EDITOR-IN-CHIEF DR. PAWAN K AGRAWAL Natural Product Inc. 7963, Anderson Park Lane, Westerville, Ohio 43081, USA
[email protected] EDITORS PROFESSOR ALEJANDRO F. BARRERO Department of Organic Chemistry, University of Granada, Campus de Fuente Nueva, s/n, 18071, Granada, Spain [email protected] PROFESSOR ALESSANDRA BRACA Dipartimento di Chimica Bioorganicae Biofarmacia, Universita di Pisa, via Bonanno 33, 56126 Pisa, Italy [email protected] PROFESSOR DEAN GUO State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100083, China [email protected] PROFESSOR YOSHIHIRO MIMAKI School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, Horinouchi 1432-1, Hachioji, Tokyo 192-0392, Japan [email protected] PROFESSOR STEPHEN G. PYNE Department of Chemistry University of Wollongong Wollongong, New South Wales, 2522, Australia [email protected] PROFESSOR MANFRED G. REINECKE Department of Chemistry, Texas Christian University, Forts Worth, TX 76129, USA [email protected] PROFESSOR WILLIAM N. SETZER Department of Chemistry The University of Alabama in Huntsville Huntsville, AL 35809, USA [email protected] PROFESSOR YASUHIRO TEZUKA Institute of Natural Medicine Institute of Natural Medicine, University of Toyama, 2630-Sugitani, Toyama 930-0194, Japan [email protected] 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 [email protected]
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Natural Product Communications
Antifungal and Antioxidant Pyrrole Derivative from Piper pedicellatum
2013 Vol. 8 No. 10 1451 - 1454
Chandan Tamulya, Partha P. Duttab, Manobjyoti Bordoloib,* and Jayanta Boraa a
Natural Products Chemistry Section, CSIR-North East Institute of Science & Technology. Br. Itanagar, Itanagar-791110, Arunachal Pradesh, India b Natural Products Chemistry Division, CSIR-North East Institute of Science & Technology, Jorhat-785006, Assam, India [email protected] Received: June 30th, 2013; Accepted: July 24th, 2013
In continuation of our search for efficient pest control natural products from the flora of the South Eastern Sub-Himalayan biodiversity region, we have investigated wild edible Piper pedicellatum C. DC (Piperaceae) from Arunachal Pradesh, India against five important plant pathogenic fungi through an activity guided method, and a new compound, pedicellamide, was isolated. The structure was determined on the basis of extensive spectroscopic studies and confirmed by X-ray crystallography. The compound exhibited antifungal activities against the phytopathogenic fungal organisms Rhizoctonia solani (MIC 38.4 ± 1.6 µg/mL), Fusarium oxysporum (MIC 29.7 ± 0.8 µg/mL), Aspergillus niger (MIC 48.6 ± 0.7 µg/mL), Puccinia gramini (MIC 46.8 ± 1.4 µg/mL) and Curvularia lunata (MIC 49.1 ± 0.1µg/mL). Additionally, the antioxidant potential of the compound was estimated by DPPH, ABTS and FRAP assay and found to be 2.87 ± 0.20, 2.19 ± 0.13 and 3.96 ± 0.17 VCEAC (µM/g), respectively. Keywords: Piper pedicellatum, Piperaceae, Pyrrole derivative, Pedicellamide, Crystal structure, Antifungal, Antioxidant.
Fungal infections are the major constraints in the production and storage of different crops, destroying at least 125 million tonnes of major food crops each year . Rhizoctonia solani, Fusarium oxysporum, Aspergillus niger, Puccinia gramini and Curvularia lunata are major causes of fungal infection in several important crops [2-9]. Existing antifungal agents are mostly of synthetic origin and are reported to have a number of side effects, such as acute renal failure, hepatotoxicity, toxic porphyria, hemolytic anemia, neuropathy, asthma, dermatitis, and hemolysis [10-19]. Moreover, the emerging resistance of many of these fungi to different fungicides is also an alarming concern [20-23]. As part of our ongoing program in the search for new efficient pest control agents [24-27] from the flora of the South Eastern subHimalayan region of the Indo-Burma biodiversity belt, Piper pedicellatum C.DC (Piperaceae) was investigated for the isolation of the active biomolecule. P. pedicellatum is a dioecious, erect shrub, woody, quite glabrous and grows at an altitude from 600-1100 m in the evergreen forest area, and is traditionally used for body pain by the tribal people of Arunachal Pradesh, India . Some steroids and one monoterpenoid ester having antituberculosis activity was earlier isolated from this plant [29,30]. In this communication, we report the isolation from the leaves of P. pedicellatum and characterization of a new compound, designated as pedicellamide (1), and its antifungal and antioxidant properties. The structure of the compound has been established through 1H and 13C NMR spectroscopy and confirmed by single crystal X-ray crystallography. The antifungal properties of the isolated compound were measured against the plant pathogenic fungi R. solani, F. oxysporum, A. niger, P. gramini and C. lunata. The antioxidant activity of the isolated biomolecule was also estimated using DPPH, ABTS and FRAP assay. Activity guided fractionation allowed the isolation of pedicellamide (1) from the concentrated light petroleum (60-80oC) extract of the
leaves of P. pedicellatum as orange colored crystals. The compound analyzed as C15H17O4N by elemental analysis and from the electron impact mass spectrum with [M]+ at m/z 275 and [M+H]+ at 276. The UV spectrum in methanol exhibited absorption maxima at 207.91 and 236.37 nm. In the IR spectrum, the absorptions at 3340 cm-1 and 1713 cm-1 were assigned to –OH and C=O present in the molecule. The ferric chloride test in ethanol showed a light blue color showing the presence of a phenolic hydroxyl group. The 1H NMR (400 MHz) spectrum revealed a singlet at δ 3.63, integrating for six protons, which was assigned to two methoxy groups. Two triplets at δ 3.05 and 3.12, with J = 6 Hz, each integrated for two protons and were assigned to two vicinal CH2 groups. The D2O exchangeable singlet at δ 5.42 revealed the presence of a phenolic –OH. The singlet at δ 7.27 is due to two aromatic protons at C-2’ and C-6’. Two doublets at δ 6.45 and δ 6.29, with J = 2 Hz, and each integrating for two protons, were assigned to the presence of two protons at C-α and C-β, respectively, in a pyrrole ring system. In the 13C NMR spectrum the peak at δ 169.45 revealed the presence of a carbonyl carbon. Other 13 C signals were at δ 30.4, 36.6, 55.9, 104.6, 112.9, 118.6, 131, 132.8, and 146 ppm. NMR data are presented in Table 1. The 1 H- 1H COSY spectrum revealed the coupled protons network in the molecule. Based on this evidence, the structure of the compound was determined as 3-(4-hydroxy-3, 5-dimethoxy-phenyl)-1-pyrrol1-yl-propan-1-one (1). The structure was further confirmed by X-ray crystallography of its single crystal. The X-ray crystallographic view of 1 is presented in Figure 1, the packing diagram of the unit cell, with hydrogen bonding, in Figure 2 A, and a ball and stick diagram of the unit cell with depiction of
short contact < (sum of vdW rad) in Figure 2 B. Selected bond lengths and angles of 1 are presented in Table 1. Bond lengths and angles are reasonable, within experimental error. As, expected, the compound contains one benzene and one pyrrole unit. It crystallizes in the monoclinic system (P21/n) in an asymmetric unit. Although there is no center of asymmetry in the molecule, it possesses asymmetry as a whole, as depicted by the crystal structure and this explains the small observed specific rotation of the molecule. The atoms O1, O2, O3 and C9, which are bonded to the aromatic (C2, C3, C4, C6, C7, C8) planar ring, are almost coplanar with it. Methoxy C1 and C5 are almost in the same plane of the aromatic ring. The rest of the atoms (C10-C14) are above the plane of the benzene ring. Intermolecular hydrogen bonding was only observed in the crystal structure. Hydrogen bonding was observed between the phenolic OH (O2) and carboxyl (O4). Pedicellamide (1) exhibited good inhibitory effects against the plant pathogenic fungi - R. solani, F. oxysporum, A. niger, P. gramini and C. lunata. It showed highest inhibition against F. oxysporum and lowest against C. lunata. The minimum inhibitory concentration (MIC) of pedicellamide was found to be 38.4 ± 1.6 µg/mL, 29.7 ± 0.8 µg/mL, 48.6 ± 0.7 µg/mL, 46.8 ± 1.4 µg/mL, and 49.1 ±0.1µg/mL against R. solani, F. oxysporum, A. niger, P. graini and C. lunata, respectively. The untreated control sets of experiments showed no inhibition of growth of the fungal pathogens. Captan was used as a positive control. The MIC values of the compound were comparable with that of captan against these five antifungal organisms (Table 2), which indicated that the compound possessed good antifungal activity and can be a potential natural antifungal agent.
Figure 3: Antioxidant activity of pedicellamide (1) in DPPH, ABTS and FRAP assays.
The strong antioxidant activity of the isolated compound (1) was evident from the DPPH, FRAP and ABTS assays. The value of antioxidant activity was expressed as Vitamin-C equivalent antioxidant capacity (VCEAC) in µM/g. The results from the three methods were comparable, ranging from 2.87-3.96 (µM VCEAC/g). The VCEAC value was highest in the ABTS assay and lowest in the FRAP assay (Figure 3). The strong antioxidant activity of the compound is due to the presence of a phenolic –OH group with two neighboring methoxyl groups in the molecule. Experimental General experimental procedures: Melting point was determined on a Buchii electro thermal apparatus and is uncorrected. UVvisible spectra were recorded on an Analyticjena UV–vis specord200 operated with Aspect plus v1.7 software. IR spectra were obtained from a Perkin Elmer System 1640FT FTIR spectrometer. 1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were recorded on a Varian 400 NMR spectrometer in CDCl3 using TMS as the internal standard. Electron Impact mass spectra (EIMS) were recorded on a Thermo GC-MS system. CHN analysis was made with a Perkin Elmer 2400S CHN Analyzer. The X-ray diffraction data were collected using a Bruker 3-circle SMART Apex diffractometer with CCD area detector with monochromated Mo-Kα radiation from a 60W micro focus. The structure was solved by a direct method and refined by full-matrix least squares against F2 of all data, using SHELXTL software. Materials: 2,2´-Diphenyl-1-picryl hydrazyl (DPPH), ferric chloride, ascorbic acid, aluminum chloride, potassium persulfate, and
Table 2: Antifungal activity of pedicellamide (1). Fungal strain R. solani F. oxysporum A. niger P. gramini C. lunata
Bioactive pyrrole derivative from Piper pedicellatum
2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) were obtained from Sigma. All other reagents and chemicals of analytical grade were procured from Merck, India and local sources of India, unless otherwise stated. Milli-Q quality water was used. Silica gel G was used for TLC. All solvents were distilled prior to use. Plant material: The leaves of P. pedicellatum C. DC were collected during January, 2010 from the Papum Pare district of Arunachal Pradesh, India. The voucher specimen was identified and deposited in the Department of Foresty, NERIST Nirjuli, Arunachal Pradesh and at NEIST, Jorhat. Extraction and isolation: Air dried and powdered leaves (50 g) were exhaustively extracted with light petroleum (60-80oC) in a Soxhlet extractor for 20 h. After removing the solvent under reduced pressure below 50oC, the concentrated extract was kept overnight to yield an orange colored crystalline compound. Recrystallization with acetone: n-hexane (1:1) led to 1 as needlelike, orange colored crystals (yield: 0.23%). 3-(4-Hydroxy-3, 5-dimethoxy-phenyl)-1-pyrrol-1-yl-propan-1one (1) MP: 97-98ºC. [α]25D: 5 (c 0.05, CHCl3). Rf: 0.55 (Ethyl acetate: light petroleum, 1:1). IR (KBr): 3440, 3149, 2938, 1713, 1614.6, 1519, 1467, 1428, 1406, 1369, 1319, 1304, 1240, 1216, 1113, 1075, 1060, 922, 771,744 cm-1. UV λmax (MEOH) nm (log ε): 207.08(2.258), 235(0.9706) (HCl): 206.39(2.359), 235.77(1.04) (NaOH): 207.08(2.011), 235.77 (0.805) nm 1 H NMR (CDCl3, 400 MHz): δ 3.05 (2H, t, J = 6 Hz, 2-CH2), 3.12 (2H, t, J = 6 Hz, 3-CH2), 3.87(6 H, s, 2OCH3), 5.42 (1H, s, -OH, D2O exchangeable), 6.29 (2H, d, J = 2 Hz, β-CH), 6.45 (2H, d, J = 2Hz, α-CH), 7.25(1H, s, 6´-CH). 13 C NMR (CDCl3, 75 MHz): δ 30.4 (C-3), 36.6 (C-2), 55.9 (OCH3), 104.6 (C-2´or C-6´), 112.9 (C-β), 118.6 (C-α), 131.0 (C-1´), 132.8 ( C-4´), 146 (C-3´ or C-5´), 169 (C-1). MS (EI, 70 eV): m/z (rel. int): 276[M+H]+(96), 275[M]+(53), 208(44), 180(84), 167(98), 165(21), 137(12). Anal. Calc. for C15H17O4N C, 65.45; H, 6.18; N, 5.09 %, found C, 65.35; H, 6.10; N, 4.96 %. Product yield: 113 mg (0.23%). Crystallographic data: C15H17O4N, MW: 275.3, Monoclinic, Space group: P-2, a = 8.9498(9)Å, b = 15.5959(17) Å, c = 10.7390(9) Å, α = 90.00º, β =108.457(6) º, γ = 90.00º, cell volume = 1421.8(2) Å3, Z = 4, T = 296K, gof: 1.040, A total 2617 number of unique reflections (1652 observed [Fo]>2σ[Fo]) were measured of a colorless crystal, size 0.32×0.22×0.14 mm3 using graphite monochromated Mo/Kα radiation (λ= 0.71073 Å). RW = 0.1213, Rall= 0.0826. Atomic coordinate’s bond lengths, bond angles and thermal parameters have been deposited with the Cambridge Crystallographic Data Centre, 12, Union road, Cambridge, CB2, IEZ, UK (CCDC 903618). Antifungal activity: Micro-organism preparation: Stock cultures of R. solani, F. oxysporum, A. niger, P. gramini and C. lunata were used throughout the study. The fungus species were maintained on Potato Dextrose (PDA) having a standard formula (per L) consisting of infusion of potatoes (300 g), dextrose (20 g) and agar (15 g)
(Hi Media M096A). Standard PDA (41g) was suspended in 1000 mL distilled water, boiled to dissolve the medium completely, sterilized by autoclaving at 15 lbs pressure (121oC) for 15 min, and mixed well before dispensing. Fungal species were grown for 72 h on PDA at 28oC. For use in experiments, the species were grown separately on Potato dextrose broth (PDB) containing infusion from potato (200 g) and dextrose (20 g) (Hi Media, M 403). The broth culture was diluted to a concentration of 1x106 cfu with sterile distilled water for preparation of spore suspensions of the test fungus. Test sample concentration: Stock solution of 1 was prepared initially by dissolving in ethanol and then diluted in water to a concentration of 100 µg/mL. Concentrations of 50, 40, 30, 20 and 10 µg/mL were prepared in water from the stock solution by standard broth dilution method. From each concentration of the sample, 0.1 mL was added to 10 mL of PDB Medium containing spores, shaken well, kept in an incubator at 28±1oC for growth and observed daily. Activity was judged by measuring the dry weight of the test fungus after one week. The experiments were conducted with 3 replications and data were statistically analyzed. Minimum inhibitory concentration: Antifungal activity was expressed as % Inhibition = Sample weight (treated) /Control weight (untreated) x 100 . Minimum Inhibitory Concentration (MIC) was considered as the highest dilution at which 100% inhibition of growth of the test fungal species was observed. Antioxidant assay DPPH assay: Reaction mixture containing 100 µL of sample, and 2.9 mL of DPPH(1,1-diphenyl-2-picrylhydrazyl) reagent (0.1 mM in methanol) was incubated in the dark at room temp. for 30 min and the absorbance of the resulting solution was measured against a blank at 517 nm . The values were expressed as vitamin C equivalents of antioxidant capacity (µmol/g). FRAP assay: Three mL of FRAP (Ferric reducing antioxidant power) reagent with appropriate concentrations of the sample were incubated for 4 min at room temperature and the absorbance of the resulting solution was measured at 593 nm . The values were expressed as vitamin C equivalent antioxidant capacity (µmol/g). ABTS radical scavenging activity: 2,2´-Azino-bis(3ethylbenzthiazoline 6-sulfonic acid) radical cation (ABTS•+) was produced by reacting ABTS stock solution with 4.9 mM potassium persulfate solution (1:1) and leaving the mixture to stand in the dark at room temperature for 12–16 h before use . The concentration of the resulting blue-green ABTS radical solution was adjusted to an absorbance of 0.700 ± 0.020 at 734 nm. Appropriately diluted standard solution dissolved in methanol was added to the solution resulting in blue-green ABTS•+. The mixture was incubated in the dark at 37°C for 10 min; absorbance at 734 nm was measured at the endpoint of 10 min. Acknowledgments - We thank the Director, CSIR-North East Institute of Science & Technology, Jorhat, Assam for providing facilities. We also thank Dr P.R. Gajurel, Dept. of Foresty, NERIST, Nirjuli, Arunachal Pradesh for identifying the plant and depositing a specimen voucher of it, and Prof J. B. Baruah, IIT, Guwahati for helping us with crystallographic studies.
Fisher MC, Henk DA, Briggs CJ, Brownstein JS Madoff LC, McCraw SL, Gurr SJ. (2012) Emerging fungal threats to animal, plant and ecosystem health. Nature, 484, 186–194.
Anderson NA. (1982) Genetics and pathology of Rhizoctonia solani. Annual Review of Phytopathology, 20, 329-347. Amadi JE, Bamgbose O, Olahan GS. (2012) The host range of Aspergillus niger and Fusarium oxysporum in the family Solanaceae. International Journal of AgriScience, 2, 451-456. Ignjatov M, Milosevic D, Nikolic Z, Varga JG, Jovicic D, Zdjelar G. (2012) Fusarium oxysporum as causal agent of tomato wilt and fruit rot. Pesticides and Phytomedicine, 27, 25–31. Narayana KJP, Srikanth M, Vijayalaksmi M, Lakshmi N. (2007) Toxic spectrum of Aspergillus niger causing black mold rot of onions. Research Journal of Microbiology, 2, 881-884. Akinbode OA. (2010) Evaluation of antifungal efficacy of some plant extracts on Curvularia lunata, the causal organism of maize leaf spot. African Journal of Environmental Science and Technology, 4, 797-800. Hajano J, Pathan MA, Rajput QA, Lodhi MA. (2011) Rice blast-mycoflora, symptomatology and pathogenicity. International Journal for Agro Veterinary and Medical Sciences, 5, 53-63. Singh RP, Hodson DP, Espino JH, Jin Y, Njau P, Wanyera R, Foessel SAH, Ward RW. (2008) Will stem rust destroy the world's wheat crop? Advances in Agronomy, 98, 271–309. Leonard KJ, Szabo LJ. (2005) Stem rust of small grains and grasses caused by Puccinia graminis. Molecular Plant Pathology, 6, 99-111. Koizumi A, Shiiojima S, Omiya M, Nakano S, Sato N, Ikeda, M. (1979) Acute renal failure and maneb (manganoius ethylenebis[dithiocarbarmate]) exposure. The Journal of the American Medical Association, 242, 2583-2585. Bakir F, Rustam H, Tikritis S, Al-Damluji SF, Shihristani H. (1980) Clinical and epidemiological aspects of methylmercury poisoning. Postgraduate Medical Journal, 56, 1-10. Israeli R, Sculsky M, Tiberin P. (1983) Acute intoxication due to exposure to maneb and Zineb: A case with behavioral and central nervous system changes. Scandinavian Journal of Work, Environment & Health, 9, 47-51. Peluso A M, Tardio M, Admao F, Venturo N. (1991) Multiple sensitization due to bis-dithiocarbamate and thiophthalimide pesticides. Contact Dermatiitis, 25, 327-328. Colosio C, Tomasini M, Cairoli S, Foa V, Minoia C, Marinovich M, Galli CL. (1991) Occupational triphenyltin acetate poisoning: a case report. British Journal of Industrial Medicine, 48, 136-139. Peters HA, Gocmen A, Cripps DJ, Bryan GT, Dogramaci I. (1992) Epidemiology of hexachlorobenzene induced porphyria in Turkey: Clinical and laboratory follow-up after 25 years. Archives of Neurology, 39, 744-749. Dannaker CJ, Maibach HI, O’Malley M. (1993) Contact urticaria and anaphylaxis to the fungicide chlorothalonil. Cutis, 52, 312-315. Vilaplana J, Romaguera C, (1993) Captan, a rare contact sensitizer in hairdressing. Contact Dermatitis, 29, 107. Royce S, Wald P, Sheppared D, Balmes J. (1993) Occupational asthma in a pesticides manufacturing worker. Chest, 103, 295-296. Grandjean P, Weihe P, Nielsen JB. (1994) Methylmercury: Significance of intrauterine and postnatal exposures. Clinical Chemistry, 40, 1395-1400. http://deltafarmpress.com/rice/fungicide-resistant-rhizoctonia-solani-found-louisiana?page=2. Accessed on 14.06.2013. Smith CM. (1988) History of benzimidazole use and resistance. Fungicide resistance in North America. Delp CJ. (Ed.). American Phytopathological Society, St Paul, MN, 23-24. Chung WH, Chung WC, Ting PF, Ru CC, Huang HC, Huang JW. (2009) Nature of resistance to methyl benzimidazole carbamate fungicides in Fusarium oxysporum f.sp. lilii and F. oxysporum f.sp. gladioli in Taiwan. Journal of Phytopathology, 157, 742–747. Engels AJ, Holub EF, Swart K, De Waard MA. (1998) Genetic analysis of resistance to fenpropimorph in Aspergillus niger. Current Genetics, 33, 145-150. Bordoloi MJ, Shukla VS, Sharma RP (1985) Absolute stereochemistry of the insect antifeedant cadinene from Eupatorium adenophorum. Tetrahedron letters, 26, 509–510. Bordoloi M, Saikia B, Mathur RK, Nath Goswami B. (1993) A meliacin from Chisocheton paniculatus. Phytochemistry, 34, 583-584. Bordoloi M, Mohan S, Barua NC, Dutta SC, Mathur RK, Ghosh AC. (1997) An alkylated coumarin from Kayea assamica. Phytochemistry, 44, 939-942. Bordoloi PK, Bhuyan PD, Boruah P, Bordoloi M, Rao PG. (2009) A long chain alkylated α-methylene-γ-butyrolactone from Artabotrys odoratissimus fruit. Phytochemistry Letters, 2, 22–24. Angami A, Gajurel PR, Rethy P, Singh B, Kalita SK. (2006) Status and potential of wild edible plants of Arunachal Pradesh. Indian Journal of Traditional Knowledge, 5, 541- 550. Jun-zhu L, Hai-yang L, Qiu D, Chang-xiang C. (2007) Chemical constituents of Piper pedicellatum C. DC. Natural Product Research & Development, 19, 620-622. Rukachaisirikul T, Prabpal S, Kongsaefree P, Suksamrarn A. (2001) (+)- Bornyl piperate, a new monoterpene ester from Piper pedicellatum aff. roots. Chemical & Pharmaceutical Bulletin, 52, 760-761. Lis-Balchin M, Deans SG, Hart S. (1996) Bioactivity of geranium oils from different commercial sources. Journal of Essential Oil Research, 8, 281-290. Aoshima H, Hideaki T, Hirofumi K, Yoshinobu K. (2004) Aging of whiskey increases 1, 1-diphenyl -2-picryl hydrozyl radical scavenging activity. Journal of Agricultural and Food Chemistry, 52, 5240–5244. Iris F, Benzie F, Strain JJ. (1999) Ferric reducing/antioxidant power assay: Direct measure of total antioxidant activity of biological fluids and modified version for simultaneous measurement of total antioxidant power and ascorbic acid concentration. Methods in Enzymology, 299, 15–27. Re R, Pellegrini N, Proteggente A, Pannala A, Yang M, Rice-Evans C. (1999) Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radical Biology & Medicine, 26, 1231–1237.
Natural Product Communications Vol. 8 (10) 2013 Published online (www.naturalproduct.us)
Inhibitory Effects of Stilbene Derivatives from Parthenocissus tricuspidata on Adipocyte Differentiation and Pancreatic Lipase Sang Hoon Lee, Qing Liu, Bang Yeon Hwang and Mi Kyeong Lee HPLC-PDA Analysis and Anti-inflammatory Effects of Mori Cortex Radicis Chang-Seob Seo, Hye-Sun Lim, Soo-Jin Jeong, Hyekyung Ha and Hyeun-Kyoo Shin Development of HPLC Fingerprint for Quality Assessment of Bulbus Lilii Kunming Qin, Hao Cai, Lijuan Zheng, Miao Zhang, Xinghai Zhang, Jie Gu and Baochang Cai Antifungal and Antioxidant Pyrrole Derivative from Piper pedicellatum Chandan Tamuly, Partha P. Dutta, Manobjyoti Bordoloi and Jayanta Bora Quorum Sensing: A Non-conventional Target for Antibiotic Discovery Varsha Naik and Girish Mahajan An Alkenylresorcinol Derivative from Hakea sericea Fruits and their Antimicrobial Activity Ângelo Luís, Carla Cruz, Ana Paula Duarte and Fernanda Domingues Glucosinolates in Two Endemic Plants of the Aurinia Genus and their Chemotaxonomic Significance Ivica Blažević, Gina Rosalinda De Nicola, Sabine Montaut and Patrick Rollin Proteinaceous Protease Inhibitor from Lawsonia inermis: Purification, Characterization and Antibacterial Activity Arvind Dabhade, Priti Patel and Ulhas Patil Essential Oils Composition of Croton Species from the Amazon Nathalie A. Turiel, Alcy F. Ribeiro, Elisangela Elena N. Carvalho, Vanessa D. Domingos, Flávia Cristina A. Lucas, Léa Maria M. Carreira, Eloisa Helena A. Andrade and José Guilherme S. Maia Comparative Analysis of the Essential Oil Composition of Murraya paniculata and M. exotica Hai-Ning Lv, Xiao-Yu Guo, Peng-Fei Tu and Yong Jiang Chemical Composition of the Essential Oil of Erechtites valerianaefolia from Mérida, Venezuela Johanna Hernández, Ismer Bracho, Luis B. Rojas-Fermin, Alfredo Usubillaga and Juan Carmona Effect of Different Drying Methods on the Essential Oils of Mint (Mentha haplocalyx) Yachun Shu, Yajun Chen, Kunming Qin, Hao Cai, Li Wu, Huan Li, Lijuan Xu and Baochang Cai Juglans regia and J. nigra, Two Trees Important in Traditional Medicine: A Comparison of Leaf Essential Oil Compositions and Biological Activities Prajwal Paudel, Prabodh Satyal, Noura S. Dosoky, Samjhana Maharjan and William N. Setzer
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Review/Account Natural Compounds against Flaviviral Infections Md Abubakr, Subhash C Mandal and Sugato Banerjee Microwave-Assisted Techniques (MATs); a Quick Way to Extract a Fragrance: A Review Antonios K. Kokolakis and Spyridon K. Golfinopoulos
Natural Product Communications 2013 Volume 8, Number 10 Contents Original Paper Guaiol - A Naturally Occurring Insecticidal Sesquiterpene Tao Liu, Chun-Juan Wang, Hui-Qin Xie and Qing Mu 3-Oxoabolene and 1-Oxocurcuphenol, Aromatic Bisabolanes from the Sponge Myrmekioderma sp. Afsaneh Yegdaneh, Sumaitt Putchakarn, Supreeya Yuenyongsawad, Alireza Ghannadi and Anuchit Plubrukarn Acanthoic Acid Inhibits Melanogenesis through Tyrosinase Down-regulation and Melanogenic Gene Expression in B16 Melanoma Cells Weon-Jong Yoon, Young-Min Ham, Hun Seok Yoon, Wook-Jae Lee, Nam Ho Lee and Chang-Gu Hyun Cembranoids from the Cultured Soft Coral Sinularia gibberosa Hsiu-Fen Lin, Huey-Jen Su, Nai-Lun Lee and Jui-Hsin Su Major Constituents of Boswellia carteri Resin Exhibit Cyclooxygenase Enzyme Inhibition and Antiproliferative Activity Sami I. Ali, Chuan-Rui Zhang, Amal A. Mohamed, Farouk K. EL-Baz, Ahmad K. Hegazy, Maimona A. Kord and Muraleedharan G. Nair Cucurbitane-type Triterpenes from Citrullus lanatus (Watermelon) Seeds Takashi Kikuchi, Rina Okada, Yu Harada, Kenji Ikushima, Takahiro Yamakawa, Takeshi Yamada and Reiko Tanaka A New Taraxerol Derivative from the Roots of Microcos tomentosa Sutin Kaennakam, Jirapast Sichaem, Suttira Khumkratok, Pongpun Siripong and Santi Tip-pyang Two New Triterpenoids from Gelsemium elegans and Aglaia odorata Bing Liu, Lin Yang, You-Kai Xu, Shang-Gao Liao, Huai-Rong Luo and Zhi Na Inhibition of Tumor Cells Multidrug Resistance by Cucumarioside A2-2, Frondoside А and their Complexes with Cholesterol Ekaterina S. Menchinskaya, Dmitry L. Aminin, Sergey A. Avilov, Aleksandra S. Silchenko, Pelageya V. Andryjashchenko, Vladimir I. Kalinin and Valentin A. Stonik Anticholinesterase and Antioxidant Activities of Fucoxanthin Purified from the Microalga Phaeodactylum tricornutum Arthitaya Kawee-ai, Ampin Kuntiya and Sang Moo Kim Impact of Ploidy Change on Secondary Metabolites and Photochemical Efficiency in Solanum bulbocastanum Immacolata Caruso, Fabrizio Dal Piaz, Nicola Malafronte, Nunziatina De Tommasi, Riccardo Aversano, Cristian Wulff Zottele, Maria-Teresa Scarano and Domenico Carputo Alkaloids from an Endophytic Streptomyces sp. YIM66017 Hao Zhou, Yabin Yang, Jucheng Zhang, Tianfeng Peng, Lixing Zhao, Lihua Xu and Zhongtao Ding Novel Decaturin Alkaloids from the Marine-Derived Fungus Penicillium oxalicum Pei-le Wang, Dan-yi Li, Lei-rui Xie, Xin Wu, Hui-ming Hua and Zhan-lin Li Monanchomycalin C, a New Pentacyclic Guanidine Alkaloid from the Far-Eastern Marine Sponge Monanchora pulchra Ksenya M. Tabakmakher, Vladimir A. Denisenko, Alla G. Guzii, Pavel S. Dmitrenok, Sergey A. Dyshlovoy, Hyi-Seung Lee and Tatyana N. Makarieva Antiinflammatory and Antioxidant Flavonoids from Helichrysum kraussii and H. odoratissimum Flowers Percival B. Legoale, Mahlori J. Mashimbye and Teunis van Ree Antiproliferative Effect of Flavonoids from the Halophyte Vitex rotundifolia on Human Cancer Cells You Ah Kim, Hojun Kim and Youngwan Seo Identification of a Xanthine Oxidase-inhibitory Component from Sophora flavescens using NMR-based Metabolomics Ryuichiro Suzuki, Yuka Hasuike, Moeka Hirabayashi, Tatsuo Fukuda, Yoshihito Okada and Yoshiaki Shirataki Flavone C-Glycosides from Lychnis senno and their Antioxidative Activity Hari Prasad Devkota, Kumiko Fukusako, Koji Ishiguro and Shoji Yahara Anti-oxidative and DNA Protecting Effects of Flavonoids-rich Scutellaria lateriflora Madhukar Lohani, Manuj Ahuja, Manal A Buabeid, Dean Schwartz, Dennis Shannon, Vishnu Suppiramaniam, Barbara Kemppainen and Muralikrishnan Dhanasekaran Polyphenolic Сompounds from Сallus Сultures of Iris pseudacorus Darya V. Tarbeeva, Sergey A. Fedoreyev, Marina V. Veselova, Anatoliy I. Kalinovskiy, Ludmila D. Seletskaya, Tamara I. Mazurok and Victor P. Bulgakov Pterocarpans from the Root Bark of Aeschynomene fascicularis Edgar Caamal-Fuentes, Rosa Moo-Puc, Luis W. Torres-Tapia and Sergio R. Peraza-Sanchez Cytotoxic Constituents of Pachyrhizus tuberosus from Peruvian Amazon Olga Leuner, Jaroslav Havlik, Milos Budesinsky, Vladimir Vrkoslav, Jessica Chu, Tracey D. Bradshaw, Jana Hummelova, Petra Miksatkova, Oldrich Lapcik, Irena Valterova and Ladislav Kokoska (+)-Rumphiin and Polyalthurea, New Compounds from the Stems of Polyalthia rumphii Tian-Shan Wang, You-Ping Luo, Jing Wang, Meng-Xiong He, Ming-Guo Zhong, Ying Li and Xiao-Ping Song Citriquinones A and B, New Benzoquinones from Penicillium citrinum P. K. Vinitha Ranji, S. Chandrani Wijeyaratne, K. Hector Jayawardana and G. M. Kamal B. Gunaherath Potent Microbial and Tyrosinase Inhibitors from Stem Bark of Bauhinia rufescens (Fabaceae) Aminu Muhammad and Hasnah Mohd Sirat Continued inside backcover