Antifouling Activity of Coumarin and its Derivatives Isolated from the Cinnamon Tree Cinnamomum loureiroi

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1 한수지 46(1), , 013 riginal Article Kor J Fish Aquat Sci 46(1), ,013 계피식물 (Cinnamomum loureiroi) 에서분리한 coumarin 과유도체의방오효과 김영도 신현웅 조지영 * 순천향대학교해양생명공학과 Antifouling Activity of Coumarin and its Derivatives Isolated from the Cinnamon Tree Cinnamomum loureiroi Young Do Kim, Hyun Woung Shin and Ji Young Cho* Department of Marine Biotechnology, Soonchunhyang University, Asan , Korea The active antifouling compounds coumarin and its derivatives were isolated from the cinnamon tree Cinnamomum loureiroi. The antifouling activities were determined using representative soft fouling organisms: the seaweed Ulvapertusa and diatom Navicula annexa. The chemical constituents with antifouling activities were identified as coumarin, hydroxylcoumarin, coumaric acid, and cinnamaldehyde by interpreting nuclear magnetic resonance, and high-resolution mass spectroscopy data. These compounds were isolated from 1.09 g of crude Cinnamomum sp. methanol extract, yielding approximately 18.4, 6.3, 9.8, and 14.7 mg of coumarin, hydroxylcoumarin, coumaric acid, and cinnamaldehyde, respectively. The compounds inhibited U. pertusa zoospores with EC 50 values of μg/ml, and the diatom N. annexa with EC 50 of μg/ml. Key words: Antifouling, Coumarin, Ulva pertusa, Navicula annexa, NMR 서 론,,, (Callow and Edyvean, 1990). (International Maritime rganization) (IM, 001) Igarol, dichlofluanid, diuron (Voulvoulis et al.000; Yamada 007; Cresswell et al. 006).. Irgarol diuron (Fernández-Alba et al. 00), (embryotoxicity) (Manzo et al., 006), dichlofluanid (Fernández-Alba et al. 00). Lee et al. (010) Irgarol ng/l ng/l dichlofluanid ng/l ng/l.,. 70,. (Lauraceae) 50,,,, (Prasad et al. 009). coumarins, cinnamaldehyde, cinnamon oil, diterpenoids, polyphenols, cinnamic acid,. cinnamon oil (Gende et al. 008; Faix et al. 009), cinnamic aldehyde Article history; Received 4 September 01; Revised 8 January 013; Accepted 13 February 013 *Corresponding author: Tel: Fax: address: jycho@sch.ac.kr Kor J Fish Aquat Sci 46(1) , February pissn: , eissn: c The Korean Society of Fishereis and Aquatic Science. All rights reserved 53

2 54 김영도 신현웅 조지영 (Kim et al. 004), cinnamon diterpene (Nohara et al. 1985).,,,,,, (Cralg 1999). cinnamic acid transcinnamic acid (Ulva fasciata) (Shin et al., 001), p-(sulphooxy) cinnamic acid (Todd et al., 1993).. 추출및분리 재료및방법 Cinnamomum loureiroi (Saigon cinnamon, Vietnamese cassia. or Vietnamese cinnamon) Jin et al. (1997) 80% mg/ml. celite (500 g; mesh) 1, hexane, ethyl acetate, methanol 0% step-gradient. ethyl acetate:methanol (4:1, v/v) HPLC (Agilent 100series; Agilent Technologies, Santa Clara, CA). ubondapak C8 reversed-phase column (10 50 mm, 10 µm; Phenomenex, Torrance, CA), acetonitrile water (HPLC grade) isocratic (30% acetonitrile). ml/min 100 UV detector (Agilent Technologies, Santa Clara, CA) 0 nm. 구조분석 high resolution fast atom bombardment mass spectrometer (HR-FABMS, JMS HX 110; JEL,Japan). (nuclear magnetic resonance: NMR) JNM-ECP 600 NMR spectrometer (JEL) methanol-d (CD 3 D) 1 H, 13 C, correlation spectroscopy (CSY), heteronuclear multiple bond correlation (HMBC), heteronuclear multiple quantum coherence (HMQC). 방오효능검증 (Ulva pertusa) (Navicula annexa) Cho et al. (001). PES (Provasoli, 1968). (1.5 cm) 10% HCl well plate well 3 ( cells/ml) PES ml Navicula annexa F/. 0 C 70 mol/m /s (light:dark=1:1) 50 rpm., cells/ ml 7 (Cho, 01). DMS DMS, Irgarol. LC 50 ( ) EC 50 ( ) (therapeutic ratio) (Clare 199). 15 (Fusetani, 011). 활성물질분리및효능 결과및고찰 ( 17.6 g) 1.09 g silica gel chromatography HPLC. silica gel chromatography 9. 6 ethyl acetate : methanol (4: 1), 4.6 g/ml EC mg. 7 (16 mg) ethyl acetate : methanol (1: 1) 5.3 g/ml EC HPLC 30% acetonitrile isocratic 4 peak. peak 9, 35, 45, 75, 18.4, 6.3, 9.8, 14.7 mg.

3 Coumarin 과유도체의방오효과 55 Table 1. Inhibition of zoospores settlement of Ulva pertusa by coumarin and its derivatives s (μg/ml) LC 50 EC 50 LC 50 /EC 50 (1) () (3) (4) LC 50 : the meian lethal dose. EC 50 : the half-maximal effective concentration. Table. Inhibition of diatom settlement of Navicula annexa by coumarin and its derivatives s (μg/ml) LC 50 EC 50 LC 50 /EC 50 (1) () (3) (4) LC 50 : the meian lethal dose. EC 50 : the half-maximal effective concentration., EC g/ml LC g/ml. () EC (Table 1). EC g/ ml LC g/ml. () EC (Table ). 구조분석 6 4 NMR HR-MS, coumarin (1), hydroxylcoumarin (), coumaric acid (3), cinnamaldehyde (4) Table3 Table 4. (1) HR-FABMS ([M+H] + ) 145, 1 H-NMR 13 C-NMR C 9 H 6. 1 H-NMR 6 signal 6.43 (H-3: 1H, d), 7.95 (H-4: 1H, d), 7.57 (H-5: 1H), 7.34 (H-6, 1H), 7.49 (H-7: 1H), 7.3 (H- 8: 1H). 13 C-NMR 9 signal 16.7 (C-), (C-3), (C-4), 19.4 (C-5), 15.8 (C-6), (C-7), (C-8), (C-9), 10.3 (C-10). NMR Günther et al. (1975), (1) coumarin (Fig.1-1). () ([M+H] + ) H-NMR 13 C-NMR C 9 H H-NMR 6.45 (H-3: 1H, d), 7.56 (H-5: 1H), 7.34 (H-6, 1H), 7.48 (H-7: 1H), 7.3(H-8: 1H) 5 signal, 13 C-NMR 16.7 (C-), 95.6 (C- 3), (C-4), 19.5 (C-5), 15.8 (C-6), (C-7), (C-8), (C-9), (C-10) 9 signal. NMR Günther et al. (1975) () hydroxylcoumarin (Fig.1-). (3) ([M+H] + ) 163, 1 H-NMR 13 C-NMR C 9 H H-NMR 6 signal 6.56 (H-: 1H), 6.95 (H-3: 1H), 7.1 (H-3a, 1H), 7.1 (H-4a: 1H), 7.19 (H-5a: 1H), 7.46 (H-6a: 1H). 13 C-NMR (C-1), 11.3 (C-), (C-3), 13.4 (C-1a), (C-a), 11.8 (C-3a), 13.4 (C-4a), 14.3 (C-5a), 19.8 (C-6a) 9 signal. Hoff et al. (1994), (3) coumaric acid (Fig. 1-3). (4) ([M+H] + ) 145 C 10 H H-NMR 8.91 (H-1: H), 6.98 (H-3: 1H), 1.91 (H-4, 3H), 7.4 (H-a: 1H), 7.35 (H-3a: 1H), 7.8 (H-4a: 1H), 7.31 (H-5a: 1H), 7.53 (H-6a: 1H) 8 signal, 13 C- NMR 191. (C-1), (C-), (C-3), 9.7 (C- 4), 14.6 (C-1a), 131. (C-a), (C-3a), 13.4 (C-4a), (C-5a), (C-6a) 10 signal. SubashBabu et al. (007), (4) cinnamaldehyde (Fig. 1-4). Coumarin benzopyrone pyrone. essential oils, cinnamon barkoil, cassia leaf oil, lavender oil (Lacy and Kennedy 004), Streptmyces, Aspergillus (El-Gendy et al. 008; Aguirre-Pranzoni et al. 011). Coumarin 6 hydroxylation 3-, 4-, 5-, 6-, 7-, 8-hydroxycoumarins 6,7-dihydroxycoumarin. pyrone o-hydroxyphenylacetal-dehyde,o-hydroxyphenylethanol,ohydroxyphenylacetic acid, o-hydroxyphenyllactic acid,ohydroxyphenylpropionic acid,o-coumaric acid (Lake 1999). Coumarin. furanocoumarins

4 56 김영도 신현웅 조지영 Table C -NMR spectral data for coumarin and its derivatives Position (1) () (3) (4) δc δc δc δc a a a a a a a (1) () 1a H H 5a (3) (4) Fig. 1. Structures of coumarin and derivatives isolated from a cinnamon extract. (1); coumarin, (); hydroxylcoumarin, (3); coumaric acid, (4); cinnamaldehyde. (Hadaček et al. 1994), scopoletin, umbelliferone, xanthotoxin, herniarin (jala et al. 000). Coumaric acid (Zang et al. 000), cinnamaldehyde Helicobacter pylori (Ali et al. 005)., Irgarol 15 coumarin a H 4 Table 4. 1 H - NMR spectral data for coumarin and derivatives Position (1) () (3) (4) δh δ H δ H δ H a a 7.4 3a a a a , coumarin hydroxylcoumarin coumaric acid cinnamaldehyde, close ring open ring., polymer biofilm. polymer biofilm (Wieczorek and Todd, 1998). (Cho, 01). U. pertusa N. annexa,.. Coumarin. 사 사 01 ( ) ( -C1ABA ).

5 Coumarin 과유도체의방오효과 57 참고문헌 Aguirre-Pranzoni C, rden AA, Bisogno FR, Ardanaz CE, Tonn CE and Kurina-Sanz M Coumarin metabolic routes in Aspergillus spp. Fungal Biol 115, dx.doi.org/ /j.funbio Ali SM, Khan AA, Ahmed I, Musaddiq M, Ahmed KS, Polasa1 H, Rao LV, Habibullah CM, Sechi LA and Ahmed N Antimicrobial activities of Eugenol and Cinnamaldehyde against the human gastric pathogen Helicobacter pylori. Annal Clinic Microbiol Antimicro 4, org/ / Callow ME and Edyvean RGV Algal fouling and corrosion. In: Introduction to applied phycology. Akatsuka I, ed. SPB Academic Publishing, Hague, Netherlands, Cho JY. 01. Antifouling steroids isolated from red alga epiphyte filamentous bacterium Leucothrixmucor. Fish Sci 78, Cho JY, Kwon EH, Choi JS, Hong SY, Shin HW and Hong YK Antifouling activity of seaweed extracts on the green alga Enteromorphaprolifera and the mussel Mytilusedulis. J App Phycol 13, Clare AS, Rittschof D, Gerhart DJ and Maki JS Molecular approaches to nontoxic antifouling. Invertebr Reprod Dev, Cralg WJ Health-promoting properties of common herbs. Amer J Clin Nutr 70, Cresswell T, Richards JP, Glegg GA and Readman JW The impact of legislation on the usage and environmental concentrations of Irgarol 1051 in UK coastal waters. Mar Pollut Bull 5, j.marpolbul El-Gendy MMA, Shaaban M, EL-Bondkly AM and Shaaban KA Bioactive benzopyrone derivatives from new recombinant fusant of marine Streptomyces. Appl Biochem- Biotechnol 150, Faix Š, Faixová Z, Plachá I and Koppel J Effect of Cinnamomumzeylanicumessential oil on antioxidative status in broiler chickens. Act Vet Brno 78, org/10.754/avb Fernández-Alba AR, Hernando MD, Piedra L and Chisti Y. 00.Toxicity evaluation of single and mixed antifouling biocides measured with acute toxicity bioassays. Analytica Chimica Acta 456, Fusetani N Antifouling marine natural products. Nat Prod Rep 8, C0NP00034E Gende, LB, Floris I, Fritz R and Eguaras MJ Antimicrobial activity of cinnamon (Cinnamomumzeylanicum) essential oil and its main components against Paenibacillus larvae from Argentine. Bull Insectol 61, 1-4. GüntherH, PrestienJ and Joseph-NathanP Carbon-13 NMR spectra of coumarin and methoxycoumarins-a reinvestigation of charge density/chemical Shift Relations. rg Magnet Reson 7, Hadaček F, Müller C, Werner A, Greger H and Proksch P Analysis, isolation and insecticidal activity of linear furanocoumarins and other coumarin derivatives from Peucedanum(Apiaceae: Apiodeae). J Chem Ecol 0, Hoff WD, Dux P, Hard K, Devreese B, Nugteren-Roodzant IM, Crielaard W, Boelens R, Kaptein R, Van Beeumen J and Hellingwerf KJ Thiol ester-linked p-coumaric acid as a new photoactive prosthetic group in a protein with rhodopsin-like photochemistry. Biochem 33, IM (The International Maritime rganization) International convention on the control of harmful anti-fouling systems on ships. (AFS convention) Jin HJ, Kim JH, Sohn CH, DeWreede RE, Choi TJ, Tower GHN, Hudson JB and Hong YK Inhibition of TaqD- NA polymerase by seaweed extracts from British Columbia, Canada and Korea. J Appl Phycol 9, Kim H, Park SW and Park HD Inactivation of Escherichia coli 157:H7 by cinnamic aldehyde purified from Cinnamomum cassia shoot. Food Microbiol 1, Lacy A and Kennedy R Studies on coumarins and coumarin-related compounds to determine their therapeutic role in the treatment of cancer. Cur Pharm Des10, Lake BG Coumarin metabolism, toxicity and carcinogenicity: relevance for human risk assessment. Food Chem- Toxico l37, Lee SE, Won HS, Lee YW and Lee DS Study on the new antifouling compounds in Korean coasts. Bull Environ Contam Toxicol 85, s Manzo S, Buono S and Cremisini C. 006.Toxic effects of Irgarol and Diuron on sea urchin Paracentrotus lividusearly development, fertilization, and offspring quality. Arch Environ Contam Toxicol 51, s Nohara T, Kashiwada Y andnishioka I Cinncassiole E, a diterpene from the bark of Cinnamomum CASSIA. Phytochem 4, jala T, Remes S, Haansuu P, Vuorela H, Hiltunen R, Haahtela K and Vuorela P. 000.Antimicrobial activity of some coumarin containing herbal plants growing in Finland. J Ethnopharma 73, Prasad KN, Yang B, Dong X, Jiang G, Zhang H, Xie H and Jiang Y. 009.Flavonoid contents and antioxidant activities from Cinnamomum species. Inno Food Sci Emer Technol 10, Provasoli L Media and prospects for the cultivation of

6 58 김영도 신현웅 조지영 marine algae. In A. Watanabe, A Hattori (eds), Cultures and Collections of Algae. Japanese Society Plant Physiology, Hakone, Japan, Shin HW and Smith CM Japan, Antifouling activity of six nontoxic chemicals on spore attachment of Ulva fasciata. J Environ Biol, SubashBabu P, Prabuseenivasan P and Ignacimuthu S 007.Cinnamaldehyde-A potential antidiabetic agent. Phytomed14, j.phymed Todd JS, Zimmerman RC, Crews P and Alberte RS The antifouling activity of natural and synthetic phenolic acid sulphate ester. Phytochem 34, Voulvoulis N, Scrimshaw MD and Lester JN ccurrence of four biocides utilised in antifouling paints, as alternatives to organotin compounds, in waters and sediments of a commercial estuary in the UK. Mar Poll Bull 40, Wieczorek SK and Todd CD Inhibition and facilitation of settlement of epifaunal marine invertebrate larvae by microbial biofilm cues. Biofouling 1, Yamada H Behaviour, occurrence, and aquatic toxicity of new antifouling biocides and preliminary assessment of risk to aquatic ecosystems. Bull Fish Res Agen 1, Zang LY, Cosma G, Gardner H, Shi X, Castranova Vand Than V Effect of antioxidant protection by p-coumaric acid on low-density lipoprotein cholesterol oxidation.am J Physiol Cell Physiol 79,

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