Coreosides A–D, C14-polyacetylene glycosides from the capitula of Coreopsis tinctoria and its anti-inflammatory activity against COX-2

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Yuan Zhang a, Shepo Shi b, Mingbo Zhao a, Xingyun Chai b, Pengfei Tu a,⁎ a State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Health Science Center, No. 38 Xueyuan Road, Beijing 100191, PR China b Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, PR China a r t i c l e i n f o a b s t r a c t Article history: Received 20 November 2012 Accepted in revised form 21 March 2013 Available online 2 April 2013 Four new C14-polyacetylene glycosides, namely coreosides A–D (1–4), were isolated from the capitula of Coreopsis tinctoria, a Snow chrysanthemum or Snow tea that is used as a folk tea for prevention of cardiovascular disease in southern Xinjiang, China. Coreosides A–D feature a long chain structure as its aglycon with two acetylenes on C-8 and C-10 and two olefinics on C-6 and C-12 sites, which construct a large conjugate system. The structures were elucidated on the basis of spectroscopic evidences and hydrolysis. Compounds 1–4 exhibited significant inhibition against cyclooxygenase-2 at the concentration of 1 × 10−6 mol/L, with its IC50 values of 0.22–8.8 × 10−2 μmol/L. © 2013 Elsevier B.V. All rights reserved. Keywords: Asteraceae Coreopsis tinctoria C14-polyacetylene glycosides Coreosides A–D Anti-inflammatory Cyclooxygenase-2 1. Introduction Coreopsis tinctoria Nutt. (Asteraceae) originated from the midwest of the USA, and is distributed all over the word. In China, it grows in the Karakorum Mountains at an altitude above 3000 m in southern Xinjiang[1,2]. Its capitulum, called as ‘Snow chrysanthemum’ or ‘Snow Tea’ locally, is traditionally used as tea-like beverage and has the medical function to prevent cardiovascular disease as a folk medicine [3]. Previous phytochemical investigations on the species are still lacking. It was reported [4,5] that only 13 flavonoids were isolated so far. Pharmacological research showed that the extracts of capitula have obvious activities against hyperpiesia and hyperlipemia [3,6,7], and the flavonoid-rich fraction of Snow Tea can promote glucose tolerance regain through pancreatic function recovery [8,9]. As we know, inflammation is associated with coronary heart disease and the cyclooxygenase (COX) is the key enzyme required for the conversion of arachidonic acid (AA) into prostaglandins (PGs) which are important inflammatory mediators involved in the information of inflammation. There are two major isoforms, COX-1 and COX-2. COX-1 is a structural enzyme in normal tissue but COX-2 is an inducible enzyme which is expressed rarely in the normal physiological conditions, and is expressed increasingly in inflammation or tumor pathologic state. AA is synthesized into prostaglandin E2 (PGE2) by COX-2 catalytic action and then produces a series of inflammatory mediators. So the COX-2 is one important enzyme to inflammation. In order to seek bioactive constituents from folk medicines, a series of plants, including C. tinctoria were biologically assayed. The results showed that the 70% MeOH extract of the capitula of C. tinctoria exhibit evident inhibition against cyclooxygenase-2 (COX-2). As followed, a further chemical investigation on this bioactive extract led to the isolation of four new C14-polyacetylene glycosides, namely coreosides A–D (1–4). We report herein their isolation, structural elucidation and the anti-inflammatory evaluation against COX-2. Fitoterapia 87 (2013) 93–97 ⁎ Corresponding author. Tel./fax: +86 10 8280 2750. E-mail address: pengfeitu@vip.163.com (P. Tu). 0367-326X/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.fitote.2013.03.024 Contents lists available at SciVerse ScienceDirect Fitoterapia journal homepage: www.elsevier.com/locate/fitote 2. Materials and methods 2.1. Plant material The capitula of C. tinctoria were collected in August 2004 from Hetian, Xinjiang Uygur Autonomous Region, in Northwestern China. Plant identification was performed by Prof. Hubiao Chen (Hong Kong Baptist University). A voucher specimen (CT-XJ-0408) is kept in the herbarium of the Modern Research Center for TCM of Peking University Health Science Center. 2.2. General experimental procedures Optical rotations were recorded on a Perkin-Elmer 243B digital polarimeter. UV spectra were obtained on a TU-1901 spectrometer. IR spectra were recorded on an AVATER-360 spectrometer. NMR spectra were recorded on an Inova 500 (500 MHz for 1H NMR and 125 MHz for 13C NMR) spectrometer with TMS as internal standard. HRESI-MS was measured on an Autospec-Ultima ETOF spectrometer in positive ion mode. HPLC was carried on an ODS column (Waters 300 × 7.8 mm, i.d. 6 μm) with a Waters 2487 Dual λ Absorbance detector. GC was measured on Agilent 6890N gas chromatograph, with an HP-5 capillary column (28 m × 0.32 mm) and an FID detector operated at 260 °C (column temp. 180 °C), 1.0 mL/min N2 as carrier gas. Column chromatography was performed on silica gel (200–300 mesh, Qingdao Haiyang Chemical Co. Ltd.) and D101 porous polymer resin (Tianjin Chem. Ind. Co. Ltd.). 2.3. Extraction and isolation The dried capitula (5 kg) of C. tinctoria were extracted with CH2Cl2–MeOH (1 1) and 70% MeOH (×3 times). After removal of the solvent under reduced pressure at 60 °C, the residue of the 70% MeOH extract (1208.2 g) was suspended in H2O and low and medium polar compounds were removed with EtOAc. The aq. layer was further partitioned with n-BuOH. A portion of the n-BuOH soluble extract (122.3 g) was subjected to D101 porous polymer resin column chromatography (CC), eluting with H2O, and 10%, 30% and 70% MeOH, successively. The fraction (0.8 g) eluted with 70% MeOH was subjected to a Sephadex LH-20 CC, eluting with MeOH–H2O (5:5, 6:4 and 7:3, v/v) to afford two fractions (Frs. 1 and 2). Fr. 1 was further subjected to an opening ODS CC, eluting with a gradient of MeOH–H2O (30%–80%) to afford three subfractions (Frs. 2-1 to 2-3). Fr. 2-1 was purified by prep. HPLC (MeOH–0.05% TFA = 2.5, 36:64 mL/min) to yield compounds 2 (11.0 mg) and 4 (7.6 mg). Fr. 2-2 was purified by prep. HPLC (MeOH–0.05% TFA = 45:55, 2.5 mL/min) to yield compound 3 (20.0 mg), and Fr. 2-3 was purified by prep. HPLC (MeOH–0.05% TFA = 57:43, 2.5 mL/min) to yield compound 1 (16.0 mg). 2.4. Spectroscopic and spectrometric data Coreoside A (1): brown amorphous powder; [α]D 20 = −11 (c = 0.06, MeOH); UV(MeOH) λmax (A) 262.0 (sh), 276.4 (0.2370), 293.6 (0.3111), 312.4 (0.2364); IR (KBr) νmax 3383, 2924, 2202, 2129, 1644, 1624, 1077, 950 cm−1; 1H NMR data (500 MHz, in CD3OD) (see Table 1); 13C NMR data (125 MHz, in CD3OD) (see Table 2); HRESI-MS m/z: 513.2331 [M + H]+ (calcd for C25H37O11, 513.2336). Coreoside B (2): brown amorphous powder; [a]D 20 = −9 (c = 0.06, MeOH); UV(MeOH) λmax (A) 262.4 (sh), 276.8 (0.2150), 294.0 (0.2746), 312.8 (0.2145); IR (KBr) νmax 3377, 2928, 2204, 2131, 1680, 1075, 952 cm−1; 1H NMR data (500 MHz, in CD3OD) (see Table 1); 13C NMR data (125 MHz, in CD3OD) (see Table 2); HRESI-MS m/z: 551.2085 [M + Na]+ (calcd for C25H36O12Na, 551.2104). Coreoside C (3): brown amorphous powder; [a]D 20 = −21 (c = 0.02, MeOH); UV(MeOH) λmax (A) 262.8 (sh), 277.2 (0.1718), 294.6 (0.2437), 313.6 (0.1940); IR (KBr) νmax 3383, 2925, 2205, 2132,1736, 1677, 1623, 1074, 951 cm−1; 1H NMR data (500 MHz, in CD3OD) (see Table 1); 13C NMR data (125 MHz, in CD3OD) (see Table 2); HRESI-MS m/z: 593.2214 [M + Na]+ (calcd for C27H38O13Na, 593.2210). Coreoside D (4): brown amorphous powder; [a]D 20 = −13 (c = 0.04, MeOH); UV(MeOH) λmax (A) 263.0 (sh), 276.8 (0.2359), 293.8 (0.2652), 312.8 (0.2050); IR(KBr) νmax 3385, 2929, 2201, 2129, 1680, 1074, 952 cm−1; 1H NMR data (125 MHz, in CD3OD) (see Table 1); 13C NMR data (500 MHz, in CD3OD) (see Table 2); HRESI-MS m/z: 419.1676 [M + Na]+ (calcd for C20H28O8Na, 419.1682). 2.5. Acid hydrolysis of compounds 1–4 Each compound (2 mg) was hydrolyzed with 2 N aq. CF3COOH (10 mL) at 95 °C for 4 h in a sealed tube. The reaction mixture was diluted with H2O (20 mL) and extracted with EtOAc (3 × 10 mL). The combined EtOAc extract was evaporated under reduced pressure and analyzed by TLC. (6E,12E)- Tetradecadiene-8,10-diyne-1,3-diol were detected for compound 1, (6E,12E)-tetradecadiene-8,10-diyne-1,3,14-triol for compounds 2–4. The aq. layer was evaporated with MeOH repeatedly under vacuum to remove the solvent completely. The residue was dissolved in anhydrous pyridine (0.100 mL) and mixed with a pyridine solution of L-cysteine methyl ester hydrochloride (0.100 mL). After warming at 60 °C for 1 h, hexamethyldisilazine (0.100 mL) and trimethylsilyl chloride (0.040 mL) were added, the warming at 60 °C was continued for another 30 min, and then the mixture was filtered through a 0.45 μm membrane to remove the precipitate and analyzed by GC (D-Glc (tR = 12.482 min), L-Ara (tR = 5.097 min)). 2.6. Assay for inhibition against COX-2 activity The assay for inhibition against COX-2 activity is based on the method previously reported [10]. Briefly, peritoneal macrophages were harvested from male C57BL-6J mice (the Experimental Animal Center, Institute of Experimental Animal, Chinese Academy of Medical Sciences & Peking Union Medical College) 3 d after the injection (ip) of brewer thioglycollate medium, washed twice in D-Hanks' buffer and re-suspended in RPMI- 1640 (GIBCO/BRL, Gaithersburg, Maryland, USA). Macrophages were incubated with test compound at different concentrations for 1 h and were stimulated with LPS 1.0 mg/L for 12 h. The amount of PGE2 in supernatants was measured by 94 Y. Zhang et al. / Fitoterapia 87 (2013) 93–97 radioimmunoassay (RIA) using a PGE2 RIA kit (PLA General Hospital, Beijing, China). 2.7. Determination of median inhibitory concentrations (IC50) IC50 values for 1–4 were determined by inhibiting COX-2 activity using the method as described in the section Assay for inhibition against COX-2 activity. A stock solution (0.1 mol/L) of each compound was prepared using sterile DMSO in modified phosphate buffer solution (PBS) and used immediately. Serial dilutions of test compound solutions were performed in a 48 well microtitre assay plate using modified PBS to give a series of 5 concentrations (10−5–10−9 mol/L) in triplicate. The IC50 was estimated by SigmaPlot 8.0. 3. Results and discussion Compound 1 was obtained as a brown amorphous powder. The HRESI-MS showed an accurate [M + H]+ ion at m/z 513. 2331, in accordance with an empirical molecular formula of C25H36O11. The IR exhibited absorption at 2129 and 2201 cm−1 attributable to acetylenes, together with 1619 and 950 cm−1 assigned to olefinics. These data suggested 1 a polyacetylene. The 1H NMR data showed four olefinic protons assignable to two trans double bonds at δ 5.55 (1H, d, J = 16.0 Hz), δ 5.58 (1H, d, J = 15.5 Hz), 6.23 (1H, dq, J = 15.5 Hz, J = 7.0 Hz), and 6.30 (1H, dt, J = 16.0 Hz, J = 7.0 Hz). The 13C NMR data of the aglycon showed fourteen signals, consisting of one methyl, four methylenes, one methane, four olefinics, and four acetylenes. Analysis of the above data in combination of its molecular formula suggested that 1 possesses a linear chain aglycon. Comparison of the 13C NMR data with those of known (6E,12E)- tetradecadiene-8,10-diyne-1,3-diol suggested that 1 possessed (6E,12E)-tetradecadiene-8,10-diyne-1,3-diol as its aglycon [11], except the chemical downshifting to δ 77.8 at C-3. Acid hydrolysis of 1 with 2 N CF3COOH afforded (6E,12E)- tetradecadiene-8,10-diyne-1,3-diol together with L-arabinose and D-glucose, which was determined by GC analysis, and in agreement with the observation of one L-arabinopyranosyl and one D-glucopyranosyl units in the 13C NMR data. The linkage of the sugars and the sugars with the aglycon was established by HMBC correlations from Glc-H-1 (δ 4.41) to C-3 (δ 77.8), and from Ara-H-1 (δ 4.55) to Glc-C-2 (δ 82.8). Thus, 1 was elucidated as (6E,12E)-tetradecadiene-8,10-diyne-1-ol-3-O- α-L-arabinopyranosyl-(1 → 2)-β-D-glucopyranoside, named coreoside A (Fig. 1). Compound 2 was obtained as a brown amorphous powder. The HRESI-MS showed an accurate [M + Na]+ ion peak at m/z 551.2085, in accordance with a molecular formula of C25H36O12. Its IR and NMR data were very similar to that of 1, indicating 2 is also a polyacetylene glycoside, except that the chemical shift of aglycon-C-14 downshift from δ 18.8 to δ 62.8 in its 13C NMR (Table 2), suggests a hydroxyl substitution at C-14 in 2. Besides the sugar moiety, the above analysis implied that 2 owns (6E,12E)-tetradecadiene-8,10-diyne-1,3,14-triol as its aglycon [12]. Confirmed by HMBC analysis, 2 was finally elucidated as Table 1 1H NMR data of compounds 1 4 (500 MHz, in CD3OD), J in Hz and δ in ppm. No. 1 2 3 4 1a 3.72 (1H, m) 3.71 (1H, m) 3.73 (1H, m) 3.71 (1H, m) 1b 3.61 (1H, m) 3.61 (1H, m) 3.60 (1H, m) 3.61 (1H, m) 2 1.71 (2H, m) 1.70 (2H, m) 1.70 (2H, m) 1.70 (2H, m) 3 3.82 (1H, m) 3.82 (1H, m) 3.81 (1H, m) 3.81 (1H, m) 4 1.64 (2H, m) 1.63 (2H, m) 1.63 (2H, m) 1.60 (2H, m) 5 2.24 (2H, m) 2.24 (2H, m) 2.25 (2H, m) 2.24 (2H, m) 6 6.30 (1H, dt, J = 16.0, 7.0) 6.32 (1H, dt, J = 16.0, 4.0) 6.32 (1H, dt, J = 16.0, 7.5) 6.32 (1H, dt, J = 16.0, 5.0) 7 5.55 (1H, d, J = 16.0) 5.59 (1H, d, J = 16.0) 5.61 (1H, d, J = 16.0) 5.59 (1H, d, J = 16.0) 12 5.58 (1H, d, J = 15.5) 5.77 (1H, d, J = 16.0) 5.81 (1H, d, J = 16.0) 5.77 (1H, d, J = 15.5) 13 6.23 (1H, dq, J = 15.5, 7.0) 6.28 (1H, dq, J = 16.0, 4.5) 6.24 (1H, dt, J = 16.0, 5.5) 6.28 (1H, dq, J = 15.5, 4.5) 14 1.75 (3H, d, J = 7.0) 4.08 (2H, d, J = 4.5) 4.57 (2H, dd, J = 5.5, 1.5) 4.08 (2H, dd, J = 4.5, 1.5) Glc 1 4.41 (1H, d, J = 8.0) 4.41 (1H, d, J = 8.0) 4.41 (1H, d, J = 7.5) 4.29 (1H, d, J = 8.0) 2 3.33 (1H, d, J = 8.0) 3.34 (1H, d, J = 8.0) 3.33 (1H, d, J = 8.0) 3.10 (1H, t, J = 8.0) 3 3.50 (1H, s) 3.50 (1H, s) 3.49 (1H, s) 3.28 (1H, d, J = 8.5) 4 3.28 (1H, d, J = 4.0) 3.28 (1H, s) 3.28 (1H, s) 3.23 (1H, m) 5 3.22 (1H, m) 3.21 (1H, m) 3.23 (1H, m) 3.23 (1H, m) 6a 3.81 (1H, dd, J = 10.5, 4.5) 3.76 (1H, m) 3.81 (1H, dd, J = 10.5, 4.5) 3.81 (1H, m) 6b 3.64 (1H, dd, J = 10.5, 4.5) 3.62 (1H, m) 3.64 (1H, dd, J = 10.5, 4.5) 3.63 (1H, m) Ara 1 4.55 (1H, d, J = 6.5) 4.51 (1H, d, J = 6.0) 4.51 (1H, d, J = 7.0) – 2 3.58 (1H, dd, J = 6.5, 3.5) 3.59 (1H, d, J = 6.0) 3.57 (1H, dd, J = 7.0, 4.0) – 3 3.51 (1H, d, J = 3.5) 3.51 (1H, d, J = 3.5) 3.50 (1H, d, J = 4.0) – 4 3.84 (1H, m) 3.74 (1H, m) 3.74 (1H, m) – 5a 3.68 (1H, dd, J = 12.5, 3.5) 3.85 (1H, dd, J = 10.5, 3.0) 3.86 (1H, dd, J = 12.5, 3.5) – 5b 3.47 (1H, dd, J = 12.5, 1.5) 3.45 (1H, d, J = 10.5) 3.46 (1H, dd, J = 12.5, 1.5) – Acetyl CH3CO – – 2.00 (3H, s) – Y. Zhang et al. / Fitoterapia 87 (2013) 93–97 95 (6E,12E)-tetradecadiene-8,10-diyne-1,14-diol-3-O-α-L-arabinopyranosyl-(1 → 2)-β-D-glucopyranoside, named coreoside B (Fig. 1). The molecular formula C27H38O13 of compound 3 was determined by an [M + Na]+ peak at m/z 593.2214 in its HRESI-MS. Its IR spectrum and NMR data are very similar to those of 2, which implied they are closely related in structure, being a polyacetylene glycoside too, with exception of an additional acetyl compared with 2. The assignment was supported by detailed comparison of their 1H and 13C NMR data (Tables 1 and 2) and confirmed by HMBC correlation from aglycon-H-14 (δ 4.57) to acetyl-C = O (δ 172.0). Therefore, 3 was elucidated as 14-acetoxy-(6E,12E)-tetradecadiene-8,10- diyne-1-ol-3-O-α-L-arabinopyranosyl-(1 → 2)-β-D-glucopyranoside, named coreoside C. Analysis of the HRESI-MS data suggested the molecular formula C20H28O8 of compound 4. Comparison of its 1H and 13C NMR data with those of 2 revealed their similarity in structure, with disappearance of one D-glucopyranosyl unit compared with 2, which was further confirmed by HMBC analysis. 4 was thus elucidated as (6E,12E)-tetradecadiene-8,10-diyne-1,14- diol-3-O-β-D-glucopyranoside, named coreoside D (Fig. 1). Previously, only two C14-polyacetylenes which own a large conjugate system with two acetylenes on C-8 and C-10 and three olefinics on C-4, C-6 and C-12 sites were isolated from Coreopsis Linn. But, no C14-polyacetylene glycoside was ever reported from this genus. Compounds 1–4 are the first four examples of C14-polyacetylene glycosides featuring a large conjugate system with two acetylenes and two olefinics. In most cases, the stereochemistry of C-3 in compounds 1–4 or other analogs can be resolved by Circular Dichroism methods [13]. However unfortunately, we failed to establish the configuration of compounds 1–4 due to fewer amounts we obtained from acid hydrolysis after finishing assay of inhibitory and other activities. Therefore, the absolute configuration of C-3 for compounds 1–4 remain unclear and need further efforts in the future. Biogenetically, polyacetylenes are derived by continuous dehydrogenation of crepenynic acid which is generated by oleic acid [14,15]. Crepenynic acid is widely found in the seeds of the Araliaceae, Apiaceae, Campanulaceae and Asteraceae plants which belong to Apiales and Asterales, respectively, in the Angiosperm Phylogeny Group, and polyacetylenes are often found in the essential oils of these plants [16,17]. Thus, the appearance of this type of compounds exhibited the considerable taxonomic relevance. Encouraged by previous reports [18–21] that polyacetylenes with the conjugate system generally own anti-inflammatory, antibiosis and antitumor activities. After taking consideration of the similar structure features and our preliminary biological data, we believed that compounds 1–4 should own the similar biological activities, and compounds 1–4 were screened for inhibitory activity against COX-2 induced by lipopolysaccharide (LPS) in murine peritoneal macrophages. The results showed that all compounds significantly exhibited inhibitory effects against COX-2 at a concentration of 1 × 10−6 mol/L, with their IC50 values of 0.22 × 10−2, 8.8 × 10−2, 5.0 × 10−2, and 3.6 × 10−2 μmol/L, respectively. Celecoxib was used as positive control (IC50 =4.0 × 10−2 μmol/L, C = 1 × 10−6 mol/L). From the IC50 values, we found that coreoside A (IC50 = 0.22 × 10−2 μmol/L) exhibited the most significant inhibition, even higher than positive control Celecoxib. The other three isolates have the similar inhibitory level with positive control. It is of interest that coreosides A–D are four C14-polyacetylene homologs except for the different the number of substituted hydroxyls at the aglycon part. Coreosides B–D have the similar aglycon with three hydroxyls located on C-1, C-3 and C-14, respectively, and coreoside A has only two at C-1 and C-3. The major difference probably suggested is that the inhibitory activity against COX-2 of the C-14 alkyl C14-polyacetylenes is better than that of the C-14 hydroxyl C14-polyacetylenes. It means to some extent that C-14 OH plays an important role in Fig. 1. Structures of compounds 1 4. enhancing the activity. Table 2 13C NMR data of compounds 1–4 (125 MHz, in CD3OD). No. 1 2 3 4 1 59.5 59.5 59.5 59.5 2 37.9 38.0 38.0 38.2 3 77.8 77.8 77.8 77.9 4 35.2 35.2 35.1 35.4 5 29.9 30.0 30.0 30.1 6 149.7 150.1 150.5 150.0 7 109.8 109.0 109.5 109.0 8 80.6 81.3 81.9 81.2 9 73.3 74.9 75.9 74.9 10 73.2 73.1 72.8 73.1 11 80.3 79.8 78.9 79.7 12 110.9 109.7 112.6 109.7 13 144.3 147.4 141.2 147.3 14 18.8 62.7 64.7 62.8 Glc 1 102.3 102.3 102.3 103.9 2 82.8 82.8 82.8 75.3 3 78.3 78.3 78.3 78.2 4 71.4 71.5 71.4 71.7 5 77.6 77.6 77.7 77.8 6 62.7 62.7 62.7 62.7 Ara 1 105.6 105.7 105.7 – 2 73.3 73.2 73.2 – 3 74.1 74.1 74.1 – 4 69.4 69.4 69.4 – 5 66.9 66.9 66.9 – Acetyl CO – – 172.0 – CH3 – – 20.6 – 96 Y. Zhang et al. / Fitoterapia 87 (2013) 93–97 As we know, as a natural Michael reaction acceptor, polyacetylene is an excellent inhibitor against the activation and expression of nuclear factor-κB (NF-κB) [22], one of critical nuclear factor by regulating the COX-2 to inhibit the formulation and development of inflammation [23]. 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