St. Joseph, MI, USA) GC × GC–ToFMS system that comprises an Agilent GC 7890A gas chromatograph with a dual stage jet cryogenic modulator (licensed from Zoex) and a secondary oven. The detector was a high-speed ToF mass spectrometer. An HP-5 column (30 m × 0.32 mm I.D., 0.25 ␮m film thickness, J&W Scientific Inc., Folsom, CA, USA) was used as first-dimension (1 D) column and a DB-FFAP (0.79 m × 0.25 mm I.D., 0.25 ␮m film thickness, J&W Scientific Inc., Folsom, CA, USA) was used as a second-dimension (2 D) column. The carrier gas was helium at a constant flow rate of 2.50 mL/min. The GC × GC–ToFMS injection port at 250 ◦ C. Split injection was used (ratio 1:200). The primary oven temperature program was: initial temperature 40 ◦ C (hold 1 min), raised to 70 ◦ C (10 ◦ C min−1 ), then raised to 140 ◦ C (1 ◦ C min−1 ), and finally raised to 220 ◦ C (70 ◦ C min−1 ) (hold 1 min). The secondary oven temperature program was 30 ◦ C offset above the primary oven. The MS transfer line temperature was 250 ◦ C and the MS source temperature was 250 ◦ C. The modulation time was 8 s; the modulator temperature was kept at 20 ◦ C offset (above primary oven). The ToFMS was operated at a spectrum storage rate of 100 spectra/s. The mass spectrometer was operated in the EI mode at 70 eV using a range of m/z 33–350 and the voltage was −1695 V. Total ion chromatograms (TIC) were processed using the automated data processing software ChromaTOF (LECO) at signal-to-noise threshold of 10. Contour plots were used to evaluate the separation general quality and for manual peak identification; a signal-tonoise threshold of 50 was used. In order to identify the different compounds, the mass spectrum of each compound detected was compared to those in mass spectral libraries which included an inhouse library of standards, and two commercial databases (Wiley 275 and US National Institute of Science and Technology (NIST) V. 2.0 – Mainlib and Replib). The identification was also supported by the experimentally determined retention index (RI) values that were compared, when available, with the values reported in the bibliography for chromatographic columns similar to that used as the first dimension column in the present work (Adams, 1995; Loayza et al., 1995; Abreu and Noronha, 1997; Fournier et al., 1997; Weyerstahl et al., 1998; Da Silva et al., 1999; Lopes et al., 1999; Tellez et al., 1999; Weyerstahl et al., 1999; Asekun and Ekundayo, 2000; Pfeifhofer, 2000; Couladis et al., 2001; Pino et al., 2001; Buchin et al., 2002; Kobaisy et al., 2002; Araujo et al., 2003; bin Ahmad and bin Jantan, 2003; Blázquez et al., 2003; Choi, 2003; Hognadottir and Rouseff, 2003; Karioti et al., 2003; Lalel et al., 2003; Lucero et al., 2003; Priestap et al., 2003; Skaltsa et al., 2003; Ament et al., 2004; Apel et al., 2004; Avato et al., 2004; Adams et al., 2005; Boskovic et al., 2005; Choi, 2005; Ghasemi et al., 2005; Javidnia et al., 2005; Szafranek et al., 2005; Adams et al., 2006; Blagojevic et al., 2006; Flamini et al., 2006; Hazzit et al., 2006; Konig et al.,

H.T. Jalali et al. / Industrial Crops and Products 44 (2013) 185–191 Table 1 Ferula gummosa essential oil composition determined by GC × GC–ToFMS. Essential oil composition (%) Monoterpenes Oxygen-containing monoterpenes Sesquiterpenes Oxygen-containing sesquiterpenes Others

1.72a 13.32a 30.55 45.25 9.16

a Results previously reported by Jalali et al. (2012) for the same sample of Ferula gummosa essential oil.

2006; Lucero et al., 2006; Perraudin et al., 2006; Rubiolo et al., 2006; Bos et al., 2007; De Marchese et al., 2007; Petronilho et al., 2011). RI values were determined using a C8 –C20 n-alkanes series and calculated according to the Van den Dool and Kratz (1963) equation. The majority (>85%) of the identified compounds presented similarity matches ≥800 (800/1000). The GC × GC areas data were used as an approach to estimate the relative content of each sesquiterpenic component. 3. Results and discussion 3.1. Chromatogram surface plot analysis The volatile composition of the essential oil, obtained from oleo-gum-resin F. gummosa, was analyzed by GC × GC–ToFMS. According to the previous preliminary study of the same sample (Jalali et al., 2012), the GC × GC data (Table 1) showed that ∼90% of the oil components are terpenic compounds (mono- and sesquiterpenic compounds), and the sesquiterpenic compounds represented the major fraction (∼76% of the oil components). These results are very interesting due to the fact that sesquiterpenic compounds are well known for their biological activities (Petronilho et al., 2012). However, this is quite different from other studies related to F. gummosa where monoterpenes were reported as the predominant components (Ghasemi et al., 2005; Mortazaienezhad and Sadeghian, 2006; Abedi et al., 2008; Kouyakhi et al., 2008). In the first step of GC × GC–ToFMS analysis, automated data processing was used to find all peaks in the chromatogram. Within the automated data processing, the software finds peaks at individual single ion traces over the whole mass range measured. Therefore, not only major sample components but also trace level compounds, hidden under total ion current (TIC) baseline, can be detected. In this work, the peak table generated automatically by ChromaToF software has been further examined and the identification has been confirmed based on the criteria described in Section 2.2 GC × GC–ToFMS analysis. The obtained GC × GC–ToFMS total ion chromatogram contour plot (data not shown) exhibited several hundreds of peaks. As the present study was focused on the sesquiterpenic pattern of F. gummosa, in a second approach, extracted ion chromatogram surface plot of m/z 93, 161, and 204 ions, characteristic of these compounds, was performed (Fig. 1). The sesquiterpenic compounds were detected in the 1 D range of 1544–4480 s and in a 2 D range of 0.96–6.91 s (Fig. 1). Fig. 1 reveals that the 1D chromatogram is very complex and exhibits several co-eluted peaks. However, the application of a second dimension that separated the compounds according to their polarity increased the GC chromatographic space and enhanced its separation potential. The GC × GC–ToFMS extracted ion chromatogram surface plot shows that the sesquiterpenic compounds were organized into two groups among the second dimension (2 Dtr): the hydrocarbons are placed in the lower retention times (lower polarity: 2 Dtr 0.96–2.50 s) and the oxygencontaining compounds placed in the higher retention times (higher

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polarity: 2 Dtr 2.58–6.91 s). Thus, according to the structured GC × GC chromatographic behavior (Jalali et al., 2012) explained by the differences in volatility (1 D – first dimension), and especially in polarity (2 D – second dimension) among the chemical compounds detected, it was possible to classify the compounds based on the presence of ordered structures in the GC × GC chromatogram (Jalali et al., 2012). The peak finding routine based on deconvolution method allowed to detect 106 sesquiterpenic components, which were tentatively identified based on comparison of their mass spectra to reference commercial and in-house MS databases, and by comparison of the RIs calculated (RIcalc ) with the values reported in the literature (RIlit ) for 5% phenylpolysilphenylene-siloxane (or equivalent) column (Table 2). A range between 0 and 23 (|RIcalc –RIlit |) was obtained for RIcal compared to the RIlit reported in the literature for one-dimensional GC with 5%-phenyl-methylpolysiloxane GC column or equivalent. Finally, it is important to point out that a database composed by the retention indices of sesquiterpenic compounds calculated in the bi-dimensional column set was created, representing a developmental step in sesquiterpene analysis using a GC × GC system. Remarkable results were also obtained in terms of compound classification based on the organized structure of the peaks of structurally related compounds in the GC × GC surface plot. This information represents a valuable approach for similar future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples.

3.2. Sesquiterpenic composition of oleo-gum-resin F. gummosa The detailed analysis of the sesquiterpenic fraction of F. gummosa allowed the detection of 106 sesquiterpenic compounds which included 61 hydrocarbons, 29 alcohols, 2 aldehydes, 10 oxides, 2 ketones, 1 furan and 1 epoxide (Table 2). According to the oil composition, globally, hydrocarbons accounted for 30.55% of the oil components, while oxygenated structures represented 45.25%, i.e. the majority of the sesquiterpenic fraction. Table 2 gives an exhaustive list of all identified/detected sesquiterpenic compounds. Among these, only 38 were reported in previous studies (Sayyah et al., 2001; Ghannadi and Amree, 2002; Ghasemi et al., 2005; Mortazaienezhad and Sadeghian, 2006; Abedi et al., 2008; Kouyakhi et al., 2008) of F. gummosa. According to these previous works, most of the identified compounds belonged to the sesquiterpene hydrocarbons (28) and alcohols (9) families. Among the detected compounds, 20 could not be unambiguously identified, but could be included into specific chemical families based on their position in the GC × GC structured chromatogram (retention times on the first and second dimension) and MS fragmentation profile. The present study reveals that sesquiterpene alcohols are the predominant components of F. gummosa essential oils, namely bulnesol (7.2%), ␣-eudesmol (4.4%), and ␣-bisabolol (3.7%). However, a significantly distinct profile was reported in previous studies (Sayyah et al., 2001; Ghasemi et al., 2005; Mortazaienezhad and Sadeghian, 2006; Kouyakhi et al., 2008), where sesquiterpene hydrocarbons as ␤-caryophyllene, germacrene B, germacrene D, ␦-cadinene, ␥- and ␣-elemene were identified as the major components of the essential oil. Previous studies aiming evaluating the biological activity of terpenic compounds showed that the oxygenated ones seem to exhibit higher potential than the hydrocarbon compounds (van Zyl et al., 2006). Thus, this bioprospection of the monoterpenic (Jalali et al., 2012) and the sesquiterpenic composition of F. gummosa

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Table 2 Sesquiterpenic compounds identified in the essential oil of Ferula gummosa by GC × GC–ToFMS. RIlit. c

Ref. RIlit. d

Compound

Compounds previously reportede

1330 1335 1359 1366 1375 1376 1379 1380 1383 1387 1390 1395 1397 1404 1411 1417 1420 1424 1428 1432 1436 1440 1444 1450 1454 1465 1466 1473 1483 1490 1490 1491 1492 1498 1500 1504 1511 1512 1513 1520 1525 1532 1539 1554 1562 1600 1628 1673 1689 1729 1738 1741 1746 1759 1772 1773 1788 1791 1795 1802 1832

1337 1338 1351 1354 1376 1373 1380 1375 1402 1390 1387 1402 1398 1409 1418 1425 1429 1422 1432 1430 1439 1436 1444 1454 1456 1458 1475 1481 1484 1480 1487 1483 1499 1502 1503 1509 1513 1518 1515 1521 1524 1533 1536 1548 1560 – – – 1683 – – – – – – – – – – – –

Kobaisy et al. (2002) Konig et al. (2006) Adams (1995) Ament et al. (2004) Adams (1995) Karioti et al. (2003) Priestap et al. (2003) Adams (1995) Perraudin et al. (2006) Adams (1995) Adams (1995) Adams (1995) Buchin et al. (2002) Adams (1995) Adams (1995) Javidnia et al. (2005) Adams (1995) Javidnia et al. (2005) Adams (1995) Araujo et al. (2003) Adams (1995) Ghasemi et al. (2005) Choi (2003) Adams (1995) Konig et al. (2006) Adams (1995) Adams (1995) Petronilho et al. (2011) Ghasemi et al. (2005) Adams (1995) Szafranek et al. (2005) Ghasemi et al. (2005) Adams (1995) Adams et al. (2005) Adams (1995) Adams (1995) Adams (1995) Skaltsa et al. (2003) Skaltsa et al. (2003) Fournier et al. (1997) Adams (1995) Lucero et al. (2003) Pfeifhofer (2000) Blázquez et al. (2003) Hognadottir and Rouseff (2003) – – – Petronilho et al. (2011) – – – – – – – – – – – – Sub-total (number of compounds)

␦-Elemene Bicycloelemene ␣-Longipinene ␣-Cubebene ␣-Copaene Isoledene ␤-Bourbonene ␤-Elemene Sativene ␤-Cubebene Isolongifolene Longifolene Clovene ␣-Cedrene ␤-Cedrene ␤-Caryophyllene Thujopsene ␤-Ylangene ␤-Gurjunene ␥-Elemene ␣-Guaiene 3,7-Guaidiene ␣-Caryophyllene ␣-Humulene Neoclovene ␤-Farnesene ␤-Chamigrene Germacrene D ␤-Selinene ␣-Muurolene Bicyclogermacrene ␣-Selinene ␤-Himachalene Cuparene Germacrene A ␤-Bisabolene ␥-Cadinene ␤-Cadinene ␥-Bisabolene Calamenene ␦-Cadinene Cadina-1,4-diene ␣-Bisabolene ␣-Calacorene Germacrene B m/z 93, 81, 161, 204 m/z 131, 105, 91 m/z 93, 81, 107, 161, 204 Dihydrocurcumene m/z 105, 91, 161, 204 m/z 121, 134, 91, 204 m/z 93, 67, 121, 204 m/z 81, 91, 133, 161, 204 m/z 119, 105, 161, 204 m/z 105, 161, 119, 81, 204 m/z 91, 133, 161, 204 m/z 91, 71, 107, 147, 204 m/z 93, 121, 161 m/z 107, 93, 161 m/z 93 81, 119, 204 m/z 105, 81, 91, 161, 189

×

1517 1535 1549 1568 1568 1570 1590 1597 1602 1604

1518 1530 1549 1565 1564 1571 1594 1597 1601 1604

Da Silva et al. (1999) bin Ahmad and bin Jantan (2003) Adams et al. (2006) Avato et al. (2004) Adams (1995) Hazzit et al. (2006) Adams (1995) Lucero et al. (2006) Adams et al. (2005) Choi (2005)

Cubebol Hedycaryol Elemol Ledol Nerolidol Spathulenol Carotol Guaiol Cedrol Cedrenol

×

Dtr (s), 2 Dtr (s) a

RIcalc.

Hydrocarbon type 1544, 0.960 1568, 1.040 1704, 0.980 1744, 1.110 1776, 1.050 1800, 1.120 1816, 1.120 1824, 1.220 1832, 1.100 1864, 1.120 1880, 1.170 1904, 1.200 1920, 1.140 1960, 1.210 2000, 1.330 2016, 1.270 2056, 1.360 2080, 1.290 2104, 1.310 2128, 1.320 2152, 1.210 2176, 1.330 2200, 1.380 2240, 1.330 2264, 1.400 2328, 1.320 2336, 1.480 2376, 1.510 2440, 1.710 2480, 1.230 2480, 1.550 2488, 1.290 2496, 1.420 2528, 1.930 2544, 1.620 2568, 1.390 2608, 1.610 2616, 1.810 2624, 1.310 2664, 1.850 2696, 1.480 2744, 1.130 2784, 1.620 2888, 1.690 2928, 1.770 3160, 1.710 3336, 1.980 3616, 1.920 3712, 2.010 3952, 1.870 4008, 2.250 4024, 2.320 4056, 2.040 4128, 2.210 4208, 2.620 4216, 2.260 4304, 2.340 4320, 2.740 4344, 2.810 4376, 2.510 4424, 2.500 Alcohol type 2648, 2.580 2760, 3.460 2848, 3.810 2968, 2.360 2968, 3.010 2976, 3.850 3104, 2.450 3144, 3.350 3176, 2.640 3192, 2.180

1

b

× × × × × ×

×

× × × × × × × × × × × × × × × ×

× × × ×

× ×

×

Percentage in oil (%)f 0.12 0.24 0.11 0.01 0.87 0.02 0.39 0.11 0.03 0.29 0.46 0.03 0.12 0.46 0.61 0.23 0.22 0.61 0.09 0.10 0.23 1.04 0.60 0.28 0.59 0.52 0.61 3.52 0.60 0.14 0.39 0.36 0.17 0.38 0.30 0.24 0.95 0.57 0.37 0.80 1.57 0.56 0.42 0.49 0.01 0.73 0.39 1.85 0.92 0.49 0.23 0.15 0.28 0.47 0.61 0.56 0.91 0.53 0.36 0.57 0.67 61 0.16 2.60 2.43 0.10 1.97 0.77 0.23 3.42 0.09 0.72

H.T. Jalali et al. / Industrial Crops and Products 44 (2013) 185–191

189

Table 2 (Continued) RIlit. c

Ref. RIlit. d

Compound

1606 1610 1619 1623 1624 1628 1630 1633 1636 1642 1643 1652 1655 1668 1674 1692 1703 1713 1761

1605 1611 1619 1620 1625 1629 1632 1630 1633 1649 1643 1650 1652 1666 1682 1683 1706 1713 1768

Konig et al. (2006) Skaltsa et al. (2003) Abreu and Noronha (1997) Weyerstahl et al. (1998) Asekun and Ekundayo (2000) Couladis et al. (2001) Weyerstahl et al. (1999) Adams (1995) Pino et al. (2001) Adams (1995) Lucero et al. (2006) Loayza et al. (1995) Adams (1995) Adams (1995) Flamini et al. (2006) Adams (1995) Apel et al. (2004) Adams (1995) Rubiolo et al. (2006) Sub-total (number of compounds)

Widdrol Epicedrol 10-Epi-␥-eudesmol 1-Epi-Cubenol ␣-Selin-11-en-4-ol ␣-Acorenol ␶-Muurolol ␥-Eudesmol ␶-Cadinol ␤-Eudesmol Cubenol ␣-Cadinol ␣-Eudesmol Bulnesol ␣-Santalol ␣-Bisabolol Farnesol (isomer cis) Farnesol (isomer trans) Jaeschkeanadiol

Aldehyde type 3816, 4.980 3920, 3.170

1706 1724

1706 1730

Hognadottir and Rouseff (2003) Blagojevic et al. (2006) Sub-total (number of compounds)

␤-Sinensal Farnesal (isomer trans)

Oxide type 2704, 2.720 3224, 4.750 3504, 3.040 3696, 6.290 3808, 6.910 3856, 5.640 3952, 4.360 3976, 5.430 3984, 6.090 4480, 2.930

1526 1610 1655 1687 1705 1713 1729 1733 1735 1867

1530 1606 1655 1685 – – – – 1740 1890

De Marchese et al. (2007) Hognadottir and Rouseff (2003) Adams (1995) Boskovic et al. (2005) – – – – Konig et al. (2006) Lalel et al. (2003) Sub-total (number of compounds)

Liguloxide Caryophyllene oxide ␣-Bisabolol oxide B ␣-Bisabolone oxide m/z 133, 91, 157, 185 m/z 91, 119, 191 m/z 91, 151, 219 m/z 51, 91, 105, 119, 159 Bisabolol oxide A Ledene oxide

Ketone type 3256, 3.800 3904, 4.170

1615 1721

1613 –

Adams (1995) – Sub-total (number of compounds)

Isolongifolanone (isomer trans) m/z 137, 109, 236 m/z

0.43 0.05 2

Furan type 3032, 2.110

1574

1574

Lopes et al. (1999) Sub-total (number of compounds)

Dendrasaline

0.67 1

Epoxide type 3240, 2.640

1612

1612

Bos et al. (2007) Sub-total (number of compounds)

Isoaromadendrene epoxide

0.52 1

1

Dtr (s), 2 Dtr (s) a 3200, 3.120 3224, 3.190 3280, 3.250 3304, 2.640 3312, 3.720 3336, 4.160 3352, 2.790 3368, 3.560 3384, 3.570 3424, 4.210 3432, 2.850 3480, 5.000 3504, 3.880 3584, 3.720 3616, 5.890 3728, 3.860 3800, 4.390 3856, 4.780 4144, 3.140

RIcalc.

b

TOTAL (number of compounds) TOTAL (% of sesquiterpenic compounds in oil)

Compounds previously reportede

×

× ×

× ×

Percentage in oil (%)f 0.59 0.96 0.96 0.17 0.12 0.14 0.16 0.31 2.36 1.28 0.10 0.50 4.30 7.11 1.70 3.55 0.19 0.10 0.18 29 0.07 0.08 2

×

0.09 0.10 0.19 0.62 0.09 0.16 0.11 0.34 0.44 0.24 10

106 75.80

a 1

Dtr (s), 2 Dtr (s): First and second dimension retention times (in seconds) of each compound identified. RI: retention index obtained through the modulated chromatogram. c RI: retention index reported in the literature for 5% phenyl polysilphenylene-siloxane GC column or equivalents. d RI bibliography found in the literature for 5% phenyl polysilphenylene-siloxane GC column or equivalents. e Sesquiterpenic compounds previously reported in the literature in m/z (essential oil and fruit): Sayyah et al. (2001), Ghannadi and Amree (2002), Ghasemi et al. (2005), Mortazaienezhad and Sadeghian (2006), Abedi et al. (2008), Kouyakhi et al. (2008). f Percentage of each component is calculated as peak area of analyte divided by total peak area. b

essential oil could be an important contribution to understand its pharmacological applications and therefore contribute to increase the value of the plant biomass raw-material and final product, as well as to promote the market confidence for F. gummosa consumption. According to the data obtained, bulnesol (7.2%), ␣eudesmol (4.4%), and ␣-bisabolol (3.7%), are the major compounds found in this F. gummosa sample. Recently, ␣-eudesmol has been reported as a compound that induces apoptosis in tumor cells (Hoang et al., 2010). Furthermore, ␣-bisabolol presented wide biological activities such as anti-microbial, antioxidant, anti-malarial,

anti-mutagenic, anti-cancer, anti-inflammatory, and also protective effects on gastric mucosa (Petronilho et al., 2011). In line with these references, it may be suggested that these compounds can explain several of the biological properties of F. gummosa. Sesquiterpenic compounds can also provide a wide spectrum of aromas, mostly perceived as very pleasant, and responsible for the aroma perception of several natural products (Rocha et al., 2006). Thus, the chemical characterization of these secondary metabolites is an imperative need for the valuation of this plant biomass rawmaterial as a potential source of bioactive compounds regarding

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Fig. 1. Blow-up of part of the GC × GC–ToFMS extracted ion chromatogram surface plot of m/z 93, 161, and 204; corresponding to the sesquiterpenic compounds of Ferula gummosa.

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