Environmental effect on essential oil composition of Aloysia citriodora from Corrientes (Argentina)

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Natural Product Communications

Environmental Effect on Essential Oil Composition of Aloysia citriodora from Corrientes (Argentina)

2011 Vol. 6 No. 11 1711 - 1714

Gabriela Ricciardia, Ana Maria Torresa, Ana Laura Bubenika, Armando Ricciardia, Daniel Lorenzob and Eduardo Dellacassab,* a

Lab. Dr G.A. Fester, Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste; Av. Libertad 5400, (3400) Corrientes, Argentina b Cátedra de Farmacognosia y Productos Naturales, Facultad de Química, Universidad de la República, Av. Gral. Flores 2124, CP-11800, Montevideo, Uruguay [email protected] Received: January 24th, 2011; Accepted: June 27th, 2011

Lemon verbena (Aloysia citriodora Palau) is indigenous to South America and was introduced into Europe. It is cultivated mainly due to the lemon-like aroma emitted from its leaves, which are utilized for the preparation of herbal tea reputed to have antispasmodic, antipyretic, sedative and digestive properties. In this work we introduce the enantiomeric distribution of sabinene and limonene by bidimensional gas chromatography (chiral GC-GC) as a genuine quantitative parameter in order to improve the knowledge so far available on A. citriodora oil. Multivariate analysis afforded information on the similarities and differences of wild and cultivated A. citriodora populations during different seasons in the same environmental conditions. The results indicated that it was possible to discard the environmental and seasonal effect on the chemical composition of A. citriodora for wild and cultivated materials belonging to the same genetic origin. Keywords: Aloysia citriodora Palau, environmental and seasonal effects, multivariate analysis, chemical markers.

Lemon verbena, Aloysia citriodora Palau [syn. Lippia triphylla (L’Her.) Kuntze, Aloysia triphylla (L’Her. Britton, Lippia citriodora Kunth] is indigenous to South America and was introduced into Europe at the end of the 17th century. It is cultivated mainly for to the lemon-like aroma emitted from its leaves that are utilized for the preparation of herbal tea, which is reputed to have antispasmodic, antipyretic, sedative and digestive properties [1]. Lemon verbena has a long history of folk uses in treating asthma, spasms, cold, fever, flatulence, colic, diarrhea, indigestion, insomnia and anxiety [1]. Antimicrobial, fumigant, contact toxicity and repellent effects of A. citriodora essential oil have also been evaluated recently [2-4].

The chemical composition of the essential oil from the leaves of A. citriodora has been studied and reviewed [1,8] and the results clearly indicate that this species shows a rich genetic diversity, enabling it to synthesize a variety of essential oil constituents in plants grown in different parts of the world [8,9]. However, the composition of the essential oil obtained from the same plant stock has been reported to remain constant under the same environmental conditions [10]. In consequence, for finding the best harvesting time to obtain more quantity and better quality of the oil, the objective of the current study was to evaluate, at different development stages, the essential oils obtained from wild and cultivated populations of A. citriodora.

A. citriodora has a wide geographical distribution in Latin America, but is specially found in northwest Argentina in the provinces of Catamarca, Jujuy, La Rioja, Salta and San Luis [4], where it is known and commercialized as “cedrón”or “hierba luisa” [5,6]. The essential oil is used in perfumery and in the flavor industry as liquors and meal flavor [2]. In Argentina, it is an official drug of the Farmacopea Argentina and is included in the Código Alimentario Argentino. However, in Europe its use in perfumery has been restricted by its possible photosensitivity activity [7].

In this work we report the enantiomeric distribution of sabinene and limonene by bidimensional gas chromatography (GC-GC chiral) as a genuine quantitative parameter in order to improve the knowledge so far available on A. citriodora oil. The plant materials were studied by means of their essential oil production and composition. The study was carried out over a two year period. Values were not significantly different for the two years of sampling, and so the values here presented represent an average of the two years determinations for each season considered. The yields and physical constants of the essential oils obtained

1712 Natural Product Communications Vol. 6 (11) 2011 Table 1: Yields and physicochemical data of essential oils of Aloysia citriodora essential oil I1 0.2 1.4879 -20.41

2

Yield (w/w) nD20 D25º

II 0.7 1.4900 -17.48

III 0.6 1.4866 -23.72

1

Ricciardi et al. Table 2: Components identified in the essential oil of A. citriodora studied at different stages. a

%

I cult 0.5 1.4909 -20.31

b

LRI DB-5

2

I (autumn), II (spring), III (summer) and Icult (autumn). Mean value of each variable over a 2-year period. 80

Monoterpene hydrocarbons

70

Oxygenated monoterpenes

Identified compounds

I

II

III

I cult

922

1033

-Thujene

0.1

0.2

0.2

-

929

1027

-Pinene

0.1

0.2

0.2

-

identity assignmentc d

C(22) A

969

1125

Sabinene

5.7

15.1

8.5

-

B

982

1315

6-Methyl-5-hepten-2-one

0.9

2.2

0.9

0.8

A

1027

1205

37.7 31.0

0.6

A

1253

Limonene -Terpinene

21.7

1053

0.1

tr

e

0.1

-

A

1092

1475

(E )-Sabinene hydrate

0.2

0.1

0.2

-

A

Sesquiterpene hydrocarbons

1100

1412

-Thujone

0.5

0.3

0.6

-

A

Oxygenated sesquiterpenes

1126

1403

0.1

0.1

0.2

0.5

A

1126

1423

(Z)-Limonene oxide (E )-Limonene oxide

0.5

0.3

0.4

tr

A

1145

1457

Citronellal -Pinene oxide

0.3

0.3

0.2

-

A

1157

0.6

0.2

0.5

1.0

A

30

1193

(Z )-Dihydrocarvone

0.8

0.3

0.7

tr

A

20

1241

1659

Neral

12.1

11.2 11.3

31.7

A

1248

1740

Piperitone

0.1

0.1

1272

1684

17.5

14.8 15.3

1327

1446

Geranial -Elemene

0.4

0.3

1360

1500

-Copaene

0.6

0.2

1368

1526

-Bourbonene

1.1

0.3

1400

1572

-Cedrene

0.4

0.1

0.3

-

A

1403

1607

-Caryophyllene

3.6

2.3

4.2

0.5

A

60 percentage

Cwax 20M

50 40

10 0 I

II

III

I cult

Figure 1: Variation of A. citriodora essential oil grouped compounds in different sampling periods: I (autumn), II (spring) and III (summer). Data obtained from cultivated plants (I cult, corresponding to autumn essential oil) are included for comparison purposes.

The components identified in the aerial parts of the plant at the different stages, their retention indices, and their percentage compositions are listed in Table 2. The essential oils from the wild population were mainly composed of sabinene (5.7-15.1%), limonene (21.737.7%), neral (11.2-12.1%), geranial (14.8-17.5%), and caryophyllene (2.3-4.2%). Similarly, the main components of the oil obtained from the cultivated material (I cult) was constituted of the same major compounds, but with differences in the grouped compounds (Figure 1). However, examination of the quantitative information on individual constituents summarized in Table 2 was not enough to evaluate the similarities and differences between the oils. Differences among individual components provided less useful information, mainly because there is often a wide variation in the volatile fraction composition from different samples of the same oils. Since multivariate analysis involves variability of either several or all of the components, it seems less affected by such variation. Thus, the statistical elaboration of the data obtained was performed using all the samples analyzed. The results are illustrated in Figure 2. Samples were grouped into two clusters, A and B, based on their essential oil components (Table 2). The dendrogram showed the greatest similarity in the compositions of the essential oils from the wild population as a result of seasonal variations. Oils from cultivated

tr

B

37.7

A

0.3

-

C(22)

0.5

-

A

0.7

1.7

C(22)

-Copaene

0.2

tr

0.1

-

A

1436

1671

-Humulene

0.3

tr

0.1

-

A

1453

1657

Alloaromadendrene

0.8

0.2

0.3

-

A

1460

1708

Germacrene D -Curcumene

0.4

0.2

0.5

-

C(22)

4.8

C(22)

1409

from A. citriodora at different stages of the year are shown in Table 1. The oil yields were not significantly different for samples II, III and Icult (0.5-0.7%), while samples I and Icult showed a different yield relationship (0.2 and 0.5 respectively).

0.1

1481

1800

1500

1722

1509

1743

2.1

4.7

1.0

Bicyclogermacrene -Cadinene

2.5

1.4

1.6

tr

C(22)

0.5

tr

0.3

-

C(22)

1525

1772

-Cadinene

0.1

tr

0.1

-

C(22)

1579

1989

(E )-Nerolidol

1.5

0.3

0.6

0.1

A

1584

2010

Caryophyllene oxide

12.3

1.0

2.8

tr

A

1617

2095

Globulol epi - -Cadinol

tr

1.2

2.9

11.4

A

1.3

0.3

0.9

-

C(23)

94,5

95.1 93.1

1645

92.1

a

Relative proportions of the essential oil constituents were expressed as percentages obtained by peak-area normalization, all relative response factors being taken as one. bThe components are reported according to their elution order from DB-5. cIdentities confirmed by comparing mass spectra and retention time with those of authentic standards supplied by: A, Aldrich (Milwaukee, WI) and B, Extrasynthese (Genay Cedex). dIdentity tentatively assigned by comparing mass spectra with those obtained from the literature [11,12]. etr, traces ≤0,05%. Values represent an average of two years determinations for each season considered. Values were not significantly different at the 0.05 probability level.

A. citriodora showed similar components to those of the wild population, but the relationship of grouped compound concentrations was completely different (Figure 1). The chemical variability of the oils has been discussed so far as regards the geographical origin of A. citriodora [13], but the compositions of the essential oils from aromatic plants are also related to their developmental stage. Previous works reported the presence of the same main components (limonene, neral, geranial) found in this work, but with significant differences in their compositions [14,15], indicating a potential controversy with the results here presented. In this context, seasonal and maturity variations are factors interlinked with each other, because the specific ontogenic growth stage will differ as the season progresses, depending on the plant genetic information [16,17]. In particular, chiral flavor and fragrance components in

Essential oil of the Aloysia citriodora

Natural Product Communications Vol. 6 (11) 2011 1713

Table 3: Values found for the enantiomeric ratios of sabinene and limonene in A. citriodora essential oil studied at the different stages. Sabinene

Compound

Limone ne Enantiomer

(1R, 5R)-(+)

(1S, 5S)-(−)

(4R )-(+)

(4S )-(-)

Se asonal stage I

99.1

0.9

1.7

98.3

II

98.2

1.8

1.6

98.4

III

97.6

2.4

1.5

98.5

Icult

98.6

1.4

1.4

98.6

The order of elution of the different compounds and their enantiomers from the chiral column was as indicated in the table. Euclidean distances

I

A

II

III

B I cult

5

10

15

20

25

30

35

40

Linkage Distance

Figure 2: Dendogram of A. citriodora for the three stages of harvesting of wild and domesticated materials obtained by Hierarchical Cluster Analysis (HCA) with average linkage between groups (Euclidean distances measure).

natural products are generally characterized by a specific distribution of enantiomers; in other words, the compounds are not always present as pure enantiomers, but rather with a specific enantiomeric ratio, which may differ according to variety and environmental conditions [18]. In this section, the parameter selected for evaluation of the seasonal variability of A. citriodora essential oils was the enantiomeric distribution of selected monoterpenes (sabinene, limonene) present in all oil samples. The results shown in Table 3 indicate that, during the different harvesting periods, there were only minor variations in the enantiomeric composition of the chiral terpenes studied between the samples examined, representing the entire population (wild and cultivated materials) of A. citriodora,. In summary, on the basis of this information, and according to the evaluation of the species behavior in response to seasonal factors in different collections over the year, we observed that we could discard the environmental and seasonal effect on the chemical composition of A. citriodora for wild and cultivated materials with the same genetic origin. In addition, characterization of the oil compounds revealed chemical markers which can assist in defining the quality of a typical Argentine lemon verbena.

Experimental Plant materials and isolation of the essential oils: Fresh leaves of A. citriodora were collected from San Lorenzo(Departamento Saladas, 28,70º S latitude, 58,47º W longitude and 65 m altitude) in 3 different growth stages: I (autumn), II (spring) and III (summer, flowering period). The number of plants sampled, selected randomly from the entire plant population, was representative of the species and its geographic area of distribution. The plants were identified by Prof. Sara G. Tressens (IBONE/UNNE) and voucher specimens were deposited at the Herbarium of the IBONE (AM Torres and G Ricciardi 9). To compare the influence of the ecological ambient conditions on the chemical composition of the oils, selected plants from the San Lorenzo population were planted in controlled conditions in an experimental field located in the neighborhood of the campus of the UNNE. The oil was extracted and identified as I cult (corresponding to autumn essential oil). The oils were obtained by hydrodistillation with a Clevenger-type apparatus immediately after the collection of the plant material (about 200 g). The isolation procedure was continued until the material was exhausted. The oils were dried with anhydrous sodium sulfate and kept in a sealed flask at -12°C until analysis. GC and GC/MS analysis: The composition of the oils was carried out by GC and GC-MS as previously described [19]. Identification and quantification: The components of the oils were identified by comparison of their Linear Retention Indices (LRIs) on two columns, determined in relation to a homologous series of n-alkanes (C8 to C20), with those of either pure standards or those reported in the literature [11,12]. Comparison of fragmentation patterns in the MS with those stored on the GC-MS database and elsewhere published [11,20] was also performed. Chiral analysis: Enantiomeric ratios of sabinene and limonene were obtained by multidimensional gas chromatography, using a bidimensional chiral gas chromatography system (Shimadzu, Japan) set up with 2 GC ovens according to the experimental conditions previously described [21]. The sabinene and limonene enantiomers were assigned by injection of enantiomeric pure standards provided by Sigma-Aldrich (Sigma-Aldrich Corp., St. Louis, USA). Chemical variability: Multivariate analysis was performed using the software Statistica 7.1 (StatSoft, Tulsa – USA, 1984-2005). Acknowledgments - The authors are grateful to the CYTED Program, Red 306RT0278 and Project 809-99264 (UCR). The assistance of Dr M. Galli (Mega, Legnano, Italy) is also gratefully acknowledged.

1714 Natural Product Communications Vol. 6 (11) 2011

Ricciardi et al.

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Natural Product Communications Vol. 6 (11) 2011 Published online (www.naturalproduct.us) Effects of pH, Sample Size, and Solvent Partitioning on Recovery of Soluble Phenolic Acids and Isoflavonoids in Leaves and Stems of Red Clover (Trifolium pratense cv. Kenland) Isabelle A. Kagan Arbutin Derivatives from the Seeds of Madhuca latifolia Shazia Khan, M. Nadeem Kardar and Bina S. Siddiqui Quinic Acids from Aster caucasicus and from Transgenic Callus Expressing a -Amyrin Synthase Paola Pecchia, Maria Cammareri, Nicola Malafronte, M. Federica Consiglio, Maria Josefina Gualtieri and Clara Conicella Cytotoxic Activity and Cell Cycle Analysis of Hexahydro-curcumin on SW 480 Human Colorectal Cancer Cells Chung-Yi Chen, Woei-Ling Yang and Soong-Yu Kuo Does the Combination of Resveratrol with Al (III) and Zn (II) Improve its Antioxidant Activity? Karina Dias and Sofia Nikolaou Photosensitization Mechanisms of Triplet Excited Stateβ-Lapachone. A Density Functional Theory Study Liang Shen AFLP Marking and Polymorphism among Progenies of Gymnema sylvestre: an Important Medicinal Plant of India Magda Abbaker Osman, Sunita Singh Dhawan, Janak Raj Bahl, Mahendra P Darokar and Suman P S Khanuja Antioxidant Activity of Protein Hydrolysates from Aqueous Extract of Velvet Antler (Cervus elaphus) as Influenced by Molecular Weight and Enzymes Lei Zhao, Yang-Chao Luo, Cheng-Tao Wang and Bao-Ping Ji Effects of Sideritis euboea (Lamiaceae) Aqueous Extract on IL-6, OPG and RANKL Secretion by Osteoblasts Eva Kassi, Anna Paliogianni, Ismene Dontas, Nektarios Aligiannis, Maria Halabalaki, Zoi Papoutsi, Alexios-Leandros Skaltsounis and Paraskevi Moutsatsou In vitro Antiprotozoal Activity of Extracts of five Turkish Lamiaceae Species Hasan Kirmizibekmez, Irem Atay, Marcel Kaiser, Erdem Yesilada and Deniz Tasdemir Antimicrobial Investigation of Linum usitatissimum for the Treatment of Acne Pratibha Nand, Sushma Drabu and Rajinder K Gupta Chemical and Biological Diversity in Fourteen Selections of Four Ocimum Species Bhaskaruni R. Rajeswara Rao, Sushil K. Kothari, Dharmendra K. Rajput, Rajendra P. Patel and Mahendra P. Darokar Environmental Effect on Essential Oil Composition of Aloysia citriodora from Corrientes (Argentina) Gabriela Ricciardi, Ana Maria Torres, Ana Laura Bubenik, Armando Ricciardi, Daniel Lorenzo and Eduardo Dellacassa Essential Oil of Three Uvaria species from Ivory Coast Koffi A. Muriel, Tonzibo Z. Félix, Gilles Figueredo, Pierre Chalard and Yao T. N’guessan Composition of the Essential Oil of Origanum tyttanthum from Tajikistan Farukh S. Sharopov, Muhamadsho A. Kukaniev and William N. Setzer Volatiles of French Ferns and “fougère” Scent in Perfumery Didier Froissard, Françoise Fons, Jean-Marie Bessière, Bruno Buatois and Sylvie Rapior Volatile Constituents of Two Species of Protium from the Atlantic Rainforest in the State of Pernambuco, Brazil José Gildo Rufino de Freitas, Claudio Augusto Gomes da Camara, Marcílio Martins de Moraes and Henrique Costa Hermenegildo da Silva Volatile Constituents of Two Hypericum Species from Tunisia Karim Hosni, Kamel Msaâda, Mouna Ben taârit, Thouraya Chahed and Brahim Marzouk Chemical Composition and Possible in vitro Antigermination Activity of Three Hypericum Essential Oils Aurelio Marandino, Laura De Martino, Emilia Mancini, Luigi Milella and Vincenzo De Feo Antioxidant, Antimicrobial Activities and Fatty Acid Components of Flower, Leaf, Stem and Seed of Hypericum scabrum Ali Shafaghat Composition of Three Essential Oils, and their Mammalian Cell Toxicity and Antimycobacterial Activity against Drug Resistant-Tuberculosis and Nontuberculous Mycobacteria Strains Juan Bueno, Patricia Escobar, Jairo René Martínez, Sandra Milena Leal and Elena E. Stashenko Antimicrobial and Antioxidant Activities of the Flower Essential Oil of Halimodendron halodendron Jihua Wang, Hao Liu, Haifeng Gao, Jianglin Zhao, Ligang Zhou, Jianguo Han, Zhu Yu and Fuyu Yang Composition and Antimicrobial Activity of the Leaf and Twig Oils of Litsea acutivena from Taiwan Chen-Lung Ho, Pei-Chun Liao, Eugene I-Chen Wang and Yu-Chang Su Chemical Composition and Antimicrobial Activity of the Volatile Oil from Fusarium tricinctum, the Endophytic Fungus in Paris polyphylla var. yunnanensis Ying Zhang, Jianglin Zhao, Jihua Wang, Tijiang Shan, Yan Mou, Ligang Zhou and Jingguo Wang Antifungal Activity of Essential Oil from Asteriscus graveolens against Postharvest Phytopathogenic Fungi in Apples Mohamed Znini, Gregory Cristofari, Lhou Majidi, Hamid Mazouz, Pierre Tomi, Julien Paolini and Jean Costa Interspecies Comparison of Chemical Composition and Anxiolytic-like Effects of Lavender Oils upon Inhalation Mizuho Takahashi, Tadaaki Satou, Mai Ohashi, Shinichiro Hayashi, Kiyomi Sadamoto and Kazuo Koike Essential Oils from the Hyptis genus- A Review (1909-2009) Megil McNeil, Petrea Facey and Roy Porter

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Antifungal Activity of Plumericin and Isoplumericin Dharmendra Singh, Umakant Sharma, Parveen Kumar, Yogesh K. Gupta, M. P. Dobhal and Sarman Singh A New Diacylated Labdane Diterpenoid from Andrographis wightiana Jalli Madhu Sudhana, Rachakunta Munikishore , Mopuru Vijayabhaskar Reddy, Duvvuru Gunasekar, Alain Blond and Bernard Bodo Triterpenoid Acids and Lactones from the Leaves of Fadogia tetraquetra var. tetraquetra (Rubiaceae) Dulcie A. Mulholland, Abdelhafeez M.A. Mohammed, Philip H. Coombes, Shafiul Haque, Leena L. Pohjala, Päivi S.M. Tammela and Neil R. Crouch Isolation of Friedelin from Black Condensate of Cork Ricardo A. Pires, Ivo Aroso, Susana P. Silva, João F. Mano and Rui L. Reis Novel Microbial Transformation of Resibufogenin by Absidia coerules Jian Zheng, Dong-hai Su, Dong-sheng Zhang, Xiu-Lan Xin, Jun-ying Liu, Yan Tian, Qing Wei and Xun Cui Antidiabetic Activity of Terminalia sericea Constituents Nolitha Nkobole, Peter James Houghton, Ahmed Hussein and Namrita Lall X-ray Crystallographic Study of Ranaconitine Yang Li, Jun-hui Zhou, Gui-jun Han, Min-juan Wang, Wen-ji Sun and Ye Zhao Obscurine: a New Cyclostachine Acid Derivative from Beilschmiedia obscura Bruno Ndjakou Lenta, Jean Rodolphe Chouna, Pepin Alango Nkeng-Efouet, Samuel Fon Kimbu, Etienne Tsamo and Norbert Sewald Alkaloids from Papaver coreanum Dong-Ung Lee, Jong Hee Park, Ludger Wessjohann and Jürgen Schmidt Isolation, Structure Elucidation, and Biological Activity of a New Alkaloid from Zanthoxylum rhetsa Karsten Krohn, Stephan Cludius-Brandt, Barbara Schulz, Mambatta Sreelekha and Pottachola Mohamed Shafi Amplexicine, an Antioxidant Flavan-3-ol from Polygonum amplexicaule Mudasir A. Tantry and Aziz A. Rahman A New Flavonoid Glycoside from Vaccaria hispanica Haijiang Zhang, Kuiwu Wang, Jie Wu, Yao Chen and Peipei He Flavonoids from Algerian Endemic Centaurea microcarpa and their Chemotaxonomical Significance Souheila Louaar, Amel Achouri, Mostefa Lefahal, Hocine Laouer, Kamel Medjroubi, Helmut Duddeck and Salah Akkal On-line (HPLC-NMR) and Off-line Phytochemical Profiling of the Australian Plant, Lasiopetalum macrophyllum Michael Timmers and Sylvia Urban Chemical Fingerprint Analysis of Phenolics of Albiziachinensis Based on Ultra-Performance LC-Electrospray Ionization-Quadrupole Time-of-Flight Mass Spectrometry and Antioxidant Activity Abha Chaudhary, Pushpinder Kaur, Neeraj Kumar, Bikram Singh, Shiv Awasthi and Brij Lal Application to Classification of Mulberry Leaves using Multivariate Analysis of Proton NMR Metabolomic Data Eriko Fukuda, Motoyuki Yoshida, Masaki Baba, Yoshihiro Uesawa, Ryuichiro Suzuki, Osamu Kamo, Koji Tsubono, Kazunori Arifuku, Kazuhisa Yatsunami and Yoshihito Okada Phenolic Constituents of Knautia arvensis Aerial Parts Jaroslaw Moldoch, Barbara Szajwaj, Milena Masullo, Lukasz Pecio, Wieslaw Oleszek, Sonia Piacente and Anna Stochmal New Acylated Anthocyanins and Other Flavonoids from the Red Flowers of Clematis Cultivars Masanori Hashimoto, Toshisada Suzuki and Tsukasa Iwashina Prenylated Isoflavonoids from Rhynchosia edulis Ifedayo V. Ogungbe, Gabrielle M. Hill, Rebecca A. Crouch, Bernhard Vogler, Meenakshi Nagarkoti, William A. Haber and William N. Setzer Antiparasitic and Antimicrobial Isoflavanquinones from Abrus schimperi Aziz A. Rahman, Volodymyr Samoylenko, Surendra K. Jain, Babu L. Tekwani, Shabana I. Khan, Melissa R. Jacob, Jacob O. Midiwo, John P. Hester, Larry A. Walker and Ilias Muhammad Two New Rotenoids from Boerhavia repens Mamona Nazir, Muhammad Saleem, Naheed Riaz, Maria Hafeez, Misbah Sultan, Abdul Jabbar and Muhammad Shaiq Ali A Comparison of the Diastereoisomers, Silybin A and Silybin B, on the Induction of Apoptosis in K562 cells Jiyong Zhang, Qiuying Luan, Yanze Liu, David Y-W Lee and Zhao Wang (Continued inside back cover)

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