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Kadsura oblongifolia Merr. leaves, stem bark and root bark essential oils a
b
b
Do N. Dai , Nguyen N. Tuan , Tran D. Thang & Isiaka A. Ogunwande
c
a
Faculty of Biology, Vinh University, Vinh City, Nghean Province, Vietnam
b
Faculty of Chemistry, Vinh University, Vinh City, Nghean Province, Vietnam
c
Natural Products Research Unit, Department of Chemistry, Faculty of Science, Lagos State University, Ojo, Lagos, Nigeria Published online: 04 Jun 2014.
To cite this article: Do N. Dai, Nguyen N. Tuan, Tran D. Thang & Isiaka A. Ogunwande (2014) Kadsura oblongifolia Merr. leaves, stem bark and root bark essential oils, Journal of Essential Oil Research, 26:5, 372-376, DOI: 10.1080/10412905.2014.922509 To link to this article: http://dx.doi.org/10.1080/10412905.2014.922509
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Journal of Essential Oil Research, 2014 Vol. 26, No. 5, 372–376, http://dx.doi.org/10.1080/10412905.2014.922509
RESEARCH ARTICLE Kadsura oblongifolia Merr. leaves, stem bark and root bark essential oils Do N. Daia, Nguyen N. Tuanb, Tran D. Thangb* and Isiaka A. Ogunwandec* a
Faculty of Biology, Vinh University, Vinh City, Nghean Province, Vietnam; bFaculty of Chemistry, Vinh University, Vinh City, Nghean Province, Vietnam; cNatural Products Research Unit, Department of Chemistry, Faculty of Science, Lagos State University, Ojo, Lagos, Nigeria
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(Received 22 May 2013; accepted 3 May 2014) Essential oils of Kadsura oblongifolia Merr. (Schisandraceae) were analyzed by capillary gas chromatography (GC) and GC coupled with mass spectrometry (GC–MS). Sixty, sixty-four and twenty-four compounds representing 99.4%, 90.5% and 99.8% of the total oil contents were identified, respectively, from the leaf, stem and root oil. Leaf oil contained cis-cadina-1,4-diene (22.6%), α-pinene (6.7%), α-amorphene (5.6%), cadina-4,10(15)-dien-3-one (5.2%) and δ-cadinene (5.2%), while the stem bark contained α-coapene (20.3%), α-pinene (9.3%) and 1,8-cineole (7.3%). The main constituents of the root were β-caryophyllene (24.9%), α-humulene (12.1%), β-selinene (8.5%) and α-amorphene (8.0%). Keywords: Kadsura oblongifolia; cis-cadina-1, 4-diene; α-coapene; β-caryophyllene; α-humulene; sesquiterpene
Introduction The family Schisandraceae consists of two genera, Schisandra and Kadsura. Kadsura oblongifolia Merr. is an evergreen climber of the Kadsura genus in the family Schisandraceae. Plants are glabrous throughout. Leaf blades are oblong-elliptic to elliptic, while the flowers are dioecious (individual flowers are either male or female, but only one sex is to be found on any one plant so both male and female plants must be grown if seed is required). The fruits are apocarps red and the seeds are one or two per apocarp, about 2.5–4 × 3–4.5 mm. Flowering is from July to November, while fruiting occurs between October and November. The fruit is edible, raw or cooked. This species is used medicinally (1, 2). Phytochemical studies on this plant revealed the isolation of several spirobenzofuranoid dibenzocyclooctadiene lignans, such as kadsulignans O, P, kadsulignans C, E, F, G and heteroclitin (3); kadsufolins A–D (4); kadoblongifolins A–C, schizanrin F, propinquanin C, schisantherin G, heteroclitin Q and kadsurarin (5). In addition, glycosides such as kaempferol-3-O-alphaL-arabinofuranoside, kaempferol-3-O-alpha-D-arabinopyranoside, quercetin-3-O-alpha-D-arabinopyranoside, quercetin-3-O-alpha-L-arabinofuranoside, quercetin-3-Obeta-D-glucopyranoside, quercetin and kaempferol (6) were also characterized from the plant. Lignans are common features of Kadsura species (7–12). Literature information is scant on the chemical composition of volatile oils from this genus. δ-Cadin-
ene (21.79%), camphene (7.27%), borneol (6.05%), cubenol (5.12%) and δ-cadinol (5.11%) were the major components of the oil of Kadsura longipedunculata (13). Cadinane type compounds and their derivatives (54.2%) and especially δ-cadinene (13.8%) have previously been characterized from K. longipedunculata (14). β-Caryophyllene (52.17%), β-himachalene (5.95%), α-humulene (5.04%), 2-β-pinene (4.38%), α-copaene (3.47%) and δ-cadinene (3.47%) were the main volatiles of root oil of Kadsura coccinea from Vietnam (15). However, the main compounds of volatile oil from roots of Radix K. coccineae are isocaryophyllene, δ-elemene, bornyl acetate, δ-cubebene, β-gurjunene and γ-muurolene (16). The main components of the essential oil of the stem of Kadsura heteroclita were α-eudesmol (17.56%), 4-terpineol (9.74%), δ-cadinene (9.27%) and δ-cadinol (6.32%), followed by δ-4-carene (4.78%) and calarene (4.01%). The essential oil of K. heteroclita shows the potential to be developed as a possible natural insecticide/nematicide for the control of stored product insects/nematodes (17). However, δ-cadinene (22.59%), δ-cadinol (17.64%), calarene (7.63%), germacrene D (5.24%) and α-muurolene (5.8%) were the main constituents in the essential oil of K. heteroclita (18). Li et al. (19) demonstrated that the essential oil of K. heteroclita from supercritical carbon dioxide fluid extraction contained high contents of δ-cadinene (14.42%), δ-cadinol (9.94%) and calarene (6.50%), while the oil obtained from steam distillation possessed
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Journal of Essential Oil Research
373
δ-cadinene (19.46%), δ-cadinol (11.14%) and calarene (8.00%) as the major compounds. In a continuation of our research into the volatile compositions of relatively unexploited flora of Vietnam (20–23), we report herein the compounds identified in the leaf, stem bark and root bark essential oils of K. oblongifolia.
used for the GC/MS analysis, under the same conditions as those used for GC analysis. The conditions were the same as described above with He (1 mL/minute) as the carrier gas. The MS conditions were as follows: ionization voltage 70 eV; emission current 40 mA; acquisitions scan mass range 35–350 amu at a sampling rate of 1.0 scan/second.
Experimental
Identification of the constituents
Plant collection
The identification of constituents was performed on the basis of retention indices determined by co-injection with reference to a homologous series of n-alkanes, under identical experimental conditions. Further identification was performed by comparison of their mass spectra with those from NIST 08, Wiley 9th Version and a home-made MS library built up from pure substances and components of known essential oils, as well as by comparison of their retention indices with literature values (25, 26). The relative amounts of individual components were calculated based on the GC peak area (FID response) without using correction factors.
Leaves, stem bark and root bark of K. oblongifolia were collected from Bạch Mã National Park, Thừa Thiên-Huế Province, Vietnam, in August 2012. Voucher specimen DND 270 was deposited at the Botany Museum, Vinh University, Vietnam. Plant samples were air dried prior to extraction. Extraction of the oils Air-dried plant samples (0.5 kg) were shredded and their oils were obtained by hydrodistillation for 4 hours at normal pressure, according to the Vietnamese Pharmacopoeia (24). The plant samples yielded a low content of essential oils: 0.15%, 0.20% and 0.20% (v/w), respectively, for leaf, stem bark and root, calculated on a dry weight basis. All the oil samples were light yellow colored. Gas chromatography (GC) analysis About 15 mg of each oil sample, dried with anhydrous sodium sulfate, was dissolved in 1 mL of n-hexane. GC analysis was performed on an Agilent Technologies HP 6890 Plus Gas chromatograph equipped with a flame ionization detector (FID) and fitted with HP-Wax and HP-5MS columns (both 30 m × 0.25 mm, film thickness 0.25 μm, Agilent Technology). The analytical conditions were: carrier gas H2 (1 mL/minute), injector temperature (PTV) 250°C, detector temperature 260°C, column temperature programmed from 40°C (2 minutes hold) to 220°C (10 minutes hold) at 4°C/minute. Samples were injected by splitting and the split ratio was 10:1. The volume injected was 1.0 μL. The inlet pressure was 6.1 kPa. Each sample was analyzed three times. Gas chromatography–mass spectrometry (GC–MS) analysis An Agilent Technologies HP 6890N Plus Chromatograph fitted with a fused silica capillary HP-5 MS column (30 m × 0.25 mm, film thickness 0.25 μm) and interfaced with a mass spectrometer HP 5973 MSD
Results and discussion Table 1 indicates the identities of ninety compounds identified from the oils of K. oblongifolia. The results indicated that sesquiterpenes (80.4%, 56.7% and 80.4%, respectively) and monoterpenes (18.6%, 34.4% and 17.6%, respectively) represents the major fractions present in the leaf, stem and root oil. cis-Cadina-1,4-diene (22.6%), along with α-pinene (6.7%), α-amorphene (5.6%), cadina-4,10(15)-dien-3-one (5.2%) and δ-cadinene (5.2%), were the major constituents of the leaf. Less prominent compounds are cis-germacrene epoxide (4.9%) and 1,8-cineole (3.7%). On the other hand, α-coapene (20.3%), α-pinene (9.3%), 1,8-cineole (7.3%), cadina-4,10(15)-dien-3-one (5.2%) and δ-cadinene (4.4%) were the main compounds of the stem oil. The main constituents of the root oil were identified as β-caryophyllene (24.9%), α-humulene (12.1%), β-selinene (8.5%) and α-amorphene (8.0%). Other notable compounds in the root oil were δ-cadinene (5.5%), α-selinene (5.3%), (Z)-β-ocimene (3.4%) and bicyclogermacrene (3.0%). Selinene type compounds were identified only in the root oil. From Table 1, it could be seen that eleven compounds were common to the oil samples. The common compounds occurring in higher amounts were α-pinene (6.7–9.3%), α-copaene (0.1–20.3%), β-caryophyllene (0.4–24.9%), α-humulene (0.2–12.1%), α-amorphene (4.2–8.0%), δ-cadinene (2.8–5.5%) and cis-cadine-1,4diene (tr–22.6%).
374 Table 1.
D.N. Dai et al. Volatile constituents of Kadsura oblongifolia from Vietnam.
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Percent composition (% ± SD) a
S/N
Compounds
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58
n-Hexanol Tricyclene α-Pinene Camphene Verbenene β-Pinene β-Myrcene α-Phellandrene ρ-Cymene Limonene 1,8-Cineole (Z)-β-Ocimene Isopropenyl toluene Dehydro-p-cymene Linalool Filifolone 1,3,8-p-Menthatriene Fenchold α-Campholenal trans-Pinocarveol trans-Verbenol p-Menth-3-en-8-ol trans-Pinocamphone Pinocarvone Borneol Terpinen-4-ol p-Cymene-8-ol α-Terpineol Myrtenol Myrtenal Verbenone trans-Carveol Carvone Carvenone Bornyl acetate p-Cymen-3-ol (Z)-Dimethoxy citral Bicycloelemene α-Cubebene Eugenol Cyclosativene Isoledene α-Copaene β-Cubebene β-Elemene Methyl eugenol α-Gurjunene β-Caryophylene trans-α-Bergamotene Aromadendrene α-Humulene dehydo-Aromadendrene 3,7-Guaiadiene γ-Gurjunene α-Amorphene Germacrene D Bicyclosesquiphellandrene β-Selinene
RI
b
864 926 931 953 968 974 988 1006 1024 1032 1034 1043 1094 1096 1100 1101 1111 1118 1122 1126 1140 1149 1158 1165 1166 1177 1180 1191 1193 1200 1205 1217 1236 1258 1284 1297 1318 1337 1351 1359 1371 1372 1377 1389 1391 1407 1412 1419 1434 1441 1454 1462 1464 1477 1484 1485 1488 1489
RI
c
863 921 932 946 961 974 988 1002 1020 1024 1026 1032 1094 1095 1095 1103 1108 1120 1122 1135 1140 1145 1158 1160 1165 1174 1179 1186 1194 1195 1204 1215 1239 1255 1287 1297 1316 1338 1345 1356 1369 1374 1374 1387 1398 1410 1409 1417 1432 1439 1452 1460 1461 1475 1483 1484 1487 1489
Leaf
Stem
tr ± ± ± ± ± ± ± ± – ± – tr – ± tr – ± – ± ± – – ± ± ± – ± – ± ± ± ± tr ± ± tr ± ± – ± ± ± ± ± – ± ± – – ± ± – ± ± ± ± –
– 0.1± 0.00 9.3 ± 0.01 1.2 ± 0.00 2.3 ± 0.00 1.7 ± 0.00 – 0.2 ± 0.00 0.4 ± 0.00 – 7.3 ± 0.02 – 0.3 ± 0.00 0.4 ± 0.00 2.1 ± 0.00 – 0.2 ± 0.00 0.2 ± 0.00 0.4 ± 0.00 – – tr 1.5 ± 0.00 0.9 ± 0.00 0.9 ± 0.001 0.1 ± 0.00 0.2 ± 0.00 1.3 ± 0.00 1.7 ± 0.00 – 1.9 ± 0.01 0.3 ± 0.00 0.1 ± 0.00 – 0.4 ± 0.00 – – – tr 0.1± 0.00 0.2 ± 0.00 0.7 ± 0.00 20.3 ± 0.02 – 0.2 ± 0.00 0.2 ± 0.00 0.1 ± 0.00 0.2 ± 0.00 0.1 ± 0.00 0.7 ± 0.00 0.1 ± 0.00 0.7 ± 0.00 0.2 ± 0.00 0.9 ± 0.01 4.2 ± 0.01 0.2 ± 0.0 1.6 ± 0.01 –
0.1 6.7 0.8 0.5 1.1 0.2 0.1 0.2 3.7
0.7 0.1 0.8 0.8 0.3 0.5 0.1 0.4 0.6 0.3 0.2 0.1 0.2 0.1 0.1 0.2 0.5 1.7 0.1 0.2 0.2 0.1 0.4 0.2 1.7 0.8 5.6 1.0 2.9
0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.01
0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.01 0.02
Root
6.7 2.9 0.6 0.6 2.0 3.4
1.4 1.3
1.2 2.2
24.9 1.5 12.1
8.0 2.3 8.5
– – ± 0.02 – – ± 0.01 ± 0.00 ± 0.00 – ± 0.002 – ± 0.01 – – – – – – – – – – – – – – – – – – – – – – ± 0.00 – – ± 0.00 – – – – ± 0.00 ± 0.01 – – – ± 0.03 – ± 0.00 ± 0.02 – – – ± 0.02 ± 0.00 – ± 0.02
(Continued)
Journal of Essential Oil Research Table 1.
375
(Continued). Percent composition (% ± SD)
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S/N
Compounds
a
59 cis-Cadina-1,4-diene 60 α-Selinene 61 α-Muurolene 62 Bicyclogermacrene 63 Germacrene A 64 cis-Z-α-Bisabolene epoxide 65 γ-Cadinene 66 Photosantalol 67 trans-Calamenene 68 δ-Cadinene 69 14-Norcadin-5-en-4-one isomer A 70 cis-Calamennee 71 α-Calacorene 72 Germacrene B 73 α-Cedrene epoxide 74 Spathulenol 75 Caryophyllene oxide 76 Widdrol 77 α-Cedrol 78 Aromadendrene oxide 79 τ-Muurolol 80 Amorphene-3-en-9-ol 81 Vulgarone B 82 Tridecanoic acid 83 Isolongifolen-5-one 84 cis-Germacrene epoxidee 85 cis-5-Hydroxycalamenene 86 Cadina-4,10(15)-dien-3-one 87 1,2-Benzenedicarboxylic acid 88 Capnellane-8-one 89 n-Hexadecanoic acid 90 (Z)-9-Octadecenamidee Total Monoterpene hydrocarbons Oxygenated monoterpenes Sesquiterpene hydrocarbons Oxygenated sesquiterpenes Non-terpenoids
RI
b
1496 1498 1499 1500 1509 1515 1516 1520 1522 1525 1526 1529 1546 1560 1574 1579 1584 1597 1601 1640 1643 1645 1647 1678 1685 1700 1715 1743 1917 1942 1970 2398
RI
c
1495 1498 1500 1500 1508 1515 1513 1511 1521 1522 1524 1528 1544 1559 1574 1577 1582 1599 1600 1639 1640 – 1649 1664 1685 – 1713 1743 1917 1942 1959 –
Leaf
Stem
Root
22.6 ± 0.02 – – – – 0.4 ± 0.00 2.3 ± 0.01 – 1.5 ± 0.00 5.2 ± 0.02 2.8 ± 0.01 2.7 ± 0.02 – – – – – 2.4 ± 0.00 – – – – 2.6 ± 0.02 0.1 ± 0.00 0.7 ± 0.00 4.9 ± 0.03 2.0 ± 0.01 5.2 ± 0.01 0.1 ± 0.00 0.4 ± 0.00 0.3 ± 0.00 – 99.4 9.7 8.9 59.0 21.4 0.4
tr – 0.1 ± 0.00 – 0.1 ± 0.00 – 0.3 ± 0.00 – 2.2 ± 0.00 2.8 ± 0.01 2.9 ± 0.01 2.1 ± 0.00 0.8 ± 0.01 2.1 ± 0.01 0.3 ± 0.00 – 1.0 ± 0.01 – 0.1 ± 0.00 1.4 ± 0.00 – 0.5 ± 0.01 – – – 5.2 ± 0.01 – 4.4 ± 0.02 0.1 ± 0.00 – 0.1 ± 0.00 0.1 ± 0.00 90.5 15.8 18.6 40.9 15.8 0.4
1.0 ± 0.00 5.3 ± 0.01 – 3.0 ± 0.01 – – – – – 5.5 ± 0.02 – – – – – 0.8 ± 0.00 – – – – 2.8 ± 0.02 – – – – – – – 0.8 ± 0.00 – – 1.4 ± 0.01 99.8 16.2 1.4 76.8 3.6 1.8
Note: aElution order on HP-5MS capillary column; bRetention indices on HP-5MS capillary column; cLiterature retention indices (see Experimental); dCorrect isomer not identified; eTentative identification; –, not identified and not present in literature; tr, trace amounts
