Volatile Composition of Curcuma Angustifolia Roxb. Rhizome from Central and Southern India

FLAVOUR AND FRAGRANCE JOURNAL VOLATILE COMPOSITION OF CURCUMA ANGUSTIFOLIA 423 Flavour Fragr. J. 2006; 21: 423–426 Published online 23 January 2006 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/ffj.1680 Volatile composition of Curcuma angustifolia Roxb. rhizome from central and southern India

A. K. Srivastava,1* S. K. Srivastava1 and K. V. Syamsundar2

1 Central Institute of Medicinal and Aromatic Plants, PO CIMAP, Lucknow 226015, India 2 Central Institute of Medicinal and Aromatic Plants, Field Station, GKVK PO, Bangalore 560065, India Received 14 October 2002; Revised 1 August 2005; Accepted 27 August 2005

ABSTRACT: The rhizome essential oils of Curcuma angustifolia from Central and Southern India were subjected to GC/ MS analysis, which resulted in the identiﬁcation of 81 and 78 constituents, accounting for more than 95 and 99% of the oil contents, respectively. The major constituents in the rhizome oil from Central India were xanthorrhizol isomer (12.7%), methyl eugenol (10.5%), palmitic acid (5.2%) and camphor (4.2%), while the rhizomes oil from Travancore (Southern India) had germacrone (12.8%), camphor (12.3%), isoborneol (8.7%), curdione (8.4%) and 1,8-cineole (4.8%) as major constituents. Copyright © 2006 John Wiley & Sons, Ltd.

KEY WORDS: Curcuma angustifolia; Zingiberaceae; essential oil composition; xanthorrhizol isomer; methyl eugenol; palmitic acid; germacrone; isoborneol, curdione

Introduction analysis of the rhizomes oils of C. angustifolia from Cen- tral and South India was carried out. Curcuma angustifolia (Zingiberaceae) is native to Central India, distributed in the west Bihar, north Bengal extend- ing to Maharastra and South India.1 Rhizomes are dried Experimental and powdered, and the starch obtained forms the chief source of Indian arrowroot. The action of the rhizome Plant materials is cooling, demulscent and nutritive, and the material is used in consumption, excessive thirst, jaundice, kidney The small rhizomes were collected from Jagdalpur, Madhya disorder, fever and for vitality and fattening the body.2 Pradesh (central India) and Travancore, Kerala (south India). The rhizomes are used in inflammation, bone fracture, Voucher specimens were deposited at the Botany Division, intestinal diseases, etc. by the tribales3 of Madhya CIMAP, Lucknow. Pradesh and Chattisgarh states of India. To the best of our knowledge there are only a few reports on the chemical composition of C. angustifolia rhizome oil. Banerjee Isolation of essential oils et al.4 in 1980 reported ar-curcumine (27.8%), β-pinene (17.9%), α-terpineol (13.4%), camphor (12.1%), The dried rhizomes from Jagdalpur and Travencore were cleaned, chopped and crushed. The crushed rhizomes (250 g zingiberol (9.5%) and borneol (7.0%) as major constitu- each) were subjected to hydrodistillation in a conventional ents in the rhizome oil of C. angustifolia of Indian origin. 5 Clevenger-type apparatus for 4 h, which gave 0.8 and 0.014% On the other hand, Nguyen et al. in 2001 reported more oils, respectively. The oils were dried over anhydrous sodium than 30 components from the fresh and dried rhizome sulfate to remove traces of moisture and stored at 4 °C until oils of C. angustifolia of Vietnamese origin in which analysis. camphor (12.6 and 12.1%) and curzerenone (>57 and 38%) were the major constituents. Apart from the above, Nguyen et al.6 also reported furanodienone and Gas chromatography (GC) isofuranodienone from the dried rhizome of C. angustifolia Roxb. GC analysis of the oil was performed on a Perkin-Elmer GC As a part of our studies on ‘chemical fingerprinting’ of 8500 with FID, using a fused silica capillary column (30 m Indian aromatic plants,7–10 detailed GC and GC-MS × 0.32 mm, film thickness 0.25 µm), coated with dimethyl polysiloxane (BP-1). Oven temperature was programmed from 60 to 220 °C at 5 °C/min and then held isothermal at 220 °C for * Correspondence to: A. K. Srivastava, Central Institute of Medicinal and 3 min; injector temperature, 250 °C; detector temperature, Aromatic Plants, PO CIMAP, Lucknow 226015, India. 300 °C; carrier gas, nitrogen at a linear velocity of 10 psi; split, E-mail: [email protected] 1:80.

Gas chromatography–mass spectrometry (GC-MS) southern India, which gave oils at 0.8 and 0.014% yield on a dry weight basis. GC and GC-MS analysis enabled GC-MS data were obtained on a Perkin-Elmer Turbo Mass the identification of 81 and 78 constituents representing Spectrometer instrument using a PE-Wax column (60 m × 95, and 99% of the oil contents from the rhizomes of 0.32 mm i.d., film thickness 0.25 µm). The carrier gas was central and southern India, respectively. The relative helium. Temperature programming was 5 min at 70 °C, rising at concentration of the volatile components identified are 2 °C/min to 120 °C and 3 °C/min to 240 °C. MS were recorded presented in Table 1 according to their elution order on at 70 eV in the range of 40–400 amu with scan rate 1 s and the BP-1 column. inter scan delay 0.1 s. The major constituents in the rhizome oil from central India were xanthorrhizol isomer (12.7%), methyl eugenol Identification of compounds (10.5%), palmitic acid (5.2%) and camphor (4.2%), while in the rhizome oil from southern India were camphor Compounds were identified by comparing the retention indices (21.3%), germacrone (12.8%), isoborneol (8.7%), of the peaks on the BP-1 column with literature values,11–15 but curdione (8.4%) borneol (4.8%) and 1,8-cineole (4.8%). finally confirmed by comparison of mass spectra of peaks with On comparing our rhizome oil results from central and published data16–18 and computer matching against the Wiley southern India with those earlier reported by Banerjee and NIST libraries. Relative amounts of individual components et al.,4 significant variations were observed with respect are based on peak areas obtained without FID response factor to the major constituents ar-curcumene (3.9, 2.6 and correction. The retention indices were obtained from gas 27.8%), β-pinene (nil, 0.2 and 17.9%), α-terpineol (0.2, chromatograms by logarithmic interpolation between bracketing 0.9 and 13.4%), camphor (4.2, 21.3 and 12.1%), borneol n-alkanes. The homologous series of n-alkanes (C8–C22; Poly (2.2, 4.8 and 7.0%) and zingiberol (nil, nil and 9.5%). Science; Niles, USA) was used as standards. Similarly, on comparing our rhizome oil results of central and southern India with those earlier reported by Nguyen et al.5 from Vietnam, significant variations were Results and discussion observed with respect to the major constituents, camphor (4.2, 21.3 and 12.1%) and curzerenone (2.4, 0.6 and The volatile oils were obtained by conventional steam 38%). On comparing our rhizome oil results from central distillation of C. angustifolia rhizomes from central and and southern India, 67 constituents were found common

Table 1. Percentage composition of Curcuma angustifolia rhizome oil from central and southern India

No. Constituents KI Jagdalpur Travancore (central India) (southern India) Percentage

1 α-Pinene 932 0.2 0.1 2 Camphene 944 — 0.2 3 β-Pinene 970 — 0.2 4 p-Cymene 1010 — 0.1 5 1,8-Cineole 1019 1.3 4.8 6 cis-Linalool oxide (furanoid) 1059 — 0.1 7 trans-Linalool oxide (furanoid) 1073 — 0.1 8 Linalool 1085 0.2 2.6 9 trans-p-Menth-2-en-1-ol 1101 — 0.1 10 Camphor 1117 4.2 21.3 11 Camphene hydrate 1128 0.6 1.2 12 Isoborneol 1140 2.4 8.7 13 Borneol 1149 2.2 4.8 14 p-Cymene-8-ol 1161 0.3 0.6 15 Myrtenal 1168 0.3 0.3 16 α-Terpineol 1172 0.2 0.9 17 Myrtenol 1178 0.9 0.8 18 cis-Carvotanacetol 1195 0.3 0.2 19 Nerol 1213 0.3 0.1 20 Piperitone 1236 0.3 0.1 21 Geranial 1244 0.1 0.1 22 Isobornyl acetate 1268 0.2 0.4 23 Thymol 1275 0.3 0.2 24 Carvacrol 1279 0.2 — 25 Sabinyl acetate 1287 0.1 —

Table 1. (Continued)

No. Constituents KI Jagdalpur Travancore (central India) (southern India) Percentage

26 Undecanol 1306 — 0.1 27 δ-Elemene 1334 0.1 — 28 Thymyl acetate 1350 0.2 0.1 29 Methyl eugenol 1361 10.5 0.1 30 5-Hydroxy-p-menth-6-en-2-one 1378 — 0.1 31 β-Elemene 1385 0.7 0.6 32 α-Longifolene 1398 0.1 0.1 33 β-Caryophyllene 1413 0.1 0.1 34 α-Cadinene 1436 0.2 0.1 35 α-Humulene 1447 0.2 0.3 36 α-Patchoulene 1456 0.7 — 37 ar-Curcumene 1469 3.9 2.6 38 β-Selinene 1478 0.9 0.3 39 Zingiberene 1484 0.5 0.2 40 α-Muurolene 1495 1.9 0.1 41 α-Selinene 1497 — 0.2 42 β-Bisabolene 1503 0.2 0.2 43 β-Sesquiphellandrene 1512 1.1 0.9 44 Elimicin 1521 0.3 — 45 cis-Sesquisabinene hydrate 1539 0.9 0.3 46 (E)-Nerolidol 1548 — 0.1 47 ar-Turmerol 1555 0.5 0.2 48 Caryophyllene oxide 1568 2.2 0.8 49 Curzerenone 1574 2.4 0.6 50 epi-Curzerenone 1584 1.2 1.1 51 Viridiﬂoral 1592 1.0 1.1 52 trans-Sesquisabinene hydrate 1598 1.3 1.2 53 Humulene epoxideII 1607 0.9 0.9 54 Cubenol 1610 0.3 — 55 10-epi-γ-Eudesmol 1614 0.2 0.1 56 δ-Cadinol 1618 1.2 — 57 1-epi-Cubenol 1623 0.4 — 58 τ-Muurolol 1625 — 0.1 59 ar-Turmerone 1638 1.0 2.3 60 α-Turmerone 1654 2.2 6.9 61 β-Bisabolol 1662 0.7 0.4 62 Tridecanoic acid 1668 0.2 — 63 Germacrone 1677 2.5 12.8 64 Curdione 1689 0.8 8.4 65 Curcuphenol 1697 0.8 0.3 66 Heptadecane 1702 0.3 — 67 Farnesol 1711 0.4 0.2 68 Xanthorrhizol 1719 1.7 0.5 69 Xanthorrhizol isomer 1727 12.7 2.2 70 (E)-α-Atlantone 1744 0.1 0.2 71 Furanodienone 1753 0.2 0.1 72 Tetradecanonic acid 1767 3.3 1.7 73 n-Heptyl salicylate 1785 1.0 0.1 74 Hexadecanol 1817 0.2 0.1 75 Isopropyl myristate 1827 2.9 0.3 76 Octadecanol 1856 0.7 0.1 77 Pentadecanoic acid 1867 1.8 0.1 78 Heptadecan-2-one 1883 1.6 0.3 79 n-Nonadecane 1893 0.3 0.1 80 Methyl palmitate 1909 0.4 0.2 81 (E,E)-Farnesyl acetone 1916 1.3 0.1 82 Oleic acid 1931 0.7 0.4 83 Palmitic acid 1963 5.2 0.7 84 Eicosane 1996 0.4 0.1 85 Hexadecyl acetate 2009 0.4 0.1 86 Hexadecanol 2067 0.3 0.1 87 Phytol 2105 0.2 0.1 88 Methyl octadecanoate 2126 1.3 0.1 89 Nonadecanol 2150 0.3 — 90 Octadecanoic acid 2161 0.4 — 91 Methyl eicosanoate 2318 0.2 — 92 Tetracosane 2394 0.1 —

Copyright © 2006 John Wiley & Sons, Ltd. Flavour Fragr. J. 2006; 21: 423–426 426 A. K. SRIVASTAVA ET AL. in both the oils and trans-sesquisabinene hydrate, epi- References curzerenone, β-sesquiphellandrene, humulene epoxide II, α-longifolene, β-caryophyllene, α-humulene, β- 1. Bhandari SC, Vanaushadhi Chandrodaya. An Encyclopaedia of Indian Botanics and Herbs, Vol. 161. Chaukhanabha Sanskrit bisabolene and viridifloral present in almost equal amount Sansthan, Varanasi, 1992; 7–8. in both oils. 2. Rao SM, Rao R. Flowering plants of Travancore, Vol. XIV. Apart from the above similarties, many significant dif- Government Press: Trivendrum (reprinted by BSMP, Dehra Dun), 1914; 400. ferences in the percentage compositions of various com- 3. Jain SK, Ethnobotany, 1995; 7(1–2): 83–88. mon constituents were recorded. The oil from central 4. Banerjee A, Kual VK, Nigam SS. Riv. Ital. Essenze. Profumi, India had 10 times more isopropyl myristate, 6–7 times Piaute Off., Aromat., Syndets Saponi Cosmet. Aerosols, 1980; 62(2): 75–76. more xanthorrhizole isomer and palmitic acid, 4–5 times 5. Nguyen TBT, Trinh DC, Do DR, Nguyen XD, Vietnam Hoa more curzerenone and heptadecan-2-one, 2–3 times more Hoc Va Cong Nghiep Hoa Chat, 2001; 5: 11–14 [CAN 136: xanthorrhizol, caryophyllene oxide and tetradecanoic 180650]. 6. Nguyen TBT, Trinh DC, Do DR, Nguyen XD, Vietnam Hoa acid, and 1.5 times more ar-curcumene than that from Hoc Va Cong Nghiep Hoa Chat, 2001; 4: 28–32 [CAN 136: southern India. It is interesting to note that significant 2944]. amounts of methyl eugenol (10.5%), α-muurolene 7. Jain N, Agarwal KK, Syamsundar KV, Srivastava SK, Kumar S, Flavour Fragr. J., 2001; 16: 44–46. (1.9%), pentadecanoic acid (1.8%), (E,E)-farnesyl ace- 8. Srivastava AK, Srivastava SK, Shah NC, J. Essent. Oil Res., tone (1.3%) and n-heptyl salicylate (1.1%) were present 2001; 13: 63–64. in the oil from central India, while these constituents 9. Raina VK, Srivastava SK, Agarwal KK, Ramesh S, Kumar S, Flavour Fragr. J., 2001; 16: 374–376. were present only up to 0.1% in the oil from southern 10. Jain N, Srivastava SK, Agarwal KK, Ramesh S, Kumar S, Fla- India. On the other hand, the oil from southern India had vour Fragr. J., 2001; 16: 408–410. 10 times more curdione; 5 times more camphor and 11. Raina VK, Srivastava SK, Jain N, Ahmad A, Syamsundar KV, α Agarwal KK, Flavour Fragr. J., 2002; 17: 99–102. germacrone, 3–4 times more -turmerone, 1,8-cineole, 12. Khan M, Srivastava SK, Syamsundar KV, Singh M, Naqvi AA, isoborneol and 2 times more borneol, ar-turmerone and Flavour Fragr. J., 2002; 17: 75–77. camphene hydrate than that from central India. Apart 13. Raina VK, Lal RK, Tripathi S, Khan M, Syamsundar KV, Srivastava SK, Flavour Fragr. J., 2002; 17: 144–146. from the above, significant amounts of linalool (2.6%) in 14. Shwal AS, Srivastava SK, Syamsundar KV, Tripathi S, Raina VK, the oil from southern India and δ-cadinol (1.2%) in the Flavour Fragr. J., 2002; 17: 165–168. oil from central India were also recorded. 15. Jain N, Sirvastava SK, Agarwal KK, Syamsundar KV, Kumar S, J. Essent. Oil Res., 2002; 14: 305–307. On the basis of above remarkable variations in the 16. Jennings W, Shibamoto T, Qualitative Analysis of Flavour and major and minor chemical constituents, the two rhizomes Fragrance Volatiles by Glass Capillary Column Gas Chromato- samples from Central and South India can be concluded graphy. Academic Press: New York, 1980. 17. Ramaswamy SK, Briseese P, Gargiullo RJ, Van Geldernt, in to be different chemotypes of C. angustifolia. Flavours and Fragrances: A World Perspectives Lawrence BM, Mookherjee BD, Willis BJ (eds). Elsevier: Amsterdam, 1988. Acknowledgements —The authors are thankful to Dr S.P.S. Khanuja 18. Adams RP, Identification of Essential Oils by Ion Trap Mass Director, CIMAP, Dr S.K. Agarwal, Head, Phytochemistry Division Spectroscopy. Academic Press: San Diego, CA, 1990. and Dr A.K. Kukreja, Head, Plant Tissue Culture, for their keen interest and encouragement in this work.