Natural Product Communications 2014

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Natural Product Communications

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]

HONORARY EDITOR PROFESSOR GERALD BLUNDEN The School of Pharmacy & Biomedical Sciences, University of Portsmouth, Portsmouth, PO1 2DT U.K. [email protected]

ADVISORY BOARD Prof. Viqar Uddin Ahmad Karachi, Pakistan Prof. Giovanni Appendino Novara, Italy Prof. Yoshinori Asakawa Tokushima, Japan Prof. Roberto G. S. Berlinck São Carlos, Brazil Prof. Anna R. Bilia Florence, Italy Prof. Maurizio Bruno Palermo, Italy Prof. César A. N. Catalán Tucumán, Argentina Prof. Josep Coll Barcelona, Spain Prof. Geoffrey Cordell Chicago, IL, USA Prof. Fatih Demirci Eskişehir, Turkey Prof. Dominique Guillaume Reims, France Prof. Ana Cristina Figueiredo Lisbon, Portugal Prof. Cristina Gracia-Viguera Murcia, Spain Prof. Duvvuru Gunasekar Tirupati, India Prof. Hisahiro Hagiwara Niigata, Japan Prof. Kurt Hostettmann Lausanne, Switzerland Prof. Martin A. Iglesias Arteaga Mexico, D. F, Mexico Prof. Leopold Jirovetz Vienna, Austria Prof. Vladimir I Kalinin Vladivostok, Russia Prof. Niel A. Koorbanally Durban, South Africa

Prof. Chiaki Kuroda Tokyo, Japan Prof. Hartmut Laatsch Gottingen, Germany Prof. Marie Lacaille-Dubois Dijon, France Prof. Shoei-Sheng Lee Taipei, Taiwan Prof. Imre Mathe Szeged, Hungary Prof. Ermino Murano Trieste, Italy Prof. M. Soledade C. Pedras Saskatoon, Canada Prof. Luc Pieters Antwerp, Belgium Prof. Peter Proksch Düsseldorf, Germany Prof. Phila Raharivelomanana Tahiti, French Polynesia Prof. Luca Rastrelli Fisciano, Italy Prof. Stefano Serra Milano, Italy Prof. Monique Simmonds Richmond, UK Dr. Bikram Singh Palampur, India Prof. John L. Sorensen Manitoba, Canada Prof. Johannes van Staden Scottsville, South Africa Prof. Valentin Stonik Vladivostok, Russia Prof. Winston F. Tinto Barbados, West Indies Prof. Sylvia Urban Melbourne, Australia Prof. Karen Valant-Vetschera Vienna, Austria

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Natural Product Communications

Single Crystal X-ray Diffraction, Spectroscopic and Mass Spectrometric Studies of Furanocoumarin Peucedanin

2014 Vol. 9 No. 1 71 - 74

Magdalena Bartnika*, Marta Arczewskab, Anna A. Hoserc, Tomasz Mroczeka, Daniel M. Kamińskid, Kazimierz Głowniaka, Mariusz Gagośb,e and Krzysztof Woźniakc a

Department of Pharmacognosy with Medicinal Plant Unit, Medical University of Lublin, Chodźki 1, 20-093 Lublin, Poland b Department of Biophysics, University of Life Sciences in Lublin, Akademicka 13, 20-950 Lublin, Poland c Department of Chemistry, Warsaw University 02-093 Warszawa, Pasteura 1, Poland d Department of Chemistry, University of Life Sciences in Lublin, Akademicka 15, 20-950 Lublin, Poland e Department of Cell Biology, Institute of Biology, Maria Curie-Skłodowska University, 20-033 Lublin, Poland [email protected] Received: July 25th, 2013; Accepted: November 7th, 2013

The structure of peucedanin, isolated from Peucedanum tauricum Bieb. (Apiaceae), has been established using single crystal X-ray diffraction. This furanocoumarin isolated from the light petroleum extract of P. tauricum fruits was characterized by high resolution EI-MS, sATR-FTIR and 2D NMR spectroscopic techniques. The EI-MS showed the typical fragmentation pattern of methoxyfuranocoumarins. Extensive 1D (1H and 13C) as well as 2D NMR data enabled complete assignment of the carbon atoms in the peucedanin molecule. The FTIR data confirms intermolecular hydrogen bonding between peucedanin molecules in polar solvents. Peucedanin crystallises in the R-3 space group from the trigonal system with one molecule in the asymmetric part of the unit cell. The crystal lattice of peucedanin consists of the molecules arranged in separate columns. They are related by two fold screw axes and centres of symmetry. Interestingly, peucedanin columns form two channels per unit cell with a diameter of 7.5Å going through the crystal lattice in the Z-direction. These channels are filled with disordered water molecules, which are surrounded by hydrophobic methyl groups and are located exactly at the centres of the channels. The peucedanin molecules are stacked in a single column with the opposite orientation of the neighbouring molecules. These results could be interesting in further application of this molecule, for example in biological tests of its activity. Keywords: Furocoumarin, Peucedanin, X-ray structure, ATR-FTIR, 2D NMR, EI-MS.

Furocoumarins are benzopyrone derivatives with several pharmacological activities and thus have significant importance in phytotherapy [1]. Peucedanin (Figure 1) is a linear furanocoumarin of a rare structural type with a restricted occurrence in the genera Peucedanum, Prangos, Heracleum and Archangelica. The presence of this furocoumarin could be considered as chemotaxonomically significant in all these Apiaceae genera [2-4]. Peucedanin was previously found to be cytotoxic to Ehrlich’s tumor cells and human carcinoma cell line HepG2 [5], and to have Ca2+ channel blocking activity [6].

The fruits of P. tauricum are also a good source of peucedanin. Analysis of peucedanin has been achieved by HPLC/DAD [10] and EI-MS [11]. Although the structure of this compound was elucidated by comparison with literature 1H NMR [12,13] and 13C NMR [7,14] spectroscopic data, extensive 2D NMR study and also the three dimensional crystallographic structure of this furanocoumarin has not been established yet. Only one single crystal X-ray structure of a peucedanin derivative (oxypeucedanin hydrate i.e., 5-(2,3-dihydroxy-3-methylbutoxy)-7H-furo[3,2g]chromen-7-one; CCDC entry number 637283) has been published so far [15]. In our study, we confirm by single crystal X-ray diffraction technique the structure of peucedanin, partly predicted by results of previous spectroscopic methods i.e., two dimensional NMR (1H-1H COSY, HMQC and HMBC), and ATR-FTIR. We also present all structural details, including weak molecular interactions.

Figure 1: Atom labelling and ORTEP representation of Atomic Displacement Parameters at 50% probability level for peucedanin molecule.

In our previous study, peucedanin showed its therapeutic potential in experiments using HeLa cells [7] presenting induction of early stages of apoptosis in tests with Annexine V, and also increased levels of anti-apoptotic heat shock proteins (Hsp) Hsp 27 and Hsp 72, which may be important from the potential anticancer properties of this furanocoumarin [7,8]. Peucedanin was first isolated from roots of Peucedanum tauricum Bieb. by Baranauskeite et al. [9].

In our study the structure of pure solid crystalline peucedanin was characterized by UV and IR spectra. It also appeared that the electronic absorption spectra of peucedanin in methanol and CCl4 solutions are available in the literature [16]. The absorption maxima are typical for a furanocoumarin [17,18]. The ATR-FTIR spectrum of peucedanin exhibits bands at 1729 cm-1 (coumarin carbonyl), 1139 cm-1 (C-O stretching), 1366 cm-1 (α,  -unsaturated lactone), 1632, 1576 and 1465 cm-1 (skeletal vibrations of aromatic rings, C=C), and 896, 874, and 823 cm-1 (furan ring) [19,20]. A broad absorption band centered at 3454 cm−1, visible in the spectrum recorded in methanol, was assigned to the OH stretching vibrations.

72 Natural Product Communications Vol. 9 (1) 2014

Interestingly, this spectral band does not appear in CCl4 solution. Based on this result, peucedanin would form an intermolecular hydrogen bond between molecules in a polar solvent. At the same time, the bands in the range from 2800 to 3070 cm-1 attributed to the CH3 and CH vibrations of the aromatic ring of the molecule in CCl4 distinctly gain in intensity. It can be noticed that the sharp band centered at 2970 cm-1 (peucedanin in methanol) is shifted to lower frequencies in the case of solution in CCl4.

Bartnik et al.

the atoms belonging to different neighbouring molecules is 2.235Å (H10B… H11C`). The oxygen O1 atom from the pyran ring is hydrogen bonded to the H1B’ hydrogen from the methoxy group (2.64 Å), as shown in Figure 4. The oxygen atom O2 from the carbonyl group forms three bonds: to H10C’ from the methyl group, to H14’ from the pyran ring and to H1A from the methoxy group. Additionally, the oxygen O21 forms a hydrogen bond to the H5’ hydrogen.

In the 1H NMR spectrum of peucedanin, the bands are consistent with those indicated in the literature [12,13]. 2D NMR techniques such as 1H-1H-COSY, HMQC and HMBC were used to prove the suggested structure and enabled a correct identification of the signals in the 13C NMR spectrum. In the peucedanin molecular structure the furanocoumarin core is typical for compounds of this type [15,21]. The methoxy group is not in the plane with the molecule. The crystal lattice of this compound consists of the peucedanin molecules arranged in separate columns around ca. spherical voids (see Figure 2a). The voids are probably filled in with disordered water molecules which seem to form a one dimensional continuous water distribution along the channel axis. Unfortunately, it was impossible to solve the disorder in positions of water molecules in channels in detail, thus the SQUEEZE program was utilized, which takes the effect of solvent moieties into account. The peucedanin columns are arranged in such a manner that they form three channels per unit cell with diameters of 7.5 Å going through the crystal lattice in the Z-direction (Figure 2b). The channels inside are hydrophobic due to the presence of the methyl groups. According to the SQUEEZE program, the volume of each channel equals ca. 190Å3, which for three channels is 570Å3. This accounts for ca. 10% of the unit cell volume. In order to better visualise the channels, the crystal voids were generated in the CrystalExplorer [22] program at 0.005 au isovalue (see Figures 2b and 2c). The peucedanin molecules in a single column have a sandwich-like packing with the opposite orientation of the neighbouring moieties, as is the common case for molecules carrying a non-zero dipole moment. They form dimers connected by weak C-H...O hydrogen bonds with a D…A distance of ca. 3.4Å. Dimers in stacks are interacting via interactions between aromatic parts of peucedanin with an inter-planar distance of ~3.2 Å (see Figure 3 and Table 1). The neighboring dimers are shifted along the shorter axis in such a manner that the C4 atom is located over the C7’ carbon atom, and C6 over C6’, where symbol ‘ denotes a given atom from the neighboring molecule. The shortest intermolecular distance between

a

b

c Figure 2: 3D stacks formed by peucedanin molecules around voids (a) projection along the Z-axis and three crystal voids generated at 0.0005 au level for projection along the Z-axis – the third void is the sum of void contributions at the corners of the unit cell (b), and the projection of the unit cell contents along the X-axis (c).

Details of all hydrogen bonds and other close and closest contacts present in this crystal structure are summarized in Table 2. It is worth stressing that structures which form channels stabilized only by weak hydrogen bonds are very rare. The structure of the analyzed compound is mainly stabilized by hydrogen bonds and interactions. In conclusion, we have isolated peucedanin from Peucedanum tauricum. The molecular structure of the compound was investigated by high resolution EI-MS, sATR-FTIR and NMR spectroscopy, and confirmed by single crystal X-ray diffraction. The FTIR data confirm that peucedanin forms an intermolecular hydrogen bond between molecules in polar solvents. Peucedanin, from methanol, crystallizes in the R-3 space group from the trigonal

a b Figure 3: Peucedanin crystal structure: (a) intermolecular HBs in the plane of the molecule (b) the stacking interactions in columns. Peucedanin forms dimers of oppositely oriented molecules by HB. These dimers are bonded by - interactions between rings.

X-ray diffraction and spectroscopic studies of Peucedanin

Natural Product Communications Vol. 9 (1) 2014 73

Table 1: Details of all hydrogen bonds and other close and closest contacts present in the crystal structure of peucedanin. D-H···A Weak hydrogen bonds: C1-H1B···O1 C5-H5···O21 C14-H14···O2 C10-H10C···O2 C1-H1A···O2 Distances in face-to-face stacking: C4···C7 C6···C6

Symm

d(D-H) [Å]

d(H···A) [Å]

d(D···A) [Å]

99%. ATR-FTIR: The crystalline peucedanin was dissolved in methanol and CCl4 and then centrifuged for 15 min at 15000×g in order to remove micro crystals of the compound remaining in the sample. Electronic absorption spectra were recorded with a Varian 670-IR spectrophotometer. The attenuated total reflection (ATR) configuration was used with 10 internal reflections of the ATR Ge crystal plate (45° cut). Typically, 25 scans were collected, Fouriertransformed and averaged for each measurement. Absorption spectra at a resolution of one data point per 1 cm−1 were obtained in the region between 4000 and 600 cm−1. The instrument was continuously purged with N2 for 40 min. before and during measurements. The Ge crystal plate was cleaned with ultrapure organic solvents from Sigma-Aldrich. The spectral analysis was performed with Grams/AI software from ThermoGalactic Industries (USA). EI-MS and NMR: EI-MS (70 eV) were measured on a Finnigan MAT-95 mass spectrometer (Finnigan MAT GmbH, Bremen, Germany). Careful m/z measurement was established with a peak matching method (n=20) using PFK (perfluorokerosene) as internal standard. NMR spectra were recorded on a Bruker AM-300 spectrometer (at 300 MHz for 1H and 75 MHz for 13C NMR), in CD3OD. X-ray diffraction: Peucedanin, re-crystallised from methanol, yielded yellow single crystals suitable for X-ray data collection. Data collection for single crystals of peucedanin was carried out on a Bruker AXS KAPPA APEX II ULTRA diffractometer controlled by APEXII software, equipped with a MoKα rotating anode X-ray source (λ = 0.71073 A, 50.0 kV, 22.0 mA) monochromatized by multi-layer optics and an APEX-II CCD detector. The experiments were carried out at 100K using the Oxford Cryostream cooling device. The data were collected using the omega scan with an angular scan width of 0.5o. The exposure time was 20 sec per frame. The data were corrected for the Lorentz and polarization effects. Indexing, integration and scaling were performed with the original Bruker Apex II software [24,25]. Multi-scan absorption correction was applied using SADABS [26].

74 Natural Product Communications Vol. 9 (1) 2014

The structure was solved by direct methods [27] and refined using SHELXL [28]. The refinement was based on squared structure factors (F2) for all reflections except those with very negative F2. Most of the hydrogen atoms were located in idealized averaged geometrical positions (Figure 1). Scattering factors were taken from Tables 6.1.1.4 and 4.2.4.2 in ref. [29]. During refinement, in order to solve problems with disordered solvent molecules in voids formed by peucedanin molecules, the SQUEEZE [30] program was utilised. CCDC936158 entry contains the supplementary crystallographic data for peucedanin crystals. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk/data_request/cif). Supplementary data: The details of 1H-, 13C- NMR, HMQC and HMBC of peucedanin are summarized in Table S1. The numerical values of bonds and the valence angles in the molecule are

Bartnik et al.

presented in Tables S2 and S3 respectively. Table S4 includes experimental details of single crystal measurement and data refinement and Figures S1 and S2 present the infrared absorption spectra of peucedanin in methanol and CCl4 deposited onto Ge crystal. All these data are placed in the Supplementary Materials. Acknowledgments - X-Ray single crystal measurements were accomplished at the Structural Research Laboratory of the Chemistry Department, Warsaw University, Poland. KW gives thanks for financial support from the National Science Centre NCN – decision DEC-2012/04/A/ST5/00609. Krystyna Dąbrowska MSc., a specialist in plant taxonomy from the Botanical Garden of UMCS, is kindly acknowledged for identification of the plant material. This work was also partially supported by DS/26/04 for Department of Pharmacognosy with Medicinal Plant Unit, Medical University of Lublin, Poland.

References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30]

Venugopala KN, Rashmi V, Odhav B. (2013) Review on natural coumarin lead compounds for their pharmacological activity. BioMed Research International, 1-14, http://dx.doi.org/10.1155/2013/963248 Hadaček F. (1989) Vergleichende Phytochemische Untersuchungen in der Gattung Peucedanum (Apiaceae-Apioideae). Stapfia, 18, 1-186. Murray RDH, Mendez J, Brown SA. (1982) The Natural Coumarins. Wiley, Chichester. Murray RDH. (1991) Natural Occurring Plant Coumarins. Springer–Verlag, Vienna, New York. Colombain M, Goll V, Muyard F, Girard C, Bévalot F, Richert L. (2001) A bioassay using the human hepatoblastoma cell line HepG2 detecting phototoxicity of furocoumarins. Planta Medica, 67, 644-646. Hadaček F, Härmälä P, Törnquist K, Vuorela H. (1991) Calcium antagonistic activity of five coumarins and one 2-methylchromone from Peucedanum species. Planta Medica, 57, 53-54. Bartnik M. (2004) Phytochemical investigations of aerial parts of Peucedanum tauricum Bieb. Doctoral dissertation, Medical University of Lublin, Lublin, 1-242. Bartnik M, Głowniak K, Jakubowicz-Gil J, Pawlikowska-Pawlęga B, Gawron A. (2006) The effect of furanocoumarins; peucedanin and bergapten (5-MOP), isolated from Peucedanum tauricum Bieb. (Apiaceae) fruits on apoptosis induction and heat shock protein expression in HeLa cells. Herba Polonica, 52, 71-78. Baranauskaite DI, Nikonov GK, Murav’eva DA. (1963) Peucedanin. Byulletin Izobretnych Tovarnyh Znakov, 4, 158. Hadaček F, Müller C, Werner A, Greger H, Proksch P. (1994) Analysis, isolation and insecticidal activity of linear furanocoumarins and other coumarin derivatives from Peucedanum (Apiaceae: Apioideae). Journal of Chemical Ecology, 20, 2035-2054. Cisowski W. (1986) Furanocoumarins in some of national species. Herba Polonica, 32, 3-7. Steck W, Mazurek M. (1972) Identification of natural coumarins by NMR spectroscopy. Lloydia, 35, 418-439. Kozovska V, Zheleva A. (1980) Natural coumarins X. A new furocoumarin, 8-methoxy – peucedanin from the roots of Peucedanum ruthenicum. Planta Medica, 40, S1, 60-63. Tesso H, König WA, Kubeczka K-H, Bartnik M, Głowniak K. (2005) Secondary metabolites of Peucedanum tauricum fruits. Phytochemistry, 66, 707-713. Deng K-Z, Gao W-Y, Xiong Y, Chen H-X, S.-J. Wang S-J. (2007) 5-(2,3-Dihydroxy-3-methylbutoxy)-7H-furo[3,2-g]chromen-7-one. Acta Crystallographica E, 63, 815-816. Shults EE, Petrova TN, Shakirov MM, Chernyak EI, Pokrovskiy LM, Nekhoroshev SA, Tolsticov GA. (2003) Coumarin compounds from roots of Peucedanum (Peucedanum morisonii Bess.). Chemistry for Sustainable Development, 11, 649-654. Terreaux C, Maillard M, Stoeckli-Evans H, Gupta MP, Downum KR, Quirke JME, Hostettmann K. (1995) Structure revision of a furanocoumarin from Dorstenia contrajerva. Phytochemistry, 39, 645-647. Myung K, Manthey JA, Narciso JA. (2008) Aspergillus niger metabolism of citrus furanocoumarin inhibitors of human cytochrome P450 3A4. Applied Microbiology and Biotechnology, 78, 343-349. Kuznetsova GA, Abyshev AZ, Perelson ME, Sheinker YN, Pek GY. (1966) A new coumarin, pranferol from the roots of Prangos ferulacea. Chemistry of Natural Compounds, 2, 252-255. Osadchii SA, Shul’ts EE, Shakirov MM, Tolsticov GA. (2006) Study of plant coumarins 1. Transformations of peucedanin. Russian Chemical Bulletin, 55, 75-79. Rajnikant, Dinesh, Shawl AS, Singh TP, Goel V, Sharma B. (2005) Crystallographic analysis of 9-(3-methylbut-2-enyloxyfurano)[3,2g]benzopyran-2-one. Journal of Chemical Crystallography, 35, 913-916. Turner MJ, McKinnon J, Jayatilaka D, Spackman MA. (2011) Visualisation and characterisation of voids in crystalline materials. CrystEngComm, 13, 1804-1813. Bartnik M, Głowniak K. (2007) Furanocoumarins from Peucedanum tauricum Bieb. and their variability in the aerial parts of the plant during development. Acta Chromatographica, 18, 5-14. Bruker Nonius (2007) APEXII-2008v1.0 Bruker Nonius (2007) SAINT V7.34A. Sheldrick GM. (1996) SADABS. Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Germany. Sheldrick GM. (1990) Phase annealing in SHELX-90: direct methods for larger structures. Acta Crystallographica A, 46, 473-478. Sheldrick GM. (1993) SHELXL-93, Program for the refinement of crystal structures. University of Göttingen, Germany. Wilson AJC ed. (1992) International Tables for Crystallography. Vol. C Kluwer Academic Publishers, Dordrecht. Spek AL. (2003) Single-crystal structure validation with the program PLATON. Journal of Applied Crystallography, 36, 7-13.

Natural Product Communications Vol. 9 (1) 2014 Published online (www.naturalproduct.us)

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Natural Product Communications 2014 Volume 9, Number 1 Contents Original Paper

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New Guaian-type Sesquiterpene from Wikstroemia indica Mamoru Kato, Yu-Min He, Dya Fita Dibwe, Feng Li, Suresh Awale, Shigetoshi Kadota and Yasuhiro Tezuka Differences in the Chemical Composition of Arnica montana Flowers from Wild Populations of North Italy Maria Clauser, Nicola Aiello, Fabrizio Scartezzini, Gabbriella Innocenti and Stefano Dall’Acqua A New Dolabellane Diterpenoid and a Sesquilignan from Aglaia odorata var. microphyllina Shuai Liu, Wei Yang, Shou-Bai Liu, Hui Wang, Zhi-Kai Guo, Yan-Bo Zeng, Wen-Hua Dong, Wen-Li Mei and Hao-Fu Dai New Diterpenes from Azorella spinosa Luis Astudillo, Margarita Gutiérrez, Luisa Quesada, Aurelio San-Martín, Luis Espinoza and Patricio Peñailillo A New Diterpenoid from the Aerial Parts of Andrographis paniculata Chun-Hua Wang, Wen Li, Rui-Xia Qiu, Miao-Miao Jiang and Guo-Qiang Li Isolation of a New Anti-inflammatory 20, 21, 22, 23, 24, 25, 26, 27-Octanorcucurbitacin-type Triterpene from Ibervillea sonorae Angel Jardón-Delgado, Gil Alfonso Magos-Guerrero and Mariano Martínez-Vázquez Determination of Triterpenic Acids and Screening for Valuable Secondary Metabolites in Salvia sp. Suspension Cultures Sibylle Kümmritz, Christiane Haas, Atanas I. Pavlov, Doris Geib, Roland Ulber, Thomas Bley and Juliane Steingroewer Inhibitory Effect of the Plant Clusia fluminensis against Biological Activities of Bothrops jararaca Snake Venom Eduardo Coriolano de Oliveira, Maria Carolina Anholeti, Thaisa Francielle Domingos, Camila Nunes Faioli, Eladio Flores Sanchez, Selma Ribeiro de Paiva and André Lopes Fuly Chiral Resolution and Absolute Configuration of 3α,6β-Dicinnamoyloxytropane and 3α,6β-Di(1-ethyl-1H-pyrrol-2-ylcarbonyloxy)tropane, Constituents of Erythroxylum Species Marcelo A. Muñoz, Solange Arriagada and Pedro Joseph-Nathan Aporphine Alkaloids of Cinnamomum mollissimum and their Bioactivities Fatin Fasihah Masnon, Najmah PS Hassan and Farediah Ahmad Antifungal Activity of Metabolites from the Marine Sponges Amphimedon sp. and Monanchora arbuscula against Aspergillus flavus Strains Isolated from Peanuts (Arachis hypogaea) Cynthia Arevabini, Yasmin D. Crivelenti, Mariana H. de Abreu, Tamires A. Bitencourt, Mário F. C. Santos, Roberto G. S. Berlinck, Eduardo Hajdu, Renê O. Beleboni, Ana L. Fachin and Mozart Marins Synthesis of Sepiapterin-C via Hydrolysis of 6-Ethynylpteridine Winston Nxumalo and Andrew Dinsmore Flavonoids Produced by Tissue Culture of Dracaena cambodiana Hui Wang, Guanyong Luo, Jiayuan Wang, Haiyan Shen, Ying Luo, Haofu Dai and Wenli Mei Determination of Catechins from Elephantorrhiza elephantina and Pentanisia prunelloides using Voltammetry and UV spectroscopy Smart J. Mpofu, Omotayo A. Arotiba, Lerato Hlekelele, Derek T. Ndinteh and Rui W.M. Krause In vitro Antioxidant Activity, Phenolic Compounds and Protective Effect against DNA Damage Provided by Leaves, Stems and Flowers of Portulaca oleracea (Purslane) Rúben Silva and Isabel S. Carvalho In Vitro Antiviral Activity of a Series of Wild Berry Fruit Extracts against Representatives of Picorna-, Orthomyxo- and Paramyxoviridae Lubomira Nikolaeva-Glomb, Luchia Mukova, Nadya Nikolova, Ilian Badjakov, Ivayla Dincheva, Violeta Kondakova, Lyuba Doumanova and Angel S. Galabov Induction of Apoptosis and Cell Cycle Arrest in Human Colon Carcinoma Cells by Corema album Leaves Antonio J. León-González, Margaret M. Manson, Miguel López-Lázaro, Inmaculada Navarro and Carmen Martín-Cordero How to Deal with Nomenclatoral Ambiguities of Trivial Names for Natural Products? – A Clarifying Case Study Exemplified for "Corymbosin" Vatsavaya Ramabharathi and Wolfgang Schuehly Chromatographic Analysis and Antioxidant Capacity of Tabernaemontana catharinensis Aline A. Boligon, Mariana Piana, Thiago G. Schawnz, Romaiana P. Pereira, João B. T. Rocha and Margareth L. Athayde Simultaneous Determination of 13 Chemical Marker Compounds in Gwakhyangjeonggi-san, a Herbal Formula, with Validated Analytical Methods Jung-Hoon Kim, Hyeun-Kyoo Shin and Chang-Seob Seo Single Crystal X-ray Diffraction, Spectroscopic and Mass Spectrometric Studies of Furanocoumarin Peucedanin Magdalena Bartnik, Marta Arczewska, Anna A. Hoser, Tomasz Mroczek, Daniel M. Kamiński, Kazimierz Głowniak, Mariusz Gagoś and Krzysztof Woźniak 8-Hydroxycudraxanthone G Suppresses IL-8 Production in SP-C1 Tongue Cancer Cells Arlette S. Setiawan, Roosje R. Oewen, Supriatno, Willyanti Soewondo, Sidik and Unang Supratman Antiausterity Activity of Arctigenin Enantiomers: Importance of (2R,3R)-Absolute Configuration Suresh Awale, Mamoru Kato, Dya Fita Dibwe, Feng Li, Chika Miyoshi, Hiroyasu Esumi, Shigetoshi Kadota, and Yasuhiro Tezuka Continued inside backcover

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