NPC Natural Product Communications

NPC

Natural Product Communications

Volatile Constituents of Murraya koenigii Fresh Leaves Using Headspace Solid Phase Microextraction – Gas Chromatography – Mass Spectrometry

2014 Vol. 9 No. 12 1783 - 1786

Sayamol Sukkaewa, Patcharee Pripdeevechb, Chalermporn Thongpoonc, Theeraphan Machanb,* and Rattana Wongchuphand,* a

Program of Science Education, Graduate School, Suratthani Rajabhat University, Surat Thani, Thailand 84100 Program of Applied Chemistry, School of Science, Mae Fah Luang University, Chiang Rai, Thailand 57100 c Program of Chemistry, Faculty of Science and Technology, Pibulsongkram Rajabhat University, Phitsanulok, Thailand 65000 d Program of Chemistry, Faculty of Science and Technology, Suratthani Rajabhat University, Surat Thani, Thailand 84100 b

[email protected], [email protected] Received: July 3rd, 2014; Accepted: October 13th, 2014

The volatile components of Murraya koenigii fresh leaves, collected from Surat Thani province, Thailand were studied by using headspace (HS) solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS). The four fibers employed to extract the volatiles were polydimethylsiloxane (PDMS), polydimethylsiloxane-divinylbenzene (PDMS-DVB), carboxane-polydimethylsiloxane (CAR-PDMS) and polydimethylsiloxane-divinylbenzene-carboxane (PDMS-DVB-CAR). The volatile constituents of M. koenigii fresh leaves were also extracted by hydrodistillation and analyzed by GC-MS. Fifty-one compounds were identified by these fibers. Five major compounds, –terpinene, -caryophyllene, -phellandrene, -selinene and -pinene, were detected in all fibers. The PDMS-DVB-CAR fiber was considered as the best for trapping key volatiles of M. koenigii fresh leaves. Keywords: Curry leaves, Murraya koenigii, Odor volatiles, SPME-GC-MS.

Murraya koenigii belongs to the Rutaceae family. The aromatic leaves of this plant are eaten as a vegetable and used in Southern Thai recipes and Indian traditional cuisine. It is also grown extensively in Sri Lanka and mainland Southeast Asia. The plant has been recognized as a common food flavor in the southern part of Thailand and called in Thai “Samui Hom”. Consumption of fresh leaves is preferable in many dishes to promote the appetite. The chemical compositions of the plant leaf extracts have been reported from a number of countries including India [1-6], Bangladesh [7], China, Malaysia, Nigeria, and Sri Lanka. In India, plants were used in medical applications including Ayurveda therapy. Likewise, the raw, green tender leaves were responsible for the cure of dysentery [8]. An essential oil extracted from M. koenigii leaves was also considered for its antibacterial activity against Listeria innocua, and for its antioxidative properties [8-10]. The methanolic and hexane extracts of the leaves of M. koenigii show anti-inflammation effects associated with microbial infections in bovine mastitis [11]. Gas chromatography-mass spectrometry (GC-MS) has been used for effective instrumental analysis to identify the volatile compounds in these leaves [1-3, 7, 12]. Recent work [3] exhibited different essential oil profiles and yields in a comparison of wild curry leaf (M. koenigii) samples collected from seven locations of three provinces from Western Ghats, India. Identification of forty essential oil components (89.5-97.2%) was achieved by GC-FIDLRI and GC-MS analysis. The highest essential oil yields belonged to M. koenigii leaves collected from Bisalakoppa, Serisi, while their yields ranged from 1.6 to 3.7 mL/kg. The significant variations with respect to the monoterpene hydrocarbons α-pinene (1.9-63.7%), β-phellandrene (1.4-45.9%), sabinene (6.9-40.6%),

and the sesquiterpene hydrocarbon β-caryophyllene (6.7-18.5%) were presented in essential oil chemical profiles. However, essential oils from all the sites showed a predominance of monoterpene hydrocarbons (58.0-81.1%), with two of them having significant amounts of sesquiterpene hydrocarbons (27.9-28.5%). Among four essential oil chemotypes, an oil containing α-pinene and β-caryophyllene predominantly was proposed as a new chemotype. Hema et al. determined the bioactive components using GC/MS analysis [2]. The ethanol extract of M. koenigii leaves collected from plants growing in Thanjavur, Tamil Nadu, India included 1-methyl-pyrrolidine-2-carboxylic acid (69.0%), ethyl-D-glucopyranoside (13.4%), 4,5-dehydro-isolongifolene (3.7%), -himachalene (2.9%), 1,2-ethanediol, monoacetate (2.8%), and 1,2benzenedicarboxylic acid, diisooctyl ester (2.6%). Chowdhury et al. reported that the two major compounds of M. koenigii leaves oil were 3-carene (54.2%) and caryophyllene (9.5%) and 39 compounds were found in total [7]. Rao et al. identified and reported 19 compounds from the essential oils from wild and cultivated M. koenigii leaves in India, which were obtained by hydrodistillation [1]. Using GC and GC-MS analyses, the principal essential oil constituents from wild and cultivated plants were caryophyllene and –selinene. In Bangladesh, M. koenigii leaves oil consisted of 39 compounds of which the dominant components were 3-carene (54.2%) and -caryophyllene (9.5%) [7]. From the leaves of a Hyderabad plant, Walde et al. reported -pinene (52.0%) and cis--ocimene (34.0%) as the major compounds [13]. Different locations are a factor affecting variations in the chemical composition of M. koenigii [14].

1784 Natural Product Communications Vol. 9 (12) 2014

This present study was carried out to identify the volatile components from the fresh leaves of M. koenigii, growing in southern Thailand, by using four SPME fibers coupled with GC-MS analysis. The volatiles of fresh M. koenigii leaves were extracted by using different SPME fibers prior to GC-MS analysis. Four different fibers, PDMS, PDMS-DVB, CAR-PDMS and PDMS-DVB-CAR, were selected to extract the odor constituents of the plant. The affinity of the volatile components extracted by each fiber was based on the “like dissolves like” concept and the thickness of the fiber. The identified volatiles and their relative peak area percentages of the SPME extracts are listed in Table 1. The chromatograms of the odor volatiles of fresh M. koenigii leaves obtained by the different SPME fibers are depicted in Figure 1. Li et al. reported that the components found in the plant could be classified into two groups, as monoterpenoids and sesquiterpenoids [15]. A total of 38 volatile constituents representing 99.7% of the total peak area were identified using the PDMS fiber with the dominant components being β-caryophyllene (29.3%), α-selinene (22.7%), -himachalene (9.8%), -humulene (6.4%) and (-trans)bergamotene (6.1%). Thirty-eight components were identified using the PDMS-DVB fiber, representing 99.5% of the total peak area. The major component was β-caryophyllene (38.7%), followed by αselinene (15.6%), -himachalene (6.6%) and α-humulene (6.6%). Thirty-seven odor volatiles representing 99.6% were identified by the PDMS-CAR fiber. The principal odor volatiles were found to be β-caryophyllene (31.1%), β-phellandrene (20.3%), α-selinene (12.5%), α-pinene (6.2%) and α-humulene (5.9%). Using the PDMS-CAR-DVB fiber, 51 constituents (100.0%) were identified with the major compounds being, β-caryophyllene (27.0%), β-phellandrene (15.4%), α-selinene (8.5%), α-pinene (6.0%) and -terpinene (5.8%). It is noted that the different fibers presented significant variability in their chemical compositions, whereas similar monoterpenoid and sesquiterpenoid components, as well as their derivatives, were present among the various SPME fibers. More components were extracted using the PDMS-DVB-CAR fiber than the PDMS-CAR, PDMS-DVB and PDMS fibers. The PDMSDVB-CAR fiber is intermediate in polarity and is more appropriate to extract the non-polar constituents. The other fibers can extract both polar and non-polar compounds due to a mutual potential effect of adsorption and distribution to the stationary phase [16-17]. The different fibers have significant effects on the percentage composition of the volatiles. β-Caryophyllene and -selinene were the dominant constituents from all fibers. While -himachalene, humulene and (-trans)-bergamotene were detected in all fibers, terpinene was detected only using the PDMS-CAR and PDMSDVB-CAR fibers, and -terpinene was detected only with PDMSDVB-CAR fiber. It is noted that the SPME technique with PDMS-DVB-CAR fiber is more sensitive for trapping the key odor volatile constituents of fresh M. koenigii leaves, these being odor components with a medium polarity. In the present study, most of the major volatile constituents found were similar to those found in the previous studies [18-23] in which the major constituents responsible for the aroma and flavor in the leaves of M. koenigii were β-caryophyllene, pinenes, carene, sabinene, cadinol and cadinene. In addition, this research was in good agreement with studies [21, 23-25] reporting β-caryophyllene as the most important constituent in M. koenigii leaves and various essential oils. The change of content and chemical composition in M. koenigii leaves is possibly related with the expression of different genes at different developmental stages of the plant or to environmental factors arising from seasonal variations, as reported by Verma et al. [26]. In addition, the

Sukkaew et al.

diversity of chemical compositions in curry leaves due to location has also been presented by Rao et al. [1]. The quantification of key volatiles in M. koenigii leaves is also affected by the method of chemical analysis. SPME is sensitive for extracting the high odor volatiles with lower boiling points which play a significant role in the key aroma character of M. koenigii leaves. SPME is more efficient for extracting light terpenes. The sampling technique permits the detection of many volatile components of M. koenigii leaves, although their proportions depend strongly on the species of each plant [27]. The overall aroma of the fresh leaves is obtained from a balance between the odorants present in different concentrations in the matrix. M. koenigii is extensively used for its intense characteristic aroma [28] in which its distinctly curry- and spicy-like sensory character results from the presence of terpene hydrocarbons, including β-caryophyllene, β-gurjunene, β-elemene and β-phellandrene [23]. Aroma of M. koenigii is described by a nice, sweet and flowery character obtained from β-caryophyllene that may be responsible for the long lasting aroma and the use of curry leaf as a spice [21].

Figure 1: SPME-GC-MS chromatograms of odor volatiles of M. koenigii leaves by various fibers at the same abundance.

By GC-MS analysis, the M. koenigii volatile oil extracted by hydrodistillation contained seventy-two compounds (only those components also detected by SPME-GC-MS are presented in Table 1, the others are listed below). The major components included βcaryophyllene (21.4%), α-selinene (10.2%) and -humulene (7.1%). The other compounds in the oil were cis-thujopsenic acid (0.6%), phenyl ethyl alcohol (0.1%), isopropyl-5-methyl-2Z-hexanal (0.6%), sabina ketone (0.1%), cryptone (0.1%), cis-sabinene hydrate acetate (0.1%), Z-ocimenone (0.1%), pipertone (0.1%), neo3-thujanol acetate (0.1%), neryl formate (0.1%), thymol (0.3%), prenyl hexanoate (0.1%), p-vinyl-guaiacol (0.2%), neo-verbanol acetate (0.2%), -selinene (6.3%), -amorphene (1.2%), cubebol (0.3%), hedycaryol (0.3%), E-nerolidol (1.9%), spathulenol (3.7%), cubeban-11-ol (2.8%), 10-epi- -eudesmol (3.7%),  -eudesmol (4.3%), selin-11-en-4--ol (8.3%), 14-hydroxy-9-epi-(E)caryophyllene (0.5%), amopha-4,9-dien-2-ol (0.1%), nootkatol (0.2%), isobicyclogermacrenal (0.1%), benzyl benzoate (0.4%), aristolene (0.5%), n-pentadecanol (0.1%), Z--trans-bergamottol acetate (0.1%), nootkatone (0.2%), isopropyl tetradecanoate (0.1%), eudesm-7(11)-en-4-ol, acetate (0.1%), phenyl ethyl actanoate (0.1%), 8S,14-cedranediol (0.1%), methyl hexadecanoate (0.1%),

Volatile components of Murraya koenigii

Natural Product Communications Vol. 9 (12) 2014 1785

Table 1: Volatile constituents of fresh M. koenigii leaves and their relative peak area (%) obtained by SPME-GC-MS. P

P-D

Fiber P-C

939

3.1

10.8

6.2

6.0

975 990 1002 1017 1029

2.0

0.6 0.6 3.1

0.6 3.2 2.0 20.3

3.6 5.7 2.6 1.2 15.4

0.4 Tr -

0.8 0.6 -

3.6 Tr 0.7

3.3 5.8 0.2 Tr 0.5 0.2

0.3 0.4 2.7 0.2 0.1 1.0 29.3 6.1 6.4 2.7

0.2 2.3 0.3 0.4 0.2 1.6 0.3 27.0 0.1 6.6 0.8

0.1 0.1 0.3 0.5 0.1 0.1 0.5 0.1 0.8 1.0 29.9 1.0 1.2 1.1 5.9 -

0.2 0.1 0.1 0.1 0.4 0.8 0.2 0.4 0.1 0.1 0.6 0.4 27.0 0.6 2.4 0.3 5.1 0.6

0.1 0.3 0.4 0.3 0.6 0.1 0.1 0.1 1.8 0.1 0.2 0.1 3.2 21.4 7.1 -

0.2

0.2

0.1

0.1

Tr

compound

LRI

α-Pinene Sabinene Myrcene α-Phellandrene α-Terpinene β-Phellandrene

E-β-Ocimene 1050 γ-Terpinene 1059 Terpinolene 1088 Linalool 1095 allo-Ocimene 1132 Lavandulol 1169 Terpinen-4-ol 1177 α-Terpineol 1188 trans-Piperitol 1208 Z-Ocimene 1229 Isobornyl acetate 1285 Carvacrol 1299 δ-Elemene 1338 α-Cububene 1348 α-Ylangene 1375 Isoledene 1376 β-Panasinsene 1382 β-Elemene 1390 Sibilene 1400 1419 -Caryophyllene 1420 -Ylangene α-trans-Bergamotene 1434 Aromadendrene 1441 α-Humulene 1454 E-β-Farnesene 1456 cis-Cadina-1(6),41463 diene (4,5-di-epi)1473 Aristolochene 1477 -Gerjunene 1482 -Himachalene α-Selinene 1498 1505 (E,E)--Farnesene 1522 7-epi--Selinene 1523 -Cardinene E-iso-γ-Bisabolene 1529 1543 -Cuprenene trans-Dauca-4(11),71557 diene Cadalene 1676 Caryophyllene oxide 1583 1602 trans--Elemenone 1654 -Cadinol 1685 -Bisabolol (6R,7R)-Bisabolone 1742 n-Hexadecanol 1875 Phytol 1947 I-Eicosene 1988 LRI: linear retention index on DB-5 P: PDMS fiber P-D: PDMS-DVB fiber P-C: PDMS-CAR fiber P-D-C: PDMS-DVB-CAR fiber Tr: Trace (0.04%)

P-D-C

Hydro distillation 4.4 0.2 0.8 0.9 3.0 2.3

0.5

1.8

-

0.3

-

1.9 9.8 22.7 1.2 1.4 0.3

0.2 6.6 15.6 0.6 0.2 -

1.1 3.7 12.5 0.7 0.1 -

0.9 4.1 8.5 0.3 0.3 0.3 0.1 0.1

1.7 Tr 10.2 0.2 -

0.4

0.1

0.2

0.1

0.6

0.5 0.5 0.6 0.1 0.2 0.1 Tr 0.1

0.1 0.1 0.1 0.1 Tr 0.3

0.1 0.1 0.1 Tr 0.1

0.1 0.2 0.1 0.2 0.2 0.1 0.1 Tr 0.1

1.0 0.6 Tr 0.1 Tr -

nootkatin (tr) and Z-jasmine (0.1%). Using a similar extraction and analysis methods, the aroma profiles of the volatile oils from various resources are varied. Ninety [1] and fifty- eight compounds [26] were found in the M. koenigii volatile oils from different parts of India, while thirty-nine compounds were reported from leaves collected in Bangladesh [7]. The fact that more compounds were detected by hydrodistillation compared with the SPME method might be due to thermal transformation of some of the volatiles in the hydrodistillation method. Experimental Plant material and chemicals: The fresh leaves of M. koenigii were collected from Kiriratnikhom district, Surat Thani Province, Thailand in April 2009. Voucher herbarium specimens (QBG No.1)

of the plant were identified by Flora of Thailand CMU Herbarium, Faculty of Science, Chiang Mai University and deposited at the Queen Sirikit Botanic Garden, Mae Rim, Chiang Mai, Thailand. Mixtures of C9 to C16 n-alkanes were purchased from Merck (Darmstadt, Germany). Extraction of volatile oil: The clean fresh leaves of M. koenigii were chopped into small pieces. The volatile oil was obtained by hydrodistillation for 4 h in Clevenger-type apparatus. The M. koenigii oil yield was 0.2% (5.75 g from 3600 g of fresh leaves). The oil sample was stored at 2-8C in air-tight container after drying over anhydrous sodium sulfate for gas chromatography-mass spectrometric analysis. Headspace-solid-phase microextraction (HS-SPME): The SPME apparatus with a SPME fiber assembly holding 1.0 cm fused-silica fibers was purchased from Supelco, Bellefonte, PA, USA. Four fibers including 100 µm polydimethylsiloxane (PDMS), 65 µm polydimethylsiloxane-divinylbenzene (PDMS-DVB), 75 µm carboxen-polydimethylsiloxane (CAR-PDMS) and 50/30 µm polydimethylsiloxane-divinylbenzene-carboxen (PDMS-DVBCAR) were selected to extract the volatiles of M. koenigii leaves in this study. All fibers were mounted in the manual SPME holder and preconditioned for 30 min in a GC injection port set at 250ºC. For each extraction, 0.1 g of fresh M. koenigii leaves were picked and immediately placed into a 250 mL headspace bottle sealed with a silicone septum and a Teflon cap. The sample bottle was equilibrated at room temperature around 25ºC for 30 min. By insertion through the septum of the sample bottle, the fiber was then exposed to the sample headspace for 30 min prior to desorption of the volatiles into the splitless injection port of the GC-MS instrument for 30 min. Gas chromatography-mass spectrometry (GC-MS): The volatile constituents of fresh M. koenigii leaves obtained from the SPME extracts with 4 fibers, and the M. koenigii volatile oil were analyzed using a Hewlett Packard model HP6890 gas chromatograph (Agilent Technologies, Palo Alto, CA, USA). It was equipped with an HP-5MS (5% phenyl-polymethylsiloxane) capillary column (30 m × 0.25 mm i.d., film thickness 0.25 μm; Agilent Technologies, USA) interfaced to an HP model 5973 mass-selective detector. The oven temperature was initially held at 60ºC and then increased by 3ºC/min to 220ºC. The injector and detector temperatures were 250 and 280ºC, respectively. Purified He was used as the carrier gas at a flow rate of 1 mL/min. Electron impact mass spectra were collected at 70 eV ionization voltages over the range of m/z 29-300 while the electron multiplier voltage was 1150 V. The ion source and quadrupole temperatures were set at 230ºC and 150ºC, respectively. Identification of odor volatile constituents was performed by comparison of their Kovát retention indices, relative to C9-C16 nalkanes. The mass spectra of individual components were compared with the reference mass spectra in the Wiley7N and NIST98 databases. The percentage composition of M. koenigii leaves extracted by SPME with different fibers is shown in Table 1. Acknowledgments - Much appreciation is given to the Scientific and Technological Instrument Center (STIC) of Mae Fah Luang University for their instrument support concerning the GC-MS. We are grateful to Flora of Thailand CMU Herbarium, Faculty of Science, Chiang Mai University, Chiang Mai for identification of M. koenigii.

1786 Natural Product Communications Vol. 9 (12) 2014

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Natural Product Communications 2014 Volume 9, Number 12 Contents Original Paper

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Biobased Lactams as Novel Arthropod Repellents Kamlesh R. Chauhan, Hemant Khanna, Nagendra Babu Bathini, Thanh C. Le and John Grieco Two New Aromadendrane Sesquiterpenes from the Stem Bark of Alafia multiflora Alembert T. Tchinda, David E. Tsala, Nnanga Nga, Ewa Cieckiewicz, Robert Kiss, Joseph D. Connolly and Michel Frédérich Isolation and Structural Characterization of a New Minor Diterpene Glycoside from Stevia rebaudiana Venkata Sai Prakash Chaturvedula and Julian Zamora ent-Kaurane Diterpenes from Annona glabra and Their Cytotoxic Activities Hoang Le Tuan Anh, Nguyen Thi Thu Hien, Dan Thi Thuy Hang, Tran Minh Ha, Nguyen Xuan Nhiem, Truong Thi Thu Hien, Vu Kim Thu, Do Thi Thao, Chau Van Minh and Phan Van Kiem Chemical Constituents of Tilia taquetii Leaves and their Inhibition of MMP-1 Expression and Elastase Activities Su Yeong Kim, Jung Eun Kim, Hee Jung Bu, Chang-Gu Hyun and Nam Ho Lee Novel C-ring Analogs of Ursolic acid: Synthesis and Cytotoxic Evaluation Uppuluri V. Mallavadhani, Banita Pattnaik, Nitasha Suri and Ajit K. Saxena Phenolic Constituents of Erigeron floribundus (Asteraceae), a Cameroonian Medicinal Plant Chiara Berto, Filippo Maggi, Prosper C. Biapa Nya, Anna Pettena, Irene Boschiero and Stefano Dall'Acqua Nortriterpene Saponins from Akebia trifoliata Keiichi Matsuzaki, Kayo Murano, Yurika Endo and Susumu Kitanaka C-24 Stereochemistry of Marine Sterols: (22E)-25,28-Dimethyl- stigmasta-5,22,28-trien-3-ol and 25,28-Dimethylstigmasta-5,28-dien-3-ol Rie Nojo, Shizue Echigo, Noriyuki Hara and Yoshinori Fujimoto Antibacterial Compounds from Glycosmis puberula Twigs Cholpisut Tantapakul, Tawanun Sripisut, Wisanu Maneerat, Thunwadee Ritthiwigrom and Surat Laphookhieo Antimicrobial Activity of Extracts and Isoquinoline Alkaloids of Selected Papaveraceae Plants Lubomír Opletal, Miroslav Ločárek, Adéla Fraňková, Jakub Chlebek, Jakub Šmíd, Anna Hošťálková, Marcela Šafratová, Daniela Hulcová, Pavel Klouček, Miroslav Rozkot and Lucie Cahlíková New Unusual Alkaloids from the Ascidian Eudistoma vannamei Antônia Torres Ávila Pimenta, Paula Christine Jimenez, Letícia Veras Costa-Lotufo, Raimundo Braz-Filho and Mary Anne Sousa Lima Synthesis and Biological Evaluation of Febrifugine Analogues Huong Doan Thi Mai, Giang Vo Thanh, Van Hieu Tran, Van Nam Vu, Van Loi Vu, Cong Vinh Le, Thuy Linh Nguyen, Thi Dao Phi, Bich Ngan Truong, Van Minh Chau and Van Cuong Pham Flavonoids from Twigs of Millettia pubinervis Zhi Na, Qi-Shi Song and Hua-Bin Hu Effect of Osajin and Pomiferin on Antidiabetic Effects from Normal and Streptozotocin-induced Diabetic Rats Hyung-In Moon Two New Homoisoflavonoids from the Bulbs of Bessera elegans Yukiko Matsuo, Risa Kurihara, Nana Akagi and Yoshihiro Mimaki Isolation of Phenolics from Rhizophora mangle by Combined Counter-current Chromatography and Gel-Filtration Fernanda das Neves Costa, Marcos Daniel da Silva, Ricardo Moreira Borges and Gilda Guimarães Leitão Angular-type Furocoumarins from the Roots of Angelica atropurpurea and their Inhibitory Activity on the NFAT Signal Transduction Pathway Azumi Nagasawa, Mitsuyoshi Sakasai, Daishi Sakaguchi, Shigeru Moriwaki, Yoshinori Nishizawa and Takashi Kitahara Isoprenylated Xanthone and Benzophenone Constituents of the Pericarp of Garcinia planchonii Duong Hoang Trinh, Ly Dieu Ha, Phuong Thu Tran and Lien-Hoa Dieu Nguyen Stemofurans X-Y from the Roots of Stemona Species from Laos Dang Ngoc Quang, Vong Anatha Khamko, Nguyen Thi Trang, Lam Thi Hai Yen and Pham Huu Dien A New Stilbenoid Compound from the Lianas of Gnetum microcarpum Nik Fatini Nik Azmin, Norizan Ahmat, Yana M. Syah, Nik Khairunissa’ Nik Abdullah Zawawi and Mohd Izwan Mohamad Yusof Phenolic Acids Profile, Antioxidant and Antibacterial Activity of Chamomile, Common Yarrow and Immortelle (Asteraceae) Ivana Generalić Mekinić, Danijela Skroza, Ivica Ljubenkov, Luka Krstulović, Sonja Smole Možina and Višnja Katalinić Activity-guided Fractionation of Ipomea fistulosa Leaves for Pro-inflammatory Cytokines and Nitric Oxide Inhibitory Constituents Neeraj K. Patel, Ramandeep and Kamlesh K. Bhutani Development and Validation of a High-Performance Liquid Chromatographic Method for the Simultaneous Quantification of Marker Constituents in Cheonwangbosimdan Chang-Seob Seo and Hyeun-Kyoo Shin Continued inside backcover

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