1.   Introduction

The genus Valeriana, belonging to the Valerianaceae family, is represented by 16 species/subspecies, of which six, namely V. jatamansi Jones, V. himalayana Grub., V. pyrolaefolia Decne., V. mussooriensis, V. hardwickii Wall. var. hardwickii, and V. hardwickii Wall. var. arnottiana (Wt. C. B. Clarke), occur in the Indian Himalayan Region (IHR) of Uttarakhand [1]. Among these, the roots and rhizomes of valeriana (Valeriana jatamansi) from the Valerianaceae family are used to prepare modern phytomedical products, mild traditional sedatives, and antianxiety and digestive formulations [1-3].  Indian Valerian, Valeriana jatamansi Jones has been used as an ingredient in Indian herbal medicine. The ancient Indian Ayurveda describe the medicinal properties of Tagar (Valeriana jatamansi) for curing various diseases like obesity, nervous disorders, epilepsy, insanity, snake poisoning and skin diseases. Today, Valeriana is still a highly respected medicinal plant described in many pharmacopoeia monographs [4]. Charak Samhita, an ancient Indian medical text, describes two forms of V. wallichii distinguishable in the field alone [5]. It has also been described as variable in general size of plants, but with no specific difference in other plant characters [6]. The major active compounds present in Valeriana are monoterpenoids, sesquiterpenoids, and valepotriates. Among these, the valepotriates have significant hypotensive properties, but the total sedative activity has also been attributed to the presence of oxygenated sesquiterpenoid constituents [7-11].

Many chemical compounds of Valeriana species including lignoids, iridoids, valeriandoids, and valepotriates, which are used to cure a variety of illnesses, were found in the plant's roots and rhizomes. Its pharmacological properties have been assessed for their antibacterial, antioxidant, and anticancer effects in vitro as well as their neuroprotective, anxiolytic, and anti-inflammatory effects in vivo [12-15].

Due to the vast biological actions and different chemical compositions of Valeriana species, we tried to compare the essential oil composition of wild and cultivated Valeriana jatamansi and their similarities/differences at their chemotype levels.

 

2.   Materials and methods

2.1 Plant material

The fresh roots sample (250 g) of wild Valeriana jatamansi (VLW) was collected from Gangolihat village (29.7146700 N, 80.0372500 E) of Pithoragarh district (Uttarakhand), (Fig.1) and 250 g of root sample taken of cultivated plant material (VLC) from the research farm (29.7762360 N, 80.0508730 E) of Himalayan Medicinal & Aromatic Plant Research Centre (HIMARC), Berinag (Uttarakhand) in the month of April (Fig. 2). The sample, identified by Botany Department, Kumaun University, Nainital (Voucher No.: HIMARC/ BSB/ VAL/2023) was deposited in the HIMARC for future reference.

 

2.2 Extraction of oil

The underground parts of the plant (250 g each wild and cultivated) were submitted to hydrodistillation for 5 h, using a Clevenger-type apparatus, according to the European Pharmacopoeia [10]. The volatile distillate was collected over anhydrous sodium sulfate and refrigerated till the time of analysis.

2.3 GC and GC-MS analysis

The oils were analyzed by using a Nucon 5765 gas chromatograph (Rtx-5 column, 30 m × 0.32 mm, FID), split ratio 1:48, N2 flow of 4 kg/cm2 and on Thermo Quest Trace GC 2000 interfaced with MAT Polaris Q Ion Trap Mass spectrometer fitted with a Rtx-5 (Restek Corp.) fused silica capillary column (30 m x 0.25 mm; 0.25 µm film coating). Analyses of essential oils and extracts were performed by following the method discussed by Mathela et al. [8].

2.4 Identification of constituents:

The essential oil was fractionated by column chromatography (CC), on silica gel CC (230-400 mesh, Merk, 600 x 25 cm column) packed with hexane, and eluted with hexane followed by gradient elution by Et2O/hexane (1-20%). The identification was done on the basis of Linear Retention Index (LRI), determined with reference to homologous series of n-alkanes (C9- C24, Polyscience Corp., Niles IL under identical experimental condition), co-injection with standard (Sigma and Aldrich), MS Library search (NIST version 2.1 and Wiley registry of mass spectral data 7th edition), by comparing with the MS literature data [11] and by NMR (1H, 13C NMR) of major isolates. The relative amounts of individual components were calculated based on GC peak area (FID response) without using correction factor.

3.   Results and discussion

Based on the dry root, the oil extracted by hydrodistillation from Valeriana jatamansi roots VLC was 0.51% and VLW was 0.26%. The results of the present work are summarized in Table 1. GC and GC/MS analyses indicated more than 25 distinct compounds in the essential oil from the roots of Valeriana jatamansi. The essential oil composition of cultivated plant material (VLC) was to be found rich in Patchouli alcohol (40.56%), α-Bulnesene (9.70%), α-guaiene (6.62%) and α-Patchoulene (4.82%) as major constituents (Fig. 3), while wild plant material (VLW) contains Patchouli alcohol (32.11%), α-Bulnesene (12.57%), α–guaiene (6.28%), α-Patchoulene (5.22%) and 8-acetoxy patchouli alcohol (8.08%) (Fig. 4). Numerous compounds, including valerenic acid, isovaleric acid, valeranone, α ‐pinene, camphene, α‐ santalene, ar‐curcumene, xanthorrhizol, α‐terpineol, bornyl isovalerate, maaliol, valtrate, didrovaltrate, patchouli alcohol, 8‑acetoxy patchouli alcohol, and α, β, and γ‐patchoulene have been identified in previous studies on Valeriana species rhizome and root essential oil [16-20]. Further 115 samples collected from the Champawat, Ukhimath & Pithoragarh regions of Uttarakhand Himalaya were found to rich in patchouli alcohol and 8-acetoxy-patchouli alcohol [8, 12-14]. A similar composition was found in our investigated samples indicating the resemblance of our samples to that chemotype.

 

Figure 3. Gas Chromatogram of Valeriana jatamansi (Cultivated, VLC)

 

Figure 4. Gas Chromatogram of Valeriana jatamansi (Wild, VLW)

From Table 1, it is clearly found that there are significant differences in the essential oil composition isolated by wild and plant material cultivated in Indian Himalayan Region and the variation in the % composition of the constituents. Both cultivated and wild plant material represent the Patchouli alcohol chemotype of Valeriana jatamansi reported earlier [8, 12-14]. But the significant variation in the % composition of Patchouli alcohol and 8-acetoxy patchouli alcohols are notable, hence their environmental factors can be further tested to determine which are responsible for generating similar/different essential oil compositions.

Table 1. Chemical constituents of Valeriana jatamansi VLC (Cultivated) and VLW (Wild)

Sl. no	Compound name	Retention time	RIR (Reported)	RIO (Observed)	VLC	VLW
1.	α -Pinene	5.067	932	935	0.27	0.43
2.	3-methyl valeric acid	5.440	940	944	2.60	2.51
3.	β -Pinene	6.008	974	979	0.30	0.51
4.	p-cymene	7.140	1020	1021	0.14	0.20
5.	Bornyl acetate	14.657	1275	1277	3.27	1.54
6.	α-copaene	17.642	1374	1373	3.21	1.83
7.	β-elemene	17.880	1389	1392	1.10	0.90
8.	β -Caryophyllene	18.783	1412	1416	0.53	0.31
9.	β -Gurjunene	19.293	1420	1425	3.65	4.27
10.	α -Guaiene	19.518	1437	1442	6.62	6.28
11.	Seychellene	19.808	1447	1451	2.32	2.39
12.	α-Patchoulene	19.907	1450	1453	4.82	5.22
13.	γ-Gurjunene	20.023	1468	1473	0.95	0.80
14.	γ-Muurolene	20.415	1474	1477	0.28	0.47
15.	Germacerene-D	20.782	1476	1480	0.59	0.61
16.	β-guaiene	21.023	1485	1489	1.75	-
17.	γ-Patchoulene	21.137	1493	1496	1.79	3.62
18.	α-Bulnesene	21.322	1512	1516	9.70	12.57
19.	δ-Cadinene	21.705	1413	1418	1.87	1.86
20.	Kessane	22.025	1519	1524	1.28	1.24
21.	α-Cadinene	22.597	1532	1538	0.10	0.09
22.	Viridifloral	24.383	1587	1594	1.18	0.41
23.	Pogostol	25.592	1610	1615	3.05	1.12
24.	Patchouli alcohol	25.795	1661	1665	40.56	32.11
25.	Bulnesol	26.302	1672	1676	0.42	0.70
26.	8-acetoxy patchouli alcohol	34.725	1999	2004	0.95	8.08
	Compound Classes
	Monoterpene Hydrocarbons (%)				0.71	1.14
	Oxygenated Monoterpenes (%)				5.87	4.05
	Sesquiterpene Hydrocarbons (%)				40.56	42.46
	Oxygenated Sesquiterpenes (%)				40.16	42.42
	Total identified compound (%)				93.3	90.07

 

4.   Conclusions

The current study's findings showed that growing circumstances associated with domesticating wild Valeriana raise the percentage of patchouli alcohol as the output of essential oils while decreasing the amount of 8-acetoxy patchouli alcohol. Patchouli alcohol has multiple biological qualities that are advantageous in a range of circumstances. These characteristics include those that are aphrodisiac, insecticidal, antioxidant, antibacterial, anti-inflammatory, and antithrombotic. Numerous products, such as soap, body lotions, fragrances, detergents, and cosmetics, are made using these qualities. The primary characteristic of this mutation was a significant increase in patchouli alcohol and decrease in 8-acetoxy patchouli alcohol. However, research is still being done to assess how certain environmental elements and cultural techniques affect the agronomic characteristics, phytochemical makeup, and other biological activities of the essential oil extracted from Valeriana jatamansi in oasis habitats.

 

Authors’ contributions

Conceptualization, B.S.B.; Methodology, B.S.B. and G.K.; Formal analysis, B.S.B., G.K. and R.C.P.; Plant material collection, B.S.B.; Original draft preparation, B.S.B.; Reviewing and editing, R.C.P.

 

Acknowledgements

The authors are grateful to the Heads of Botany and Chemistry Departments, Kumaun University for plant identification and providing necessary research facilities respectively. The authors are also grateful to Central Institute of Medicinal and Aromatic Plants (CIMAP), Pantnagar for instrumental analysis. 

 

Funding

This research has been funded by the Uttarakhand State Council for Science & Technology (UCOST), Dehradun (Uttarakhand). 

 

Availability of data and materials

All data will be made available on request, according to the journal policy.

Conflicts of interest

There is no conflict of interest.

 

References

1.         Prakash, V. Indian Valerianaceae: A Monograph on a Medicinally Important Family, Scientific Publishers, Jodhpur, India, 1999.

2.         Polydeonny, L.V.; Juravleev, U.P.; Hlapseev, H.J. Cultivation and Processing, Kolos Press, Moscow, 1979, 360.

3.         Blumenthal, M. Herbal Gram. 2000, 51, 69.

4.         Strachey, R. Catalogue of the Plants of Kumaon and Adjacent Portions of Garhwal and Tibet, New Delhi, 1918, 84.

5.         Newall, C.A.; Anderson, L.A.; Phillipson, J.D. Herbal Medicines-A Guide for Health-Care Professionals, The Pharmaceutical Press, London, 1996, 86.

6.         Acharya, J.T. Charak Samhita: Ayurveda Dipika, Chaukhamb Sanskrita Samasthana, Varanasi, 1994, 89.

7.         Thies, P.W. Die konstitution der valepotriate: Mitteilung über die wirkstoffe des baldrians. Tetrahedron Lett. 1966, 7, 1163. https://doi.org/10.1016/0040-4020(68)89032-5.

8.         Mathela, C.S.; Chanotiya, C.S.; Sammal, S.S.; Pant, A.K.; Pandey, S. Compositional diversity of terpenoids in the Himalayan Valeriana genera. Chem. Biod. 2005, 2(9), 1174-1182. https://doi.org/110.1002/ cbdv.200590087.

9.         Safaralie, A.; Fatemi, S.; Sefidkon, F. Essential oil composition of Valeriana officinalis L. roots cultivated in Iran Comparative analysis between supercritical CO₂ extraction and hydrodistillation. J. Chromatogr. A. 2007, 1180, 159-164. https://doi.org/110.1016/j.chroma.2007.12.011.

10.     European Pharmacopoeia, Council of Europe, Strasbourg, third ed., 1997, p. 121.

11.     Adams, R.P. Identification of essential oil components by Gas Chromatography/ Mass Spectrometry; 4th ed.; Allured Publishing: Carol Stream, IL, USA, 2007.

12.     Mathela, C.S.; Chanotiya, C.S.; Sati, S.; Tiwari, M.; Sammal, S.S. Chemical perspective of tagar-An Ayurvedic Drug. Ind. J. Trad. Know. 5(4), 2006, 474-477. https://nopr.niscpr.res.in/bitstream/123456789/30683/1/ IJTK%205(4)%20474-477.pdf.

13.     Bhatt, I.D.; Dauthal, P.; Rawat, S.; Gaira, K.S.; Jugran, A.; Rawal, R.S. and Dhar, U. Characterization of essential oil composition, phenolic content, and antioxidant properties in wild and planted individuals of Valeriana jatamansi Jones. Sci. Hort. 2012, 136, 61-68. https://doi.org/110. 1016/j.scienta.2011.12.032.

14.     Rawat, S.; Jugran, A.K.; Bhatt, I.D.; Rawal, R.S.; Andola, H.C. and Dhar, U. Essential oil composition and antioxidant activity in Valeriana jatamansi Jones: influence of seasons and growing sources. J. Essent. Oil Res. 2017, 29(1), 101- 107. https://doi.org/110.1080/10412905.2016.1189856.

15.     Li, J.; Li, X.; Wang C.; Zhang, M.; Ye, M.; Wang Q. The potential of Valeriana as a traditional Chinese medicine: traditional clinical applications, bioactivities, and phytochemistry. Front. Pharmacol. 2022, 13 1-23. https://doi.org/10.3389/fphar.2022.973138.

16.     Arora, R.B.; Arora, C.K. Hypotensive and tranquillizing activity of jatamansone (valeranone) a sesquiterpene from Nardostachys jatamansi DC. In: Chen KK, Mukerji B. (Eds.), Pharmacology of Oriental Plants. Pergamon Press, Oxford. 1963, 51–60. DOI:10.1016/B978-0-08-010809-4.50010-2.

17.     Bos, R.; Woerdenbag, H.J.; Hendriks, H.; Smit, H.F.; Wikstrom, H.V.; Scheffer, J.J. Composition of the essential oil from roots and rhizomes of Valeriana wallichii DC. Flav. Frag. J., 12, 123–131. https:// doi.org/10.1002/(SICI)1099‐1026(199703)12:23.0.

18.     Kapoor, L.D. CRC handbook of ayurvedic medicinal plants. Boca Raton: CRC Press. 1990, 330.

19.     Keochanthala, B.C.; Haag, B.M.; Beck, J.P.; Anton, R. (1993). Effects of two monoterpene esters, valtrate and didrovaltrate, isolated from Valeriana wallichi, on the ultrastructure of hepatoma cells in culture. Phytother. Res., 1993, 7, 124–127. https://doi.org/ 10.1002/ptr.2650070206.

20.     Sati, S.; Chanotiya, C.S.; Mathela, C.S. Comparative investigations on the leaf and root oils of Valeriana wallichii DC. from northwestern Himalaya. J. Essent. Oil Res., 2005, 17, 408–409. https://doi.org/10.1080/10412905.2005.9698945.