Volume 4. Issue 4. Pages 457-590. 2009 ISSN 1934-578X (printed); ISSN 1555-9475 (online)

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NPC Natural Product Communications

EDITOR-IN-CHIEF

DR. PAWAN K AGRAWAL Natural Product Inc. 7963, Anderson Park Lane, Westerville, Ohio 43081, USA agrawal@naturalproduct.us EDITORS

PROFESSOR ALESSANDRA BRACA Dipartimento di Chimica Bioorganicae Biofarmacia, Universita di Pisa, via Bonanno 33, 56126 Pisa, Italy braca@farm.unipi.it

PROFESSOR DEAN GUO State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100083, China gda5958@163.com

PROFESSOR J. ALBERTO MARCO Departamento de Quimica Organica, Universidade de Valencia, E-46100 Burjassot, Valencia, Spain alberto.marco@uv.es

PROFESSOR YOSHIHIRO MIMAKI School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, Horinouchi 1432-1, Hachioji, Tokyo 192-0392, Japan mimakiy@ps.toyaku.ac.jp

PROFESSOR STEPHEN G. PYNE Department of Chemistry University of Wollongong Wollongong, New South Wales, 2522, Australia spyne@uow.edu.au

PROFESSOR MANFRED G. REINECKE Department of Chemistry, Texas Christian University, Forts Worth, TX 76129, USA m.reinecke@tcu.edu

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PROFESSOR YASUHIRO TEZUKA Institute of Natural Medicine Institute of Natural Medicine, University of Toyama, 2630-Sugitani, Toyama 930-0194, Japan tezuka@inm.u-toyama.ac.jp

PROFESSOR DAVID E. THURSTON Department of Pharmaceutical and Biological Chemistry, The School of Pharmacy, University of London, 29-39 Brunswick Square, London WC1N 1AX, UK david.thurston@pharmacy.ac.uk

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HONORARY EDITOR

PROFESSOR GERALD BLUNDEN The School of Pharmacy & Biomedical Sciences,

University of Portsmouth, Portsmouth, PO1 2DT U.K.

axuf64@dsl.pipex.com

Antioxidant and Larvicidal Activities of Tephrosia egregia Sandw against Aedes aegypti Ângela M. C. Arriagaa,*, Jefferson Q. Limaa,b, Jackson N. e Vasconcelosa, Maria C. F. de Oliveiraa, Telma L. G. Lemosa, Aluisio M. Fonsecaa, Grazielle T. Malchera,c, Gilvandete M. P. Santiagoa,d, J. Mafezolia and Raimundo Braz-Filhoe aDepartamento de Química Orgânica e Inorgânica, Curso de Pós-Graduação em Química, Universidade Federal do Ceará, CP. 12 200, CEP 60 451-970, Fortaleza, Ceará-Brazil

bInstituto Federal de Educação, Ciência e Tecnologia do Ceará, Curso de Engenharia Ambiental, CEP 63040-000, Juazeiro do Norte, Ceará-Brazil

cUniversidade Federal do Rio G. Norte, Caixa Postal 1662, Campus Universitário, Lagoa Nova, CEP 59072-970 Natal, Rio Grande do Norte-Brazil

dDepartamento de Farmácia, Universidade Federal do Ceará, Rua Capitão Francisco Pedro 1210, CEP 60430-37, Fortaleza, Ceará-Brazil

ePesquisador Visitante Emérito – FAPERJ /LCQUI/CCT - Universidade Estadual do Norte Fluminense Darcy Ribeiro (UENF) /PPGQO/DEQUIM/ ICE - Universidade Federal Rural do Rio de Janeiro, CEP 28013-603, Campus, Rio de Janeiro-Brazil angelamcarriaga@yahoo.com.br

Received: November 18th, 2008; Accepted: March 9th, 2009

The antioxidant and larvicidal activities of Tephrosia egregia extracts and its major component, dehydrorotenone, were studied. High antioxidant activity was found for dehydrorotenone and methanol and ethyl acetate extracts from roots and stems, respectively. Among the tested extracts, the hexane extract from stems showed potent larvicidal activity (LC50 12.88 ± 0.64) while low activity was found for dehydrorotenone. Keywords: Tephrosia egregia, flavonoids, antioxidant activity, larvicidal activity, Aedes aegypti. The genus Tephrosia (Leguminoseae Papilonoideae Fabaceae) is constituted of approximately 300 species, that are distributed in tropical and subtropical regions [1a]. These species present, in their chemical composition, steroids, amino acids and flavonoids, including the rotenoids [1b]. The composition of the essential oil of leaves and stems from Tephrosia egregia has been reported [1c]. Restrictions on the use of synthetic antioxidants, are being imposed because of their potential carcinogenicity [1d]. The indiscriminate use of insecticides such as organochlorines, carbamates and pyrethroids as well the widely used larvicide Temephos, is creating problems of environmental pollution, insecticide resistance and toxic hazards to humans [1e]. Consequently, the need to identify alternative natural and safe sources of antioxidants and larvicides has arisen, and the search for natural agents has therefore increased in recent years.

The ethyl acetate extract from fresh leaves LEA; extract from fresh stems: hexane SH, dichloromethane SD and ethyl acetate SEA; methanol extract from fresh roots RM and dehydrorotenone 1 were evaluated and the results of antioxidants and larvicidal activities are recorded in Tables 1 and 2 respectively. The present results indicate that Tephrosia egregia exhibits antioxidant ability in all investigated plant extracts, especially in the fresh root methanolic extract RM (76.18% radical scavenging activity at a concentration of 1.0 mg/mL). Dehydrorotenone 1 has demonstrated very good antioxidant potential (73.79% radical scavenging activity at a concentration of 1.0 mg/mL and 56.77% at concentration of 0.25 mg/mL). These results are in agreement with the literature that describes polyphenols and flavonoids as the plant constituents with probable free radical scavenging action [1f]. A

NPC Natural Product Communications 2009 Vol. 4 No. 4

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530 Natural Product Communications Vol. 4 (4) 2009 Arriaga et al.

Table 1: The DPPH free radical scavenging activity of T. egregia extracts and dehydrorotenone 1.

Table 2: LC50 values for larval mortality caused by the T. egregia extracts and dehydrorotenone 1.

high larvicidal activity against Aedes aegypti was observed for SH, with an LC50 12.88 μg/mL whereas dehydrorotenone 1 was less active. These results suggest that Tephrosia egregia could be a potential source of free radical scavengers, indicating possible future use as a medicinal agent and a natural larvicide in the control of Aedes aegypti. Experimental

Plant material: Leaves, stems and roots of T. egregia Sandw were collected at the flowering stage in July 2001 in Trairi-Ceará (Brazil). A voucher specimen (#EAC30839) is deposited at the Herbário Prisco Bezerra, Universidade Federal do Ceará- Brazil. Isolation of dehydrorotenone (1): The fresh roots (320 g) of T. egregia were extracted successively

with methanol. The extract obtained (6.58 g, 2.05%) was chromatographed on a silica gel column eluted with hexane, dichloromethane, ethyl acetate and methanol. The fraction dichloromethane was submitted to successive chromatographic fractiona-tion in silica gel using hexane and CH2Cl2 as eluent to yield 1 (24.8 mg) which, based 2D NMR analysis, was identified as dehydrorotenone [2a]. Free radical scavenging activity: The antioxidant activities of extracts and dehydrorotenone 1, were assayed on the basis of the radical scavenging effect of the stable DPPH free radical. One milliliter of a 60 µM DPPH ethanol solution was added to sample solutions of different concentrations and allowed to react at r.t. After 30 min the absorbance values were measured at 517 nm and the antioxidant activity was determined [2b,2c]. Each test was performed in triplicate. Data were evaluated through regression analysis. From regression line, the IC50 values were read representing percentage of scavenging free radical DPPH for 50% activity. Larvicidal bioassay: Aliquots of the essential oils tested (12.5 to 500 μg/mL) were placed in a beaker (50 mL) and dissolved in DMSO/H2O 1.5% (20 mL). 50 instar III larvae of Aedes aegypti were delivered to each beaker. After 24 hours, at room temperature, the number of dead larvae was counted and the lethal percentage calculated. A control using DMSO/H2O 1.5% was carried out in parallel. For each sample, three independent experiments were run [3]. Acknowledgments - Authors are indebted to Prof. F. S. Cavalcante for botanical identification, CENAUREMN for NMR, and to Brazilian agencies FUNCAP, CAPES and CNPq for financial support.

References [1] (a) Sinhá B, Natu AA. (1982) Prenylated flavonoids from Tephrosia purpurea seeds. Phytochemistry, 21, 1468-1470; (b) Angioni

A, Cabizza M, Cabras M, Melis M, Tuberojo C, Cabras P. (2004) Effect of the epicuticular waxes of fruits and vegetables on the photodegradation of rotenone. Journal of Agricultural and Food Chemistry, 52, 3451-3455; (c) Arriaga AMC, Magalhães FEA, Feitosa EMA, Malcher GT, Andrade-Neto M, Nascimento RF. (2005) Composition of the essential oil of Tephrosia egregia Sandw. Journal of Essential Oil Research, 17, 451-452; (d) Singh G, Marimuthu P, De Heluani CS, Catalan CAN. (2006) Antioxidant and biocidal activities of Carum nigrum (Seed) essential oil, oleoresin, and their selected components. Journal of Agricultural and Food Chemistry, 54, 174-181; (e) Kiran SR, Bhavani K, Devi PS, Rao BRR, Reddy KJ. (2006) Composition and larvicidal activity of leaves and stem essential oils of Chloroxylon swietenia DC against Aedes aegypti and Anopheles stephensi. Bioresource Technology, 97, 2481-2484; (f) Vellosa JCR, Khalil NM, Formenton VAF, Ximenes VF, Fonseca LM, Furlan M, Brunetti IL, Oliveira OMMF. (2006) Antioxidant activity of Maytenus ilicifolia root bark. Fitoterapia, 77, 243-244.

[2] Fang N, Casida JE. (1997) Novel bioactive cubé insecticide constituents: Isolation and preparation of 13-homo-oxa-6a,12a-dehydrorotenoids. Journal of Organic Chemistry, 62, 350-353; (b) Hegazi AG, Abd El Hady FK. (2002) Antioxidant, antimicrobial activities and chemical composition of propolis from reclaimed lands. Zeitschrift fur Naturforschung C: Journal of Biosciences, 57, 395-402; (c) Banskota AH, Usia T, Tezuka Y, Kouda K, Nguyen NT, Kadota S. (2002) Three new C-14 oxygenated taxanes from the wood of Taxus yunnanensis, Journal of Natural Products, 65, 1700-1702.

[3] Oliveira MF, Lemos TLG, Mattos MC, Segundo TA, Santiago GMP, Braz- Filho R. (2002) New enamines derivatives of lapachol and biological activity. Anais da Academia Brasileira de Ciências, 74, 211-221.

Concentration (mg/mL) 1.0 0.5 0.25

Sample % Antioxidant IC 50 (mg/mL) Trolox 95.84 95.81 95.78 0.004 BHT 86.11 70.90 60.21 0.166 LEA 55.00 50.95 46.55 0.441 SD 73.01 65.59 58.17 0.126 SH 69.81 54.49 35.43 0.446 SEA 73.79 67.19 61.37 0.081 RM 76.17 68.75 59.22 0.130 1 73.79 64.94 56.77 0.152

Sample LC50 (μg/mL) LEA 70.79 ± 1.55 RM 30.20 ± 0.98 SEA 26.30 ± 1.11 SD 25.12 ± 2.03 SH 12.88 ± 0.64 1 197.71 ± 0.41

Induction of Neuronal Differentiation in Neurosphere Stem Cells by Ellagic Acid Derivatives Turibio Kuiate Tabopda, Joseph Ngoupayo, Jia Wei Liu, Anne-Claire Mitaine-Offer, Bonaventure Tchaleu Ngadjui, Marie-Aleth Lacaille-Dubois and Bang Luu 517

Synthesis and Characterization of Novel Cardanol Based Benzoxazines Andrea Minigher, Elena Benedetti, Ornela De Giacomo, Pietro Campaner and Vincent Aroulmoji 521

Antioxidant and Larvicidal Activities of Tephrosia egregia Sandw against Aedes aegypti Ângela M. C. Arriaga, Jefferson Q. Lima, Jackson N. e Vasconcelos, Maria C. F. de Oliveira, Telma L. G. Lemos, Aluisio M. Fonseca, Grazielle T. Malcher, Gilvandete M. P. Santiago, J. Mafezoli and Raimundo Braz-Filho 529

Phenolic Compounds from Hypericum calycinum and Their Antioxidant Activity Hasan Kırmızıbekmez, Carla Bassarello, Sonia Piacente, Engin Celep, İrem Atay, Güldem Mercanoğlu and Erdem Yeşilada 531

Phenolic Profile and Antioxidant Evaluation of Mentha x piperita L. (Peppermint) Extracts H.J. Damien Dorman, Müberra Koşar, K Hüsnü C Başer and Raimo Hiltunen 535

Anti-inflammatory Potential and Fatty Acid Content of Lipophilic Leaf Extracts of Four Staphylea L. Species Lubica Lacikova, Eva-Maria Pferschy-Wenzig, Irena Masterova, Daniel Grancai and Rudolf Bauer 543

Structural Characterization of Dietary Fiber of Green Chalcumra (Benincasa hispida) Fruit by NMR Spectroscopic Analysis Debsankar Das, Subhas Mondal, Debabrata Maiti, Sadhan K. Roy and Syed S. Islam 547

A Protein Containing Glucan from an Edible Mushroom, Termitomyces microcarpus (var) Krishnendu Chandra, Kaushik Ghosh, Arnab K. Ojha and Syed S. Islam 553

Mutagenesis and Genotypic Characterization of Aspergillus niger FCBP-02 for Improvement in Cellulolytic Potential Shazia Shafique, Rukhsana Bajwa and Sobiya Shafique 557

Enantiomeric Composition of (3R)-(-)- and (3S)-(+)-Linalool in Various Essential Oils of Indian Origin by Enantioselective Capillary Gas Chromatography-Flame Ionization and Mass Spectrometry Detection Methods Chandan S. Chanotiya and Anju Yadav 563

Essential Oil Composition of Tanacetum vulgare subsp. siculum (Guss.) Raimondo et Spadaro (Asteraceae) from Sicily Carmen Formisano, Felice Senatore, Maurizio Bruno, Sergio Rosselli, Gabriella Bellone and Vivienne Spadaro 567

The Chemical Composition of the Essential Oils of Euphorbia caracasana and E. cotinifolia (Euphorbiaceae) from Venezuela Janne Rojas, Shirley Baldovino, Marietta Vizcaya, Luis B. Rojas and Antonio Morales 571

Constituents of Cajanus cajan (L.) Millsp., Moringa oleifera Lam., Heliotropium indicum L. and Bidens pilosa L. from Nigeria Akinola O. Ogunbinu, Guido Flamini, Pier L. Cioni, Muritala A. Adebayo and Isiaka A. Ogunwande 573

Antimicrobial Activity and Chemical Composition of Senecio sandrasicus on Antibiotic Resistant Staphylococci Aysel Ugur, Nurdan Sarac and M. Emin Duru 579

Essential Oil Composition and Antimicrobial Activity of Ballota nigra L. ssp foetida Daniele Fraternale, Anahi Bucchini, Laura Giamperi and Donata Ricci 585

Natural Product Communications 2009

Volume 4, Number 4

Contents

Original Paper Page

Monoterpene Hydrocarbons May Serve as Antipredation Defensive Compounds in Boisea trivittata, the Boxelder Bug Maria C. Palazzo and William N. Setzer 457

Three Novel Sesquiterpene Esters from Celastrus angulatus Shaopeng Wei, Mingan Wang, Jiwen Zhang, Yong Qian, Zhiqin Ji and Wenjun Wu 461

Sesquiterpenes with Quinone Reductase-Inducing Activity from Liriodendron chinense Ying Dong, Dong Liang, Jianjin Huang and Peng Zhang 467

First Evidence for an Anxiolytic Effect of a Diterpenoid from Salvia cinnabarina Francesco Maione, Maria Camela Bonito, Mariantonella Colucci, Virginia Cozzolino, Angela Bisio, Giovanni Romussi, Carla Cicala, Stefano Pieretti and Nicola Mascolo 469

Variation of Major Limonoids in Azadirachta indica Fruits at Different Ripening Stages and Toxicity against Aedes aegypti Bina Shaheen Siddiqui, Syed Kashif Ali, Syed Tariq Ali, Syed Naeem ul Hassan Naqvi and Rajput Muhammad Tariq 473

Cycloartane-type Glycosides from two Species of Astragalus (Fabaceae) Jens Linnek, Anne-Claire Mitaine-Offer, Tomofumi Miyamoto, Olivier Duchamp, Jean-François Mirjolet

and Marie-Aleth Lacaille-Dubois 477

Glycowithanolides accumulation in in vitro Shoot Cultures of Indian Ginseng (Withania somnifera Dunal) Ashok Ahuja, Devinder Kaur, Mallubhotla Sharada, Arun Kumar, Krishan Avtar Suri and Prabhu Dutt 479

Structure Activity Studies on the Crinane Alkaloid Apoptosis-inducing Pharmacophore James McNulty, Jerald J. Nair, Jaume Bastida, Siyaram Pandey and Carly Griffin 483

HPLC and NMR Studies of Phenoxazone Alkaloids from Pycnoporus cinnabarinus Daniel A. Dias and Sylvia Urban 489

A new Pyranone Derivative from the Leaves of Livistona australis Samy K. El-Desouky, Mona E. S. Kassem, Zarag I. A. Al - Fifi and Amira M. Gamal El-Deen 499

Isolation, Structure Elucidation and Apoptosis-inducing Activity of New Compounds from the Edible Fungus Lentinus striguellus Yongbiao Zheng, Baobing Zhao, Chunhua Lu, Xinjian Lin, Zhonghui Zheng and Wenjin Su 501

New Benzophenone O-Glucoside from Hypericum ellipticum Elyse Petrunak, Andrew C. Kester, Yunbao Liu, Camile S. Bowen-Forbes, Muraleedharan G. Nair and Geneive E. Henry 507

Structures of New Phenolic Glycosides from the Seeds of Cucurbita moschata Li Fa-Sheng, Xu Jing, Dou De-Qiang, Chi Xiao-Feng, Kang Ting-Guo and Kuang Hai Xue 511

Myricarborin A and n-Butyl-α-L-rhamnopyranoside, Two Novel Compounds from the Bark of Myrica rubra Zhiguo Liu, Shuang Ji, Yuchuan Zhang, Dali Meng and Xian Li 513

Continued inside back cover