Pyrrole and furan oligoglycosides from the starfish Asterina batheri and their inhibitory effect on the production of pro-inflammatory cytokines in lipopolysaccharide-stimulated bone marrow-derived dendritic cells Nguyen Phuong Thao a,b , Le Duc Dat a , Ninh Thi Ngoc a , Vu Anh Tu a , Tran Thi Hong Hanh a , Phan Thi Thanh Huong a , Nguyen Xuan Nhiem a , Bui Huu Tai a , Nguyen Xuan Cuong a,⇑ , Nguyen Hoai Nam a , Pham Van Cuong a , Seo Young Yang b , Sohyun Kim c , Doobyeong Chae c , Young-Sang Koh c , Phan Van Kiem a , Chau Van Minh a , Young Ho Kim b,⇑ a Institute of Marine Biochemistry, Vietnam Academy of Science and Technology (VAST), 18 Hoang Quoc Viet, Nghiado, Caugiay, Hanoi, Viet Nam b College of Pharmacy, Chungnam National University, Daejeon 305-764, Republic of Korea c School of Medicine, Brain Korea 21 Program, Institute of Medical Science, Jeju National University, Jeju 690-756, Republic of Korea article info Article history: Received 9 November 2012 Revised 4 January 2013 Accepted 8 January 2013 Available online 23 January 2013 Keywords: Asterina batheri Starfish Pyrrole oligoglycoside Furan oligoglycoside Pro-inflammatory cytokine abstract Three new pyrrole oligoglycosides, astebatheriosides A–C (1–3), and a new furan oligoglycoside, aste- batherioside D (4), were isolated from the starfish Asterina batheri by various chromatographic methods. Their structures were elucidated by spectroscopic and chemical methods. Compounds 2, 3, and 4 moderately inhibited IL-12 p40 production in lipopolysaccharide (LPS)-stimulated bone marrow-derived dendritic cells (BMDCs) with IC 50 values of 36.4, 31.6, and 22.8 lM, respectively. Ó 2013 Elsevier Ltd. All rights reserved. Starfish are invertebrates in the order Spinulosa, class Asteroi- dea, and phylum Echinodermata. They feed on oysters, abalone, and other echinoderms. Historically, starfish have been used as to- nic agents in Vietnamese folk medicines; they exhibit pharmaco- logical effects similar to those of sea cucumbers. Asterina species are abundant in the Vietnamese sea. 1 Previous investigations indi- cated that hydroxylated sterols, saponins, and cerebrosides are main constituents of Asterina species with some exhibited antimu- tagenic, 2 neuritogenic, 3 cytotoxic, and antiviral 4 activities. A novel pyrrole oligoglycoside exhibiting a moderate activation effect on the proliferation of mice spleen B-lymphocytes has been also re- ported from Asterina pectinifera. 5 As a part of our investigations on Vietnamese echinoderms, the current report details the isola- tion and structural elucidation of four pyrrole oligoglycosides, including three new compounds (1–3), and one new furan oligo- glycoside (4) from the starfish Asterina batheri. The inhibitory effects of these compounds on the production of pro-inflammatory cytokine TNF-a in LPS-stimulated BMDCs were also evaluated. Samples of A. batheri were collected at Catba, Haiphong, Vietnam, in October 2011 and identified by Professor Do Cong Thung (Institute of Marine Environment and Resources, VAST). A voucher specimen (AB-10-2011_01) was deposited at the Institute of Marine Environment and Resources and Institute of Marine Bio- chemistry, VAST. A methanol extract (150 g) of A. batheri was sus- pended in water and successively extracted with CH 2 Cl 2 . The water layer was passed through Diaion HP-20 chromatographic col- umns (CC) followed by subsequent Sephadex, silica gel, and YMC RP-18 CC, to provide compounds 1–5 (see Fig. 1 and Supplementary data). The known compound was identified as 3-[O-b-D-fucopyr- anosyl-(1 ? 3)-b-D-fucopyranosyl-(1 ? 4)-{b-D-quinovopyranosyl- (1 ? 2)}-b-D-quinovopyranosyl]-2-acetyl-pyrrole (5) 5 by detailed analyses of its spectroscopic data (1D and 2D NMR and MS) and comparisons with previously reported values. Astebatherioside A (1) 6 was obtained as a white powder. Its molecular formula was defined as C 35 H 55 O 22 N by a pseudo-molecu- lar ion peak at m/z 842.32887 [M+H] + (calcd for C 35 H 56 O 22 N, 0960-894X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bmcl.2013.01.032 ⇑ Corresponding authors. Tel.: +84 43 791 7053; fax: +84 43 791 7054 (N.X.C.); tel.: +82 42 821 5933; fax: +82 42 823 6566 (Y.H.K.). E-mail addresses: cuongnx@imbc.vast.vn (N.X. Cuong), yhk@cnu.ac.kr (Y.H. Kim). Bioorganic & Medicinal Chemistry Letters 23 (2013) 1823–1827 Contents lists available at SciVerse ScienceDirect Bioorganic & Medicinal Chemistry Letters journal homepage: www.elsevier.com/locate/bmcl